JP2008144006A - Block copolymer using (meth)acrylate - Google Patents
Block copolymer using (meth)acrylate Download PDFInfo
- Publication number
- JP2008144006A JP2008144006A JP2006331635A JP2006331635A JP2008144006A JP 2008144006 A JP2008144006 A JP 2008144006A JP 2006331635 A JP2006331635 A JP 2006331635A JP 2006331635 A JP2006331635 A JP 2006331635A JP 2008144006 A JP2008144006 A JP 2008144006A
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- meth
- polymerization
- skeleton
- block
- 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
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 9
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 69
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 125000001424 substituent group Chemical group 0.000 claims abstract description 22
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 claims abstract description 12
- 125000004185 ester group Chemical group 0.000 claims abstract description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 25
- 239000010408 film Substances 0.000 claims description 17
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 10
- 238000010551 living anionic polymerization reaction Methods 0.000 claims description 8
- 229920006257 Heat-shrinkable film Polymers 0.000 claims description 7
- 239000012788 optical film Substances 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 description 65
- 238000006243 chemical reaction Methods 0.000 description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 28
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 2
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- OQILCOQZDHPEAZ-UHFFFAOYSA-N octyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCCCCCC OQILCOQZDHPEAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NTWODZFMPSMQFA-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 2-hydroxybenzoate Chemical class CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O NTWODZFMPSMQFA-UHFFFAOYSA-N 0.000 description 1
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- FBYNQOUSQWZSTB-UHFFFAOYSA-N (3-cyano-4-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2CC(C#N)C1(OC(=O)C=C)C2 FBYNQOUSQWZSTB-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 241000206601 Carnobacterium mobile Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 description 1
- PSGCQDPCAWOCSH-OPQQBVKSSA-N [(1s,3r,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@]2(C)[C@H](OC(=O)C=C)C[C@H]1C2(C)C PSGCQDPCAWOCSH-OPQQBVKSSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-QIIDTADFSA-N [(1s,4r)-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C(=C)C)C[C@@H]1C2 SKKHNUKNMQLBTJ-QIIDTADFSA-N 0.000 description 1
- TYOFSGRJVCRJCK-UHFFFAOYSA-N [2,3-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound C(C=C)(=O)OC1=C(C(=CC=C1)C(C)(C)CC)C(C)(C)CC TYOFSGRJVCRJCK-UHFFFAOYSA-N 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は（メタ）アクリル酸エステルを用いたブロック共重合体に関する。 The present invention relates to a block copolymer using (meth) acrylic acid ester.
リビングアニオン重合で（メタ）アクリル酸エステルを用いると、例えばそれがメタクリル酸メチルであった場合は、成長反応や失活反応ともに非常に速く、重合開始剤化合物や成長中のリビングアニオン鎖の末端と二次反応を起こすため重合制御が困難である。従って、これを用いたリビングアニオン重合は−７８℃〜−３０℃といった極めて低い反応温度が必要とされ、工業的な生産に適していなかった。また、ルイス酸やアルコラート等の配位性化合物を添加する方法もあるが、やはり−２０℃程度の低温での重合が必要であった。さらに、上記方法で得られたスチレン−ブタジエン−メタクリル酸メチル等のポリマーはジブロック体の発生や添加された配位性化合物の影響で、透明性が低く、力学特性等の実用的な特性も低かった。 When a (meth) acrylic acid ester is used in living anionic polymerization, for example, when it is methyl methacrylate, both the growth reaction and the deactivation reaction are very fast. It is difficult to control polymerization because of the secondary reaction. Therefore, living anionic polymerization using this requires a very low reaction temperature of −78 ° C. to −30 ° C. and is not suitable for industrial production. Also, there is a method of adding a coordinating compound such as Lewis acid or alcoholate, but polymerization at a low temperature of about −20 ° C. is still necessary. Furthermore, polymers such as styrene-butadiene-methyl methacrylate obtained by the above method have low transparency due to the generation of diblock bodies and the influence of added coordination compounds, and also have practical properties such as mechanical properties. It was low.
このような特殊な重合条件で（メタ）アクリル酸エステルを用いたブロック共重合体を得た例は特許文献１、特許文献２に開示されている。
本発明は、特定の構造をもつ（メタ）アクリル酸エステルからなるブロック部、芳香族ビニル化合物からなるブロック部および共役ジエン化合物からなるブロック部を有するブロック共重合体を提供するものであり、その製造方法の提供並びに上記ブロック共重合体を用いた組成物、シートおよびフィルムを提供するものである。 The present invention provides a block copolymer having a block part composed of (meth) acrylic acid ester having a specific structure, a block part composed of an aromatic vinyl compound, and a block part composed of a conjugated diene compound. Provided are a production method and a composition, a sheet and a film using the block copolymer.
即ち、本発明は、
（１）（メタ）アクリル酸エステルからなるブロック部と、芳香族ビニル化合物のブロック部および共役ジエン化合物のブロック部から選ばれた少なくとも一つのブロック部を有するブロック共重合体であって、（メタ）アクリル酸エステルからなるブロック部がブロック共重合体の一つの末端に位置し、かつ（メタ）アクリル酸エステルのエステル基の酸素原子に結合している置換基が、ノルボルニル骨格またはアダマンチル骨格を有することを特徴とするブロック共重合体。
（２）ノルボルニル骨格を有する置換基が、ジシクロペンタニル骨格を有することを特徴とする（１）記載のブロック共重合体。
（３）ジシクロペンタニル骨格を有する置換基が、ジシクロペンタニル基であることを特徴とする（２）記載のブロック共重合体。
（４）ノルボルニル骨格を有する置換基が、イソボルニル基であることを特徴とする（１）記載のブロック共重合体。
（５）アダマンチル骨格を有する置換基が、アダマンチル基であることを特徴とする（１）記載のブロック共重合体。
（６）（メタ）アクリル酸エステルが１〜５０（1〜３０）質量％であり、芳香族ビニル化合物が０〜９０（４０〜９０）質量％であり、共役ジエン化合物が０〜５９（９〜５９）質量％であり、その合計が１００質量％である請求項１〜請求項５のいずれか一項記載のブロック共重合体。
（７）（１）〜（６）いずれか１項記載のブロック共重合体を使用した成形品。
（８）成形品が、シートまたはフィルムである（７）記載の成形品。
（９）成形品が、熱収縮性フィルムである（７）記載の成形品。
（１０）成形品が、光学フィルムである（７）記載の成形品。
（１１）（メタ）アクリル酸エステルからなるブロック部、芳香族ビニル化合物のブロック部および共役ジエン化合物のブロック部を有するブロック共重合体であって、（メタ）アクリル酸エステルのエステル基の酸素原子に結合している置換基がノルボルニル骨格またはアダマンチル骨格である（メタ）アクリル酸エステルのブロック部を形成する際のリビングアニオン重合の温度を、−２０〜８０℃とすることを特徴とするブロック共重合体の製造方法、
である。
That is, the present invention
(1) A block copolymer having a block portion made of (meth) acrylic acid ester, at least one block portion selected from a block portion of an aromatic vinyl compound and a block portion of a conjugated diene compound, ) The block part consisting of an acrylate ester is located at one end of the block copolymer, and the substituent bonded to the oxygen atom of the ester group of the (meth) acrylate ester has a norbornyl skeleton or an adamantyl skeleton The block copolymer characterized by the above-mentioned.
(2) The block copolymer according to (1), wherein the substituent having a norbornyl skeleton has a dicyclopentanyl skeleton.
(3) The block copolymer according to (2), wherein the substituent having a dicyclopentanyl skeleton is a dicyclopentanyl group.
(4) The block copolymer according to (1), wherein the substituent having a norbornyl skeleton is an isobornyl group.
(5) The block copolymer according to (1), wherein the substituent having an adamantyl skeleton is an adamantyl group.
(6) The (meth) acrylic acid ester is 1 to 50 (1 to 30) mass%, the aromatic vinyl compound is 0 to 90 (40 to 90) mass%, and the conjugated diene compound is 0 to 59 (9). -59) The block copolymer according to any one of claims 1 to 5, wherein the block copolymer is 100% by mass.
(7) A molded article using the block copolymer according to any one of (1) to (6).
(8) The molded product according to (7), wherein the molded product is a sheet or a film.
(9) The molded product according to (7), wherein the molded product is a heat-shrinkable film.
(10) The molded product according to (7), wherein the molded product is an optical film.
(11) A block copolymer having a block portion made of (meth) acrylic acid ester, a block portion of an aromatic vinyl compound, and a block portion of a conjugated diene compound, and an oxygen atom of the ester group of (meth) acrylic acid ester The block copolymer is characterized in that the temperature of living anionic polymerization when forming a (meth) acrylic acid ester block portion in which the substituent bonded to is a norbornyl skeleton or an adamantyl skeleton is -20 to 80 ° C. Production method of polymer,
It is.
特定の（メタ）アクリル酸エステルを用いることで、−２０℃以上の条件でも、特殊な添加剤の必要なくリビングアニオン重合が可能であり、得られたブロック共重合体は耐衝撃性、耐熱性、透明性に優れる。 By using a specific (meth) acrylic acid ester, living anion polymerization is possible without the need for a special additive even under conditions of −20 ° C. or higher, and the resulting block copolymer has impact resistance and heat resistance. Excellent transparency.
本発明における（メタ）アクリル酸エステルは、メタクリル酸エステルおよびアクリル酸エステルの総称であり、下記の一般式（Ｉ）で表される。
本発明で用いる（メタ）アクリル酸エステルは、エステル基の酸素原子に結合している置換基が、ノルボルニル骨格（ビシクロ［２，２，１］ヘプチル骨格）またはアダマンチル骨格（トリシクロ［３，３，１，１３，７］デシル骨格）を有することを特徴とする（メタ）アクリル酸エステルである。 In the (meth) acrylic acid ester used in the present invention, the substituent bonded to the oxygen atom of the ester group is a norbornyl skeleton (bicyclo [2,2,1] heptyl skeleton) or an adamantyl skeleton (tricyclo [3,3,3]. 1,1 3,7 ] decyl skeleton).
（メタ）アクリル酸エステルのエステル基の酸素原子に結合している置換基が、ノルボルニル骨格を有する（メタ）アクリル酸エステルとしては、例えば、アクリル酸ノルボルニル、アクリル酸ノルボルニルメチル、アクリル酸フェニルノルボルニル、アクリル酸シアノノルボルニル、アクリル酸イソボルニル、アクリル酸ボルニル、アクリル酸フェンキル、メタクリル酸ノルボルニル、メタクリル酸ノルボルニルメチル、メタクリル酸フェニルノルボルニル、メタクリル酸シアノノルボルニル、メタクリル酸イソボルニル、メタクリル酸ボルニル、メタクリル酸フェンキルが挙げられる。 Examples of the (meth) acrylate ester in which the substituent bonded to the oxygen atom of the ester group of (meth) acrylate ester has a norbornyl skeleton include, for example, norbornyl acrylate, norbornyl methyl acrylate, phenyl acrylate Norbornyl, cyanonorbornyl acrylate, isobornyl acrylate, bornyl acrylate, fenalkyl acrylate, norbornyl methacrylate, norbornyl methyl methacrylate, phenyl norbornyl methacrylate, cyano norbornyl methacrylate, methacrylic acid Examples thereof include isobornyl, bornyl methacrylate, and fenalkyl methacrylate.
ノルボルニル骨格を有する（メタ）アクリル酸エステルであっても、更に好ましいのはその骨格がジシクロペンタニル骨格（トリシクロ［５，２，１，０２，６］デシル骨格）を有する（メタ）アクリル酸エステルであって、例えば、アクリル酸ジシクロペンタニル、アクリル酸トリシクロペンタジエニル、メタクリル酸ジシクロペンタニル、メタクリル酸トリシクロペンタジエニル等が挙げられ、この中でもメタクリル酸ジシクロペンタニルが最も好ましい。 Even (meth) acrylic acid ester having a norbornyl skeleton, more preferably has its skeleton dicyclopentanyl skeleton (tricyclo [5,2,1,0 2,6] decyl skeleton) (meth) acrylic Acid esters, for example, dicyclopentanyl acrylate, tricyclopentadienyl acrylate, dicyclopentanyl methacrylate, tricyclopentadienyl methacrylate, among which dicyclopentanyl methacrylate Is most preferred.
（メタ）アクリル酸エステルのエステル基の酸素原子に結合している置換基が、アダマンチル骨格を有する（メタ）アクリル酸エステルとしては、例えば、特に限定されるものではないが、例えば、アクリル酸アダマンチル、アクリル酸ジメチルアダマンチル、メタクリル酸アダマンチル、メタクリル酸ジメチルアダマンチルが挙げられる。 The (meth) acrylic acid ester in which the substituent bonded to the oxygen atom of the ester group of (meth) acrylic acid ester has an adamantyl skeleton is not particularly limited, for example, but for example, adamantyl acrylate Dimethyl adamantyl acrylate, adamantyl methacrylate, and dimethyl adamantyl methacrylate.
本発明でいう芳香族ビニル化合物とは、エチレン性不飽和結合を有する芳香族単量体であって、例えば、スチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、α−メチルスチレン、ビニルナフタレン、ビニルアントラセンなどがあるが、とくに好ましくはスチレンである。これらは１種でもよく、または２種以上を用いてもよい。 The aromatic vinyl compound referred to in the present invention is an aromatic monomer having an ethylenically unsaturated bond, such as styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2, There are 4-dimethylstyrene, 2,5-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, and the like, and styrene is particularly preferable. These may be used alone or in combination of two or more.
本発明でいう共役ジエン化合物としては、例えば、１，３−ブタジエン、２−メチル−１，３−ブタジエン（イソプレン）、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエンなどであるが、とくに好ましくは１，３−ブタジエン、イソプレンである。これら１種でもよく、また２種以上を用いてもよい。 Examples of the conjugated diene compound used in the present invention include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like, with 1,3-butadiene and isoprene being particularly preferred. One of these may be used, or two or more may be used.
本発明におけるブロック共重合体の分子構造は下記の一般式で示され、以下の（ａ）〜（ｄ）を満たしていることが好ましい。
Ａｎ−Ｂ−Ｄ−Ｃ ・・・・・ ｎは１以上の整数。
（ａ）Ａは芳香族ビニル化合物からなる連鎖を有するブロックもしくは共役ジエン化合物からなる連鎖を有するブロック、または芳香族ビニル化合物と共役ジエン化合物とからなる連鎖を有するブロックであって、後者の場合その構造はクリアカット構造、テーパー構造、ランダム構造などから適宜選択することができる。ｎが２以上である場合、Ａの構造は同一であっても、それぞれ異なっていてもよい。
（ｂ）Ｂは芳香族ビニル化合物からなる連鎖を有するブロックである。
（ｃ）Ｃは（メタ）アクリル酸エステルからなる連鎖を有するブロックである。
（ｄ）Ｄはビニル基に芳香族基またはアルキル基から選ばれた置換基を有する芳香族ビニル化合物である。
The molecular structure of the block copolymer in the present invention is represented by the following general formula, and preferably satisfies the following (a) to (d).
A n -BD-C n is an integer of 1 or more.
(A) A is a block having a chain composed of an aromatic vinyl compound, a block having a chain composed of a conjugated diene compound, or a block having a chain composed of an aromatic vinyl compound and a conjugated diene compound, and in the latter case The structure can be appropriately selected from a clear cut structure, a tapered structure, a random structure, and the like. When n is 2 or more, the structures of A may be the same or different.
(B) B is a block having a chain composed of an aromatic vinyl compound.
(C) C is a block having a chain composed of (meth) acrylic acid ester.
(D) D is an aromatic vinyl compound having a vinyl group having a substituent selected from an aromatic group or an alkyl group.
ここでＤは、リビングアニオン鎖末端の反応性を制御するために用いられる芳香族ビニル化合物であり、ビニル基に芳香族基またはアルキル基から選ばれた置換基を有していることが必須である。このような化合物としては、たとえばα−メチルスチレン、スチルベン、１，１−ジフェニルエチレンなどが挙げられる。単独重合性を持たない点で１，１−ジフェニルエチレンが好ましい。 Here, D is an aromatic vinyl compound used for controlling the reactivity of the living anion chain end, and it is essential that the vinyl group has a substituent selected from an aromatic group or an alkyl group. is there. Examples of such a compound include α-methylstyrene, stilbene, 1,1-diphenylethylene and the like. 1,1-diphenylethylene is preferred in that it does not have homopolymerizability.
本発明におけるブロック共重合体の分子量はとくに制限されるものではないが、好ましくはゲルパーミエ−ションクロマトグラフィー（ＧＰＣ）測定におけるポリスチレン換算の重量平均分子量（Ｍｗ）が、３０，０００≦Ｍｗ≦３００，０００の範囲、さらに好ましくは４０，０００≦Ｍｗ≦２５０，０００、最も好ましくは５０，０００≦Ｍｗ≦２００，０００であることが好ましい。Ｍｗが３０，０００未満であると得られた共重合体において充分な強度が得られず、３００，０００を越えるとシートやフィルムに加工することが困難となる場合がある。 The molecular weight of the block copolymer in the present invention is not particularly limited. Preferably, the weight average molecular weight (Mw) in terms of polystyrene in gel permeation chromatography (GPC) measurement is 30,000 ≦ Mw ≦ 300, 000, more preferably 40,000 ≦ Mw ≦ 250,000, and most preferably 50,000 ≦ Mw ≦ 200,000. When the Mw is less than 30,000, sufficient strength cannot be obtained in the obtained copolymer, and when it exceeds 300,000, it may be difficult to process into a sheet or film.
ブロック共重合体の製造における原料の組成について特に制限はないが共重合体の強度、耐熱性および透明性の点から、（メタ）アクリル酸エステルが1〜４０質量％、芳香族ビニル化合物が３０〜９４質量％、共役ジエン化合物が５〜５９質量％が好ましく、（メタ）アクリル酸エステルが1〜３０質量％、芳香族ビニル化合物が４０〜９０質量％、共役ジエン化合物が９〜５９質量％が特に好ましい。（メタ）アクリル酸エステルが１質量％未満では得られるブロック共重合体の強度、耐熱性および透明性が充分でない場合があり、４０質量％を超えると成形加工性が悪くなる場合がある。芳香族ビニル化合物が３０質量％未満では得られるブロック共重合体の成形加工性が悪くなる場合があり、９４質量％を超えると強度が不足する場合がある。 Although there is no restriction | limiting in particular about the composition of the raw material in manufacture of a block copolymer, From the point of the intensity | strength of a copolymer, heat resistance, and transparency, (meth) acrylic acid ester is 1-40 mass%, and aromatic vinyl compound is 30. ~ 94 mass%, conjugated diene compound is preferably 5 to 59 mass%, (meth) acrylic acid ester is 1 to 30 mass%, aromatic vinyl compound is 40 to 90 mass%, and conjugated diene compound is 9 to 59 mass%. Is particularly preferred. If the (meth) acrylic acid ester is less than 1% by mass, the resulting block copolymer may not have sufficient strength, heat resistance and transparency, and if it exceeds 40% by mass, the moldability may deteriorate. If the aromatic vinyl compound is less than 30% by mass, the moldability of the resulting block copolymer may deteriorate, and if it exceeds 94% by mass, the strength may be insufficient.
リビングアニオン重合反応に用いる有機溶媒としてはブタン、ペンタン、ヘキサン、イソペンタン、ヘプタン、オクタン、イソオクタンなどの脂肪族炭化水素、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、などの脂環式炭化水素、或いはベンゼン、トルエン、エチルベンゼン、キシレンなどの芳香族炭化水素などが使用できる。 Organic solvents used in the living anionic polymerization reaction include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, and cycloaliphatics such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Hydrocarbons or aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used.
ブロック共重合体の製造においては少量の極性化合物を有機溶剤に溶解してもよい。極性化合物は開始剤の効率を向上させるため、または共役ジエンのミクロ構造（組成）を調整するため使用され、芳香族ビニル化合物と共役ジエン化合物を同時に共重合させる場合はランダム化剤としての効果を有する。これらの極性化合物としては、例えば、テトラヒドロフラン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル等のエーテル類、トリエチルアミン、テトラメチルエチレンジアミン等のアミン類、チオエーテル類、ホスフィン類、ホスホルアミド類、アルキルペンゼンスルホン酸塩、カリウムやナトリウムのアルコキシド等が挙げられるが、好ましくはテトラヒドロフランである。 In the production of the block copolymer, a small amount of a polar compound may be dissolved in an organic solvent. Polar compounds are used to improve the efficiency of the initiator or to adjust the microstructure (composition) of the conjugated diene. When the aromatic vinyl compound and the conjugated diene compound are simultaneously copolymerized, they are effective as a randomizing agent. Have. These polar compounds include, for example, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, amines such as triethylamine and tetramethylethylenediamine, thioethers, phosphines, phosphoramides, alkyl benzene sulfonates, potassium and the like. Sodium alkoxide and the like can be mentioned, and tetrahydrofuran is preferred.
ブロック共重合体を製造する際のリビングアニオン重合温度は共重合する単量体によって異なる。芳香族ビニル化合物および共役ジエン化合物を重合する際の重合温度は−１０〜１５０℃、好ましくは３０〜１２０℃である。（メタ）アクリル酸エステルを重合する際における重合温度は−２０〜８０℃であり、−２０〜４０℃が好ましい。重合に要する時間は条件によって異なるが、通常は４８時間以内であり、特に好適には０．５〜１０時間である。また、重合系の雰囲気は重合開始前に窒素ガスなどの不活性ガスをもって置換することが望ましい。重合圧力は、上記重合温度範囲でモノマー及び溶媒を液層に維持するのに十分な圧力の範囲で行なえばよく、特に限定されるものではない。さらに重合系内には開始剤およびリビングポリマーを不活性化させるような不純物、例えば、水、酸素、炭酸ガスなどが混入しないように留意する必要がある。 The living anionic polymerization temperature when producing the block copolymer varies depending on the monomer to be copolymerized. The polymerization temperature for polymerizing the aromatic vinyl compound and the conjugated diene compound is -10 to 150 ° C, preferably 30 to 120 ° C. The polymerization temperature for polymerizing the (meth) acrylic acid ester is -20 to 80 ° C, and preferably -20 to 40 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 48 hours, particularly preferably 0.5 to 10 hours. Also, it is desirable to replace the polymerization atmosphere with an inert gas such as nitrogen gas before the start of polymerization. The polymerization pressure is not particularly limited as long as it is carried out within a range of pressure sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range. Furthermore, care must be taken so that impurities that inactivate the initiator and the living polymer, such as water, oxygen, carbon dioxide, etc., do not enter the polymerization system.
リビングアニオン重合の開始剤である有機リチウム化合物は、分子中に１個以上のリチウム原子が結合した化合物であり、本発明では例えば、エチルリチウム、ｎ−プロピルリチウム、イソプロピルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウムなどの単官能性重合開始剤、ヘキサメチレンジリチウム、ブタジエニルジリチウム、イソプレニルジリチウムなどの多官能性重合開始剤が使用できる。 The organic lithium compound that is an initiator of the living anion polymerization is a compound in which one or more lithium atoms are bonded in the molecule. In the present invention, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, Monofunctional polymerization initiators such as sec-butyl lithium and tert-butyl lithium, and polyfunctional polymerization initiators such as hexamethylene dilithium, butadienyl dilithium, and isoprenyl dilithium can be used.
リビングアニオン重合を行う際には、アルカリ金属、アルカリ土類金属、アルミニウムのアルコキシド、フェノキシド等の化合物を添加することにより、反応の選択性、反応速度を制御させることができるが、本発明ではこれらの添加量を少量、または無添加としてもよい。ポリマー中のリチウム、ナトリウム、アルミニウム含量を、たとえば200ppm以下とすることができる。 When performing living anionic polymerization, the selectivity of the reaction and the reaction rate can be controlled by adding a compound such as an alkali metal, alkaline earth metal, aluminum alkoxide, or phenoxide. A small amount or no additive may be added. The lithium, sodium, and aluminum contents in the polymer can be, for example, 200 ppm or less.
リビングアニオン重合における重合停止剤として、水、アルコール、無機酸、有機酸、およびフェノール系化合物から選ばれる少なくとも１種以上を用い、反応系中に添加されて重合が停止することができる。重合停止剤として水はとくに賞用できる。 As a polymerization terminator in living anionic polymerization, at least one selected from water, alcohol, inorganic acid, organic acid, and phenolic compound can be used and added to the reaction system to terminate the polymerization. Water can be used in particular as a polymerization terminator.
なお、重合活性末端の失活数は加えた重合停止剤の化学量論数に比例するので、重合停止剤は活性末端数より少ない化学量論数の量を数回に分けて添加することとして、重合中の活性末端の一部のみを失活させ、残った活性末端による重合をさらに継続させながら所定の重合率に達したところで残りの活性末端を失活させることで分子量の異なるブロック共重合体の混合物を得ることができる。その必要がない場合は一度に全ての活性末端を失活させても良い。但し、重合の完了時にはその時点における活性末端数に対して充分な量の重合停止剤を添加して活性末端を全て失活させることが必要である。 In addition, since the deactivation number of the polymerization active terminal is proportional to the stoichiometric number of the added polymerization terminator, it is assumed that the polymerization terminator is added in a number of stoichiometric numbers smaller than the number of active terminal in several times. Block copolymer having different molecular weights by deactivating only a part of the active ends during polymerization and deactivating the remaining active ends when the predetermined polymerization rate is reached while further continuing the polymerization with the remaining active ends. A mixture of coalescence can be obtained. If it is not necessary, all active ends may be inactivated at once. However, when the polymerization is completed, it is necessary to add a sufficient amount of a polymerization terminator to the number of active terminals at that time to deactivate all the active terminals.
失活処理の終わったブロック共重合体溶液から共重合体を分離するための方法としては、（１）メタノールなどの貧溶媒中にブロック共重合体溶液を投入してブロック共重合体を析出させる方法、（２）加熱ロールなどにブロック共重合体溶液を供給し、溶剤のみを蒸発させてブロック共重合体を分離する方法（ドラムドライヤー法）、（３）加熱したブロック共重合体（組成物）溶液を、そこに含まれる有機溶剤の該温度における平衡蒸気圧よりも低い圧力に保った缶中に連続的、あるいは間欠的に供給して脱揮する方法（フラッシュ蒸発法）、（４）ベント式押出機に通して脱揮させる方法、（５）温水中に撹拌しながら、ブロック共重合体溶液を吹き込んで溶剤を蒸発させる方法（スチームストリッピング法）などや、これらを組み合わせた方法が挙げられる。 As a method for separating the copolymer from the block copolymer solution after the deactivation treatment, (1) depositing the block copolymer solution in a poor solvent such as methanol to precipitate the block copolymer Method, (2) a method of supplying a block copolymer solution to a heated roll, etc., and evaporating only the solvent to separate the block copolymer (drum dryer method), (3) a heated block copolymer (composition) ) A method in which a solution is continuously or intermittently supplied into a can maintained at a pressure lower than the equilibrium vapor pressure at the temperature of the organic solvent contained therein (flash evaporation method), (4) A method of devolatilization through a vent type extruder, (5) a method of blowing a block copolymer solution while stirring in warm water to evaporate the solvent (steam stripping method), and the like How was the like.
本発明におけるブロック共重合体は、例えば以下の方法で製造することができる。ただし、以下の方法に限定されるものでない。 The block copolymer in the present invention can be produced, for example, by the following method. However, it is not limited to the following method.
有機溶媒中、有機リチウム化合物を開始剤として、ビニル芳香族炭化水素および共役ジエンの少なくとも一方からなる単量体を重合し（第１工程）、次にビニル芳香族炭化水素からなる単量体を重合し（第２工程）、次いで置換基を有するビニル芳香族炭化水素からなる単量体を重合し（第３工程）、その後、（メタ）アクリル酸からなる単量体を重合する（第４工程）。 In an organic solvent, an organic lithium compound is used as an initiator to polymerize a monomer composed of at least one of a vinyl aromatic hydrocarbon and a conjugated diene (first step), and then a monomer composed of a vinyl aromatic hydrocarbon. Polymerization (second step), then a monomer composed of a vinyl aromatic hydrocarbon having a substituent (third step), and then a monomer composed of (meth) acrylic acid (fourth step) Process).
ここで第１工程は必ずしも単一の工程である必要はなく、２つ以上のブロック部分を有するブロック共重合体を得る複数の工程でもよい。たとえば第１工程において、芳香族ビニル化合物連鎖のみのブロック部分を重合した後に芳香族ビニル化合物と共役ジエン化合物とからなるブロック部分を重合することができる。 Here, the first step is not necessarily a single step, and may be a plurality of steps for obtaining a block copolymer having two or more block portions. For example, in the first step, the block portion composed of the aromatic vinyl compound and the conjugated diene compound can be polymerized after the block portion of only the aromatic vinyl compound chain is polymerized.
本発明で得られるブロック共重合体には、本発明の効果を阻害しない範囲で必要に応じて各種の添加剤を配合することができる。添加剤としては、たとえば、安定剤、滑剤、加工助剤、ブロッキング防止剤、帯電防止剤、防曇剤、耐候性向上剤、軟化剤、可塑剤、顔料などがあり、これらを適宜添加することによって、ブロック共重合体が各種の加熱処理を受ける場合や、酸化性雰囲気や紫外線などの照射下にて使用される場合に物性の劣化を防ぐことができ、また使用目的に適した物性をさらに付与することができる。 In the block copolymer obtained by the present invention, various additives can be blended as necessary within a range not inhibiting the effects of the present invention. Examples of additives include stabilizers, lubricants, processing aids, antiblocking agents, antistatic agents, antifogging agents, weather resistance improvers, softeners, plasticizers, pigments, and the like. Can prevent deterioration of physical properties when the block copolymer is subjected to various heat treatments, or when used under irradiation of an oxidizing atmosphere or ultraviolet rays, and further provides physical properties suitable for the purpose of use. Can be granted.
安定剤としては、例えば、２−［１−（２−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ペンチルフェニル）エチル］−４，６−ジ−ｔｅｒｔ−ペンチルフェニルアクリレート、２−ｔｅｒｔ−ブチル−６−（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレートや、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールなどのフェノール系酸化防止剤、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルフォスファイト、トリスノニルフェニルフォスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−フォスファイトなどのリン系酸化防止剤などが挙げられる。 Examples of the stabilizer include 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 2-tert-butyl-6. -(3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6 Phenolic antioxidants such as -di-tert-butyl-4-methylphenol, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, trisnonylphenyl phosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite, etc. And phosphorus-based antioxidants.
また、滑剤、加工助剤、ブロッキング防止剤、帯電防止剤、防曇剤としては、パルミチン酸、ステアリン酸、ベヘニン酸などの飽和脂肪酸、パルミチン酸オクチル、ステアリン酸オクチルなどの脂肪酸エステルやペンタエリスリトール脂肪酸エステル、さらにエルカ酸アマイド、オレイン酸アマイド、ステアリン酸アマイドなどの脂肪酸アマイドや、エチレンビスステアリン酸アマイド、またグリセリン−モノ−脂肪酸エステル、グリセリン−ジ−脂肪酸エステル、その他にソルビタン−モノ−パルミチン酸エステル、ソルビタン−モノ−ステアリン酸エステルなどのソルビタン脂肪酸エステル、ミリスチルアルコール、セチルアルコール、ステアリルアルコールなどに代表される高級アルコールなどが挙げられる。 In addition, as lubricants, processing aids, antiblocking agents, antistatic agents, and antifogging agents, saturated fatty acids such as palmitic acid, stearic acid and behenic acid, fatty acid esters such as octyl palmitate and octyl stearate, and pentaerythritol fatty acid Esters, fatty acid amides such as erucic acid amide, oleic acid amide, stearic acid amide, ethylene bis stearic acid amide, glycerin-mono-fatty acid ester, glycerin-di-fatty acid ester, and sorbitan-mono-palmitic acid ester Sorbitan fatty acid esters such as sorbitan-mono-stearate, myristyl alcohol, cetyl alcohol, higher alcohols represented by stearyl alcohol and the like.
さらに耐候性向上剤としては２−（２’−ヒドロキシ−３’−ｔｅｒｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾールなどのベンゾトリアゾール系や２，４−ジ−ｔｅｒｔ−ブチルフェニル−３’，５’−ジ−ｔｅｒｔ−ブチル−４’−ヒドロキシベンゾエートなどのサリシレート系、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノンなどのベンゾフェノン系紫外線吸収剤、また、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレートなどのヒンダードアミン型耐候性向上剤が例として挙げられる。さらにホワイトオイルや、シリコーンオイルなども加えることができる。 Further, as weather resistance improvers, benzotriazoles such as 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole and 2,4-di-tert-butylphenyl Salicylates such as -3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, benzophenone UV absorbers such as 2-hydroxy-4-n-octoxybenzophenone, and tetrakis (2,2, Examples include hindered amine type weather resistance improvers such as 6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate. White oil and silicone oil can also be added.
これらの添加剤はブロック共重合体１００重量部に対し５重量部以下の範囲で使用することが望ましい。 These additives are preferably used in an amount of 5 parts by weight or less based on 100 parts by weight of the block copolymer.
本発明のブロック共重合体は、たとえば射出成形、押出成形、圧縮成形、真空成形等の公知の方法により各種成形体に加工され実用に供されるが、シートやフィルム形状で実用に供されることが好ましく、熱収縮性フィルム、熱収縮性多層フィルムおよび光学用フィルムとして実用に供されることも可能である。 The block copolymer of the present invention is processed into various molded products by a known method such as injection molding, extrusion molding, compression molding, vacuum molding, and the like, and is practically used in sheet or film shape. It is preferable that it can be put to practical use as a heat-shrinkable film, a heat-shrinkable multilayer film and an optical film.
熱収縮性フィルムや熱収縮性多層フィルムの製造方法は公知の手法が採用できる。例えば熱収縮性フィルムは、ブロック共重合体を押出機で溶融し、それをＴダイ、環状ダイなどのダイを使用してフィルム形状として押出し、一軸、二軸あるいは多軸に延伸することによって得られる。また、熱収縮性多層フィルムは別々に溶融したブロック共重合体をダイ内又はフィードブロックなどで多層化後フィルム形状として押出し、一軸、二軸あるいは多軸に延伸することによって得られる。 A known method can be adopted as a method for producing the heat-shrinkable film or the heat-shrinkable multilayer film. For example, a heat-shrinkable film can be obtained by melting a block copolymer with an extruder, extruding it into a film shape using a die such as a T die or an annular die, and stretching it uniaxially, biaxially or multiaxially. It is done. The heat-shrinkable multilayer film can be obtained by extruding a separately melted block copolymer in a die or a feed block as a film shape after being multilayered and stretching it uniaxially, biaxially or multiaxially.
この延伸するときの温度は６０〜１２０℃が好ましい。６０℃未満では延伸時にシートやフィルムが破断しやすくなり、また、１２０℃を越える場合は良好な収縮性が得られにくい。延伸倍率は、１．５〜８倍が好ましい。１．５倍では熱収縮性が不足してしまい、また、８倍を越える場合は延伸が困難となるため好ましくない。これらのフィルムを熱収縮性ラベルや包装材料として使用する場合、熱収縮率は温度８０℃において１５％以上、好ましくは７０℃において１５％以上、特に好ましくは７０℃において２０％以上であることが、低温でかつ迅速に収縮する点で望まれている。フィルムの厚さは１０〜３００μｍが好ましく、２０〜１００μｍがさらに好ましい。 The stretching temperature is preferably 60 to 120 ° C. If it is less than 60 ° C., the sheet or film tends to break during stretching, and if it exceeds 120 ° C., it is difficult to obtain good shrinkage. The draw ratio is preferably 1.5 to 8 times. If it is 1.5 times, the heat shrinkability is insufficient, and if it exceeds 8 times, stretching becomes difficult, which is not preferable. When these films are used as heat-shrinkable labels and packaging materials, the heat shrinkage rate is 15% or more at a temperature of 80 ° C., preferably 15% or more at 70 ° C., particularly preferably 20% or more at 70 ° C. It is desired in that it shrinks quickly at a low temperature. The thickness of the film is preferably 10 to 300 μm, more preferably 20 to 100 μm.
また、本発明では、得られたフィルムの表面特性を良好にするために帯電防止剤や滑剤などを表面に塗布してもよい。 In the present invention, an antistatic agent or a lubricant may be applied to the surface in order to improve the surface characteristics of the obtained film.
本発明の熱収縮性フィルムの用途としては、熱収縮性ラベル、熱収縮性キャップシール、瓶の保護フィルム、パックガード収縮包装、コンデンサ・乾電池等の電気絶縁被膜などが特に好適であるが、その他、包装フィルム、蓋材などにも適宜利用することができる。 The heat-shrinkable film of the present invention is particularly suitable for heat-shrinkable labels, heat-shrinkable cap seals, bottle protective films, pack guard shrinkable packaging, electrical insulating coatings for capacitors and dry cells, etc. It can also be used as appropriate for packaging films, lids and the like.
以下、本発明を実施例によりさらに詳細に説明する。但し、本発明は以下の実施例により限定されるものではない。実施例に用いたブロック共重合体の製造方法を実施例、比較例として以下に述べる。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. The manufacturing method of the block copolymer used for the Example is described below as an Example and a comparative example.
［実施例１］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン４８６ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液１５５０ｍＬを加えておき、次いで７５．６ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３７．８ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、６２．３ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．５９ｋｇの１，１−ジフェニルエチレン（新日鐵化学製商品名１，１−ジフェニルエチレン）を一括添加し３０分間反応させ、反応系の内温を４０℃に下げてさらに１０分間保った。
（６）１３．６ｋｇのメタクリル酸ジシクロペンタニル（日立化成製商品名ＦＡ−５１３Ｍ）を同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（５）の最後に全て重合活性末端を水により失活させて、重量平均分子量が１２万の重合体を含む重合液を得た。
[Example 1]
(1) Under a nitrogen atmosphere, 486 kg of cyclohexane as a polymerization solvent was charged into a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) Add 1550 mL of a 10 wt% cyclohexane solution of n-butyllithium as a polymerization catalyst solution, and then add 75.6 kg of styrene monomer all at once to raise the internal temperature of the reaction system to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 37.8 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization. The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 62.3 kg of styrene monomer was added all at once and copolymerized.
(5) 0.59 kg of 1,1-diphenylethylene (trade name 1,1-diphenylethylene manufactured by Nippon Steel Chemical Co., Ltd.) was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to 40 ° C. to further increase 10 Kept for a minute.
(6) After diluting 13.6 kg of dicyclopentanyl methacrylate (trade name FA-513M, manufactured by Hitachi Chemical Co., Ltd.) with the same weight of cyclohexane, the mixture was added to the reaction system and reacted for 15 minutes to complete the polymerization. .
At the end of (5), the polymerization active terminals were all deactivated with water to obtain a polymerization solution containing a polymer having a weight average molecular weight of 120,000.
［実施例２］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン５０４ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液２４５０ｍＬを加えておき、次いで６７．２ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３３．６ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、５０．４ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．７６ｋｇの１，１−ジフェニルエチレンを一括添加し３０分間反応させ、反応系の内温を４０℃に下げてさらに１０分間保った。
（６）１７．１ｋｇのメタクリル酸ジシクロペンタニルを同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（５）の最後に全て重合活性末端を水により失活させて、重量平均分子量が９万の重合体を含む重合液を得た。
[Example 2]
(1) Under a nitrogen atmosphere, 504 kg of cyclohexane as a polymerization solvent was charged into a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) Add 2450 mL of a 10 wt% cyclohexane solution of n-butyllithium as a polymerization catalyst solution, then add 67.2 kg of styrene monomer all at once, and raise the internal temperature of the reaction system to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 33.6 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization, and then the reaction system The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 50.4 kg of styrene monomer was added all at once and copolymerized.
(5) 0.76 kg of 1,1-diphenylethylene was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to 40 ° C. and kept for another 10 minutes.
(6) After diluting 17.1 kg of dicyclopentanyl methacrylate with the same weight of cyclohexane, it was added to the reaction system and reacted for 15 minutes, and then the polymerization was completed.
At the end of (5), the polymerization active terminals were all deactivated with water to obtain a polymerization solution containing a polymer having a weight average molecular weight of 90,000.
［実施例３］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン５０４ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液２５５０ｍＬを加えておき、次いで６７．２ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３３．６ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、４１．９ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．７６ｋｇの１，１−ジフェニルエチレンを一括添加し３０分間反応させ、反応系の内温を４０℃に下げてさらに１０分間保った。
（６）２５．６ｋｇのメタクリル酸ジシクロペンタニルを同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（５）の最後に全て重合活性末端を水により失活させて、重量平均分子量が８万の重合体を含む重合液を得た。
[Example 3]
(1) Under a nitrogen atmosphere, 504 kg of cyclohexane as a polymerization solvent was charged into a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) Add 2550 mL of a 10 wt% cyclohexane solution of n-butyllithium as a polymerization catalyst solution, and then add 67.2 kg of styrene monomer all at once to raise the internal temperature of the reaction system to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 33.6 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization, and then the reaction system The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 41.9 kg of styrene monomer was added all at once and copolymerized.
(5) 0.76 kg of 1,1-diphenylethylene was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to 40 ° C. and kept for another 10 minutes.
(6) After diluting 25.6 kg of dicyclopentanyl methacrylate with the same weight of cyclohexane, it was added to the reaction system and reacted for 15 minutes, and then the polymerization was completed.
At the end of (5), the polymerization active terminals were all deactivated with water to obtain a polymerization solution containing a polymer having a weight average molecular weight of 80,000.
［実施例４］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン５０４ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液２５５０ｍＬを加えておき、次いで６７．２ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３３．６ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、３３．３ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．７６ｋｇの１，１−ジフェニルエチレンを一括添加し３０分間反応させ、反応系の内温を４０℃に下げてさらに１０分間保った。
（６）３４．０ｋｇのメタクリル酸ジシクロペンタニルを同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（５）の最後に全て重合活性末端を水により失活させて、重量平均分子量が８万の重合体を含む重合液を得た。
[Example 4]
(1) Under a nitrogen atmosphere, 504 kg of cyclohexane as a polymerization solvent was charged into a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) Add 2550 mL of a 10 wt% cyclohexane solution of n-butyllithium as a polymerization catalyst solution, then add 67.2 kg of styrene monomer all at once, and raise the internal temperature of the reaction system to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 33.6 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization, and then the reaction system The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 33.3 kg of styrene monomer was added all at once and copolymerized.
(5) 0.76 kg of 1,1-diphenylethylene was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to 40 ° C. and kept for another 10 minutes.
(6) After diluting 34.0 kg of dicyclopentanyl methacrylate with the same weight of cyclohexane, it was added to the reaction system and reacted for 15 minutes, and then the polymerization was completed.
At the end of (5), the polymerization active terminals were all deactivated with water to obtain a polymerization solution containing a polymer having a weight average molecular weight of 80,000.
［実施例５］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン５０４ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液２４５０ｍＬを加えておき、次いで６７．２ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３３．６ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、５０．４ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．７６ｋｇの１，１−ジフェニルエチレンを一括添加し３０分間反応させ、反応系の内温を４０℃に下げてさらに１０分間保った。
（６）１７．１ｋｇのメタクリル酸イソボルニル（共栄社化学製商品名ライトエステルＩＢ−Ｘ）を同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（５）の最後に全て重合活性末端を水により失活させて、重量平均分子量が９万の重合体を含む重合液を得た。
[Example 5]
(1) Under a nitrogen atmosphere, 504 kg of cyclohexane as a polymerization solvent was charged into a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) Add 2450 mL of a 10 wt% cyclohexane solution of n-butyllithium as a polymerization catalyst solution, then add 67.2 kg of styrene monomer all at once, and raise the internal temperature of the reaction system to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 33.6 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization, and then the reaction system The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 50.4 kg of styrene monomer was added all at once and copolymerized.
(5) 0.76 kg of 1,1-diphenylethylene was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to 40 ° C. and kept for another 10 minutes.
(6) After diluting 17.1 kg of isobornyl methacrylate (trade name Light Ester IB-X, manufactured by Kyoeisha Chemical Co., Ltd.) with the same weight of cyclohexane, the mixture was added to the reaction system and reacted for 15 minutes to complete the polymerization.
At the end of (5), the polymerization active terminals were all deactivated with water to obtain a polymerization solution containing a polymer having a weight average molecular weight of 90,000.
［実施例６］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン５０４ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液２４５０ｍＬを加えておき、次いで６７．２ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３３．６ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、５０．４ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．７６ｋｇの１，１−ジフェニルエチレンを一括添加し３０分間反応させ、反応系の内温を４０℃に下げてさらに１０分間保った。
（６）１６．８ｋｇのメタクリル酸アダマンチル（出光石油製商品名Ａｄａｍａｎｔａｔｅ ＡＭ）を同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（５）の最後に全て重合活性末端を水により失活させて、重量平均分子量が９万の重合体を含む重合液を得た。
[Example 6]
(1) Under a nitrogen atmosphere, 504 kg of cyclohexane as a polymerization solvent was charged into a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) Add 2450 mL of a 10 wt% cyclohexane solution of n-butyllithium as a polymerization catalyst solution, then add 67.2 kg of styrene monomer all at once, and raise the internal temperature of the reaction system to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 33.6 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization, and then the reaction system The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 50.4 kg of styrene monomer was added all at once and copolymerized.
(5) 0.76 kg of 1,1-diphenylethylene was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to 40 ° C. and kept for another 10 minutes.
(6) After diluting 16.8 kg of adamantyl methacrylate (trade name Adamantate AM, manufactured by Idemitsu Petroleum) with the same weight of cyclohexane, it was added to the reaction system and reacted for 15 minutes to complete the polymerization.
At the end of (5), the polymerization active terminals were all deactivated with water to obtain a polymerization solution containing a polymer having a weight average molecular weight of 90,000.
［比較例１］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン４９０ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液１６００ｍＬを加えておき、次いで７５．６ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３７．８ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、６２．３ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．５ｋｇの１，１−ジフェニルエチレンを一括添加し３０分間反応させ、反応系の内温を４０℃に下げてさらに１０分間保った。
（６）１３．６ｋｇのスチレンモノマーを同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（５）の最後に全て重合活性末端を水により失活させて、重量平均分子量が１４万の重合体を含む重合液を得た。
[Comparative Example 1]
(1) Under a nitrogen atmosphere, 490 kg of cyclohexane as a polymerization solvent was charged in a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) In this, 1600 mL of a 10 wt% cyclohexane solution of n-butyllithium was added as a polymerization catalyst solution, then 75.6 kg of styrene monomer was added all at once, and the internal temperature of the reaction system was raised to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 37.8 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization. The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 62.3 kg of styrene monomer was added all at once and copolymerized.
(5) 0.5 kg of 1,1-diphenylethylene was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to 40 ° C. and kept for another 10 minutes.
(6) After 13.6 kg of styrene monomer was diluted with the same weight of cyclohexane, it was added all at once to the reaction system and reacted for 15 minutes to complete the polymerization.
At the end of (5), the polymerization active terminals were all deactivated with water to obtain a polymerization solution containing a polymer having a weight average molecular weight of 140,000.
［比較例２］
（１）窒素雰囲気下、ステンレス製内容量１５００リットルの反応容器中に重合溶媒としてシクロヘキサン４９０ｋｇを仕込み、３０℃に保った。
（２）この中に重合触媒溶液としてｎ−ブチルリチウムの１０重量％シクロヘキサン溶液１６００ｍＬを加えておき、次いで７５．６ｋｇのスチレンモノマーを一括で添加し、反応系の内温を５０℃に上昇させてこれをリビングアニオン重合させた。
（３）スチレンモノマーの重合率が９９％を超えた後、３７．８ｋｇのブタジエンを同時に一括で添加したのち、反応系の内温を６５℃まで上昇させて共重合を促し、その後反応系の内温を５０℃に調整し２０分間保った。
（４）その後、６２．３ｋｇのスチレンモノマーを一括添加し共重合させた。
（５）０．５ｋｇの１，１−ジフェニルエチレンを一括添加し３０分間反応させ、反応系の内温を−７８℃に下げてさらに１０分間保った。
（６）１３．６ｋｇのメタクリル酸メチルを同重量のシクロヘキサンで希釈した後、反応系に一括添加し１５分間反応させた後重合を完了させた。
（７）最後に全ての重合活性末端を水により失活させたが、得られた重合体の重量平均分子量は設計値８万に対し１４万となった。ＧＰＣ測定結果から高分子量側に広い分子量分布が確認され、多量のカップリング体を含んでいた。
[Comparative Example 2]
(1) Under a nitrogen atmosphere, 490 kg of cyclohexane as a polymerization solvent was charged in a 1500 liter stainless steel reaction vessel and kept at 30 ° C.
(2) In this, 1600 mL of a 10 wt% cyclohexane solution of n-butyllithium was added as a polymerization catalyst solution, then 75.6 kg of styrene monomer was added all at once, and the internal temperature of the reaction system was raised to 50 ° C. This was subjected to living anion polymerization.
(3) After the polymerization rate of the styrene monomer exceeded 99%, 37.8 kg of butadiene was added simultaneously, and then the internal temperature of the reaction system was raised to 65 ° C. to promote copolymerization. The internal temperature was adjusted to 50 ° C. and kept for 20 minutes.
(4) Thereafter, 62.3 kg of styrene monomer was added all at once and copolymerized.
(5) 0.5 kg of 1,1-diphenylethylene was added all at once and reacted for 30 minutes, and the internal temperature of the reaction system was lowered to -78 ° C. and kept for another 10 minutes.
(6) After 13.6 kg of methyl methacrylate was diluted with the same weight of cyclohexane, it was added all at once to the reaction system and reacted for 15 minutes to complete the polymerization.
(7) Finally, all the polymerization active terminals were deactivated with water. The weight average molecular weight of the obtained polymer was 140,000 with respect to the design value of 80,000. From the GPC measurement results, a wide molecular weight distribution was confirmed on the high molecular weight side, and a large amount of coupling body was contained.
比較例３，４として、２種のスチレン−ブタジエン−メタクリル酸メチルブロック共重合体（アルケマ社製商品名Ｎａｎｏｓｔｒｅｎｇｔｈ Ａ１２３および同社製商品名Ｎａｎｏｓｔｒｅｎｇｔｈ Ａ２５０）を用いた。 As Comparative Examples 3 and 4, two types of styrene-butadiene-methyl methacrylate block copolymers (trade name Nanostrength A123 manufactured by Arkema Co., Ltd. and trade name Nanostrength A250 manufactured by the same company) were used.
ＧＰＣ測定は、液体クロマトグラフィー装置（東ソー製商品名「ＨＬＣ−８２２０」）を用いて以下の条件で測定した。最もピーク高さの大きいピークの分子量を基準とし、基準の２倍の分子量値を示すピークをカップリング体と見なした。
検出方法：示差屈折法
使用カラム：昭和電工製商品名Ｓｈｏｄｅｘ ＧＰＣ ＫＦ−４００ ＨＱ 直列４本
カラム温度：４０℃
移動相：テトラヒドロフラン
サンプル濃度：２重量％
検量線：標準ポリスチレン（東ソー製）
GPC measurement was performed under the following conditions using a liquid chromatography apparatus (trade name “HLC-8220” manufactured by Tosoh Corporation). Based on the molecular weight of the peak having the largest peak height, a peak showing a molecular weight value twice that of the reference was regarded as a coupling body.
Detection method: differential refraction method column: Showa Denko product name Shodex GPC KF-400 HQ 4 in-line column temperature: 40 ° C.
Mobile phase: tetrahydrofuran Sample concentration: 2% by weight
Calibration curve: Standard polystyrene (manufactured by Tosoh)
ガスクロマトグラフィー測定は、メタクリル酸エステルの反応量を評価するために行い、ガスクロマトグラフィー装置（Ａｇｉｌｅｎｔ社製６８９０型）を用いて以下の条件で測定した。
検出方法：ＦＩＤ法
使用カラム：Ａｇｉｌｅｎｔ社製ＤＢ−ＷＡＸ
導入部・検出部温度：２００℃
カラム温度条件：８０℃で５分間保ったのち毎分３０℃で昇温し、１７０℃で９分間保持
移動相：ヘリウムガス
移動相流速：毎分４ｍｌ
The gas chromatography measurement was performed in order to evaluate the reaction amount of the methacrylic acid ester, and the measurement was performed under the following conditions using a gas chromatography apparatus (Agilent 6890 type).
Detection method: FID method column used: DB-WAX manufactured by Agilent
Inlet / detector temperature: 200 ° C
Column temperature condition: maintained at 80 ° C. for 5 minutes, then heated up at 30 ° C. per minute, held at 170 ° C. for 9 minutes Mobile phase: helium gas mobile phase flow rate: 4 ml per minute
シャルピー衝撃強度測定は、全自動衝撃試験機（安田精機製作所製Ｎｏ．２５８−ＰＣＡ型）を用いてＪＩＳ Ｋ−７１１１にしたがって測定した。試験片はＩＳＯ １７９にしたがって作成したものでエッジワイズ方向ノッチ付き試験片とした。 Charpy impact strength was measured according to JIS K-7111 using a fully automatic impact tester (No. 258-PCA manufactured by Yasuda Seiki Seisakusho). The test piece was prepared in accordance with ISO 179 and was a test piece with an edgewise notch.
ビカット軟化点測定は、全自動ビカット軟化点測定機（安田精機製作所製Ｎｏ．１４８−ＨＤＡ型）を用いてＪＩＳ Ｋ−７２０６ Ａ５０法にしたがって測定した。 Vicat softening point measurement was performed according to JIS K-7206 A50 method using a fully automatic Vicat softening point measuring machine (No.148-HDA type manufactured by Yasuda Seiki Seisakusho).
曇り度は、濁度計（日本電色製ＮＤＨ３００Ａ型）を用いてＪＩＳ Ｋ−７１３６（ＩＳＯ １４７８２）にしたがって測定した。 The haze was measured according to JIS K-7136 (ISO 14782) using a turbidimeter (Nippon Denshoku NDH300A type).
実施例１〜６、および比較例１に示したブロック共重合体を含む重合液または市販の共重合体（比較例３、４）について、重量平均分子量、カップリング体存在率を評価した。また実施例１〜６、および比較例２についてメタクリル酸エステルの反応率を評価した。評価結果は表１に示した。 About the polymerization liquid containing the block copolymer shown in Examples 1-6 and Comparative Example 1, or a commercially available copolymer (Comparative Examples 3 and 4), the weight average molecular weight and the coupling body presence rate were evaluated. Moreover, the reaction rate of methacrylic acid ester was evaluated about Examples 1-6 and Comparative Example 2. The evaluation results are shown in Table 1.
実施例１〜６、および比較例１に示したブロック共重合体を含む重合液について、２−［１−（２−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ペンチルフェニル）エチル］−４，６−ジ−ｔｅｒｔ−ペンチルフェニルアクリレート（住友化学製商品名「スミライザー ＧＳ」）をブロック共重合体に対して０．２質量％と、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（チバ・スペシャルティ・ケミカルズ製商品名「ＩＲＧＡＮＯＸ １０７６」）をブロック共重合体に対して０．１質量％と、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト（旭電化製商品名「アデカスタブ ＨＰ−１０」）をブロック共重合体に対して０．１質量％とをそれぞれ酸化防止剤として混合し、５７ｍｍφ二軸脱揮押出機に供給してダイスから溶融ストランドを引き出し、水冷後カッターにて切断してペレット状の樹脂を得た。その後、得られた共重合体組成物の物性を評価した。評価結果は表２に記載した。比較例２に示したブロック共重合体を含む重合液を同様に造粒しようとしたが、高分子量成分が多いためと思われるが溶融ストランドがうまく得られず、物性評価に使用できる樹脂が得られなかった。また、比較例３、４については組成と曇り度を評価した。 About the polymerization liquid containing the block copolymer shown in Examples 1 to 6 and Comparative Example 1, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6 -0.2% by mass of di-tert-pentylphenyl acrylate (trade name “Sumilyzer GS” manufactured by Sumitomo Chemical Co., Ltd.) with respect to the block copolymer, octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate (trade name “IRGANOX 1076” manufactured by Ciba Specialty Chemicals) is 0.1% by mass with respect to the block copolymer, and 2,2-methylenebis (4,6-di-tert-butylphenyl). ) Oxyl phosphite (trade name “Adeka Stub HP-10” manufactured by Asahi Denka) was oxidized to 0.1% by mass with respect to the block copolymer. Mixing the sealant, pull the melt strand from the die in fed into 57mmφ twin-screw devolatilizing extruder to obtain a pellet-like resin is cut by water cooling after cutter. Thereafter, the physical properties of the obtained copolymer composition were evaluated. The evaluation results are shown in Table 2. An attempt was made to granulate the polymerization liquid containing the block copolymer shown in Comparative Example 2 in the same manner, but it seems that there are many high molecular weight components, but a melt strand could not be obtained well, and a resin that can be used for physical property evaluation was obtained. I couldn't. For Comparative Examples 3 and 4, the composition and haze were evaluated.
表２に示された結果から、本発明のブロック共重合体に係わる実施例は（メタ）アクリル酸エステルを共重合しない比較例１に比べ、いずれも耐衝撃性、耐熱性に優れ、比較例１およびメタクリル酸メチルを共重合させた比較例３〜４より曇り度が低く抑えられていた。この結果から、本発明のブロック共重合体は、従来の芳香族ビニル化合物と共役ジエン化合物とからなるブロック共重合体より耐衝撃性、耐熱性、透明性に優れることが分かった。 From the results shown in Table 2, the examples relating to the block copolymer of the present invention are both superior in impact resistance and heat resistance as compared with Comparative Example 1 in which (meth) acrylic acid ester is not copolymerized. Haze was suppressed lower than Comparative Examples 3 and 4 copolymerized with 1 and methyl methacrylate. From this result, it was found that the block copolymer of the present invention was superior in impact resistance, heat resistance and transparency to a block copolymer comprising a conventional aromatic vinyl compound and a conjugated diene compound.
本発明のブロック共重合体および本発明のブロック共重合体を用いた樹脂組成物は、ラベル用シュリンク材に好適な熱収縮フィルムのほか、位相差フィルムや反射防止フィルムなどの光学フィルム、光学素子中の絶縁材の用途にも適応できる。
The block copolymer of the present invention and the resin composition using the block copolymer of the present invention include an optical film such as a retardation film and an antireflection film, an optical element, in addition to a heat-shrinkable film suitable for a shrink material for labels. It can also be applied to the use of insulating materials inside.
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| WO2009054553A2 (en) * | 2008-12-25 | 2009-04-30 | Kuraray Co., Ltd. | Optical component comprising acrylic block copolymer |
| WO2013069642A1 (en) * | 2011-11-10 | 2013-05-16 | Ｊｘ日鉱日石エネルギー株式会社 | Phase difference film and liquid crystal display device provided with same |
| WO2015041146A1 (en) * | 2013-09-20 | 2015-03-26 | Dic株式会社 | Method for producing block copolymer, and block copolymer obtained using same |
| JP2015147888A (en) * | 2014-02-07 | 2015-08-20 | Dic株式会社 | Method for producing kneaded product for aqueous pigment dispersion and method for producing aqueous pigment dispersion using the same and ink composition |
| JPWO2020255726A1 (en) * | 2019-06-20 | 2020-12-24 | ||
| WO2021117295A1 (en) * | 2019-12-10 | 2021-06-17 | 株式会社ブリヂストン | Composition and polymer molded article |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009054553A2 (en) * | 2008-12-25 | 2009-04-30 | Kuraray Co., Ltd. | Optical component comprising acrylic block copolymer |
| WO2009054553A3 (en) * | 2008-12-25 | 2009-06-18 | Kuraray Co | Optical component comprising acrylic block copolymer |
| WO2013069642A1 (en) * | 2011-11-10 | 2013-05-16 | Ｊｘ日鉱日石エネルギー株式会社 | Phase difference film and liquid crystal display device provided with same |
| JPWO2013069642A1 (en) * | 2011-11-10 | 2015-04-02 | Ｊｘ日鉱日石エネルギー株式会社 | Retardation film and liquid crystal display device including the same |
| WO2015041146A1 (en) * | 2013-09-20 | 2015-03-26 | Dic株式会社 | Method for producing block copolymer, and block copolymer obtained using same |
| JP5741780B1 (en) * | 2013-09-20 | 2015-07-01 | Dic株式会社 | Process for producing block copolymer |
| US9975984B2 (en) | 2013-09-20 | 2018-05-22 | Dic Corporation | Method for producing block copolymer, and block copolymer obtained using same |
| JP2015147888A (en) * | 2014-02-07 | 2015-08-20 | Dic株式会社 | Method for producing kneaded product for aqueous pigment dispersion and method for producing aqueous pigment dispersion using the same and ink composition |
| JPWO2020255726A1 (en) * | 2019-06-20 | 2020-12-24 | ||
| JP7040672B2 (en) | 2019-06-20 | 2022-03-23 | Dic株式会社 | Intermediates for block copolymers, block copolymers and methods for producing them |
| WO2021117295A1 (en) * | 2019-12-10 | 2021-06-17 | 株式会社ブリヂストン | Composition and polymer molded article |
| JP7403297B2 (en) | 2019-12-10 | 2023-12-22 | 株式会社ブリヂストン | Compositions and polymer moldings |
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