JP2021070809A - Method for Producing N-Vinyl Lactam Copolymer - Google Patents
Method for Producing N-Vinyl Lactam Copolymer Download PDFInfo
- Publication number
- JP2021070809A JP2021070809A JP2020119976A JP2020119976A JP2021070809A JP 2021070809 A JP2021070809 A JP 2021070809A JP 2020119976 A JP2020119976 A JP 2020119976A JP 2020119976 A JP2020119976 A JP 2020119976A JP 2021070809 A JP2021070809 A JP 2021070809A
- Authority
- JP
- Japan
- Prior art keywords
- vinyllactam
- monomer
- minutes
- meth
- mass
- 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.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 101
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 229920002554 vinyl polymer Polymers 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 135
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 230000009477 glass transition Effects 0.000 claims abstract description 49
- 125000001424 substituent group Chemical group 0.000 claims abstract description 31
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 28
- 229920001519 homopolymer Polymers 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 239000000470 constituent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 5
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 239000000843 powder Substances 0.000 abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 27
- 239000000203 mixture Substances 0.000 abstract description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 93
- 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 71
- 239000000243 solution Substances 0.000 description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 38
- 239000007877 V-601 Substances 0.000 description 36
- 229960004592 isopropanol Drugs 0.000 description 31
- 229920000642 polymer Polymers 0.000 description 23
- 229920000058 polyacrylate Polymers 0.000 description 22
- -1 peracids salts Chemical class 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- AVTLBBWTUPQRAY-BUHFOSPRSA-N V-59 Substances CCC(C)(C#N)\N=N\C(C)(CC)C#N AVTLBBWTUPQRAY-BUHFOSPRSA-N 0.000 description 10
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 10
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011342 resin composition Substances 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 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 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 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 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
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 3
- 229940011051 isopropyl acetate Drugs 0.000 description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 3
- 229940017219 methyl propionate Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 3
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 1
- 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 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
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- HQGPZXPTJWUDQR-UHFFFAOYSA-N 1-ethenyl-5-methylpyrrolidin-2-one Chemical compound CC1CCC(=O)N1C=C HQGPZXPTJWUDQR-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- OOHZIRUJZFRULE-UHFFFAOYSA-N 2,2-dimethylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)C OOHZIRUJZFRULE-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BHYVPLASKPLRRX-UHFFFAOYSA-N 2-methyl-1-pyrrolidin-1-ylpropan-1-imine Chemical compound CC(C)C(=N)N1CCCC1 BHYVPLASKPLRRX-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- HDCMRFUDMYGBFU-UHFFFAOYSA-N 2-methylbutan-2-yl 7-methyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)C HDCMRFUDMYGBFU-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- NHKJNWKLSOOMTQ-UHFFFAOYSA-N 2-prop-1-enyl-4,5-dihydro-1,3-oxazole Chemical compound CC=CC1=NCCO1 NHKJNWKLSOOMTQ-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- NMZSJIQGMAGSSO-UHFFFAOYSA-N 3-[[1-amino-2-[[1-amino-1-(2-carboxyethylimino)-2-methylpropan-2-yl]diazenyl]-2-methylpropylidene]amino]propanoic acid Chemical compound OC(=O)CCNC(=N)C(C)(C)N=NC(C)(C)C(=N)NCCC(O)=O NMZSJIQGMAGSSO-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 0 C*(C1C(*)=C(*)*)C1N(C(*)C*(C)(C)C)C(C)=O Chemical compound C*(C1C(*)=C(*)*)C1N(C(*)C*(C)(C)C)C(C)=O 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- TVYMSUIWROJZLM-UHFFFAOYSA-N N(=NC(C#N)(CC)C)C(C#N)(CC)C.CC(C#N)CC Chemical compound N(=NC(C#N)(CC)C)C(C#N)(CC)C.CC(C#N)CC TVYMSUIWROJZLM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- PIDIRTPCSWPEEI-UHFFFAOYSA-N bis[2-(4,5-dihydro-1H-imidazol-2-yl)propan-2-yl]diazene sulfo hydrogen sulfate hydrate Chemical compound O.S(=O)(=O)(O)OS(=O)(=O)O.N(=NC(C)(C)C=1NCCN1)C(C)(C)C=1NCCN1 PIDIRTPCSWPEEI-UHFFFAOYSA-N 0.000 description 1
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical compound NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])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])[H] 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])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])[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、Ｎ−ビニルラクタム系共重合体の製造方法に関する。より詳しくは、ガラス転移温度が高く、粉体加工性に優れたＮ−ビニルラクタム系共重合体を効率良く製造することができるＮ−ビニルラクタム系共重合体の製造方法に関する。 The present invention relates to a method for producing an N-vinyllactam-based copolymer. More specifically, the present invention relates to a method for producing an N-vinyllactam-based copolymer capable of efficiently producing an N-vinyllactam-based copolymer having a high glass transition temperature and excellent powder processability.
Ｎ−ビニルラクタム系共重合体は、Ｎ−ビニルラクタム系単量体由来の構成単位を有する重合体であり、安全な機能性ポリマーとして、化粧品、医農薬中間体、食品添加物、感光性電子材料、粘着付与剤等の各種用途や、種々の特殊工業用途（例えば、中空糸膜の製造）等の幅広い工業用途において使用されている。 The N-vinyllactam-based copolymer is a polymer having a structural unit derived from the N-vinyllactam-based monomer, and is a safe functional polymer such as cosmetics, medical and agricultural chemical intermediates, food additives, and photosensitive electrons. It is used in a wide range of industrial applications such as various applications such as materials and tackifiers, and various special industrial applications (for example, production of hollow fiber membranes).
Ｎ−ビニルラクタム系共重合体に種々の特性を付与するために、様々なＮ−ビニルラクタム系共重合体を製造するための方法が検討されている。
例えば、特許文献１には、開始剤の存在下、水溶液中で遊離基重合により、水溶性Ｎ−ビニルラクタムと疎水性モノマーからなり、水に溶解して透明な溶液を与えることのできる水溶性コポリマーを製造する方法であって、開始剤は、アゾ開始剤、Ｈ２Ｏ２、還元剤と組み合わせたヒドロペルオキシド及び過酸塩からなる群より選ばれ、水溶液及び／又はＣ１〜Ｃ４アルコール溶液の形で反応混合物に添加される方法が記載されている。
In order to impart various properties to N-vinyllactam-based copolymers, methods for producing various N-vinyllactam-based copolymers have been studied.
For example, Patent Document 1 describes a water-soluble solution composed of water-soluble N-vinyllactam and a hydrophobic monomer by free group polymerization in an aqueous solution in the presence of an initiator, which can be dissolved in water to give a transparent solution. a method for preparing copolymers, the initiator, azo initiators, H 2 O 2, selected from the group consisting of hydroperoxides and peracids salts in combination with a reducing agent, an aqueous solution and / or C 1 -C 4 alcohol The method of addition to the reaction mixture in the form of a solution is described.
また、例えば、特許文献２には、有機溶媒中、開始剤の存在下で、少なくとも１種の水溶性Ｎ−ビニルラクタムと少なくとも１種の疎水性コモノマーをフリーラジカル重合させることによりＮ−ビニルラクタムコポリマーを製造する方法が記載されている。 Further, for example, Patent Document 2 describes N-vinyllactam by free radical polymerization of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer in an organic solvent in the presence of an initiator. A method for producing a copolymer is described.
しかしながら、Ｎ−ビニルラクタム系単量体を含む単量体成分を重合する場合、従来の重合方法では反応性が低く、残存モノマー量が多くなり、均一な組成の共重合体が効率良く得られないという問題があった。また、Ｎ−ビニルラクタム系共重合体の粉体を製造する場合、共重合体のガラス転移温度が比較的高いと室温でも粉体化しやすいといったメリットがあるが、従来の重合方法では、ガラス転移温度が充分に高いＮ−ビニルラクタム系共重合体を効率良く得ることはできず、未だ改善の余地があった。 However, when a monomer component containing an N-vinyllactam-based monomer is polymerized, the conventional polymerization method has low reactivity, a large amount of residual monomer, and a copolymer having a uniform composition can be efficiently obtained. There was a problem that there was no. Further, when producing a powder of an N-vinyllactam-based copolymer, there is an advantage that if the glass transition temperature of the copolymer is relatively high, it is easy to powder even at room temperature, but in the conventional polymerization method, the glass transition is achieved. It was not possible to efficiently obtain an N-vinyllactam-based copolymer having a sufficiently high temperature, and there was still room for improvement.
本発明は、上記現状に鑑みて、組成が均一で、ガラス転移温度が高く、粉体加工性に優れたＮ−ビニルラクタム系共重合体を、残存モノマー量が少なく、効率良く製造することができるＮ−ビニルラクタム系共重合体の製造方法を提供することを目的とする。 In view of the above situation, the present invention can efficiently produce an N-vinyllactam-based copolymer having a uniform composition, a high glass transition temperature, and excellent powder processability with a small amount of residual monomers. An object of the present invention is to provide a method for producing an N-vinyllactam-based copolymer capable of producing the same.
本発明者は、上記課題を解決すべく、Ｎ−ビニルラクタム系共重合体を製造する方法について種々検討したところ、特定の溶媒の存在下で、Ｎ−ビニルラクタム系単量体と特定の（メタ）アクリル酸エステル系単量体を含む単量体成分を重合することにより、残存モノマー量が少なく、均一な組成を有し、ガラス転移温度が高いＮ−ビニルラクタム系共重合体を製造することができることを見いだし、本発明を完成するに至った。 The present inventor has studied various methods for producing an N-vinyllactam-based copolymer in order to solve the above problems, and found that the N-vinyllactam-based monomer is specific to the N-vinyllactam-based monomer in the presence of a specific solvent. By polymerizing a monomer component containing a meta) acrylic acid ester-based monomer, an N-vinyllactam-based copolymer having a small amount of residual monomer, a uniform composition, and a high glass transition temperature can be produced. We have found that we can do it, and have completed the present invention.
すなわち、本発明は、有機溶媒を含む重合溶媒の存在下で、Ｎ−ビニルラクタム系単量体、及び、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体を含む単量体成分を重合する工程を含むことを特徴とするＮ−ビニルラクタム系共重合体の製造方法である。 That is, in the present invention, in the presence of a polymerization solvent containing an organic solvent, the glass transition temperature of the N-vinyllactam-based monomer and the homopolymer may be 0 ° C. or higher and may have a substituent. An N-vinyllactam-based copolymer comprising a step of polymerizing a monomer component containing a (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms. It is a manufacturing method.
上記Ｎ−ビニルラクタム系共重合体の製造方法において、上記有機溶媒は、沸点が７０〜１７０℃であることが好ましい。 In the method for producing an N-vinyllactam-based copolymer, the organic solvent preferably has a boiling point of 70 to 170 ° C.
上記Ｎ−ビニルラクタム系共重合体の製造方法において、上記重合工程は、更に、有機過酸化物及び／又はアゾ系化合物を含む重合開始剤の存在下で行うことが好ましい。 In the method for producing an N-vinyllactam-based copolymer, the polymerization step is preferably carried out in the presence of a polymerization initiator containing an organic peroxide and / or an azo-based compound.
上記Ｎ−ビニルラクタム系共重合体の製造方法において、更に、上記重合工程で得られたＮ−ビニルラクタム系共重合体溶液を乾燥する工程を含むことが好ましい。 The method for producing an N-vinyllactam-based copolymer preferably further includes a step of drying the N-vinyllactam-based copolymer solution obtained in the above-mentioned polymerization step.
上記Ｎ−ビニルラクタム系共重合体の製造方法において、上記Ｎ−ビニルラクタム系単量体は、下記一般式（１）で表される化合物であることが好ましい。 In the method for producing an N-vinyllactam-based copolymer, the N-vinyllactam-based monomer is preferably a compound represented by the following general formula (1).
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、同一又は異なって、水素原子、又は、置換基を有していてもよい炭素数１〜１０のアルキル基を表す。ｘは、０〜４の整数を表す。ｙは、１〜３の整数を表す。） (In the formula, R 1 , R 2 , R 3 , and R 4 represent the same or different alkyl groups having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. X represents. Represents an integer from 0 to 4. y represents an integer from 1 to 3.)
本発明はまた、Ｎ−ビニルラクタム系単量体由来の構成単位と、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体由来の構成単位とを有することを特徴とするＮ−ビニルラクタム系共重合体でもある。 The present invention also comprises a constituent unit derived from an N-vinyllactam-based monomer, a copolymer having a glass transition temperature of 0 ° C. or higher, and an aliphatic group having 1 to 25 carbon atoms which may have a substituent. It is also an N-vinyllactam-based copolymer characterized by having a constituent unit derived from a (meth) acrylic acid ester-based monomer having a hydrocarbon group.
上記Ｎ−ビニルラクタム系単量体は、下記一般式（１）で表される化合物であることが好ましい。 The N-vinyllactam-based monomer is preferably a compound represented by the following general formula (1).
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、同一又は異なって、水素原子、又は、置換基を有していてもよい炭素数１〜１０のアルキル基を表す。ｘは、０〜４の整数を表す。ｙは、１〜３の整数を表す。） (In the formula, R 1 , R 2 , R 3 , and R 4 represent the same or different alkyl groups having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. X represents. Represents an integer from 0 to 4. y represents an integer from 1 to 3.)
上記Ｎ−ビニルラクタム系共重合体は、ガラス転移温度が８０℃以上であることが好ましい。 The N-vinyllactam copolymer preferably has a glass transition temperature of 80 ° C. or higher.
本発明によれば、残存モノマーの量が少なく、組成が均一で、ガラス転移温度が高く、粉体加工性に優れたＮ−ビニルラクタム系共重合体を効率良く製造することができる。 According to the present invention, an N-vinyllactam copolymer having a small amount of residual monomers, a uniform composition, a high glass transition temperature, and excellent powder processability can be efficiently produced.
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。
なお、本明細書において、「（メタ）アクリル酸」は「アクリル酸」及び「メタクリル酸」の総称であり、「（メタ）アクリレート」は「アクリレート」及び「メタクリレート」の総称である。
The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
In the present specification, "(meth) acrylic acid" is a general term for "acrylic acid" and "methacrylic acid", and "(meth) acrylate" is a general term for "acrylate" and "methacrylate".
１．Ｎ−ビニルラクタム系共重合体の製造方法
本発明は、有機溶媒を含む重合溶媒の存在下で、Ｎ−ビニルラクタム系単量体、及び、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体を含む単量体成分を重合する工程を含むことを特徴とするＮ−ビニルラクタム系共重合体の製造方法である。本発明のＮ−ビニルラクタム系共重合体の製造方法により、残存モノマー量が少なく、組成が均一で、ガラス転移温度の高いＮ−ビニルラクタム系共重合体を効率良く得ることができる。
1. 1. Method for Producing N-Vinyl Lactum Copolymer In the present invention, the glass transition temperature of the N-vinyl lactam monomer and the homopolymer is 0 ° C. or higher in the presence of a polymerization solvent containing an organic solvent. It is characterized by comprising a step of polymerizing a monomer component containing a (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent. This is a method for producing an N-vinyllactam-based copolymer. According to the method for producing an N-vinyllactam-based copolymer of the present invention, an N-vinyllactam-based copolymer having a small amount of residual monomers, a uniform composition, and a high glass transition temperature can be efficiently obtained.
本発明の製造方法により、組成が均一で、ガラス転移温度が高いＮ−ビニルラクタム系共重合体を効率良く製造することができるのは、有機溶媒を含む重合溶媒の存在下で、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体を共重合することによると考えられる。 According to the production method of the present invention, an N-vinyllactam-based copolymer having a uniform composition and a high glass transition temperature can be efficiently produced as a homopolymer in the presence of a polymerization solvent containing an organic solvent. According to the copolymerization of a (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which has a glass transition temperature of 0 ° C. or higher and may have a substituent. Conceivable.
本発明の製造方法は、有機溶媒を含む重合溶媒の存在下で、Ｎ−ビニルラクタム系単量体、及び、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体を含む単量体成分を重合する工程を含む。 In the production method of the present invention, even if the glass transition temperature of the N-vinyllactam-based monomer and the homopolymer is 0 ° C. or higher and has a substituent in the presence of a polymerization solvent containing an organic solvent. A good step of polymerizing a monomer component containing a (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms is included.
上記有機溶媒としては、例えば、メタノール、エタノール、プロピルアルコール、イソプロピルアルコール（２−プロパノール）、ｎ−ブチルアルコール、シクロヘキサノール、エチレングリコール、ジエチレングリコール等のアルコール系溶媒；テトラヒドロフラン、ジオキサン等の環状エーテル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、３−メトキシブタノール等のグリコールモノエーテル類；アセトン、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン等のケトン系溶媒；酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、プロピオン酸メチル等のアルキルエステル系溶媒；ベンゼン、トルエン、エチルベンゼン、キシレン等の芳香族炭化水素系溶媒；ヘキサン、シクロヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類；等が挙げられる。これらは１種のみ使用してもよいし、２種以上を併用してもよい。 Examples of the organic solvent include alcohol solvents such as methanol, ethanol, propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, cyclohexanol, ethylene glycol and diethylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, etc. Glycol monoethers; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone; alkyl ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate; benzene, toluene, Aromatic hydrocarbon solvents such as ethylbenzene and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane and octane; and the like can be mentioned. Only one of these may be used, or two or more thereof may be used in combination.
上記有機溶媒は、沸点が７０〜１７０℃であることが好ましい。沸点が上述の範囲の有機溶媒を用いることにより、溶媒の除去が容易になり、粉体の共重合体を容易に得ることができる。上記有機溶媒の沸点は、重合効率が上がり、単量体の反応率が上がる点で、７３℃以上であることがより好ましく、７５℃以上であることが更に好ましく、重合体の乾燥の際に、（メタ）アクリル酸エステル系単量体の分解等の重合体の劣化を伴うことなく溶媒の除去が可能である点で、１４０℃以下であることがより好ましく、１２０℃以下であることが更に好ましい。 The organic solvent preferably has a boiling point of 70 to 170 ° C. By using an organic solvent having a boiling point in the above range, the solvent can be easily removed and a powder copolymer can be easily obtained. The boiling point of the organic solvent is more preferably 73 ° C. or higher, further preferably 75 ° C. or higher, in terms of increasing the polymerization efficiency and the reaction rate of the monomer, and when the polymer is dried. , 140 ° C. or lower is more preferable, and 120 ° C. or lower is preferable in that the solvent can be removed without deterioration of the polymer such as decomposition of the (meth) acrylic acid ester-based monomer. More preferred.
上記有機溶媒として、好ましくは、アルコール系溶媒、ケトン系溶媒、アルキルエステル系溶媒、芳香族炭化水素系溶媒が挙げられ、より好ましくは、エタノール、イソプロピルアルコール、メチルイソブチルケトン、メチルエチルケトン、酢酸エチル、酢酸プロピル、酢酸イソプロピル、プロピオン酸メチル、トルエンが挙げられ、更に好ましくは、エタノール、イソプロピルアルコール、酢酸エチル、酢酸イソプロピル、プロピオン酸メチルが挙げられる。 The organic solvent preferably includes an alcohol solvent, a ketone solvent, an alkyl ester solvent, and an aromatic hydrocarbon solvent, and more preferably ethanol, isopropyl alcohol, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, and acetate. Examples thereof include propyl, isopropyl acetate, methyl propionate and toluene, and more preferably, ethanol, isopropyl alcohol, ethyl acetate, isopropyl acetate and methyl propionate can be mentioned.
上記有機溶媒を含む重合溶媒の使用量は、重合制御が容易で組成が均一になり、単量体の反応率も上がる点で、使用する単量体成分総量１００質量部に対して、４５質量部以上であることが好ましく、６５質量部以上であることがより好ましく、８０質量部以上であることが更に好ましく、また、９００質量部以下であることが好ましく、６００質量部以下であることがより好ましく、４００質量部以下であることが更に好ましい。 The amount of the polymerization solvent containing the organic solvent used is 45% by mass with respect to 100 parts by mass of the total amount of the monomer components used in that the polymerization control is easy, the composition becomes uniform, and the reaction rate of the monomer increases. It is preferably parts or more, more preferably 65 parts by mass or more, further preferably 80 parts by mass or more, preferably 900 parts by mass or less, and preferably 600 parts by mass or less. More preferably, it is 400 parts by mass or less.
重合溶媒中の、上記有機溶媒の含有割合は、重合溶媒１００質量％中７０〜１００質量％であることが好ましく、８０〜１００質量％であることがより好ましく、８５〜１００質量％であることが更に好ましい。 The content ratio of the organic solvent in the polymerization solvent is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 85 to 100% by mass in 100% by mass of the polymerization solvent. Is more preferable.
上記重合溶媒は、上述した有機溶媒以外に、水を含んでいてもよい。上記重合溶媒は、Ｎ−ビニルラクタム系単量体の反応性が上がり、残存Ｎ−ビニルラクタム系単量体の量がより低減しやすくなる点で、水を含むことが好ましい。上記水としては、超純水、純水、イオン交換水、蒸留水等が使用できる。
上記水の含有割合は、重合溶媒１００質量％中０〜３０質量％であることが好ましく、０〜２０質量％であることがより好ましく、０〜１５質量％であることが更に好ましい。
The polymerization solvent may contain water in addition to the organic solvent described above. The polymerization solvent preferably contains water in that the reactivity of the N-vinyllactam-based monomer is increased and the amount of the residual N-vinyllactam-based monomer is more likely to be reduced. As the water, ultrapure water, pure water, ion-exchanged water, distilled water and the like can be used.
The content ratio of the water is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 15% by mass in 100% by mass of the polymerization solvent.
本発明の製造方法において使用するＮ−ビニルラクタム系単量体としては、Ｎ−ビニルラクタム構造を有する単量体であれば特に限定されないが、下記式（１）で表される化合物が好ましい。 The N-vinyllactam-based monomer used in the production method of the present invention is not particularly limited as long as it is a monomer having an N-vinyllactam structure, but a compound represented by the following formula (1) is preferable.
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、同一又は異なって、水素原子、又は、置換基を有していてもよい炭素数１〜１０のアルキル基を表す。ｘは、０〜４の整数を表す。ｙは、１〜３の整数を表す。） (In the formula, R 1 , R 2 , R 3 , and R 4 represent the same or different alkyl groups having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. X represents. Represents an integer from 0 to 4. y represents an integer from 1 to 3.)
上記Ｒ１〜Ｒ４で表されるアルキル基としては、炭素数１〜６のアルキル基が好ましく、炭素数１〜４のアルキル基がより好ましく、メチル基、エチル基が更に好ましく、メチル基が特に好ましい。 As the alkyl group represented by R 1 to R 4 , an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, a methyl group and an ethyl group are further preferable, and a methyl group is preferable. Especially preferable.
上記置換基としては、例えば、エチレン性不飽和炭化水素基；カルボキシル基、スルホン酸基及びこれらのエステルや塩；アミノ基、水酸基等の架橋剤と縮合反応可能な反応性官能基；等が挙げられる。 Examples of the substituent include an ethylenically unsaturated hydrocarbon group; a carboxyl group, a sulfonic acid group and an ester or salt thereof; a reactive functional group capable of condensing with a cross-linking agent such as an amino group or a hydroxyl group; Be done.
なかでも、上記Ｒ１、Ｒ２、Ｒ３は、水素原子であることが好ましい。
上記Ｒ４は、水素原子又はメチル基であることが好ましく、水素原子であることがより好ましい。
Among them, the above R 1 , R 2 and R 3 are preferably hydrogen atoms.
The R 4 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
上記一般式（１）において、ｘは、０〜２の整数であることが好ましく、０〜１の整数であることがより好ましく、０であることが更に好ましい。
ｙは、１又は２であることが好ましく、１であることがより好ましい。
In the above general formula (1), x is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and even more preferably 0.
y is preferably 1 or 2, and more preferably 1.
上記一般式（１）で表される化合物の具体例としては、例えば、Ｎ−ビニルピロリドン、Ｎ−ビニル−５−メチルピロリドン、Ｎ−ビニルピペリドン、Ｎ−ビニルカプロラクタム、１−（２−プロペニル）−２−ピロリドン等が挙げられる。なかでも、Ｎ−ビニルピロリドンが好ましい。 Specific examples of the compound represented by the general formula (1) include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, 1- (2-propenyl)-. 2-Pyrrolidone and the like can be mentioned. Of these, N-vinylpyrrolidone is preferable.
本発明の製造方法において、使用する単量体成分は、Ｎ−ビニルラクタム系単量体を１種のみ含んでもよいし、２種以上含んでいてもよい。 In the production method of the present invention, the monomer component used may contain only one type of N-vinyllactam-based monomer, or may contain two or more types.
本発明の製造方法においては、更に、単独重合体（ホモポリマー）のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体を使用する。 In the production method of the present invention, the homopolymer has an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which has a glass transition temperature of 0 ° C. or higher and may have a substituent. A (meth) acrylic acid ester-based monomer is used.
上記置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体としては、例えば、下記一般式（２）で表される化合物が好ましく挙げられる。 Examples of the (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have the above-mentioned substituent include a compound represented by the following general formula (2). Preferred.
（式中、Ｒ５は、水素原子又はメチル基を表す。Ｒ６は、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を表す。） (In the formula, R 5 represents a hydrogen atom or a methyl group. R 6 represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
上記脂肪族炭化水素基は、飽和又は不飽和のいずれであってもよいが、飽和脂肪族炭化水素基であることが好ましい。 The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon group.
上記脂肪族炭化水素基の炭素数は、１〜２０であることが好ましく、３〜１８であることがより好ましく、６〜１５であることが更に好ましい。
上記脂肪族炭化水素基が置換基を有する場合、上記炭素数は、置換基の炭素数も含めた数である。
The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 3 to 18, and even more preferably 6 to 15.
When the aliphatic hydrocarbon group has a substituent, the number of carbon atoms includes the number of carbon atoms of the substituent.
上記置換基としては、アルコキシ基、アリール基、アリールオキシ基等が挙げられる。
上記アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｔｅｒｔ−ブトキシ基等が挙げられる。
上記アリール基としては、例えば、フェニル基、キシリル基、メシチル基、ビフェニル基、ナフチル基等が挙げられる。
上記アリールオキシ基としては、例えば、フェノキシ基、ナフトキシ基、ビフェニルオキシ基、ピレニルオキシ基等が挙げられる。
上記置換基の数は、特に限定されないが、３個以下が好ましく、１個以下がより好ましい。
Examples of the substituent include an alkoxy group, an aryl group, an aryloxy group and the like.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group and the like.
Examples of the aryl group include a phenyl group, a xsilyl group, a mesitylene group, a biphenyl group, a naphthyl group and the like.
Examples of the aryloxy group include a phenoxy group, a naphthoxy group, a biphenyloxy group, a pyrenyloxy group and the like.
The number of the above-mentioned substituents is not particularly limited, but is preferably 3 or less, and more preferably 1 or less.
上記置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体は、単独重合体（ホモポリマー）のガラス転移温度（Ｔｇ）が０℃以上である。
上記単独重合体のガラス転移温度（Ｔｇ）は、得られるＮ−ビニルラクタム系共重合体において、上記（メタ）アクリル酸エステル系単量体の共重合比率を上げても粉体が取得しやすい点で、１０℃以上であることが好ましく、２０℃以上であることがより好ましく、４０℃以上であることが更に好ましい。
上記（メタ）アクリル酸エステル系単量体の単独重合体のガラス転移温度（Ｔｇ）としては、ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ（ポリマーハンドブック、第４版、Ｗｉｌｙ Ｉｎｔｅｒｓｃｉｅｎｃｅ、第６章、２００頁等）に記載の値を使用することができる。
これらに記載されていない単独重合体のガラス転移温度（Ｔｇ）については、Ｊ． Ｂｒａｎｄｒｕｐ，Ｅ． Ｈ． Ｉｍｍｅｒｇｕｔ， Ｐｏｌｙｍｅｒ Ｈａｎｄｂｏｏｋ， ２ｎｄ Ｅｄ．， Ｊ． Ｗｉｌｅｙ， Ｎｅｗ Ｙｏｒｋ １９７５、光硬化技術データブック（テクノネットブックス社）等に記載の値を使用することができる。
The (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which may have the above-mentioned substituent, has a glass transition temperature (Tg) of a homopolymer. It is 0 ° C. or higher.
The glass transition temperature (Tg) of the homopolymer can be easily obtained as a powder in the obtained N-vinyllactam-based copolymer even if the copolymerization ratio of the (meth) acrylic acid ester-based monomer is increased. In terms of points, it is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and even more preferably 40 ° C. or higher.
The glass transition temperature (Tg) of the homopolymer of the (meth) acrylic acid ester-based monomer is the value described in POLYMER HANDBOOK (Polymer Handbook, 4th Edition, Willy Interscience, Chapter 6, p. 200, etc.). Can be used.
Regarding the glass transition temperature (Tg) of homopolymers not described in these, J. Brandrup, E.I. H. Immunogut, Polymer Handbook, 2nd Ed. , J. The values described in Wiley, New York 1975, Photocuring Technology Data Book (Technonet Books), etc. can be used.
上記単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体（以下、「上記（メタ）アクリル酸エステル系単量体」とも称す。）としては、具体的には、例えば、メチル（メタ）アクリレート、エチルメタクリレート、ブチルメタクリレート、イソブチルメタクリレート、ｔ−ブチルメタクリレート、ｓｅｃ−ブチルメタクリレート、ｎ−アミルメタクリレート、ｓ−アミルメタクリレート、ｔ−アミルメタクリレート、ｎ−ヘキシルメタクリレート、トリデシルアクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、セチル（メタ）アクリレート、２−デシルテトラデシル（メタ）アクリレート、２−デシルテトラデカニル（メタ）アクリレート、エイコシル（メタ）アクリレート、ベヘニル（メタ）アクリレート等の直鎖状又は分岐鎖状の脂肪族炭化水素基を有する化合物；シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート等の環状の脂肪族炭化水素基を有する化合物；ベンジル（メタ）アクリレート、２−（ｏ−フェニルフェノキシ）エチルアクリレート等の置換基を有する脂肪族炭化水素基を有する化合物；等を挙げることができる。
なかでも、Ｎ−ビニルラクタム系単量体と共重合しやすく、また、（メタ）アクリル酸エステル系単量体の共重合比率を上げやすい点で、上記環状の脂肪族炭化水素基を有する化合物及び上記置換基を有する脂肪族炭化水素基が好ましく、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ベンジル（メタ）アクリレートがより好ましく、イソボルニル（メタ）アクリレートが更に好ましい。
The (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which has a glass transition temperature of 0 ° C. or higher and may have a substituent (hereinafter, Specific examples of the above-mentioned (meth) acrylic acid ester-based monomer) include methyl (meth) acrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, and sec-butyl. Methacrylate, n-amyl methacrylate, s-amyl methacrylate, t-amyl methacrylate, n-hexyl methacrylate, tridecyl acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, Linear or linear such as stearyl (meth) acrylate, cetyl (meth) acrylate, 2-decyltetradecyl (meth) acrylate, 2-decyltetradecanyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, etc. Compounds with branched aliphatic hydrocarbon groups; having cyclic aliphatic hydrocarbon groups such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate. Compounds; compounds having an aliphatic hydrocarbon group having a substituent such as benzyl (meth) acrylate and 2- (o-phenylphenoxy) ethyl acrylate; and the like can be mentioned.
Among them, the compound having a cyclic aliphatic hydrocarbon group is easy to copolymerize with an N-vinyllactam-based monomer and easily increase the copolymerization ratio of a (meth) acrylic acid ester-based monomer. And an aliphatic hydrocarbon group having the above-mentioned substituent is preferable, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and benzyl (meth) acrylate are more preferable. Isobornyl (meth) acrylate is more preferred.
また、上記（メタ）アクリル酸エステル系単量体は、上記Ｎ−ビニルラクタム系単量体との反応性が良好で、残存モノマー量がより一層少なくなる点で、単独重合体のガラス転移温度が０℃以上であり、炭素数１〜２５の脂肪族炭化水素基を有するアクリル酸エステル系単量体であることが好ましい。 Further, the (meth) acrylic acid ester-based monomer has good reactivity with the N-vinyllactam-based monomer, and the amount of residual monomer is further reduced, so that the glass transition temperature of the homopolymer Is preferably an acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms and having a temperature of 0 ° C. or higher.
上記単量体成分は、上記（メタ）アクリル酸エステル系単量体を１種のみ含んでもよいし、２種以上含んでいてもよい。 The monomer component may contain only one type of the (meth) acrylic acid ester-based monomer, or may contain two or more types.
上記単量体成分は、更に、上記Ｎ−ビニルラクタム系単量体と上記（メタ）アクリル酸エステル系単量体以外の他の単量体を含んでいてもよい。
上記他の単量体としては、例えば、（メタ）アクリルアミド、Ｎ−モノメチル（メタ）アクリルアミド、Ｎ−モノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド等の（メタ）アクリルアミド誘導体類；（メタ）アクリル酸ジメチルアミノエチル、ジメチルアミノエチル（メタ）アクリルアミド、ビニルピリジン、ビニルイミダゾール等の塩基性不飽和単量体及びその塩又は第４級化物；ビニルホルムアミド、ビニルアセトアミド、ビニルオキサゾリン、イソプロペニルオキサゾリン等のビニルアミド類；（メタ）アクリル酸、イタコン酸、マレイン酸、フマル酸等のカルボキシル基含有不飽和単量体及びその塩；無水マレイン酸、無水イタコン酸等の不飽和無水物類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；ビニルエチレンカーボネート及びその誘導体；（メタ）アクリル酸−２−スルホン酸エチル及びその誘導体；ビニルスルホン酸及びその誘導体；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類；エチレン、プロピレン、オクテン、ブタジエン等のオレフィン類等が挙げられる。これらは１種のみ使用してもよいし、２種以上を併用してもよい。
The monomer component may further contain a monomer other than the N-vinyllactam-based monomer and the (meth) acrylic acid ester-based monomer.
Examples of the other monomer include (meth) acrylamide derivatives such as (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide; Basic unsaturated monomers such as dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, vinylpyridine, vinylimidazole and salts or quaternized products thereof; vinylformamide, vinylacetamide, vinyloxazoline, iso Vinyl amides such as propenyloxazoline; carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, itaconic acid, maleic acid, and fumaric acid and salts thereof; unsaturated anhydrides such as maleic anhydride and itaconic anhydride; Vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethylene carbonate and its derivatives; ethyl (meth) acrylic acid-2-sulfonate and its derivatives; vinyl sulfonic acid and its derivatives; methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and the like Vinyl ethers; olefins such as ethylene, propylene, octene, butadiene and the like can be mentioned. Only one of these may be used, or two or more thereof may be used in combination.
上記単量体成分において、上記Ｎ−ビニルラクタム系単量体の含有量は、全単量体成分１００質量％中、３０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましく、また、９５質量％以下であることが好ましく、９０質量％以下であることがより好ましく、８５質量％以下であることが更に好ましく、８０質量％以下であることが更により好ましい。 In the monomer component, the content of the N-vinyllactam-based monomer is preferably 30% by mass or more, more preferably 40% by mass or more, based on 100% by mass of all the monomer components. It is preferably 50% by mass or more, more preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and 80% by mass. The following is even more preferable.
上記単量体成分において、上記（メタ）アクリル酸エステル系単量体の含有量は、全単量体成分１００質量％中、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、１５質量％以上であることが更に好ましく、２０質量％以上であることが更により好ましく、７０質量％以下であることが好ましく、６０質量％以下であることがより好ましく、５０質量％以下であることが更に好ましい。 In the monomer component, the content of the (meth) acrylic acid ester-based monomer is preferably 5% by mass or more, preferably 10% by mass or more, based on 100% by mass of all the monomer components. Is more preferably 15% by mass or more, further preferably 20% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and 50% by mass. It is more preferably% or less.
上記単量体成分において、上記他の単量体成分の含有量は、全単量体成分１００質量％中、０〜３０質量％であることが好ましく、０〜１０質量％であることがより好ましく、０〜５質量％であることが更に好ましい。 In the above-mentioned monomer component, the content of the above-mentioned other monomer component is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, based on 100% by mass of all the monomer components. It is preferably 0 to 5% by mass, and more preferably 0 to 5% by mass.
上記単量体成分を重合する方法としては、重合溶媒として有機溶媒を使用すること以外は、特に限定されず、重合開始剤等を用いてラジカル重合する等の公知の方法で行うことができる。
上記重合工程においては、上記Ｎ−ビニルラクタム系単量体と上記（メタ）アクリル酸エステル系単量体を含む単量体成分を混合して反応させる場合、一方の成分を一括添加して混合してもよいし、逐次添加して混合して反応させてもよい。
The method for polymerizing the above-mentioned monomer component is not particularly limited except that an organic solvent is used as the polymerization solvent, and a known method such as radical polymerization using a polymerization initiator or the like can be used.
In the polymerization step, when a monomer component containing the N-vinyllactam-based monomer and the (meth) acrylic acid ester-based monomer is mixed and reacted, one of the components is collectively added and mixed. Alternatively, they may be added sequentially and mixed to react.
上記重合工程において、重合温度は、特に限定されないが、３０℃以上が好ましく、４０℃以上がより好ましく、５０℃以上が更に好ましい。また、重合制御が容易であり、上記（メタ）アクリル酸エステル系単量体の分解を抑制することができる点で、１４０℃以下が好ましく、１２０℃以下がより好ましく、１００℃以下が更に好ましい。 In the above polymerization step, the polymerization temperature is not particularly limited, but is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and even more preferably 50 ° C. or higher. Further, in that polymerization control is easy and decomposition of the (meth) acrylic acid ester-based monomer can be suppressed, 140 ° C. or lower is preferable, 120 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable. ..
上記重合工程において、重合時間は、特に限定されないが、１時間以上が好ましく、２時間以上がより好ましく、３時間以上が更に好ましい。また、生産性が良好である点で、２０時間以下が好ましく、１０時間以下がより好ましく、８時間以下が更に好ましい。 In the above polymerization step, the polymerization time is not particularly limited, but is preferably 1 hour or more, more preferably 2 hours or more, still more preferably 3 hours or more. Further, in terms of good productivity, 20 hours or less is preferable, 10 hours or less is more preferable, and 8 hours or less is further preferable.
上記重合工程は、大気下で行ってもよいし、窒素等の不活性ガス雰囲気下で行ってもよい。また、重合反応は、常圧、加圧、減圧のいずれの条件下で行ってもよい。
上記重合工程においては、水が存在してもよい。
The polymerization step may be carried out in the atmosphere or in an atmosphere of an inert gas such as nitrogen. Further, the polymerization reaction may be carried out under any conditions of normal pressure, pressurization and reduced pressure.
Water may be present in the polymerization step.
上記重合工程はまた、１種又は２種以上の重合開始剤の存在下で行うことが好ましい。上記重合開始剤としては、公知のラジカル重合開始剤を使用することができる。 The polymerization step is also preferably carried out in the presence of one or more polymerization initiators. As the polymerization initiator, a known radical polymerization initiator can be used.
上記重合開始剤としては、例えば、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸塩；過酸化水素； ジ−ｔ−ブチルパーオキサイド、ジ−ｔ−アミルパーオキサイド、ジ−ｔ−ヘキシルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン等のジアルキルパーオキサイド類、ｔ−ブチルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエート、ｔ−アミルパーオキシイソノナノエート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシピバレート等のパーオキシエステル類、１，１−ジ（ｔ−ブチルパーオキシ）シクロヘキサン、４，４−ビス［（ｔ−ブチル）ペルオキシ］ペンタン酸ブチル等のパーオキシケタール類、ｔ−ブチルハイドロパーオキシド、クメンハイドロパーオキサイド、ジイソプロピルベンゼン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、メチルエチルケトンパーオキサイド等のケトンパーオキサイド類、ジラウリルパーオキサイド、ジベンゾイルパーオキサイド等のジアシルパーオキサイド類、ジ（２−エチルヘキシル）パーオキシジカーボネート等のパーオキシジカーボネート類、等の有機過酸化物；ジメチル２，２’−アゾビス（２−メチルプロピオネート）、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（２−メチルプロピオンアミジン）二塩酸塩、２，２’−アゾビス［Ｎ−（２−カルボキシエチル）−２−メチルプロピオンアミジン］水和物、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二塩酸塩、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二硫酸塩水和物、２，２’−アゾビス（１−イミノ−１−ピロリジノ−２−メチルプロパン）二塩酸塩、２，２’−アゾビス［Ｎ−（２−カルボキシエチル）−２−メチルプロピオンアミジン］ｎ水和物、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］等のアゾ系化合物；等が挙げられる。なかでも、重合反応が効率よく進行し、残存モノマーを少なくできる点で、有機過酸化物及び／又はアゾ系化合物が好ましく、アゾ系化合物がより好ましい。 Examples of the polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; hydrogen peroxide; di-t-butyl peroxide, di-t-amyl peroxide, and di-t-hexyl. Dialkyl peroxides such as peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butylperoxyisopropyl Monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxylaurate, t-butylperoxybenzoate, t-amylperoxyisononanoate, t-amylperoxy-2-ethylhexanoate Peroxy esters such as ate and t-butylperoxypivalate, peroxy such as 1,1-di (t-butylperoxy) cyclohexane and 4,4-bis [(t-butyl) peroxy] butylpentanoate Hydroperoxides such as ketals, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, ketone peroxides such as methyl ethyl ketone peroxide, and diacylpers such as dilauryl peroxide and dibenzoyl peroxide. Organic peroxides such as oxides, peroxydicarbonates such as di (2-ethylhexyl) peroxydicarbonate; dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (Isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2) -Carboxyethyl) -2-methylpropion amidine] hydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (2-imidazolin-) 2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate hydrate, 2,2'-azobis (1-imino-1-pyrrolidino) -2-Methylpropane) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, 2,2'-azobis [2-methyl-N- (2-Hydroxyethyl) propionamide] and other azo compounds; etc. Of these, organic peroxides and / or azo compounds are preferable, and azo compounds are more preferable, in that the polymerization reaction proceeds efficiently and the amount of residual monomers can be reduced.
上記重合開始剤の使用量としては、特に限定されないが、低不純物量で分子量の調節が可能である点で、上記単量体成分総量１００質量部に対し０．１〜１０質量部が好ましく、０．２〜５質量部がより好ましく、０．３〜３質量部が更に好ましく、０．４〜３質量部が更により好ましい。 The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer components in that the molecular weight can be adjusted with a low impurity amount. 0.2 to 5 parts by mass is more preferable, 0.3 to 3 parts by mass is further preferable, and 0.4 to 3 parts by mass is even more preferable.
上記重合工程では、上述した成分以外に、連鎖移動剤、触媒、ｐＨ調整剤等の、重合反応において通常使用される他の成分を使用してもよい。これらの種類や量は公知技術から適宜選択することができる。 In the above-mentioned polymerization step, in addition to the above-mentioned components, other components usually used in the polymerization reaction such as a chain transfer agent, a catalyst, and a pH adjuster may be used. These types and amounts can be appropriately selected from known techniques.
本発明の製造方法は、更に、上記重合工程で得られたＮ−ビニルラクタム系共重合体溶液を乾燥する工程を含むことが好ましい。上記重合工程により、Ｎ−ビニルラクタム系共重合体を含む重合体溶液が得られる。この重合体溶液を乾燥して、必要に応じて粉砕することで、粉体のＮ−ビニルラクタム系共重合体を得ることができる。 The production method of the present invention preferably further includes a step of drying the N-vinyllactam-based copolymer solution obtained in the above polymerization step. By the above polymerization step, a polymer solution containing an N-vinyllactam-based copolymer is obtained. A powdery N-vinyllactam copolymer can be obtained by drying this polymer solution and pulverizing it if necessary.
上記乾燥方法としては、特に限定されず、一般に公知の方法を用いればよく、例えば、スプレードライヤー、ドラムドライヤー、（真空）乾燥機等を用いた乾燥方法等が挙げられる。乾燥の温度や時間については、Ｎ−ビニルラクタム系共重合体の量等に応じて適宜設定すればよく、例えば、８０〜２００℃で０．１〜４８０分間、好ましくは１００〜１５０℃で０．５〜３６０分間乾燥する方法が挙げられる。 The drying method is not particularly limited, and a generally known method may be used. Examples thereof include a drying method using a spray dryer, a drum dryer, a (vacuum) dryer, and the like. The drying temperature and time may be appropriately set according to the amount of the N-vinyllactam copolymer and the like. For example, it is 0 at 80 to 200 ° C. for 0.1 to 480 minutes, preferably 100 to 150 ° C. A method of drying for 5 to 360 minutes can be mentioned.
上記粉砕方法としては、重合体を粉砕することができる方法であれば特に限定されず、公知の方法を用いることができ、乾式粉砕、湿式粉砕あるいは凍結粉砕等のいずれでもよく、例えば、ボールミル、ビーズミル、ロールミル、ロッドミル、ハンマーミル、フリーザーミル、ジェットミル、スクリューミル、振動ミル、円筒型ミキサー等が挙げられる。これらは２種以上を併用してもよい。 The pulverization method is not particularly limited as long as it can pulverize the polymer, and a known method can be used. Any of dry pulverization, wet pulverization, freeze pulverization and the like can be used, for example, a ball mill. Examples thereof include bead mills, roll mills, rod mills, hammer mills, freezer mills, jet mills, screw mills, vibration mills, and cylindrical mixers. These may be used in combination of two or more.
上記乾燥、粉砕の後、更に分級工程を設けてもよい。分級方法は特に限定されず、ＪＩＳ標準篩等の公知の分級装置を用いて行うとよい。 After the drying and pulverization, a classification step may be further provided. The classification method is not particularly limited, and it is preferable to use a known classification device such as a JIS standard sieve.
上記粉砕して得られる粉体のＮ−ビニルラクタム系共重合体の形状は、特に限定されず、粒状、顆粒状、球状、塊状、鱗片状、無定形等のいずれの形状であってもよい。 The shape of the N-vinyllactam copolymer of the powder obtained by pulverization is not particularly limited, and may be any shape such as granular, granular, spherical, lumpy, scaly, and amorphous. ..
上記粉体のＮ−ビニルラクタム系共重合体の平均粒径は、特に限定されず、Ｎ−ビニルラクタム系共重合体の目的、用途に応じて適宜選択すればよいが、例えば、１〜５００μｍであることが好ましく、１０〜４００μｍであることがより好ましく、２０〜３００μｍであることが更に好ましい。
上記平均粒径は、乾式の粒子径分布測定装置（スペクトリス株式会社マルバーン事業部製 型式：マスターサイザー３０００ 乾式）等のレーザ回折・散乱法を採用した粒子径分布測定装置により求めることができる。
The average particle size of the N-vinyllactam-based copolymer of the above powder is not particularly limited and may be appropriately selected depending on the purpose and application of the N-vinyllactam-based copolymer. For example, 1 to 500 μm. It is preferably 10 to 400 μm, more preferably 20 to 300 μm.
The average particle size can be determined by a particle size distribution measuring device that employs a laser diffraction / scattering method such as a dry particle size distribution measuring device (Spectris Co., Ltd. Malvern Division model: Mastersizer 3000 dry type).
本発明の製造方法は、上述した工程以外に、他の工程を有していてもよい。例えば、熟成工程、中和工程、重合開始剤等の失活工程、希釈工程、濃縮工程、精製工程等が挙げられる。これらの工程は、公知の方法により行うことができる。また、これらの工程の順序も公知の方法により適宜選択することができる。 The production method of the present invention may have other steps in addition to the above-mentioned steps. Examples thereof include a aging step, a neutralization step, a deactivation step of a polymerization initiator and the like, a dilution step, a concentration step, a purification step and the like. These steps can be performed by a known method. Further, the order of these steps can be appropriately selected by a known method.
本発明の製造方法により得られるＮ−ビニルラクタム系共重合体のガラス転移温度（Ｔｇ）は、８０℃以上であることが好ましい。ガラス転移温度が８０℃以上であると、粉体のＮ−ビニルラクタム系共重合体を室温で製造するのが容易になる。
上記Ｎ−ビニルラクタム系共重合体のガラス転移温度（Ｔｇ）は、より好ましくは１００℃以上、更に好ましくは１２０℃以上である。上記ガラス転移温度（Ｔｇ）の上限値は、好ましくは４００℃以下、より好ましくは３５０℃以下である。
上記ガラス転移温度（Ｔｇ）は、日本工業規格ＪＩＳ Ｋ ７１２１に準拠した方法により求めることができ、具体的には、後述の実施例に記載の方法で求めることができる。
The glass transition temperature (Tg) of the N-vinyllactam copolymer obtained by the production method of the present invention is preferably 80 ° C. or higher. When the glass transition temperature is 80 ° C. or higher, it becomes easy to produce a powdered N-vinyllactam copolymer at room temperature.
The glass transition temperature (Tg) of the N-vinyllactam copolymer is more preferably 100 ° C. or higher, still more preferably 120 ° C. or higher. The upper limit of the glass transition temperature (Tg) is preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
The glass transition temperature (Tg) can be obtained by a method conforming to the Japanese Industrial Standards JIS K 7121, and specifically, can be obtained by the method described in Examples described later.
上記Ｎ−ビニルラクタム系共重合体の重量平均分子量は、上記共重合体の目的、用途に応じて適宜設定すればよいが、１０００以上であることが好ましく、３０００以上であることがより好ましく、５０００以上であることが更に好ましく、１００００以上であることが更により好ましく、１５０００００以下であることが好ましく、１４０００００以下であることがより好ましく、１００００００以下であることが更に好ましく、８０００００以下であることが更により好ましく、５０００００以下であることが特に好ましく、２０００００以下であることが最も好ましい。
上記重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）法により求めることができ、具体的には、後述する実施例に記載の方法で求めることができる。
The weight average molecular weight of the N-vinyllactam-based copolymer may be appropriately set according to the purpose and application of the copolymer, but is preferably 1000 or more, more preferably 3000 or more. It is more preferably 5000 or more, further preferably 10000 or more, preferably 1500,000 or less, further preferably 1400000 or less, further preferably 1000000 or less, and further preferably 800,000 or less. Is even more preferable, and is particularly preferably 500,000 or less, and most preferably 200,000 or less.
The weight average molecular weight can be determined by a gel permeation chromatography (GPC) method, and specifically, can be determined by the method described in Examples described later.
上記Ｎ−ビニルラクタム系共重合体のモノマー反応率は、８０％以上であることが好ましく、８５％以上であることがより好ましく、９０％以上であることが更に好ましい。
上記モノマー反応率は、ガスクロマトグラフ、液体クロマトグラフ、ゲル浸透クロマトグラフ等の重合体の残存単量体が測定可能な方法により求めることができる。具体的には、後述する実施例に記載の方法で共重合体中の単量体の含有率を求め、（添加した単量体量）から（共重合体中の単量体量）をひいた値を（反応したモノマー量）とし、（添加した単量体量）に対する（反応したモノマー量）の割合をモノマー反応率とする。
The monomer reaction rate of the N-vinyllactam copolymer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
The monomer reaction rate can be determined by a method such as a gas chromatograph, a liquid chromatograph, or a gel permeation chromatograph in which the residual monomer of the polymer can be measured. Specifically, the content of the monomer in the copolymer is determined by the method described in Examples described later, and (the amount of the monomer added) is subtracted from (the amount of the monomer in the copolymer). The value is defined as (the amount of the reacted monomer), and the ratio of (the amount of the reacted monomer) to (the amount of the added monomer) is defined as the monomer reaction rate.
上記Ｎ−ビニルラクタム系共重合体の副生成物量は、５質量％以下であることが好ましく、３質量％以下であることがより好ましく、１質量％以下であることが更に好ましい。
例えば、上記Ｎ−ビニルラクタム系単量体として、Ｎ−ビニルピロリドンを使用する場合、副生成物として、２−ピロリドンが生成する。
上記副生成物量の測定は、生成される副生成物の種類に応じて公知の方法から適宜選択して行うことができる。例えば、２−ピロリドンの場合、ガスクロマトグラフ、液体クロマトグラフ、ゲル浸透クロマトグラフ等の重合体の副生成物が測定可能な方法により測定することができるが、具体的には、後述する実施例に記載の方法で求めることができる。
The amount of by-products of the N-vinyllactam copolymer is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.
For example, when N-vinylpyrrolidone is used as the N-vinyllactam-based monomer, 2-pyrrolidone is produced as a by-product.
The measurement of the amount of by-products can be carried out by appropriately selecting from known methods according to the type of by-products produced. For example, in the case of 2-pyrrolidone, by-products of a polymer such as a gas chromatograph, a liquid chromatograph, and a gel permeation chromatograph can be measured by a measurable method. It can be obtained by the method described.
本発明の製造方法により得られるＮ−ビニルラクタム系共重合体は、組成が均一で、ガラス転移温度が高く、粉体加工性に優れる。そのため、高いガラス転移温度の粉体が必要とされる用途に好適に使用することができる。上記Ｎ−ビニルラクタム系共重合体の用途としては、例えば、光学材料、電子材料、繊維材料、樹脂材料、インク、家電製品、電子材料、電気部品、容器、フィルム、住宅建材等の各種用途が挙げられる。 The N-vinyllactam-based copolymer obtained by the production method of the present invention has a uniform composition, a high glass transition temperature, and is excellent in powder processability. Therefore, it can be suitably used for applications that require a powder having a high glass transition temperature. Applications of the N-vinyllactam-based copolymer include, for example, various applications such as optical materials, electronic materials, fiber materials, resin materials, inks, home appliances, electronic materials, electrical parts, containers, films, and housing building materials. Can be mentioned.
上記Ｎ−ビニルラクタム系共重合体は、単独で、あるいは他の成分と混合して樹脂組成物として使用することができる。上記他の成分としては、例えば、樹脂；色材；分散剤；耐熱向上剤；レベリング剤；シリカ微粒子等の無機微粒子；カップリング剤；フィラー；硬化助剤；可塑剤；重合禁止剤；紫外線吸収剤；酸化防止剤；艶消し剤；消泡剤；帯電防止剤；滑剤；表面改質剤；揺変化剤；揺変助剤；難燃剤；防錆剤；酸発生剤；溶剤等が挙げられる。これらは、公知のものから適宜選択して使用することができる。また、その使用量についても、樹脂組成物の目的、用途に応じて適宜設定することができる。 The N-vinyllactam copolymer can be used alone or in combination with other components as a resin composition. Other components include, for example, resin; coloring material; dispersant; heat resistant agent; leveling agent; inorganic fine particles such as silica fine particles; coupling agent; filler; curing aid; plasticizer; polymerization inhibitor; ultraviolet absorption. Agents; antioxidants; matting agents; defoaming agents; antistatic agents; lubricants; surface modifiers; rocking agents; rocking aids; flame retardants; rust preventives; acid generators; solvents and the like. .. These can be appropriately selected and used from known ones. In addition, the amount used can be appropriately set according to the purpose and application of the resin composition.
上記樹脂組成物を調製する方法としては、特に限定されず公知の方法を用いればよく、各成分をブレンダーやミキサー、押出機、ニーダー等の公知の各種混合機、分散機、混練機等を用いて混合する方法が挙げられる。こうして得られた樹脂組成物もまた、上述した用途に使用することができる。 The method for preparing the above resin composition is not particularly limited, and a known method may be used, and each component may be used in various known mixers such as blenders, mixers, extruders, kneaders, dispersers, kneaders and the like. There is a method of mixing. The resin composition thus obtained can also be used for the above-mentioned applications.
２．Ｎ−ビニルラクタム系共重合体
本発明はまた、Ｎ−ビニルラクタム系単量体由来の構成単位と、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体由来の構成単位を有することを特徴とするＮ−ビニルラクタム系共重合体である。本発明のＮ−ビニルラクタム系共重合体は、ガラス転移温度が高く、粉体加工性に優れる。
2. N-vinyllactam-based copolymer The present invention also comprises a structural unit derived from an N-vinyllactam-based monomer, a homopolymer having a glass transition temperature of 0 ° C. or higher, and may have a substituent. It is an N-vinyllactam-based copolymer characterized by having a structural unit derived from a (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms. The N-vinyllactam copolymer of the present invention has a high glass transition temperature and is excellent in powder processability.
本発明のＮ−ビニルラクタム系共重合体が、高いガラス転移温度を有し、粉体加工性に優れるのは、Ｎ−ビニルラクタム系単量体由来の構成単位と、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル由来の構成単位とを有するためであると考えられる。 The N-vinyllactam-based copolymer of the present invention has a high glass transition temperature and is excellent in powder processability because of the constituent units derived from the N-vinyllactam-based monomer and the glass transition of the homopolymer. It is considered that this is because the temperature is 0 ° C. or higher and the constituent unit is derived from a (meth) acrylic acid ester having an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent.
上記Ｎ−ビニルラクタム系単量体、及び、上記単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体としては、上述した「１．Ｎ−ビニルラクタム系共重合体の製造方法」に記載のＮ−ビニルラクタム系単量体、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル単量体とそれぞれ同様のものが挙げられる。 The N-vinyllactam-based monomer and the homopolymer have an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which has a glass transition temperature of 0 ° C. or higher and may have a substituent (). As the meta) acrylic acid ester-based monomer, the glass transition temperature of the N-vinyllactam-based monomer and homopolymer described in "1. Method for producing N-vinyllactam-based copolymer" described above is 0. Examples thereof include (meth) acrylic acid ester monomers having an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which are at ° C. or higher and may have a substituent.
上記Ｎ−ビニルラクタム系単量体由来の構成単位の含有割合は、Ｎ−ビニルラクタム系共重合体の全構成単位１００質量％に対して、３０質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。また、９５質量％以下であることが好ましく、９０質量％以下であることがより好ましく、８５質量％以下であることが更に好ましく、８０質量％以下であることが更により好ましい。 The content ratio of the structural unit derived from the N-vinyllactam-based monomer is preferably 30% by mass or more, preferably 40% by mass, based on 100% by mass of all the structural units of the N-vinyllactam-based copolymer. The above is more preferable, and 50% by mass or more is further preferable. Further, it is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, and further preferably 80% by mass or less.
上記単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体由来の構成単位の含有割合は、Ｎ−ビニルラクタム系共重合体の全構成単位１００質量％に対して、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、１５質量％以上であることが更に好ましく、２０質量％以上であることが更により好ましい。また、ガラス転移温度が高く、粉体加工性に優れる点で、７０質量％以下であることが好ましく、６０質量％以下であることがより好ましく、５０質量％以下であることが更に好ましい。 The composition derived from a (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which has a glass transition temperature of 0 ° C. or higher and may have a substituent. The content ratio of the unit is preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass or more, based on 100% by mass of all the constituent units of the N-vinyllactam-based copolymer. Is even more preferable, and 20% by mass or more is even more preferable. Further, in terms of high glass transition temperature and excellent powder processability, it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
本発明のＮ−ビニルラクタム系共重合体は、上述した構成単位以外に他の構成単位を有していてもよい。上記他の構成単位としては、上述した「１．Ｎ−ビニルラクタム系共重合体の製造方法」に記載の「他の単量体」由来の構成単位を挙げることができる。 The N-vinyllactam-based copolymer of the present invention may have other structural units in addition to the above-mentioned structural units. Examples of the other structural unit include a structural unit derived from “another monomer” described in “1. Method for Producing N-Vinyllactam Copolymer” described above.
上記他の単量体由来の構成単位の含有割合は、Ｎ−ビニルラクタム系共重合体の全構成単位１００質量％に対して、ガラス転移温度が高く、粉体加工性に優れる点で、０〜３０質量％であることが好ましく、０〜１０質量％であることがより好ましく、０〜５質量％であることが更に好ましい。 The content ratio of the structural units derived from the other monomers is 0 in that the glass transition temperature is high and the powder processability is excellent with respect to 100% by mass of all the structural units of the N-vinyllactam-based copolymer. It is preferably ~ 30% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass.
本発明のＮ−ビニルラクタム系共重合体のガラス転移温度、重量平均分子量は、上述した「１．Ｎ−ビニルラクタム系共重合体の製造方法」に記載のＮ−ビニルラクタム系共重合体のガラス転移温度、重量平均分子量と同じであることが好ましい。 The glass transition temperature and weight average molecular weight of the N-vinyllactam copolymer of the present invention are the same as those of the N-vinyllactam copolymer described in "1. Method for producing N-vinyllactam copolymer" described above. It is preferably the same as the glass transition temperature and the weight average molecular weight.
本発明のＮ−ビニルラクタム系共重合体は、上述した「１．Ｎ−ビニルラクタム系共重合体の製造方法」に記載の方法により好適に製造することができる。 The N-vinyllactam-based copolymer of the present invention can be suitably produced by the method described in "1. Method for producing N-vinyllactam-based copolymer" described above.
上記Ｎ−ビニルラクタム系共重合体は、単独で、あるいは他の成分と混合して樹脂組成物として使用することができる。上記他の成分としては、上述した「１．Ｎ−ビニルラクタム系共重合体の製造方法」に記載の他の成分と同様のものが挙げられる。
また、上記Ｎ−ビニルラクタム系共重合体の用途としては、上述した「１．Ｎ−ビニルラクタム系共重合体の製造方法」に記載の用途と同様の用途が挙げられる。
The N-vinyllactam copolymer can be used alone or in combination with other components as a resin composition. Examples of the other components include the same components as those described in "1. Method for Producing N-Vinyllactam Copolymer" described above.
In addition, examples of the use of the N-vinyllactam-based copolymer include the same uses as those described in "1. Method for producing N-vinyllactam-based copolymer" described above.
以上のとおり、本発明のＮ−ビニルラクタム系共重合体の製造方法は、残存モノマー量が少なく、組成が均一で、ガラス転移温度の高いＮ−ビニルラクタム系共重合体を好適に製造することができる。 As described above, the method for producing an N-vinyllactam-based copolymer of the present invention preferably produces an N-vinyllactam-based copolymer having a small amount of residual monomers, a uniform composition, and a high glass transition temperature. Can be done.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".
共重合体についての各評価を下記の方法で行った。
＜共重合体の固形分の測定＞
底面の直径が約５ｃｍの秤量缶（質量Ｗ１（ｇ））に、約１ｇの共重合体を量り取り（質量Ｗ２（ｇ））、これを１５０℃の定温乾燥機中において１時間静置し、乾燥させた。乾燥後の秤量缶と共重合体の合計質量（Ｗ３（ｇ））を測定し、下記式より固形分を求めた。
固形分（質量％）＝［（Ｗ３−Ｗ１）／Ｗ２］×１００
Each evaluation of the copolymer was carried out by the following method.
<Measurement of solid content of copolymer>
About 1 g of the copolymer is weighed in a weighing can (mass W1 (g)) having a bottom diameter of about 5 cm (mass W2 (g)), and this is allowed to stand in a constant temperature dryer at 150 ° C. for 1 hour. , Dried. The total mass (W3 (g)) of the weighed can and the copolymer after drying was measured, and the solid content was determined by the following formula.
Solid content (mass%) = [(W3-W1) / W2] x 100
＜共重合体の残存モノマー量、副生成物量の測定＞
共重合体中の単量体（Ｎ−ビニルピロリドン、（メタ）アクリル酸エステル、アクリル酸）、及び、副生成物（２−ピロリドン）の含有率は、ガスクロマトグラフ（装置：株式会社島津製作所製 ＧＣ−２０１４、検出器：ＦＩＤ、カラム：化学物質評価研究機構製 Ｇ−３００）を用いて求めた。
<Measurement of residual monomer amount and by-product amount of copolymer>
The content of the monomer (N-vinylpyrrolidone, (meth) acrylic acid ester, acrylic acid) and the by-product (2-pyrrolidone) in the copolymer is a gas chromatograph (device: manufactured by Shimadzu Corporation). It was determined using GC-2014, detector: FID, column: Chemical substance evaluation research organization G-300).
＜共重合体の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）の測定＞
共重合体の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）について、ゲル浸透クロマトグラフィー（ＧＰＣ）法により下記の条件Ａ又は条件Ｂで測定して求めた。Ｍｗ／Ｍｎは、Ｍｗの値をＭｎの値で除することにより求めた。
（条件Ａ）
装置：東ソー製 ＨＬＣ−８３２０ＧＰＣ
検出器：ＲＩ
カラム：昭和電工株式会社製 Ｓｈｏｄｅｘ ＫＤ−８０６Ｍ（２本）、ＫＤ−Ｇ ４Ａ
カラム温度：４０℃
流速：０．８ｍｌ／ｍｉｎ
検量線：Ｐｏｌｙｓｔｙｒｅｎｅ Ｓｔａｎｄａｒｄｓ
溶離液：Ｎ，Ｎ−ジメチルホルムアミド（０．１％ＬｉＢｒ含有）
（条件Ｂ）
装置：東ソー製 ＨＬＣ−８３２０ＧＰＣ
検出器：ＲＩ
カラム：東ソー株式会社製 ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ−Ｍ
カラム温度：４０℃
流速：０．１８ｍｌ／ｍｉｎ
検量線：Ｐｏｌｙｓｔｙｒｅｎｅ Ｓｔａｎｄａｒｄｓ
溶離液：テトラヒドロフラン（１質量％トリエチルアミン含有）
<Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) of copolymer>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer were measured and determined by the gel permeation chromatography (GPC) method under the following condition A or condition B. Mw / Mn was determined by dividing the value of Mw by the value of Mn.
(Condition A)
Equipment: Tosoh HLC-8320GPC
Detector: RI
Column: Showa Denko KD-806M (2 pcs), KD-G 4A
Column temperature: 40 ° C
Flow velocity: 0.8 ml / min
Calibration curve: Polystyrene Standards
Eluent: N, N-dimethylformamide (containing 0.1% LiBr)
(Condition B)
Equipment: Tosoh HLC-8320GPC
Detector: RI
Column: TSKgel SuperMultipore HZ-M manufactured by Tosoh Corporation
Column temperature: 40 ° C
Flow velocity: 0.18 ml / min
Calibration curve: Polystyrene Standards
Eluent: Tetrahydrofuran (containing 1% by mass triethylamine)
＜ガラス転移温度（Ｔｇ）の測定＞
共重合体のＴｇについて、示差走査熱量計（リガク製、Ｔｈｅｒｍｏ ｐｌｕｓ ＥＶＯ ＤＳＣ−８２３０、又は、ネッチ製、ＤＳＣ−３５００）を用い、窒素ガス雰囲気下、約１０ｍｇのサンプルを常温から２００℃もしくは２４０℃まで昇温（昇温速度２０℃／分）（比較例１は−１００℃から２００℃まで昇温（昇温速度２０℃／分））して得られたＤＳＣ曲線から、始点法により評価した。リファレンスには、α−アルミナを用いた。
<Measurement of glass transition temperature (Tg)>
For the Tg of the copolymer, use a differential scanning calorimeter (Rigaku, Thermo plus EVO DSC-8230, or Netch, DSC-3500) to sample about 10 mg of the sample from room temperature to 200 ° C or 240 under a nitrogen gas atmosphere. Evaluate by the start point method from the DSC curve obtained by raising the temperature to ° C. (heating rate 20 ° C./min) (Comparative Example 1 raises the temperature from -100 ° C to 200 ° C. (heating rate 20 ° C./min)) did. As a reference, α-alumina was used.
（実施例１）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、酢酸エチル（富士フイルム和光純薬株式会社製）６１５．４ｇ仕込んだ。２５０ｒｐｍで撹拌しながら、反応器の内温が７５℃になるように加熱した。次いで、７５℃を維持しながら、Ｎ−ビニルピロリドン（株式会社日本触媒製、以下、「ＶＰ」とも称する）４６．７ｇは３０分間、２，２’−アゾビス（２−メチルブチロニトリル）（富士フイルム和光純薬株式会社製、以下、「Ｖ−５９」とも称する）の５％酢酸エチル溶液３９．９ｇは２８５分間かけて、それぞれ滴下し重合を開始させた。重合発熱を確認後（ＶＰ滴下開始５分後）、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）３５ｇを６０分間かけて滴下した。ＶＰの３０分間の滴下終了後、ＶＰ９３．３ｇを１２０分間かけて滴下した。また、アクリル酸イソボルニルの６０分間の滴下終了後、アクリル酸イソボルニル１０５ｇを２２０分間かけて滴下した。全ＶＰに対する全アクリル酸イソボルニルの量は１００％、全単量体（ＶＰ＋アクリル酸イソボルニル）に対するＶ−５９の量は０．７％であった。
Ｖ−５９の滴下終了後、さらに７５℃で５５分間保持して、ＶＰ／アクリル酸イソボルニル重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル重合体溶液をエバポレーターで濃縮し、９０℃真空乾燥４時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、さらに粉体を１５０℃窒素雰囲気下で３時間乾燥して、ＶＰ／アクリル酸イソボルニル重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル＝５０／５０（質量比）であった。
(Example 1)
615.4 g of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was charged into a 1 L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket. The reactor was heated to 75 ° C. with stirring at 250 rpm. Next, while maintaining 75 ° C., 46.7 g of N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., hereinafter also referred to as "VP") was added to 2,2'-azobis (2-methylbutyronitrile) (2-methylbutyronitrile) for 30 minutes. 39.9 g of a 5% ethyl acetate solution manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (hereinafter, also referred to as "V-59") was added dropwise over 285 minutes to initiate polymerization. After confirming the heat generation of polymerization (5 minutes after the start of dropping VP), 35 g of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C.) was added dropwise over 60 minutes. After the completion of the 30-minute dropping of VP, 93.3 g of VP was dropped over 120 minutes. Further, after the completion of dropping of isobornyl acrylate for 60 minutes, 105 g of isobornyl acrylate was dropped over 220 minutes. The amount of total isobornyl acrylate to total VP was 100%, and the amount of V-59 to total monomer (VP + isobornyl acrylate) was 0.7%.
After completion of the dropping of V-59, the mixture was further held at 75 ° C. for 55 minutes to obtain a VP / isobornyl acrylate polymer solution.
The obtained VP / isobornyl acrylate polymer solution is concentrated by an evaporator, dried in a vacuum at 90 ° C. for 4 hours, pulverized until it passes through a JIS standard sieve having a mesh size of 500 μm, and the powder is further powdered in a nitrogen atmosphere at 150 ° C. 3 Drying for hours gave a VP / isobornyl acrylate polymer (powder). The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate = 50/50 (mass ratio).
（実施例２）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、２−プロパノール（富士フイルム和光純薬株式会社製）４２１．５ｇ、ＶＰ９０ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器の内温が８０℃になるように加熱した。次いで、８０℃を維持しながら、Ｖ−５９の５％２−プロパノール溶液３０ｇを２４０分間かけて滴下し重合を開始させた。Ｖ−５９滴下開始２０分後、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）１５０ｇ、アクリル酸（株式会社日本触媒製）６０ｇをそれぞれ１２０分間かけて滴下した。全単量体（ＶＰ＋アクリル酸イソボルニル＋アクリル酸）に対するＶ−５９の量は０．５％であった。
Ｖ−５９の滴下終了後、さらに８０℃で６０分間保持して、ＶＰ／アクリル酸イソボルニル／アクリル酸重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル／アクリル酸重合体溶液を９０℃真空乾燥４時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、さらに粉体を１２０℃で１時間真空乾燥して、ＶＰ／アクリル酸イソボルニル／アクリル酸重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル／アクリル酸重合体＝３０／５０／２０（質量比）であった。
(Example 2)
2-Propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 421.5 g and VP 90 g were charged into a 1 L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket. .. The reactor was heated to 80 ° C. with stirring at 250 rpm. Then, while maintaining 80 ° C., 30 g of a 5% 2-propanol solution of V-59 was added dropwise over 240 minutes to initiate polymerization. Twenty minutes after the start of dropping V-59, 150 g of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C.) and 60 g of acrylic acid (manufactured by Nippon Shokubai Co., Ltd.) were added dropwise over 120 minutes. The amount of V-59 relative to all monomers (VP + isobornyl acrylate + acrylic acid) was 0.5%.
After completion of the dropping of V-59, the mixture was further held at 80 ° C. for 60 minutes to obtain a VP / isobornyl acrylate / acrylic acid polymer solution.
The obtained VP / isobornyl acrylate / acrylic acid polymer solution was vacuum dried at 90 ° C. for 4 hours, pulverized until it passed through a JIS standard sieve having a mesh size of 500 μm, and the powder was vacuum dried at 120 ° C. for 1 hour. , VP / isobornyl acrylate / acrylic acid polymer (powder) was obtained. The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate / acrylic acid polymer = 30/50/20 (mass ratio).
（実施例３）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、酢酸エチル（富士フイルム和光純薬株式会社製）１８８．６ｇ、２−プロパノール（富士フイルム和光純薬株式会社製）１２１．６ｇ、脱イオン水２３．２ｇ、及びＶＰ３６．７ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器のジャケット温度が７８℃（内温が７６℃で一定）になるように加熱した。次いで、ジャケット温度７８℃を維持しながら、ＶＰ１８３．３ｇを１５０分間、ジメチル２，２’−アゾビス（２−メチルプロピオネート）（富士フイルム和光純薬株式会社製、以下、「Ｖ−６０１」とも称する）５％の２−プロパノール溶液２６．４ｇを２６０分間かけて、それぞれ滴下し重合を開始させた。Ｖ−６０１滴下開始１０分後、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）５５．０ｇを５０分間かけて滴下した。
また、アクリル酸イソボルニルの５０分間の滴下終了後、アクリル酸イソボルニル１３３．６ｇを１００分間かけて滴下した。その後、更に、アクリル酸イソボルニル３１．４ｇを８０分間かけて滴下した。この間に液の粘度が高くなったため、追加で酢酸エチルを計７５ｇ、３度に分けて添加した。全ＶＰに対する全アクリル酸イソボルニルの量は１００％、全単量体（ＶＰ＋アクリル酸イソボルニル）に対するＶ−６０１の量は０．３％であった。
Ｖ−６０１の滴下終了後、Ｖ−６０１の１０％の２−プロパノール溶液４．４ｇを添加し、その２０分後に、同量のＶ−６０１の１０％２−プロパノール溶液を添加し、さらにジャケット温度７８℃で４０分間保持して、ＶＰ／アクリル酸イソボルニル重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル重合体溶液をエバポレーターで濃縮し、８０℃真空乾燥４時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、さらに粉体を１３０℃窒素雰囲気下で３時間乾燥して、ＶＰ／アクリル酸イソボルニル重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル＝５０／５０（質量比）であった。
(Example 3)
1L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), thermometer, perfusion tube, and jacket, ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 188.6 g, 2-propanol (manufactured by Fuji) 121.6 g of film Wako Pure Chemical Industries, Ltd., 23.2 g of deionized water, and 36.7 g of VP were charged. While stirring at 250 rpm, the reactor was heated so that the jacket temperature was 78 ° C. (internal temperature was constant at 76 ° C.). Next, while maintaining the jacket temperature of 78 ° C., VP183.3 g was added to dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter "V-601") for 150 minutes. 26.4 g of a 5% 2-propanol solution (also referred to as) was added dropwise over 260 minutes to initiate polymerization. 10 minutes after the start of dropping V-601, 55.0 g of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C.) was added dropwise over 50 minutes.
Further, after the completion of the addition of isobornyl acrylate for 50 minutes, 133.6 g of isobornyl acrylate was added dropwise over 100 minutes. Then, 31.4 g of isobornyl acrylate was further added dropwise over 80 minutes. During this period, the viscosity of the liquid increased, so an additional 75 g of ethyl acetate was added in 3 portions. The amount of total isobornyl acrylate to total VP was 100%, and the amount of V-601 to all monomers (VP + isobornyl acrylate) was 0.3%.
After completion of the dropping of V-601, 4.4 g of a 10% 2-propanol solution of V-601 was added, and 20 minutes later, the same amount of a 10% 2-propanol solution of V-601 was added, and a jacket was further added. The solution was maintained at a temperature of 78 ° C. for 40 minutes to obtain a VP / isopropanol acrylate polymer solution.
The obtained VP / isobornyl acrylate polymer solution is concentrated by an evaporator, dried in a vacuum at 80 ° C. for 4 hours, pulverized until it passes through a JIS standard sieve having a mesh size of 500 μm, and the powder is further powdered in a nitrogen atmosphere at 130 ° C. 3 Drying for hours gave a VP / isobornyl acrylate polymer (powder). The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate = 50/50 (mass ratio).
（実施例４）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、２−プロパノール（富士フイルム和光純薬株式会社製）２７３．０ｇ、脱イオン水３４．０ｇ、及びＶＰ１７．０ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器のジャケット温度が８５℃（内温が８２℃で一定）になるように加熱した。次いで、ジャケット温度８５℃を維持しながら、ＶＰ８５．０ｇを１５０分間、Ｖ−６０１の３％２−プロパノール溶液３４．０ｇを２６０分間かけて、それぞれ滴下し重合を開始させた。Ｖ−６０１滴下開始１０分後、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）５９．５ｇを４０分間かけて滴下した。
また、アクリル酸イソボルニルの４０分間の滴下終了後、アクリル酸イソボルニル１４４．５ｇを９０分間かけて滴下した。更に、アクリル酸イソボルニル３４．０ｇを８０分間かけて滴下した。全ＶＰに対する全アクリル酸イソボルニルの量は２３３％、全単量体（ＶＰ＋アクリル酸イソボルニル）に対するＶ−６０１の量は０．３％であった。
Ｖ−６０１の滴下終了後、Ｖ−６０１の１０％２−プロパノール溶液３．４ｇを添加し、その２０分後に、同量のＶ−６０１の１０％２−プロパノール溶液を添加し、さらにジャケット温度８５℃で６０分間保持して、ＶＰ／アクリル酸イソボルニル重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル重合体溶液をエバポレーターで濃縮し、９０℃真空乾燥２時間、次いで１００℃真空乾燥２時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、さらに粉体を１５０℃窒素雰囲気下で３時間乾燥して、ＶＰ／アクリル酸イソボルニル重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル＝３０／７０（質量比）であった。
(Example 4)
2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 273.0 g, deionized water 34 in a 1 L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket. .0 g and 17.0 g of VP were charged. While stirring at 250 rpm, the reactor was heated so that the jacket temperature was 85 ° C. (internal temperature was constant at 82 ° C.). Then, while maintaining the jacket temperature of 85 ° C., 85.0 g of VP was added dropwise over 150 minutes and 34.0 g of a 3% 2-propanol solution of V-601 was added dropwise over 260 minutes to initiate polymerization. 10 minutes after the start of dropping V-601, 59.5 g of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C.) was added dropwise over 40 minutes.
Further, after the completion of the 40-minute dropping of isobornyl acrylate, 144.5 g of isobornyl acrylate was added dropwise over 90 minutes. Further, 34.0 g of isobornyl acrylate was added dropwise over 80 minutes. The amount of total isobornyl acrylate to total VP was 233%, and the amount of V-601 to total monomer (VP + isobornyl acrylate) was 0.3%.
After completion of the dropping of V-601, 3.4 g of a 10% 2-propanol solution of V-601 was added, and 20 minutes later, the same amount of a 10% 2-propanol solution of V-601 was added, and the jacket temperature was further increased. The mixture was held at 85 ° C. for 60 minutes to obtain a VP / isobornyl acrylate polymer solution.
The obtained VP / isobornyl acrylate polymer solution is concentrated by an evaporator, vacuum dried at 90 ° C. for 2 hours, then vacuum dried at 100 ° C. for 2 hours, and then pulverized until it passes through a JIS standard sieve having a mesh size of 500 μm, and further powdered. Was dried in a nitrogen atmosphere at 150 ° C. for 3 hours to obtain a VP / isobornyl acrylate polymer (powder). The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate = 30/70 (mass ratio).
（実施例５）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、酢酸エチル２１５．４ｇ、２−プロパノール（富士フイルム和光純薬株式会社）２１．６ｇ、脱イオン水２１．１ｇ、及びＶＰ２０．０ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器のジャケット温度が７８℃（内温が７６℃で一定）になるように加熱した。次いで、ジャケット温度７８℃を維持しながら、ＶＰ１００．０ｇを１５０分間、Ｖ−６０１の５％２−プロパノール溶液２４．０ｇを２６０分間かけて、それぞれ滴下し重合を開始させた。Ｖ−６０１滴下開始１０分後、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）７０．０ｇを４０分間かけて滴下した。
また、アクリル酸イソボルニルの４０分間の滴下終了後、アクリル酸イソボルニル１７０．０ｇを９０分間かけて滴下した。その後更に、アクリル酸イソボルニル４０．０ｇを８０分間かけて滴下した。この間に液の粘度が高くなったため、追加で酢酸エチルを計１００ｇ、２度に分けて添加した。全ＶＰに対する全アクリル酸イソボルニルの量は２３３％、全単量体（ＶＰ＋アクリル酸イソボルニル）に対するＶ−６０１の量は０．３％であった。
Ｖ−６０１の滴下終了後、Ｖ−６０１の１０％の２−プロパノール溶液６．０ｇを添加し、その２０分後に、同量のＶ−６０１の１０％の２−プロパノール溶液を添加し、更にジャケット温度７８℃で４０分間保持して、ＶＰ／アクリル酸イソボルニル重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル重合体溶液をエバポレーターで濃縮し、９０℃真空乾燥４時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、さらに粉体を９０℃窒素雰囲気下で４時間乾燥して、ＶＰ／アクリル酸イソボルニル重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル＝３０／７０（質量比）であった。
(Example 5)
Ethyl acetate 215.4 g, 2-propanol (Fujifilm Wako Pure Chemical Industries, Ltd.) 21.6 g in a 1 L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket. , 21.1 g of deionized water, and 20.0 g of VP were charged. While stirring at 250 rpm, the reactor was heated so that the jacket temperature was 78 ° C. (internal temperature was constant at 76 ° C.). Then, while maintaining the jacket temperature of 78 ° C., 100.0 g of VP was added dropwise over 150 minutes and 24.0 g of a 5% 2-propanol solution of V-601 was added dropwise over 260 minutes to initiate polymerization. 10 minutes after the start of dropping V-601, 70.0 g of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C.) was added dropwise over 40 minutes.
After the 40-minute dropping of isobornyl acrylate was completed, 170.0 g of isobornyl acrylate was added dropwise over 90 minutes. After that, 40.0 g of isobornyl acrylate was further added dropwise over 80 minutes. During this period, the viscosity of the liquid increased, so an additional 100 g of ethyl acetate was added in two portions. The amount of total isobornyl acrylate to total VP was 233%, and the amount of V-601 to total monomer (VP + isobornyl acrylate) was 0.3%.
After completion of the dropwise addition of V-601, 6.0 g of a 10% 2-propanol solution of V-601 was added, and 20 minutes later, the same amount of a 10% 2-propanol solution of V-601 was added, and further. The jacket temperature was maintained at 78 ° C. for 40 minutes to obtain a VP / isopropanol acrylate polymer solution.
The obtained VP / isobornyl acrylate polymer solution is concentrated by an evaporator, dried in a vacuum at 90 ° C. for 4 hours, pulverized until it passes through a JIS standard sieve having a mesh size of 500 μm, and the powder is further powdered in a nitrogen atmosphere at 90 ° C. 4 Drying for hours gave a VP / isobornyl acrylate polymer (powder). The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate = 30/70 (mass ratio).
（実施例６）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、２−プロパノール（富士フイルム和光純薬株式会社製）３４８．１ｇ、脱イオン水４１．７ｇ、及びＶＰ４１．７ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器のジャケット温度が８５℃（内温が８３℃で一定）になるように加熱した。次いで、ジャケット温度８５℃を維持しながら、ＶＰ２０８．３ｇを１５０分間、Ｖ−６０１の３％２−プロパノール溶液２７．８ｇを２４０分間かけて、それぞれ滴下し重合を開始させた。Ｖ−６０１滴下開始１０分後、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）６．９ｇを５０分間かけて滴下した。
また、アクリル酸イソボルニルの５０分間の滴下終了後、アクリル酸イソボルニル１６．９ｇを１００分間かけて滴下した。更に、アクリル酸イソボルニル４．０ｇを６０分間かけて滴下した。全ＶＰに対する全アクリル酸イソボルニルの量は１１％、全単量体（ＶＰ＋アクリル酸イソボルニル）に対するＶ−６０１の量は０．３％であった。
Ｖ−６０１の滴下終了後、Ｖ−６０１の１０％の２−プロパノール溶液２．８ｇを添加し、その２０分後に、同量のＶ−６０１の１０％２−プロパノール溶液を添加し、さらにジャケット温度８５℃で４０分間保持して、ＶＰ／アクリル酸イソボルニル重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル重合体溶液を濃縮し、９０℃真空乾燥２時間、１００℃真空乾燥２時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、ＶＰ／アクリル酸イソボルニル重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル＝９０／１０（質量比）であった。
(Example 6)
1L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket, 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 348.1 g, deionized water 41 .7 g and VP 41.7 g were charged. While stirring at 250 rpm, the reactor was heated so that the jacket temperature was 85 ° C. (internal temperature was constant at 83 ° C.). Then, while maintaining the jacket temperature of 85 ° C., 208.3 g of VP was added dropwise over 150 minutes and 27.8 g of a 3% 2-propanol solution of V-601 was added dropwise over 240 minutes to initiate polymerization. 10 minutes after the start of dropping V-601, 6.9 g of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C.) was added dropwise over 50 minutes.
Further, after the completion of the addition of isobornyl acrylate for 50 minutes, 16.9 g of isobornyl acrylate was added dropwise over 100 minutes. Further, 4.0 g of isobornyl acrylate was added dropwise over 60 minutes. The amount of total isobornyl acrylate to total VP was 11%, and the amount of V-601 to all monomers (VP + isobornyl acrylate) was 0.3%.
After completion of the dropping of V-601, 2.8 g of a 10% 2-propanol solution of V-601 was added, and 20 minutes later, the same amount of a 10% 2-propanol solution of V-601 was added, and a jacket was further added. The solution was maintained at a temperature of 85 ° C. for 40 minutes to obtain a VP / isopropanol acrylate polymer solution.
The obtained VP / isobornyl acrylate polymer solution is concentrated, vacuum dried at 90 ° C. for 2 hours, dried at 100 ° C. for 2 hours, and then pulverized until it passes through a JIS standard sieve having a mesh size of 500 μm. A coalescence (powder) was obtained. The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate = 90/10 (mass ratio).
（実施例７）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、酢酸エチル２０８．３ｇ、２−プロパノール（富士フイルム和光純薬株式会社製）１８７．５ｇ、脱イオン水３７．５ｇ、及びＶＰ２５．０ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器のジャケット温度が７８℃（内温が７７℃で一定）になるように加熱した。次いで、ジャケット温度７８℃を維持しながら、ＶＰ１２５．０ｇを１５０分間、ｔ−ブチルペルオキシピバレート（日本油脂株式会社製 パーブチルＰＶ、純分７０％、以下、「パーブチルＰＶ」とも称する）の５％酢酸エチル溶液１８．０ｇを２６０分間かけて、それぞれ滴下し重合を開始させた。パーブチルＰＶ滴下開始１０分後、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）３７．５ｇを５０分間かけて滴下した。
また、アクリル酸イソボルニルの５０分間の滴下終了後、アクリル酸イソボルニル９１．１ｇを１００分間かけて滴下した。その後更に、アクリル酸イソボルニル２１．４ｇを８０分間かけて滴下した。全ＶＰに対する全アクリル酸イソボルニルの量は１００％、全単量体（ＶＰ＋アクリル酸イソボルニル）に対するパーブチルＰＶの量は０．３％であった。
パーブチルＰＶの滴下終了後、パーブチルＰＶの１０％の酢酸エチル溶液３．０ｇを添加し、その２０分後に、同量のパーブチルＰＶの１０％酢酸エチル溶液を添加し、さらにジャケット温度７８℃で４０分間保持して、ＶＰ／アクリル酸イソボルニル重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル重合体溶液を濃縮し、９０℃真空乾燥２時間、１００℃真空乾燥２時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、ＶＰ／アクリル酸イソボルニル重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル＝５０／５０（質量比）であった。
(Example 7)
In a 1L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket, 208.3 g of ethyl acetate and 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 187. 5 g, 37.5 g of deionized water, and 25.0 g of VP were charged. While stirring at 250 rpm, the reactor was heated so that the jacket temperature was 78 ° C. (internal temperature was constant at 77 ° C.). Next, while maintaining the jacket temperature of 78 ° C., 125.0 g of VP was applied for 150 minutes to 5% of t-butylperoxypivalate (Perbutyl PV manufactured by NOF CORPORATION, pure content 70%, hereinafter also referred to as "perbutyl PV"). 18.0 g of an ethyl acetate solution was added dropwise over 260 minutes to initiate polymerization. 10 minutes after the start of dropping of perbutyl PV, 37.5 g of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C.) was added dropwise over 50 minutes.
Further, after the completion of the addition of isobornyl acrylate for 50 minutes, 91.1 g of isobornyl acrylate was added dropwise over 100 minutes. After that, 21.4 g of isobornyl acrylate was further added dropwise over 80 minutes. The amount of total isobornyl acrylate to total VP was 100%, and the amount of perbutyl PV to total monomer (VP + isobornyl acrylate) was 0.3%.
After the completion of dropping of the perbutyl PV, 3.0 g of a 10% ethyl acetate solution of the perbutyl PV was added, and 20 minutes later, the same amount of the 10% ethyl acetate solution of the perbutyl PV was added, and further 40 at a jacket temperature of 78 ° C. The mixture was held for 1 minute to obtain a VP / isobornyl acrylate polymer solution.
The obtained VP / isobornyl acrylate polymer solution is concentrated, vacuum dried at 90 ° C. for 2 hours, dried at 100 ° C. for 2 hours, and then pulverized until it passes through a JIS standard sieve having a mesh size of 500 μm. A coalescence (powder) was obtained. The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate = 50/50 (mass ratio).
（実施例８）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、酢酸エチル２２５．０ｇ、２−プロパノール（富士フイルム和光純薬株式会社製）１６５．９ｇ、脱イオン水３７．５ｇ、及びＶＰ２５．０ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器のジャケット温度が７８℃（内温が７６℃で一定）になるように加熱した。次いで、ジャケット温度７８℃を維持しながら、ＶＰ１２５．０ｇを１５０分間、Ｖ−６０１の４％２−プロパノール溶液２２．５ｇを２９０分間かけて、それぞれ滴下し重合を開始させた。Ｖ−６０１滴下開始１０分後、アクリル酸イソボルニル（株式会社日本触媒製、ホモポリマーのＴｇ：９４℃）とアクリル酸ベンジル（大阪有機化学工業製、ホモポリマーのＴｇ：６℃）の重量比４：１混合液３７．５ｇを６０分間かけて滴下した。
また、アクリル酸イソボルニル／アクリル酸ベンジル（４：１）の６０分間の滴下終了後、アクリル酸イソボルニル／アクリル酸ベンジル（４：１）９１．１ｇを１２０分間かけて滴下した。その後更に、アクリル酸イソボルニル／アクリル酸ベンジル（４：１）２１．４ｇを８０分間かけて滴下した。全ＶＰに対する全アクリル酸エステル（アクリル酸イソボルニル＋アクリル酸ベンジル）の量は１００％、全単量体（ＶＰ＋アクリル酸イソボルニル＋アクリル酸ベンジル）に対するＶ−６０１の量は０．３％であった。
Ｖ−６０１の滴下終了後、Ｖ−６０１の１０％の２−プロパノール溶液３．０ｇを添加し、その３０分後に、同量のＶ−６０１の１０％２−プロパノール溶液を添加し、さらにジャケット温度７８℃で４０分間保持して、ＶＰ／アクリル酸イソボルニル／アクリル酸ベンジル重合体溶液を得た。
得られたＶＰ／アクリル酸イソボルニル／アクリル酸ベンジル重合体溶液を濃縮し、９０℃真空乾燥２時間、１００℃真空乾燥２時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、ＶＰ／アクリル酸イソボルニル／アクリル酸ベンジル重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／アクリル酸イソボルニル／アクリル酸ベンジル＝５０／４０／１０（質量比）であった。
(Example 8)
In a 1L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket, 225.0 g of ethyl acetate and 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 165. 9 g, 37.5 g of deionized water, and 25.0 g of VP were charged. While stirring at 250 rpm, the reactor was heated so that the jacket temperature was 78 ° C. (internal temperature was constant at 76 ° C.). Then, while maintaining the jacket temperature of 78 ° C., 125.0 g of VP was added dropwise over 150 minutes and 22.5 g of a 4% 2-propanol solution of V-601 was added dropwise over 290 minutes to initiate polymerization. 10 minutes after the start of dropping V-601, the weight ratio of isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd., homopolymer Tg: 94 ° C) and benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., homopolymer Tg: 6 ° C) 4 1) 37.5 g of the mixed solution was added dropwise over 60 minutes.
Further, after the completion of dropping of isobornyl acrylate / benzyl acrylate (4: 1) for 60 minutes, 91.1 g of isobornyl acrylate / benzyl acrylate (4: 1) was added dropwise over 120 minutes. After that, 21.4 g of isobornyl acrylate / benzyl acrylate (4: 1) was added dropwise over 80 minutes. The amount of total acrylate (isobornyl acrylate + benzyl acrylate) to all VPs was 100%, and the amount of V-601 to all monomers (VP + isobornyl acrylate + benzyl acrylate) was 0.3%. ..
After completion of the dropping of V-601, 3.0 g of a 10% 2-propanol solution of V-601 was added, and 30 minutes later, the same amount of a 10% 2-propanol solution of V-601 was added, and a jacket was further added. The solution was maintained at a temperature of 78 ° C. for 40 minutes to obtain a VP / isobornyl acrylate / benzyl acrylate polymer solution.
The obtained VP / isobornyl acrylate / benzyl acrylate polymer solution is concentrated, vacuum dried at 90 ° C. for 2 hours, dried at 100 ° C. for 2 hours, and then pulverized until it passes through a JIS standard sieve having an opening of 500 μm. Isobornyl acrylate / benzyl acrylate polymer (powder) was obtained. The constituent monomer ratio of the obtained polymer was VP / isobornyl acrylate / benzyl acrylate = 50/40/10 (mass ratio).
（実施例９）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、酢酸エチル２２５．０ｇ、２−プロパノール（富士フイルム和光純薬株式会社製）１７０．４ｇ、脱イオン水３７．５ｇ、及びＶＰ２５．０ｇを仕込んだ。２５０ｒｐｍで撹拌しながら、反応器のジャケット温度が７８℃（内温が７６℃で一定）になるように加熱した。次いで、ジャケット温度７８℃を維持しながら、ＶＰ１２５．０ｇを１５０分間、Ｖ−６０１の５％２−プロパノール溶液１８．０ｇを２６０分間かけて、それぞれ滴下し重合を開始させた。Ｖ−６０１滴下開始１０分後、２−（ｏ−フェニルフェノキシ）エチルアクリレート（日触テクノファインケミカル株式会社製 ＨＲＤ−０１、ホモポリマーのＴｇ：３３℃、以下、「ＨＲＤ」とも称する）３７．５ｇを５０分間かけて滴下した。
また、ＨＲＤの５０分間の滴下終了後、ＨＲＤ９１．１ｇを１００分間かけて滴下した。その後更に、ＨＲＤ２１．４ｇを８０分間かけて滴下した。全ＶＰに対する全ＨＲＤの量は１００％、全単量体（ＶＰ＋ＨＲＤ）に対するＶ−６０１の量は０．３％であった。
Ｖ−６０１の滴下終了後、Ｖ−６０１の１０％の２−プロパノール溶液３．０ｇを添加し、その２０分後に、同量のＶ−６０１の１０％の２−プロパノール溶液を添加し、さらにジャケット温度７８℃で４０分間保持して、ＶＰ／ＨＲＤ重合体溶液を得た。
得られたＶＰ／ＨＲＤ重合体溶液を濃縮し、９０℃真空乾燥２時間、１００℃真空乾燥２時間後、目開き５００μｍのＪＩＳ標準篩を通過するまで粉砕し、ＶＰ／ＨＲＤ重合体（粉体）を得た。得られた重合体の構成モノマー比は、ＶＰ／ＨＲＤ＝５０／５０（質量比）であった。
(Example 9)
In a 1L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket, 225.0 g of ethyl acetate and 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 170. 4 g, 37.5 g of deionized water, and 25.0 g of VP were charged. While stirring at 250 rpm, the reactor was heated so that the jacket temperature was 78 ° C. (internal temperature was constant at 76 ° C.). Then, while maintaining the jacket temperature of 78 ° C., 125.0 g of VP was added dropwise over 150 minutes and 18.0 g of a 5% 2-propanol solution of V-601 was added dropwise over 260 minutes to initiate polymerization. 10 minutes after the start of dropping V-601, 2- (o-phenylphenoxy) ethyl acrylate (HRD-01 manufactured by Nikko Technofine Chemical Co., Ltd., homopolymer Tg: 33 ° C., hereinafter also referred to as "HRD") 37.5 g Was added dropwise over 50 minutes.
Further, after the completion of the 50-minute dropping of HRD, 91.1 g of HRD was dropped over 100 minutes. After that, 21.4 g of HRD was further added dropwise over 80 minutes. The amount of total HRD to all VP was 100% and the amount of V-601 to all monomers (VP + HRD) was 0.3%.
After completion of the dropwise addition of V-601, 3.0 g of a 10% 2-propanol solution of V-601 was added, and 20 minutes later, the same amount of a 10% 2-propanol solution of V-601 was added, and further. The jacket temperature was maintained at 78 ° C. for 40 minutes to obtain a VP / HRD polymer solution.
The obtained VP / HRD polymer solution is concentrated, vacuum dried at 90 ° C. for 2 hours, dried at 100 ° C. for 2 hours, and then pulverized until it passes through a JIS standard sieve having a mesh size of 500 μm to obtain a VP / HRD polymer (powder). ) Was obtained. The constituent monomer ratio of the obtained polymer was VP / HRD = 50/50 (mass ratio).
（比較例１）
マックスブレンド型攪拌翼（ＳＵＳ３０４製）、温度計、還流管、ジャケットを備えた１Ｌ反応器（ＳＵＳ３０４製）に、酢酸エチル（富士フイルム和光純薬株式会社製）６１８．８ｇ仕込んだ。２５０ｒｐｍで撹拌しながら、反応器の内温が７５℃になるように加熱した。次いで、７５℃を維持しながら、ＶＰ４６．７ｇは３０分間、アクリル酸２−エチルヘキシル（東京化成工業株式会社製、ホモポリマーのＴｇ：−５０℃）３５ｇは８０分間、Ｖ−５９の５％酢酸エチル溶液３６．４ｇは２６０分間かけて、それぞれ滴下し重合を開始させた。ＶＰの３０分間の滴下終了後、ＶＰ９３．３ｇを１５０分間かけて滴下した。また、アクリル酸２−エチルヘキシルの８０分間の滴下終了後、アクリル酸２−エチルヘキシル１０５ｇを１８０分間かけて滴下した。全ＶＰに対する全アクリル酸２−エチルヘキシルの量は１００％、全単量体（ＶＰ＋アクリル酸２−エチルヘキシル）に対するＶ−５９の量は０．７％であった。
Ｖ−５９の滴下終了後、さらに７５℃で６０分間保持して、ＶＰ／アクリル酸２−エチルヘキシル重合体溶液を得た。
得られたＶＰ／アクリル酸２−エチルヘキシル重合体溶液について、９０℃真空乾燥を４時間行って粉体化を試みたが、ゴム状態となり、ＶＰ／アクリル酸２−エチルヘキシル重合体（粉体）は得られなかった。
(Comparative Example 1)
318.8 g of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was charged into a 1 L reactor (manufactured by SUS304) equipped with a max blend type stirring blade (manufactured by SUS304), a thermometer, a reflux tube, and a jacket. The reactor was heated to 75 ° C. with stirring at 250 rpm. Then, while maintaining 75 ° C., 46.7 g of VP for 30 minutes and 35 g of 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., homopolymer Tg: -50 ° C.) for 80 minutes, 5% acetate of V-59. 36.4 g of the ethyl solution was added dropwise over 260 minutes to initiate polymerization. After the completion of the 30-minute dropping of VP, 93.3 g of VP was dropped over 150 minutes. Further, after the completion of the addition of 2-ethylhexyl acrylate for 80 minutes, 105 g of 2-ethylhexyl acrylate was added dropwise over 180 minutes. The amount of 2-ethylhexyl acrylate to total VP was 100%, and the amount of V-59 to total monomer (VP + 2-ethylhexyl acrylate) was 0.7%.
After completion of the dropping of V-59, the mixture was further held at 75 ° C. for 60 minutes to obtain a VP / 2-ethylhexyl acrylate polymer solution.
The obtained VP / 2-ethylhexyl acrylate polymer solution was vacuum dried at 90 ° C. for 4 hours to try to powder it, but it became a rubber state, and the VP / 2-ethylhexyl acrylate polymer (powder) became a rubber state. I couldn't get it.
実施例及び比較例で得られた共重合体について、上記の方法で、残存モノマー量、副生成物量、重量平均分子量（実施例４、５、７は条件Ｂで、その他は条件Ａで測定した。）、ガラス転移温度を評価した。得られた結果を表１に示す。 The copolymers obtained in Examples and Comparative Examples were measured by the above method in terms of residual monomer amount, by-product amount, and weight average molecular weight (Examples 4, 5 and 7 were measured under Condition B, and the others were measured under Condition A). ), The glass transition temperature was evaluated. The results obtained are shown in Table 1.
表１より、Ｎ−ビニルラクタム系単量体であるＮ−ビニルピロリドンと、単独重合体のガラス転移温度が０℃以上であり、置換基を有してもよい、炭素数１〜２５の脂肪族炭化水素基を有する（メタ）アクリル酸エステル系単量体であるアクリル酸イソボルニルとを含む単量体成分を、有機溶媒を含む重合溶媒の存在下で重合した場合（実施例）は、Ｎ−ビニルピロリドンと、上記（メタ）アクリル酸エステル系単量体に該当しないアクリル酸２−エチルヘキシルとを含む単量体成分を、有機溶媒を含む重合溶媒の存在下で重合した場合（比較例１）と比べて、残存モノマー量が少なく、２−ビニルピロリドンの副生成物量も少なく、Ｎ−ビニルラクタム系共重合体を効率良く製造できることが分かった。
また、実施例で得られた共重合体は、比較例で得られた共重合体と比べて、ガラス転移温度が高く、粉体加工性も良好であることが分かった。
From Table 1, N-vinylpyrrolidone, which is an N-vinyllactam-based monomer, and a fat having 1 to 25 carbon atoms which has a glass transition temperature of 0 ° C. or higher and may have a substituent. When a monomer component containing isobornyl acrylate, which is a (meth) acrylic acid ester-based monomer having a group hydrocarbon group, is polymerized in the presence of a polymerization solvent containing an organic solvent (Example), N -When a monomer component containing vinylpyrrolidone and 2-ethylhexyl acrylate, which does not correspond to the above (meth) acrylic acid ester-based monomer, is polymerized in the presence of a polymerization solvent containing an organic solvent (Comparative Example 1). ), The amount of residual monomer is small, the amount of by-products of 2-vinylpyrrolidone is also small, and it was found that an N-vinyllactam-based copolymer can be efficiently produced.
Further, it was found that the copolymer obtained in the examples had a higher glass transition temperature and better powder processability than the copolymer obtained in the comparative example.
Claims (8)
ことを特徴とするＮ−ビニルラクタム系共重合体の製造方法。 In the presence of a polymerization solvent containing an organic solvent, the glass transition temperature of the N-vinyllactam-based monomer and the homopolymer is 0 ° C. or higher, and may have a substituent, and has 1 to 25 carbon atoms. A method for producing an N-vinyllactam-based copolymer, which comprises a step of polymerizing a monomer component containing a (meth) acrylic acid ester-based monomer having an aliphatic hydrocarbon group of.
The N-vinyllactam-based copolymer according to claim 6 or 7, wherein the N-vinyllactam-based copolymer has a glass transition temperature of 80 ° C. or higher.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019197414 | 2019-10-30 | ||
| JP2019197414 | 2019-10-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021070809A true JP2021070809A (en) | 2021-05-06 |
Family
ID=75712452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020119976A Pending JP2021070809A (en) | 2019-10-30 | 2020-07-13 | Method for Producing N-Vinyl Lactam Copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021070809A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102022109414A1 (en) | 2021-04-20 | 2022-10-20 | Toyota Jidosha Kabushiki Kaisha | Method for updating software in a vehicle controller and vehicle operating system |
| WO2023002853A1 (en) * | 2021-07-21 | 2023-01-26 | 株式会社日本触媒 | Acrylic resin for ink |
-
2020
- 2020-07-13 JP JP2020119976A patent/JP2021070809A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102022109414A1 (en) | 2021-04-20 | 2022-10-20 | Toyota Jidosha Kabushiki Kaisha | Method for updating software in a vehicle controller and vehicle operating system |
| WO2023002853A1 (en) * | 2021-07-21 | 2023-01-26 | 株式会社日本触媒 | Acrylic resin for ink |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2784024C (en) | Emulsion polymerization of esters of itaconic acid | |
| US6150468A (en) | Water soluble amphiphilic heteratom star polymers and their use as emulsion stabilizers in emulsion polymerization | |
| JP2021070809A (en) | Method for Producing N-Vinyl Lactam Copolymer | |
| CN103282340A (en) | Substituted 3-xopentanoates and their uses in coating compositions | |
| JP3999022B2 (en) | Vinyl pyrrolidone polymer | |
| JP5637500B2 (en) | Method for producing vinyl polymer and vinyl polymer | |
| JP7418907B2 (en) | Method for producing N-vinyl lactam copolymer | |
| US9410005B2 (en) | Polymer, preparation method thereof, composition and film comprising the same | |
| JP2022018857A (en) | Method for producing n-vinylamide-based polymer and n-vinylamide-based polymer | |
| JP7395297B2 (en) | Method for producing graft copolymer | |
| EP1290036A1 (en) | Water soluble ampiphilic heteroarm star polymers and their use as emulsion stabilizers in emulsion polymerization | |
| CN112759707A (en) | Multi-component copolymer and preparation method and application thereof | |
| JP6506072B2 (en) | Process for producing N-vinyl lactam polymer and N-vinyl lactam polymer | |
| JP2010047693A (en) | N-vinyl cyclic lactam-based graft polymer and method for producing it | |
| JP2001278922A (en) | N-vinyl cyclic lactam graft polymer and its production method | |
| JP2009001785A (en) | Silane varnish comprising aminosilane and epoxy-functional polyacrylate | |
| WO2021106687A1 (en) | Thermoplastic copolymer and resin molded body | |
| WO2021045041A1 (en) | Core-shell-type polymer fine particles having phosphonic acid or phosphonic acid ester structure, particle dispersion, molded article, and method for producing said fine particles | |
| WO2015083744A1 (en) | Cyclic amide group-containing polymer, cyclic amide acrylate-containing composition, and method for producing cyclic amide acrylate | |
| JP2007177217A (en) | Method for producing acrylic copolymer | |
| JP2023140062A (en) | Copolymer and resin composition | |
| JP2007119770A (en) | Process for producing n-pyrrolidone graft polymer composition and n-pyrrolidone graft polymer composition | |
| JP2004137408A (en) | Composition composed of oh group-containing fluorine copolymer | |
| JP6195461B2 (en) | Maleic acid copolymer composition, production method thereof and use thereof | |
| JP6245948B2 (en) | Polyamide resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230411 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240124 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240130 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240328 |