JP7596811B2 - Composition, adhesive, and adhesive sheet - Google Patents
Composition, adhesive, and adhesive sheet Download PDFInfo
- Publication number
- JP7596811B2 JP7596811B2 JP2021008952A JP2021008952A JP7596811B2 JP 7596811 B2 JP7596811 B2 JP 7596811B2 JP 2021008952 A JP2021008952 A JP 2021008952A JP 2021008952 A JP2021008952 A JP 2021008952A JP 7596811 B2 JP7596811 B2 JP 7596811B2
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- JP
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- group
- meth
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- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 75
- 239000000853 adhesive Substances 0.000 title description 39
- 230000001070 adhesive effect Effects 0.000 title description 39
- 239000000178 monomer Substances 0.000 claims description 65
- 229920000642 polymer Polymers 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 44
- 230000001443 photoexcitation Effects 0.000 claims description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 21
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- 229920006243 acrylic copolymer Polymers 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 150000007942 carboxylates Chemical group 0.000 claims description 7
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 7
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 7
- 125000005375 organosiloxane group Chemical group 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 7
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- 125000001302 tertiary amino group Chemical group 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 116
- -1 2-(hydroxymethyl)acryloyl group Chemical group 0.000 description 57
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 16
- 239000012790 adhesive layer Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229940049920 malate Drugs 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 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 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 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
- 229920000359 diblock copolymer Polymers 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- RYWGNBFHIFRNEP-UHFFFAOYSA-N (4-benzoylphenyl) 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 RYWGNBFHIFRNEP-UHFFFAOYSA-N 0.000 description 1
- JJZONEUCDUQVGR-WXUKJITCSA-N (NE)-N-[(2E)-2-hydroxyimino-1,2-diphenylethylidene]hydroxylamine Chemical compound c1ccccc1\C(=N/O)\C(=N\O)\c1ccccc1 JJZONEUCDUQVGR-WXUKJITCSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- VTWGIDKXXZRLGH-CMDGGOBGSA-N (e)-4-octoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCCOC(=O)\C=C\C(O)=O VTWGIDKXXZRLGH-CMDGGOBGSA-N 0.000 description 1
- HVZKWAQLXHTHSG-PLNGDYQASA-N (z)-2-ethyl-3-methylbut-2-enedioic acid Chemical compound CC\C(C(O)=O)=C(/C)C(O)=O HVZKWAQLXHTHSG-PLNGDYQASA-N 0.000 description 1
- IQBLWPLYPNOTJC-FPLPWBNLSA-N (z)-4-(2-ethylhexoxy)-4-oxobut-2-enoic acid Chemical compound CCCCC(CC)COC(=O)\C=C/C(O)=O IQBLWPLYPNOTJC-FPLPWBNLSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- XXSDRURBACQHHW-UHFFFAOYSA-N 1-cyclohexyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)OC1CCCCC1 XXSDRURBACQHHW-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- LPXLPHGAFJLXDZ-ISLYRVAYSA-N 1-o-butyl 4-o-[tert-butyl(diphenyl)silyl] (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1[Si](C(C)(C)C)(OC(=O)/C=C/C(=O)OCCCC)C1=CC=CC=C1 LPXLPHGAFJLXDZ-ISLYRVAYSA-N 0.000 description 1
- GFLNKAGUAXZJCD-CMDGGOBGSA-N 1-o-methyl 4-o-tri(propan-2-yl)silyl (e)-but-2-enedioate Chemical compound COC(=O)\C=C\C(=O)O[Si](C(C)C)(C(C)C)C(C)C GFLNKAGUAXZJCD-CMDGGOBGSA-N 0.000 description 1
- YBEIZKBTJYSSFT-VAWYXSNFSA-N 1-o-pentyl 4-o-tri(propan-2-yl)silyl (e)-but-2-enedioate Chemical compound CCCCCOC(=O)\C=C\C(=O)O[Si](C(C)C)(C(C)C)C(C)C YBEIZKBTJYSSFT-VAWYXSNFSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- HSHGCMOSQZDCTG-UHFFFAOYSA-N 2,3,3-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C(C)(C)CC HSHGCMOSQZDCTG-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WLIVGKZSWFDOQX-UHFFFAOYSA-N 2-(3-prop-2-enoyloxypropyl)butanedioic acid Chemical compound C(C=C)(=O)OCCCC(C(=O)O)CC(=O)O WLIVGKZSWFDOQX-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TXHZNLCKXHJYNX-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C TXHZNLCKXHJYNX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RMMHOFFPGKSRDI-UHFFFAOYSA-N 3-bromoprop-1-en-2-ylbenzene Chemical compound BrCC(=C)C1=CC=CC=C1 RMMHOFFPGKSRDI-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
- PEJTXKFLHJIZEY-UHFFFAOYSA-N 3-octoxycarbonylbut-3-enoic acid Chemical compound CCCCCCCCOC(=O)C(=C)CC(O)=O PEJTXKFLHJIZEY-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 description 1
- RTTAGBVNSDJDTE-UHFFFAOYSA-N 4-ethoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCOC(=O)CC(=C)C(O)=O RTTAGBVNSDJDTE-UHFFFAOYSA-N 0.000 description 1
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- JVTOYSICJJAYOI-FOCLMDBBSA-N 4-o-[tert-butyl(diphenyl)silyl] 1-o-methyl (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1[Si](C(C)(C)C)(OC(=O)/C=C/C(=O)OC)C1=CC=CC=C1 JVTOYSICJJAYOI-FOCLMDBBSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VTWUAZLFPRUHDB-UHFFFAOYSA-N S(=O)(=O)(O)CC[Na].C(C(=C)C)(=O)O Chemical compound S(=O)(=O)(O)CC[Na].C(C(=C)C)(=O)O VTWUAZLFPRUHDB-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 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
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001241 acetals Chemical group 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- RTSODCRZYKSCLO-UHFFFAOYSA-N malic acid monomethyl ester Natural products COC(=O)C(O)CC(O)=O RTSODCRZYKSCLO-UHFFFAOYSA-N 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-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
- 238000002156 mixing Methods 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、粘着剤の粘着力、保持力等の性能の向上に有効な組成物、前記組成物を含む粘着剤、及び粘着シートに関する。 The present invention relates to a composition that is effective in improving the adhesive strength, holding power, and other performance of an adhesive, an adhesive containing the composition, and an adhesive sheet.
重合体や化合物などを含む組成物を用いた粘着剤は、目的に応じて、粘着テープ、感圧接着剤、ホットメルト接着剤など様々な用途に用いられている。このような組成物を含む粘着剤として、特許文献１には、特定の構造を重合体主鎖中に有し、重量平均分子量／数平均分子量の比が特定の範囲内にあるブロック共重合体と、特定のジブロック共重合体とを含み、ブロック共重合体とジブロック共重合体との重量比が特定範囲内にあり、溶融粘度が所定値以下である粘着剤が開示されている。 Adhesives using compositions containing polymers, compounds, etc. are used in a variety of applications, such as adhesive tapes, pressure-sensitive adhesives, and hot melt adhesives, depending on the purpose. As an adhesive containing such a composition, Patent Document 1 discloses an adhesive that has a specific structure in the polymer main chain, contains a block copolymer having a weight average molecular weight/number average molecular weight ratio within a specific range, and a specific diblock copolymer, has a weight ratio of the block copolymer to the diblock copolymer within a specific range, and has a melt viscosity below a predetermined value.
また、特許文献２には、接着性と高温下での保持力の向上を目的として、アクリル系ブロック共重合体を用いた粘着剤組成物の例が開示されている。 Patent Document 2 also discloses an example of a pressure-sensitive adhesive composition that uses an acrylic block copolymer to improve adhesion and retention at high temperatures.
しかし、特許文献１に記載の粘着剤は、保持力に優れているものの、粘着力の発現が十分ではなかった。また、特許文献２に記載の粘着剤は、粘着力と保持力の向上を目指しているものの、両方の性能を十分に向上させているとは言い難い状況であった。 However, although the adhesive described in Patent Document 1 has excellent holding power, it does not fully express its adhesive power. In addition, although the adhesive described in Patent Document 2 aims to improve both adhesive power and holding power, it is difficult to say that it has sufficiently improved both performances.
そこで、本発明は、粘着力と保持力の両方の性能に優れた粘着剤を提供することを目的とする。また、本発明は、粘着力と保持力の両方の性能に優れた粘着剤に用いることができる組成物を提供することを目的とする。 Therefore, the present invention aims to provide an adhesive that has excellent performance in both adhesive strength and holding power. In addition, the present invention aims to provide a composition that can be used for an adhesive that has excellent performance in both adhesive strength and holding power.
本発明は、以下の態様を有する。
［１］光励起によって新たな結合を形成できる単量体Ｍ由来の構成単位を含む重合体Ａと、式（１）で表される単量体ｍ由来の構成単位を２以上含み、末端にラジカル重合性基を有する化合物ａとを含む組成物。
The present invention has the following aspects.
[1] A composition comprising: a polymer A including a structural unit derived from a monomer M capable of forming a new bond upon photoexcitation; and a compound a including two or more structural units derived from a monomer m represented by formula (1) and having a radical polymerizable group at an end.
（式中、Ｘは水素原子又はメチル基を表し、Ｙは光励起によって活性種を生成する構造を有する基、炭素数２～１６の非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、非置換の若しくは置換基を有するアラルキル基、非置換の若しくは置換基を有するアルカリール基、非置換の若しくは置換基を有するオルガノシリル基、又は非置換の若しくは置換基を有する（ポリ）オルガノシロキサン基を表す。これらの基における置換基はそれぞれ、アルキル基、アリール基、ヘテロアリール基、非芳香族の複素環式基、アラルキル基、アルカリール基、カルボン酸基、カルボン酸エステル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホン酸基、及びハロゲン原子からなる群から選ばれる少なくとも１種である。）
［２］前記新たな結合が架橋構造である［１］に記載の組成物。
［３］前記単量体Ｍは光励起によって活性種を生成し、前記架橋構造を形成する［２］に記載の組成物。
［４］前記活性種がラジカルである［３］に記載の組成物。
［５］前記化合物ａのガラス転移温度が－１００℃以上１００℃以下である［１］～［４］のいずれかに記載の組成物。
［６］前記単量体Ｍが式（２）の構造を有する［１］～［５］のいずれかに記載の組成物。
(In the formula, X represents a hydrogen atom or a methyl group, Y represents a group having a structure that generates an active species upon photoexcitation, an unsubstituted or substituted alkyl group having 2 to 16 carbon atoms, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, an unsubstituted or substituted organosilyl group, or an unsubstituted or substituted (poly)organosiloxane group. The substituents in these groups are at least one selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, non-aromatic heterocyclic groups, aralkyl groups, alkaryl groups, carboxylic acid groups, carboxylate groups, epoxy groups, hydroxy groups, alkoxy groups, primary amino groups, secondary amino groups, tertiary amino groups, isocyanato groups, sulfonic acid groups, and halogen atoms.)
[2] The composition described in [1], wherein the new bond is a crosslinked structure.
[3] The composition according to [2], wherein the monomer M generates an active species upon photoexcitation and forms the crosslinked structure.
[4] The composition according to [3], wherein the active species is a radical.
[5] The composition according to any one of [1] to [4], wherein the glass transition temperature of the compound a is −100° C. or higher and 100° C. or lower.
[6] The composition according to any one of [1] to [5], wherein the monomer M has a structure represented by formula (2):
（式中、ＲＡ、ＲＢはそれぞれ独立にアルキル基、カルボキシ基、又はハロゲン原子を示し、ｎは０～５の整数、ｍは０～４の整数を示し、Ｘは、（メタ）アクリロイルオキシ基、又は（メタ）アクリロイルオキシアルキレンオキシ基を示す。）
［７］前記単量体Ｍ由来の構成単位の含有量が前記組成物の合計質量１００質量％に対して０．０１質量％以上５０質量％以下である［１］～［６］のいずれかに記載の組成物。
［８］前記重合体Ａのガラス転移温度が０℃以下である［１］～［７］のいずれかに記載の組成物。
［９］前記化合物ａと前記重合体Ａの比率が０．１：９９．９～３０：７０である［１］～［８］のいずれかに記載の組成物。
［１０］前記化合物ａが式（３）で表される構造を有する［１］～［９］のいずれかに記載の組成物。
(In the formula, R A and R B each independently represent an alkyl group, a carboxy group, or a halogen atom, n represents an integer of 0 to 5, m represents an integer of 0 to 4, and X represents a (meth)acryloyloxy group or a (meth)acryloyloxyalkyleneoxy group.)
[7] The composition according to any one of [1] to [6], wherein the content of the structural unit derived from the monomer M is 0.01% by mass or more and 50% by mass or less, relative to the total mass of the composition (100% by mass).
[8] The composition according to any one of [1] to [7], wherein the glass transition temperature of the polymer A is 0° C. or lower.
[9] The composition according to any one of [1] to [8], wherein a ratio of the compound a to the polymer A is 0.1:99.9 to 30:70.
[10] The composition according to any one of [1] to [9], wherein the compound a has a structure represented by formula (3).
（式中、Ｒは光励起によって活性種を生成する構造を有する基、又は炭素数１～３０の直鎖若しくは分岐アルキル基であり、Ｚは末端基であり、Ｒ２１は水素原子又はメチル基を示し、Ｒ２２は光励起によって活性種を生成する構造を有する基、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、非置換の若しくは置換基を有するアラルキル基、非置換の若しくは置換基を有するアルカリール基、非置換の若しくは置換基を有するオルガノシリル基、又は非置換の若しくは置換基を有する（ポリ）オルガノシロキサン基を示し、これらの基における置換基はそれぞれ、アルキル基、アリール基、ヘテロアリール基、非芳香族の複素環式基、アラルキル基、アルカリール基、カルボン酸基、カルボン酸エステル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホン酸基、及びハロゲン原子からなる群から選ばれる少なくとも１種であり、ｎは２以上の自然数を示す。Ｚにおける末端基は、水素原子又はラジカル重合開始剤に由来する基である。）
［１１］前記重合体Ａが（メタ）アクリル系共重合体を含む［１］～［１０］のいずれかに記載の組成物。
［１２］［１］～［１１］のいずれかに記載の組成物に紫外線を照射してなる粘着剤。
［１３］［１］～［１１］のいずれかに記載の組成物を含む粘着剤。
［１４］［１２］又は［１３］に記載の粘着剤を含む粘着シート。
(In the formula, R represents a group having a structure that generates an active species upon photoexcitation, or a linear or branched alkyl group having 1 to 30 carbon atoms, Z represents a terminal group, R represents a hydrogen atom or a methyl group, and R 22 represents a group having a structure that generates an active species by photoexcitation, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, an unsubstituted or substituted organosilyl group, or an unsubstituted or substituted (poly)organosiloxane group, each of which is at least one selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, a non-aromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group, a carboxylate group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, a tertiary amino group, an isocyanato group, a sulfonic acid group, and a halogen atom, and n represents a natural number of 2 or more. The terminal group in Z is a hydrogen atom or a group derived from a radical polymerization initiator.)
[11] The composition according to any one of [1] to [10], wherein the polymer A contains a (meth)acrylic copolymer.
[12] A pressure-sensitive adhesive obtained by irradiating the composition according to any one of [1] to [11] with ultraviolet light.
[13] A pressure-sensitive adhesive comprising the composition according to any one of [1] to [11].
[14] A pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive according to [12] or [13].
本発明によれば、粘着力と保持力の両方に優れた粘着剤を提供することができる。また、本発明によれば、粘着力と保持力の両方に優れた粘着剤に使用できる組成物を提供することができる。 According to the present invention, it is possible to provide an adhesive having both excellent adhesion and retention. In addition, according to the present invention, it is possible to provide a composition that can be used for an adhesive having both excellent adhesion and retention.
以下に本発明の実施の形態を詳細に説明するが、以下の説明は、本発明の実施の形態の一例であり、本発明はその要旨を超えない限り、以下の記載内容に限定されるものではない。
なお、本明細書において「～」という表現を用いる場合、その前後の数値又は物性値を含む表現として用いるものとする。また、本発明において、「（メタ）アクリル」という表現を用いた場合、「アクリル」と「メタクリル」の一方又は両方を意味するものとする。「（メタ）アクリレート」、「（メタ）アクリロイル」等についても同様である。
The following describes in detail an embodiment of the present invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the contents of the following description as long as it does not go beyond the gist of the present invention.
In this specification, when the expression "~" is used, it is used as an expression including the numerical value or physical property value before and after it. Furthermore, in the present invention, when the expression "(meth)acrylic" is used, it means one or both of "acrylic" and "methacrylic". The same applies to "(meth)acrylate", "(meth)acryloyl", etc.
本発明の一態様に係る組成物（以下、「本組成物」とも記す。）は、光励起によって新たな結合を形成できる単量体Ｍ由来の構成単位を２以上含む重合体Ａと、式（１）で表される単量体ｍ由来の構成単位を２以上含み、末端にラジカル重合性基を有する化合物ａとを有する。 A composition according to one embodiment of the present invention (hereinafter also referred to as "the composition") comprises a polymer A containing two or more structural units derived from a monomer M capable of forming a new bond upon photoexcitation, and a compound a containing two or more structural units derived from a monomer m represented by formula (1) and having a radical polymerizable group at its end.
（式中、Ｘは水素原子又はメチル基を表し、Ｙは光励起によって活性種を生成する構造を有する基、炭素数２～１６の非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、非置換の若しくは置換基を有するアラルキル基、非置換の若しくは置換基を有するアルカリール基、非置換の若しくは置換基を有するオルガノシリル基、又は非置換の若しくは置換基を有する（ポリ）オルガノシロキサン基を表す。これらの基における置換基はそれぞれ、アルキル基、アリール基、ヘテロアリール基、非芳香族の複素環式基、アラルキル基、アルカリール基、カルボン酸基、カルボン酸エステル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホン酸基、及びハロゲン原子からなる群から選ばれる少なくとも１種である。）
(In the formula, X represents a hydrogen atom or a methyl group, Y represents a group having a structure that generates an active species upon photoexcitation, an unsubstituted or substituted alkyl group having 2 to 16 carbon atoms, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, an unsubstituted or substituted organosilyl group, or an unsubstituted or substituted (poly)organosiloxane group. The substituents in these groups are at least one selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, non-aromatic heterocyclic groups, aralkyl groups, alkaryl groups, carboxylic acid groups, carboxylate groups, epoxy groups, hydroxy groups, alkoxy groups, primary amino groups, secondary amino groups, tertiary amino groups, isocyanato groups, sulfonic acid groups, and halogen atoms.)
本組成物は、化合物ａと重合体Ａ、又は複数の重合体Ａ同士が、光励起によって架橋構造を形成することにより、組成物の凝集力が向上する。架橋構造の形成は、光励起によって化合物ａの末端のラジカル重合性基に活性種（ラジカル）が生成することで化合物ａと重合体Ａとの間に新たな結合が形成される場合や、光励起によって単量体Ｍ由来の構成単位に活性種が生成することで化合物ａと重合体Ａとの間、又は複数の重合体Ａ同士の間で新たな結合が形成される場合などがある。また、光励起によって化合物ａの末端のラジカル重合性基に活性種が生成することで、他の化合物ａとの間で架橋構造を形成する場合もある。 In this composition, the compound a and the polymer A, or multiple polymers A together, form a crosslinked structure by photoexcitation, thereby improving the cohesive strength of the composition. The crosslinked structure may be formed by photoexcitation to generate active species (radicals) in the radical polymerizable group at the end of the compound a, thereby forming a new bond between the compound a and the polymer A, or by photoexcitation to generate active species in the structural unit derived from the monomer M, thereby forming a new bond between the compound a and the polymer A, or between multiple polymers A together. In addition, photoexcitation may generate active species in the radical polymerizable group at the end of the compound a, thereby forming a crosslinked structure with another compound a.
ラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。エチレン性不飽和結合を有する基としては、例えば、ＣＨ２＝Ｃ（ＣＯＯＲ）－ＣＨ２－、（メタ）アクリロイル基、２－（ヒドロキシメチル）アクリロイル基、ビニル基等が挙げられる。
ここで、Ｒは水素原子、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、又は非置換の若しくは置換基を有する複素環基を示す。
The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include CH 2 ═C(COOR)—CH 2 —, a (meth)acryloyl group, a 2-(hydroxymethyl)acryloyl group, and a vinyl group.
Here, R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heterocyclic group.
〔重合体Ａ〕
重合体Ａは、光励起によって新たな結合を形成できる単量体Ｍ由来の構成単位を含む重合体である。単量体Ｍは、紫外線などの光を照射されることで活性種（ラジカル）を生成し、他の分子との新たな結合を形成できる構造を有する。つまり、単量体Ｍ由来の構成単位は、光励起により他の分子と新たな結合を形成することで、分子間の架橋構造を形成することができる機能を有する。ここで架橋とは、高分子中の原子同士が化学結合することにより、分子内あるいは分子間に橋かけ構造を形成するプロセスであり、橋かけにより化学結合された構造を架橋構造という。
[Polymer A]
The polymer A is a polymer containing a structural unit derived from a monomer M capable of forming a new bond by photoexcitation. The monomer M has a structure capable of generating an active species (radical) by irradiation with light such as ultraviolet light and forming a new bond with another molecule. In other words, the structural unit derived from the monomer M has a function of forming a crosslinked structure between molecules by forming a new bond with another molecule by photoexcitation. Here, crosslinking is a process in which atoms in a polymer are chemically bonded to each other to form a bridged structure within or between molecules, and a structure chemically bonded by crosslinking is called a crosslinked structure.
単量体Ｍに含まれる活性種を生成する構造としては、例えば、ベンゾフェノン骨格、チオキサントン骨格、アントラキノン骨格等が挙げられる。光励起によって活性種を生成する構造を有する単量体Ｍ由来の構成単位を含む重合体を本組成物に用いることで、紫外線照射等による架橋構造を形成することが可能となり、優れた粘着力、保持力、耐基材汚染性を有する組成物となる。また、そのような組成物を含む粘着剤は、優れた粘着力、保持力、耐基材汚染性を示す。 Examples of structures that generate active species contained in monomer M include a benzophenone skeleton, a thioxanthone skeleton, and an anthraquinone skeleton. By using a polymer containing a structural unit derived from monomer M, which has a structure that generates active species upon photoexcitation, in the present composition, it becomes possible to form a crosslinked structure by irradiation with ultraviolet light, etc., resulting in a composition with excellent adhesion, holding power, and resistance to substrate contamination. Furthermore, an adhesive containing such a composition exhibits excellent adhesion, holding power, and resistance to substrate contamination.
さらに、重合体Ａは粘着特性の点から（メタ）アクリル系共重合体が好ましい。
（メタ）アクリル系共重合体は、構成単位の少なくとも一部が（メタ）アクリル系単量体由来の構成単位である共重合体を意味する。（メタ）アクリル系共重合体は、（メタ）アクリル系単量体以外の単量体（たとえばスチレン等）由来の構成単位をさらに含んでいてもよい。
（メタ）アクリル系単量体は、（メタ）アクリロイル基を有する単量体を意味し、後述の単量体ｍと同様の（メタ）アクリル系単量体が挙げられる。
さらに、（メタ）アクリル系共重合体のガラス転移温度（Ｔｇ）は、粘着性の点から０℃以下が好ましく、－５℃以下がより好ましい。
Furthermore, from the viewpoint of adhesive properties, polymer A is preferably a (meth)acrylic copolymer.
The (meth)acrylic copolymer refers to a copolymer in which at least a part of the constituent units is derived from a (meth)acrylic monomer. The (meth)acrylic copolymer may further contain a constituent unit derived from a monomer other than the (meth)acrylic monomer (e.g., styrene, etc.).
The (meth)acrylic monomer means a monomer having a (meth)acryloyl group, and examples thereof include the same (meth)acrylic monomers as the monomer m described below.
Furthermore, the glass transition temperature (Tg) of the (meth)acrylic copolymer is preferably 0° C. or lower, more preferably −5° C. or lower, from the viewpoint of adhesion.
また、粘着力が向上することから、（メタ）アクリル系共重合体は、カルボキシ基含有（メタ）アクリル系単量体由来の構成単位を含むことが好ましい。
なお、（メタ）アクリル系共重合体の総質量に対して、カルボキシ基含有（メタ）アクリル系単量体由来の構成単位の含有量は０．１～２０質量％であることが好ましく、０．３～１５質量％であることがより好ましく、０．５～１０質量％であることがさらに好ましい。
カルボキシ基含有（メタ）アクリル系単量体としては、（メタ）アクリル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシプロピルフタル酸、２－（メタ）アクリロイルオキシエチルマレイン酸、２－（メタ）アクリロイルオキシプロピルマレイン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシプロピルコハク酸、等が挙げられる。
In addition, the (meth)acrylic copolymer preferably contains a structural unit derived from a carboxy group-containing (meth)acrylic monomer, since this improves adhesive strength.
The content of the structural unit derived from the carboxy group-containing (meth)acrylic monomer relative to the total mass of the (meth)acrylic copolymer is preferably 0.1 to 20 mass%, more preferably 0.3 to 15 mass%, and even more preferably 0.5 to 10 mass%.
Examples of the carboxy group-containing (meth)acrylic monomer include (meth)acrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxypropyl succinic acid.
重合体Ａの、ゲル浸透クロマトグラフィー（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）は５０００～２００００００が好ましく、１００００～１００００００がより好ましく、３００００～３５００００がさらに好ましい。前記Ｍｗが前記下限値以上であると、粘着層の耐久性に優れ、前記上限値以下であると、取り扱い性（他の成分との相溶性、塗工性、ホットメルト加工性等）に優れる。 The weight average molecular weight (Mw) of polymer A measured by gel permeation chromatography (GPC) is preferably 5,000 to 2,000,000, more preferably 10,000 to 1,000,000, and even more preferably 30,000 to 350,000. When the Mw is equal to or greater than the lower limit, the adhesive layer has excellent durability, and when the Mw is equal to or less than the upper limit, the adhesive layer has excellent handleability (compatibility with other components, coatability, hot melt processability, etc.).
重合体Ａのガラス転移温度は溶融粘度の点から０℃以下が好ましく、－１０℃以下がより好ましい。
なお、ガラス転移温度（Ｔｇ）は、下記式より算出される絶対温度（Ｋ）を摂氏（℃）に換算した値である。
１／Ｔｇ＝Σ（ｗｉ／Ｔｇｉ）
上記式において、ｗｉは、重合体を構成する単量体ｉの質量分率を示し、Ｔｇｉは、重合体を構成する単量体ｉのホモポリマーのガラス転移温度を示す。
上記式中のＴｇおよびＴｇｉは、絶対温度（Ｋ）で表した値である。また、単量体ｉのホモポリマーのガラス転移温度は、ポリマーハンドブック〔Ｐｏｌｙｍｅｒ ＨａｎｄＢｏｏｋ，Ｊ．Ｂｒａｎｄｒｕｐ，Ｉｎｔｅｒｓｃｉｅｎｃｅ，１９８９〕に記載されている値である。
The glass transition temperature of the polymer A is preferably 0° C. or lower, more preferably −10° C. or lower, from the viewpoint of melt viscosity.
The glass transition temperature (Tg) is a value calculated by the following formula, converted from absolute temperature (K) to Celsius (° C.).
1/Tg=Σ(wi/Tgi)
In the above formula, wi represents the mass fraction of monomer i constituting the polymer, and Tgi represents the glass transition temperature of a homopolymer of monomer i constituting the polymer.
In the above formula, Tg and Tgi are values expressed in absolute temperature (K). The glass transition temperature of the homopolymer of monomer i is the value described in Polymer Handbook [Polymer Handbook, J. Brandrup, Interscience, 1989].
なお、重合体Ａは、公知の重合開始剤を用いて、公知の方法で製造することができる。重合方法としては、例えば、溶液重合法、懸濁重合法、塊状重合法、乳化重合法等の公知の重合方法が適用でき、溶液重合法が好ましい。 Polymer A can be produced by a known method using a known polymerization initiator. For example, known polymerization methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization can be used, with solution polymerization being preferred.
〔単量体Ｍ〕
単量体Ｍは、光励起によって活性種を生成する構造を有する単量体である。
光励起によって活性種を生成する構造を有する単量体としては、例えば、ベンゾフェノン骨格、チオキサントン骨格、アントラキノン骨格等を有する単量体が挙げられ、特に下記式（２）で表されるベンゾフェノン誘導体が反応性の点から好ましい。
[Monomer M]
The monomer M is a monomer having a structure that generates an active species upon photoexcitation.
Examples of monomers having a structure that generates active species by photoexcitation include monomers having a benzophenone skeleton, a thioxanthone skeleton, an anthraquinone skeleton, etc., and in particular, a benzophenone derivative represented by the following formula (2) is preferred in terms of reactivity.
（式中、ＲＡ、ＲＢはそれぞれ独立にアルキル基、カルボキシ基、又はハロゲン原子を示し、ｎは０～５の整数、ｍは０～４の整数を示し、Ｘは、（メタ）アクリロイルオキシ基、又は（メタ）アクリロイルオキシアルキレンオキシ基を示す。）
(In the formula, R A and R B each independently represent an alkyl group, a carboxy group, or a halogen atom, n represents an integer of 0 to 5, m represents an integer of 0 to 4, and X represents a (meth)acryloyloxy group or a (meth)acryloyloxyalkyleneoxy group.)
本組成物中の単量体Ｍ由来の構成単位の含有量は、性能のバランスを取る点から、組成物の合計質量１００質量％に対して０．０１質量％以上５０質量％以下が好ましく、０．０３質量％以上４０質量％以下がより好ましく、０．０５質量％以上３０質量％以下がさらに好ましく、０．１質量％以上１０質量％以下が最も好ましい。単量体Ｍ由来の構成単位の含有量が上記下限値より高いことで、組成物の保持力が向上する。また、単量体Ｍ由来の構成単位の含有量が上記上限値より低いことで、他の成分との相溶性が向上する。 In order to balance the performance, the content of the constituent units derived from monomer M in the present composition is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.03% by mass or more and 40% by mass or less, even more preferably 0.05% by mass or more and 30% by mass or less, and most preferably 0.1% by mass or more and 10% by mass or less, relative to the total mass of the composition (100% by mass). When the content of the constituent units derived from monomer M is higher than the lower limit, the holding power of the composition is improved. Also, when the content of the constituent units derived from monomer M is lower than the upper limit, the compatibility with other components is improved.
〔単量体ｍ〕
単量体ｍは式（１）で表される構造を有する単量体である。
[Monomer m]
The monomer m is a monomer having a structure represented by formula (1).
（式中、Ｘは水素原子又はメチル基を表し、Ｙは光励起によって活性種を生成する構造を有する基、炭素数２～１６の非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、非置換の若しくは置換基を有するアラルキル基、非置換の若しくは置換基を有するアルカリール基、非置換の若しくは置換基を有するオルガノシリル基、又は非置換の若しくは置換基を有する（ポリ）オルガノシロキサン基を表す。これらの基における置換基はそれぞれ、アルキル基、アリール基、ヘテロアリール基、非芳香族の複素環式基、アラルキル基、アルカリール基、カルボン酸基、カルボン酸エステル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホン酸基、及びハロゲン原子からなる群から選ばれる少なくとも１種である。）
(In the formula, X represents a hydrogen atom or a methyl group, Y represents a group having a structure that generates an active species upon photoexcitation, an unsubstituted or substituted alkyl group having 2 to 16 carbon atoms, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, an unsubstituted or substituted organosilyl group, or an unsubstituted or substituted (poly)organosiloxane group. The substituents in these groups are at least one selected from the group consisting of alkyl groups, aryl groups, heteroaryl groups, non-aromatic heterocyclic groups, aralkyl groups, alkaryl groups, carboxylic acid groups, carboxylate groups, epoxy groups, hydroxy groups, alkoxy groups, primary amino groups, secondary amino groups, tertiary amino groups, isocyanato groups, sulfonic acid groups, and halogen atoms.)
単量体ｍとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸イソステアリル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸フェニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸３，５，５－トリメチルシクロヘキシル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸ジシクロペンテニル、（メタ）アクリル酸ジシクロペンテニルオキシエチル、テルペンアクリレートやその誘導体、水添ロジンアクリレートやその誘導体、（メタ）アクリル酸ドコシル等の炭化水素基含有（メタ）アクリル酸エステル；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル、グリセロール（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル；（メタ）アクリル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシプロピルフタル酸、２－（メタ）アクリロイルオキシエチルマレイン酸、２－（メタ）アクリロイルオキシプロピルマレイン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシプロピルコハク酸、クロトン酸、フマル酸、マレイン酸、イタコン酸、シトラコン酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノオクチル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノブチル、イタコン酸モノオクチル、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノブチル、フマル酸モノオクチル、シトラコン酸モノエチル等のカルボキシル基含有ビニル系単量体；無水マレイン酸、無水イタコン酸等の酸無水物基含有ビニル系単量体；ジメチルマレート、ジブチルマレート、ジメチルフマレート、ジブチルフマレート、ジブチルイタコネート、ジパーフルオロシクロヘキシルフマレート等の不飽和ジカルボン酸ジエステル単量体；（メタ）アクリル酸グリシジル、α－エチルアクリル酸グリシジル、（メタ）アクリル酸３，４－エポキシブチル等のエポキシ基含有ビニル系単量体；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有（メタ）アクリル酸エステル系のビニル系単量体；（メタ）アクリルアミド、Ｎ－ｔ－ブチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－イソプロピルアクリルアミド、ヒドロキシエチルアクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、ダイアセトンアクリルアミド、マレイン酸アミド、マレイミド等のアミド基を含有するビニル系単量体；スチレン、α－メチルスチレン、ビニルトルエン、（メタ）アクリロニトリル、酢酸ビニル、プロピオン酸ビニル等のビニル系単量体；ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、アリル（メタ）アクリレート、トリアリルシアヌレート、マレイン酸ジアリル、ポリプロピレングリコールジアリルエーテル、Ｎ，Ｎ’－メチレンビス（メタ）アクリルアミド等の多官能性のビニル系単量体；アクリロイルモルホリン、（メタ）アクリル酸ポリエチレングリコール、（メタ）アクリル酸ポリプロピレングリコール、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸ｎ－ブトキシエチル、（メタ）アクリル酸イソブトキシエチル、（メタ）アクリル酸ｔ－ブトキシエチル、（メタ）アクリル酸エトキシエトキシエチル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸ノニルフェノキシエチル、（メタ）アクリル酸３－メトキシブチル、（メタ）アクリル酸アセトキシエチル、「プラクセル（登録商標。以下同様。）ＦＭ」（ダイセル化学（株）製カプロラクトン付加モノマー、商品名）、「ブレンマー（登録商標。以下同様。）ＰＭＥ－１００」（日油（株）製メトキシポリエチレングリコールメタクリレート（エチレングリコールの連鎖が２であるもの）、商品名）、「ブレンマーＰＭＥ－２００」（日油（株）製メトキシポリエチレングリコールメタクリレート（エチレングリコールの連鎖が４であるもの）、商品名）、「ブレンマーＰＭＥ－４００」（日油（株）製メトキシポリエチレングリコールメタクリレート（エチレングリコールの連鎖が９であるもの）、商品名）、「ブレンマー５０ＰＯＥＰ－８００Ｂ」（日油（株）製オクトキシポリエチレングリコール－ポリプロピレングリコール－メタクリレート（エチレングリコールの連鎖が８であり、プロピレングリコールの連鎖が６であるもの）、商品名）及び「ブレンマー２０ＡＮＥＰ－６００」（日油（株）製ノニルフェノキシ（エチレングリコール－ポリプロピレングリコール）モノアクリレート、商品名）、「ブレンマーＡＭＥ－１００」（日油（株）製、商品名）、「ブレンマーＡＭＥ－２００」（日油（株）製、商品名）及び「ブレンマー５０ＡＯＥＰ－８００Ｂ」（日油（株）製、商品名）；トリメチルシリル（メタ）アクリレート、トリエチルシリル（メタ）アクリレート、トリ－ｎ－プロピルシリル（メタ）アクリレート、トリ－ｎ－ブチルシリル（メタ）アクリレート、トリ－ｎ－アミルシリル（メタ）アクリレート、トリ－ｎ－ヘキシルシリル（メタ）アクリレート、トリ－ｎ－オクチルシリル（メタ）アクリレート、トリ－ｎ－ドデシルシリル（メタ）アクリレート、トリフェニルシリル（メタ）アクリレート、トリ－ｐ－メチルフェニルシリル（メタ）アクリレート、トリベンジルシリル（メタ）アクリレート、トリイソプロピルシリル（メタ）アクリレート、トリイソブチルシリル（メタ）アクリレート、トリ（Ｓ－ブチル）シリル（メタ）アクリレート、トリ（２－メチルイソプロピル）シリル（メタ）アクリレート、トリ（ｔ－ブチル）シリル（メタ）アクリレート、エチルジメチルシリル（メタ）アクリレート、ｎ－ブチルジメチルシリル（メタ）アクリレート、ジイソプロピル（ｎ－ブチル）シリル（メタ）アクリレート、ｎ－オクチルジ（ｎ－ブチル）シリル（メタ）アクリレート、ジイソプロピルステアリルシリル（メタ）アクリレート、ジシクロヘキシルフェニルシリル（メタ）アクリレート、ｔ－ブチルジフェニルシリル（メタ）アクリレート、ラウリルジフェニルシリル（メタ）アクリレート、トリイソプロピルシリルメチルマレート、トリイソプロピルシリルアミルマレート、トリ（ｎ－ブチル）シリル（ｎ－ブチル）マレート、（ｔ－ブチルジフェニルシリル）（メチル）マレート、（ｔ－ブチルジフェニルシリル）（ｎ－ブチル）マレート、（トリイソプロピルシリル）（メチル）フマレート、（トリイソプロピルシリル）（アミル）フマレート、（トリ（ｎ－ブチルシリル））（ｎ－ブチル）フマレート、（ｔ－ブチルジフェニルシリル）（メチル）フマレート、（ｔ－ブチルジフェニルシリル）（ｎ－ブチル）フマレート、サイラプレーンＦＭ－０７１１（ＪＮＣ（株）製、商品名）、サイラプレーン（登録商標。以下同様。）ＦＭ－０７２１（ＪＮＣ（株）製、商品名）、サイラプレーンＦＭ－０７２５（ＪＮＣ（株）製、商品名）、サイラプレーンＴＭ－０７０１（ＪＮＣ（株）製、商品名）、サイラプレーンＴＭ－０７０１Ｔ（ＪＮＣ（株）製、商品名）、Ｘ－２２－１７４ＡＳＸ（信越化学工業（株）製、商品名）、Ｘ－２２－１７４ＢＸ（信越化学工業（株）製、商品名）、ＫＦ－２０１２（信越化学工業（株）製、商品名）、Ｘ－２２－２４２６（信越化学工業（株）製、商品名）、Ｘ－２２－２４０４（信越化学工業（株）製、商品名）等の、シランカップリング剤含有モノマー以外のオルガノシリル基含有単量体；塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、クロロトリフルオロエチレン等のハロゲン化オレフィン；２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３，３－ペンタフルオロフェニル（メタ）アクリレート、２－（パーフルオロブチル）エチル（メタ）アクリレート、３－（パーフルオロブチル）－２－ヒドロキシプロピル（メタ）アクリレート、２－（パーフルオロヘキシル）エチル（メタ）アクリレート、３－パーフルオロヘキシル－２－ヒドロキシプロピル（メタ）アクリレート、３－（パーフルオロ－３－メチルブチル）－２－ヒドロキシプロピル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロオクチル（メタ）アクリレート、１Ｈ－１－（トリフルオロメチル）トリフルオロエチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ－ヘキサフルオロブチル（メタ）アクリレート、１，２，２，２－テトラフルオロ－１－（トリフルオロメチル）エチル（メタ）アクリレート等のフッ素含有単量体（ただしハロゲン化オレフィンを除く）；１－ブトキシエチル（メタ）アクリレート、１－（２－エチルへキシルオキシ）エチル（メタ）アクリレート、１－（シクロへキシルオキシ）エチルメタクリレート）、２－テトラヒドロピラニル（メタ）アクリレート等のアセタール構造を持つ単量体；が挙げられる。 Examples of monomer m include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, hexadecyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, and phenyl (meth)acrylate. (meth)acrylic acid esters containing a hydrocarbon group such as benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, terpene acrylate and derivatives thereof, hydrogenated rosin acrylate and derivatives thereof, and docosyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid esters containing a hydrocarbon group such as benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, terpene acrylate and derivatives thereof, hydrogenated rosin acrylate and derivatives thereof, and docosyl (meth)acrylate; Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate; (meth)acrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl ... meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid, and other carboxyl group-containing vinyl monomers; acid anhydride group-containing vinyl monomers, such as maleic anhydride and itaconic anhydride; dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, and other unsaturated dicarboxylic acid diester monomers such as diperfluorocyclohexyl fumarate; epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, α-ethyl glycidyl acrylate, 3,4-epoxybutyl (meth)acrylate; amino group-containing (meth)acrylic acid ester-based vinyl monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; (meth)acrylamide, N-t-butyl (meth)acrylamide, N-methylol (meth)acrylamide, N-isopropylacrylamide, hydroxyethylacrylamide, N-methoxymethyl (meth)acrylamide vinyl monomers containing an amide group, such as diacetone acrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide; vinyl monomers containing an amide group, such as styrene, α-methylstyrene, vinyl toluene, (meth)acrylonitrile, vinyl acetate, and vinyl propionate; divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra ... Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, N,N'-methylene bis(meth)acrylate Polyfunctional vinyl monomers such as (meth)acrylamide; acryloylmorpholine, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, isobutoxyethyl (meth)acrylate, t-butoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, acetoxyethyl (meth)acrylate, and "Placcel (registered trademark, the same applies below). )FM" (caprolactone addition monomer, product name, manufactured by Daicel Chemical Industries, Ltd.), "BLEMMER (registered trademark, the same applies below) PME-100" (methoxypolyethylene glycol methacrylate (having 2 ethylene glycol chains), product name, manufactured by NOF Corporation), "BLEMMER PME-200" (methoxypolyethylene glycol methacrylate (having 4 ethylene glycol chains), product name, manufactured by NOF Corporation), "BLEMMER PME-400" (methoxypolyethylene glycol methacrylate (having 9 ethylene glycol chains), product name, manufactured by NOF Corporation), "BLEMMER 50POEP-800B" (octoxypolyethylene glycol-polypropylene glycol-methacrylate (having 8 ethylene glycol chains, propylene glycol) manufactured by NOF Corporation), "BLEMMER 20ANEP-600" (nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate, product name, manufactured by NOF Corp.), "BLEMMER AME-100" (product name, manufactured by NOF Corp.), "BLEMMER AME-200" (product name, manufactured by NOF Corp.), and "BLEMMER 50AOEP-800B" (product name, manufactured by NOF Corp.); trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, tri-n-amylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-n-dodecyl Silyl (meth)acrylate, triphenylsilyl (meth)acrylate, tri-p-methylphenylsilyl (meth)acrylate, tribenzylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri(s-butyl)silyl (meth)acrylate, tri(2-methylisopropyl)silyl (meth)acrylate, tri(t-butyl)silyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, n-butyldimethylsilyl (meth)acrylate, diisopropyl(n-butyl)silyl (meth)acrylate, n-octyldi(n-butyl)silyl (meth)acrylate, diisopropylstearylsilyl (meth)acrylate, dicyclohexylphenylsilyl (meth)acrylate, (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, lauryldiphenylsilyl (meth)acrylate, triisopropylsilyl methyl malate, triisopropylsilyl amyl malate, tri(n-butyl)silyl (n-butyl) malate, (t-butyldiphenylsilyl) (methyl) malate, (t-butyldiphenylsilyl) (n-butyl) malate, (triisopropylsilyl) (methyl) fumarate, (triisopropylsilyl) (amyl) fumarate, (tri(n-butylsilyl)) (n-butyl) fumarate, (t-butyldiphenylsilyl) (methyl) fumarate, (t-butyldiphenylsilyl) (n-butyl) fumarate, Silaplane FM-0711 (manufactured by JNC Corporation, trade name), Silaplane (registered trademark; the same applies below). ) FM-0721 (manufactured by JNC Corporation, trade name), Silaplane FM-0725 (manufactured by JNC Corporation, trade name), Silaplane TM-0701 (manufactured by JNC Corporation, trade name), Silaplane TM-0701T (manufactured by JNC Corporation, trade name), X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-174BX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), KF-2012 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-2404 (Shin-Etsu Chemical Co., Ltd. organosilyl group-containing monomers other than silane coupling agent-containing monomers, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene; halogenated olefins, such as 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluorophenyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 3-(perfluorobutyl)-2-hydroxypropyl ... fluorohexyl)ethyl (meth)acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate fluorine-containing monomers (excluding halogenated olefins) such as 1H,1H,3H-hexafluorobutyl (meth)acrylate, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl (meth)acrylate; monomers with an acetal structure such as 1-butoxyethyl (meth)acrylate, 1-(2-ethylhexyloxy)ethyl (meth)acrylate, 1-(cyclohexyloxy)ethyl methacrylate, and 2-tetrahydropyranyl (meth)acrylate.
〔化合物ａ〕
化合物ａは、末端にラジカル重合性基を有することにより、重合体Ａや他の化合物ａと架橋構造を形成することができる化合物である。
[Compound a]
The compound a has a radically polymerizable group at its terminal, and is therefore capable of forming a crosslinked structure with the polymer A or another compound a.
化合物ａとしては、下記式（３）で表される構造を有する化合物が好ましい。 Compound a is preferably a compound having a structure represented by the following formula (3):
（式中、Ｒは光励起によって活性種を生成する構造を有する基、又は炭素数１～３０の直鎖若しくは分岐アルキル基であり、Ｚは末端基であり、Ｒ２１は水素原子又はメチル基を示し、Ｒ２２は光励起によって活性種を生成する構造を有する基、非置換の若しくは置換基を有するアルキル基、非置換の若しくは置換基を有する脂環式基、非置換の若しくは置換基を有するアリール基、非置換の若しくは置換基を有するヘテロアリール基、非置換の若しくは置換基を有するアラルキル基、非置換の若しくは置換基を有するアルカリール基、非置換の若しくは置換基を有するオルガノシリル基、又は非置換の若しくは置換基を有する（ポリ）オルガノシロキサン基を示し、これらの基における置換基はそれぞれ、アルキル基、アリール基、ヘテロアリール基、非芳香族の複素環式基、アラルキル基、アルカリール基、カルボン酸基、カルボン酸エステル基、エポキシ基、ヒドロキシ基、アルコキシ基、１級アミノ基、２級アミノ基、３級アミノ基、イソシアナト基、スルホン酸基、及びハロゲン原子からなる群から選ばれる少なくとも１種であり、ｎは２以上の自然数を示す。Ｚは、水素原子、又はラジカル重合開始剤に由来する基である。）なお、末端基Ｚは、公知のラジカル重合で得られるポリマーの末端基と同様のものを用いることができる。また、光励起によって活性種を生成する構造としては、ベンゾフェノン骨格、チオキサントン骨格、アントラキノン骨格等が挙げられる。
(In the formula, R represents a group having a structure that generates an active species upon photoexcitation, or a linear or branched alkyl group having 1 to 30 carbon atoms, Z represents a terminal group, R represents a hydrogen atom or a methyl group, and R 22 indicates a group having a structure that generates active species by photoexcitation, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, an unsubstituted or substituted organosilyl group, or an unsubstituted or substituted (poly)organosiloxane group, each of which is at least one selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, a non-aromatic heterocyclic group, an aralkyl group, an alkaryl group, a carboxylic acid group, a carboxylate group, an epoxy group, a hydroxy group, an alkoxy group, a primary amino group, a secondary amino group, a tertiary amino group, an isocyanato group, a sulfonic acid group, and a halogen atom, and n indicates a natural number of 2 or more. Z is a hydrogen atom or a group derived from a radical polymerization initiator. ) The terminal group Z can be the same as the terminal group of a polymer obtained by known radical polymerization. Examples of structures that generate active species upon photoexcitation include a benzophenone skeleton, a thioxanthone skeleton, and an anthraquinone skeleton.
化合物ａは、ラジカル重合性基を有する単量体ｍを含む単量体の混合物を公知の方法で重合すればよく、例えば、コバルト連鎖移動剤を用いる方法（米国特許４６８０３５２号）、α‐ブロモメチルスチレン等のα置換不飽和化合物を連鎖移動剤として用いる方法（国際公開８８／０４３０４号）、重合性基を化学的に結合させる方法（特開昭６０－１３３００７号公報）及び熱分解による方法（特開平１１－２４０８５４号公報）等が挙げられる。これらの中で、製造工程数が少なく、連鎖移動定数の高い触媒を使用する点でコバルト連鎖移動剤を用いる方法が好ましい。 Compound a can be prepared by polymerizing a mixture of monomers including monomer m having a radical polymerizable group by a known method, such as a method using a cobalt chain transfer agent (U.S. Patent No. 4,680,352), a method using an α-substituted unsaturated compound such as α-bromomethylstyrene as a chain transfer agent (WO 88/04304), a method of chemically bonding a polymerizable group (JP Patent Publication No. 60-133007), and a method using thermal decomposition (JP Patent Publication No. 11-240854). Among these, the method using a cobalt chain transfer agent is preferred in that it requires fewer manufacturing steps and uses a catalyst with a high chain transfer constant.
ゲル浸透クロマトグラフィー（ＧＰＣ）で測定した化合物ａの重量平均分子量（Ｍｗ）は、１０００以上１０００００以下が好ましく、１５００以上７００００以下がより好ましく、２０００以上５００００以下がさらに好ましく、３０００以上２００００以下が最も好ましい。化合物ａの重量平均分子量は、化合物ａを含む組成物として使用した場合の保持力向上の点から高いほうが好ましく、製造安定性の点から低いほうが好ましい。 The weight average molecular weight (Mw) of compound a measured by gel permeation chromatography (GPC) is preferably 1000 to 100,000, more preferably 1500 to 70,000, even more preferably 2000 to 50,000, and most preferably 3000 to 20,000. The weight average molecular weight of compound a is preferably higher from the viewpoint of improving retention when used as a composition containing compound a, and is preferably lower from the viewpoint of manufacturing stability.
〔粘着剤〕
粘着剤は、化合物ａと重合体Ａとを含む組成物を含むものである。組成物において、化合物ａと重合体Ａの比率は、性能のバランスを取る点から０．１：９９．９～３０：７０の範囲が好ましく、０．５：９９．５～２０：８０がより好ましく、１：９９～１５：８５がより好ましい。化合物ａの含有比率が上記下限値より高いことで、組成物の保持力が向上する。また、化合物ａの含有比率が上記上限値より低いことで、組成物に含まれる他の成分との相溶性が向上する。
[Adhesive]
The pressure-sensitive adhesive comprises a composition containing compound a and polymer A. In the composition, the ratio of compound a to polymer A is preferably in the range of 0.1:99.9 to 30:70, more preferably 0.5:99.5 to 20:80, and more preferably 1:99 to 15:85, in terms of balancing the performance. When the content ratio of compound a is higher than the lower limit, the holding power of the composition is improved. When the content ratio of compound a is lower than the upper limit, the compatibility with other components contained in the composition is improved.
粘着剤は、さらにその他の成分を含有してもよい。その他の成分としては、例えば、溶剤、充填剤、架橋剤、粘着付与樹脂、酸化防止剤、光安定化剤、金属不活性化剤、老化防止剤、吸湿剤、防錆剤、加水分解防止剤、反応触媒を含有することができる。
酸化防止剤としては、例えば、フェノール系、リン系、ヒドロキシルアミン系、イオウ系の酸化防止剤が挙げられる。
The pressure-sensitive adhesive may further contain other components, such as a solvent, a filler, a crosslinking agent, a tackifier resin, an antioxidant, a light stabilizer, a metal deactivator, an anti-aging agent, a moisture absorbent, a rust inhibitor, a hydrolysis inhibitor, and a reaction catalyst.
Examples of the antioxidant include phenol-based, phosphorus-based, hydroxylamine-based, and sulfur-based antioxidants.
粘着剤は、溶剤を含む液状の粘着剤でもよく、溶剤を含まないホットメルト型の粘着剤でもよい。 The adhesive may be a liquid adhesive containing a solvent, or a hot melt adhesive containing no solvent.
粘着剤は、活性エネルギー線で必要に応じて硬化させた粘着剤として用いることができる。活性エネルギー線としては、汎用性の点から、紫外線が好ましい。紫外線の光源としては、例えばキセノンランプ、高圧水銀灯、メタルハライドランプ等が挙げられる。 The adhesive can be used as an adhesive cured with active energy rays as necessary. From the viewpoint of versatility, ultraviolet rays are preferred as active energy rays. Examples of sources of ultraviolet rays include xenon lamps, high-pressure mercury lamps, and metal halide lamps.
〔粘着シート〕
粘着シートは、粘着剤を用いて形成した粘着層を有する。粘着シートは、粘着剤をシート状に成形した粘着層のみからなるシートでもよく、粘着剤をシート状に成形した粘着層の片面または両面に剥離性基材を積層したものでもよい。
[Adhesive sheet]
The pressure-sensitive adhesive sheet has a pressure-sensitive adhesive layer formed using a pressure-sensitive adhesive. The pressure-sensitive adhesive sheet may be a sheet consisting of only a pressure-sensitive adhesive layer formed into a sheet shape, or may be a sheet formed of a pressure-sensitive adhesive layer formed into a sheet shape with a release substrate laminated on one or both sides thereof.
粘着層は、粘着剤からなるものであってもよく、粘着剤の硬化物からなるものであってもよい。粘着シートの取り扱い性の点では、粘着剤を紫外線により硬化させた粘着剤からなることが好ましい。
粘着層の厚さは、用途に応じて適宜設定できる。例えば１０～５００μｍが好ましく、２０～１００μｍがより好ましい。
粘着剤を用いて貼り合せる部材は特に限定されないが、例えば、車両用、建築用等の窓貼りフィルムの貼り合せ、ラベル表示におけるラベルの貼り合せ、液晶パネル等の各種パネルの貼り合せ、ガラス等の透明板材の貼り合せ等に用いることができる。
The adhesive layer may be made of an adhesive or a cured product of the adhesive. From the viewpoint of handling of the adhesive sheet, it is preferable that the adhesive layer is made of an adhesive cured by ultraviolet light.
The thickness of the adhesive layer can be appropriately set depending on the application, and is preferably, for example, 10 to 500 μm, and more preferably 20 to 100 μm.
The materials to be bonded using the adhesive are not particularly limited, but can be used, for example, for bonding window films for vehicles, buildings, etc., bonding labels for labeling, bonding various panels such as liquid crystal panels, bonding transparent plate materials such as glass, etc.
以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。以下において、「部」は「質量部」である。評価は以下の方法で行った。 The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following, "parts" means "parts by mass." Evaluations were performed using the following methods.
＜化合物ａの分子量＞
ゲル浸透クロマトグラフィー（ＧＰＣ）装置（東ソー株式会社製、ＨＬＣ－８３２０）を用いて測定した。化合物の０．２質量％テトラヒドロフラン（ＴＨＦ）溶液を調製し、東ソー社製カラム（ＴＳＫｇｅｌ ＳｕｐｅｒＨＺＭ－Ｍ×ＨＺＭ－Ｍ×ＨＺ２０００、ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨＺ－Ｌ）が装着された上記装置に上記溶液１０ｍＬを注入し、流量：０．３５ｍＬ／分、溶離液：ＴＨＦ（安定剤：ブチルヒドロキシトルエン（ＢＨＴ））、カラム温度：４０℃の条件で測定した。数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）は、ポリスチレン換算にて算出した。
<Molecular weight of compound a>
Measurement was performed using a gel permeation chromatography (GPC) device (Tosoh Corporation, HLC-8320). A 0.2% by mass tetrahydrofuran (THF) solution of the compound was prepared, and 10 mL of the solution was injected into the device equipped with a Tosoh Corporation column (TSKgel SuperHZM-M×HZM-M×HZ2000, TSKguardcolumn SuperHZ-L), and the measurement was performed under the following conditions: flow rate: 0.35 mL/min, eluent: THF (stabilizer: butylhydroxytoluene (BHT)), column temperature: 40° C. The number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated in terms of polystyrene.
＜重合体Ａの分子量＞
ＧＰＣ装置（東ソー株式会社製、ＨＬＣ－８１２０）を用いて測定した。重合体の０．３質量％ＴＨＦ溶液を調製し、東ソー社製カラム（ＴＳＫｇｅｌ ＳｕｐｅｒＨＭ－Ｈ×４、ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＳｕｐｅｒＨ－Ｈ）が装着された上記装置に上記溶液２０ｍＬを注入し、流量：０．６ｍＬ／分、溶離液：ＴＨＦ（安定剤ＢＨＴ）、カラム温度：４０℃の条件で測定した。数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）は、ポリスチレン換算にて算出した。
<Molecular Weight of Polymer A>
Measurement was performed using a GPC device (HLC-8120, manufactured by Tosoh Corporation). A 0.3% by mass THF solution of the polymer was prepared, and 20 mL of the solution was injected into the device equipped with a Tosoh Corporation column (TSKgel SuperHM-H x 4, TSKguard column SuperH-H), and measurement was performed under the following conditions: flow rate: 0.6 mL/min, eluent: THF (stabilizer BHT), column temperature: 40°C. The number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated in terms of polystyrene.
＜Ｔｇについて＞
前記ガラス転移温度（Ｔｇ）は、下記式より算出される絶対温度（Ｋ）を摂氏（℃）に換算した値である。
１／Ｔｇ＝Σ（ｗｉ／Ｔｇｉ）
上記式において、ｗｉは、重合体を構成する単量体ｉの質量分率を示し、Ｔｇｉは、重合体を構成する単量体ｉのホモポリマーのガラス転移温度を示す。
上記式中のＴｇおよびＴｇｉは、絶対温度（Ｋ）で表した値である。また、単量体Ｉのホモポリマーのガラス転移温度は、ポリマーハンドブック〔Ｐｏｌｙｍｅｒ ＨａｎｄＢｏｏｋ，Ｊ．Ｂｒａｎｄｒｕｐ，Ｉｎｔｅｒｓｃｉｅｎｃｅ，１９８９〕
に記載されている値である。
<Regarding Tg>
The glass transition temperature (Tg) is a value calculated by the following formula, converted from absolute temperature (K) to Celsius (° C.):
1/Tg=Σ(wi/Tgi)
In the above formula, wi represents the mass fraction of monomer i constituting the polymer, and Tgi represents the glass transition temperature of a homopolymer of monomer i constituting the polymer.
In the above formula, Tg and Tgi are values expressed in absolute temperature (K). The glass transition temperature of the homopolymer of the monomer I is given by the formula (1) in Polymer Handbook [J. Brandrup, Interscience, 1989].
The value is listed in.
＜試験片の作製＞
組成物が３３．３％の固形分となるように重合体Ａを酢酸エチルで希釈した後、化合物ａを入れて混合し、化合物ａの溶け残りがないことを目視で確認し、常温（２３℃）で液状の粘着剤組成物とした。
膜厚３８μｍのＰＥＴフィルム上に、前記粘着剤組成物をアプリケーターで塗工し、９０℃で１時間乾燥して粘着層を形成した。
粘着層を形成したＰＥＴフィルム（ＰＥＴ）に、高圧水銀ランプを使用して、空気中で紫外線を照射し、粘着層を硬化させた。照射エネルギーは３５ｍＪ／ｃｍ２（積算光量計ＵＶ ＰＯＷＥＲ ＰＵＣＫ ＩＩ（Ｓ／Ｎ １３６８５）（米国ＥＩＴ製）による実測値）とした。その上面に、剥離処理をしたＰＥＴフィルム（剥離ＰＥＴ）を重ねて、剥離ＰＥＴ－粘着層－ＰＥＴの構成の積層体を得た。
粘着層の厚さは５０μｍとした。硬化後の積層体を２５ｍｍ幅、長さ２５０ｍｍの短冊状に裁断し、試験片とした。
＜試験片の外観 ＞
試験片の外観を目視で観察し、白濁の有無を確認した。
<Preparation of test specimen>
After diluting polymer A with ethyl acetate so that the composition had a solid content of 33.3%, compound a was added and mixed, and it was visually confirmed that no undissolved compound a remained, to obtain a pressure-sensitive adhesive composition that was liquid at room temperature (23°C).
The pressure-sensitive adhesive composition was applied onto a PET film having a thickness of 38 μm using an applicator, and dried at 90° C. for 1 hour to form a pressure-sensitive adhesive layer.
The PET film (PET) on which the adhesive layer was formed was irradiated with ultraviolet light in air using a high-pressure mercury lamp to cure the adhesive layer. The irradiation energy was 35 mJ/ cm2 (measured value using an integrating light meter UV POWER PUCK II (S/N 13685) (manufactured by EIT, USA)). A release-treated PET film (release PET) was layered on the upper surface to obtain a laminate having a release PET-adhesive layer-PET configuration.
The thickness of the adhesive layer was 50 μm. The cured laminate was cut into a rectangular shape having a width of 25 mm and a length of 250 mm to prepare a test piece.
<Appearance of test piece>
The appearance of the test piece was visually observed to confirm the presence or absence of cloudiness.
＜溶融粘度＞
粘着剤組成物をアプリケーターで塗工し、９０℃で１時間乾燥した前記粘着層を、粘弾性測定装置ＨＡＡＫＥ ＭＡＲＳを用いて測定した。直径３５ｍｍのコーンプレートを用い、１３０℃、周波数０．０２Ｈｚで測定した時の粘度（η＊）値を１３０℃における溶融粘度の値とした。
＜塗工性＞
上記の方法で測定した溶融粘度で以下の基準に従って塗工性を判定した。
Ａ：溶融粘度が ≦１００Ｐａ・ｓ。
Ｂ：溶融粘度が ＞１００Ｐａ・ｓ。
<Melt Viscosity>
The adhesive composition was applied with an applicator, and the adhesive layer was dried at 90° C. for 1 hour, and the adhesive layer was measured using a HAAKE MARS viscoelasticity measuring device. The viscosity (η*) value measured at 130° C. and a frequency of 0.02 Hz using a cone plate with a diameter of 35 mm was taken as the melt viscosity value at 130° C.
<Coatability>
The coatability was evaluated based on the melt viscosity measured by the above method according to the following criteria.
A: Melt viscosity is ≦100 Pa·s.
B: Melt viscosity is >100 Pa·s.
＜粘着力＞
試験片の剥離ＰＥＴを剥がして粘着層を露出させ、貼り合せ面が２５ｍｍ×７０ｍｍになるように３０ｍｍ×１１０ｍｍのステンレス（ＳＵＳ）板に３ｋｇのハンドローラーを用いて貼り合せ、剥離角度１８０°、引張速度３００ｍｍ／ｍｉｎで、ＳＵＳ板に対する剥離強度（Ｎ／２５ｍｍ）を測定し、粘着力とした。
<Adhesive strength>
The release PET of the test piece was peeled off to expose the adhesive layer, and the test piece was attached to a 30 mm x 110 mm stainless steel (SUS) plate using a 3 kg hand roller so that the bonding surface was 25 mm x 70 mm. The peel strength (N/25 mm) against the SUS plate was measured at a peel angle of 180° and a tensile speed of 300 mm/min, and this was taken as the adhesive strength.
＜保持力＞
試験片の一端において、剥離ＰＥＴを剥がして粘着層を露出させ、３０ｍｍ×１１０ｍｍのＳＵＳ板に３ｋｇのハンドローラーを用いて、貼り合せ面が２５×２５ｍｍとなるように水平に貼り合せた。温度８０℃、湿度４５％又は８５％の恒温恒湿層試験機内にて１５分放置した。その直後に、貼り合せ面に対して剪断方向に力がかかるようにＳＵＳ板を設置し、試験片の他端を下にして１．２ｋｇの荷重をかけ、保持時間を測定し、保持力とした。
<Holding power>
At one end of the test piece, the release PET was peeled off to expose the adhesive layer, and the test piece was horizontally attached to a 30 mm x 110 mm SUS plate using a 3 kg hand roller so that the bonding surface was 25 x 25 mm. The test piece was left for 15 minutes in a thermo-hygrostat tester at a temperature of 80°C and a humidity of 45% or 85%. Immediately after that, a SUS plate was placed so that a force was applied to the bonding surface in the shear direction, and a load of 1.2 kg was applied with the other end of the test piece facing down, and the holding time was measured and recorded as the holding force.
＜製造例１［分散剤１］＞
撹拌機、冷却管、温度計、及び窒素ガス導入管を備えた重合装置中に、脱イオン水を９００部、メタクリル酸２－スルホエチルナトリウムを６０部、メタクリル酸カリウムを１０部、及びメタクリル酸メチル（ＭＭＡ）を１２部入れて撹拌し、重合装置内を窒素置換しながら５０℃に昇温した。さらに、重合開始剤として２，２’－アゾビス（２－メチルプロピオンアミジン）二塩酸塩を０．０８部添加し、６０℃に昇温した。昇温後、滴下ポンプを使用して、ＭＭＡを０．２４部／分の速度で７５分間連続的に滴下した。混合物を６０℃で６時間保持した後、室温に冷却して、固形分１０質量％の分散剤１を得た。
<Production Example 1 [Dispersant 1]>
In a polymerization apparatus equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas inlet tube, 900 parts of deionized water, 60 parts of 2-sulfoethyl sodium methacrylate, 10 parts of potassium methacrylate, and 12 parts of methyl methacrylate (MMA) were placed and stirred, and the temperature was raised to 50 ° C. while replacing the inside of the polymerization apparatus with nitrogen. Furthermore, 0.08 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added as a polymerization initiator, and the temperature was raised to 60 ° C. After the temperature was raised, MMA was continuously dropped at a rate of 0.24 parts / min for 75 minutes using a dropping pump. The mixture was held at 60 ° C. for 6 hours, and then cooled to room temperature to obtain a dispersant 1 with a solid content of 10 mass %.
＜製造例２［連鎖移動剤１］＞
撹拌装置を備えた合成装置中に、窒素雰囲気下で、酢酸コバルト（ＩＩ）四水和物を１．００ｇ、ジフェニルグリオキシムを１．９３ｇ、あらかじめ窒素バブリングにより脱酸素したジエチルエーテルを８０ｍＬ加え、室温で３０分間撹拌した。さらに、三フッ化ホウ素ジエチルエーテル錯体を１０ｍＬ加え、６時間撹拌した。混合物をろ過し、固体をジエチルエーテルで洗浄し、１５時間真空乾燥して、赤褐色固体である連鎖移動剤１を２．１２ｇ得た。
<Production Example 2 [Chain Transfer Agent 1]>
In a synthesis apparatus equipped with a stirrer, 1.00 g of cobalt (II) acetate tetrahydrate, 1.93 g of diphenylglyoxime, and 80 mL of diethyl ether previously deoxygenated by nitrogen bubbling were added under a nitrogen atmosphere and stirred at room temperature for 30 minutes. Furthermore, 10 mL of boron trifluoride diethyl ether complex was added and stirred for 6 hours. The mixture was filtered, the solid was washed with diethyl ether, and vacuum dried for 15 hours to obtain 2.12 g of chain transfer agent 1, which was a reddish brown solid.
＜製造例３［化合物ａ－１］＞
撹拌機、冷却管、温度計、及び窒素ガス導入管を備えた重合装置中に、脱イオン水を１４５部、硫酸ナトリウムを０．１部、及び分散剤１（固形分１０質量％）を０．２５部入れて撹拌し、均一な水溶液とした。さらに、ＭＭＡを１００部、連鎖移動剤１を０．００２２部、及び重合開始剤としてパーオクタ（登録商標）Ｏ（１，１，３，３－テトラメチルブチルパーオキシ２－エチルヘキサノエート、日油株式会社製）を０．４部加え、水性懸濁液とした。
さらに、重合装置内を窒素置換し、８０℃に昇温して３．５時間攪拌し、さらに重合率を上げるため、９０℃に昇温して１時間保持した。その後、混合物を４０℃に冷却して、化合物を含む水性懸濁液を得た。得られた水性懸濁液をフィルタで濾過し、フィルタ上に残った残留物を脱イオン水で洗浄し、脱水し、４０℃で１６時間乾燥して、化合物ａ－１を得た。分子量の測定結果を表１に示す。
<Production Example 3 [Compound a-1]>
In a polymerization apparatus equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas inlet tube, 145 parts of deionized water, 0.1 parts of sodium sulfate, and 0.1 parts of dispersant 1 (solid content 10% by mass) were added. 0.0022 parts of chain transfer agent 1, and Perocta (registered trademark) O (1,1,3,3) as a polymerization initiator were added and stirred to obtain a uniform aqueous solution. To the mixture was added 0.4 parts of tetramethylbutylperoxy 2-ethylhexanoate (manufactured by NOF Corporation) to prepare an aqueous suspension.
The inside of the polymerization apparatus was then replaced with nitrogen, the temperature was raised to 80° C. and the mixture was stirred for 3.5 hours, and then the temperature was raised to 90° C. and held there for 1 hour in order to further increase the polymerization rate. After cooling, an aqueous suspension containing the compound was obtained. The aqueous suspension was filtered through a filter, and the residue on the filter was washed with deionized water, dehydrated, and then heated at 40° C. for 16 h. The molecular weight measurement results are shown in Table 1.
＜製造例４～５［化合物ａ－２～ａ－３］＞
表１に記載の通りに配合を変更した以外は、製造例３と同様にして化合物ａ－２～ａ－３を製造した。表１に示す配合の単位は質量部である。
<Production Examples 4 to 5 [Compounds a-2 to a-3]>
Compounds a-2 to a-3 were produced in the same manner as in Production Example 3, except that the formulation was changed as shown in Table 1. The units of the formulations shown in Table 1 are parts by mass.
なお、各表中の記号は以下の通りである。
ＭＭＡ：メタクリル酸メチル
ＥＨＭＡ：メタクリル酸２－エチルヘキシル
ＳＬＭＡ：メタクリル酸アルキル（アクリエステルＳＬ 三菱ケミカル社製）
The symbols in each table are as follows:
MMA: methyl methacrylate EHMA: 2-ethylhexyl methacrylate SLMA: alkyl methacrylate (Acryester SL, manufactured by Mitsubishi Chemical Corporation)
＜製造例６［（メタ）アクリル系共重合体Ａ－１］＞
撹拌装置、温度計、冷却管、及び窒素ガス導入口を備えた四つ口フラスコに、酢酸エチルを４０部、イソプロピルアルコール（ＩＰＡ）を７．７部入れ、窒素ガス通気下で外温を８５℃に昇温した。外温が８５℃に達し、内温が安定した後、２５部の酢酸エチル、８９．７部のｎ－ブチルアクリレート（ｎ－ＢＡ）、５部のアクリル酸（ＡＡ）、５部の化合物Ａ－１、０．３部の４－ＭＢＰ、０．１３部のナイパー（登録商標）ＢＭＴ－Ｋ４０（日油製、商品名）からなる混合物を４時間かけて滴下した。滴下終了後１時間保持した後、０．５部のパーオクタＯ及び１０部の酢酸エチルからなる混合物を３０分間かけて添加した。その後、２時間保持した後、酸化防止剤（ＢＡＳＦ社製、商品名「イルガノックス（登録商標）１０１０」）を０．５部投入し、固形分（（単量体＋溶剤仕込量）中の単量体仕込量の割合）が５３質量％になるように酢酸エチルを添加した後、室温まで冷却して（メタ）アクリル系共重合体Ａ－１を含む共重合体溶液Ａ－１を得た。
<Production Example 6 [(Meth)acrylic copolymer A-1]>
A four-neck flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet was charged with 40 parts of ethyl acetate and 7.7 parts of isopropyl alcohol (IPA), and the external temperature was raised to 85 ° C. under nitrogen gas aeration. After the external temperature reached 85 ° C. and the internal temperature stabilized, a mixture consisting of 25 parts of ethyl acetate, 89.7 parts of n-butyl acrylate (n-BA), 5 parts of acrylic acid (AA), 5 parts of compound A-1, 0.3 parts of 4-MBP, and 0.13 parts of Niper (registered trademark) BMT-K40 (manufactured by NOF Corp., trade name) was added dropwise over 4 hours. After holding for 1 hour after the end of the dropwise addition, a mixture consisting of 0.5 parts of Perocta O and 10 parts of ethyl acetate was added over 30 minutes. After that, after maintaining the mixture for 2 hours, 0.5 parts of an antioxidant (manufactured by BASF, product name "Irganox (registered trademark) 1010") was added, and ethyl acetate was added so that the solid content (the ratio of the charged amount of monomer in (charged amount of monomer + solvent)) became 53 mass %, and then the mixture was cooled to room temperature to obtain a copolymer solution A-1 containing a (meth)acrylic copolymer A-1.
＜製造例７［（メタ）アクリル系共重合体Ａ－２］＞
撹拌装置、温度計、冷却管、及び窒素ガス導入口を備えた四つ口フラスコに、酢酸エチルを４０部、イソプロピルアルコール（ＩＰＡ）を９．７部、化合物Ａ－１を５部入れ、窒素ガス通気下で外温を８５℃に昇温した。外温が８５℃に達し、内温が安定した後、２５部の酢酸エチル、８９．７部のｎ－ブチルアクリレート（ｎ－ＢＡ）、５部のアクリル酸（ＡＡ）、０．３部の４－ＭＢＰ、０．１３部のナイパー（登録商標）ＢＭＴ－Ｋ４０（日油製、商品名）からなる混合物を４時間かけて滴下した。滴下終了後１時間保持した後、０．５部のパーオクタＯ及び１０部の酢酸エチルからなる混合物を３０分間かけて添加した。その後、２時間保持した後、酸化防止剤（ＢＡＳＦ社製、商品名「イルガノックス（登録商標）１０１０」）を０．５部投入し、固形分（（単量体＋溶剤仕込量）中の単量体仕込量の割合）が５３質量％になるように酢酸エチルを添加した後、室温まで冷却して（メタ）アクリル系共重合体Ａ－２を含む共重合体溶液Ａ－２を得た。
<Production Example 7 [(Meth)Acrylic Copolymer A-2]>
A four-neck flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet was charged with 40 parts of ethyl acetate, 9.7 parts of isopropyl alcohol (IPA), and 5 parts of compound A-1, and the external temperature was raised to 85 ° C. under nitrogen gas aeration. After the external temperature reached 85 ° C. and the internal temperature stabilized, a mixture consisting of 25 parts of ethyl acetate, 89.7 parts of n-butyl acrylate (n-BA), 5 parts of acrylic acid (AA), 0.3 parts of 4-MBP, and 0.13 parts of Niper (registered trademark) BMT-K40 (manufactured by NOF Corp., trade name) was added dropwise over 4 hours. After holding for 1 hour after the end of the dropwise addition, a mixture consisting of 0.5 parts of Perocta O and 10 parts of ethyl acetate was added over 30 minutes. After that, after maintaining the mixture for 2 hours, 0.5 parts of an antioxidant (manufactured by BASF, product name "Irganox (registered trademark) 1010") was added, and ethyl acetate was added so that the solid content (the ratio of the charged amount of monomer in (the charged amount of monomer + solvent)) became 53 mass %, and the mixture was cooled to room temperature to obtain a copolymer solution A-2 containing a (meth)acrylic copolymer A-2.
製造例６および７で得られた（メタ）アクリル系共重合体Ａ－１及びＡ－２の組成及び特性を表２に示す。 The compositions and properties of the (meth)acrylic copolymers A-1 and A-2 obtained in Production Examples 6 and 7 are shown in Table 2.
なお、各表中の記号は以下の通りである。
ＩＰＡ：イソプロピルアルコール
ｎ－ＢＡ：ｎ－ブチルアクリレート
ＡＡ：アクリル酸
４－ＭＢＰ：４－メタクリロイルオキシベンゾフェノン
The symbols in each table are as follows:
IPA: Isopropyl alcohol n-BA: n-butyl acrylate AA: Acrylic acid 4-MBP: 4-methacryloyloxybenzophenone
＜実施例１～６、比較例１～３＞
表３に記載の通りに重合体と化合物を配合して得られた重合体組成物を用い、上記の方法で試験片を作製し、試験片の外観、粘着力、保持力、耐基材汚染性を評価した。評価結果を表３に示す。
<Examples 1 to 6 and Comparative Examples 1 to 3>
Test pieces were prepared by the above-mentioned method using the polymer compositions obtained by blending the polymers and compounds as shown in Table 3, and the appearance, adhesive strength, holding strength, and resistance to substrate contamination of the test pieces were evaluated. The evaluation results are shown in Table 3.
実施例１～６の重合体組成物は、比較例１～３の重合体組成物に比べ、外観、粘着力、保持力について、優れていることを確認した。
比較例１と２は、本発明の化合物を配合していないため、粘着力、保持力が不十分となった。
比較例３は、ＭＭＡ単一組成で作製した化合物を配合したため、重合体組成物との相溶性が不十分で白濁し、外観不良となった。また、ＵＶ未照射時の１３０℃溶融粘度も高く塗工性に課題があることが分かった。
It was confirmed that the polymer compositions of Examples 1 to 6 were superior to the polymer compositions of Comparative Examples 1 to 3 in appearance, adhesive strength, and holding strength.
Comparative Examples 1 and 2 did not contain the compound of the present invention, and therefore the adhesive strength and holding power were insufficient.
In Comparative Example 3, a compound made of a single MMA composition was blended, and therefore the compatibility with the polymer composition was insufficient, causing the product to become cloudy and resulting in poor appearance. In addition, the melt viscosity at 130°C before UV irradiation was high, and it was found that there was a problem with the coatability.
Claims (12)
前記単量体Ｍが式（２）の構造を有し、
前記重合体Ａの重量平均分子量が５０００～２００００００であり、
前記化合物ａの重量平均分子量が１０００～１０００００であり、
前記化合物ａと前記重合体Ａの比率が０．１：９９．９～３０：７０である組成物。
The monomer M has a structure of formula (2),
The weight average molecular weight of the polymer A is 5,000 to 2,000,000,
The weight average molecular weight of the compound a is 1,000 to 100,000;
A composition in which the ratio of the compound a to the polymer A is 0.1:99.9 to 30:70.
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