WO2022092201A1 - Adhesive tape - Google Patents
Adhesive tape Download PDFInfo
- Publication number
- WO2022092201A1 WO2022092201A1 PCT/JP2021/039822 JP2021039822W WO2022092201A1 WO 2022092201 A1 WO2022092201 A1 WO 2022092201A1 JP 2021039822 W JP2021039822 W JP 2021039822W WO 2022092201 A1 WO2022092201 A1 WO 2022092201A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- adhesive tape
- base material
- meth
- monomer
- Prior art date
Links
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims description 113
- 239000000463 material Substances 0.000 claims description 82
- 239000010410 layer Substances 0.000 claims description 66
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 43
- 229920001577 copolymer Polymers 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- 239000006260 foam Substances 0.000 claims description 22
- 229920001400 block copolymer Polymers 0.000 claims description 20
- 239000000758 substrate Substances 0.000 abstract description 32
- 239000012790 adhesive layer Substances 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 description 48
- 239000011347 resin Substances 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 33
- 239000003431 cross linking reagent Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 18
- 239000000499 gel Substances 0.000 description 16
- -1 2-ethylhexyl group Chemical group 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 15
- 229920006243 acrylic copolymer Polymers 0.000 description 14
- 238000005187 foaming Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000004088 foaming agent Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000004899 motility Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229920006223 adhesive resin Polymers 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000012987 RAFT agent Substances 0.000 description 4
- 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 4
- 238000004040 coloring Methods 0.000 description 4
- 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 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011146 organic particle Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007348 radical reaction Methods 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 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 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 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 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- FNIBRUOFKCBDGB-UHFFFAOYSA-N 2-bromo-2-phenylpropanoic acid Chemical compound OC(=O)C(Br)(C)C1=CC=CC=C1 FNIBRUOFKCBDGB-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- HOZMLTCHTRHKRK-UHFFFAOYSA-N 2-methyl-1-silylprop-2-en-1-one Chemical class CC(=C)C([SiH3])=O HOZMLTCHTRHKRK-UHFFFAOYSA-N 0.000 description 1
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- OKTJSMMVPCPJKN-BJUDXGSMSA-N carbon-11 Chemical compound [11C] OKTJSMMVPCPJKN-BJUDXGSMSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 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 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 230000002427 irreversible effect Effects 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
- 238000004898 kneading Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-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
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to an adhesive tape.
- Adhesive tapes are used for assembly in mobile electronic devices such as mobile phones and personal digital assistants (PDAs) (for example, Patent Documents 1 and 2). Adhesive tapes are also used for fixing in-vehicle electronic device parts such as in-vehicle panels to the vehicle body.
- PDAs personal digital assistants
- Adhesive tapes used for fixing portable electronic device parts, in-vehicle electronic device parts, and the like are required to have high adhesive strength and impact resistance that does not peel off even when impacted.
- portable electronic devices, in-vehicle electronic devices, etc. tend to have more complicated shapes due to higher functionality. be.
- the adhesive tape is required to have excellent flexibility to follow the shape of the adherend.
- an adhesive tape having excellent flexibility and impact resistance for example, an adhesive tape using a foam base material obtained by foaming a polyolefin resin or the like is known.
- electronic devices have been increasingly used for a long time at higher temperatures than before due to harsher usage conditions, application to the car electronics field, etc., and adhesive tapes using conventional foam base materials have been used. Then, there is a problem that it is easy to peel off when a load is applied to the shearing direction or the like at high temperature.
- An object of the present invention is to provide an adhesive tape having excellent heat-retaining properties, which is difficult to peel off when a load is applied under high temperature.
- the present invention is an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate, and is obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR. This is an adhesive tape having a relaxation time ( TL25 ) of the L component of 0.9 ms or less. Further, the present invention is an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate, which is measured by the Han Echo method at 85 ° C. using pulse NMR. It is an adhesive tape having a relaxation time ( TL85 ) of the obtained L component of 3.3 ms or less.
- the present invention will be described in detail below.
- the present inventors analyzed an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate by using pulse NMR for measuring 1H nuclei.
- pulse NMR the obtained 1H nucleus spin - spin relaxation free induction decay curve is waveform-separated into multiple components, and the "relaxation time" of each component is obtained to evaluate the molecular motility of that component. can do.
- the present inventors adjust the relaxation time ( TL25 ) of the L component obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR to a specific value or less, whereby a load is applied at a high temperature. It has been found that an adhesive tape having excellent heat-retaining properties, which is difficult to peel off at the time, can be obtained.
- the present inventors can also adjust the relaxation time ( TL85 ) of the L component obtained by the Han Echo method at 85 ° C. using pulsed NMR to a specific value or less to load the product under high temperature.
- TL85 the relaxation time of the L component obtained by the Han Echo method at 85 ° C. using pulsed NMR
- the pressure-sensitive adhesive tape of the present invention has a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material.
- the upper limit of the relaxation time ( TL25 ) of the L component obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR is 0.9 ms.
- the upper limit of the relaxation time ( TL85 ) of the L component obtained by measuring at 85 ° C. by the Han Echo method using pulse NMR is 3.3 milliseconds.
- the "L component obtained by measuring with the Han Echo method at 25 ° C. using pulse NMR” is 1 H obtained by measuring with the Han Echo method at 25 ° C. using pulsed NMR. It means the component with the longest relaxation time when the free induction decay curve of nuclear spin-spin relaxation is waveform-separated into three components in the order of shortest relaxation time. Waveform separation into three components (S component, M component and L component, respectively in the order of shorter relaxation time) is performed by analyzing the free induction decay curve by the method of least squares.
- the "relaxation time” is the time from the excited state to the ground state of the electron spin after the magnetic field is applied, and the longer the “relaxation time” is, the higher the molecular motility is. That is, the S component is a hard component having a relatively low molecular motility, having the shortest relaxation time and immediately decaying the magnetization strength.
- the M component is a component having an intermediate relaxation time and molecular motility between the S component and the L component.
- the L component is a soft component having a relatively high molecular motility, which has the longest relaxation time and takes a long time to decay the magnetization strength.
- the adhesive tape of the present invention has a relatively high molecular mobility of the L component at 25 ° C. By being suppressed, it becomes difficult to peel off when a load is applied under high temperature.
- the preferred upper limit of the relaxation time ( TL25 ) of the L component at 25 ° C. is 0.8 ms, the more preferred upper limit is 0.6 ms, and the more preferred upper limit is 0.4 ms.
- the relaxation time of the L component ( TL25 ) at 25 ° C. was determined by using a pulse NMR device (for example, the minispec mq20, manufactured by BRUKER, etc.) and analysis software (for example, TD-NMRA, manufactured by BRUKER, etc.).
- Adhesive tape can be used as a measurement sample and measured by the Han Echo method at 25 ° C.
- the L component obtained by measuring with the Han Echo method at 85 ° C. using pulse NMR was obtained by measuring with the Han Echo method at 85 ° C. using pulse NMR. 1 It means the L component when the free induction decay curve of spin-spin relaxation of H nucleus is waveform-separated into two components, S component and L component, in the order of shortest relaxation time. The waveform separation into two components is performed by analyzing the free induction decay curve by the method of least squares.
- the adhesive tape of the present invention has a relatively high molecular mobility of the L component at 85 ° C. By being suppressed, it becomes difficult to peel off when a load is applied under high temperature.
- the more preferable upper limit of the relaxation time ( TL85 ) of the L component at 85 ° C. is 3 ms, and the more preferable upper limit is 2.5 ms.
- the lower limit of the relaxation time ( TL85 ) of the L component at 85 ° C. is not particularly limited, but from the viewpoint of ensuring the flexibility of the adhesive tape, the preferable lower limit is 0.5 ms, and the more preferable lower limit is 1 ms. be.
- the method for adjusting the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) within the above ranges is not particularly limited, and for example, the substrate can be used.
- a method using a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer, which will be described later, and the like can be mentioned.
- a method of adjusting the weight average molecular weight (Mw) of such a copolymer, a method of adjusting the content of foamed particles in the above-mentioned substrate, and the like can be mentioned.
- a method of adjusting the composition of the pressure-sensitive adhesive layer a method of adjusting the weight average molecular weight (Mw) of the resin constituting the pressure-sensitive adhesive layer, and the like can be mentioned. More specifically, as a method for shortening the relaxation time, a method for introducing a structure derived from a vinyl aromatic monomer in the base material or the pressure-sensitive adhesive layer, and the content of hard blocks described later in the block copolymer. Examples thereof include a method of increasing the number of crosslinks, a method of introducing a crosslinked structure, and a method of increasing the degree of crosslinking thereof.
- a method of increasing the entanglement between molecules that is, increasing the number of monomers having a short side chain or decreasing the number of monomers having a long side chain
- reducing the motility of the molecular chain examples include a method (for example, introducing an alicyclic structure), a method of increasing polar interaction (for example, introducing an acid or a hydroxyl group, or increasing the amount thereof), and the like.
- a method of selecting a raw material monomer so that the glass transition temperature (Tg) becomes higher in the base material or the pressure-sensitive adhesive layer, a method of increasing the molecular weight, a method of adding a filler, and the like can be mentioned.
- the base material is not particularly limited, but preferably contains a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer.
- the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) are within the above ranges. It becomes easy to adjust to, and it becomes more difficult for the adhesive tape to peel off when a load is applied under high temperature.
- vinyl aromatic monomer examples include styrene, alpha-methylstyrene, paramethylstyrene, chlorostyrene and the like. These vinyl aromatic monomers may be used alone or in combination of two or more. Of these, styrene is preferable because the adhesive tape is more difficult to peel off when a load is applied under high temperature.
- the structure derived from the vinyl aromatic monomer refers to the structure represented by the following general formulas (1) and (2).
- R 1 represents a substituent having an aromatic ring.
- substituent R1 having an aromatic ring include a phenyl group, a methylphenyl group, a chlorophenyl group and the like.
- the content of the structure derived from the vinyl aromatic monomer in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, but is 1% by weight or more. It is preferably 30% by weight or less.
- the adhesive tape is less likely to be peeled off when a load is applied at a high temperature.
- a more preferable lower limit of the content of the structure derived from the vinyl aromatic monomer is 1.5% by weight, a further preferable lower limit is 2% by weight, a further preferable lower limit is 2.5% by weight, and a particularly preferable lower limit is 3% by weight.
- a particularly preferable lower limit is 4% by weight, a more preferable upper limit is 25% by weight, a further preferable upper limit is 20% by weight, and a particularly preferable upper limit is 15% by weight.
- the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer further has a structure derived from the monomer having a crosslinkable functional group.
- a copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer has a crosslinkable functional group, the cohesive force of the copolymer is enhanced by the crosslinking. It becomes easy to adjust the relaxation time of the L component at ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) within the above ranges. This makes it more difficult for the adhesive tape to peel off when a load is applied under high temperature.
- the crosslinkable functional group may or may not be crosslinked, but is more preferably crosslinked. However, even if the structure remains uncrosslinked, the cohesive force in the hard block or soft block (particularly the hard block) described later is improved by the interaction between the functional groups, and a load is applied at high temperature. At that time, the adhesive tape becomes more difficult to peel off.
- the structure derived from the monomer having a crosslinkable functional group refers to the structure represented by the following general formulas (3) and (4).
- R 2 represents a substituent containing at least one functional group.
- the functional group include a carboxyl group, a hydroxyl group, an epoxy group, a double bond, a triple bond, an amino group, an amide group, a nitrile group and the like.
- the substituent R2 containing at least one functional group may contain an alkyl group, an ether group, a carbonyl group, an ester group, a carbonate group, an amide group, a urethane group and the like as its constituent elements.
- the monomer having a crosslinkable functional group is not particularly limited, and for example, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, an amino group-containing monomer, and an amide group-containing monomer. , A nitrile group-containing monomer and the like.
- These crosslinkable functional groups may be used alone or in combination of two or more.
- a carboxyl group-containing monomer a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, and an amide group.
- At least one selected from the group consisting of contained monomers is preferable.
- the carboxyl group-containing monomer include (meth) acrylic acid-based monomers such as (meth) acrylic acid.
- the hydroxyl group-containing monomer include 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
- the epoxy group-containing monomer include glycidyl (meth) acrylate and the like.
- Examples of the double bond-containing monomer include allyl (meth) acrylate and hexanediol di (meth) acrylate.
- Examples of the triple bond-containing monomer include propargyl (meth) acrylate and the like.
- Examples of the amide group-containing monomer include (meth) acrylamide and the like. Of these, a carboxyl group-containing monomer and a hydroxyl group-containing monomer are preferable because the adhesive tape is more difficult to peel off when a load is applied at a high temperature.
- a (meth) acrylic acid-based monomer containing a carboxyl group and a (meth) acrylic acid-based monomer containing a hydroxyl group are more preferable, and (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) are preferable. Acrylic is more preferred.
- the content of the structure derived from the crosslinkable functional group in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, but is 0. It is preferably 1% by weight or more and 30% by weight or less.
- the adhesive tape is less likely to be peeled off when a load is applied at a high temperature.
- a more preferable lower limit of the content of the structure derived from the monomer having a crosslinkable functional group is 0.5% by weight, a further preferable lower limit is 1% by weight, a more preferable upper limit is 25% by weight, and a further preferable upper limit is 20% by weight. be.
- the (meth) acrylic monomer may be a single monomer or may use a plurality of monomers.
- the structure derived from the (meth) acrylic monomer refers to the structure represented by the following general formulas (5) and (6).
- R 3 represents a side chain.
- the side chain R 3 includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group and a lauryl group. Examples thereof include an isostearyl group.
- Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and heptyl (meth). Meta) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate And so on.
- (meth) acrylic monomers may be used alone or in combination of two or more.
- methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Is preferable, and methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are more preferable.
- the (meth) acrylic monomer it is preferable to use a (meth) acrylic monomer having 2 or less side chain carbon atoms.
- the (meth) acrylic monomer having 2 or less side chains has been used, the entanglement between the obtained copolymer chains is increased, the cohesive force is improved, and the relaxation time of the L component at 25 ° C. is increased.
- TL25 ) and the relaxation time of the L component ( TL85 ) at 85 ° C. can be easily adjusted to the above range, and the adhesive tape becomes more difficult to peel off when a load is applied under high temperature.
- Examples of the (meth) acrylic monomer having 2 or less side chain carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate, and methyl acrylate and ethyl acrylate are particularly preferable.
- the content of the structure derived from the (meth) acrylic monomer in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, and the content of the structure derived from the (meth) acrylic monomer is not particularly limited. The effect may be exhibited, but it is preferably 30% by weight or more and 99% by weight or less.
- the content of the structure derived from the (meth) acrylic monomer is more preferably 40% by weight or more and 98% by weight or less, and further preferably 50% by weight or more and 97% by weight or less.
- the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is particularly limited.
- the preferred lower limit is 5% by weight and the preferred upper limit is 90% by weight.
- the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 5% by weight or more, the effect of improving the cohesive force is likely to be exhibited. If the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 90% by weight or less, the cohesive force becomes too high, the flexibility becomes low, and the flexibility as an adhesive tape is lost. Can be prevented.
- a more preferable lower limit of the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 10% by weight, a further preferable lower limit is 20% by weight, a further preferable lower limit is 25% by weight, and a particularly preferable lower limit is 30% by weight.
- the more preferable upper limit is 85% by weight, the further preferable upper limit is 80% by weight, the still more preferable upper limit is 75% by weight, and the particularly preferable upper limit is 70% by weight.
- the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is not particularly limited as long as it has each structure as described above, and is a random copolymer. It may be a block copolymer or a block copolymer. From the viewpoint of further enhancing the flexibility of the base material, a random copolymer is preferable, and from the viewpoint of further enhancing the balance between the heat resistance retention property and the flexibility of the base material, a block copolymer is preferable.
- the block copolymer is a copolymer containing a rigid structure (hereinafter, also referred to as "hard block”) and a flexible structure (hereinafter, also referred to as "soft block”).
- the block copolymer may have a non-uniform phase-separated structure in which two blocks are difficult to be compatible with each other and islands formed by agglomeration of the hard blocks are scattered in the sea of the soft blocks. Since the islands serve as pseudo-crosslinking points, rubber elasticity can be imparted to the block copolymer, so that the adhesive tape is less likely to be peeled off when a load is applied at a high temperature.
- the adhesive tape becomes more difficult to peel off when a load is applied at a high temperature.
- the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is a random copolymer, the adhesive tape is subjected to a load at a high temperature. It is an adhesive tape with excellent heat retention that is hard to peel off. It is considered that this is because the same interaction as the above-mentioned phase-separated structure works at a very small scale such as the nano level and the molecular level.
- the block copolymer contains a structure derived from the vinyl aromatic monomer in the hard block and a structure derived from the (meth) acrylic monomer in the soft block.
- the hard block is not particularly limited as long as it has a rigid structure, and in addition to the structure derived from the vinyl aromatic monomer, for example, a compound having a cyclic structure, a compound having a short side chain substituent, or the like can be used. It may have a structure derived from the above (meth) acrylic monomer as long as the effect of the present invention is not lost.
- the soft block may have a structure derived from a monomer other than the (meth) acrylic monomer as long as the effect of the present invention is not lost.
- the block copolymer may have any structure such as a diblock structure or a triblock structure, but the adhesive tape is more difficult to peel off when a load is applied at a high temperature, so that the hard block It is preferable to have a triblock structure having the soft block between the two.
- the block copolymer may be a graft copolymer in which the hard block and the soft block are separated into a main chain and a side chain. Examples of the graft copolymer include a styrene macromer- (meth) acrylic monomer copolymer and the like.
- the content of the hard block in the block copolymer is not particularly limited, but is preferably 1% by weight or more and 40% by weight or less.
- the adhesive tape is less likely to be peeled off when a load is applied at a high temperature.
- the more preferable lower limit of the content of the hard block is 2% by weight, the more preferable lower limit is 2.5% by weight, and the particularly preferable lower limit is 3% by weight.
- a more preferable upper limit of the content of the hard block is 35% by weight, a further preferable upper limit is 30% by weight, a further preferable upper limit is 25% by weight, a further preferable upper limit is 20% by weight, and a particularly preferable upper limit is 15% by weight.
- the weight average molecular weight (Mw) of the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is not particularly limited, but is preferably 50,000 or more and 800,000 or less. ..
- the more preferable lower limit of the weight average molecular weight is 75,000, and the more preferable upper limit is 600,000.
- the weight average molecular weight can be determined, for example, by a GPC (Gel Permeation Chromatography) method in terms of standard polystyrene.
- the raw material monomers of the hard block and the soft block are used in the presence of a polymerization initiator.
- the hard block and the soft block may be obtained by radical reaction, respectively, and then the two may be reacted or copolymerized. Further, after obtaining the hard block, the raw material monomer of the soft block may be continuously added and copolymerized.
- a solution mixed with the raw material monomers may be subjected to a radical reaction in the presence of a polymerization initiator.
- the method for causing the radical reaction that is, the polymerization method
- a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
- the substrate may contain additives such as antistatic agents, mold release agents, antioxidants, weathering agents, and crystal nucleating agents, and resin modifiers such as polyolefins, polyesters, polyamides, and elastomers. ..
- the above substrate was at least in a region of 10 ° C. or lower and a region of 50 ° C. or higher when DSC measurement (differential scanning calorimetry) was performed under the conditions of a temperature rise rate of 10 ° C./min and a temperature range of -80 to 200 ° C. It is preferable to have one peak.
- the substrate has at least one peak in the region of 10 ° C. or lower and the region of 50 ° C. or higher when DSC measurement is performed, the substrate is a block copolymer having two blocks as described above. It can be said that it contains. From the viewpoint of achieving both heat retention and flexibility, it is preferable that the base material contains the block copolymer in this way.
- the peak in the region of 10 ° C. or lower when the DSC measurement is performed may be referred to as the peak derived from the soft block, and the peak in the region of 50 ° C. or higher may be referred to as the peak derived from the hard block.
- the peak region can be adjusted by the type of the raw material monomer of the hard block and the soft block.
- the DSC measurement of the base material can be performed on 100 mg of the base material using a differential scanning calorimeter (for example, 220C manufactured by Seiko Instruments Inc.).
- the base material may have a single-layer structure or a multi-layer structure.
- the base material is preferably a foam base material. Since the base material is the foam base material, the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) are adjusted within the above ranges. This makes it easier to remove the adhesive tape when a load is applied at high temperature.
- the foam base material may have an open cell structure or a closed cell structure, but is preferably a closed cell structure.
- the foaming ratio is not particularly limited, but the preferable lower limit is 1.1 cm 3 / g and the preferable upper limit is 5 cm 3 / g.
- the foaming ratio is in the above range, the balance between the heat resistance retention property and the flexibility of the adhesive tape can be further improved.
- the more preferable lower limit of the foaming ratio is 1.2 cm 3 / g
- the more preferable upper limit is 4.5 cm 3 / g
- the more preferable lower limit is 1.3 cm. 3 / g
- a more preferred upper limit is 4 cm 3 / g.
- the expansion ratio of the base material can be calculated from the reciprocal of the density of the base material, and can be measured using an electronic hydrometer (for example, "ED120T” manufactured by Mirage Co., Ltd.) in accordance with JIS K 7222.
- the average bubble diameter is not particularly limited, but is preferably 80 ⁇ m or less. When the average cell diameter is 80 ⁇ m or less, the balance between the heat resistance retention and the flexibility of the adhesive tape can be further improved.
- the average bubble diameter is more preferably 60 ⁇ m or less, and further preferably 55 ⁇ m or less.
- the lower limit of the average bubble diameter is not particularly limited, but is preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more, from the viewpoint of ensuring the flexibility of the adhesive tape.
- the average bubble diameter of the base material can be measured by the following method.
- the base material is cut into 50 mm squares, immersed in liquid nitrogen for 1 minute, and then cut in a plane perpendicular to the thickness direction of the base material using a razor blade. Then, using a digital microscope (for example, "VHX-900" manufactured by KEYENCE Corporation), a magnified photograph of the cut surface was taken at a magnification of 200 times, and the most bubbles existing in the range of thickness ⁇ 2 mm were taken. Measure a long bubble diameter (bubble diameter). This operation is repeated 5 times, and the average bubble diameter is calculated by averaging all the obtained bubble diameters.
- VHX-900 digital microscope
- the base material preferably has a gel fraction of 90% by weight or less.
- the adhesive tape can exhibit more excellent flexibility.
- the more preferable upper limit of the gel fraction is 85% by weight, and the more preferable upper limit is 80% by weight.
- the lower limit of the gel fraction is not particularly limited, but from the viewpoint of making it more difficult for the adhesive tape to peel off when a load is applied at a high temperature, for example, it is 10% by weight or more, particularly 20% by weight or more, particularly 35% by weight or more. be.
- the gel fraction can be adjusted by cross-linking the resin constituting the substrate.
- the gel fraction of the base material can be measured by the following method.
- the base material has a cross-linked structure formed between the main chains of the resin constituting the base material by adding a cross-linking agent.
- a cross-linking agent By forming a crosslinked structure between the main chains of the resin constituting the base material, the stress applied intermittently can be dispersed, and the adhesive tape becomes more difficult to peel off when a load is applied at a high temperature.
- the cross-linking agent is not particularly limited, and can be appropriately selected depending on the functional group of the resin constituting the base material. Specific examples thereof include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-type cross-linking agents. Among them, an epoxy-based cross-linking agent or an isocyanate-based cross-linking agent is preferable because a resin having an alcoholic hydroxyl group or a carboxyl group that can further improve flexibility can be cross-linked.
- the isocyanate-based cross-linking agent When the isocyanate-based cross-linking agent is used, the alcoholic hydroxyl group or carboxyl group in the resin constituting the substrate is crosslinked with the isocyanate group of the isocyanate-based cross-linking agent.
- the epoxy-based cross-linking agent When the epoxy-based cross-linking agent is used, the carboxyl group in the resin constituting the base material and the epoxy group of the epoxy-based cross-linking agent are cross-linked.
- the amount of the cross-linking agent added is not particularly limited, but is preferably 0.01 parts by weight or more and 10 parts by weight or less, and 0.1 parts by weight or more and 7 parts by weight or less with respect to 100 parts by weight of the resin constituting the base material. Is more preferable.
- the thickness of the base material is not particularly limited, but the preferred lower limit is 40 ⁇ m and the preferred upper limit is 2900 ⁇ m.
- the thickness of the base material is not particularly limited, but the preferred lower limit is 40 ⁇ m and the preferred upper limit is 2900 ⁇ m.
- the more preferable lower limit of the thickness of the base material is 60 ⁇ m
- the more preferable upper limit is 1900 ⁇ m
- the further preferable lower limit is 80 ⁇ m
- the further preferable upper limit is 1400 ⁇ m
- the particularly preferable lower limit is 100 ⁇ m.
- a particularly preferable upper limit is 1000 ⁇ m.
- the method for producing the above-mentioned base material is not particularly limited.
- examples of the method for producing the foam base material include a method of producing by the action of foaming gas and a method of producing by blending hollow spheres in a raw material matrix.
- the base material produced by the latter method is called syntactic foam, and is excellent in strength, flexibility and heat resistance. Therefore, the base material is preferably syntactic foam.
- syntactic foam Since the base material is syntactic foam, it becomes a closed cell type foam having a more uniform size distribution, so that the density of the entire base material becomes more constant, and the strength, flexibility and heat resistance are further improved. do. In addition, syntactic foam exhibits higher heat resistance than other foams because it is less likely to cause irreversible disintegration under high temperature and high pressure.
- Syntactic foam includes those having a foamed structure made of hollow inorganic particles and those having a foamed structure made of hollow organic particles. From the viewpoint of flexibility, syntactic foam having a foamed structure made of hollow organic particles. Foam is preferred.
- Examples of the hollow organic particles include Expancel DU series (manufactured by Nippon Philite Co., Ltd.), Advancel EM series (manufactured by Sekisui Chemical Co., Ltd.) and the like. Among them, since it is easy to design the bubble diameter after foaming in a region with higher effect, Expandel 461-DU-20 (average bubble diameter after foaming under optimum conditions 20 ⁇ m), Expandel 461-DU- 40 (average cell diameter after foaming under optimum conditions 40 ⁇ m), Expandel 043-80 (average cell diameter after foaming under optimum conditions 80 ⁇ m), Advansel EML101 (average cell diameter after foaming under optimum conditions 50 ⁇ m) ) Is preferable.
- the content of the hollow organic particles is not particularly limited, but since the adhesive tape is more difficult to peel off when a load is applied at a high temperature, the preferable lower limit with respect to 100 parts by weight of the resin constituting the base material is 0.1.
- the preferred upper limit is 10 parts by weight
- the more preferred lower limit is 0.3 parts by weight
- the more preferred upper limit is 7 parts by weight.
- the foaming agent is not particularly limited, and a conventionally known foaming agent such as a pyrolytic foaming agent can be used.
- the pressure-sensitive adhesive layer may be laminated on only one surface of the base material, or may be laminated on both sides.
- the pressure-sensitive adhesive layers on both sides may have the same composition and physical properties, or may have different compositions and physical properties.
- the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include an acrylic pressure-sensitive adhesive layer, a rubber-based pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and a silicone-based pressure-sensitive adhesive layer.
- an acrylic pressure-sensitive adhesive layer containing an acrylic copolymer is preferable because it has excellent heat resistance and can be adhered to a wide variety of adherends.
- the acrylic copolymer can be obtained by copolymerizing a monomer mixture containing butyl acrylate and / or 2-ethylhexyl acrylate from the viewpoint of improving the initial tack and making it easy to attach at low temperature. preferable. Above all, it is more preferable to obtain it by copolymerizing a monomer mixture containing butyl acrylate and 2-ethylhexyl acrylate.
- the preferable lower limit of the content of the butyl acrylate in the total monomer mixture is 40% by weight, and the preferable upper limit is 80% by weight.
- the preferable lower limit of the content of the 2-ethylhexyl acrylate in the total monomer mixture is 10% by weight, the preferable upper limit is 100% by weight, the more preferable lower limit is 30% by weight, the more preferable upper limit is 80% by weight, and the further preferable lower limit is 50% by weight. %, A more preferred upper limit is 60% by weight.
- the monomer mixture may contain other copolymerizable monomers other than butyl acrylate and 2-ethylhexyl acrylate, if necessary.
- the other copolymerizable monomer include a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and a (meth) acrylic acid alkyl ester having an alkyl group having 13 to 18 carbon atoms. Examples include functional monomers.
- Examples of the (meth) acrylic acid alkyl ester having 1 to 8 carbon atoms in the alkyl group include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and (meth) acrylic acid.
- the (meth) acrylic acid alkyl ester having 13 to 18 carbon atoms in the alkyl group include tridecylic methacrylic acid and stearyl (meth) acrylic acid.
- Examples of the functional monomer include (meth) acrylic acid hydroxyalkyl, glycerin dimethacrylate, (meth) glycidyl acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, and crotonic acid. Maleic acid, fumaric acid and the like can be mentioned.
- the monomer mixture may be subjected to a radical reaction in the presence of a polymerization initiator.
- a method of radically reacting the monomer mixture that is, a polymerization method
- a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
- the weight average molecular weight (Mw) of the acrylic copolymer is not particularly limited, but the preferred lower limit is 400,000 and the preferred upper limit is 1.5 million.
- Mw weight average molecular weight
- the more preferable lower limit of the weight average molecular weight is 500,000, and the more preferable upper limit is 1.4 million.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic copolymer is preferably 10.0.
- Mw / Mn is 10.0 or less, the proportion of small molecule components is suppressed, the pressure-sensitive adhesive layer is softened at high temperatures, the bulk strength is lowered, and the adhesive strength is suppressed.
- the adhesive tape is less likely to come off when a load is applied underneath.
- the more preferable upper limit of Mw / Mn is 5.0, and the more preferable upper limit is 3.0.
- the pressure-sensitive adhesive layer may contain a pressure-sensitive adhesive resin.
- the tackifier resin include rosin ester resin, hydrogenated rosin resin, terpene resin, terpene phenol resin, Kumaron inden resin, alicyclic saturated hydrocarbon resin, C5 petroleum resin, and C9 resin. Examples thereof include petroleum resins and C5-C9 copolymerized petroleum resins. These tackifier resins may be used alone or in combination of two or more.
- the content of the tackifier resin is not particularly limited, but the preferable lower limit is 10 parts by weight and the preferable upper limit is 60 parts by weight with respect to 100 parts by weight of the resin (for example, acrylic copolymer) which is the main component of the pressure-sensitive adhesive layer. ..
- the content of the pressure-sensitive adhesive resin is 10 parts by weight or more, the pressure-sensitive adhesive layer can exert a high pressure-sensitive adhesive force, and the pressure-sensitive adhesive tape becomes more difficult to peel off when a load is applied at a high temperature.
- the content of the pressure-sensitive adhesive resin is 60 parts by weight or less, it is possible to suppress a decrease in adhesive strength or tackiness due to the hardening of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer has a cross-linked structure formed between the main chains of the resin (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.) constituting the pressure-sensitive adhesive layer by adding a cross-linking agent.
- a cross-linking agent for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.
- the above-mentioned cross-linking agent is not particularly limited, and examples thereof include an isocyanate-based cross-linking agent, an aziridine-based cross-linking agent, an epoxy-based cross-linking agent, and a metal chelate-type cross-linking agent. Of these, isocyanate-based cross-linking agents are preferable.
- the pressure-sensitive adhesive layer By adding an isocyanate-based cross-linking agent to the pressure-sensitive adhesive layer, the isocyanate group of the isocyanate-based cross-linking agent and the alcohol in the resin constituting the pressure-sensitive adhesive layer (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.)
- the pressure-sensitive adhesive layer is crosslinked by reacting with the sex hydroxylate.
- the amount of the cross-linking agent added is preferably 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the resin (for example, the acrylic copolymer) which is the main component of the pressure-sensitive adhesive layer. Is more preferable.
- the pressure-sensitive adhesive layer may contain a silane coupling agent for the purpose of improving the pressure-sensitive adhesive strength.
- the silane coupling agent is not particularly limited, and examples thereof include epoxysilanes, acrylicsilanes, methacrylsilanes, aminosilanes, and isocyanatesilanes.
- the pressure-sensitive adhesive layer may contain a coloring material for the purpose of imparting light-shielding properties.
- the coloring material is not particularly limited, and examples thereof include carbon black, aniline black, and titanium oxide. Of these, carbon black is preferable because it is relatively inexpensive and chemically stable.
- the pressure-sensitive adhesive layer may contain conventionally known particles and additives such as inorganic particles, conductive particles, antioxidants, foaming agents, organic fillers, and inorganic fillers, if necessary.
- the preferable lower limit of the gel fraction is 10% by weight, and the preferable upper limit is 80% by weight.
- the adhesive tape is less likely to be peeled off when a load is applied under high temperature.
- the more preferable lower limit of the gel fraction is 20% by weight, and the more preferable upper limit is 70% by weight.
- the gel fraction of the pressure-sensitive adhesive layer can be measured by the same method as the gel fraction of the base material.
- the preferable lower limit of the storage elastic modulus G'in the dynamic viscoelasticity measurement at 23 ° C. is 105 Pa, and the preferable upper limit is 106 Pa.
- the storage elastic modulus G'at 23 ° C. is within the above range, the adhesive tape is less likely to be peeled off when a load is applied under high temperature.
- the more preferable lower limit of the storage elastic modulus G'at 23 ° C. of the pressure-sensitive adhesive layer is 2 ⁇ 10 5 Pa, and the more preferable upper limit is 8 ⁇ 10 5 Pa.
- the storage elastic modulus G'of the pressure-sensitive adhesive layer at 23 ° C. can be adjusted by the composition of the raw material monomer of the pressure-sensitive adhesive layer.
- the storage elastic modulus G'at 23 ° C. of the pressure-sensitive adhesive layer was set to 10 ° C./min in a constant-speed temperature rise tension mode using a viscoelasticity spectrometer (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.). It can be obtained as the storage elastic modulus at 23 ° C. when the dynamic viscoelasticity spectrum at ⁇ 40 to 140 ° C. is measured under the condition of 10 Hz.
- a viscoelasticity spectrometer for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but a preferable lower limit is 0.01 mm, a preferable upper limit is 0.1 mm, a more preferable lower limit is 0.015 mm, and a more preferable upper limit is 0.09 mm.
- a preferable lower limit is 0.01 mm
- a preferable upper limit is 0.1 mm
- a more preferable lower limit is 0.015 mm
- a more preferable upper limit is 0.09 mm.
- the adhesive tape of the present invention may further have a resin layer laminated on at least one surface of the base material.
- the resin layer may be laminated on only one surface of the base material or may be laminated on both sides, but it is preferable that the resin layer is laminated on only one surface of the base material.
- the resin constituting the resin layer preferably has heat resistance.
- the resin constituting the heat-resistant resin layer include polyester resins such as polyethylene terephthalate, acrylic resins, silicone resins, phenol resins, polyimides, and polycarbonates. Among them, acrylic resin and polyester resin are preferable, and polyethylene terephthalate is more preferable, because an adhesive tape having excellent flexibility can be obtained.
- the resin layer may be colored.
- coloring the resin layer it is possible to impart light-shielding properties to the adhesive tape.
- the method of coloring the resin layer is not particularly limited, and for example, a method of kneading particles such as carbon black or titanium oxide or fine bubbles into the resin constituting the resin layer, or applying ink to the surface of the resin layer. The method and the like can be mentioned.
- the resin layer may contain conventionally known particles and additives such as inorganic particles, conductive particles, plasticizers, tackifiers, ultraviolet absorbers, antioxidants, foaming agents, organic fillers, and inorganic fillers, if necessary. May be contained.
- the thickness of the resin layer is not particularly limited, but the preferred lower limit is 5 ⁇ m and the preferred upper limit is 100 ⁇ m.
- the thickness of the resin layer is not particularly limited, but the preferred lower limit is 5 ⁇ m and the preferred upper limit is 100 ⁇ m.
- the more preferable lower limit of the thickness of the resin layer is 10 ⁇ m, and the more preferable upper limit is 70 ⁇ m.
- the thickness of the entire adhesive tape of the present invention is not particularly limited, but a preferable lower limit is 0.04 mm, a more preferable lower limit is 0.05 mm, a preferable upper limit is 2 mm, and a more preferable upper limit is 1.5 mm.
- a preferable lower limit is 0.04 mm
- a more preferable lower limit is 0.05 mm
- a preferable upper limit is 2 mm
- a more preferable upper limit is 1.5 mm.
- the shape of the adhesive tape of the present invention is not particularly limited, and examples thereof include a rectangle, a square, a frame shape, a circle shape, an ellipse shape, and a donut shape.
- the method for producing the adhesive tape of the present invention is not particularly limited, and examples thereof include the following methods. First, a pressure-sensitive adhesive solution is applied to a release film and dried to form a pressure-sensitive adhesive layer. Next, an unfoamed base material is manufactured, and a resin layer is laminated on the unfoamed base material to form a laminated body. Then, an adhesive layer is attached to both sides of the obtained laminate, and the unfoamed base material is foamed by heating to form a foam base material, and an adhesive tape is manufactured.
- the use of the adhesive tape of the present invention is not particularly limited, but since it is an adhesive tape having excellent heat retention and heat retention that is difficult to peel off when a load is applied under high temperature, it can be used for portable electronic device parts, in-vehicle electronic device parts, and the like. It is preferably used for assembling or fixing electronic device parts.
- an adhesive tape having excellent heat retention and holding property, which is difficult to peel off when a load is applied at a high temperature.
- Example 1 Production of unfoamed base material 0.902 g of 1,6-hexanedithiol, 1.83 g of carbon disulfide, and 11 mL of dimethylformamide were placed in a two-necked flask and stirred at 25 ° C. To this, 2.49 g of triethylamine was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 3 hours. Then, 2.75 g of methyl- ⁇ -bromophenylacetic acid was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 4 hours.
- the blending amount of the mixture was adjusted so that the content of the hard block in the obtained block copolymer was 3% by weight and the content of the soft block was 97% by weight.
- a part of the reaction solution is collected, 4000 parts by weight of n-hexane is added thereto, and the mixture is stirred to precipitate the reaction product, and then the unreacted monomers (MA, BA, AAc) and the solvent are filtered to react.
- the product was dried under reduced pressure at 70 ° C. to obtain a block copolymer.
- the weight average molecular weight of the obtained block copolymer was measured by the GPC method and found to be 391,000.
- "2690 Separations Module" manufactured by Water Co., Ltd.
- the obtained block copolymer was dissolved in ethyl acetate so that the solid content was 35%.
- 3.3 parts by weight of Expandel 461-DU-40 (461DU40) manufactured by Nippon Philite
- Tetrad C epoxy-based cross-linking
- Agent manufactured by Mitsubishi Gas Chemical Company, Ltd. 0.16 parts by weight was added at a solid content ratio and further sufficiently stirred to obtain a substrate solution.
- the obtained base material solution was applied onto one side of a 23 ⁇ m polyethylene terephthalate (PET) film having corona treatment on both sides as a resin layer, and dried at 90 ° C. for 7 minutes to obtain an unfoamed base material and a resin. A laminate with the layer was obtained.
- PET polyethylene terephthalate
- the obtained adhesive solution was applied with a doctor knife so that the thickness of the dry film was 75 ⁇ m, and 110 The coating solution was dried by heating at ° C. for 5 minutes to obtain a pressure-sensitive adhesive layer.
- Another pressure-sensitive adhesive layer was manufactured by the same operation. Then, the pressure-sensitive adhesive layer was laminated on each surface of the laminate of the unfoamed base material and the resin layer obtained above to obtain a laminate.
- the unfoamed substrate is allowed to stand in an environment of 40 ° C. for 48 hours, removed from the environment at 40 ° C. after 48 hours, and heated at 130 ° C. for 1 minute to foam the unfoamed substrate to form a foamed substrate (thickness 127 ⁇ m), which is an adhesive tape.
- the S component is Gaussian type, M component and L in the relaxation curve obtained at 25 ° C according to the product manual.
- the components used were the exponential type, and all the relaxation curves obtained at 85 ° C. were fitted with the exponential type.
- the following formulas were used for fitting at 25 ° C and 85 ° C, respectively.
- w1 to w3 are Weibull coefficients. At 25 ° C, w1 takes a value of 2 and w2 and w3 take a value of 1.
- A1 is the S component
- B1 is the M component
- C1 is the L component ratio
- T2A is the S component
- T2B is the M component
- T2C is the L component.
- t is time.
- w1 and 2 take a value of 1.
- A1 is the component ratio of the S component
- B1 is the component ratio of the L component
- T2A is the relaxation time of the S component
- T2B is the relaxation time of the L component.
- t is time.
- Examples 2 to 9, Comparative Examples 1 to 2 An adhesive tape was obtained in the same manner as in Example 1 except that the base material and the resin layer were changed as shown in Table 1.
- a copolymer was obtained by a one-step synthetic reaction (random copolymerization) using only ABN-E without using a RAFT agent.
- Comparative Example 2 a 30% toluene solution of Septon 2063 (styrene-ethylene-propylene-styrene block polymer resin, manufactured by Kuraray Co., Ltd.) was used, and Tetrad C (epoxy-based cross-linking agent, manufactured by Mitsubishi Gas Chemical Company, Inc.) was used as a cross-linking agent. was not added.
- the raw materials in the table are as follows.
- Foaming agent (foaming particles)
- Advansel EML101 manufactured by Sekisui Chemical Co., Ltd., the heating and foaming process of the unfoamed substrate was performed at 150 ° C. for 1 minute
- Evaluation of heat retention (holding power test) 1 and 2 show a diagram schematically showing a holding force test of the adhesive tape.
- one surface (surface) of the test piece 1 having an adhesive tape size of 25 mm ⁇ 25 mm is attached to the SUS plate 2 and the other side of the test piece 1 is attached.
- a 2 kg rubber roller was reciprocated once from the front surface (back surface) side at a speed of 300 mm / min.
- the aluminum plate 3 is attached to the back surface of the test piece 1, pressed from the side of the aluminum plate 3 with a weight of 0.5 kg for 10 seconds to be crimped, and then left in an environment of 23 ° C. and 50% relative humidity for 24 hours.
- a sample for holding force test was prepared.
- a 1 kg weight 4 is attached to one end of the aluminum plate 3 so that a load is applied horizontally to the test piece 1 and the aluminum plate 3 at 85 ° C. for the holding force test sample, and the amount of deviation of the weight after 1 hour ( The deviation length) was measured.
- ⁇ when the amount of deviation was larger than 0 mm and less than 1 mm the amount of deviation was 1 mm or more, or the adhesive tape fell off.
- the case was set to x.
- an adhesive tape having excellent heat retention and holding property, which is difficult to peel off when a load is applied at a high temperature.
- Test piece (adhesive tape) 2 SUS plate 3 Aluminum plate 4 Weight (1 kg)
Abstract
The purpose of the present invention is to provide an adhesive tape that has excellent heat resistance retention and does not easily peel when subjected to loads at high temperatures. The present invention is an adhesive tape that includes a substrate and an adhesive layer that is layered on at least one surface of the substrate, the relaxation time (TL25) of the L component as measured by the Hahn Echo method at 25°C using pulse NMR being no more than 0.9 miliseconds. The present invention is also an adhesive tape that includes a substrate and an adhesive layer that is layered on at least one surface of the substrate, the relaxation time (TL85) of the L component as measured by the Hahn Echo method at 85°C using pulse NMR being no more than 3.3 miliseconds.
Description
本発明は、粘着テープに関する。
The present invention relates to an adhesive tape.
携帯電話、携帯情報端末（Ｐｅｒｓｏｎａｌ Ｄｉｇｉｔａｌ Ａｓｓｉｓｔａｎｔｓ、ＰＤＡ）等の携帯電子機器においては、組み立てのために粘着テープが用いられている（例えば、特許文献１、２）。また、車載用パネル等の車載用電子機器部品を車両本体に固定する用途にも粘着テープが用いられている。
Adhesive tapes are used for assembly in mobile electronic devices such as mobile phones and personal digital assistants (PDAs) (for example, Patent Documents 1 and 2). Adhesive tapes are also used for fixing in-vehicle electronic device parts such as in-vehicle panels to the vehicle body.
携帯電子機器部品、車載用電子機器部品等の固定に用いられる粘着テープには、高い粘着力が求められるとともに衝撃によっても剥離しない耐衝撃性が求められる。一方、近年の携帯電子機器、車載用電子機器等は、高機能化に伴って形状がより複雑化する傾向にあるため、段差、角、非平面部等に粘着テープを貼り付けて用いることがある。このような場合、粘着テープには被着体の形状に追従できる優れた柔軟性が要求される。
Adhesive tapes used for fixing portable electronic device parts, in-vehicle electronic device parts, and the like are required to have high adhesive strength and impact resistance that does not peel off even when impacted. On the other hand, in recent years, portable electronic devices, in-vehicle electronic devices, etc. tend to have more complicated shapes due to higher functionality. be. In such a case, the adhesive tape is required to have excellent flexibility to follow the shape of the adherend.
柔軟性と耐衝撃性とに優れた粘着テープとして、例えば、ポリオレフィン樹脂等を発泡させた発泡体基材を用いた粘着テープが知られている。しかしながら、近年、電子機器は、使用条件の過酷化、カーエレクトロニクス分野への適用等によって従来以上に高温下で長時間使用されることが増えており、従来の発泡体基材を用いた粘着テープでは、高温下でせん断方向等に負荷がかかった際に剥離しやすいという問題がある。
As an adhesive tape having excellent flexibility and impact resistance, for example, an adhesive tape using a foam base material obtained by foaming a polyolefin resin or the like is known. However, in recent years, electronic devices have been increasingly used for a long time at higher temperatures than before due to harsher usage conditions, application to the car electronics field, etc., and adhesive tapes using conventional foam base materials have been used. Then, there is a problem that it is easy to peel off when a load is applied to the shearing direction or the like at high temperature.
本発明は、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープを提供することを目的とする。
An object of the present invention is to provide an adhesive tape having excellent heat-retaining properties, which is difficult to peel off when a load is applied under high temperature.
本発明は、基材と、上記基材の少なくとも一方の面に積層された粘着剤層とを有する粘着テープであって、パルスＮＭＲを用いて２５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ２５）が０．９ミリ秒以下である粘着テープである。また、本発明は、基材と、上記基材の少なくとも一方の面に積層された粘着剤層とを有する粘着テープであって、パルスＮＭＲを用いて８５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ８５）が３．３ミリ秒以下である粘着テープである。
以下に本発明を詳述する。 The present invention is an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate, and is obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR. This is an adhesive tape having a relaxation time ( TL25 ) of the L component of 0.9 ms or less. Further, the present invention is an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate, which is measured by the Han Echo method at 85 ° C. using pulse NMR. It is an adhesive tape having a relaxation time ( TL85 ) of the obtained L component of 3.3 ms or less.
The present invention will be described in detail below.
以下に本発明を詳述する。 The present invention is an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate, and is obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR. This is an adhesive tape having a relaxation time ( TL25 ) of the L component of 0.9 ms or less. Further, the present invention is an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate, which is measured by the Han Echo method at 85 ° C. using pulse NMR. It is an adhesive tape having a relaxation time ( TL85 ) of the obtained L component of 3.3 ms or less.
The present invention will be described in detail below.
本発明者らは、基材と、該基材の少なくとも一方の面に積層された粘着剤層とを有する粘着テープについて、１Ｈ核を測定するパルスＮＭＲを用いて分析を行った。パルスＮＭＲでは、得られた１Ｈ核のスピン－スピン緩和の自由誘導減衰曲線を複数の成分に波形分離し、それぞれの成分の「緩和時間」を得ることで、その成分の分子運動性を評価することができる。
本発明者らは、パルスＮＭＲを用いて２５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ２５）を特定値以下に調整することで、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープが得られることを見出した。また、本発明者らは、パルスＮＭＲを用いて８５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ８５）を特定値以下に調整することでも、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープが得られることを見出し、本発明を完成させるに至った。 The present inventors analyzed an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate by using pulse NMR for measuring 1H nuclei. In pulse NMR, the obtained 1H nucleus spin - spin relaxation free induction decay curve is waveform-separated into multiple components, and the "relaxation time" of each component is obtained to evaluate the molecular motility of that component. can do.
The present inventors adjust the relaxation time ( TL25 ) of the L component obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR to a specific value or less, whereby a load is applied at a high temperature. It has been found that an adhesive tape having excellent heat-retaining properties, which is difficult to peel off at the time, can be obtained. In addition, the present inventors can also adjust the relaxation time ( TL85 ) of the L component obtained by the Han Echo method at 85 ° C. using pulsed NMR to a specific value or less to load the product under high temperature. We have found that an adhesive tape having excellent heat-retaining properties, which is difficult to peel off when it is applied, can be obtained, and have completed the present invention.
本発明者らは、パルスＮＭＲを用いて２５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ２５）を特定値以下に調整することで、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープが得られることを見出した。また、本発明者らは、パルスＮＭＲを用いて８５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ８５）を特定値以下に調整することでも、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープが得られることを見出し、本発明を完成させるに至った。 The present inventors analyzed an adhesive tape having a substrate and an adhesive layer laminated on at least one surface of the substrate by using pulse NMR for measuring 1H nuclei. In pulse NMR, the obtained 1H nucleus spin - spin relaxation free induction decay curve is waveform-separated into multiple components, and the "relaxation time" of each component is obtained to evaluate the molecular motility of that component. can do.
The present inventors adjust the relaxation time ( TL25 ) of the L component obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR to a specific value or less, whereby a load is applied at a high temperature. It has been found that an adhesive tape having excellent heat-retaining properties, which is difficult to peel off at the time, can be obtained. In addition, the present inventors can also adjust the relaxation time ( TL85 ) of the L component obtained by the Han Echo method at 85 ° C. using pulsed NMR to a specific value or less to load the product under high temperature. We have found that an adhesive tape having excellent heat-retaining properties, which is difficult to peel off when it is applied, can be obtained, and have completed the present invention.
本発明の粘着テープは、基材と、上記基材の少なくとも一方の面に積層された粘着剤層とを有する。
The pressure-sensitive adhesive tape of the present invention has a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material.
本発明の粘着テープは、パルスＮＭＲを用いて２５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ２５）の上限が０．９ミリ秒である。或いは、本発明の粘着テープは、パルスＮＭＲを用いて８５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ８５）の上限が３．３ミリ秒である。
In the adhesive tape of the present invention, the upper limit of the relaxation time ( TL25 ) of the L component obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR is 0.9 ms. Alternatively, in the adhesive tape of the present invention, the upper limit of the relaxation time ( TL85 ) of the L component obtained by measuring at 85 ° C. by the Han Echo method using pulse NMR is 3.3 milliseconds.
ここで、「パルスＮＭＲを用いて２５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分」とは、パルスＮＭＲを用いて２５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られた１Ｈ核のスピン－スピン緩和の自由誘導減衰曲線を、緩和時間の短い順に３つの成分に波形分離したときの、緩和時間が最も長い成分を意味する。３つの成分（緩和時間の短い順にそれぞれＳ成分、Ｍ成分及びＬ成分）への波形分離は、自由誘導減衰曲線を最小二乗法で解析することにより行う。
Here, the "L component obtained by measuring with the Han Echo method at 25 ° C. using pulse NMR" is 1 H obtained by measuring with the Han Echo method at 25 ° C. using pulsed NMR. It means the component with the longest relaxation time when the free induction decay curve of nuclear spin-spin relaxation is waveform-separated into three components in the order of shortest relaxation time. Waveform separation into three components (S component, M component and L component, respectively in the order of shorter relaxation time) is performed by analyzing the free induction decay curve by the method of least squares.
「緩和時間」とは、磁場をかけた後、電子スピンが励起状態から基底状態に戻るまでの時間であり、「緩和時間」が長いほど、分子運動性が高いことを意味する。即ち、Ｓ成分は、緩和時間が最も短く、磁化強度がすぐに減衰する、分子運動性が比較的低い硬い成分である。Ｍ成分は、Ｓ成分とＬ成分との中間の緩和時間及び分子運動性を有する成分である。Ｌ成分は、緩和時間が最も長く、磁化強度の減衰に時間がかかる、分子運動性が比較的高い柔らかい成分である。
上記２５℃でのＬ成分の緩和時間（ＴＬ２５）が０．９ミリ秒以下であれば、本発明の粘着テープは、分子運動性が比較的高いＬ成分の２５℃での分子運動性が抑えられることで、高温下で負荷がかかった際に剥離しにくくなる。上記２５℃でのＬ成分の緩和時間（ＴＬ２５）の好ましい上限は０．８ミリ秒、より好ましい上限は０．６ミリ秒、更に好ましい上限は０．４ミリ秒である。上記２５℃でのＬ成分の緩和時間（ＴＬ２５）の下限は特に限定されないが、粘着テープの柔軟性を確保する観点から、好ましい下限は０．０５ミリ秒、より好ましい下限は０．１ミリ秒である。
なお、２５℃でのＬ成分の緩和時間（ＴＬ２５）は、パルスＮＭＲ装置（例えば、ｔｈｅ ｍｉｎｉｓｐｅｃ ｍｑ２０、ＢＲＵＫＥＲ社製等）及び解析ソフトウエア（例えば、ＴＤ－ＮＭＲＡ、ＢＲＵＫＥＲ社製等）を用い、粘着テープを測定サンプルとして、２５℃でＨａｈｎ Ｅｃｈｏ法にて測定することができる。 The "relaxation time" is the time from the excited state to the ground state of the electron spin after the magnetic field is applied, and the longer the "relaxation time" is, the higher the molecular motility is. That is, the S component is a hard component having a relatively low molecular motility, having the shortest relaxation time and immediately decaying the magnetization strength. The M component is a component having an intermediate relaxation time and molecular motility between the S component and the L component. The L component is a soft component having a relatively high molecular motility, which has the longest relaxation time and takes a long time to decay the magnetization strength.
If the relaxation time ( TL25 ) of the L component at 25 ° C is 0.9 ms or less, the adhesive tape of the present invention has a relatively high molecular mobility of the L component at 25 ° C. By being suppressed, it becomes difficult to peel off when a load is applied under high temperature. The preferred upper limit of the relaxation time ( TL25 ) of the L component at 25 ° C. is 0.8 ms, the more preferred upper limit is 0.6 ms, and the more preferred upper limit is 0.4 ms. The lower limit of the relaxation time ( TL25 ) of the L component at 25 ° C. is not particularly limited, but from the viewpoint of ensuring the flexibility of the adhesive tape, the preferable lower limit is 0.05 ms and the more preferable lower limit is 0.1 mm. Seconds.
The relaxation time of the L component ( TL25 ) at 25 ° C. was determined by using a pulse NMR device (for example, the minispec mq20, manufactured by BRUKER, etc.) and analysis software (for example, TD-NMRA, manufactured by BRUKER, etc.). , Adhesive tape can be used as a measurement sample and measured by the Han Echo method at 25 ° C.
上記２５℃でのＬ成分の緩和時間（ＴＬ２５）が０．９ミリ秒以下であれば、本発明の粘着テープは、分子運動性が比較的高いＬ成分の２５℃での分子運動性が抑えられることで、高温下で負荷がかかった際に剥離しにくくなる。上記２５℃でのＬ成分の緩和時間（ＴＬ２５）の好ましい上限は０．８ミリ秒、より好ましい上限は０．６ミリ秒、更に好ましい上限は０．４ミリ秒である。上記２５℃でのＬ成分の緩和時間（ＴＬ２５）の下限は特に限定されないが、粘着テープの柔軟性を確保する観点から、好ましい下限は０．０５ミリ秒、より好ましい下限は０．１ミリ秒である。
なお、２５℃でのＬ成分の緩和時間（ＴＬ２５）は、パルスＮＭＲ装置（例えば、ｔｈｅ ｍｉｎｉｓｐｅｃ ｍｑ２０、ＢＲＵＫＥＲ社製等）及び解析ソフトウエア（例えば、ＴＤ－ＮＭＲＡ、ＢＲＵＫＥＲ社製等）を用い、粘着テープを測定サンプルとして、２５℃でＨａｈｎ Ｅｃｈｏ法にて測定することができる。 The "relaxation time" is the time from the excited state to the ground state of the electron spin after the magnetic field is applied, and the longer the "relaxation time" is, the higher the molecular motility is. That is, the S component is a hard component having a relatively low molecular motility, having the shortest relaxation time and immediately decaying the magnetization strength. The M component is a component having an intermediate relaxation time and molecular motility between the S component and the L component. The L component is a soft component having a relatively high molecular motility, which has the longest relaxation time and takes a long time to decay the magnetization strength.
If the relaxation time ( TL25 ) of the L component at 25 ° C is 0.9 ms or less, the adhesive tape of the present invention has a relatively high molecular mobility of the L component at 25 ° C. By being suppressed, it becomes difficult to peel off when a load is applied under high temperature. The preferred upper limit of the relaxation time ( TL25 ) of the L component at 25 ° C. is 0.8 ms, the more preferred upper limit is 0.6 ms, and the more preferred upper limit is 0.4 ms. The lower limit of the relaxation time ( TL25 ) of the L component at 25 ° C. is not particularly limited, but from the viewpoint of ensuring the flexibility of the adhesive tape, the preferable lower limit is 0.05 ms and the more preferable lower limit is 0.1 mm. Seconds.
The relaxation time of the L component ( TL25 ) at 25 ° C. was determined by using a pulse NMR device (for example, the minispec mq20, manufactured by BRUKER, etc.) and analysis software (for example, TD-NMRA, manufactured by BRUKER, etc.). , Adhesive tape can be used as a measurement sample and measured by the Han Echo method at 25 ° C.
また、ここで、「パルスＮＭＲを用いて８５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分」とは、パルスＮＭＲを用いて８５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られた１Ｈ核のスピン－スピン緩和の自由誘導減衰曲線を、緩和時間の短い順にＳ成分及びＬ成分の２つの成分に波形分離したときのＬ成分を意味する。２つの成分への波形分離は、自由誘導減衰曲線を最小二乗法で解析することにより行う。
Further, here, "the L component obtained by measuring with the Han Echo method at 85 ° C. using pulse NMR" was obtained by measuring with the Han Echo method at 85 ° C. using pulse NMR. 1 It means the L component when the free induction decay curve of spin-spin relaxation of H nucleus is waveform-separated into two components, S component and L component, in the order of shortest relaxation time. The waveform separation into two components is performed by analyzing the free induction decay curve by the method of least squares.
上記８５℃でのＬ成分の緩和時間（ＴＬ８５）が３．３ミリ秒以下であれば、本発明の粘着テープは、分子運動性が比較的高いＬ成分の８５℃での分子運動性が抑えられることで、高温下で負荷がかかった際に剥離しにくくなる。上記８５℃でのＬ成分の緩和時間（ＴＬ８５）のより好ましい上限は３ミリ秒、更に好ましい上限は２．５ミリ秒である。上記８５℃でのＬ成分の緩和時間（ＴＬ８５）の下限は特に限定されないが、粘着テープの柔軟性を確保する観点から、好ましい下限は０．５ミリ秒、より好ましい下限は１ミリ秒である。
If the relaxation time ( TL85 ) of the L component at 85 ° C. is 3.3 ms or less, the adhesive tape of the present invention has a relatively high molecular mobility of the L component at 85 ° C. By being suppressed, it becomes difficult to peel off when a load is applied under high temperature. The more preferable upper limit of the relaxation time ( TL85 ) of the L component at 85 ° C. is 3 ms, and the more preferable upper limit is 2.5 ms. The lower limit of the relaxation time ( TL85 ) of the L component at 85 ° C. is not particularly limited, but from the viewpoint of ensuring the flexibility of the adhesive tape, the preferable lower limit is 0.5 ms, and the more preferable lower limit is 1 ms. be.
上記２５℃でのＬ成分の緩和時間（ＴＬ２５）、及び、上記８５℃でのＬ成分の緩和時間（ＴＬ８５）を上記範囲に調整する方法は特に限定されず、例えば、上記基材に、後述するようなビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体を用いる方法等が挙げられる。また、このような共重合体の重量平均分子量（Ｍｗ）を調整する方法、上記基材における発泡粒子の含有量を調整する方法等も挙げられる。更に、上記粘着剤層の組成を調整する方法、上記粘着剤層を構成する樹脂の重量平均分子量（Ｍｗ）を調整する方法等も挙げられる。
より具体的には、緩和時間を短くする方法としては、上記基材又は上記粘着剤層において、ビニル芳香族モノマーに由来する構造を導入する方法、ブロック共重合体における後述するハードブロックの含有量を増加させる方法、架橋構造を導入したり、その架橋度を増加させたりする方法等が挙げられる。更に、上記基材又は上記粘着剤層において、分子間の絡み合いを増加させる（即ち、側鎖の短いモノマーを増やしたり、側鎖の長いモノマーを減らしたりする）方法、分子鎖の運動性を下げる（例えば、脂環式構造を導入する）方法、極性相互作用を増加させる（例えば、酸又は水酸基を導入したり、その量を増やしたりする）方法等も挙げられる。更に、上記基材又は上記粘着剤層において、ガラス転移温度（Ｔｇ）がより高くなるように原料モノマーを選定する方法、分子量を増やす方法、フィラーを添加する方法等も挙げられる。 The method for adjusting the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) within the above ranges is not particularly limited, and for example, the substrate can be used. , A method using a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer, which will be described later, and the like can be mentioned. Further, a method of adjusting the weight average molecular weight (Mw) of such a copolymer, a method of adjusting the content of foamed particles in the above-mentioned substrate, and the like can be mentioned. Further, a method of adjusting the composition of the pressure-sensitive adhesive layer, a method of adjusting the weight average molecular weight (Mw) of the resin constituting the pressure-sensitive adhesive layer, and the like can be mentioned.
More specifically, as a method for shortening the relaxation time, a method for introducing a structure derived from a vinyl aromatic monomer in the base material or the pressure-sensitive adhesive layer, and the content of hard blocks described later in the block copolymer. Examples thereof include a method of increasing the number of crosslinks, a method of introducing a crosslinked structure, and a method of increasing the degree of crosslinking thereof. Further, in the substrate or the pressure-sensitive adhesive layer, a method of increasing the entanglement between molecules (that is, increasing the number of monomers having a short side chain or decreasing the number of monomers having a long side chain), and reducing the motility of the molecular chain. Examples include a method (for example, introducing an alicyclic structure), a method of increasing polar interaction (for example, introducing an acid or a hydroxyl group, or increasing the amount thereof), and the like. Further, a method of selecting a raw material monomer so that the glass transition temperature (Tg) becomes higher in the base material or the pressure-sensitive adhesive layer, a method of increasing the molecular weight, a method of adding a filler, and the like can be mentioned.
より具体的には、緩和時間を短くする方法としては、上記基材又は上記粘着剤層において、ビニル芳香族モノマーに由来する構造を導入する方法、ブロック共重合体における後述するハードブロックの含有量を増加させる方法、架橋構造を導入したり、その架橋度を増加させたりする方法等が挙げられる。更に、上記基材又は上記粘着剤層において、分子間の絡み合いを増加させる（即ち、側鎖の短いモノマーを増やしたり、側鎖の長いモノマーを減らしたりする）方法、分子鎖の運動性を下げる（例えば、脂環式構造を導入する）方法、極性相互作用を増加させる（例えば、酸又は水酸基を導入したり、その量を増やしたりする）方法等も挙げられる。更に、上記基材又は上記粘着剤層において、ガラス転移温度（Ｔｇ）がより高くなるように原料モノマーを選定する方法、分子量を増やす方法、フィラーを添加する方法等も挙げられる。 The method for adjusting the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) within the above ranges is not particularly limited, and for example, the substrate can be used. , A method using a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer, which will be described later, and the like can be mentioned. Further, a method of adjusting the weight average molecular weight (Mw) of such a copolymer, a method of adjusting the content of foamed particles in the above-mentioned substrate, and the like can be mentioned. Further, a method of adjusting the composition of the pressure-sensitive adhesive layer, a method of adjusting the weight average molecular weight (Mw) of the resin constituting the pressure-sensitive adhesive layer, and the like can be mentioned.
More specifically, as a method for shortening the relaxation time, a method for introducing a structure derived from a vinyl aromatic monomer in the base material or the pressure-sensitive adhesive layer, and the content of hard blocks described later in the block copolymer. Examples thereof include a method of increasing the number of crosslinks, a method of introducing a crosslinked structure, and a method of increasing the degree of crosslinking thereof. Further, in the substrate or the pressure-sensitive adhesive layer, a method of increasing the entanglement between molecules (that is, increasing the number of monomers having a short side chain or decreasing the number of monomers having a long side chain), and reducing the motility of the molecular chain. Examples include a method (for example, introducing an alicyclic structure), a method of increasing polar interaction (for example, introducing an acid or a hydroxyl group, or increasing the amount thereof), and the like. Further, a method of selecting a raw material monomer so that the glass transition temperature (Tg) becomes higher in the base material or the pressure-sensitive adhesive layer, a method of increasing the molecular weight, a method of adding a filler, and the like can be mentioned.
上記基材は特に限定されないが、ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体を含有することが好ましい。上記基材がこのような共重合体を含有することにより、上記２５℃でのＬ成分の緩和時間（ＴＬ２５）、及び、上記８５℃でのＬ成分の緩和時間（ＴＬ８５）を上記範囲に調整することが容易となり、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。
The base material is not particularly limited, but preferably contains a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer. When the substrate contains such a copolymer, the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) are within the above ranges. It becomes easy to adjust to, and it becomes more difficult for the adhesive tape to peel off when a load is applied under high temperature.
上記ビニル芳香族モノマーとしては例えば、スチレン、アルファメチルスチレン、パラメチルスチレン、クロロスチレン等が挙げられる。これらのビニル芳香族モノマーは単独で用いられてもよく、２種以上が併用されてもよい。なかでも、高温下で負荷がかかった際に粘着テープがより剥離しにくくなることから、スチレンが好ましい。なお、本明細書においてビニル芳香族モノマーに由来する構造とは、下記一般式（１）及び（２）に示すような構造のことを指す。
Examples of the vinyl aromatic monomer include styrene, alpha-methylstyrene, paramethylstyrene, chlorostyrene and the like. These vinyl aromatic monomers may be used alone or in combination of two or more. Of these, styrene is preferable because the adhesive tape is more difficult to peel off when a load is applied under high temperature. In the present specification, the structure derived from the vinyl aromatic monomer refers to the structure represented by the following general formulas (1) and (2).
一般式（１）及び（２）中、Ｒ１は芳香環を有する置換基を表す。芳香環を有する置換基Ｒ１としては、フェニル基、メチルフェニル基、クロロフェニル基等が挙げられる。
In the general formulas (1) and (2), R 1 represents a substituent having an aromatic ring. Examples of the substituent R1 having an aromatic ring include a phenyl group, a methylphenyl group, a chlorophenyl group and the like.
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体中、上記ビニル芳香族モノマーに由来する構造の含有量は特に限定されないが、１重量％以上、３０重量％以下であることが好ましい。上記ビニル芳香族モノマーに由来する構造の含有量が上記範囲であることで、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記ビニル芳香族モノマーに由来する構造の含有量のより好ましい下限は１．５重量％、更に好ましい下限は２重量％、更により好ましい下限は２．５重量％、特に好ましい下限は３重量％、とりわけ好ましい下限は４重量％、より好ましい上限は２５重量％、更に好ましい上限は２０重量％、特に好ましい上限は１５重量％である。
The content of the structure derived from the vinyl aromatic monomer in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, but is 1% by weight or more. It is preferably 30% by weight or less. When the content of the structure derived from the vinyl aromatic monomer is in the above range, the adhesive tape is less likely to be peeled off when a load is applied at a high temperature. A more preferable lower limit of the content of the structure derived from the vinyl aromatic monomer is 1.5% by weight, a further preferable lower limit is 2% by weight, a further preferable lower limit is 2.5% by weight, and a particularly preferable lower limit is 3% by weight. A particularly preferable lower limit is 4% by weight, a more preferable upper limit is 25% by weight, a further preferable upper limit is 20% by weight, and a particularly preferable upper limit is 15% by weight.
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体は、更に、架橋性官能基を有するモノマーに由来する構造を有することが好ましい。
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体が架橋性官能基を有すると、架橋によって該共重合体の凝集力が高まることから、上記２５℃でのＬ成分の緩和時間（ＴＬ２５）、及び、上記８５℃でのＬ成分の緩和時間（ＴＬ８５）を上記範囲に調整することが容易となる。これにより、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記架橋性官能基は架橋されていても架橋されていなくてもよいが、架橋されていることがより好ましい。ただし、架橋されていない構造のままであったとしても、官能基間の相互作用により後述するハードブロック又はソフトブロック（特に、ハードブロック）内の凝集力が向上して、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。なお、本明細書において架橋性官能基を有するモノマーに由来する構造とは、下記一般式（３）及び（４）に示すような構造のことを指す。 It is preferable that the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer further has a structure derived from the monomer having a crosslinkable functional group.
When a copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer has a crosslinkable functional group, the cohesive force of the copolymer is enhanced by the crosslinking. It becomes easy to adjust the relaxation time of the L component at ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) within the above ranges. This makes it more difficult for the adhesive tape to peel off when a load is applied under high temperature. The crosslinkable functional group may or may not be crosslinked, but is more preferably crosslinked. However, even if the structure remains uncrosslinked, the cohesive force in the hard block or soft block (particularly the hard block) described later is improved by the interaction between the functional groups, and a load is applied at high temperature. At that time, the adhesive tape becomes more difficult to peel off. In the present specification, the structure derived from the monomer having a crosslinkable functional group refers to the structure represented by the following general formulas (3) and (4).
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体が架橋性官能基を有すると、架橋によって該共重合体の凝集力が高まることから、上記２５℃でのＬ成分の緩和時間（ＴＬ２５）、及び、上記８５℃でのＬ成分の緩和時間（ＴＬ８５）を上記範囲に調整することが容易となる。これにより、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記架橋性官能基は架橋されていても架橋されていなくてもよいが、架橋されていることがより好ましい。ただし、架橋されていない構造のままであったとしても、官能基間の相互作用により後述するハードブロック又はソフトブロック（特に、ハードブロック）内の凝集力が向上して、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。なお、本明細書において架橋性官能基を有するモノマーに由来する構造とは、下記一般式（３）及び（４）に示すような構造のことを指す。 It is preferable that the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer further has a structure derived from the monomer having a crosslinkable functional group.
When a copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer has a crosslinkable functional group, the cohesive force of the copolymer is enhanced by the crosslinking. It becomes easy to adjust the relaxation time of the L component at ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) within the above ranges. This makes it more difficult for the adhesive tape to peel off when a load is applied under high temperature. The crosslinkable functional group may or may not be crosslinked, but is more preferably crosslinked. However, even if the structure remains uncrosslinked, the cohesive force in the hard block or soft block (particularly the hard block) described later is improved by the interaction between the functional groups, and a load is applied at high temperature. At that time, the adhesive tape becomes more difficult to peel off. In the present specification, the structure derived from the monomer having a crosslinkable functional group refers to the structure represented by the following general formulas (3) and (4).
一般式（３）及び（４）中、Ｒ２は少なくとも１つの官能基を含む置換基を表す。官能基としては、例えば、カルボキシル基、水酸基、エポキシ基、二重結合、三重結合、アミノ基、アミド基、ニトリル基等が挙げられる。なお、少なくとも１つの官能基を含む置換基Ｒ２は、その構成要素として、アルキル基、エーテル基、カルボニル基、エステル基、カーボネート基、アミド基、ウレタン基等を含んでいてもよい。
In the general formulas (3) and (4), R 2 represents a substituent containing at least one functional group. Examples of the functional group include a carboxyl group, a hydroxyl group, an epoxy group, a double bond, a triple bond, an amino group, an amide group, a nitrile group and the like. The substituent R2 containing at least one functional group may contain an alkyl group, an ether group, a carbonyl group, an ester group, a carbonate group, an amide group, a urethane group and the like as its constituent elements.
上記架橋性官能基を有するモノマーは特に限定されず、例えば、カルボキシル基含有モノマー、水酸基含有モノマー、エポキシ基含有モノマー、二重結合含有モノマー、三重結合含有モノマー、アミノ基含有モノマー、アミド基含有モノマー、ニトリル基含有モノマー等が挙げられる。これらの架橋性官能基を有するモノマーは単独で用いられてもよく、２種以上が併用されてもよい。なかでも、高温下で負荷がかかった際に粘着テープがより剥離しにくくなることから、カルボキシル基含有モノマー、水酸基含有モノマー、エポキシ基含有モノマー、二重結合含有モノマー、三重結合含有モノマー及びアミド基含有モノマーからなる群から選択される少なくとも１種が好ましい。
上記カルボキシル基含有モノマーとしては、（メタ）アクリル酸等の（メタ）アクリル酸系モノマーが挙げられる。上記水酸基含有モノマーとしては、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート等が挙げられる。上記エポキシ基含有モノマーとしては、グリシジル（メタ）アクリレート等が挙げられる。上記二重結合含有モノマーとしては、アリル（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート等が挙げられる。上記三重結合含有モノマーとしては、プロパルギル（メタ）アクリレート等が挙げられる。上記アミド基含有モノマーとしては、（メタ）アクリルアミド等が挙げられる。なかでも、高温下で負荷がかかった際に粘着テープが更に剥離しにくくなることから、カルボキシル基含有モノマー、水酸基含有モノマーが好ましい。更に、カルボキシル基を含む（メタ）アクリル酸系モノマー、水酸基を含む（メタ）アクリル酸系モノマーがより好ましく、（メタ）アクリル酸、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレートが更に好ましい。 The monomer having a crosslinkable functional group is not particularly limited, and for example, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, an amino group-containing monomer, and an amide group-containing monomer. , A nitrile group-containing monomer and the like. These crosslinkable functional groups may be used alone or in combination of two or more. In particular, since the adhesive tape is more difficult to peel off when a load is applied at high temperature, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, and an amide group. At least one selected from the group consisting of contained monomers is preferable.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid-based monomers such as (meth) acrylic acid. Examples of the hydroxyl group-containing monomer include 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and the like. Examples of the double bond-containing monomer include allyl (meth) acrylate and hexanediol di (meth) acrylate. Examples of the triple bond-containing monomer include propargyl (meth) acrylate and the like. Examples of the amide group-containing monomer include (meth) acrylamide and the like. Of these, a carboxyl group-containing monomer and a hydroxyl group-containing monomer are preferable because the adhesive tape is more difficult to peel off when a load is applied at a high temperature. Further, a (meth) acrylic acid-based monomer containing a carboxyl group and a (meth) acrylic acid-based monomer containing a hydroxyl group are more preferable, and (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) are preferable. Acrylic is more preferred.
上記カルボキシル基含有モノマーとしては、（メタ）アクリル酸等の（メタ）アクリル酸系モノマーが挙げられる。上記水酸基含有モノマーとしては、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート等が挙げられる。上記エポキシ基含有モノマーとしては、グリシジル（メタ）アクリレート等が挙げられる。上記二重結合含有モノマーとしては、アリル（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート等が挙げられる。上記三重結合含有モノマーとしては、プロパルギル（メタ）アクリレート等が挙げられる。上記アミド基含有モノマーとしては、（メタ）アクリルアミド等が挙げられる。なかでも、高温下で負荷がかかった際に粘着テープが更に剥離しにくくなることから、カルボキシル基含有モノマー、水酸基含有モノマーが好ましい。更に、カルボキシル基を含む（メタ）アクリル酸系モノマー、水酸基を含む（メタ）アクリル酸系モノマーがより好ましく、（メタ）アクリル酸、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレートが更に好ましい。 The monomer having a crosslinkable functional group is not particularly limited, and for example, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, an amino group-containing monomer, and an amide group-containing monomer. , A nitrile group-containing monomer and the like. These crosslinkable functional groups may be used alone or in combination of two or more. In particular, since the adhesive tape is more difficult to peel off when a load is applied at high temperature, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, and an amide group. At least one selected from the group consisting of contained monomers is preferable.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid-based monomers such as (meth) acrylic acid. Examples of the hydroxyl group-containing monomer include 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and the like. Examples of the double bond-containing monomer include allyl (meth) acrylate and hexanediol di (meth) acrylate. Examples of the triple bond-containing monomer include propargyl (meth) acrylate and the like. Examples of the amide group-containing monomer include (meth) acrylamide and the like. Of these, a carboxyl group-containing monomer and a hydroxyl group-containing monomer are preferable because the adhesive tape is more difficult to peel off when a load is applied at a high temperature. Further, a (meth) acrylic acid-based monomer containing a carboxyl group and a (meth) acrylic acid-based monomer containing a hydroxyl group are more preferable, and (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) are preferable. Acrylic is more preferred.
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体中、上記架橋性官能基を有するモノマーに由来する構造の含有量は特に限定されないが、０．１重量％以上、３０重量％以下であることが好ましい。上記架橋性官能基を有するモノマーに由来する構造の含有量が上記範囲であることで、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記架橋性官能基を有するモノマーに由来する構造の含有量のより好ましい下限は０．５重量％、更に好ましい下限は１重量％、より好ましい上限は２５重量％、更に好ましい上限は２０重量％である。
The content of the structure derived from the crosslinkable functional group in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, but is 0. It is preferably 1% by weight or more and 30% by weight or less. When the content of the structure derived from the monomer having a crosslinkable functional group is in the above range, the adhesive tape is less likely to be peeled off when a load is applied at a high temperature. A more preferable lower limit of the content of the structure derived from the monomer having a crosslinkable functional group is 0.5% by weight, a further preferable lower limit is 1% by weight, a more preferable upper limit is 25% by weight, and a further preferable upper limit is 20% by weight. be.
上記（メタ）アクリル系モノマーは、単一のものであってもよいし、複数のモノマーを用いてもよい。なお、本明細書において（メタ）アクリル系モノマーに由来する構造とは、下記一般式（５）及び（６）に示すような構造のことを指す。
The (meth) acrylic monomer may be a single monomer or may use a plurality of monomers. In the present specification, the structure derived from the (meth) acrylic monomer refers to the structure represented by the following general formulas (5) and (6).
一般式（５）及び（６）中、Ｒ３は側鎖を表す。側鎖Ｒ３としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルへキシル基、ノニル基、デシル基、ドデシル基、ラウリル基、イソステアリル基等が挙げられる。
In the general formulas (5) and (6), R 3 represents a side chain. The side chain R 3 includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group and a lauryl group. Examples thereof include an isostearyl group.
上記（メタ）アクリル系モノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルへキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソステアリル（メタ）アクリレート等が挙げられる。これらの（メタ）アクリル系モノマーは単独で用いられてもよく、２種以上が併用されてもよい。なかでも、高温下で負荷がかかった際に粘着テープがより剥離しにくくなることから、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルへキシル（メタ）アクリレートが好ましく、メチルアクリレート、エチルアクリレート、ブチルアクリレート、２－エチルへキシルアクリレートが更に好ましい。
Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and heptyl (meth). Meta) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate And so on. These (meth) acrylic monomers may be used alone or in combination of two or more. In particular, since the adhesive tape is more difficult to peel off when a load is applied under high temperature, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Is preferable, and methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are more preferable.
また、上記（メタ）アクリル系モノマーとしては、側鎖炭素数が２以下の（メタ）アクリル系モノマーを用いることが好ましい。上記側鎖炭素数が２以下の（メタ）アクリル系モノマーを用いると、得られる共重合体鎖同士の絡み合いが増加し、凝集力が向上して、上記２５℃でのＬ成分の緩和時間（ＴＬ２５）、及び、上記８５℃でのＬ成分の緩和時間（ＴＬ８５）を上記範囲に調整することが容易となり、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。
上記側鎖炭素数が２以下の（メタ）アクリル系モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレートが挙げられ、特にメチルアクリレート、エチルアクリレートが好ましい。 Further, as the (meth) acrylic monomer, it is preferable to use a (meth) acrylic monomer having 2 or less side chain carbon atoms. When the (meth) acrylic monomer having 2 or less side chains has been used, the entanglement between the obtained copolymer chains is increased, the cohesive force is improved, and the relaxation time of the L component at 25 ° C. is increased. TL25 ) and the relaxation time of the L component ( TL85 ) at 85 ° C. can be easily adjusted to the above range, and the adhesive tape becomes more difficult to peel off when a load is applied under high temperature.
Examples of the (meth) acrylic monomer having 2 or less side chain carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate, and methyl acrylate and ethyl acrylate are particularly preferable.
上記側鎖炭素数が２以下の（メタ）アクリル系モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレートが挙げられ、特にメチルアクリレート、エチルアクリレートが好ましい。 Further, as the (meth) acrylic monomer, it is preferable to use a (meth) acrylic monomer having 2 or less side chain carbon atoms. When the (meth) acrylic monomer having 2 or less side chains has been used, the entanglement between the obtained copolymer chains is increased, the cohesive force is improved, and the relaxation time of the L component at 25 ° C. is increased. TL25 ) and the relaxation time of the L component ( TL85 ) at 85 ° C. can be easily adjusted to the above range, and the adhesive tape becomes more difficult to peel off when a load is applied under high temperature.
Examples of the (meth) acrylic monomer having 2 or less side chain carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate, and methyl acrylate and ethyl acrylate are particularly preferable.
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体中、上記（メタ）アクリル系モノマーに由来する構造の含有量は特に限定されず、本発明の効果が発揮されればよいが、３０重量％以上、９９重量％以下であることが好ましい。上記（メタ）アクリル系モノマーに由来する構造の含有量は、４０重量％以上、９８重量％以下であることがより好ましく、５０重量％以上、９７重量％以下であることが更に好ましい。
The content of the structure derived from the (meth) acrylic monomer in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, and the content of the structure derived from the (meth) acrylic monomer is not particularly limited. The effect may be exhibited, but it is preferably 30% by weight or more and 99% by weight or less. The content of the structure derived from the (meth) acrylic monomer is more preferably 40% by weight or more and 98% by weight or less, and further preferably 50% by weight or more and 97% by weight or less.
また、上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体中、上記側鎖炭素数が２以下の（メタ）アクリル系モノマーの含有量は特に限定されないが、好ましい下限は５重量％、好ましい上限は９０重量％である。上記側鎖炭素数が２以下の（メタ）アクリル系モノマーの含有量が５重量％以上であれば、凝集力向上効果が発現しやすくなる。上記側鎖炭素数が２以下の（メタ）アクリル系モノマーの含有量が９０重量％以下であれば、凝集力が高くなりすぎて柔軟性が低くなって粘着テープとしての柔軟性が失われることを防ぐことができる。上記側鎖炭素数が２以下の（メタ）アクリル系モノマーの含有量のより好ましい下限は１０重量％、更に好ましい下限は２０重量％、更により好ましい下限は２５重量％、特に好ましい下限は３０重量％であり、より好ましい上限は８５重量％、更に好ましい上限は８０重量％、更により好ましい上限は７５重量％、特に好ましい上限は７０重量％である。
Further, in the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer, the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is particularly limited. However, the preferred lower limit is 5% by weight and the preferred upper limit is 90% by weight. When the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 5% by weight or more, the effect of improving the cohesive force is likely to be exhibited. If the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 90% by weight or less, the cohesive force becomes too high, the flexibility becomes low, and the flexibility as an adhesive tape is lost. Can be prevented. A more preferable lower limit of the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 10% by weight, a further preferable lower limit is 20% by weight, a further preferable lower limit is 25% by weight, and a particularly preferable lower limit is 30% by weight. The more preferable upper limit is 85% by weight, the further preferable upper limit is 80% by weight, the still more preferable upper limit is 75% by weight, and the particularly preferable upper limit is 70% by weight.
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体は、上述したような各構造を有していれば特に限定されず、ランダム共重合体であってもよく、ブロック共重合体であってもよい。上記基材の柔軟性をより高める観点からは、ランダム共重合体が好ましく、上記基材の耐熱保持性と柔軟性とのバランスをより高める観点からは、ブロック共重合体が好ましい。
The copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is not particularly limited as long as it has each structure as described above, and is a random copolymer. It may be a block copolymer or a block copolymer. From the viewpoint of further enhancing the flexibility of the base material, a random copolymer is preferable, and from the viewpoint of further enhancing the balance between the heat resistance retention property and the flexibility of the base material, a block copolymer is preferable.
上記ブロック共重合体とは、剛直な構造（以下、「ハードブロック」ともいう）と柔軟な構造（以下、「ソフトブロック」ともいう）とを含む共重合体である。
上記ブロック共重合体は、２つのブロックが相溶し難く、上記ソフトブロックの海の中に上記ハードブロックが凝集してできた島が点在する不均一な相分離構造をとることがある。そして、上記島が疑似架橋点となることで、上記ブロック共重合体にゴム弾性を付与できることから、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記ハードブロックに上述したような架橋性官能基を導入することで、高温下で負荷がかかった際に粘着テープが更に剥離しにくくなる。
なお、上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体がランダム共重合体である場合にも、粘着テープは、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープとなる。これは、ナノレベルや分子レベルといった極小さなスケールにおいて上記相分離構造と同様の相互作用が働いているためではないかと考えられる。 The block copolymer is a copolymer containing a rigid structure (hereinafter, also referred to as "hard block") and a flexible structure (hereinafter, also referred to as "soft block").
The block copolymer may have a non-uniform phase-separated structure in which two blocks are difficult to be compatible with each other and islands formed by agglomeration of the hard blocks are scattered in the sea of the soft blocks. Since the islands serve as pseudo-crosslinking points, rubber elasticity can be imparted to the block copolymer, so that the adhesive tape is less likely to be peeled off when a load is applied at a high temperature. By introducing the crosslinkable functional group as described above into the hard block, the adhesive tape becomes more difficult to peel off when a load is applied at a high temperature.
Even when the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is a random copolymer, the adhesive tape is subjected to a load at a high temperature. It is an adhesive tape with excellent heat retention that is hard to peel off. It is considered that this is because the same interaction as the above-mentioned phase-separated structure works at a very small scale such as the nano level and the molecular level.
上記ブロック共重合体は、２つのブロックが相溶し難く、上記ソフトブロックの海の中に上記ハードブロックが凝集してできた島が点在する不均一な相分離構造をとることがある。そして、上記島が疑似架橋点となることで、上記ブロック共重合体にゴム弾性を付与できることから、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記ハードブロックに上述したような架橋性官能基を導入することで、高温下で負荷がかかった際に粘着テープが更に剥離しにくくなる。
なお、上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体がランダム共重合体である場合にも、粘着テープは、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープとなる。これは、ナノレベルや分子レベルといった極小さなスケールにおいて上記相分離構造と同様の相互作用が働いているためではないかと考えられる。 The block copolymer is a copolymer containing a rigid structure (hereinafter, also referred to as "hard block") and a flexible structure (hereinafter, also referred to as "soft block").
The block copolymer may have a non-uniform phase-separated structure in which two blocks are difficult to be compatible with each other and islands formed by agglomeration of the hard blocks are scattered in the sea of the soft blocks. Since the islands serve as pseudo-crosslinking points, rubber elasticity can be imparted to the block copolymer, so that the adhesive tape is less likely to be peeled off when a load is applied at a high temperature. By introducing the crosslinkable functional group as described above into the hard block, the adhesive tape becomes more difficult to peel off when a load is applied at a high temperature.
Even when the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is a random copolymer, the adhesive tape is subjected to a load at a high temperature. It is an adhesive tape with excellent heat retention that is hard to peel off. It is considered that this is because the same interaction as the above-mentioned phase-separated structure works at a very small scale such as the nano level and the molecular level.
上記ブロック共重合体は、上記ビニル芳香族モノマーに由来する構造が上記ハードブロックに含まれ、上記（メタ）アクリル系モノマーに由来する構造が上記ソフトブロックに含まれていることが好ましい。
上記ハードブロックは、剛直な構造を有していれば特に限定されず、上記ビニル芳香族モノマーに由来する構造に加えて更に、例えば、環状構造を有する化合物、側鎖置換基が短い化合物等に由来する構造を有していてもよく、本発明の効果を失わない範囲で、上記（メタ）アクリル系モノマーに由来する構造を有していてもよい。上記ソフトブロックは、本発明の効果を失わない範囲で、上記（メタ）アクリル系モノマー以外のモノマーに由来する構造を有していてもよい。 It is preferable that the block copolymer contains a structure derived from the vinyl aromatic monomer in the hard block and a structure derived from the (meth) acrylic monomer in the soft block.
The hard block is not particularly limited as long as it has a rigid structure, and in addition to the structure derived from the vinyl aromatic monomer, for example, a compound having a cyclic structure, a compound having a short side chain substituent, or the like can be used. It may have a structure derived from the above (meth) acrylic monomer as long as the effect of the present invention is not lost. The soft block may have a structure derived from a monomer other than the (meth) acrylic monomer as long as the effect of the present invention is not lost.
上記ハードブロックは、剛直な構造を有していれば特に限定されず、上記ビニル芳香族モノマーに由来する構造に加えて更に、例えば、環状構造を有する化合物、側鎖置換基が短い化合物等に由来する構造を有していてもよく、本発明の効果を失わない範囲で、上記（メタ）アクリル系モノマーに由来する構造を有していてもよい。上記ソフトブロックは、本発明の効果を失わない範囲で、上記（メタ）アクリル系モノマー以外のモノマーに由来する構造を有していてもよい。 It is preferable that the block copolymer contains a structure derived from the vinyl aromatic monomer in the hard block and a structure derived from the (meth) acrylic monomer in the soft block.
The hard block is not particularly limited as long as it has a rigid structure, and in addition to the structure derived from the vinyl aromatic monomer, for example, a compound having a cyclic structure, a compound having a short side chain substituent, or the like can be used. It may have a structure derived from the above (meth) acrylic monomer as long as the effect of the present invention is not lost. The soft block may have a structure derived from a monomer other than the (meth) acrylic monomer as long as the effect of the present invention is not lost.
上記ブロック共重合体は、ジブロック構造、トリブロック構造等どのような構造をとっていてもよいが、高温下で負荷がかかった際に粘着テープがより剥離しにくくなることから、上記ハードブロックの間に上記ソフトブロックを有するトリブロック構造を有することが好ましい。
また、上記ブロック共重合体は、上記ハードブロックと上記ソフトブロックとが主鎖と側鎖とに分かれて存在しているようなグラフト共重合体であってもよい。上記グラフト共重合体としては、例えば、スチレンマクロマー－（メタ）アクリル系モノマー共重合体等が挙げられる。 The block copolymer may have any structure such as a diblock structure or a triblock structure, but the adhesive tape is more difficult to peel off when a load is applied at a high temperature, so that the hard block It is preferable to have a triblock structure having the soft block between the two.
Further, the block copolymer may be a graft copolymer in which the hard block and the soft block are separated into a main chain and a side chain. Examples of the graft copolymer include a styrene macromer- (meth) acrylic monomer copolymer and the like.
また、上記ブロック共重合体は、上記ハードブロックと上記ソフトブロックとが主鎖と側鎖とに分かれて存在しているようなグラフト共重合体であってもよい。上記グラフト共重合体としては、例えば、スチレンマクロマー－（メタ）アクリル系モノマー共重合体等が挙げられる。 The block copolymer may have any structure such as a diblock structure or a triblock structure, but the adhesive tape is more difficult to peel off when a load is applied at a high temperature, so that the hard block It is preferable to have a triblock structure having the soft block between the two.
Further, the block copolymer may be a graft copolymer in which the hard block and the soft block are separated into a main chain and a side chain. Examples of the graft copolymer include a styrene macromer- (meth) acrylic monomer copolymer and the like.
上記ブロック共重合体中、上記ハードブロックの含有量は特に限定されないが、１重量％以上、４０重量％以下であることが好ましい。上記ハードブロックの含有量が上記範囲であることで、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。耐熱保持性及び柔軟性を更に高める観点から、上記ハードブロックの含有量のより好ましい下限は２重量％、更に好ましい下限は２．５重量％、特に好ましい下限は３重量％である。上記ハードブロックの含有量のより好ましい上限は３５重量％、更に好ましい上限は３０重量％、更に好ましい上限は２５重量％、更により好ましい上限は２０重量％、特に好ましい上限は１５重量％である。
The content of the hard block in the block copolymer is not particularly limited, but is preferably 1% by weight or more and 40% by weight or less. When the content of the hard block is in the above range, the adhesive tape is less likely to be peeled off when a load is applied at a high temperature. From the viewpoint of further enhancing heat retention and flexibility, the more preferable lower limit of the content of the hard block is 2% by weight, the more preferable lower limit is 2.5% by weight, and the particularly preferable lower limit is 3% by weight. A more preferable upper limit of the content of the hard block is 35% by weight, a further preferable upper limit is 30% by weight, a further preferable upper limit is 25% by weight, a further preferable upper limit is 20% by weight, and a particularly preferable upper limit is 15% by weight.
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体の重量平均分子量（Ｍｗ）は特に限定されないが、５万以上、８０万以下であることが好ましい。上記重量平均分子量が上記範囲であることで、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記重量平均分子量のより好ましい下限は７５０００、より好ましい上限は６０万である。
なお、重量平均分子量は、例えば、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：ゲルパーミエーションクロマトグラフィ）法により標準ポリスチレン換算にて求めることができる。より具体的には、例えば、測定機器としてＷａｔｅｒ社製「２６９０ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｕｌｅ」、カラムとして昭和電工社製「ＧＰＣ ＫＦ－８０６Ｌ」、溶媒として酢酸エチルを用い、サンプル流量１ｍＬ／ｍｉｎ、カラム温度４０℃の条件で測定することができる。 The weight average molecular weight (Mw) of the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is not particularly limited, but is preferably 50,000 or more and 800,000 or less. .. When the weight average molecular weight is in the above range, the adhesive tape is less likely to be peeled off when a load is applied at a high temperature. The more preferable lower limit of the weight average molecular weight is 75,000, and the more preferable upper limit is 600,000.
The weight average molecular weight can be determined, for example, by a GPC (Gel Permeation Chromatography) method in terms of standard polystyrene. More specifically, for example, "2690 Separations Module" manufactured by Water Co., Ltd., "GPC KF-806L" manufactured by Showa Denko Co., Ltd. as a column, and ethyl acetate as a solvent are used as a measuring device, a sample flow rate of 1 mL / min, and a column temperature of 40 ° C. It can be measured under the conditions of.
なお、重量平均分子量は、例えば、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：ゲルパーミエーションクロマトグラフィ）法により標準ポリスチレン換算にて求めることができる。より具体的には、例えば、測定機器としてＷａｔｅｒ社製「２６９０ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｕｌｅ」、カラムとして昭和電工社製「ＧＰＣ ＫＦ－８０６Ｌ」、溶媒として酢酸エチルを用い、サンプル流量１ｍＬ／ｍｉｎ、カラム温度４０℃の条件で測定することができる。 The weight average molecular weight (Mw) of the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is not particularly limited, but is preferably 50,000 or more and 800,000 or less. .. When the weight average molecular weight is in the above range, the adhesive tape is less likely to be peeled off when a load is applied at a high temperature. The more preferable lower limit of the weight average molecular weight is 75,000, and the more preferable upper limit is 600,000.
The weight average molecular weight can be determined, for example, by a GPC (Gel Permeation Chromatography) method in terms of standard polystyrene. More specifically, for example, "2690 Separations Module" manufactured by Water Co., Ltd., "GPC KF-806L" manufactured by Showa Denko Co., Ltd. as a column, and ethyl acetate as a solvent are used as a measuring device, a sample flow rate of 1 mL / min, and a column temperature of 40 ° C. It can be measured under the conditions of.
上記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体を得るには、上記ハードブロック及び上記ソフトブロックの原料モノマーを、重合開始剤の存在下にてそれぞれラジカル反応させて上記ハードブロック及び上記ソフトブロックを得た後、両者を反応させる又は共重合すればよい。また、上記ハードブロックを得た後、続けて上記ソフトブロックの原料モノマーを投入し、共重合してもよい。ランダム共重合体の場合には、原料モノマーを混合した溶液を、重合開始剤の存在下にてラジカル反応させればよい。
上記ラジカル反応をさせる方法、即ち、重合方法としては、従来公知の方法が用いられ、例えば、溶液重合（沸点重合又は定温重合）、乳化重合、懸濁重合、塊状重合等が挙げられる。 In order to obtain a copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer, the raw material monomers of the hard block and the soft block are used in the presence of a polymerization initiator. The hard block and the soft block may be obtained by radical reaction, respectively, and then the two may be reacted or copolymerized. Further, after obtaining the hard block, the raw material monomer of the soft block may be continuously added and copolymerized. In the case of a random copolymer, a solution mixed with the raw material monomers may be subjected to a radical reaction in the presence of a polymerization initiator.
As the method for causing the radical reaction, that is, the polymerization method, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
上記ラジカル反応をさせる方法、即ち、重合方法としては、従来公知の方法が用いられ、例えば、溶液重合（沸点重合又は定温重合）、乳化重合、懸濁重合、塊状重合等が挙げられる。 In order to obtain a copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer, the raw material monomers of the hard block and the soft block are used in the presence of a polymerization initiator. The hard block and the soft block may be obtained by radical reaction, respectively, and then the two may be reacted or copolymerized. Further, after obtaining the hard block, the raw material monomer of the soft block may be continuously added and copolymerized. In the case of a random copolymer, a solution mixed with the raw material monomers may be subjected to a radical reaction in the presence of a polymerization initiator.
As the method for causing the radical reaction, that is, the polymerization method, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
上記基材は、帯電防止剤、離型剤、酸化防止剤、耐候剤、結晶核剤等の添加剤や、ポリオレフィン、ポリエステル、ポリアミド、エラストマー等の樹脂改質剤等を含有していてもよい。
The substrate may contain additives such as antistatic agents, mold release agents, antioxidants, weathering agents, and crystal nucleating agents, and resin modifiers such as polyolefins, polyesters, polyamides, and elastomers. ..
上記基材は、昇温速度１０℃／分、温度範囲－８０～２００℃の条件でＤＳＣ測定（示差走査熱量測定）を行ったときに１０℃以下の領域及び５０℃以上の領域にそれぞれ少なくとも一つのピークを有することが好ましい。
上記基材がＤＳＣ測定を行ったときに１０℃以下の領域及び５０℃以上の領域にそれぞれ少なくとも一つのピークを有する場合、上記基材は、上述したような２つのブロックを有するブロック共重合体を含有しているといえる。耐熱保持性と柔軟性とを両立する観点からは、このように上記基材が上記ブロック共重合体を含有していることが好ましい。本発明においては、ＤＳＣ測定を行ったときの１０℃以下の領域のピークを上記ソフトブロックに由来するピーク、５０℃以上の領域のピークを上記ハードブロックに由来するピークと呼んで差し支えない。上記ピークの領域は上記ハードブロック及び上記ソフトブロックの原料モノマーの種類によって調節することができる。
なお、基材のＤＳＣ測定は、示差走査熱量計（例えば、セイコーインスツルメンツ社製、２２０Ｃ等）を用いて基材１００ｍｇに対して行うことができる。 The above substrate was at least in a region of 10 ° C. or lower and a region of 50 ° C. or higher when DSC measurement (differential scanning calorimetry) was performed under the conditions of a temperature rise rate of 10 ° C./min and a temperature range of -80 to 200 ° C. It is preferable to have one peak.
When the substrate has at least one peak in the region of 10 ° C. or lower and the region of 50 ° C. or higher when DSC measurement is performed, the substrate is a block copolymer having two blocks as described above. It can be said that it contains. From the viewpoint of achieving both heat retention and flexibility, it is preferable that the base material contains the block copolymer in this way. In the present invention, the peak in the region of 10 ° C. or lower when the DSC measurement is performed may be referred to as the peak derived from the soft block, and the peak in the region of 50 ° C. or higher may be referred to as the peak derived from the hard block. The peak region can be adjusted by the type of the raw material monomer of the hard block and the soft block.
The DSC measurement of the base material can be performed on 100 mg of the base material using a differential scanning calorimeter (for example, 220C manufactured by Seiko Instruments Inc.).
上記基材がＤＳＣ測定を行ったときに１０℃以下の領域及び５０℃以上の領域にそれぞれ少なくとも一つのピークを有する場合、上記基材は、上述したような２つのブロックを有するブロック共重合体を含有しているといえる。耐熱保持性と柔軟性とを両立する観点からは、このように上記基材が上記ブロック共重合体を含有していることが好ましい。本発明においては、ＤＳＣ測定を行ったときの１０℃以下の領域のピークを上記ソフトブロックに由来するピーク、５０℃以上の領域のピークを上記ハードブロックに由来するピークと呼んで差し支えない。上記ピークの領域は上記ハードブロック及び上記ソフトブロックの原料モノマーの種類によって調節することができる。
なお、基材のＤＳＣ測定は、示差走査熱量計（例えば、セイコーインスツルメンツ社製、２２０Ｃ等）を用いて基材１００ｍｇに対して行うことができる。 The above substrate was at least in a region of 10 ° C. or lower and a region of 50 ° C. or higher when DSC measurement (differential scanning calorimetry) was performed under the conditions of a temperature rise rate of 10 ° C./min and a temperature range of -80 to 200 ° C. It is preferable to have one peak.
When the substrate has at least one peak in the region of 10 ° C. or lower and the region of 50 ° C. or higher when DSC measurement is performed, the substrate is a block copolymer having two blocks as described above. It can be said that it contains. From the viewpoint of achieving both heat retention and flexibility, it is preferable that the base material contains the block copolymer in this way. In the present invention, the peak in the region of 10 ° C. or lower when the DSC measurement is performed may be referred to as the peak derived from the soft block, and the peak in the region of 50 ° C. or higher may be referred to as the peak derived from the hard block. The peak region can be adjusted by the type of the raw material monomer of the hard block and the soft block.
The DSC measurement of the base material can be performed on 100 mg of the base material using a differential scanning calorimeter (for example, 220C manufactured by Seiko Instruments Inc.).
上記基材は、単層構造であっても多層構造であってもよい。
上記基材は、発泡体基材であることが好ましい。上記基材が上記発泡体基材であることにより、上記２５℃でのＬ成分の緩和時間（ＴＬ２５）、及び、上記８５℃でのＬ成分の緩和時間（ＴＬ８５）を上記範囲に調整することが容易となり、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。
上記発泡体基材は、連続気泡構造を有していても独立気泡構造を有していてもよいが、独立気泡構造を有することが好ましい。 The base material may have a single-layer structure or a multi-layer structure.
The base material is preferably a foam base material. Since the base material is the foam base material, the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) are adjusted within the above ranges. This makes it easier to remove the adhesive tape when a load is applied at high temperature.
The foam base material may have an open cell structure or a closed cell structure, but is preferably a closed cell structure.
上記基材は、発泡体基材であることが好ましい。上記基材が上記発泡体基材であることにより、上記２５℃でのＬ成分の緩和時間（ＴＬ２５）、及び、上記８５℃でのＬ成分の緩和時間（ＴＬ８５）を上記範囲に調整することが容易となり、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。
上記発泡体基材は、連続気泡構造を有していても独立気泡構造を有していてもよいが、独立気泡構造を有することが好ましい。 The base material may have a single-layer structure or a multi-layer structure.
The base material is preferably a foam base material. Since the base material is the foam base material, the relaxation time of the L component at 25 ° C. ( TL25 ) and the relaxation time of the L component at 85 ° C. ( TL85 ) are adjusted within the above ranges. This makes it easier to remove the adhesive tape when a load is applied at high temperature.
The foam base material may have an open cell structure or a closed cell structure, but is preferably a closed cell structure.
上記基材が上記発泡体基材である場合、発泡倍率は特に限定されないが、好ましい下限が１．１ｃｍ３／ｇ、好ましい上限が５ｃｍ３／ｇである。上記発泡倍率が上記範囲であることで、粘着テープの耐熱保持性と柔軟性とのバランスをより高めることができる。耐熱保持性と柔軟性とのバランスを更に高める観点から、上記発泡倍率のより好ましい下限は１．２ｃｍ３／ｇ、より好ましい上限は４．５ｃｍ３／ｇであり、更に好ましい下限は１．３ｃｍ３／ｇ、更に好ましい上限は４ｃｍ３／ｇである。
なお、基材の発泡倍率とは、基材の密度の逆数から算出でき、ＪＩＳ Ｋ ７２２２に準拠して電子比重計（例えば、ミラージュ社製、「ＥＤ１２０Ｔ」）を使用して測定できる。 When the base material is the foam base material, the foaming ratio is not particularly limited, but the preferable lower limit is 1.1 cm 3 / g and the preferable upper limit is 5 cm 3 / g. When the foaming ratio is in the above range, the balance between the heat resistance retention property and the flexibility of the adhesive tape can be further improved. From the viewpoint of further enhancing the balance between heat retention and flexibility, the more preferable lower limit of the foaming ratio is 1.2 cm 3 / g, the more preferable upper limit is 4.5 cm 3 / g, and the more preferable lower limit is 1.3 cm. 3 / g, a more preferred upper limit is 4 cm 3 / g.
The expansion ratio of the base material can be calculated from the reciprocal of the density of the base material, and can be measured using an electronic hydrometer (for example, "ED120T" manufactured by Mirage Co., Ltd.) in accordance with JIS K 7222.
なお、基材の発泡倍率とは、基材の密度の逆数から算出でき、ＪＩＳ Ｋ ７２２２に準拠して電子比重計（例えば、ミラージュ社製、「ＥＤ１２０Ｔ」）を使用して測定できる。 When the base material is the foam base material, the foaming ratio is not particularly limited, but the preferable lower limit is 1.1 cm 3 / g and the preferable upper limit is 5 cm 3 / g. When the foaming ratio is in the above range, the balance between the heat resistance retention property and the flexibility of the adhesive tape can be further improved. From the viewpoint of further enhancing the balance between heat retention and flexibility, the more preferable lower limit of the foaming ratio is 1.2 cm 3 / g, the more preferable upper limit is 4.5 cm 3 / g, and the more preferable lower limit is 1.3 cm. 3 / g, a more preferred upper limit is 4 cm 3 / g.
The expansion ratio of the base material can be calculated from the reciprocal of the density of the base material, and can be measured using an electronic hydrometer (for example, "ED120T" manufactured by Mirage Co., Ltd.) in accordance with JIS K 7222.
上記基材が上記発泡体基材である場合、平均気泡径は特に限定されないが、８０μｍ以下であることが好ましい。上記平均気泡径が８０μｍ以下であることで、粘着テープの耐熱保持性と柔軟性とのバランスをより高めることができる。上記平均気泡径は、６０μｍ以下であることがより好ましく、５５μｍ以下であることが更に好ましい。
上記平均気泡径の下限は特に限定されないが、粘着テープの柔軟性を確保する観点から、１０μｍ以上であることが好ましく、２０μｍ以上であることがより好ましい。
なお、基材の平均気泡径は、次の方法により測定することができる。まず、基材を５０ｍｍ四方にカットし、液体窒素に１分間浸した後、カミソリ刃を用いて基材の厚み方向に対して垂直な面で切断する。次いで、デジタルマイクロスコープ（例えば、キーエンス社製、「ＶＨＸ－９００」等）を用いて、２００倍の倍率で切断面の拡大写真を撮影し、厚み×２ｍｍの範囲に存在する全ての気泡について最も長い気泡径（気泡の直径）を測定する。この操作を５回繰り返し、得られたすべての気泡径を平均することで平均気泡径を算出する。 When the base material is the foam base material, the average bubble diameter is not particularly limited, but is preferably 80 μm or less. When the average cell diameter is 80 μm or less, the balance between the heat resistance retention and the flexibility of the adhesive tape can be further improved. The average bubble diameter is more preferably 60 μm or less, and further preferably 55 μm or less.
The lower limit of the average bubble diameter is not particularly limited, but is preferably 10 μm or more, and more preferably 20 μm or more, from the viewpoint of ensuring the flexibility of the adhesive tape.
The average bubble diameter of the base material can be measured by the following method. First, the base material is cut into 50 mm squares, immersed in liquid nitrogen for 1 minute, and then cut in a plane perpendicular to the thickness direction of the base material using a razor blade. Then, using a digital microscope (for example, "VHX-900" manufactured by KEYENCE Corporation), a magnified photograph of the cut surface was taken at a magnification of 200 times, and the most bubbles existing in the range of thickness × 2 mm were taken. Measure a long bubble diameter (bubble diameter). This operation is repeated 5 times, and the average bubble diameter is calculated by averaging all the obtained bubble diameters.
上記平均気泡径の下限は特に限定されないが、粘着テープの柔軟性を確保する観点から、１０μｍ以上であることが好ましく、２０μｍ以上であることがより好ましい。
なお、基材の平均気泡径は、次の方法により測定することができる。まず、基材を５０ｍｍ四方にカットし、液体窒素に１分間浸した後、カミソリ刃を用いて基材の厚み方向に対して垂直な面で切断する。次いで、デジタルマイクロスコープ（例えば、キーエンス社製、「ＶＨＸ－９００」等）を用いて、２００倍の倍率で切断面の拡大写真を撮影し、厚み×２ｍｍの範囲に存在する全ての気泡について最も長い気泡径（気泡の直径）を測定する。この操作を５回繰り返し、得られたすべての気泡径を平均することで平均気泡径を算出する。 When the base material is the foam base material, the average bubble diameter is not particularly limited, but is preferably 80 μm or less. When the average cell diameter is 80 μm or less, the balance between the heat resistance retention and the flexibility of the adhesive tape can be further improved. The average bubble diameter is more preferably 60 μm or less, and further preferably 55 μm or less.
The lower limit of the average bubble diameter is not particularly limited, but is preferably 10 μm or more, and more preferably 20 μm or more, from the viewpoint of ensuring the flexibility of the adhesive tape.
The average bubble diameter of the base material can be measured by the following method. First, the base material is cut into 50 mm squares, immersed in liquid nitrogen for 1 minute, and then cut in a plane perpendicular to the thickness direction of the base material using a razor blade. Then, using a digital microscope (for example, "VHX-900" manufactured by KEYENCE Corporation), a magnified photograph of the cut surface was taken at a magnification of 200 times, and the most bubbles existing in the range of thickness × 2 mm were taken. Measure a long bubble diameter (bubble diameter). This operation is repeated 5 times, and the average bubble diameter is calculated by averaging all the obtained bubble diameters.
上記基材は、ゲル分率が９０重量％以下であることが好ましい。
上記基材のゲル分率が上記範囲であることで、粘着テープは、より優れた柔軟性を発揮することができる。粘着テープの柔軟性を更に高める観点から、上記ゲル分率のより好ましい上限は８５重量％、更に好ましい上限は８０重量％である。上記ゲル分率の下限は特に限定されないが、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる観点から、例えば１０重量％以上、とりわけ２０重量％以上、特に３５重量％以上である。上記ゲル分率は、上記基材を構成する樹脂を架橋させることによって調節することができる。
なお、基材のゲル分率は、次の方法で測定することができる。粘着テープから基材のみを０．１ｇ取り出し、酢酸エチル５０ｍＬ中に浸漬し、振とう機で温度２３度、１２０ｒｐｍの条件で２４時間振とうする。振とう後、金属メッシュ（目開き＃２００メッシュ）を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した基材を分離する。分離後の基材を１１０℃の条件下で１時間乾燥させる。乾燥後の金属メッシュを含む基材の重量を測定し、下記式を用いて基材のゲル分率を算出する。
ゲル分率（重量％）＝１００×（Ｗ１－Ｗ２）／Ｗ０
（Ｗ０：初期基材重量、Ｗ１：乾燥後の金属メッシュを含む基材重量、Ｗ２：金属メッシュの初期重量） The base material preferably has a gel fraction of 90% by weight or less.
When the gel fraction of the base material is within the above range, the adhesive tape can exhibit more excellent flexibility. From the viewpoint of further increasing the flexibility of the adhesive tape, the more preferable upper limit of the gel fraction is 85% by weight, and the more preferable upper limit is 80% by weight. The lower limit of the gel fraction is not particularly limited, but from the viewpoint of making it more difficult for the adhesive tape to peel off when a load is applied at a high temperature, for example, it is 10% by weight or more, particularly 20% by weight or more, particularly 35% by weight or more. be. The gel fraction can be adjusted by cross-linking the resin constituting the substrate.
The gel fraction of the base material can be measured by the following method. Only 0.1 g of the substrate is taken out from the adhesive tape, immersed in 50 mL of ethyl acetate, and shaken with a shaker at a temperature of 23 ° C. and 120 rpm for 24 hours. After shaking, a metal mesh (opening # 200 mesh) is used to absorb ethyl acetate and ethyl acetate and separate the swollen substrate. The separated substrate is dried under the condition of 110 ° C. for 1 hour. The weight of the base material including the metal mesh after drying is measured, and the gel fraction of the base material is calculated using the following formula.
Gel fraction (% by weight) = 100 x (W 1 -W 2 ) / W 0
(W 0 : weight of initial base material, W 1 : weight of base material including dried metal mesh, W 2 : initial weight of metal mesh)
上記基材のゲル分率が上記範囲であることで、粘着テープは、より優れた柔軟性を発揮することができる。粘着テープの柔軟性を更に高める観点から、上記ゲル分率のより好ましい上限は８５重量％、更に好ましい上限は８０重量％である。上記ゲル分率の下限は特に限定されないが、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる観点から、例えば１０重量％以上、とりわけ２０重量％以上、特に３５重量％以上である。上記ゲル分率は、上記基材を構成する樹脂を架橋させることによって調節することができる。
なお、基材のゲル分率は、次の方法で測定することができる。粘着テープから基材のみを０．１ｇ取り出し、酢酸エチル５０ｍＬ中に浸漬し、振とう機で温度２３度、１２０ｒｐｍの条件で２４時間振とうする。振とう後、金属メッシュ（目開き＃２００メッシュ）を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した基材を分離する。分離後の基材を１１０℃の条件下で１時間乾燥させる。乾燥後の金属メッシュを含む基材の重量を測定し、下記式を用いて基材のゲル分率を算出する。
ゲル分率（重量％）＝１００×（Ｗ１－Ｗ２）／Ｗ０
（Ｗ０：初期基材重量、Ｗ１：乾燥後の金属メッシュを含む基材重量、Ｗ２：金属メッシュの初期重量） The base material preferably has a gel fraction of 90% by weight or less.
When the gel fraction of the base material is within the above range, the adhesive tape can exhibit more excellent flexibility. From the viewpoint of further increasing the flexibility of the adhesive tape, the more preferable upper limit of the gel fraction is 85% by weight, and the more preferable upper limit is 80% by weight. The lower limit of the gel fraction is not particularly limited, but from the viewpoint of making it more difficult for the adhesive tape to peel off when a load is applied at a high temperature, for example, it is 10% by weight or more, particularly 20% by weight or more, particularly 35% by weight or more. be. The gel fraction can be adjusted by cross-linking the resin constituting the substrate.
The gel fraction of the base material can be measured by the following method. Only 0.1 g of the substrate is taken out from the adhesive tape, immersed in 50 mL of ethyl acetate, and shaken with a shaker at a temperature of 23 ° C. and 120 rpm for 24 hours. After shaking, a metal mesh (opening # 200 mesh) is used to absorb ethyl acetate and ethyl acetate and separate the swollen substrate. The separated substrate is dried under the condition of 110 ° C. for 1 hour. The weight of the base material including the metal mesh after drying is measured, and the gel fraction of the base material is calculated using the following formula.
Gel fraction (% by weight) = 100 x (W 1 -W 2 ) / W 0
(W 0 : weight of initial base material, W 1 : weight of base material including dried metal mesh, W 2 : initial weight of metal mesh)
上記基材は、架橋剤が添加されることにより上記基材を構成する樹脂の主鎖間に架橋構造が形成されていることが好ましい。
上記基材を構成する樹脂の主鎖間に架橋構造を形成することで、断続的に加わる応力を分散させることができ、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。 It is preferable that the base material has a cross-linked structure formed between the main chains of the resin constituting the base material by adding a cross-linking agent.
By forming a crosslinked structure between the main chains of the resin constituting the base material, the stress applied intermittently can be dispersed, and the adhesive tape becomes more difficult to peel off when a load is applied at a high temperature.
上記基材を構成する樹脂の主鎖間に架橋構造を形成することで、断続的に加わる応力を分散させることができ、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。 It is preferable that the base material has a cross-linked structure formed between the main chains of the resin constituting the base material by adding a cross-linking agent.
By forming a crosslinked structure between the main chains of the resin constituting the base material, the stress applied intermittently can be dispersed, and the adhesive tape becomes more difficult to peel off when a load is applied at a high temperature.
上記架橋剤は特に限定されず、上記基材を構成する樹脂が有する官能基に応じて適宜選択することができる。具体的には例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、より柔軟性を向上させることができるアルコール性水酸基やカルボキシル基を有する樹脂を架橋できることから、エポキシ系架橋剤又はイソシアネート系架橋剤が好ましい。なお、上記イソシアネート系架橋剤を用いた場合、上記基材を構成する樹脂中のアルコール性水酸基やカルボキシル基と、上記イソシアネート系架橋剤のイソシアネート基との間が架橋される。また、上記エポキシ系架橋剤を用いた場合、上記基材を構成する樹脂中のカルボキシル基と、上記エポキシ系架橋剤のエポキシ基との間が架橋される。
上記架橋剤の添加量は特に限定されないが、上記基材を構成する樹脂１００重量部に対して０．０１重量部以上、１０重量部以下が好ましく、０．１重量部以上、７重量部以下がより好ましい。 The cross-linking agent is not particularly limited, and can be appropriately selected depending on the functional group of the resin constituting the base material. Specific examples thereof include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-type cross-linking agents. Among them, an epoxy-based cross-linking agent or an isocyanate-based cross-linking agent is preferable because a resin having an alcoholic hydroxyl group or a carboxyl group that can further improve flexibility can be cross-linked. When the isocyanate-based cross-linking agent is used, the alcoholic hydroxyl group or carboxyl group in the resin constituting the substrate is crosslinked with the isocyanate group of the isocyanate-based cross-linking agent. When the epoxy-based cross-linking agent is used, the carboxyl group in the resin constituting the base material and the epoxy group of the epoxy-based cross-linking agent are cross-linked.
The amount of the cross-linking agent added is not particularly limited, but is preferably 0.01 parts by weight or more and 10 parts by weight or less, and 0.1 parts by weight or more and 7 parts by weight or less with respect to 100 parts by weight of the resin constituting the base material. Is more preferable.
上記架橋剤の添加量は特に限定されないが、上記基材を構成する樹脂１００重量部に対して０．０１重量部以上、１０重量部以下が好ましく、０．１重量部以上、７重量部以下がより好ましい。 The cross-linking agent is not particularly limited, and can be appropriately selected depending on the functional group of the resin constituting the base material. Specific examples thereof include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-type cross-linking agents. Among them, an epoxy-based cross-linking agent or an isocyanate-based cross-linking agent is preferable because a resin having an alcoholic hydroxyl group or a carboxyl group that can further improve flexibility can be cross-linked. When the isocyanate-based cross-linking agent is used, the alcoholic hydroxyl group or carboxyl group in the resin constituting the substrate is crosslinked with the isocyanate group of the isocyanate-based cross-linking agent. When the epoxy-based cross-linking agent is used, the carboxyl group in the resin constituting the base material and the epoxy group of the epoxy-based cross-linking agent are cross-linked.
The amount of the cross-linking agent added is not particularly limited, but is preferably 0.01 parts by weight or more and 10 parts by weight or less, and 0.1 parts by weight or more and 7 parts by weight or less with respect to 100 parts by weight of the resin constituting the base material. Is more preferable.
上記基材の厚みは特に限定されないが、好ましい下限は４０μｍ、好ましい上限は２９００μｍである。上記基材の厚みを上記範囲とすることにより、柔軟性、耐熱保持性、取り扱い性等に優れた粘着テープとすることができるとともに、粘着テープを携帯電子機器部品、車載用電子機器部品等の電子機器部品の固定に好適に用いることができる。上記部品等の固定により好適に用いることができる観点から、上記基材の厚みのより好ましい下限は６０μｍ、より好ましい上限は１９００μｍ、更に好ましい下限は８０μｍ、更に好ましい上限は１４００μｍ、特に好ましい下限は１００μｍ、特に好ましい上限は１０００μｍである。
The thickness of the base material is not particularly limited, but the preferred lower limit is 40 μm and the preferred upper limit is 2900 μm. By setting the thickness of the base material within the above range, it is possible to obtain an adhesive tape having excellent flexibility, heat retention, handleability, etc., and the adhesive tape can be used as a portable electronic device component, an in-vehicle electronic device component, or the like. It can be suitably used for fixing electronic device parts. From the viewpoint that it can be more preferably used for fixing the parts and the like, the more preferable lower limit of the thickness of the base material is 60 μm, the more preferable upper limit is 1900 μm, the further preferable lower limit is 80 μm, the further preferable upper limit is 1400 μm, and the particularly preferable lower limit is 100 μm. A particularly preferable upper limit is 1000 μm.
上記基材の製造方法は特に限定されない。上記基材のうち、上記発泡体基材の製造方法としては、例えば、発泡ガスの作用により製造する方法や、原材料マトリックス中に中空球を配合することによって製造する方法が挙げられる。なかでも、後者の方法で製造された基材はシンタクチックフォームと称され、強度、柔軟性及び耐熱性により優れることから、上記基材は、シンタクチックフォームであることが好ましい。
The method for producing the above-mentioned base material is not particularly limited. Among the above base materials, examples of the method for producing the foam base material include a method of producing by the action of foaming gas and a method of producing by blending hollow spheres in a raw material matrix. Among them, the base material produced by the latter method is called syntactic foam, and is excellent in strength, flexibility and heat resistance. Therefore, the base material is preferably syntactic foam.
上記基材がシンタクチックフォームであることで、より均一なサイズ分布を有する独立気泡型の発泡体となるため、上記基材全体の密度がより一定となり、強度、柔軟性及び耐熱性がより向上する。また、シンタクチックフォームは、その他の発泡体と比較して、高温及び高圧下での不可逆的な崩壊を起こしにくいため、より高い耐熱性を示す。シンタクチックフォームとしては、中空無機粒子からなる発泡構造を有するものと、中空有機粒子からなる発泡構造を有するものとがあるが、柔軟性の観点から、中空有機粒子からなる発泡構造を有するシンタクチックフォームが好ましい。
Since the base material is syntactic foam, it becomes a closed cell type foam having a more uniform size distribution, so that the density of the entire base material becomes more constant, and the strength, flexibility and heat resistance are further improved. do. In addition, syntactic foam exhibits higher heat resistance than other foams because it is less likely to cause irreversible disintegration under high temperature and high pressure. Syntactic foam includes those having a foamed structure made of hollow inorganic particles and those having a foamed structure made of hollow organic particles. From the viewpoint of flexibility, syntactic foam having a foamed structure made of hollow organic particles. Foam is preferred.
上記中空有機粒子としては例えば、エクスパンセルＤＵシリーズ（日本フィライト社製）、アドバンセルＥＭシリーズ（積水化学工業社製）等が挙げられる。なかでも、発泡後の気泡径をより効果の高い領域に設計しやすいことから、エクスパンセル４６１－ＤＵ－２０（最適条件での発泡後の平均気泡径２０μｍ）、エクスパンセル４６１－ＤＵ－４０（最適条件での発泡後の平均気泡径４０μｍ）、エクスパンセル０４３－８０（最適条件での発泡後の平均気泡径８０μｍ）、アドバンセルＥＭＬ１０１（最適条件での発泡後の平均気泡径５０μｍ）が好ましい。
上記中空有機粒子の含有量は特に限定されないが、高温下で負荷がかかった際に粘着テープがより剥離しにくくなることから、上記基材を構成する樹脂１００重量部に対する好ましい下限が０．１重量部、好ましい上限が１０重量部であり、より好ましい下限が０．３重量部、より好ましい上限が７重量部である。 Examples of the hollow organic particles include Expancel DU series (manufactured by Nippon Philite Co., Ltd.), Advancel EM series (manufactured by Sekisui Chemical Co., Ltd.) and the like. Among them, since it is easy to design the bubble diameter after foaming in a region with higher effect, Expandel 461-DU-20 (average bubble diameter after foaming under optimum conditions 20 μm), Expandel 461-DU- 40 (average cell diameter after foaming under optimum conditions 40 μm), Expandel 043-80 (average cell diameter after foaming under optimum conditions 80 μm), Advansel EML101 (average cell diameter after foaming under optimum conditions 50 μm) ) Is preferable.
The content of the hollow organic particles is not particularly limited, but since the adhesive tape is more difficult to peel off when a load is applied at a high temperature, the preferable lower limit with respect to 100 parts by weight of the resin constituting the base material is 0.1. By weight, the preferred upper limit is 10 parts by weight, the more preferred lower limit is 0.3 parts by weight, and the more preferred upper limit is 7 parts by weight.
上記中空有機粒子の含有量は特に限定されないが、高温下で負荷がかかった際に粘着テープがより剥離しにくくなることから、上記基材を構成する樹脂１００重量部に対する好ましい下限が０．１重量部、好ましい上限が１０重量部であり、より好ましい下限が０．３重量部、より好ましい上限が７重量部である。 Examples of the hollow organic particles include Expancel DU series (manufactured by Nippon Philite Co., Ltd.), Advancel EM series (manufactured by Sekisui Chemical Co., Ltd.) and the like. Among them, since it is easy to design the bubble diameter after foaming in a region with higher effect, Expandel 461-DU-20 (average bubble diameter after foaming under optimum conditions 20 μm), Expandel 461-DU- 40 (average cell diameter after foaming under optimum conditions 40 μm), Expandel 043-80 (average cell diameter after foaming under optimum conditions 80 μm), Advansel EML101 (average cell diameter after foaming under optimum conditions 50 μm) ) Is preferable.
The content of the hollow organic particles is not particularly limited, but since the adhesive tape is more difficult to peel off when a load is applied at a high temperature, the preferable lower limit with respect to 100 parts by weight of the resin constituting the base material is 0.1. By weight, the preferred upper limit is 10 parts by weight, the more preferred lower limit is 0.3 parts by weight, and the more preferred upper limit is 7 parts by weight.
上記基材が上記シンタクチックフォーム以外の発泡体からなる場合の発泡剤は特に限定されず、熱分解型発泡剤等の従来公知の発泡剤を用いることができる。
When the base material is made of a foam other than the syntactic foam, the foaming agent is not particularly limited, and a conventionally known foaming agent such as a pyrolytic foaming agent can be used.
上記粘着剤層は、上記基材の一方の面のみに積層されていてもよいし、両面に積層されていてもよい。上記粘着剤層が上記基材の両面に積層されている場合、両面の粘着剤層はそれぞれ同じ組成及び物性を有していてもよいし、異なる組成及び物性を有していてもよい。
上記粘着剤層は特に限定されず、例えば、アクリル粘着剤層、ゴム系粘着剤層、ウレタン粘着剤層、シリコーン系粘着剤層等が挙げられる。なかでも、耐熱性に優れ、幅広い種類の被着体に接着が可能であることから、アクリル共重合体を含有するアクリル粘着剤層が好ましい。 The pressure-sensitive adhesive layer may be laminated on only one surface of the base material, or may be laminated on both sides. When the pressure-sensitive adhesive layer is laminated on both sides of the base material, the pressure-sensitive adhesive layers on both sides may have the same composition and physical properties, or may have different compositions and physical properties.
The pressure-sensitive adhesive layer is not particularly limited, and examples thereof include an acrylic pressure-sensitive adhesive layer, a rubber-based pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and a silicone-based pressure-sensitive adhesive layer. Among them, an acrylic pressure-sensitive adhesive layer containing an acrylic copolymer is preferable because it has excellent heat resistance and can be adhered to a wide variety of adherends.
上記粘着剤層は特に限定されず、例えば、アクリル粘着剤層、ゴム系粘着剤層、ウレタン粘着剤層、シリコーン系粘着剤層等が挙げられる。なかでも、耐熱性に優れ、幅広い種類の被着体に接着が可能であることから、アクリル共重合体を含有するアクリル粘着剤層が好ましい。 The pressure-sensitive adhesive layer may be laminated on only one surface of the base material, or may be laminated on both sides. When the pressure-sensitive adhesive layer is laminated on both sides of the base material, the pressure-sensitive adhesive layers on both sides may have the same composition and physical properties, or may have different compositions and physical properties.
The pressure-sensitive adhesive layer is not particularly limited, and examples thereof include an acrylic pressure-sensitive adhesive layer, a rubber-based pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and a silicone-based pressure-sensitive adhesive layer. Among them, an acrylic pressure-sensitive adhesive layer containing an acrylic copolymer is preferable because it has excellent heat resistance and can be adhered to a wide variety of adherends.
上記アクリル共重合体は、初期のタックが向上するため低温時の貼り付け易さが良好となる観点から、ブチルアクリレート及び／又は２－エチルヘキシルアクリレートを含むモノマー混合物を共重合して得られることが好ましい。なかでも、ブチルアクリレートと２－エチルヘキシルアクリレートとを含むモノマー混合物を共重合して得られることがより好ましい。
全モノマー混合物に占める上記ブチルアクリレートの含有量の好ましい下限は４０重量％、好ましい上限は８０重量％である。上記ブチルアクリレートの含有量を上記範囲とすることにより、高い粘着力とタック性とを両立することができる。
全モノマー混合物に占める上記２－エチルヘキシルアクリレートの含有量の好ましい下限は１０重量％、好ましい上限は１００重量％、より好ましい下限は３０重量％、より好ましい上限は８０重量％、更に好ましい下限は５０重量％、更に好ましい上限は６０重量％である。上記２－エチルヘキシルアクリレートの含有量を上記範囲とすることにより、高い粘着力を発揮することができる。 The acrylic copolymer can be obtained by copolymerizing a monomer mixture containing butyl acrylate and / or 2-ethylhexyl acrylate from the viewpoint of improving the initial tack and making it easy to attach at low temperature. preferable. Above all, it is more preferable to obtain it by copolymerizing a monomer mixture containing butyl acrylate and 2-ethylhexyl acrylate.
The preferable lower limit of the content of the butyl acrylate in the total monomer mixture is 40% by weight, and the preferable upper limit is 80% by weight. By setting the content of the butyl acrylate in the above range, both high adhesive strength and tackiness can be achieved at the same time.
The preferable lower limit of the content of the 2-ethylhexyl acrylate in the total monomer mixture is 10% by weight, the preferable upper limit is 100% by weight, the more preferable lower limit is 30% by weight, the more preferable upper limit is 80% by weight, and the further preferable lower limit is 50% by weight. %, A more preferred upper limit is 60% by weight. By setting the content of the 2-ethylhexyl acrylate in the above range, high adhesive strength can be exhibited.
全モノマー混合物に占める上記ブチルアクリレートの含有量の好ましい下限は４０重量％、好ましい上限は８０重量％である。上記ブチルアクリレートの含有量を上記範囲とすることにより、高い粘着力とタック性とを両立することができる。
全モノマー混合物に占める上記２－エチルヘキシルアクリレートの含有量の好ましい下限は１０重量％、好ましい上限は１００重量％、より好ましい下限は３０重量％、より好ましい上限は８０重量％、更に好ましい下限は５０重量％、更に好ましい上限は６０重量％である。上記２－エチルヘキシルアクリレートの含有量を上記範囲とすることにより、高い粘着力を発揮することができる。 The acrylic copolymer can be obtained by copolymerizing a monomer mixture containing butyl acrylate and / or 2-ethylhexyl acrylate from the viewpoint of improving the initial tack and making it easy to attach at low temperature. preferable. Above all, it is more preferable to obtain it by copolymerizing a monomer mixture containing butyl acrylate and 2-ethylhexyl acrylate.
The preferable lower limit of the content of the butyl acrylate in the total monomer mixture is 40% by weight, and the preferable upper limit is 80% by weight. By setting the content of the butyl acrylate in the above range, both high adhesive strength and tackiness can be achieved at the same time.
The preferable lower limit of the content of the 2-ethylhexyl acrylate in the total monomer mixture is 10% by weight, the preferable upper limit is 100% by weight, the more preferable lower limit is 30% by weight, the more preferable upper limit is 80% by weight, and the further preferable lower limit is 50% by weight. %, A more preferred upper limit is 60% by weight. By setting the content of the 2-ethylhexyl acrylate in the above range, high adhesive strength can be exhibited.
上記モノマー混合物は、必要に応じてブチルアクリレート及び２－エチルヘキシルアクリレート以外の共重合可能な他の重合性モノマーを含んでいてもよい。上記共重合可能な他の重合性モノマーとして、例えば、アルキル基の炭素数が１～８の（メタ）アクリル酸アルキルエステル、アルキル基の炭素数が１３～１８の（メタ）アクリル酸アルキルエステル、官能性モノマー等が挙げられる。
上記アルキル基の炭素数が１～８の（メタ）アクリル酸アルキルエステルとして、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）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル等が挙げられる。上記アルキル基の炭素数が１３～１８の（メタ）アクリル酸アルキルエステルとして、例えば、メタクリル酸トリデシル、（メタ）アクリル酸ステアリル等が挙げられる。上記官能性モノマーとして、例えば、（メタ）アクリル酸ヒドロキシアルキル、グリセリンジメタクリレート、（メタ）アクリル酸グリシジル、２－メタクリロイルオキシエチルイソシアネート、（メタ）アクリル酸、イタコン酸、無水マレイン酸、クロトン酸、マレイン酸、フマル酸等が挙げられる。 The monomer mixture may contain other copolymerizable monomers other than butyl acrylate and 2-ethylhexyl acrylate, if necessary. Examples of the other copolymerizable monomer include a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and a (meth) acrylic acid alkyl ester having an alkyl group having 13 to 18 carbon atoms. Examples include functional monomers.
Examples of the (meth) acrylic acid alkyl ester having 1 to 8 carbon atoms in the alkyl group include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and (meth) acrylic acid. Isobutyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) ) Isooctyl acrylate and the like. Examples of the (meth) acrylic acid alkyl ester having 13 to 18 carbon atoms in the alkyl group include tridecylic methacrylic acid and stearyl (meth) acrylic acid. Examples of the functional monomer include (meth) acrylic acid hydroxyalkyl, glycerin dimethacrylate, (meth) glycidyl acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, and crotonic acid. Maleic acid, fumaric acid and the like can be mentioned.
上記アルキル基の炭素数が１～８の（メタ）アクリル酸アルキルエステルとして、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）アクリル酸イソブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル等が挙げられる。上記アルキル基の炭素数が１３～１８の（メタ）アクリル酸アルキルエステルとして、例えば、メタクリル酸トリデシル、（メタ）アクリル酸ステアリル等が挙げられる。上記官能性モノマーとして、例えば、（メタ）アクリル酸ヒドロキシアルキル、グリセリンジメタクリレート、（メタ）アクリル酸グリシジル、２－メタクリロイルオキシエチルイソシアネート、（メタ）アクリル酸、イタコン酸、無水マレイン酸、クロトン酸、マレイン酸、フマル酸等が挙げられる。 The monomer mixture may contain other copolymerizable monomers other than butyl acrylate and 2-ethylhexyl acrylate, if necessary. Examples of the other copolymerizable monomer include a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms and a (meth) acrylic acid alkyl ester having an alkyl group having 13 to 18 carbon atoms. Examples include functional monomers.
Examples of the (meth) acrylic acid alkyl ester having 1 to 8 carbon atoms in the alkyl group include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and (meth) acrylic acid. Isobutyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) ) Isooctyl acrylate and the like. Examples of the (meth) acrylic acid alkyl ester having 13 to 18 carbon atoms in the alkyl group include tridecylic methacrylic acid and stearyl (meth) acrylic acid. Examples of the functional monomer include (meth) acrylic acid hydroxyalkyl, glycerin dimethacrylate, (meth) glycidyl acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, itaconic acid, maleic anhydride, and crotonic acid. Maleic acid, fumaric acid and the like can be mentioned.
上記モノマー混合物を共重合して上記アクリル共重合体を得るには、上記モノマー混合物を、重合開始剤の存在下にてラジカル反応させればよい。上記モノマー混合物をラジカル反応させる方法、即ち、重合方法としては、従来公知の方法が用いられ、例えば、溶液重合（沸点重合又は定温重合）、乳化重合、懸濁重合、塊状重合等が挙げられる。
In order to copolymerize the monomer mixture to obtain the acrylic copolymer, the monomer mixture may be subjected to a radical reaction in the presence of a polymerization initiator. As a method of radically reacting the monomer mixture, that is, a polymerization method, a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
上記アクリル共重合体の重量平均分子量（Ｍｗ）は特に限定されないが、好ましい下限が４０万、好ましい上限が１５０万である。上記アクリル共重合体の重量平均分子量を上記範囲とすることにより、高い粘着力を発揮することができ、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。粘着力及び耐熱保持性の更なる向上の観点から、上記重量平均分子量のより好ましい下限は５０万、より好ましい上限は１４０万である。
The weight average molecular weight (Mw) of the acrylic copolymer is not particularly limited, but the preferred lower limit is 400,000 and the preferred upper limit is 1.5 million. By setting the weight average molecular weight of the acrylic copolymer in the above range, high adhesive strength can be exhibited, and the adhesive tape becomes more difficult to peel off when a load is applied under high temperature. From the viewpoint of further improving the adhesive strength and heat retention, the more preferable lower limit of the weight average molecular weight is 500,000, and the more preferable upper limit is 1.4 million.
上記アクリル共重合体の数平均分子量（Ｍｎ）に対する重量平均分子量（Ｍｗ）の比（Ｍｗ／Ｍｎ）は、好ましい上限が１０．０である。Ｍｗ／Ｍｎが１０．０以下であると、低分子成分の割合が抑えられ、上記粘着剤層が高温下で軟化し、バルク強度が下がり接着強度が低下することが抑制されることから、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。同様の観点から、Ｍｗ／Ｍｎのより好ましい上限は５．０であり、更に好ましい上限は３．０である。
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic copolymer is preferably 10.0. When Mw / Mn is 10.0 or less, the proportion of small molecule components is suppressed, the pressure-sensitive adhesive layer is softened at high temperatures, the bulk strength is lowered, and the adhesive strength is suppressed. The adhesive tape is less likely to come off when a load is applied underneath. From the same viewpoint, the more preferable upper limit of Mw / Mn is 5.0, and the more preferable upper limit is 3.0.
上記粘着剤層は、粘着付与樹脂を含有してもよい。
上記粘着付与樹脂として、例えば、ロジンエステル系樹脂、水添ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、脂環族飽和炭化水素系樹脂、Ｃ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５－Ｃ９共重合系石油樹脂等が挙げられる。これらの粘着付与樹脂は単独で用いてもよいし、２種以上を併用してもよい。 The pressure-sensitive adhesive layer may contain a pressure-sensitive adhesive resin.
Examples of the tackifier resin include rosin ester resin, hydrogenated rosin resin, terpene resin, terpene phenol resin, Kumaron inden resin, alicyclic saturated hydrocarbon resin, C5 petroleum resin, and C9 resin. Examples thereof include petroleum resins and C5-C9 copolymerized petroleum resins. These tackifier resins may be used alone or in combination of two or more.
上記粘着付与樹脂として、例えば、ロジンエステル系樹脂、水添ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、脂環族飽和炭化水素系樹脂、Ｃ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５－Ｃ９共重合系石油樹脂等が挙げられる。これらの粘着付与樹脂は単独で用いてもよいし、２種以上を併用してもよい。 The pressure-sensitive adhesive layer may contain a pressure-sensitive adhesive resin.
Examples of the tackifier resin include rosin ester resin, hydrogenated rosin resin, terpene resin, terpene phenol resin, Kumaron inden resin, alicyclic saturated hydrocarbon resin, C5 petroleum resin, and C9 resin. Examples thereof include petroleum resins and C5-C9 copolymerized petroleum resins. These tackifier resins may be used alone or in combination of two or more.
上記粘着付与樹脂の含有量は特に限定されないが、上記粘着剤層の主成分となる樹脂（例えば、アクリル共重合体）１００重量部に対する好ましい下限は１０重量部、好ましい上限は６０重量部である。上記粘着付与樹脂の含有量が１０重量部以上であると、上記粘着剤層が高い粘着力を発揮することができ、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記粘着付与樹脂の含有量が６０重量部以下であると、上記粘着剤層が硬くなることによる粘着力又はタック性の低下を抑制することができる。
The content of the tackifier resin is not particularly limited, but the preferable lower limit is 10 parts by weight and the preferable upper limit is 60 parts by weight with respect to 100 parts by weight of the resin (for example, acrylic copolymer) which is the main component of the pressure-sensitive adhesive layer. .. When the content of the pressure-sensitive adhesive resin is 10 parts by weight or more, the pressure-sensitive adhesive layer can exert a high pressure-sensitive adhesive force, and the pressure-sensitive adhesive tape becomes more difficult to peel off when a load is applied at a high temperature. When the content of the pressure-sensitive adhesive resin is 60 parts by weight or less, it is possible to suppress a decrease in adhesive strength or tackiness due to the hardening of the pressure-sensitive adhesive layer.
上記粘着剤層は、架橋剤が添加されることにより上記粘着剤層を構成する樹脂（例えば、上記アクリル共重合体、上記粘着付与樹脂等）の主鎖間に架橋構造が形成されていることが好ましい。
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤が好ましい。上記粘着剤層にイソシアネート系架橋剤が添加されることで、イソシアネート系架橋剤のイソシアネート基と上記粘着剤層を構成する樹脂（例えば、上記アクリル共重合体、上記粘着付与樹脂等）中のアルコール性水酸基とが反応して、上記粘着剤層が架橋する。上記粘着剤層を構成する樹脂の主鎖間に架橋構造が形成されていることで、断続的に加わる応力を分散させることができ、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。
上記架橋剤の添加量は、上記粘着剤層の主成分となる樹脂（例えば、上記アクリル共重合体）１００重量部に対して０．０１～１０重量部が好ましく、０．１～７重量部がより好ましい。 The pressure-sensitive adhesive layer has a cross-linked structure formed between the main chains of the resin (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.) constituting the pressure-sensitive adhesive layer by adding a cross-linking agent. Is preferable.
The above-mentioned cross-linking agent is not particularly limited, and examples thereof include an isocyanate-based cross-linking agent, an aziridine-based cross-linking agent, an epoxy-based cross-linking agent, and a metal chelate-type cross-linking agent. Of these, isocyanate-based cross-linking agents are preferable. By adding an isocyanate-based cross-linking agent to the pressure-sensitive adhesive layer, the isocyanate group of the isocyanate-based cross-linking agent and the alcohol in the resin constituting the pressure-sensitive adhesive layer (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.) The pressure-sensitive adhesive layer is crosslinked by reacting with the sex hydroxylate. By forming a crosslinked structure between the main chains of the resin constituting the pressure-sensitive adhesive layer, it is possible to disperse the stress applied intermittently, and the pressure-sensitive adhesive tape is more peeled off when a load is applied at high temperature. It becomes difficult.
The amount of the cross-linking agent added is preferably 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the resin (for example, the acrylic copolymer) which is the main component of the pressure-sensitive adhesive layer. Is more preferable.
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、イソシアネート系架橋剤が好ましい。上記粘着剤層にイソシアネート系架橋剤が添加されることで、イソシアネート系架橋剤のイソシアネート基と上記粘着剤層を構成する樹脂（例えば、上記アクリル共重合体、上記粘着付与樹脂等）中のアルコール性水酸基とが反応して、上記粘着剤層が架橋する。上記粘着剤層を構成する樹脂の主鎖間に架橋構造が形成されていることで、断続的に加わる応力を分散させることができ、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。
上記架橋剤の添加量は、上記粘着剤層の主成分となる樹脂（例えば、上記アクリル共重合体）１００重量部に対して０．０１～１０重量部が好ましく、０．１～７重量部がより好ましい。 The pressure-sensitive adhesive layer has a cross-linked structure formed between the main chains of the resin (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.) constituting the pressure-sensitive adhesive layer by adding a cross-linking agent. Is preferable.
The above-mentioned cross-linking agent is not particularly limited, and examples thereof include an isocyanate-based cross-linking agent, an aziridine-based cross-linking agent, an epoxy-based cross-linking agent, and a metal chelate-type cross-linking agent. Of these, isocyanate-based cross-linking agents are preferable. By adding an isocyanate-based cross-linking agent to the pressure-sensitive adhesive layer, the isocyanate group of the isocyanate-based cross-linking agent and the alcohol in the resin constituting the pressure-sensitive adhesive layer (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.) The pressure-sensitive adhesive layer is crosslinked by reacting with the sex hydroxylate. By forming a crosslinked structure between the main chains of the resin constituting the pressure-sensitive adhesive layer, it is possible to disperse the stress applied intermittently, and the pressure-sensitive adhesive tape is more peeled off when a load is applied at high temperature. It becomes difficult.
The amount of the cross-linking agent added is preferably 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the resin (for example, the acrylic copolymer) which is the main component of the pressure-sensitive adhesive layer. Is more preferable.
上記粘着剤層は、粘着力を向上させる目的で、シランカップリング剤を含有してもよい。上記シランカップリング剤は特に限定されず、例えば、エポキシシラン類、アクリルシラン類、メタクリルシラン類、アミノシラン類、イソシアネートシラン類等が挙げられる。
The pressure-sensitive adhesive layer may contain a silane coupling agent for the purpose of improving the pressure-sensitive adhesive strength. The silane coupling agent is not particularly limited, and examples thereof include epoxysilanes, acrylicsilanes, methacrylsilanes, aminosilanes, and isocyanatesilanes.
上記粘着剤層は、遮光性を付与する目的で、着色材を含有してもよい。上記着色材は特に限定されず、例えば、カーボンブラック、アニリンブラック、酸化チタン等が挙げられる。なかでも、比較的安価で化学的に安定であることから、カーボンブラックが好ましい。
上記粘着剤層は、必要に応じて、無機粒子、導電粒子、酸化防止剤、発泡剤、有機充填剤、無機充填剤等の従来公知の粒子及び添加剤を含有してもよい。 The pressure-sensitive adhesive layer may contain a coloring material for the purpose of imparting light-shielding properties. The coloring material is not particularly limited, and examples thereof include carbon black, aniline black, and titanium oxide. Of these, carbon black is preferable because it is relatively inexpensive and chemically stable.
The pressure-sensitive adhesive layer may contain conventionally known particles and additives such as inorganic particles, conductive particles, antioxidants, foaming agents, organic fillers, and inorganic fillers, if necessary.
上記粘着剤層は、必要に応じて、無機粒子、導電粒子、酸化防止剤、発泡剤、有機充填剤、無機充填剤等の従来公知の粒子及び添加剤を含有してもよい。 The pressure-sensitive adhesive layer may contain a coloring material for the purpose of imparting light-shielding properties. The coloring material is not particularly limited, and examples thereof include carbon black, aniline black, and titanium oxide. Of these, carbon black is preferable because it is relatively inexpensive and chemically stable.
The pressure-sensitive adhesive layer may contain conventionally known particles and additives such as inorganic particles, conductive particles, antioxidants, foaming agents, organic fillers, and inorganic fillers, if necessary.
上記粘着剤層は、ゲル分率の好ましい下限が１０重量％、好ましい上限が８０重量％である。上記ゲル分率が上記範囲内であれば、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記ゲル分率のより好ましい下限は２０重量％、より好ましい上限は７０重量％である。
なお、粘着剤層のゲル分率は、基材のゲル分率と同様の方法で測定することができる。 In the pressure-sensitive adhesive layer, the preferable lower limit of the gel fraction is 10% by weight, and the preferable upper limit is 80% by weight. When the gel fraction is within the above range, the adhesive tape is less likely to be peeled off when a load is applied under high temperature. The more preferable lower limit of the gel fraction is 20% by weight, and the more preferable upper limit is 70% by weight.
The gel fraction of the pressure-sensitive adhesive layer can be measured by the same method as the gel fraction of the base material.
なお、粘着剤層のゲル分率は、基材のゲル分率と同様の方法で測定することができる。 In the pressure-sensitive adhesive layer, the preferable lower limit of the gel fraction is 10% by weight, and the preferable upper limit is 80% by weight. When the gel fraction is within the above range, the adhesive tape is less likely to be peeled off when a load is applied under high temperature. The more preferable lower limit of the gel fraction is 20% by weight, and the more preferable upper limit is 70% by weight.
The gel fraction of the pressure-sensitive adhesive layer can be measured by the same method as the gel fraction of the base material.
上記粘着剤層は、２３℃での動的粘弾性測定における貯蔵弾性率Ｇ’の好ましい下限が１０５Ｐａ、好ましい上限が１０６Ｐａである。上記２３℃での貯蔵弾性率Ｇ’が上記範囲内であれば、高温下で負荷がかかった際に粘着テープがより剥離しにくくなる。上記粘着剤層の２３℃での貯蔵弾性率Ｇ’のより好ましい下限は２×１０５Ｐａ、より好ましい上限は８×１０５Ｐａである。上記粘着剤層の２３℃での貯蔵弾性率Ｇ’は、上記粘着剤層の原料モノマーの組成によって調整することができる。
なお、粘着剤層の２３℃における貯蔵弾性率Ｇ’は、粘弾性スペクトロメーター（例えば、アイティー計測制御社製、ＤＶＡ－２００等）を用い、定速昇温引張モードの１０℃／分、１０Ｈｚの条件で－４０～１４０℃の動的粘弾性スペクトルを測定した時の、２３℃における貯蔵弾性率として得ることができる。 In the pressure-sensitive adhesive layer, the preferable lower limit of the storage elastic modulus G'in the dynamic viscoelasticity measurement at 23 ° C. is 105 Pa, and the preferable upper limit is 106 Pa. When the storage elastic modulus G'at 23 ° C. is within the above range, the adhesive tape is less likely to be peeled off when a load is applied under high temperature. The more preferable lower limit of the storage elastic modulus G'at 23 ° C. of the pressure-sensitive adhesive layer is 2 × 10 5 Pa, and the more preferable upper limit is 8 × 10 5 Pa. The storage elastic modulus G'of the pressure-sensitive adhesive layer at 23 ° C. can be adjusted by the composition of the raw material monomer of the pressure-sensitive adhesive layer.
The storage elastic modulus G'at 23 ° C. of the pressure-sensitive adhesive layer was set to 10 ° C./min in a constant-speed temperature rise tension mode using a viscoelasticity spectrometer (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.). It can be obtained as the storage elastic modulus at 23 ° C. when the dynamic viscoelasticity spectrum at −40 to 140 ° C. is measured under the condition of 10 Hz.
なお、粘着剤層の２３℃における貯蔵弾性率Ｇ’は、粘弾性スペクトロメーター（例えば、アイティー計測制御社製、ＤＶＡ－２００等）を用い、定速昇温引張モードの１０℃／分、１０Ｈｚの条件で－４０～１４０℃の動的粘弾性スペクトルを測定した時の、２３℃における貯蔵弾性率として得ることができる。 In the pressure-sensitive adhesive layer, the preferable lower limit of the storage elastic modulus G'in the dynamic viscoelasticity measurement at 23 ° C. is 105 Pa, and the preferable upper limit is 106 Pa. When the storage elastic modulus G'at 23 ° C. is within the above range, the adhesive tape is less likely to be peeled off when a load is applied under high temperature. The more preferable lower limit of the storage elastic modulus G'at 23 ° C. of the pressure-sensitive adhesive layer is 2 × 10 5 Pa, and the more preferable upper limit is 8 × 10 5 Pa. The storage elastic modulus G'of the pressure-sensitive adhesive layer at 23 ° C. can be adjusted by the composition of the raw material monomer of the pressure-sensitive adhesive layer.
The storage elastic modulus G'at 23 ° C. of the pressure-sensitive adhesive layer was set to 10 ° C./min in a constant-speed temperature rise tension mode using a viscoelasticity spectrometer (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.). It can be obtained as the storage elastic modulus at 23 ° C. when the dynamic viscoelasticity spectrum at −40 to 140 ° C. is measured under the condition of 10 Hz.
上記粘着剤層の厚みは特に限定されないが、好ましい下限は０．０１ｍｍ、好ましい上限は０．１ｍｍであり、より好ましい下限は０．０１５ｍｍ、より好ましい上限は０．０９ｍｍである。上記粘着剤層の厚みを上記範囲とすることにより、柔軟性、耐熱保持性、取り扱い性等に優れた粘着テープとすることができるとともに、粘着テープを携帯電子機器部品、車載用電子機器部品等の電子機器部品の固定に好適に用いることができる。
The thickness of the pressure-sensitive adhesive layer is not particularly limited, but a preferable lower limit is 0.01 mm, a preferable upper limit is 0.1 mm, a more preferable lower limit is 0.015 mm, and a more preferable upper limit is 0.09 mm. By setting the thickness of the adhesive layer within the above range, it is possible to obtain an adhesive tape having excellent flexibility, heat retention, handleability, etc., and the adhesive tape can be used as a portable electronic device component, an in-vehicle electronic device component, or the like. It can be suitably used for fixing electronic device parts.
本発明の粘着テープは、更に、上記基材の少なくとも一方の面に積層された樹脂層を有していてもよい。
上記樹脂層を有することにより、粘着テープの強度及び耐熱保持性がより高くなる。上記樹脂層は、上記基材の一方の面のみに積層されていてもよいし、両面に積層されていてもよいが、上記基材の一方の面のみに積層されていることが好ましい。 The adhesive tape of the present invention may further have a resin layer laminated on at least one surface of the base material.
By having the resin layer, the strength and heat resistance of the adhesive tape are further increased. The resin layer may be laminated on only one surface of the base material or may be laminated on both sides, but it is preferable that the resin layer is laminated on only one surface of the base material.
上記樹脂層を有することにより、粘着テープの強度及び耐熱保持性がより高くなる。上記樹脂層は、上記基材の一方の面のみに積層されていてもよいし、両面に積層されていてもよいが、上記基材の一方の面のみに積層されていることが好ましい。 The adhesive tape of the present invention may further have a resin layer laminated on at least one surface of the base material.
By having the resin layer, the strength and heat resistance of the adhesive tape are further increased. The resin layer may be laminated on only one surface of the base material or may be laminated on both sides, but it is preferable that the resin layer is laminated on only one surface of the base material.
上記樹脂層を構成する樹脂は、耐熱性を有することが好ましい。耐熱性を有する上記樹脂層を構成する樹脂としては、例えば、ポリエチレンテレフタレート等のポリエステル系樹脂、アクリル系樹脂、シリコーン樹脂、フェノール樹脂、ポリイミド、ポリカーボネート等が挙げられる。なかでも、柔軟性に優れる粘着テープが得られることから、アクリル系樹脂、ポリエステル系樹脂が好ましく、ポリエチレンテレフタレートがより好ましい。
The resin constituting the resin layer preferably has heat resistance. Examples of the resin constituting the heat-resistant resin layer include polyester resins such as polyethylene terephthalate, acrylic resins, silicone resins, phenol resins, polyimides, and polycarbonates. Among them, acrylic resin and polyester resin are preferable, and polyethylene terephthalate is more preferable, because an adhesive tape having excellent flexibility can be obtained.
上記樹脂層は、着色されていてもよい。上記樹脂層を着色することにより、粘着テープに遮光性を付与することができる。
上記樹脂層を着色する方法は特に限定されず、例えば、上記樹脂層を構成する樹脂にカーボンブラック、酸化チタン等の粒子又は微細な気泡を練り込む方法、上記樹脂層の表面にインクを塗布する方法等が挙げられる。 The resin layer may be colored. By coloring the resin layer, it is possible to impart light-shielding properties to the adhesive tape.
The method of coloring the resin layer is not particularly limited, and for example, a method of kneading particles such as carbon black or titanium oxide or fine bubbles into the resin constituting the resin layer, or applying ink to the surface of the resin layer. The method and the like can be mentioned.
上記樹脂層を着色する方法は特に限定されず、例えば、上記樹脂層を構成する樹脂にカーボンブラック、酸化チタン等の粒子又は微細な気泡を練り込む方法、上記樹脂層の表面にインクを塗布する方法等が挙げられる。 The resin layer may be colored. By coloring the resin layer, it is possible to impart light-shielding properties to the adhesive tape.
The method of coloring the resin layer is not particularly limited, and for example, a method of kneading particles such as carbon black or titanium oxide or fine bubbles into the resin constituting the resin layer, or applying ink to the surface of the resin layer. The method and the like can be mentioned.
上記樹脂層は、必要に応じて、無機粒子、導電粒子、可塑剤、粘着付与剤、紫外線吸収剤、酸化防止剤、発泡剤、有機充填剤、無機充填剤等の従来公知の粒子及び添加剤を含有してもよい。
The resin layer may contain conventionally known particles and additives such as inorganic particles, conductive particles, plasticizers, tackifiers, ultraviolet absorbers, antioxidants, foaming agents, organic fillers, and inorganic fillers, if necessary. May be contained.
上記樹脂層の厚みは特に限定されないが、好ましい下限は５μｍ、好ましい上限は１００μｍである。上記樹脂層の厚みを上記範囲とすることにより、粘着テープの取り扱い性と耐熱保持性とを両立することができる。取り扱い性と耐熱保持性とを更に両立する観点から、上記樹脂層の厚みのより好ましい下限は１０μｍ、より好ましい上限は７０μｍである。
The thickness of the resin layer is not particularly limited, but the preferred lower limit is 5 μm and the preferred upper limit is 100 μm. By setting the thickness of the resin layer within the above range, it is possible to achieve both handleability and heat resistance retention of the adhesive tape. From the viewpoint of further achieving both handleability and heat resistance retention, the more preferable lower limit of the thickness of the resin layer is 10 μm, and the more preferable upper limit is 70 μm.
本発明の粘着テープ全体の厚みは特に限定されないが、好ましい下限は０．０４ｍｍ、より好ましい下限は０．０５ｍｍ、好ましい上限は２ｍｍ、より好ましい上限は１．５ｍｍである。本発明の粘着テープ全体の厚みを上記範囲とすることにより、柔軟性、耐熱保持性、取り扱い性等に優れた粘着テープとすることができる。
本発明の粘着テープの形状は特に限定されないが、長方形、正方形、額縁状、円形、楕円形、ドーナツ型等が挙げられる。 The thickness of the entire adhesive tape of the present invention is not particularly limited, but a preferable lower limit is 0.04 mm, a more preferable lower limit is 0.05 mm, a preferable upper limit is 2 mm, and a more preferable upper limit is 1.5 mm. By setting the thickness of the entire adhesive tape of the present invention within the above range, it is possible to obtain an adhesive tape having excellent flexibility, heat retention, handleability and the like.
The shape of the adhesive tape of the present invention is not particularly limited, and examples thereof include a rectangle, a square, a frame shape, a circle shape, an ellipse shape, and a donut shape.
本発明の粘着テープの形状は特に限定されないが、長方形、正方形、額縁状、円形、楕円形、ドーナツ型等が挙げられる。 The thickness of the entire adhesive tape of the present invention is not particularly limited, but a preferable lower limit is 0.04 mm, a more preferable lower limit is 0.05 mm, a preferable upper limit is 2 mm, and a more preferable upper limit is 1.5 mm. By setting the thickness of the entire adhesive tape of the present invention within the above range, it is possible to obtain an adhesive tape having excellent flexibility, heat retention, handleability and the like.
The shape of the adhesive tape of the present invention is not particularly limited, and examples thereof include a rectangle, a square, a frame shape, a circle shape, an ellipse shape, and a donut shape.
本発明の粘着テープの製造方法としては特に限定されず、例えば、次のような方法が挙げられる。まず、離型フィルムに粘着剤溶液を塗工、乾燥して粘着剤層を形成する。次いで、未発泡体基材を製造し、該未発泡体基材に樹脂層を積層して積層体を形成する。その後、得られた積層体の両面に粘着剤層を貼り合わせ、加熱することで未発泡体基材を発泡させて発泡体基材とし、粘着テープを製造する。
The method for producing the adhesive tape of the present invention is not particularly limited, and examples thereof include the following methods. First, a pressure-sensitive adhesive solution is applied to a release film and dried to form a pressure-sensitive adhesive layer. Next, an unfoamed base material is manufactured, and a resin layer is laminated on the unfoamed base material to form a laminated body. Then, an adhesive layer is attached to both sides of the obtained laminate, and the unfoamed base material is foamed by heating to form a foam base material, and an adhesive tape is manufactured.
本発明の粘着テープの用途は特に限定されないが、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープであることから、携帯電子機器部品、車載用電子機器部品等の電子機器部品の組み立て又は固定に用いられることが好ましい。
The use of the adhesive tape of the present invention is not particularly limited, but since it is an adhesive tape having excellent heat retention and heat retention that is difficult to peel off when a load is applied under high temperature, it can be used for portable electronic device parts, in-vehicle electronic device parts, and the like. It is preferably used for assembling or fixing electronic device parts.
本発明によれば、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープを提供することができる。
According to the present invention, it is possible to provide an adhesive tape having excellent heat retention and holding property, which is difficult to peel off when a load is applied at a high temperature.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（実施例１）
（１）未発泡体基材の製造
１，６－ヘキサンジチオール０．９０２ｇと、二硫化炭素１．８３ｇと、ジメチルホルムアミド１１ｍＬとを２口フラスコに投入し、２５℃で攪拌した。これに、トリエチルアミン２．４９ｇを１５分かけて滴下し、２５℃で３時間攪拌した。次いで、メチル－α－ブロモフェニル酢酸２．７５ｇを１５分かけて滴下し、２５℃で４時間攪拌した。その後、反応液に抽出溶媒（ｎ－ヘキサン：酢酸エチル＝５０：５０）１００ｍＬと水５０ｍＬとを加えて分液抽出した。１回目と２回目の分液抽出で得られた有機層を混合し、１Ｍ塩酸５０ｍＬ、水５０ｍＬ、飽和食塩水５０ｍＬで順に洗浄した。洗浄後の有機層に硫酸ナトリウムを加えて乾燥した後、硫酸ナトリウムをろ過し、ろ液をエバポレーターで濃縮して、有機溶媒を除去した。得られた濃縮物をシリカゲルカラムクロマトグラフィにて精製することでＲＡＦＴ剤を得た。 (Example 1)
(1) Production of unfoamed base material 0.902 g of 1,6-hexanedithiol, 1.83 g of carbon disulfide, and 11 mL of dimethylformamide were placed in a two-necked flask and stirred at 25 ° C. To this, 2.49 g of triethylamine was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 3 hours. Then, 2.75 g of methyl-α-bromophenylacetic acid was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 4 hours. Then, 100 mL of an extraction solvent (n-hexane: ethyl acetate = 50: 50) and 50 mL of water were added to the reaction solution for liquid-liquid extraction. The organic layers obtained by the first and second liquid separation extractions were mixed and washed in order with 50 mL of 1 M hydrochloric acid, 50 mL of water and 50 mL of saturated brine. Sodium sulfate was added to the washed organic layer and dried, and then the sodium sulfate was filtered, and the filtrate was concentrated with an evaporator to remove the organic solvent. The obtained concentrate was purified by silica gel column chromatography to obtain a RAFT agent.
（１）未発泡体基材の製造
１，６－ヘキサンジチオール０．９０２ｇと、二硫化炭素１．８３ｇと、ジメチルホルムアミド１１ｍＬとを２口フラスコに投入し、２５℃で攪拌した。これに、トリエチルアミン２．４９ｇを１５分かけて滴下し、２５℃で３時間攪拌した。次いで、メチル－α－ブロモフェニル酢酸２．７５ｇを１５分かけて滴下し、２５℃で４時間攪拌した。その後、反応液に抽出溶媒（ｎ－ヘキサン：酢酸エチル＝５０：５０）１００ｍＬと水５０ｍＬとを加えて分液抽出した。１回目と２回目の分液抽出で得られた有機層を混合し、１Ｍ塩酸５０ｍＬ、水５０ｍＬ、飽和食塩水５０ｍＬで順に洗浄した。洗浄後の有機層に硫酸ナトリウムを加えて乾燥した後、硫酸ナトリウムをろ過し、ろ液をエバポレーターで濃縮して、有機溶媒を除去した。得られた濃縮物をシリカゲルカラムクロマトグラフィにて精製することでＲＡＦＴ剤を得た。 (Example 1)
(1) Production of unfoamed base material 0.902 g of 1,6-hexanedithiol, 1.83 g of carbon disulfide, and 11 mL of dimethylformamide were placed in a two-necked flask and stirred at 25 ° C. To this, 2.49 g of triethylamine was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 3 hours. Then, 2.75 g of methyl-α-bromophenylacetic acid was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 4 hours. Then, 100 mL of an extraction solvent (n-hexane: ethyl acetate = 50: 50) and 50 mL of water were added to the reaction solution for liquid-liquid extraction. The organic layers obtained by the first and second liquid separation extractions were mixed and washed in order with 50 mL of 1 M hydrochloric acid, 50 mL of water and 50 mL of saturated brine. Sodium sulfate was added to the washed organic layer and dried, and then the sodium sulfate was filtered, and the filtrate was concentrated with an evaporator to remove the organic solvent. The obtained concentrate was purified by silica gel column chromatography to obtain a RAFT agent.
スチレン（Ｓｔ）９３重量部と、アクリル酸（ＡＡｃ）６重量部と、ヒドロキシエチルアクリレート（ＨＥＡ）１重量部と、ＲＡＦＴ剤２．８重量部と、２，２’－アゾビス（２－メチルブチロニトリル）（ＡＢＮ－Ｅ）０．３５重量部とを２口フラスコに投入し、フラスコ内を窒素ガスで置換しながら８５℃に昇温した。その後、８５℃で６時間撹拌して重合反応を行った（第一段階反応）。
反応終了後、フラスコ内にｎ－ヘキサン４０００重量部を投入し、撹拌して反応物を沈殿させた後、未反応のモノマー（Ｓｔ、ＡＡｃ、ＨＥＡ）及びＲＡＦＴ剤をろ過し、反応物を７０℃で減圧乾燥して共重合体（ハードブロック）を得た。 93 parts by weight of styrene (St), 6 parts by weight of acrylic acid (AAc), 1 part by weight of hydroxyethyl acrylate (HEA), 2.8 parts by weight of RAFT agent, and 2,2'-azobis (2-methylbuty). 0.35 part by weight of bnitrile) (ABN-E) was put into a two-port flask, and the temperature was raised to 85 ° C. while replacing the inside of the flask with nitrogen gas. Then, the polymerization reaction was carried out by stirring at 85 ° C. for 6 hours (first step reaction).
After completion of the reaction, 4000 parts by weight of n-hexane was put into the flask and stirred to precipitate the reaction product, and then the unreacted monomers (St, AAc, HEA) and the RAFT agent were filtered to obtain 70 parts of the reaction product. A copolymer (hard block) was obtained by drying under reduced pressure at ° C.
反応終了後、フラスコ内にｎ－ヘキサン４０００重量部を投入し、撹拌して反応物を沈殿させた後、未反応のモノマー（Ｓｔ、ＡＡｃ、ＨＥＡ）及びＲＡＦＴ剤をろ過し、反応物を７０℃で減圧乾燥して共重合体（ハードブロック）を得た。 93 parts by weight of styrene (St), 6 parts by weight of acrylic acid (AAc), 1 part by weight of hydroxyethyl acrylate (HEA), 2.8 parts by weight of RAFT agent, and 2,2'-azobis (2-methylbuty). 0.35 part by weight of bnitrile) (ABN-E) was put into a two-port flask, and the temperature was raised to 85 ° C. while replacing the inside of the flask with nitrogen gas. Then, the polymerization reaction was carried out by stirring at 85 ° C. for 6 hours (first step reaction).
After completion of the reaction, 4000 parts by weight of n-hexane was put into the flask and stirred to precipitate the reaction product, and then the unreacted monomers (St, AAc, HEA) and the RAFT agent were filtered to obtain 70 parts of the reaction product. A copolymer (hard block) was obtained by drying under reduced pressure at ° C.
アクリル酸メチル（ＭＡ）４９．５重量部、アクリル酸ブチル（ＢＡ）４９．５重量部、アクリル酸（ＡＡｃ）１重量部、ＡＢＮ－Ｅ０．０５８重量部及び酢酸エチル５０重量部を含む混合物と、上記で得られた共重合体（ハードブロック）とを２口フラスコに投入し、フラスコ内を窒素ガスで置換しながら８５℃に昇温した。その後、８５℃で６時間撹拌して重合反応を行い（第二段階反応）、ハードブロックとソフトブロックとから形成されるブロック共重合体を含む反応液を得た。なお、混合物の配合量は、得られるブロック共重合体におけるハードブロックの含有量が３重量％、ソフトブロックの含有量が９７重量％となるように調整した。
反応液の一部を採取し、これにｎ－ヘキサン４０００重量部を投入し、撹拌して反応物を沈殿させた後、未反応のモノマー（ＭＡ、ＢＡ、ＡＡｃ）及び溶媒をろ過し、反応物を７０℃で減圧乾燥してブロック共重合体を得た。
得られたブロック共重合体について、ＧＰＣ法により重量平均分子量を測定したところ、３９．１万であった。なお、測定機器としてＷａｔｅｒ社製「２６９０ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｕｌｅ」、カラムとして昭和電工社製「ＧＰＣ ＫＦ－８０６Ｌ」、溶媒として酢酸エチルを用い、サンプル流量１ｍＬ／ｍｉｎ、カラム温度４０℃の条件で測定した。 With a mixture containing 49.5 parts by weight of methyl acrylate (MA), 49.5 parts by weight of butyl acrylate (BA), 1 part by weight of acrylic acid (AAc), 0.058 parts by weight of ABN-E, and 50 parts by weight of ethyl acetate. The copolymer (hard block) obtained above was put into a two-necked flask, and the temperature was raised to 85 ° C. while replacing the inside of the flask with nitrogen gas. Then, the polymerization reaction was carried out by stirring at 85 ° C. for 6 hours (second stage reaction) to obtain a reaction solution containing a block copolymer formed from a hard block and a soft block. The blending amount of the mixture was adjusted so that the content of the hard block in the obtained block copolymer was 3% by weight and the content of the soft block was 97% by weight.
A part of the reaction solution is collected, 4000 parts by weight of n-hexane is added thereto, and the mixture is stirred to precipitate the reaction product, and then the unreacted monomers (MA, BA, AAc) and the solvent are filtered to react. The product was dried under reduced pressure at 70 ° C. to obtain a block copolymer.
The weight average molecular weight of the obtained block copolymer was measured by the GPC method and found to be 391,000. In addition, "2690 Separations Module" manufactured by Water Co., Ltd. was used as a measuring instrument, "GPC KF-806L" manufactured by Showa Denko Co., Ltd. was used as a column, and ethyl acetate was used as a solvent, and the measurement was performed under the conditions of a sample flow rate of 1 mL / min and a column temperature of 40 ° C.
反応液の一部を採取し、これにｎ－ヘキサン４０００重量部を投入し、撹拌して反応物を沈殿させた後、未反応のモノマー（ＭＡ、ＢＡ、ＡＡｃ）及び溶媒をろ過し、反応物を７０℃で減圧乾燥してブロック共重合体を得た。
得られたブロック共重合体について、ＧＰＣ法により重量平均分子量を測定したところ、３９．１万であった。なお、測定機器としてＷａｔｅｒ社製「２６９０ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｕｌｅ」、カラムとして昭和電工社製「ＧＰＣ ＫＦ－８０６Ｌ」、溶媒として酢酸エチルを用い、サンプル流量１ｍＬ／ｍｉｎ、カラム温度４０℃の条件で測定した。 With a mixture containing 49.5 parts by weight of methyl acrylate (MA), 49.5 parts by weight of butyl acrylate (BA), 1 part by weight of acrylic acid (AAc), 0.058 parts by weight of ABN-E, and 50 parts by weight of ethyl acetate. The copolymer (hard block) obtained above was put into a two-necked flask, and the temperature was raised to 85 ° C. while replacing the inside of the flask with nitrogen gas. Then, the polymerization reaction was carried out by stirring at 85 ° C. for 6 hours (second stage reaction) to obtain a reaction solution containing a block copolymer formed from a hard block and a soft block. The blending amount of the mixture was adjusted so that the content of the hard block in the obtained block copolymer was 3% by weight and the content of the soft block was 97% by weight.
A part of the reaction solution is collected, 4000 parts by weight of n-hexane is added thereto, and the mixture is stirred to precipitate the reaction product, and then the unreacted monomers (MA, BA, AAc) and the solvent are filtered to react. The product was dried under reduced pressure at 70 ° C. to obtain a block copolymer.
The weight average molecular weight of the obtained block copolymer was measured by the GPC method and found to be 391,000. In addition, "2690 Separations Module" manufactured by Water Co., Ltd. was used as a measuring instrument, "GPC KF-806L" manufactured by Showa Denko Co., Ltd. was used as a column, and ethyl acetate was used as a solvent, and the measurement was performed under the conditions of a sample flow rate of 1 mL / min and a column temperature of 40 ° C.
得られたブロック共重合体を固形分率が３５％になるよう酢酸エチルに溶解させた。ブロック共重合体１００重量部に対して、発泡剤（発泡粒子）としてエクスパンセル４６１－ＤＵ－４０（４６１ＤＵ４０）（日本フィライト社製）３．３重量部、架橋剤としてテトラッドＣ（エポキシ系架橋剤、三菱ガス化学社製）０．１６重量部を固形分率比で加えて更に充分に撹拌し、基材溶液を得た。得られた基材溶液を、樹脂層としての両面にコロナ処理を施した２３μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムの片面上に塗工し、９０℃７分間乾燥させることで未発泡体基材と樹脂層との積層体を得た。
The obtained block copolymer was dissolved in ethyl acetate so that the solid content was 35%. With respect to 100 parts by weight of the block copolymer, 3.3 parts by weight of Expandel 461-DU-40 (461DU40) (manufactured by Nippon Philite) as a foaming agent (foaming particles) and Tetrad C (epoxy-based cross-linking) as a cross-linking agent. Agent, manufactured by Mitsubishi Gas Chemical Company, Ltd.) 0.16 parts by weight was added at a solid content ratio and further sufficiently stirred to obtain a substrate solution. The obtained base material solution was applied onto one side of a 23 μm polyethylene terephthalate (PET) film having corona treatment on both sides as a resin layer, and dried at 90 ° C. for 7 minutes to obtain an unfoamed base material and a resin. A laminate with the layer was obtained.
（２）アクリル共重合体の製造
温度計、攪拌機、冷却管を備えた反応器に酢酸エチル５２重量部を入れて、窒素置換した後、反応器を加熱して還流を開始した。酢酸エチルが沸騰してから、３０分後に重合開始剤としてアゾビスイソブチロニトリル０．０８重量部を投入した。ここにブチルアクリレート７０重量部、２－エチルヘキシルアクリレート２７重量部、アクリル酸３重量部、２－ヒドロキシエチルアクリレート０．２重量部からなるモノマー混合物を１時間３０分かけて、均等かつ徐々に滴下し反応させた。滴下終了３０分後にアゾビスイソブチロニトリル０．１重量部を添加し、更に５時間重合反応させ、反応器内に酢酸エチルを加えて希釈しながら冷却することにより、固形分４０重量％のアクリル共重合体の溶液を得た。
得られたアクリル共重合体について、カラムとしてＷａｔｅｒ社製「２６９０ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｅｌ」を用いてＧＰＣ法により重量平均分子量を測定したところ、７１万であった。数平均分子量（Ｍｎ）に対する重量平均分子量（Ｍｗ）の比（Ｍｗ／Ｍｎ）は５．５であった。 (2) Production of Acrylic Copolymer 52 parts by weight of ethyl acetate was placed in a reactor equipped with a thermometer, a stirrer, and a cooling tube, and after nitrogen substitution, the reactor was heated to start reflux. Thirty minutes after the ethyl acetate boiled, 0.08 part by weight of azobisisobutyronitrile was added as a polymerization initiator. A monomer mixture consisting of 70 parts by weight of butyl acrylate, 27 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, and 0.2 parts by weight of 2-hydroxyethyl acrylate was added dropwise thereto evenly and gradually over 1 hour and 30 minutes. It was reacted. Thirty minutes after the completion of the dropping, 0.1 part by weight of azobisisobutyronitrile was added, and the polymerization reaction was further carried out for 5 hours. Ethyl acetate was added to the reactor and cooled while diluting to obtain a solid content of 40% by weight. A solution of acrylic copolymer was obtained.
The weight average molecular weight of the obtained acrylic copolymer was 710,000 as a result of measuring the weight average molecular weight by the GPC method using "2690 Separations Model" manufactured by Water Co., Ltd. as a column. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 5.5.
温度計、攪拌機、冷却管を備えた反応器に酢酸エチル５２重量部を入れて、窒素置換した後、反応器を加熱して還流を開始した。酢酸エチルが沸騰してから、３０分後に重合開始剤としてアゾビスイソブチロニトリル０．０８重量部を投入した。ここにブチルアクリレート７０重量部、２－エチルヘキシルアクリレート２７重量部、アクリル酸３重量部、２－ヒドロキシエチルアクリレート０．２重量部からなるモノマー混合物を１時間３０分かけて、均等かつ徐々に滴下し反応させた。滴下終了３０分後にアゾビスイソブチロニトリル０．１重量部を添加し、更に５時間重合反応させ、反応器内に酢酸エチルを加えて希釈しながら冷却することにより、固形分４０重量％のアクリル共重合体の溶液を得た。
得られたアクリル共重合体について、カラムとしてＷａｔｅｒ社製「２６９０ Ｓｅｐａｒａｔｉｏｎｓ Ｍｏｄｅｌ」を用いてＧＰＣ法により重量平均分子量を測定したところ、７１万であった。数平均分子量（Ｍｎ）に対する重量平均分子量（Ｍｗ）の比（Ｍｗ／Ｍｎ）は５．５であった。 (2) Production of Acrylic Copolymer 52 parts by weight of ethyl acetate was placed in a reactor equipped with a thermometer, a stirrer, and a cooling tube, and after nitrogen substitution, the reactor was heated to start reflux. Thirty minutes after the ethyl acetate boiled, 0.08 part by weight of azobisisobutyronitrile was added as a polymerization initiator. A monomer mixture consisting of 70 parts by weight of butyl acrylate, 27 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, and 0.2 parts by weight of 2-hydroxyethyl acrylate was added dropwise thereto evenly and gradually over 1 hour and 30 minutes. It was reacted. Thirty minutes after the completion of the dropping, 0.1 part by weight of azobisisobutyronitrile was added, and the polymerization reaction was further carried out for 5 hours. Ethyl acetate was added to the reactor and cooled while diluting to obtain a solid content of 40% by weight. A solution of acrylic copolymer was obtained.
The weight average molecular weight of the obtained acrylic copolymer was 710,000 as a result of measuring the weight average molecular weight by the GPC method using "2690 Separations Model" manufactured by Water Co., Ltd. as a column. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was 5.5.
（３）粘着テープの製造
得られたアクリル共重合体の固形分１００重量部に対して、軟化点１５０℃の重合ロジンエステル１５重量部、軟化点１４５℃のテルペンフェノール１０重量部、軟化点７０℃のロジンエステル１０重量部を添加した。更に、酢酸エチル（不二化学薬品社製）３０重量部、イソシアネート系架橋剤（東ソー社製 コロネートＬ４５）３．０重量部を添加し、攪拌して、粘着剤溶液を得た。
片面に離型処理を施した５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムの離型処理面上に、得られた粘着剤溶液を乾燥皮膜の厚さが７５μｍとなるようにドクターナイフで塗工し、１１０℃、５分間加熱して塗工溶液を乾燥させ、粘着剤層を得た。同様の操作で粘着剤層をもう１つ製造した。その後、上記で得られた未発泡体基材と樹脂層との積層体に粘着剤層をそれぞれの面へラミネート積層し、積層体を得た。４０℃の環境下に４８時間静置し、４８時間後に４０℃環境から取り出し、１３０℃１分加熱することで未発泡体基材を発泡させて発泡体基材（厚み１２７μｍ）とし、粘着テープを得た。 (3) Production of Adhesive Tape With respect to 100 parts by weight of the solid content of the obtained acrylic copolymer, 15 parts by weight of the polymerized rosin ester having a softening point of 150 ° C., 10 parts by weight of terpenphenol having a softening point of 145 ° C., and 70 parts by weight of the softening point. 10 parts by weight of rosin ester at ° C was added. Further, 30 parts by weight of ethyl acetate (manufactured by Fuji Chemical Co., Ltd.) and 3.0 parts by weight of an isocyanate-based cross-linking agent (Coronate L45 manufactured by Tosoh Co., Ltd.) were added and stirred to obtain a pressure-sensitive adhesive solution.
On the release-treated surface of a 50 μm polyethylene terephthalate (PET) film with a mold release treatment on one side, the obtained adhesive solution was applied with a doctor knife so that the thickness of the dry film was 75 μm, and 110 The coating solution was dried by heating at ° C. for 5 minutes to obtain a pressure-sensitive adhesive layer. Another pressure-sensitive adhesive layer was manufactured by the same operation. Then, the pressure-sensitive adhesive layer was laminated on each surface of the laminate of the unfoamed base material and the resin layer obtained above to obtain a laminate. The unfoamed substrate is allowed to stand in an environment of 40 ° C. for 48 hours, removed from the environment at 40 ° C. after 48 hours, and heated at 130 ° C. for 1 minute to foam the unfoamed substrate to form a foamed substrate (thickness 127 μm), which is an adhesive tape. Got
得られたアクリル共重合体の固形分１００重量部に対して、軟化点１５０℃の重合ロジンエステル１５重量部、軟化点１４５℃のテルペンフェノール１０重量部、軟化点７０℃のロジンエステル１０重量部を添加した。更に、酢酸エチル（不二化学薬品社製）３０重量部、イソシアネート系架橋剤（東ソー社製 コロネートＬ４５）３．０重量部を添加し、攪拌して、粘着剤溶液を得た。
片面に離型処理を施した５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムの離型処理面上に、得られた粘着剤溶液を乾燥皮膜の厚さが７５μｍとなるようにドクターナイフで塗工し、１１０℃、５分間加熱して塗工溶液を乾燥させ、粘着剤層を得た。同様の操作で粘着剤層をもう１つ製造した。その後、上記で得られた未発泡体基材と樹脂層との積層体に粘着剤層をそれぞれの面へラミネート積層し、積層体を得た。４０℃の環境下に４８時間静置し、４８時間後に４０℃環境から取り出し、１３０℃１分加熱することで未発泡体基材を発泡させて発泡体基材（厚み１２７μｍ）とし、粘着テープを得た。 (3) Production of Adhesive Tape With respect to 100 parts by weight of the solid content of the obtained acrylic copolymer, 15 parts by weight of the polymerized rosin ester having a softening point of 150 ° C., 10 parts by weight of terpenphenol having a softening point of 145 ° C., and 70 parts by weight of the softening point. 10 parts by weight of rosin ester at ° C was added. Further, 30 parts by weight of ethyl acetate (manufactured by Fuji Chemical Co., Ltd.) and 3.0 parts by weight of an isocyanate-based cross-linking agent (Coronate L45 manufactured by Tosoh Co., Ltd.) were added and stirred to obtain a pressure-sensitive adhesive solution.
On the release-treated surface of a 50 μm polyethylene terephthalate (PET) film with a mold release treatment on one side, the obtained adhesive solution was applied with a doctor knife so that the thickness of the dry film was 75 μm, and 110 The coating solution was dried by heating at ° C. for 5 minutes to obtain a pressure-sensitive adhesive layer. Another pressure-sensitive adhesive layer was manufactured by the same operation. Then, the pressure-sensitive adhesive layer was laminated on each surface of the laminate of the unfoamed base material and the resin layer obtained above to obtain a laminate. The unfoamed substrate is allowed to stand in an environment of 40 ° C. for 48 hours, removed from the environment at 40 ° C. after 48 hours, and heated at 130 ° C. for 1 minute to foam the unfoamed substrate to form a foamed substrate (thickness 127 μm), which is an adhesive tape. Got
（４）基材のゲル分率の測定
粘着テープから基材のみを０．１ｇ取り出し、酢酸エチル５０ｍＬ中に浸漬し、振とう機で温度２３度、１２０ｒｐｍの条件で２４時間振とうした。振とう後、金属メッシュ（目開き＃２００メッシュ）を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した基材を分離した。分離後の基材を１１０℃の条件下で１時間乾燥させた。乾燥後の金属メッシュを含む基材の重量を測定し、下記式を用いて基材のゲル分率を算出した。
ゲル分率（重量％）＝１００×（Ｗ１－Ｗ２）／Ｗ０
（Ｗ０：初期基材重量、Ｗ１：乾燥後の金属メッシュを含む基材重量、Ｗ２：金属メッシュの初期重量） (4) Measurement of gel fraction of the substrate Only 0.1 g of the substrate was taken out from the adhesive tape, immersed in 50 mL of ethyl acetate, and shaken with a shaker at a temperature of 23 ° C. and 120 rpm for 24 hours. After shaking, a metal mesh (opening # 200 mesh) was used to absorb ethyl acetate and ethyl acetate, and the swollen substrate was separated. The separated substrate was dried under the condition of 110 ° C. for 1 hour. The weight of the base material including the metal mesh after drying was measured, and the gel fraction of the base material was calculated using the following formula.
Gel fraction (% by weight) = 100 x (W 1 -W 2 ) / W 0
(W 0 : weight of initial base material, W 1 : weight of base material including dried metal mesh, W 2 : initial weight of metal mesh)
粘着テープから基材のみを０．１ｇ取り出し、酢酸エチル５０ｍＬ中に浸漬し、振とう機で温度２３度、１２０ｒｐｍの条件で２４時間振とうした。振とう後、金属メッシュ（目開き＃２００メッシュ）を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した基材を分離した。分離後の基材を１１０℃の条件下で１時間乾燥させた。乾燥後の金属メッシュを含む基材の重量を測定し、下記式を用いて基材のゲル分率を算出した。
ゲル分率（重量％）＝１００×（Ｗ１－Ｗ２）／Ｗ０
（Ｗ０：初期基材重量、Ｗ１：乾燥後の金属メッシュを含む基材重量、Ｗ２：金属メッシュの初期重量） (4) Measurement of gel fraction of the substrate Only 0.1 g of the substrate was taken out from the adhesive tape, immersed in 50 mL of ethyl acetate, and shaken with a shaker at a temperature of 23 ° C. and 120 rpm for 24 hours. After shaking, a metal mesh (opening # 200 mesh) was used to absorb ethyl acetate and ethyl acetate, and the swollen substrate was separated. The separated substrate was dried under the condition of 110 ° C. for 1 hour. The weight of the base material including the metal mesh after drying was measured, and the gel fraction of the base material was calculated using the following formula.
Gel fraction (% by weight) = 100 x (W 1 -W 2 ) / W 0
(W 0 : weight of initial base material, W 1 : weight of base material including dried metal mesh, W 2 : initial weight of metal mesh)
（５）粘着テープのＬ成分の緩和時間の測定
粘着テープを直径１０ｍｍのガラス製のサンプル管（ＢＲＵＫＥＲ製、品番１８２４５１１、１０ｍｍ径、長さ１８０ｍｍ、フラットボトム）に約７００ｍｇ（高さ約２ｃｍ）導入した。サンプルをパルスＮＭＲ装置（ｔｈｅ ｍｉｎｉｓｐｅｃ ｍｑ２０、ＢＲＵＫＥＲ製）に設置し、２５℃又は８５℃で１０分保持後、Ｈａｈｎ Ｅｃｈｏ法を行った。得られた１Ｈ核のスピン－スピン緩和の自由誘導減衰曲線を、Ｓ成分、Ｍ成分及びＬ成分の３成分に由来する３つの曲線、又は、Ｓ成分及びＬ成分の２成分に由来する２つの曲線に波形分離し、Ｌ成分の緩和時間を求めた。波形分離は、ガウシアン型とエクスポーネンシャル型との両方を用いて、フィッティングさせることで行った。 (5) Measurement of relaxation time of L component of adhesive tape Approximately 700 mg (height approximately 2 cm) of the adhesive tape in a glass sample tube (BRUKER, product number 1824511, 10 mm diameter, length 180 mm, flat bottom) with a diameter of 10 mm. Introduced. The sample was placed in a pulse NMR apparatus (the minispec mq20, manufactured by BRUKER) and held at 25 ° C. or 85 ° C. for 10 minutes, and then the Han Echo method was performed. The obtained 1H nucleus spin-spin relaxation free induction decay curve is derived from three curves derived from the S component, the M component and the L component, or two derived from the two components of the S component and the L component. The waveform was separated into two curves, and the relaxation time of the L component was obtained. Waveform separation was performed by fitting using both Gaussian type and exponential type.
粘着テープを直径１０ｍｍのガラス製のサンプル管（ＢＲＵＫＥＲ製、品番１８２４５１１、１０ｍｍ径、長さ１８０ｍｍ、フラットボトム）に約７００ｍｇ（高さ約２ｃｍ）導入した。サンプルをパルスＮＭＲ装置（ｔｈｅ ｍｉｎｉｓｐｅｃ ｍｑ２０、ＢＲＵＫＥＲ製）に設置し、２５℃又は８５℃で１０分保持後、Ｈａｈｎ Ｅｃｈｏ法を行った。得られた１Ｈ核のスピン－スピン緩和の自由誘導減衰曲線を、Ｓ成分、Ｍ成分及びＬ成分の３成分に由来する３つの曲線、又は、Ｓ成分及びＬ成分の２成分に由来する２つの曲線に波形分離し、Ｌ成分の緩和時間を求めた。波形分離は、ガウシアン型とエクスポーネンシャル型との両方を用いて、フィッティングさせることで行った。 (5) Measurement of relaxation time of L component of adhesive tape Approximately 700 mg (height approximately 2 cm) of the adhesive tape in a glass sample tube (BRUKER, product number 1824511, 10 mm diameter, length 180 mm, flat bottom) with a diameter of 10 mm. Introduced. The sample was placed in a pulse NMR apparatus (the minispec mq20, manufactured by BRUKER) and held at 25 ° C. or 85 ° C. for 10 minutes, and then the Han Echo method was performed. The obtained 1H nucleus spin-spin relaxation free induction decay curve is derived from three curves derived from the S component, the M component and the L component, or two derived from the two components of the S component and the L component. The waveform was separated into two curves, and the relaxation time of the L component was obtained. Waveform separation was performed by fitting using both Gaussian type and exponential type.
なお、ＢＲＵＫＥＲ社製の解析ソフトウエア「ＴＤ－ＮＭＲＡ（Ｖｅｒｓｉｏｎ ４．３ Ｒｅｖ ０．８）」を用い、製品マニュアルに従って、２５℃で得られた緩和曲線ではＳ成分はガウシアン型、Ｍ成分及びＬ成分はエクスポーネンシャル型を用い、８５℃で得られた緩和曲線では全てエクスポーネンシャル型でフィッティングを行った。また、フィッティングには２５℃及び８５℃のそれぞれで以下の式を用いた。
In addition, using the analysis software "TD-NMRA (Version 4.3 Rev 0.8)" manufactured by BRUKER, the S component is Gaussian type, M component and L in the relaxation curve obtained at 25 ° C according to the product manual. The components used were the exponential type, and all the relaxation curves obtained at 85 ° C. were fitted with the exponential type. The following formulas were used for fitting at 25 ° C and 85 ° C, respectively.
ここで、ｗ１～ｗ３はワイブル係数である。
２５℃の場合はｗ１は２、ｗ２及びｗ３は１の値を取る。Ａ１はＳ成分の、Ｂ１はＭ成分の、Ｃ１はＬ成分のそれぞれ成分比であり、Ｔ２ＡはＳ成分の、Ｔ２ＢはＭ成分の、Ｔ２ＣはＬ成分のそれぞれ緩和時間を示す。ｔは時間である。
８５℃の場合はｗ１及び２は１の値を取る。Ａ１はＳ成分の、Ｂ１はＬ成分のそれぞれ成分比であり、Ｔ２ＡはＳ成分の、Ｔ２ＢはＬ成分のそれぞれ緩和時間を示す。ｔは時間である。 Here, w1 to w3 are Weibull coefficients.
At 25 ° C, w1 takes a value of 2 and w2 and w3 take a value of 1. A1 is the S component, B1 is the M component, C1 is the L component ratio, T2A is the S component, T2B is the M component, and T2C is the L component. t is time.
At 85 ° C, w1 and 2 take a value of 1. A1 is the component ratio of the S component, B1 is the component ratio of the L component, T2A is the relaxation time of the S component, and T2B is the relaxation time of the L component. t is time.
２５℃の場合はｗ１は２、ｗ２及びｗ３は１の値を取る。Ａ１はＳ成分の、Ｂ１はＭ成分の、Ｃ１はＬ成分のそれぞれ成分比であり、Ｔ２ＡはＳ成分の、Ｔ２ＢはＭ成分の、Ｔ２ＣはＬ成分のそれぞれ緩和時間を示す。ｔは時間である。
８５℃の場合はｗ１及び２は１の値を取る。Ａ１はＳ成分の、Ｂ１はＬ成分のそれぞれ成分比であり、Ｔ２ＡはＳ成分の、Ｔ２ＢはＬ成分のそれぞれ緩和時間を示す。ｔは時間である。 Here, w1 to w3 are Weibull coefficients.
At 25 ° C, w1 takes a value of 2 and w2 and w3 take a value of 1. A1 is the S component, B1 is the M component, C1 is the L component ratio, T2A is the S component, T2B is the M component, and T2C is the L component. t is time.
At 85 ° C, w1 and 2 take a value of 1. A1 is the component ratio of the S component, B1 is the component ratio of the L component, T2A is the relaxation time of the S component, and T2B is the relaxation time of the L component. t is time.
［測定条件］
Ｓｃａｎｓ：１６
Ｒｅｃｙｃｌｅ Ｄｅｒａｙ：１ｓｅｃ
Ｆｉｒｓｔ ９０－１８０ Ｐｕｌｓｅ Ｓｅｐａｒａｔｉｏｎ：０．００８２
Ｆｉｎａｌ Ｐｕｌｓｅ Ｓｅｐａｒａｔｉｏｎ（ｍｓ）：５（２５℃）、５０（８５℃）
Ｎｕｍｂｅｒ ｏｆ Ｄａｔａ Ｐｏｉｎｔｓ ｆｏｒ Ｆｉｔｔｉｎｇ：１００ [Measurement condition]
Scans: 16
Recycle Day: 1sec
First 90-180 Pulse Separation: 0.0082
Final Pulse Separation (ms): 5 (25 ° C), 50 (85 ° C)
Number of Data Points for Fitting: 100
Ｓｃａｎｓ：１６
Ｒｅｃｙｃｌｅ Ｄｅｒａｙ：１ｓｅｃ
Ｆｉｒｓｔ ９０－１８０ Ｐｕｌｓｅ Ｓｅｐａｒａｔｉｏｎ：０．００８２
Ｆｉｎａｌ Ｐｕｌｓｅ Ｓｅｐａｒａｔｉｏｎ（ｍｓ）：５（２５℃）、５０（８５℃）
Ｎｕｍｂｅｒ ｏｆ Ｄａｔａ Ｐｏｉｎｔｓ ｆｏｒ Ｆｉｔｔｉｎｇ：１００ [Measurement condition]
Scans: 16
Recycle Day: 1sec
First 90-180 Pulse Separation: 0.0082
Final Pulse Separation (ms): 5 (25 ° C), 50 (85 ° C)
Number of Data Points for Fitting: 100
（実施例２～９、比較例１～２）
基材及び樹脂層を表１に示すように変更したこと以外は実施例１と同様にして、粘着テープを得た。なお、実施例８～９ではＲＡＦＴ剤は用いず、ＡＢＮ－Ｅのみを用いた一段階の合成反応（ランダム共重合）により共重合体を得た。また、比較例２ではセプトン２０６３（スチレン－エチレン－プロピレン－スチレンブロックポリマー樹脂、クラレ社製）のトルエン３０％溶液を用い、架橋剤としてのテトラッドＣ（エポキシ系架橋剤、三菱ガス化学社製）は添加しなかった。表中の原料は以下のとおりである。 (Examples 2 to 9, Comparative Examples 1 to 2)
An adhesive tape was obtained in the same manner as in Example 1 except that the base material and the resin layer were changed as shown in Table 1. In Examples 8 to 9, a copolymer was obtained by a one-step synthetic reaction (random copolymerization) using only ABN-E without using a RAFT agent. Further, in Comparative Example 2, a 30% toluene solution of Septon 2063 (styrene-ethylene-propylene-styrene block polymer resin, manufactured by Kuraray Co., Ltd.) was used, and Tetrad C (epoxy-based cross-linking agent, manufactured by Mitsubishi Gas Chemical Company, Inc.) was used as a cross-linking agent. Was not added. The raw materials in the table are as follows.
基材及び樹脂層を表１に示すように変更したこと以外は実施例１と同様にして、粘着テープを得た。なお、実施例８～９ではＲＡＦＴ剤は用いず、ＡＢＮ－Ｅのみを用いた一段階の合成反応（ランダム共重合）により共重合体を得た。また、比較例２ではセプトン２０６３（スチレン－エチレン－プロピレン－スチレンブロックポリマー樹脂、クラレ社製）のトルエン３０％溶液を用い、架橋剤としてのテトラッドＣ（エポキシ系架橋剤、三菱ガス化学社製）は添加しなかった。表中の原料は以下のとおりである。 (Examples 2 to 9, Comparative Examples 1 to 2)
An adhesive tape was obtained in the same manner as in Example 1 except that the base material and the resin layer were changed as shown in Table 1. In Examples 8 to 9, a copolymer was obtained by a one-step synthetic reaction (random copolymerization) using only ABN-E without using a RAFT agent. Further, in Comparative Example 2, a 30% toluene solution of Septon 2063 (styrene-ethylene-propylene-styrene block polymer resin, manufactured by Kuraray Co., Ltd.) was used, and Tetrad C (epoxy-based cross-linking agent, manufactured by Mitsubishi Gas Chemical Company, Inc.) was used as a cross-linking agent. Was not added. The raw materials in the table are as follows.
・発泡剤（発泡粒子）
アドバンセルＥＭＬ１０１（積水化学工業社製、未発泡基材の加熱発泡工程を１５０℃１分にて行った） ・ Foaming agent (foaming particles)
Advansel EML101 (manufactured by Sekisui Chemical Co., Ltd., the heating and foaming process of the unfoamed substrate was performed at 150 ° C. for 1 minute)
アドバンセルＥＭＬ１０１（積水化学工業社製、未発泡基材の加熱発泡工程を１５０℃１分にて行った） ・ Foaming agent (foaming particles)
Advansel EML101 (manufactured by Sekisui Chemical Co., Ltd., the heating and foaming process of the unfoamed substrate was performed at 150 ° C. for 1 minute)
・基材の原料モノマー
２ＥＨＡ（２－エチルヘキシルアクリレート）
ＡＳ－６Ｓ（スチレンマクロマー、東亞合成社製）
オレフィン（セプトン２０６３、スチレン－エチレン－プロピレン－スチレンブロックポリマー樹脂、クラレ社製） ・ Raw material monomer 2EHA (2-ethylhexyl acrylate) for the base material
AS-6S (Styrene Macromer, manufactured by Toagosei Co., Ltd.)
Olefin (Septon 2063, Styrene-Ethylene-Propene-Styrene Block Polymer Resin, manufactured by Kuraray)
２ＥＨＡ（２－エチルヘキシルアクリレート）
ＡＳ－６Ｓ（スチレンマクロマー、東亞合成社製）
オレフィン（セプトン２０６３、スチレン－エチレン－プロピレン－スチレンブロックポリマー樹脂、クラレ社製） ・ Raw material monomer 2EHA (2-ethylhexyl acrylate) for the base material
AS-6S (Styrene Macromer, manufactured by Toagosei Co., Ltd.)
Olefin (Septon 2063, Styrene-Ethylene-Propene-Styrene Block Polymer Resin, manufactured by Kuraray)
＜評価＞
実施例、比較例で得られた粘着テープについて以下の評価を行った。結果を表１に示した。 <Evaluation>
The following evaluations were performed on the adhesive tapes obtained in Examples and Comparative Examples. The results are shown in Table 1.
実施例、比較例で得られた粘着テープについて以下の評価を行った。結果を表１に示した。 <Evaluation>
The following evaluations were performed on the adhesive tapes obtained in Examples and Comparative Examples. The results are shown in Table 1.
（１）耐熱保持性の評価（保持力試験）
図１及び図２に、粘着テープの保持力試験を模式的に示す図を示す。
図１（正面図）及び図２（側面図）に示すように、粘着テープのサイズ２５ｍｍ×２５ｍｍの試験片１の一方の面（表面）をＳＵＳ板２に貼り合わせ、試験片１の他方の面（裏面）側から２ｋｇのゴムローラを３００ｍｍ／分の速度で一往復させた。次いで、試験片１の裏面にアルミ板３を貼り合わせ、アルミ板３側から０．５ｋｇの重りで１０秒間加圧して圧着させた後、２３℃、相対湿度５０％の環境下に２４時間放置し、保持力試験用サンプルを作製した。
保持力試験用サンプルを８５℃において、アルミ板３の一端に試験片１及びアルミ板３に対して水平方向に荷重がかかるように１ｋｇの重り４を取り付け、１時間後の重りのズレ量（ズレ長さ）を測定した。ズレ量が０ｍｍであった（ズレがなかった）場合を◎、ズレ量が０ｍｍより大きく、１ｍｍ未満であった場合を〇、ズレ量が１ｍｍ以上又は粘着テープが剥離して落下してしまった場合を×とした。 (1) Evaluation of heat retention (holding power test)
1 and 2 show a diagram schematically showing a holding force test of the adhesive tape.
As shown in FIGS. 1 (front view) and 2 (side view), one surface (surface) of thetest piece 1 having an adhesive tape size of 25 mm × 25 mm is attached to the SUS plate 2 and the other side of the test piece 1 is attached. A 2 kg rubber roller was reciprocated once from the front surface (back surface) side at a speed of 300 mm / min. Next, the aluminum plate 3 is attached to the back surface of the test piece 1, pressed from the side of the aluminum plate 3 with a weight of 0.5 kg for 10 seconds to be crimped, and then left in an environment of 23 ° C. and 50% relative humidity for 24 hours. Then, a sample for holding force test was prepared.
A 1kg weight 4 is attached to one end of the aluminum plate 3 so that a load is applied horizontally to the test piece 1 and the aluminum plate 3 at 85 ° C. for the holding force test sample, and the amount of deviation of the weight after 1 hour ( The deviation length) was measured. ◎ when the amount of deviation was 0 mm (no deviation), 〇 when the amount of deviation was larger than 0 mm and less than 1 mm, the amount of deviation was 1 mm or more, or the adhesive tape fell off. The case was set to x.
図１及び図２に、粘着テープの保持力試験を模式的に示す図を示す。
図１（正面図）及び図２（側面図）に示すように、粘着テープのサイズ２５ｍｍ×２５ｍｍの試験片１の一方の面（表面）をＳＵＳ板２に貼り合わせ、試験片１の他方の面（裏面）側から２ｋｇのゴムローラを３００ｍｍ／分の速度で一往復させた。次いで、試験片１の裏面にアルミ板３を貼り合わせ、アルミ板３側から０．５ｋｇの重りで１０秒間加圧して圧着させた後、２３℃、相対湿度５０％の環境下に２４時間放置し、保持力試験用サンプルを作製した。
保持力試験用サンプルを８５℃において、アルミ板３の一端に試験片１及びアルミ板３に対して水平方向に荷重がかかるように１ｋｇの重り４を取り付け、１時間後の重りのズレ量（ズレ長さ）を測定した。ズレ量が０ｍｍであった（ズレがなかった）場合を◎、ズレ量が０ｍｍより大きく、１ｍｍ未満であった場合を〇、ズレ量が１ｍｍ以上又は粘着テープが剥離して落下してしまった場合を×とした。 (1) Evaluation of heat retention (holding power test)
1 and 2 show a diagram schematically showing a holding force test of the adhesive tape.
As shown in FIGS. 1 (front view) and 2 (side view), one surface (surface) of the
A 1
本発明によれば、高温下で負荷がかかった際に剥離しにくい耐熱保持性に優れた粘着テープを提供することができる。
According to the present invention, it is possible to provide an adhesive tape having excellent heat retention and holding property, which is difficult to peel off when a load is applied at a high temperature.
１ 試験片（粘着テープ）
２ ＳＵＳ板
３ アルミ板
４ 重り（１ｋｇ）
1 Test piece (adhesive tape)
2 SUS plate 3 Aluminum plate 4 Weight (1 kg)
２ ＳＵＳ板
３ アルミ板
４ 重り（１ｋｇ）
1 Test piece (adhesive tape)
Claims (7)
- 基材と、前記基材の少なくとも一方の面に積層された粘着剤層とを有する粘着テープであって、
パルスＮＭＲを用いて２５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ２５）が０．９ミリ秒以下である
ことを特徴とする粘着テープ。 An adhesive tape having a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material.
An adhesive tape characterized in that the relaxation time ( TL25 ) of the L component obtained by measuring at 25 ° C. by the Han Echo method using pulse NMR is 0.9 ms or less. - 基材と、前記基材の少なくとも一方の面に積層された粘着剤層とを有する粘着テープであって、
パルスＮＭＲを用いて８５℃でＨａｈｎ Ｅｃｈｏ法にて測定して得られたＬ成分の緩和時間（ＴＬ８５）が３．３ミリ秒以下である
ことを特徴とする粘着テープ。 An adhesive tape having a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material.
An adhesive tape characterized in that the relaxation time ( TL85 ) of the L component obtained by measuring at 85 ° C. by the Han Echo method using pulse NMR is 3.3 milliseconds or less. - 前記基材は、ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体を含有することを特徴とする請求項１又は２記載の粘着テープ。 The adhesive tape according to claim 1 or 2, wherein the base material contains a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer.
- 前記ビニル芳香族モノマーに由来する構造及び（メタ）アクリル系モノマーに由来する構造を有する共重合体は、ブロック共重合体であることを特徴とする請求項３記載の粘着テープ。 The adhesive tape according to claim 3, wherein the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is a block copolymer.
- 前記基材は、発泡体基材であることを特徴とする請求項１、２、３又は４記載の粘着テープ。 The adhesive tape according to claim 1, 2, 3 or 4, wherein the base material is a foam base material.
- 前記粘着剤層が前記基材の両面に積層されていることを特徴とする請求項１、２、３、４又は５記載の粘着テープ。 The pressure-sensitive adhesive tape according to claim 1, 2, 3, 4 or 5, wherein the pressure-sensitive adhesive layer is laminated on both surfaces of the base material.
- 電子機器部品の組み立て又は固定に用いられることを特徴とする請求項１、２、３、４、５又は６記載の粘着テープ。 The adhesive tape according to claim 1, 2, 3, 4, 5 or 6, which is used for assembling or fixing electronic device parts.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022507716A JPWO2022092201A1 (en) | 2020-10-28 | 2021-10-28 | |
| KR1020237000292A KR20230092862A (en) | 2020-10-28 | 2021-10-28 | adhesive tape |
| CN202180058188.3A CN116096829A (en) | 2020-10-28 | 2021-10-28 | Adhesive tape |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-180950 | 2020-10-28 | ||
| JP2020180950 | 2020-10-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022092201A1 true WO2022092201A1 (en) | 2022-05-05 |
Family
ID=81383353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2021/039822 WO2022092201A1 (en) | 2020-10-28 | 2021-10-28 | Adhesive tape |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2022092201A1 (en) |
| KR (1) | KR20230092862A (en) |
| CN (1) | CN116096829A (en) |
| WO (1) | WO2022092201A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016037592A (en) * | 2014-08-11 | 2016-03-22 | 積水化学工業株式会社 | Acryl adhesive and adhesive sheet for electronic apparatus |
| JP2016183275A (en) * | 2015-03-26 | 2016-10-20 | 積水化学工業株式会社 | Adhesive composition and adhesive tape |
| JP2020012106A (en) * | 2018-07-04 | 2020-01-23 | 積水化学工業株式会社 | Double-sided adhesive tape |
| WO2020218430A1 (en) * | 2019-04-24 | 2020-10-29 | 積水化学工業株式会社 | Pressure-sensitive adhesive tape |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009242541A (en) | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | Impact-absorbing tape |
| JP5249625B2 (en) | 2008-04-15 | 2013-07-31 | 積水化学工業株式会社 | Adhesive sheet for display device front plate |
-
2021
- 2021-10-28 KR KR1020237000292A patent/KR20230092862A/en unknown
- 2021-10-28 CN CN202180058188.3A patent/CN116096829A/en active Pending
- 2021-10-28 WO PCT/JP2021/039822 patent/WO2022092201A1/en active Application Filing
- 2021-10-28 JP JP2022507716A patent/JPWO2022092201A1/ja active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016037592A (en) * | 2014-08-11 | 2016-03-22 | 積水化学工業株式会社 | Acryl adhesive and adhesive sheet for electronic apparatus |
| JP2016183275A (en) * | 2015-03-26 | 2016-10-20 | 積水化学工業株式会社 | Adhesive composition and adhesive tape |
| JP2020012106A (en) * | 2018-07-04 | 2020-01-23 | 積水化学工業株式会社 | Double-sided adhesive tape |
| WO2020218430A1 (en) * | 2019-04-24 | 2020-10-29 | 積水化学工業株式会社 | Pressure-sensitive adhesive tape |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2022092201A1 (en) | 2022-05-05 |
| CN116096829A (en) | 2023-05-09 |
| KR20230092862A (en) | 2023-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6966650B2 (en) | Adhesive tape | |
| JP5517015B1 (en) | Adhesive tape | |
| JP5582327B2 (en) | Oil-resistant double-sided adhesive tape | |
| JP5048994B2 (en) | Adhesive composition and optical functional film | |
| JP7036715B2 (en) | Double-sided adhesive tape | |
| KR20140019759A (en) | Double-sided pressure-sensitive adhesive sheet and portable electronic device | |
| JP2019512028A (en) | Pressure sensitive adhesive strip | |
| JP2019523720A (en) | Pressure sensitive adhesive strip | |
| JPWO2005111167A1 (en) | Adhesive composition | |
| TWI819096B (en) | Double sided adhesive tape | |
| JPWO2011118182A1 (en) | Acrylic adhesive tape | |
| TW201819577A (en) | Optically clear adhesive composition, and optically clear adhesive film comprising the same, and flat panel display | |
| JP2010126707A (en) | Protect film for optical member | |
| WO2022092201A1 (en) | Adhesive tape | |
| WO2022092149A1 (en) | Pressure-sensitive adhesive tape | |
| WO2022092199A1 (en) | Adhesive tape | |
| JP2022071863A (en) | Adhesive tape | |
| JP2022071864A (en) | Adhesive tape | |
| JP2022071845A (en) | Adhesive tape | |
| TWI833947B (en) | Adhesive tape | |
| JP2022071862A (en) | Adhesive tape | |
| JP7211457B1 (en) | Adhesive sheet for flexible image display device, laminate for flexible image display device, and flexible image display device. | |
| JP6867164B2 (en) | Colored adhesive tape and colored adhesive tape for fixing mobile electronic device parts | |
| WO2022219969A1 (en) | Adhesive composition and adhesive sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENP | Entry into the national phase |
Ref document number: 2022507716 Country of ref document: JP Kind code of ref document: A |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21886318 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21886318 Country of ref document: EP Kind code of ref document: A1 |