TWI853792B - Thermosensitive adhesive agent, thermosensitive adhesive sheet and thermosensitive adhesive tape - Google Patents
Thermosensitive adhesive agent, thermosensitive adhesive sheet and thermosensitive adhesive tape Download PDFInfo
- Publication number
- TWI853792B TWI853792B TW107130844A TW107130844A TWI853792B TW I853792 B TWI853792 B TW I853792B TW 107130844 A TW107130844 A TW 107130844A TW 107130844 A TW107130844 A TW 107130844A TW I853792 B TWI853792 B TW I853792B
- Authority
- TW
- Taiwan
- Prior art keywords
- temperature
- meth
- acrylate
- adhesive
- crystalline polymer
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 133
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 131
- 239000002390 adhesive tape Substances 0.000 title claims description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- -1 acrylate ester Chemical class 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 230000007423 decrease Effects 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 66
- 229920001577 copolymer Polymers 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 19
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 229940042596 viscoat Drugs 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 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 3
- 229920002799 BoPET Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 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 3
- 238000011282 treatment Methods 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-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
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NIMXEFLZWRGNFN-UHFFFAOYSA-K [Al+3].CC(=O)C(C(C)=O)(C(C)=O)C(=O)C([O-])=O.CC(=O)C(C(C)=O)(C(C)=O)C(=O)C([O-])=O.CC(=O)C(C(C)=O)(C(C)=O)C(=O)C([O-])=O Chemical compound [Al+3].CC(=O)C(C(C)=O)(C(C)=O)C(=O)C([O-])=O.CC(=O)C(C(C)=O)(C(C)=O)C(=O)C([O-])=O.CC(=O)C(C(C)=O)(C(C)=O)C(=O)C([O-])=O NIMXEFLZWRGNFN-UHFFFAOYSA-K 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000003486 chemical etching 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
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000000945 filler 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
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09J133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
-
- 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
- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本發明係有關感溫性黏著劑、感溫性黏著片及感溫性黏著帶。 The present invention relates to a temperature-sensitive adhesive, a temperature-sensitive adhesive sheet and a temperature-sensitive adhesive tape.
已知一種具有感溫性的感溫性樹脂，其對應於溫度變化可逆的顯示結晶狀態與流動狀態。含有此種樹脂的感溫性黏著劑係例如公開在專利文獻1中。在感溫性黏著劑中，存在一種加溫剝離(warm off)型黏著劑，其在感溫性樹脂的熔點以下之溫度中發揮固定性，在感溫性樹脂的熔點以上之溫度中其黏著力明顯降低而剝離。 A thermosensitive resin having temperature sensitivity is known, which reversibly exhibits a crystal state and a flow state in response to temperature changes. A thermosensitive adhesive containing such a resin is disclosed in, for example, Patent Document 1. Among thermosensitive adhesives, there is a warm-off type adhesive, which exhibits fixation at a temperature below the melting point of the thermosensitive resin, and peels off due to a significant decrease in adhesiveness at a temperature above the melting point of the thermosensitive resin.
傳統的加溫剝離型黏著劑，對於如無機系黏附體(不銹鋼鋼板、玻璃等)及結晶性的有機系黏附體(聚醯胺、聚甲醛(polyoxymethylene)等)之黏附體，在感溫性樹脂的熔點以上之溫度中其黏著性明顯降低，容易剝離。不過，對於非晶性的有機系黏附體(聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚碳酸酯等)，即使在感溫性樹脂的熔點以上之溫度中，其黏著性也不會降低。其結果是，對於 非晶性的有機系黏附體使用傳統的加溫剝離型黏著劑時，黏著劑不易剝離。 Conventional heat-peel adhesives have a significantly reduced adhesiveness and are easy to peel off when the temperature is above the melting point of the thermosensitive resin, such as inorganic adhesives (stainless steel plates, glass, etc.) and crystalline organic adhesives (polyamide, polyoxymethylene, etc.). However, the adhesiveness of amorphous organic adhesives (polyethylene terephthalate, polymethyl methacrylate, polycarbonate, etc.) does not decrease even at temperatures above the melting point of the thermosensitive resin. As a result, when conventional heat-peel adhesives are used on amorphous organic adhesives, the adhesive is not easy to peel off.
[專利文獻1]日本特表平6-510548號公報 [Patent Document 1] Japanese Patent Publication No. 6-510548
本發明的目的是提供：一種感溫性黏著劑，其對於非晶性有機系黏附體也可在室溫下牢固的接著，同時黏著性在感溫性樹脂的熔點以上之溫度中會降低，可容易剝離，以及含有此種感溫性黏著劑的感溫性黏著片及感溫性黏著帶。 The purpose of the present invention is to provide: a temperature-sensitive adhesive that can firmly adhere to amorphous organic adherends at room temperature, and at the same time, the adhesiveness decreases at a temperature above the melting point of the temperature-sensitive resin, and can be easily peeled off, as well as a temperature-sensitive adhesive sheet and a temperature-sensitive adhesive tape containing such a temperature-sensitive adhesive.
本發明人等為解決上述問題而深入研究的結果，發現了包括下列構成之解決方式，而完成本發明。 As a result of in-depth research to solve the above problems, the inventors discovered a solution including the following structure and completed the present invention.
(1)一種感溫性黏著劑，其含有：基質樹脂(A)，係具有18±2的SP值；以及側鏈結晶性聚合物(B)，係以含有(甲基)丙烯酸酯(B1)的單體成分作為構成單元，該(甲基)丙烯酸酯(B1)具有碳數14至30的直鏈狀烷基；其中，側鏈結晶性聚合物(B)具有滿足下述式(I)的SP值，在側鏈結晶性聚合物(B)的熔點以上之溫度中黏著力會降低。 (1) A temperature-sensitive adhesive comprising: a base resin (A) having an SP value of 18±2; and a side-chain crystalline polymer (B) having a monomer component containing a (meth)acrylate (B1) as a constituent unit, wherein the (meth)acrylate (B1) has a linear alkyl group having 14 to 30 carbon atoms; wherein the side-chain crystalline polymer (B) has an SP value satisfying the following formula (I), and the adhesive force decreases at a temperature above the melting point of the side-chain crystalline polymer (B).
(A)的SP值-2≦(B)的SP值≦(A)的SP值+2 (I) (A)'s SP value -2 ≦ (B)'s SP value ≦ (A)'s SP value +2 (I)
(2)如上述(1)項所述之感溫性黏著劑，其中側鏈結晶 性聚合物(B)的單體成分係以30至70質量%的比例含有(甲基)丙烯酸酯(B1)，且以0至50質量%的比例含有分子內具有氟原子的(甲基)丙烯酸酯(B2)，及以10至70質量%的比例含有具有碳數1至6的烷基之(甲基)丙烯酸酯(B3)。 (2) The temperature-sensitive adhesive as described in item (1) above, wherein the monomer components of the side-chain crystalline polymer (B) contain 30 to 70% by mass of a (meth)acrylate (B1), 0 to 50% by mass of a (meth)acrylate having a fluorine atom in the molecule (B2), and 10 to 70% by mass of a (meth)acrylate having an alkyl group having 1 to 6 carbon atoms (B3).
(3)如上述(1)或(2)項所述之感溫性黏著劑，其中側鏈結晶性聚合物(B6)具有4,000至40,000的重量平均分子量。 (3) The temperature-sensitive adhesive as described in item (1) or (2) above, wherein the side-chain crystalline polymer (B6) has a weight average molecular weight of 4,000 to 40,000.
(4)如上述(1)至(3)項中任一項所述之感溫性黏著劑，其中，基質樹脂(A)為含有下列者的單體之共聚物：含有羧基的乙烯性不飽和單體，與具有碳數8以上的烴基之(甲基)丙烯酸酯。 (4) A thermosensitive adhesive as described in any one of the above (1) to (3), wherein the base resin (A) is a copolymer of monomers containing: an ethylenically unsaturated monomer containing a carboxyl group and a (meth)acrylate having a carbon number of 8 or more.
(5)如上述(1)至(4)項中任一項所述之感溫性黏著劑，其對於非晶性有機系黏附體的黏著強度，於23℃中係2N/25mm以上，於側鏈結晶性聚合物的熔點以上之溫度中係0.05N/25mm以下。 (5) The temperature-sensitive adhesive described in any one of the above items (1) to (4), wherein the adhesive strength to the amorphous organic adhesive is 2N/25mm or more at 23°C and 0.05N/25mm or less at a temperature above the melting point of the side-chain crystalline polymer.
(6)一種感溫性黏著劑，含有：基質樹脂(A)，為含有下列者的單體之共聚物：含有羧基的乙烯性不飽和單體，與具有碳數8以上的烴基之(甲基)丙烯酸酯；以及側鏈結晶性聚合物(B)，係以含有30至70質量%的比例之具有碳數14至30的直鏈烷基之(甲基)丙烯酸酯(B1)、0至50質量%的比例之分子內具有氟原子的(甲基)丙烯酸酯(B2)、以及10至70質量%的比例之具有碳數1至6的烷基之(甲基)丙烯酸酯(B3)之單體成分作為構成單元；其中，對於非 晶性有機系黏附體的黏著強度，於23℃中係2N/25mm以上，於側鏈結晶性聚合物的熔點以上之溫度中係0.05N/25mm以下。 (6) A temperature-sensitive adhesive comprising: a base resin (A) which is a copolymer of monomers comprising: an ethylenically unsaturated monomer containing a carboxyl group and a (meth)acrylate having a alkyl group with a carbon number of 8 or more; and a side-chain crystalline polymer (B) which comprises a (meth)acrylate (B1) having a linear alkyl group with a carbon number of 14 to 30 in a ratio of 30 to 70 mass %, a (meth)acrylate (B2) having a linear alkyl group with a carbon number of 14 to 30 in a ratio of 0 to 50 mass %. The monomer components of (meth)acrylate (B2) having fluorine atoms in the molecule and (meth)acrylate (B3) having an alkyl group with 1 to 6 carbon atoms in a ratio of 10 to 70 mass % are used as constituent units; wherein the adhesive strength to the amorphous organic system adhesive is 2N/25mm or more at 23°C and 0.05N/25mm or less at a temperature above the melting point of the side chain crystalline polymer.
(7)如上述(5)或(6)項所述之感溫性黏著劑，其中非晶性有機系黏附體係選自由聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚萘二甲酸乙二酯及聚碳酸酯所組成之群組中的至少一種樹脂之成形物。 (7) The temperature-sensitive adhesive as described in item (5) or (6) above, wherein the amorphous organic adhesive is a molded product of at least one resin selected from the group consisting of polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate and polycarbonate.
(8)一種感溫性黏著片，係含有上述(1)至(7)項中任一項所述之感溫性黏著劑。 (8) A temperature-sensitive adhesive sheet containing the temperature-sensitive adhesive described in any one of the above items (1) to (7).
(9)一種感溫性黏著帶，其係在基材的至少一面上形成含有上述(1)至(7)項中任一項所述之感溫性黏著劑的黏著劑層。 (9) A temperature-sensitive adhesive tape, wherein an adhesive layer containing the temperature-sensitive adhesive described in any one of items (1) to (7) above is formed on at least one side of a substrate.
若藉由本發明，即使對於非晶性的有機系黏附體也可在室溫下牢固的接著，同時可在感溫性樹脂的熔點以上的溫度中使黏著性降低，容易剝離。即，可由基質樹脂(A)的黏著性及側鏈結晶性聚合物(B)的凝聚力而牢固的接著。另一方面，基質樹脂(A)的SP值比較小，側鏈結晶性聚合物(B)的SP值也設成近似基質樹脂(A)的SP值(基質樹脂(A)的SP值±2)。進一步地，由於構成非晶性的有機系黏附體之樹脂的SP值比較大，故非晶性的有機系黏附體與具有比較大的SP值之基質樹脂(A)及側鏈結晶性聚合物(B)之間的相溶性低。因此，可推測當加熱至側鏈結晶性聚合物(B)的熔點以上之溫度時，側鏈結晶性聚合物(B) 具有流動性，容易和相溶性優良的基質樹脂(A)一起從相溶性低的非晶性之有機系黏附體剝離。 According to the present invention, even amorphous organic adhesives can be firmly bonded at room temperature, and at the same time, the adhesiveness can be reduced at a temperature above the melting point of the thermosensitive resin, making it easy to peel off. That is, it can be firmly bonded by the adhesiveness of the base resin (A) and the cohesive force of the side chain crystalline polymer (B). On the other hand, the SP value of the base resin (A) is relatively small, and the SP value of the side chain crystalline polymer (B) is also set to be close to the SP value of the base resin (A) (SP value of the base resin (A) ± 2). Furthermore, since the SP value of the resin constituting the amorphous organic adhesive is relatively large, the compatibility between the amorphous organic adhesive and the base resin (A) and the side chain crystalline polymer (B) having a relatively large SP value is low. Therefore, it can be inferred that when heated to a temperature above the melting point of the side chain crystalline polymer (B), the side chain crystalline polymer (B) has fluidity and is easily peeled off from the amorphous organic adhesive with low compatibility together with the base resin (A) with excellent compatibility.
詳細說明本公開中的一實施形態之感溫性黏著劑。一實施形態的感溫性黏著劑係含有：基質樹脂(A)，係具有18±2的SP值；以及側鏈結晶性聚合物(B)，係以含有(甲基)丙烯酸酯(B1)的單體成分作為構成單元，該(甲基)丙烯酸酯(B1)具有碳數14至30的直鏈狀烷基，且在側鏈結晶性聚合物(B)(相當於感溫性樹脂)的熔點以上之溫度中黏著性會降低。本說明書中，「(甲基)丙烯酸基」係指「丙烯酸基」或「甲基丙烯酸基」。 A thermosensitive adhesive in one embodiment of the present disclosure is described in detail. A thermosensitive adhesive in one embodiment comprises: a base resin (A) having an SP value of 18±2; and a side-chain crystalline polymer (B) having a monomer component containing (meth)acrylate (B1) as a constituent unit, wherein the (meth)acrylate (B1) has a linear alkyl group with 14 to 30 carbon atoms, and the adhesiveness decreases at a temperature above the melting point of the side-chain crystalline polymer (B) (equivalent to the thermosensitive resin). In this specification, "(meth)acrylate" means "acrylic" or "methacrylic".
基質樹脂(A)只要是具有18±2的SP值之樹脂即無特別的限制。SP值是溶解度參數(solubility parameter)，例如將2種以上的樹脂混合時，SP值相近的樹脂之間的相溶性優良，SP值之差越大則越缺乏相溶性。 There is no particular restriction on the base resin (A) as long as it has an SP value of 18±2. The SP value is a solubility parameter. For example, when two or more resins are mixed, resins with similar SP values have good compatibility, and the greater the difference in SP values, the less compatibility.
基質樹脂(A)可列舉：例如極性單體(A1)與可和極性單體共聚合的單體(A2)之共聚物等，並以具有0℃以下的玻璃轉移點(Tg)之共聚物為佳。此等之中，係以不包含具有碳數1至4的烷基之(甲基)丙烯酸酯作為單體成分的共聚物為佳。若不使用此種單體成分，在側鏈結晶性聚合物(B)的熔點以上之溫度中，不易使感溫性黏著劑的表面自由能值變高，即難以接近非晶性的有機系黏附體之 表面自由能之值。因此，分子間的相互作用不易變大，容易使黏著力更降低。 The base resin (A) can be exemplified by: for example, copolymers of polar monomers (A1) and monomers (A2) copolymerizable with polar monomers, and copolymers having a glass transition point (Tg) below 0°C are preferred. Among these, copolymers that do not contain (meth)acrylates having an alkyl group with 1 to 4 carbon atoms as a monomer component are preferred. If such monomer components are not used, it is difficult to increase the surface free energy value of the temperature-sensitive adhesive at a temperature above the melting point of the side-chain crystalline polymer (B), that is, it is difficult to approach the surface free energy value of the amorphous organic adhesive. Therefore, the interaction between molecules is not easy to increase, and the adhesion is easily reduced.
此外，作為極性單體(A1)，係以不單獨使用含有羥基的單體者為佳。只要不單獨使用含有羥基的單體，即可使側鏈結晶性聚合物(B)的熔點以上之溫度中的損失彈性率難以變高，更不易使剝離能消散。因此，難以使剝離上必要之能變大，而更提高剝離性。 In addition, as the polar monomer (A1), it is preferred not to use a monomer containing a hydroxyl group alone. As long as a monomer containing a hydroxyl group is not used alone, the loss elasticity rate of the side chain crystalline polymer (B) at a temperature above the melting point is difficult to increase, and the stripping energy is difficult to dissipate. Therefore, it is difficult to increase the energy required for stripping, and the stripping property is further improved.
基質樹脂(A)具體上是含有極性單體(A1)與具有碳數8以上的烴基之(甲基)丙烯酸酯(A2’)之單體的共聚物，較佳的可舉出含有(甲基)丙烯酸與具有碳數8至18的烴基之(甲基)丙烯酸酯的單體之共聚物。單體成分中，可含有可與此等化合物共聚合的單體。具有碳數8以上的烴基之(甲基)丙烯酸酯(A2’)可列舉：例如(甲基)丙烯酸乙酯己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十二烷酯等具有碳數8以上的烷基之(甲基)丙烯酸酯、(甲基)丙烯酸異莰酯等具有碳數8以上的環式烴基之(甲基)丙烯酸酯。具有碳數8以上的烴基之(甲基)丙烯酸酯可僅使用1種，也可將2種以上組合使用。 Specifically, the base resin (A) is a copolymer containing a polar monomer (A1) and a (meth)acrylate (A2') having a carbon number of 8 or more. A preferred copolymer is a copolymer containing a (meth)acrylic acid and a (meth)acrylate having a carbon number of 8 to 18. The monomer component may contain a monomer copolymerizable with these compounds. Examples of the (meth)acrylate (A2') having a carbon number of 8 or more include: (meth)acrylates having an alkyl group having a carbon number of 8 or more such as ethyl hexyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, and (meth)acrylates having a cyclic carbon number of 8 or more such as isoborneol (meth)acrylate. The (meth)acrylate having a carbon number of 8 or more may be used alone or in combination of two or more.
極性單體(A1)可使用：例如丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、順丁烯二酸、反丁烯二酸、丙烯酸β-羧酯乙酯等含有羧基的乙烯性不飽和單體。也可將(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基己酯、2-羥基乙基丙烯醯胺等具有 羥基的乙烯性不飽和單體等組合使用。使用丙烯酸或甲基丙烯酸等含有羧基之乙烯性不飽和單體作為極性單體(A1)時，係以在構成基質樹脂(A)的單體成分中，以1至20質量%的比例含有為佳。因為以此種比例含有含羧基的乙烯性不飽和單體時，可使所得的感溫性黏著劑具有適度的黏度、處理性優異，且在室溫中具有高固定性，另外由於會使側鏈結晶性聚合物(B)的熔點以上的溫度中之損失彈性率降低，故可更容易剝離。 Polar monomers (A1) include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, succinic acid, fumaric acid, β-carboxyethyl acrylate, and other ethylenically unsaturated monomers containing a carboxyl group. Combinations of ethylenically unsaturated monomers containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, and 2-hydroxyethylacrylamide, may also be used. When ethylenically unsaturated monomers containing a carboxyl group, such as acrylic acid or methacrylic acid, are used as polar monomers (A1), they are preferably contained in a ratio of 1 to 20% by mass in the monomer components constituting the base resin (A). When the carboxyl-containing ethylenically unsaturated monomer is contained in such a ratio, the resulting temperature-sensitive adhesive has an appropriate viscosity, excellent handling properties, and high fixation at room temperature. In addition, since the elastic loss rate at a temperature above the melting point of the side-chain crystalline polymer (B) is reduced, it can be more easily peeled.
用以得到基質樹脂(A)之單體成分的聚合方法，並無特別的限制，可列舉：例如溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等。例如採用溶液聚合法時，只要將單體成分與溶劑混合，視需要添加聚合起始劑或鏈轉移劑，一邊攪拌一邊使其在50至100℃左右反應1至24小時左右即可。 There is no particular limitation on the polymerization method for obtaining the monomer component of the base resin (A), and examples thereof include solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. For example, when the solution polymerization method is used, the monomer component is mixed with a solvent, a polymerization initiator or a chain transfer agent is added as needed, and the mixture is stirred while reacting at about 50 to 100°C for about 1 to 24 hours.
側鏈結晶性聚合物(B)係將含有具有碳數14至30的直鏈狀烷基之(甲基)丙烯酸酯(B1)的單體成分作為構成單元。具有碳數14至30的直鏈狀烷基之(甲基)丙烯酸酯(B1)可列舉：例如(甲基)丙烯酸十六烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十烷酯、(甲基)丙烯酸二十二烷酯、(甲基)丙烯酸二十三烷酯等。此種(甲基)丙烯酸酯(A)之中，以具有碳數18至22的直鏈狀烷基之(甲基)丙烯酸酯為佳。(甲基)丙烯酸酯(A)可僅使用1種，也可將2種以上組合使用。 The side-chain crystalline polymer (B) has a monomer component containing a (meth)acrylate (B1) having a linear alkyl group with a carbon number of 14 to 30 as a constituent unit. Examples of the (meth)acrylate (B1) having a linear alkyl group with a carbon number of 14 to 30 include hexadecyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and tricosyl (meth)acrylate. Among such (meth)acrylates (A), a (meth)acrylate having a linear alkyl group with a carbon number of 18 to 22 is preferred. The (meth)acrylate (A) may be used alone or in combination of two or more.
構成側鏈結晶性聚合物(B)的單體成分，只 要含有(甲基)丙烯酸酯(B1)，即無特別的限制。例如在單體成分中，除了(甲基)丙烯酸酯(B1)以外，也可含有分子內具有氟原子的(甲基)丙烯酸酯(B2)、具有碳數1至6的烷基之(甲基)丙烯酸酯(B3)等。 The monomer component constituting the side-chain crystalline polymer (B) is not particularly limited as long as it contains (meth)acrylate (B1). For example, in addition to (meth)acrylate (B1), the monomer component may also contain (meth)acrylate (B2) having a fluorine atom in the molecule, (meth)acrylate (B3) having an alkyl group with 1 to 6 carbon atoms, etc.
分子內具有氟原子的(甲基)丙烯酸酯(B2)可列舉：例如通式(i)表示的化合物等。 Examples of (meth)acrylates (B2) having fluorine atoms in the molecule include compounds represented by general formula (i).
R1-CF3 (i)式中，R1是表示CH2=CHCOOR2-或CH2=C(CH3)COOR2-。而R2是表示伸烷基。 R 1 -CF 3 (i) In the formula, R 1 represents CH 2 =CHCOOR 2 - or CH 2 =C(CH 3 )COOR 2 -, and R 2 represents an alkylene group.
伸烷基可列舉：例如亞甲基、伸乙基、三亞甲基、伸丙基、四亞甲基、五亞甲基、六亞甲基等碳數1至6的直鏈或分枝之伸烷基等。 Alkylene groups include: for example, methylene, ethyl, trimethylene, propyl, tetramethylene, pentamethylene, hexamethylene, and other straight chain or branched alkylene groups with 1 to 6 carbon atoms.
分子內具有氟原子的(甲基)丙烯酸酯(B2)，具體上可舉出2,2,2-三氟丙烯酸乙酯、2,2,2-三氟甲基丙烯酸乙酯等。分子內具有氟原子的(甲基)丙烯酸酯(B2)可僅使用1種，也可將2種以上組合使用。 Specific examples of (meth)acrylates (B2) having fluorine atoms in the molecule include 2,2,2-trifluoroethyl acrylate and 2,2,2-trifluoroethyl methacrylate. The (meth)acrylates (B2) having fluorine atoms in the molecule may be used alone or in combination of two or more.
分子內具有氟原子的(甲基)丙烯酸酯(B2)，也可使用市售品，例如已有市售「Viscoat 3F」、「Viscoat 3FM」、「Viscoat 4F」、「Viscoat 8F」、「Viscoat 8FM」(均是大阪有機化學工業股份有限公司製造)、「輕酯(Lightester)M-3F」(共榮社化學製造)等。 Commercially available (meth)acrylates (B2) having fluorine atoms in the molecule may also be used, such as "Viscoat 3F", "Viscoat 3FM", "Viscoat 4F", "Viscoat 8F", "Viscoat 8FM" (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), "Lightester M-3F" (manufactured by Kyoeisha Chemical Co., Ltd.), etc.
具有碳數1至6的烷基之(甲基)丙烯酸酯(B3)可列舉：例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁 酯等。 Examples of (meth)acrylates (B3) having an alkyl group with 1 to 6 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, etc.
構成側鏈結晶性聚合物(B)的單體成分中，係以下述表示的比例含有具有碳數14至30的直鏈狀烷基之(甲基)丙烯酸酯(B1)、分子內具有氟原子的(甲基)丙烯酸酯(B2)及具有碳數1至6的烷基之(甲基)丙烯酸酯(B3)為佳。 The monomer components constituting the side-chain crystalline polymer (B) preferably contain (meth)acrylate (B1) having a linear alkyl group with 14 to 30 carbon atoms, (meth)acrylate (B2) having a fluorine atom in the molecule, and (meth)acrylate (B3) having an alkyl group with 1 to 6 carbon atoms in the following ratios.
(甲基)丙烯酸酯(B1)：30至70質量%，更佳為40至60質量% (Meth)acrylate (B1): 30 to 70% by mass, preferably 40 to 60% by mass
(甲基)丙烯酸酯(B2)：0至50質量%，更佳為0至40質量% (Meth)acrylate (B2): 0 to 50% by mass, preferably 0 to 40% by mass
(甲基)丙烯酸酯(B3)：10至70質量%，更佳為20至60質量% (Meth)acrylate (B3): 10 to 70% by mass, preferably 20 to 60% by mass
用以得到側鏈結晶性聚合物(B)之單體成分的聚合方法，並無特別的限制，可列舉：例如溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等。例如採用溶液聚合法時，只要將單體成分與溶劑混合，視需要添加聚合起始劑或鏈轉移劑，一邊攪拌一邊使其在50至100℃左右反應1至6小時左右即可。 There is no particular limitation on the polymerization method of the monomer components used to obtain the side chain crystalline polymer (B), and examples thereof include solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. For example, when the solution polymerization method is used, the monomer components are mixed with a solvent, a polymerization initiator or a chain transfer agent is added as needed, and the mixture is stirred while reacting at about 50 to 100°C for about 1 to 6 hours.
側鏈結晶性聚合物(B)具有滿足下述式(I)的SP值，較佳為具有滿足下述式(I’)的SP值。 The side-chain crystalline polymer (B) has an SP value satisfying the following formula (I), preferably an SP value satisfying the following formula (I').
(A)的SP值-2≦(B)的SP值≦(A)的SP值+2 (I) (A)'s SP value -2 ≦ (B)'s SP value ≦ (A)'s SP value +2 (I)
(A)的SP值-1≦(B)的SP值≦(A)的SP值+1 (I’) (A)'s SP value -1 ≦ (B)'s SP value ≦ (A)'s SP value +1 (I')
此種側鏈結晶性聚合物(B)的重量平均分子量(Mn)並無特別的限制。側鏈結晶性聚合物(B)較佳為具有 4,000至40,000的重量平均分子量，更佳為具有6,000至15,000的重量平均分子量。 The weight average molecular weight (Mn) of such side chain crystalline polymer (B) is not particularly limited. The side chain crystalline polymer (B) preferably has a weight average molecular weight of 4,000 to 40,000, and more preferably has a weight average molecular weight of 6,000 to 15,000.
側鏈結晶性聚合物(B)在熔點(Tm)以上的溫度中黏著性會降低。亦即，側鏈結晶性聚合物(B)在未達熔點的溫度中結晶，且在熔點以上的溫度中相轉移而顯示流動性。側鏈結晶性聚合物的熔點並無特別的限制。側鏈結晶性聚合物係以具有70℃以下的熔點為佳，並以具有60℃以下的熔點更佳。本說明書中的「熔點」係指藉由某種平衡程序，而使最初有秩序排列整齊的聚合物之特定部分變成無秩序狀態的溫度，可由示差熱掃描熱量計(DSC)以每分鐘10℃的條件測定。 The side-chain crystalline polymer (B) has reduced adhesion at temperatures above the melting point (Tm). That is, the side-chain crystalline polymer (B) crystallizes at a temperature below the melting point, and exhibits fluidity by phase transition at a temperature above the melting point. There is no particular restriction on the melting point of the side-chain crystalline polymer. The side-chain crystalline polymer preferably has a melting point below 70°C, and more preferably has a melting point below 60°C. The "melting point" in this specification refers to the temperature at which a specific part of the polymer that was originally arranged in an orderly manner becomes a disordered state through a certain equilibrium process, and can be measured by a differential scanning calorimeter (DSC) at 10°C per minute.
本公開的一實施形態之感溫性黏著劑，係以任意比例含有具有18±2的SP值之基質樹脂(A)與側鏈結晶性聚合物(B)，相對於基質樹脂(A)100質量份，係以1至30質量份的比例含有側鏈結晶性聚合物(B)為佳，並以3至20質量份的比例含有更佳。本公開的一實施形態之感溫性黏著劑，可由將基質樹脂(A)與側鏈結晶性聚合物(B)混合後攪拌而得。 The temperature-sensitive adhesive of one embodiment of the present disclosure contains a base resin (A) having an SP value of 18±2 and a side-chain crystalline polymer (B) in any proportion. The side-chain crystalline polymer (B) is preferably contained in a proportion of 1 to 30 parts by mass, and more preferably in a proportion of 3 to 20 parts by mass, relative to 100 parts by mass of the base resin (A). The temperature-sensitive adhesive of one embodiment of the present disclosure can be obtained by mixing the base resin (A) and the side-chain crystalline polymer (B) and then stirring.
本公開的一實施形態之感溫性黏著劑，可視需要而添加塑化劑、增黏劑(tackifier)、填料、抗氧化劑等。例如，增黏劑可舉出有特殊松香酯系、萜烯酚系、石油樹脂系、高羥基價松香酯系、氫化松香酯系等。此外，也可添加丙烯酸系、橡膠系等通常的感壓性黏著劑，以進一步改善與被加工物間的密合性。 The temperature-sensitive adhesive of one embodiment of the present disclosure may be added with plasticizers, tackifiers, fillers, antioxidants, etc. as needed. For example, the tackifiers include special rosin esters, terpene phenols, petroleum resins, high hydroxyl rosin esters, hydrogenated rosin esters, etc. In addition, conventional pressure-sensitive adhesives such as acrylic and rubber adhesives may also be added to further improve the adhesion with the workpiece.
另外，本公開的一實施形態之感溫性黏著劑中，也可含有交聯劑，以改善凝聚力。交聯劑並無特別的限制，可列舉：例如異氰酸酯系化合物、氮丙環(Aziridine)系化合物、環氧系化合物、金屬螯合物系化合物等。 In addition, the thermosensitive adhesive of one embodiment of the present disclosure may also contain a crosslinking agent to improve cohesion. There is no particular limitation on the crosslinking agent, and examples thereof include isocyanate compounds, aziridine compounds, epoxy compounds, metal chelate compounds, etc.
本公開的一實施形態之感溫性黏著劑的黏著強度，對於非晶性的有機系黏附體，較佳的是於23℃中係2N/25mm以上，於側鏈結晶性聚合物(B)的熔點以上之溫度中係0.05N/25mm以下。本說明書中，黏著強度係依據JIS Z0237以每分鐘300mm測定相對於非晶性有機系黏附體之值。當感溫性黏著劑具有此種範圍的黏著強度時，在室溫(未達側鏈結晶性聚合物(B)的熔點之溫度)中可更牢固的被附黏附體，在側鏈結晶性聚合物(B)的熔點以上的溫度中，黏著劑可更容易的從黏附體上剝離。感溫性黏著劑的黏著強度更佳的是於23℃中係5N/25mm，於側鏈結晶性聚合物(B)的熔點以上之溫度中係0.05N/25mm以下。 The adhesive strength of the temperature-sensitive adhesive of one embodiment of the present disclosure is preferably 2N/25mm or more at 23°C and 0.05N/25mm or less at a temperature above the melting point of the side-chain crystalline polymer (B) for an amorphous organic adhesive. In this specification, the adhesive strength is a value measured at 300mm per minute relative to an amorphous organic adhesive in accordance with JIS Z0237. When the temperature-sensitive adhesive has an adhesive strength in this range, it can be more firmly attached to an adherend at room temperature (a temperature below the melting point of the side-chain crystalline polymer (B)), and the adhesive can be more easily peeled off from the adherend at a temperature above the melting point of the side-chain crystalline polymer (B). The better adhesion strength of the thermosensitive adhesive is 5N/25mm at 23°C and below 0.05N/25mm at a temperature above the melting point of the side-chain crystalline polymer (B).
在剝離感溫性黏著劑時，大多是以高於JIS規定的速度(例如，每分鐘3,000mm左右)剝離。通常在以高速剝離時，可趨使剝離強度變高。但是，在以JIS規定的每分鐘300mm之剝離強度為0.05N/25mm以下的非常低的情況，即使以高速剝離也難以使剝離強度上昇。因此，一實施形態的感溫性黏著劑不論剝離速度如何，對非晶性的有機系黏附體均可無傷害的剝離。 When peeling a temperature-sensitive adhesive, it is usually peeled at a speed higher than that specified by JIS (for example, about 3,000 mm per minute). Generally, when peeling at a high speed, the peeling strength tends to be higher. However, when the peeling strength at 300 mm per minute specified by JIS is very low, which is less than 0.05N/25mm, it is difficult to increase the peeling strength even at a high speed. Therefore, a temperature-sensitive adhesive of one embodiment can peel amorphous organic adhesives without damaging them regardless of the peeling speed.
非晶性的有機系黏附體可列舉：例如聚對 苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚萘二甲酸乙二酯、聚碳酸酯、聚氯乙烯、聚苯乙烯、環烯烴聚合物等樹脂的成形物。此等非晶性的有機系黏附體之中，本公開的一實施形態之感溫性黏著劑，對於選自聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚萘二甲酸乙二酯及聚碳酸酯所組成之群組中的至少1種樹脂之成形物，可發揮更優良的效果。 Examples of amorphous organic adhesives include molded products of resins such as polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, and cycloolefin polymers. Among these amorphous organic adhesives, the temperature-sensitive adhesive of one embodiment of the present disclosure can exert a better effect on molded products of at least one resin selected from the group consisting of polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, and polycarbonate.
本公開的一實施形態之感溫性黏著劑的使用方法，並無特別的限制，可使用例如將感溫性黏著劑塗布在作為對象的黏附體上，也可將感溫性黏著劑成形為片狀而以如無基材膠帶的方式使用。 There is no particular limitation on the method of using the temperature-sensitive adhesive of one embodiment of the present disclosure. For example, the temperature-sensitive adhesive can be applied to the adherend, or the temperature-sensitive adhesive can be formed into a sheet and used as a tape without a substrate.
或是，含有本公開的一實施形態之感溫性黏著劑的黏著劑層，能以形成在基材的至少一面上之感溫性黏著帶的形態使用。基材較佳是薄膜狀，而薄膜狀中也包含片狀者。基材的構成材料可列舉：例如聚乙烯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚丙烯、聚酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚碳酸酯、乙烯乙酸乙烯酯共聚物、乙烯丙烯酸乙酯共聚物、乙烯聚丙烯共聚物、聚氯乙烯、聚醚醚酮等合成樹脂。 Alternatively, an adhesive layer containing a temperature-sensitive adhesive of an embodiment of the present disclosure can be used in the form of a temperature-sensitive adhesive tape formed on at least one side of a substrate. The substrate is preferably in the form of a film, and the film also includes a sheet. The constituent materials of the substrate can be listed as follows: for example, synthetic resins such as polyethylene, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyester, polyamide, polyimide, polyamide imide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, polyvinyl chloride, and polyetheretherketone.
基材可具有單層結構，也可具有多層結構。基材通常具有5至500μm左右的厚度。另外，基材上，為提高相對於黏著劑層之密合性的目的，也可施加例如電暈放電處理、電漿處理、噴沙(blast)處理、化學蝕刻處理、底漆處理等表面處理。 The substrate may have a single-layer structure or a multi-layer structure. The substrate generally has a thickness of about 5 to 500 μm. In addition, the substrate may be subjected to surface treatments such as corona discharge treatment, plasma treatment, sandblasting treatment, chemical etching treatment, primer treatment, etc., in order to improve the adhesion relative to the adhesive layer.
基材的至少一面上形成含有感溫性黏著劑的黏著劑層之方法，並無特別的限制。可列舉：例如將在感溫性黏著劑中視需要加入溶劑的塗布液，藉由塗布機等而塗布在基材的一面或兩面上後乾燥的方法等。塗布機可列舉：例如刀塗機、滾塗機、壓延塗布機、刮刀式(comma)塗布機、凹版塗布機、棒塗機等。黏著劑層的厚度並無特別的限制。黏著劑層，係以具有1至500μm左右的厚度為佳，並以具有5至60μm左右更佳。 There is no particular limitation on the method of forming an adhesive layer containing a thermosensitive adhesive on at least one side of a substrate. Examples include: for example, adding a solvent to the thermosensitive adhesive as needed, applying a coating liquid on one or both sides of the substrate by a coating machine, etc., and then drying. Examples of coating machines include: for example, knife coaters, roller coaters, calender coaters, comma coaters, gravure coaters, rod coaters, etc. There is no particular limitation on the thickness of the adhesive layer. The adhesive layer preferably has a thickness of about 1 to 500 μm, and more preferably about 5 to 60 μm.
僅在基材的一側的表面上形成含有感溫性黏著劑的黏著劑層之感溫性黏著帶，可在另一面上形成例如感壓接著劑之層，也可形成含有感溫性黏著劑與感壓接著劑之層。感壓接著劑可列舉：例如天然橡膠接著劑、合成橡膠接著劑、苯乙烯-丁二烯乳膠基質接著劑、塊狀共聚物型的熱可塑性橡膠、丁基橡膠、聚異丁烯、丙烯酸接著劑、乙烯醚系共聚物等。感壓接著劑也可使用市售品。 A temperature-sensitive adhesive tape having an adhesive layer containing a temperature-sensitive adhesive formed only on the surface of one side of the substrate may have a layer of, for example, a pressure-sensitive adhesive formed on the other side, or may have a layer containing a temperature-sensitive adhesive and a pressure-sensitive adhesive formed. Examples of pressure-sensitive adhesives include natural rubber adhesives, synthetic rubber adhesives, styrene-butadiene latex-based adhesives, block copolymer-type thermoplastic rubbers, butyl rubber, polyisobutylene, acrylic adhesives, vinyl ether copolymers, etc. Commercially available pressure-sensitive adhesives may also be used.
若藉由本公開的一實施形態之感溫性黏著劑，即使對於如聚對苯二甲酸乙二酯或聚甲基丙烯酸甲酯等非晶性的有機系黏附體，在感溫性樹脂的熔點以上的溫度中也可使黏著明顯下降，容易剝離。因此，藉由使用本公開的一實施形態之感溫性黏著劑，可使此種非晶性的有機系黏附體在室溫中固定後加工成黏附體。加工後，藉由使其昇溫至感溫性黏著劑中含有的側鏈結晶性聚合物(B)之熔點以上的溫度，可使感溫性黏著劑容易從非晶性的有機系黏附體上剝離。使用本公開的一實施形態之感溫性黏 著劑的感溫性黏著片及感溫性黏著帶也是一樣。 If a thermosensitive adhesive according to an embodiment of the present disclosure is used, even for amorphous organic adhesives such as polyethylene terephthalate or polymethyl methacrylate, the adhesion can be significantly reduced at a temperature above the melting point of the thermosensitive resin, making it easy to peel off. Therefore, by using a thermosensitive adhesive according to an embodiment of the present disclosure, such amorphous organic adhesive can be fixed at room temperature and then processed into an adhesive. After processing, the thermosensitive adhesive can be easily peeled off from the amorphous organic adhesive by heating it to a temperature above the melting point of the side chain crystalline polymer (B) contained in the thermosensitive adhesive. The same is true for thermosensitive adhesive sheets and thermosensitive adhesive tapes using a thermosensitive adhesive according to an embodiment of the present disclosure.
本公開的一實施形態之感溫性黏著劑、感溫性黏著片及感溫性黏著帶，係例如可使用在載體膠帶或遮蔽膠帶，或是切割(dicing)時的固定或轉印程序時之固定等上。 The temperature-sensitive adhesive, temperature-sensitive adhesive sheet and temperature-sensitive adhesive tape of one embodiment of the present disclosure can be used, for example, as a carrier tape or a masking tape, or for fixing during dicing or during a transfer process.
此外，本公開的其他實施形態之感溫性黏著劑係含有：基質樹脂(A)，為含有(甲基)丙烯酸與具有碳數8以上的烴基之(甲基)丙烯酸酯的單體之共聚物；以及側鏈結晶性聚合物(B)，係以下述比例含有下列者之單體成分作為構成單元：30至70質量%的比例之具有碳數14至30的直鏈狀烷基之(甲基)丙烯酸酯(B1)、0至50質量%的比例之分子內具有氟原子的(甲基)丙烯酸酯(B2)、以及10至70質量%的比例之具有碳數1至6的烷基之(甲基)丙烯酸酯(B3)；其中對於非晶性的有機系黏附體之黏著強度，於23℃中係2N/25mm以上，於側鏈結晶性聚合物的熔點以上之溫度中係0.05N/25mm以下。各成分的說明如上述，並省略詳細的說明。 In addition, the temperature-sensitive adhesive of another embodiment of the present disclosure comprises: a base resin (A) which is a copolymer of monomers containing (meth)acrylic acid and (meth)acrylate having an alkyl group with 8 or more carbon atoms; and a side-chain crystalline polymer (B) which contains the following monomer components as constituent units in the following ratios: 30 to 70% by mass of a (meth)acrylate having a linear alkyl group with 14 to 30 carbon atoms (B1), 0 to 50% by mass of a (meth)acrylate having a fluorine atom in the molecule (B2), and 10 to 70% by mass of a (meth)acrylate having an alkyl group with 1 to 6 carbon atoms (B3); wherein the adhesive strength to an amorphous organic adhesive is 2 N/25 mm or more at 23° C. and 0.05 N/25 mm or less at a temperature above the melting point of the side-chain crystalline polymer. The description of each component is as above, and the detailed description is omitted.
以下，雖然是舉出實施例及比較例以更具體的說明本發明，但本發明並非侷限於此等實施例之範圍者。 Although embodiments and comparative examples are given below to more specifically illustrate the present invention, the present invention is not limited to the scope of these embodiments.
(合成例A1：基質樹脂的合成) (Synthesis Example A1: Synthesis of base resin)
如表1所示，將98質量%的丙烯酸乙酯己酯與2質量%的丙烯酸混合，獲得單體混合物。對此單體混合物100 質量份，添加0.5質量份比例的PERBUTYL ND(日油股份有限公司製造)作為聚合起始劑及230質量份比例的乙酸甲酯作為溶劑，使其在55℃聚合4小時。然後，昇溫至80℃，對於單體混合物100質量份，添加0.5質量份比例的PERHEXYL PV(日油股份有限公司製造)作為聚合起始劑。添加後使其聚合2小時，獲得共聚物(重量平均分子量(Mw)：約55萬)。獲得的基質樹脂具有約17.2的SP值。 As shown in Table 1, 98% by mass of ethylhexyl acrylate and 2% by mass of acrylic acid were mixed to obtain a monomer mixture. 0.5 parts by mass of PERBUTYL ND (manufactured by NOF Corporation) as a polymerization initiator and 230 parts by mass of methyl acetate as a solvent were added to 100 parts by mass of this monomer mixture, and the mixture was polymerized at 55°C for 4 hours. Then, the temperature was raised to 80°C, and 0.5 parts by mass of PERHEXYL PV (manufactured by NOF Corporation) as a polymerization initiator was added to 100 parts by mass of the monomer mixture. After the addition, the mixture was polymerized for 2 hours to obtain a copolymer (weight average molecular weight (Mw): about 550,000). The obtained base resin has an SP value of about 17.2.
(合成例A2至A7：基質樹脂的合成) (Synthesis Examples A2 to A7: Synthesis of Base Resin)
除了以表1所述之比例使用表1所述之單體成分以外，以和合成例A1相同的程序獲得共聚物(基質樹脂)。將各基質樹脂的Mw及SP值表示於表1中。「Blemmer VMA-70」，係具有碳數18至24的直鏈狀烷基之甲基丙烯酸酯的混合物，可從日油股份有限公司購得。「Blemmer LMA」，係甲基丙烯酸月桂酯，可從日油股份有限公司購得。 A copolymer (base resin) was obtained by the same procedure as in Synthesis Example A1 except that the monomer components described in Table 1 were used in the proportions described in Table 1. The Mw and SP values of each base resin are shown in Table 1. "Blemmer VMA-70" is a mixture of methacrylates having a linear alkyl group with a carbon number of 18 to 24, and can be purchased from NOF Corporation. "Blemmer LMA" is lauryl methacrylate, and can be purchased from NOF Corporation.
(比較合成例A1至A5：基質樹脂的合成) (Comparative Synthesis Examples A1 to A5: Synthesis of Base Resin)
除了以表1所述之比例使用表1所述之單體成分以外，以和合成例A1相同的程序獲得共聚物(基質樹脂)。將各基質樹脂的Mw及SP值表示於表1中。 Except that the monomer components described in Table 1 are used in the proportions described in Table 1, a copolymer (base resin) is obtained by the same procedure as in Synthesis Example A1. The Mw and SP values of each base resin are shown in Table 1.
VMA-70：日油股份有限公司製的Blemmer-VMA-70 VMA-70: Blemmer-VMA-70 manufactured by NOF Corporation
EHA：丙烯酸乙酯己酯 EHA: Ethyl Hexyl Acrylate
IBXA：丙烯酸異莰酯 IBXA: Isoborneol acrylate
AA：丙烯酸 AA: Acrylic acid
LMA：日油股份有限公司製的Blemmer-LMA LMA: Blemmer-LMA manufactured by NOF Corporation
C1A：丙烯酸甲酯 C1A: Methyl acrylate
C4A：丙烯酸丁酯 C4A: Butyl acrylate
HEA：丙烯酸2-羥基乙酯 HEA: 2-Hydroxyethyl acrylate
β CEA：丙烯酸β-羧酯乙酯 β CEA: β-carboxyethyl acrylate
(合成例B1：側鏈結晶性聚合物的合成) (Synthesis Example B1: Synthesis of side-chain crystalline polymer)
如表2所示，將45質量%的丙烯酸二十二酯(日油股份有限公司製造)與55質量%的丙烯酸混合，獲得單體混合物。對此單體混合物100質量份，添加1質量份比例的PERHEXYL PV(日油股份有限公司製造)與6質量份比例的 十二烷基硫醇(東京化成工業股份有限公司製造)作為聚合起始劑，及100質量份比例的甲苯作為溶劑，使其在80℃中聚合3小時，獲得共聚物(側鏈結晶性聚合物，重量平均分子量(Mw)：約7,000)。所得的側鏈結晶性聚合物，具有約51℃的熔點(Tm)及約19.8的SP值。 As shown in Table 2, 45% by mass of behenyl acrylate (manufactured by NOF Corporation) and 55% by mass of acrylic acid were mixed to obtain a monomer mixture. To 100 parts by mass of this monomer mixture, 1 part by mass of PERHEXYL PV (manufactured by NOF Corporation) and 6 parts by mass of dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) were added as polymerization initiators, and 100 parts by mass of toluene as a solvent were added, and the mixture was polymerized at 80°C for 3 hours to obtain a copolymer (side-chain crystalline polymer, weight average molecular weight (Mw): about 7,000). The obtained side-chain crystalline polymer has a melting point (Tm) of about 51°C and an SP value of about 19.8.
(合成例B2至B3：側鏈結晶性聚合物的合成) (Synthesis Examples B2 to B3: Synthesis of Side-Chain Crystalline Polymers)
除了以表2所述之比例使用表2所述之單體成分以外，以和合成例B1相同的程序獲得共聚物(側鏈結晶性聚合物)。將各側鏈結晶性聚合物的Mw、SP值及Tm表示於表2中。「Viscoat 3F」是2,2,2-三氟丙烯酸乙酯，為大阪有機化學工業股份有限公司販售。 A copolymer (side-chain crystalline polymer) was obtained by the same procedure as in Synthesis Example B1 except that the monomer components described in Table 2 were used in the proportions described in Table 2. The Mw, SP value and Tm of each side-chain crystalline polymer are shown in Table 2. "Viscoat 3F" is ethyl 2,2,2-trifluoroacrylate, sold by Osaka Organic Chemical Industry Co., Ltd.
(合成例B4：側鏈結晶性聚合物的合成) (Synthesis Example B4: Synthesis of side-chain crystalline polymer)
除了以表2所述之比例使用表2所述之單體成分、將十二烷基硫醇(東京化成工業股份有限公司製造)變更為12質量份以外，以和合成例B1相同的程序獲得共聚物(側鏈結晶性聚合物)。將各側鏈結晶性聚合物的Mw、SP值及Tm表示於表2中。 A copolymer (side-chain crystalline polymer) was obtained by the same procedure as in Synthesis Example B1, except that the monomer components described in Table 2 were used in the proportions described in Table 2 and dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 12 parts by mass. The Mw, SP value and Tm of each side-chain crystalline polymer are shown in Table 2.
(合成例B5：側鏈結晶性聚合物的合成) (Synthesis Example B5: Synthesis of side-chain crystalline polymer)
除了以表2所述之比例使用表2所述之單體成分、將十二烷基硫醇(東京化成工業股份有限公司製造)變更為2質量份以外，以和合成例B1相同的程序獲得共聚物(側鏈結晶性聚合物)。將各側鏈結晶性聚合物的Mw、SP值及Tm表示於表2中。 A copolymer (side-chain crystalline polymer) was obtained by the same procedure as in Synthesis Example B1, except that the monomer components described in Table 2 were used in the proportions described in Table 2 and dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 2 parts by mass. The Mw, SP value and Tm of each side-chain crystalline polymer are shown in Table 2.
(比較合成例B1至B3：側鏈結晶性聚合物的合成) (Comparative Synthesis Examples B1 to B3: Synthesis of Side-Chain Crystalline Polymers)
除了以表2所述之比例使用表2所述之單體成分以外，以和合成例B1相同的程序獲得共聚物(側鏈結晶性聚合物)。將各側鏈結晶性聚合物的Mw、SP值及Tm表示於表2中。 Except that the monomer components described in Table 2 are used in the proportions described in Table 2, a copolymer (side-chain crystalline polymer) is obtained by the same procedure as in Synthesis Example B1. The Mw, SP value and Tm of each side-chain crystalline polymer are shown in Table 2.
(實施例1) (Implementation Example 1)
對合成例A1中獲得的基質樹脂100質量份，以5質量份的比例混合合成例B1中獲得的側鏈結晶性聚合物，獲得感溫性黏著劑。使獲得的感溫性黏著劑溶解於乙酸乙酯中至濃度成為30質量%，調製成感溫性黏著劑溶液。在獲得的溶液中，對於基質樹脂100質量份，以1質量份的 比例添加金屬螯合物交聯劑(三乙醯基丙酮酸鋁，川研精密化學股份有限公司製造)作為交聯劑，獲得感溫性黏著劑組成物。藉由將獲得的感溫性黏著劑組成物塗布在基材(具有100μm厚度的PET膜)的一面上，形成黏著劑層。黏著劑層具有30μm的厚度。如此得到感溫性黏著帶。 A temperature-sensitive adhesive was obtained by mixing 5 parts by mass of the side-chain crystalline polymer obtained in Synthesis Example B1 with 100 parts by mass of the base resin obtained in Synthesis Example A1. The obtained temperature-sensitive adhesive was dissolved in ethyl acetate to a concentration of 30% by mass to prepare a temperature-sensitive adhesive solution. A metal chelate crosslinking agent (aluminum triacetylpyruvate, manufactured by Kawaken Fine Chemicals Co., Ltd.) was added as a crosslinking agent to the obtained solution at a ratio of 1 part by mass to 100 parts by mass of the base resin to obtain a temperature-sensitive adhesive composition. The obtained temperature-sensitive adhesive composition is applied to one side of a substrate (PET film having a thickness of 100 μm) to form an adhesive layer. The adhesive layer has a thickness of 30 μm. In this way, a temperature-sensitive adhesive tape is obtained.
依照JIS Z0237測定所得的感溫性黏著帶之黏著強度。具體上，係將感溫性黏著帶沖壓成25mm寬的矩形狀，利用2公斤的輥黏附在黏附體上。在23℃中靜置20分鐘使其固定，利用測力器(load cell)以每分鐘300mm的速度將感溫性黏著帶剝離180°，測定黏著劑/黏附體界面中的無膠殘留之剝離試樣在23℃中的接著強度。以下述基準評估所得的接著強度，A或B時評估為具有充分的固定性。將結果表示於表3中。 The adhesive strength of the obtained temperature-sensitive adhesive tape was measured according to JIS Z0237. Specifically, the temperature-sensitive adhesive tape was punched into a 25mm wide rectangle and adhered to the adherend using a 2kg roller. It was fixed at 23°C for 20 minutes, and the temperature-sensitive adhesive tape was peeled off 180° at a speed of 300mm per minute using a load cell, and the adhesive strength of the peeled specimen without glue residue at the adhesive/adhesive interface at 23°C was measured. The obtained adhesive strength was evaluated according to the following criteria, and A or B was evaluated as having sufficient fixation. The results are shown in Table 3.
<評估基準> <Evaluation Criteria>
A：接著強度為5N/25mm以上時。 A: Then the strength is 5N/25mm or above.
B：接著強度為2N/25mm以上、未達5N/25mm時。 B: When the strength is above 2N/25mm and below 5N/25mm.
C：接著強度未達2N/25mm時。 C: Then the strength does not reach 2N/25mm.
其次，在23℃中靜置20分鐘直至固定中，進行和上述相同的程序。然後，在60℃中靜置20分鐘，利用測力器以每分鐘300mm的速度將PET膜剝離180°，測定於60℃中的接著強度。以下述基準評估所得的接著強度，A或B時評估為具有充分的固定性。將結果表示於表3中。 Next, place it at 23°C for 20 minutes until it is fixed, and perform the same procedure as above. Then, place it at 60°C for 20 minutes, peel the PET film 180° at a speed of 300 mm per minute using a force gauge, and measure the bonding strength at 60°C. The bonding strength obtained was evaluated based on the following criteria, and A or B was evaluated as having sufficient fixation. The results are shown in Table 3.
<評估基準> <Evaluation Criteria>
A：接著強度為0.05N/25mm以下時。 A: When the strength is below 0.05N/25mm.
B：接著強度超過0.05N/25mm、0.1N/25mm時。 B: Then the strength exceeds 0.05N/25mm, 0.1N/25mm.
C：接強度超過0.1N/25mm時。 C: When the joint strength exceeds 0.1N/25mm.
另外，使用聚甲基丙烯酸甲酯(PMMA)製膜、聚萘二甲酸乙二酯(PEN)製膜及聚碳酸酯(PC)製膜取代PET製膜，以和上述相同的程序，分別測定23℃及60℃中的接著強度。將結果表示於表3中。 In addition, polymethyl methacrylate (PMMA) film, polyethylene naphthalate (PEN) film and polycarbonate (PC) film were used instead of PET film, and the bonding strength at 23°C and 60°C was measured using the same procedure as above. The results are shown in Table 3.
(實施例2至11) (Examples 2 to 11)
除了以表3所示之比例使用表3所示之基質樹脂及側鏈結晶性聚合物以外，以和實施例1相同的程序獲得感溫性黏著劑。除了分別使用獲得的感溫性黏著劑以外，以和實施例1相同的程序獲得感溫性黏著劑組成物。除了分別使用獲得的感溫性黏著劑組成物以外，以和實施例1相同的程序獲得感溫性黏著帶。感溫性黏著帶的黏著劑層具有30μm的厚度。對實施例2至11中獲得的感溫性黏著帶，以和實施例1相同的程序分別測定於23℃及60℃中之接著強度。將結果表示於表3中。 A thermosensitive adhesive was obtained by the same procedure as in Example 1, except that the base resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. A thermosensitive adhesive composition was obtained by the same procedure as in Example 1, except that the obtained thermosensitive adhesive was used separately. A thermosensitive adhesive tape was obtained by the same procedure as in Example 1, except that the obtained thermosensitive adhesive composition was used separately. The adhesive layer of the thermosensitive adhesive tape had a thickness of 30 μm. For the thermosensitive adhesive tapes obtained in Examples 2 to 11, the bonding strength at 23°C and 60°C was measured respectively by the same procedure as in Example 1. The results are shown in Table 3.
(比較例1至4) (Compare Examples 1 to 4)
除了以表3所示的比例使用表3所示的基質樹脂及側鏈結晶性聚合物以外，以和實施例1相同的程序獲得感溫性黏著劑。分別使用獲得的感溫性黏著劑，對基質樹脂100質量份，在比較例1至2中以5質量份的比例、在比較例3至4中以0.5質量份的比例添加異氰酸酯系交聯劑(Coronate L45，Tosoh(東曹)股份有限公司製造)作為交聯 劑，獲得感溫性黏著劑組成物。除了分別使用獲得的感溫性黏著劑組成物以外，以和實施例1相同的程序獲得感溫性黏著帶。感溫性黏著帶的黏著劑層具有30μm的厚度。分別對比較例1至4中獲得的感溫性黏著帶，以和實施例1相同的程序測定於23℃及60℃中的接著強度。將結果表示於表3中。 A temperature-sensitive adhesive was obtained in the same procedure as in Example 1 except that the base resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. Using the obtained temperature-sensitive adhesive, an isocyanate crosslinking agent (Coronate L45, manufactured by Tosoh Co., Ltd.) was added as a crosslinking agent to 100 parts by mass of the base resin in Comparative Examples 1 to 2 at a ratio of 5 parts by mass and in Comparative Examples 3 to 4 at a ratio of 0.5 parts by mass to obtain a temperature-sensitive adhesive composition. A temperature-sensitive adhesive tape was obtained in the same procedure as in Example 1 except that the obtained temperature-sensitive adhesive composition was used. The adhesive layer of the temperature-sensitive adhesive tape had a thickness of 30 μm. The temperature-sensitive adhesive tapes obtained in Examples 1 to 4 were compared and their bonding strength at 23°C and 60°C was measured using the same procedure as Example 1. The results are shown in Table 3.
(比較例5至8) (Compare Examples 5 to 8)
除了以表3表示之比例使用表3表示的基質樹脂及側鏈結晶性聚合物以外，以和實施例1相同的程序獲得感溫性黏著劑。除了分別使用獲得的感溫性黏著劑以外，以和實施例1相同的程序獲得感溫性黏著劑組成物。除了分別使用獲得的感溫性黏著劑組成物以外，以和實施例1相同的程序獲得感溫性黏著帶。感溫性黏著帶的黏著劑層具有30μm的厚度。對比較例5至8中分別獲得的感溫性黏著帶，以和實施例1相同的程序測定23℃及60℃中的接著強度。將結果表示於表3中。 A thermosensitive adhesive was obtained by the same procedure as in Example 1, except that the base resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. A thermosensitive adhesive composition was obtained by the same procedure as in Example 1, except that the obtained thermosensitive adhesive was used separately. A thermosensitive adhesive tape was obtained by the same procedure as in Example 1, except that the obtained thermosensitive adhesive composition was used separately. The adhesive layer of the thermosensitive adhesive tape had a thickness of 30 μm. The thermosensitive adhesive tapes obtained in Comparative Examples 5 to 8 were respectively measured for bonding strength at 23°C and 60°C by the same procedure as in Example 1. The results are shown in Table 3.
如表3所示可知，實施例1至11中獲得的感溫性黏著劑(感溫性黏著帶)，在23℃(室溫)中具有足夠 的固定性，於60℃(側鏈結晶性聚合物的熔點以上之溫度)中具有足夠的剝離性。因此，實施例1至11中獲得的感溫性黏著劑(感溫性黏著膠帶)，在室溫中，可充分的固定非晶性之有機系黏附體，側鏈結晶性聚合物的熔點以上之溫度中，可容易的從非晶性之有機系黏附體上剝離。 As shown in Table 3, the temperature-sensitive adhesive (temperature-sensitive adhesive tape) obtained in Examples 1 to 11 has sufficient fixation at 23°C (room temperature) and sufficient peeling at 60°C (temperature above the melting point of the side-chain crystalline polymer). Therefore, the temperature-sensitive adhesive (temperature-sensitive adhesive tape) obtained in Examples 1 to 11 can fully fix the amorphous organic adhesive at room temperature, and can be easily peeled from the amorphous organic adhesive at a temperature above the melting point of the side-chain crystalline polymer.
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| JP2017-169452 | 2017-09-04 | ||
| JP2017169452A JP7053194B2 (en) | 2017-09-04 | 2017-09-04 | Heat-sensitive adhesives, temperature-sensitive adhesive sheets and temperature-sensitive adhesive tapes |
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| KR (1) | KR102655512B1 (en) |
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| CN111019549A (en) * | 2019-11-07 | 2020-04-17 | 南京清尚新材料科技有限公司 | Acid and alkali resistant cold-seal adhesive, preparation method thereof and adhesive tape prepared from same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003129029A (en) * | 1991-02-12 | 2003-05-08 | Nitta Ind Corp | Temperature-zone-specific pressure-sensitive adhesive composition, adhesive assembly and method of using the same |
| JP2010254803A (en) * | 2009-04-24 | 2010-11-11 | Nitta Ind Corp | Temperature-sensitive adhesive and temperature-sensitive adhesive tape |
| JP2011021049A (en) * | 2009-07-13 | 2011-02-03 | Nitta Corp | Protective tape for etching processing, and etching processing method |
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| JP3601892B2 (en) * | 1995-11-21 | 2004-12-15 | 三井化学株式会社 | Adhesive film for backside grinding of semiconductor wafer and method of using the same |
| JP4888928B2 (en) | 2001-06-08 | 2012-02-29 | 日東電工株式会社 | Method for manufacturing ceramic green sheet, method for manufacturing multilayer ceramic electronic component, and carrier sheet for ceramic green sheet |
| JP5358086B2 (en) | 2007-11-15 | 2013-12-04 | ニッタ株式会社 | Temperature sensitive adhesive |
| JP5379453B2 (en) | 2008-11-21 | 2013-12-25 | ニッタ株式会社 | Temperature-sensitive adhesive tape and chip-type electronic component manufacturing method using the same |
| JP2011037944A (en) | 2009-08-07 | 2011-02-24 | Nitta Corp | Temperature-sensitive adhesive and temperature-sensitive adhesive tape |
| JP6390366B2 (en) | 2014-11-13 | 2018-09-19 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition, method for producing the same, adhesive tape |
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| JP2003129029A (en) * | 1991-02-12 | 2003-05-08 | Nitta Ind Corp | Temperature-zone-specific pressure-sensitive adhesive composition, adhesive assembly and method of using the same |
| JP2010254803A (en) * | 2009-04-24 | 2010-11-11 | Nitta Ind Corp | Temperature-sensitive adhesive and temperature-sensitive adhesive tape |
| JP2011021049A (en) * | 2009-07-13 | 2011-02-03 | Nitta Corp | Protective tape for etching processing, and etching processing method |
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| KR20200047517A (en) | 2020-05-07 |
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