TW201920563A - Temperature sensitive adhesive, temperature sensitive adhesive sheet and temperature sensitive adhesive tape - Google Patents
Temperature sensitive adhesive, temperature sensitive adhesive sheet and temperature sensitive adhesive tape Download PDFInfo
- Publication number
- TW201920563A TW201920563A TW107130844A TW107130844A TW201920563A TW 201920563 A TW201920563 A TW 201920563A TW 107130844 A TW107130844 A TW 107130844A TW 107130844 A TW107130844 A TW 107130844A TW 201920563 A TW201920563 A TW 201920563A
- Authority
- TW
- Taiwan
- Prior art keywords
- temperature
- meth
- sensitive adhesive
- acrylate
- side chain
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 107
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 106
- 239000002390 adhesive tape Substances 0.000 title claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 86
- 229920000642 polymer Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 55
- 239000011159 matrix material Substances 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 239000000470 constituent Substances 0.000 claims abstract description 9
- 230000007423 decrease Effects 0.000 claims abstract description 6
- -1 polyethylene terephthalate Polymers 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000417 polynaphthalene Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229940042596 viscoat Drugs 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000003431 cross linking reagent 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000010410 layer Substances 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
- 238000003756 stirring Methods 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004642 Polyimide 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
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 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
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 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
- 125000004178 (C1-C4) alkyl group Chemical group 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- IKCQWKJZLSDDSS-UHFFFAOYSA-N 2-formyloxyethyl formate Chemical compound O=COCCOC=O IKCQWKJZLSDDSS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SENMPMXZMGNQAG-UHFFFAOYSA-N 3,4-dihydro-2,5-benzodioxocine-1,6-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC=C12 SENMPMXZMGNQAG-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-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
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229920001400 block copolymer Polymers 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 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
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 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
- 230000000873 masking effect Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000005397 methacrylic acid ester 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
- 238000002156 mixing Methods 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine 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
- 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
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 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
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
本發明的感溫性黏著劑含有：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；其中，側鏈結晶性聚合物(B)具有滿足下述式(I)的SP值，且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。The temperature-sensitive adhesive of the present invention contains: a matrix resin (A) having an SP value of 18±2; and a side chain crystalline polymer (B) containing a linear alkyl group having 14 to 30 carbon atoms The monomer component of the (meth)acrylate (B1) serves as a constituent unit; wherein, the side chain crystalline polymer (B) has an SP value that satisfies the following formula (I), and the side chain crystalline polymer (B) B) Adhesion will decrease at temperatures above the melting point.
(A)的SP值-2≦(B)的SP值≦(A)的SP值+2 (I)(A) SP value-2≦(B)SP value≦(A)SP value+2 (I)
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 invention relates to a thermosensitive adhesive, a thermosensitive adhesive sheet, and a thermosensitive 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 thermo-sensitive resin having thermo-sensitivity is known, which displays a crystalline state and a fluid state in accordance with a reversible temperature change. A thermosensitive adhesive containing such a resin is disclosed in Patent Document 1, for example. Among the thermosensitive adhesives, there is a warm-off type adhesive, which exhibits fixability at a temperature below the melting point of the thermosensitive resin, and adheres at a temperature above the melting point of the thermosensitive resin. The force was significantly reduced and peeled.
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。 The traditional heating peel-off adhesive is temperature-sensitive for the adhesion of inorganic adherends (stainless steel plate, glass, etc.) and crystalline organic adherends (polyamine, polyoxymethylene, etc.). At a temperature above the melting point of the resin, the adhesiveness is significantly reduced, and the resin is easily peeled. However, for amorphous organic adherends (polyethylene terephthalate, polymethyl methacrylate, polycarbonate, etc.), even at temperatures above the melting point of the temperature-sensitive resin, the adhesiveness It will not decrease. As a result, for When a conventional heated peel-type adhesive is used for the amorphous organic adherend, the adhesive is not easily peeled.
[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。 An object of the present invention is to provide a thermosensitive adhesive which can be firmly adhered to an amorphous organic adhesive body at room temperature, and at the same time, the adhesiveness is reduced at a temperature above the melting point of the thermosensitive resin. It can be easily peeled, and 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 intensive research to solve the above problems, the present inventors have found a solution including the following constitutions, 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 thermosensitive adhesive containing: a matrix resin (A) having an SP value of 18 ± 2; and a side chain crystalline polymer (B) containing a (meth) acrylate (B1) ) As a constituent unit, and the (meth) acrylate (B1) has a linear alkyl group having 14 to 30 carbon atoms; wherein the side chain crystalline polymer (B) has a formula (I) The SP value of) decreases the adhesive force 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) SP value-2 ≤ (B) SP value ≤ (A) 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 thermosensitive adhesive according to the above item (1), wherein the side chain is crystallized The monomer component of the polymer (B) contains (meth) acrylate (B1) in a proportion of 30 to 70% by mass, and (meth) having a fluorine atom in the molecule in a proportion of 0 to 50% by mass. An acrylate (B2), and a (meth) acrylate (B3) containing an alkyl group having 1 to 6 carbons in a proportion of 10 to 70% by mass.
(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 according to the above item (1) or (2), 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) The temperature-sensitive adhesive according to any one of the above items (1) to (3), wherein the matrix resin (A) is a copolymer of a monomer containing the following: A saturated monomer and a (meth) acrylate having a hydrocarbon group of 8 or more carbon atoms.
(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 according to any one of the above items (1) to (4), wherein the adhesive strength to the amorphous organic adherend is 2N / 25mm or more at 23 ° C, at The temperature above the melting point of the side chain crystalline polymer is 0.05 N / 25 mm or less.
(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 thermosensitive adhesive containing: a matrix resin (A), a copolymer of monomers including: a carboxyl group-containing ethylenically unsaturated monomer, and a hydrocarbon group having a carbon number of 8 or more (a Group) acrylate; and side chain crystalline polymer (B), which are (meth) acrylates (B1), 0 having a linear alkyl group having 14 to 30 carbon atoms in a proportion of 30 to 70% by mass (Meth) acrylate (B2) having a fluorine atom in the molecule at a ratio of 50 to 50% by mass, and (meth) acrylate (B3) having an alkyl group having 1 to 6 carbons at a ratio of 10 to 70% by mass ) As a constituent unit; The adhesion strength of the crystalline organic adherend 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 according to the above item (5) or (6), wherein the amorphous organic adhesion system is selected from the group consisting of polyethylene terephthalate, polymethyl methacrylate, and polynaphthalene A molded article of at least one resin in the group consisting of ethylene diformate 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 (1) to (7) above.
(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 (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 an amorphous organic adherend can be firmly adhered at room temperature, and at the same time, the adhesiveness can be reduced at a temperature equal to or higher than the melting point of the thermosensitive resin, and it can be easily peeled. That is, it can be firmly adhered by the adhesiveness of the matrix resin (A) and the cohesive force of the side chain crystalline polymer (B). On the other hand, the SP value of the matrix resin (A) is relatively small, and the SP value of the side chain crystalline polymer (B) is also set to approximately the SP value of the matrix resin (A) (the SP value of the matrix resin (A) ± 2). ). Furthermore, since the SP value of the resin constituting the amorphous organic adherend is relatively large, the amorphous organic adherend and the matrix resin (A) and the side chain crystalline polymer having a relatively large SP value The compatibility between (B) is low. Therefore, it is presumed that the side-chain crystalline polymer (B) is heated to a temperature above the melting point of the side-chain crystalline polymer (B). It has fluidity and is easily peeled from an amorphous organic adherend having low compatibility with a matrix resin (A) having 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 temperature-sensitive adhesive according to an embodiment of the present disclosure will be described in detail. The temperature-sensitive adhesive according to one embodiment includes: a matrix resin (A) having an SP value of 18 ± 2; and a side chain crystalline polymer (B) containing a (meth) acrylate (B1) The (meth) acrylic acid ester (B1) has a linear alkyl group having 14 to 30 carbon atoms and a crystalline polymer (B) in the side chain (equivalent to a thermosensitive resin) as a constituent unit. At temperatures above the melting point, tackiness decreases. In this specification, "(meth) acryl group" means "acryl group" or "methacryl group."
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。 The matrix resin (A) is not particularly limited as long as it is a resin having an SP value of 18 ± 2. The SP value is a solubility parameter. For example, when two or more resins are mixed, the compatibility between the resins having similar SP values is excellent, and the larger the difference between the SP values, the less the compatibility is.
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。 Examples of the matrix resin (A) include copolymers of a polar monomer (A1) and a monomer (A2) copolymerizable with the polar monomer, and copolymers having a glass transition point (Tg) of 0 ° C or lower. Better. Among these, a copolymer which does not contain a (meth) acrylic acid ester having a C1-C4 alkyl group as a monomer component is preferable. If such a monomer component is 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 amorphous organic system. Adherent The value of surface free energy. Therefore, the intermolecular interaction is not easy to increase, and it is easy to reduce the adhesion.
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), a monomer containing a hydroxyl group is preferably not used alone. As long as the monomer containing a hydroxyl group is not used alone, it is difficult to increase the loss elasticity at a temperature higher than the melting point of the side chain crystalline polymer (B), and it is difficult to dissipate the peeling energy. Therefore, it is difficult to increase the energy necessary for peeling and to further improve the peelability.
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。 The matrix resin (A) is specifically a copolymer containing a polar monomer (A1) and a monomer having a (meth) acrylic acid ester (A2 ') having a hydrocarbon group of 8 or more carbon atoms, and preferably contains (a A copolymer of acrylic acid) and a monomer of a (meth) acrylic acid ester having a hydrocarbon group of 8 to 18 carbon atoms. The monomer component may contain a monomer copolymerizable with these compounds. Examples of the (meth) acrylate (A2 ′) having a hydrocarbon group having 8 or more carbon atoms include ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, (Meth) acrylic acid esters such as (meth) acrylic acid stearyl ester, behenyl (meth) acrylic acid esters, and alkyl groups having 8 or more carbon atoms, isoisopropyl (meth) acrylates, or the like having 8 or more carbon atoms (Meth) acrylates of cyclic hydrocarbon groups. The (meth) acrylate having a hydrocarbon group having 8 or more carbon atoms may be used alone, or two or more thereof may be used in combination.
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。 The polar monomer (A1) can be used: for example, acrylic unsaturated acids containing carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, β-carboxyethyl acrylate, etc monomer. You may have 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 2-hydroxyethylpropenamide, etc. Hydroxyl ethylenically unsaturated monomers are used in combination. When an ethylenically unsaturated monomer containing a carboxyl group such as acrylic acid or methacrylic acid is used as the polar monomer (A1), the monomer component constituting the matrix resin (A) is contained in a proportion of 1 to 20% by mass as good. This is because when a carboxyl group-containing ethylenically unsaturated monomer is contained in such a ratio, the obtained thermosensitive adhesive can have a moderate viscosity, excellent handling properties, and high fixability at room temperature. Since the loss elastic modulus at a temperature above the melting point of the chain crystalline polymer (B) is reduced, the chain crystalline polymer (B) 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。 The polymerization method for obtaining the monomer component of the matrix resin (A) is not particularly limited, and examples thereof include a solution polymerization method, a block polymerization method, a suspension polymerization method, and an emulsion polymerization method. For example, in the case of a solution polymerization method, as long as the monomer components are mixed with a solvent, a polymerization initiator or a chain transfer agent is added as needed, and the mixture is allowed to react at about 50 to 100 ° C. for about 1 to 24 hours while stirring.
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) uses a monomer component containing a (meth) acrylate (B1) having a linear alkyl group having 14 to 30 carbon atoms as a constituent unit. Examples of the (meth) acrylate (B1) having a linear alkyl group having 14 to 30 carbon atoms include, for example, cetyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Eicosyl esters, behenyl (meth) acrylate, behenyl (meth) acrylate, and the like. Among such (meth) acrylates (A), a (meth) acrylate having a linear alkyl group having 18 to 22 carbon atoms 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 only The (meth) acrylate (B1) is not specifically limited. For example, in the monomer component, in addition to the (meth) acrylate (B1), a (meth) acrylate (B2) having a fluorine atom in the molecule, and (a) Group) acrylate (B3) and the like.
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 the (meth) acrylate (B2) having a fluorine atom in the molecule include a compound represented by the 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。 In the formula R 1 -CF 3 (i), 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。 Examples of the alkylene group include straight or branched carbons having 1 to 6 carbon atoms such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and hexamethylene. Alkylene etc.
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 the (meth) acrylate (B2) having a fluorine atom in the molecule include ethyl 2,2,2-trifluoroacrylate and ethyl 2,2,2-trifluoromethacrylate. The (meth) acrylate (B2) having a fluorine atom 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。 (Meth) acrylate (B2) having a fluorine atom in the molecule may be a commercially available product, 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 the (meth) acrylate (B3) having an alkyl group having 1 to 6 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) ) Isopropyl acrylate, butyl (meth) acrylate Esters, 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 component constituting the side chain crystalline polymer (B) contains a (meth) acrylic acid ester (B1) having a linear alkyl group having 14 to 30 carbon atoms in a proportion shown below, and has fluorine in the molecule An atomic (meth) acrylate (B2) and a (meth) acrylate (B3) having an alkyl group having 1 to 6 carbon atoms are preferred.
(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, more 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, more 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, more 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。 The polymerization method for obtaining the monomer component of the side chain crystalline polymer (B) is not particularly limited, and examples thereof include a solution polymerization method, a block polymerization method, a suspension polymerization method, and an emulsion polymerization method. For example, when a solution polymerization method is used, as long as the monomer components are mixed with a solvent, a polymerization initiator or a chain transfer agent is added as needed, and the reaction is performed at about 50 to 100 ° C. for about 1 to 6 hours while stirring.
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), and preferably has an SP value satisfying the following formula (I ').
(A)的SP值-2≦(B)的SP值≦(A)的SP值+2 (I) (A) SP value-2 ≤ (B) SP value ≤ (A) SP value + 2 (I)
(A)的SP值-1≦(B)的SP值≦(A)的SP值+1 (I’) SP value of (A) -1 ≦ SP value of (B) ≦ SP value of (A) +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 a 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, more preferably 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 viscosity of the side chain crystalline polymer (B) decreases at a temperature above the melting point (Tm). That is, the side chain crystalline polymer (B) is crystallized at a temperature lower than the melting point, and is phase-transferred at a temperature higher than the melting point to show fluidity. The melting point of the side chain crystalline polymer is not particularly limited. The side chain crystalline polymer preferably has a melting point of 70 ° C or lower, and more preferably has a melting point of 60 ° C or lower. The "melting point" in this specification refers to the temperature at which certain parts of the polymer that are initially arranged in an orderly manner become disordered by some equilibrium procedure. It can be measured by a differential scanning calorimeter (DSC) at 10 ° C per minute. Condition determination.
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。 A temperature-sensitive adhesive according to an embodiment of the present disclosure includes a matrix resin (A) and a side chain crystalline polymer (B) having an SP value of 18 ± 2 in an arbitrary ratio, and 100% relative to the matrix resin (A). It is preferable that the side chain crystalline polymer (B) is contained in a proportion of 1 to 30 parts by mass, and more preferably contained in a proportion of 3 to 20 parts by mass. The thermosensitive adhesive according to an embodiment of the present disclosure can be obtained by mixing the matrix resin (A) and the side chain crystalline polymer (B) and stirring them.
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。 A temperature-sensitive adhesive according to an embodiment of the present disclosure may include a plasticizer, a tackifier, a filler, an antioxidant, and the like, as necessary. Examples of the tackifier include special rosin esters, terpene phenols, petroleum resins, high hydroxyl rosin esters, and hydrogenated rosin esters. In addition, ordinary pressure-sensitive adhesives such as acrylics and rubbers can be added to further improve the adhesion to 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 temperature-sensitive adhesive according to an embodiment of the present disclosure may further include a crosslinking agent to improve cohesion. The crosslinking agent is not particularly limited, and examples thereof include an isocyanate-based compound, an aziridine-based compound, an epoxy-based compound, and a metal chelate-based compound.
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 thermosensitive adhesive according to an embodiment of the present disclosure is preferably 2N / 25mm or more at 23 ° C for the amorphous organic adherend, and is a crystalline polymer (B) at a side chain. The temperature above the melting point is 0.05N / 25mm or less. In this specification, the adhesive strength is a value measured with respect to an amorphous organic adherend at 300 mm per minute in accordance with JIS Z0237. When the temperature-sensitive adhesive has such a range of adhesion strength, the adherend can be more firmly attached at room temperature (temperature below the melting point of the side chain crystalline polymer (B)), and the side chain is crystalline. At a temperature above the melting point of the polymer (B), the adhesive can be more easily peeled from the adherend. The temperature-sensitive adhesive has better adhesion strength of 5N / 25mm at 23 ° C, and 0.05N / 25mm or less 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。 In peeling the thermosensitive adhesive, it is often peeled at a speed higher than the JIS regulation (for example, about 3,000 mm per minute). Generally, when peeling at a high speed, the peel strength tends to be high. However, in the case where the peel strength at 300 mm per minute prescribed by JIS is very low of 0.05 N / 25 mm or less, it is difficult to increase the peel strength even at high speed peeling. Therefore, regardless of the peeling speed, the temperature-sensitive adhesive of one embodiment can be peeled off without damage to the amorphous organic adherend.
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 adherends include: Molded products of resins such as ethylene phthalate, polymethyl methacrylate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, and cycloolefin polymers. Among these amorphous organic adherends, the thermosensitive adhesive according to an embodiment of the present disclosure is selected from polyethylene terephthalate, polymethyl methacrylate, and polyethylene naphthalate. A molded product of at least one resin in the group consisting of a diester and a polycarbonate can exhibit more excellent effects.
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。 The method for using the temperature-sensitive adhesive according to one embodiment of the present disclosure is not particularly limited. For example, a temperature-sensitive adhesive can be applied to a target adherend, or the temperature-sensitive adhesive can be formed into It is used in the form of a sheet like a substrateless tape.
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, the pressure-sensitive adhesive layer containing the temperature-sensitive adhesive according to 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 the substrate. The substrate is preferably a film, and the film also includes a sheet. Examples of the constituent materials of the substrate include polyethylene, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyester, polyamide, polyimide, polyimide , Polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, polyvinyl chloride, polyetheretherketone and other synthetic resins.
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 multilayer structure. The substrate usually has a thickness of about 5 to 500 μm. In addition, on the substrate, for the purpose of improving the adhesion to the adhesive layer, surface treatments such as corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, and primer treatment may be applied. .
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。 The method for forming an adhesive layer containing a thermosensitive adhesive on at least one side of the substrate is not particularly limited. Examples thereof include a method of adding a coating solution of a solvent to the thermosensitive adhesive if necessary, applying the coating solution to one or both sides of a substrate by a coater, and then drying. Examples of the coater include a knife coater, a roll coater, a calendar coater, a comma coater, a gravure coater, and a bar coater. The thickness of the adhesive layer is not particularly limited. The adhesive layer preferably has a thickness of about 1 to 500 μm, and more preferably has a thickness of 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 containing a pressure-sensitive adhesive layer containing a temperature-sensitive adhesive is formed only on one surface of the substrate, and a layer such as a pressure-sensitive adhesive can be formed on the other surface, or a temperature-sensitive adhesive Agent and pressure-sensitive adhesive layer. Examples of pressure-sensitive adhesives include natural rubber adhesives, synthetic rubber adhesives, styrene-butadiene latex matrix adhesives, block copolymer thermoplastic rubbers, butyl rubbers, polyisobutylene, acrylic adhesives, Vinyl ether copolymers and the like. A commercially available pressure sensitive adhesive can 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。 With the temperature-sensitive adhesive according to an embodiment of the present disclosure, even for amorphous organic adherends such as polyethylene terephthalate or polymethyl methacrylate, the melting point of the temperature-sensitive resin is At these temperatures, the adhesion can be significantly reduced, and peeling is easy. Therefore, by using the temperature-sensitive adhesive according to one embodiment of the present disclosure, such an amorphous organic adherend can be processed into an adherend after being fixed at room temperature. After processing, the temperature-sensitive adhesive can be easily removed from the amorphous organic adherend by increasing the temperature to a temperature higher than the melting point of the side chain crystalline polymer (B) contained in the temperature-sensitive adhesive. Peel off. Thermosensitive stickiness using an embodiment of the present disclosure The same applies to the thermosensitive adhesive sheet and the thermosensitive adhesive tape of the adhesive.
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, the temperature-sensitive adhesive sheet, and the temperature-sensitive adhesive tape according to an embodiment of the present disclosure can be used, for example, in a carrier tape or a masking tape, or during a fixing or transfer process during dicing. Wait for it.
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 thermosensitive adhesive according to another embodiment of the present disclosure contains a matrix resin (A), which is a copolymer of (meth) acrylic acid and a (meth) acrylic acid ester-containing monomer having a hydrocarbon group having 8 or more carbon atoms. And a side chain crystalline polymer (B), which is a constituent unit containing the following monomer components in the following proportions: 30 to 70% by mass of a linear alkyl group having 14 to 30 carbon atoms ( (Meth) acrylate (B1), (meth) acrylate (B2) having a fluorine atom in the molecule at a ratio of 0 to 50% by mass, and alkane having 1 to 6 carbon atoms at a ratio of 10 to 70% by mass (Meth) acrylic acid ester (B3); the adhesion strength to the amorphous organic adherend is 2N / 25mm or more at 23 ° C, and the temperature is above the melting point of the side chain crystalline polymer. Below 0.05N / 25mm. The description of each component is as described above, and 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。 Hereinafter, although the present invention will be described more specifically with reference to examples and comparative examples, the present invention is not limited to the scope of these examples.
(合成例A1：基質樹脂的合成) (Synthesis example A1: Synthesis of matrix 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 ethyl hexyl acrylate was mixed with 2% by mass of acrylic acid to obtain a monomer mixture. For this monomer mixture 100 Per mass parts, 0.5 parts by mass of PERBUTYL ND (manufactured by Nippon Oil Co., Ltd.) was added as a polymerization initiator and 230 parts by mass of methyl acetate was used as a solvent, and polymerization was performed at 55 ° C. for 4 hours. Then, the temperature was raised to 80 ° C, and PERHEXYL PV (manufactured by Nippon Oil Co., Ltd.) was added as a polymerization initiator to 100 parts by mass of the monomer mixture. After the addition, polymerization was performed for 2 hours to obtain a copolymer (weight average molecular weight (Mw): about 550,000). The obtained matrix resin had 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 Matrix 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 (matrix resin) was obtained in 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 matrix resin are shown in Table 1. "Blemmer VMA-70" is a mixture of methacrylic acid esters having linear alkyl groups having 18 to 24 carbon atoms and is commercially available from Nippon Oil Corporation. "Blemmer LMA", a lauryl methacrylate, is available from Nippon Oil Corporation.
(比較合成例A1至A5：基質樹脂的合成) (Comparative Synthesis Examples A1 to A5: Synthesis of Matrix 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。 A copolymer (matrix resin) was obtained in 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 matrix resin are shown in Table 1.
(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PERHEXVL 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 Nippon Oil Co., Ltd.) and 55% by mass of acrylic acid were mixed to obtain a monomer mixture. 100 parts by mass of this monomer mixture was added with 1 part by mass of PERHEXVL PV (manufactured by Nippon Oil Co., Ltd.) and 6 parts by mass of Dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization initiator and 100 parts by mass of toluene as a solvent were polymerized at 80 ° C for 3 hours to obtain a copolymer (side chain crystalline polymerization). Material, weight average molecular weight (Mw): about 7,000). The obtained side chain crystalline polymer had 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 polymer)
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 in 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. Table 2 shows the Mw, SP value and Tm of each side chain crystalline polymer. "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。 Obtained in 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. Copolymer (side chain crystalline polymer). Table 2 shows the Mw, SP value and Tm of each side chain crystalline polymer.
(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。 Obtained in 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. Copolymer (side chain crystalline polymer). Table 2 shows the Mw, SP value and Tm of each side chain crystalline polymer.
(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 Polymer)
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。 A copolymer (side chain crystalline polymer) was obtained in 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. Table 2 shows the Mw, SP value and Tm of each side chain crystalline polymer.
(實施例1) (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。 About 100 parts by mass of the matrix resin obtained in Synthesis Example A1, the side chain crystalline polymer obtained in Synthesis Example B1 was mixed at a ratio of 5 parts by mass to obtain a thermosensitive adhesive. The obtained thermosensitive adhesive was dissolved in ethyl acetate to a concentration of 30% by mass to prepare a thermosensitive adhesive solution. In the obtained solution, for 100 parts by mass of the matrix resin, 1 part by mass of A metal chelate cross-linking agent (triethylamidopyruvate, manufactured by Kawaken Precision Chemical Co., Ltd.) was added in proportion as a cross-linking agent to obtain a thermosensitive adhesive composition. An adhesive layer was formed by coating the obtained thermosensitive adhesive composition on one side of a substrate (a PET film having a thickness of 100 μm). The adhesive layer has a thickness of 30 μm. In this way, a temperature-sensitive adhesive tape was 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 thermosensitive adhesive tape was measured in accordance with JIS Z0237. Specifically, the thermosensitive adhesive tape was punched into a 25 mm wide rectangular shape, and adhered to the adherend with a 2 kg roller. Allow it to stand for 20 minutes at 23 ° C to fix it. Use a load cell to peel the temperature-sensitive adhesive tape 180 ° at a speed of 300 mm per minute, and measure the peeling without adhesive residue in the adhesive / adhesive body interface. Adhesion strength of the sample at 23 ° C. The adhesive strength obtained was evaluated on the basis of the following criteria, and it was evaluated as having sufficient fixation at A or B. 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: When the bonding strength is 5N / 25mm or more.
B：接著強度為2N/25mm以上、未達5N/25mm時。 B: When the bonding strength is 2N / 25mm or more and less than 5N / 25mm.
C：接著強度未達2N/25mm時。 C: When the bonding strength is less than 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, it was left to stand at 23 ° C for 20 minutes until being fixed, and the same procedure as above was performed. Then, it was left to stand at 60 ° C for 20 minutes, and the PET film was peeled 180 ° at a speed of 300 mm per minute using a dynamometer, and the adhesive strength at 60 ° C was measured. The adhesive strength obtained was evaluated on the basis of the following criteria, and it was evaluated as having sufficient fixation at A or B. 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 bonding strength is 0.05 N / 25 mm or less.
B：接著強度超過0.05N/25mm、0.1N/25mm時。 B: When the strength exceeds 0.05N / 25mm and 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, instead of PET film, polymethyl methacrylate (PMMA) film, polyethylene naphthalate (PEN) film, and polycarbonate (PC) film were used. Adhesive strength at 23 ° C and 60 ° C. 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 matrix resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. A temperature-sensitive adhesive composition was obtained in the same procedure as in Example 1, except that the obtained temperature-sensitive adhesive was used separately. A temperature-sensitive adhesive tape was obtained by the same procedure as in Example 1 except that the obtained temperature-sensitive adhesive composition was used separately. The adhesive layer of the thermosensitive adhesive tape has a thickness of 30 μm. For the temperature-sensitive adhesive tapes obtained in Examples 2 to 11, the adhesion strengths at 23 ° C and 60 ° C were measured by the same procedures as in Example 1, respectively. The results are shown in Table 3.
(比較例1至4) (Comparative 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 thermosensitive adhesive was obtained in the same procedure as in Example 1 except that the matrix resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. Using the obtained thermosensitive adhesive, 100 parts by mass of the matrix resin was added in Comparative Examples 1 to 2 at a ratio of 5 parts by mass, and Comparative Examples 3 to 4 were added at a ratio of 0.5 parts by mass in an isocyanate-based crosslinking agent. (Coronate L45, manufactured by Tosoh) Agent to obtain a thermosensitive adhesive composition. A temperature-sensitive adhesive tape was obtained by the same procedure as in Example 1 except that the obtained temperature-sensitive adhesive composition was used separately. The adhesive layer of the thermosensitive adhesive tape has a thickness of 30 μm. For the thermosensitive adhesive tapes obtained in Comparative Examples 1 to 4, the adhesive strengths at 23 ° C and 60 ° C were measured in the same procedure as in Example 1. The results are shown in Table 3.
(比較例5至8) (Comparative 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 in the same procedure as in Example 1 except that the matrix resin and the side chain crystalline polymer shown in Table 3 were used in the proportions shown in Table 3. A temperature-sensitive adhesive composition was obtained in the same procedure as in Example 1, except that the obtained temperature-sensitive adhesive was used separately. A temperature-sensitive adhesive tape was obtained by the same procedure as in Example 1 except that the obtained temperature-sensitive adhesive composition was used separately. The adhesive layer of the thermosensitive adhesive tape has a thickness of 30 μm. With respect to the thermosensitive adhesive tapes obtained in Comparative Examples 5 to 8, the adhesive strengths at 23 ° C and 60 ° C were measured using 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, it can be seen that the temperature-sensitive adhesive (temperature-sensitive adhesive tape) obtained in Examples 1 to 11 is sufficient at 23 ° C (room temperature). It has sufficient releasability at 60 ° C (temperature higher than the melting point of the side chain crystalline polymer). Therefore, the thermosensitive adhesive (thermosensitive adhesive tape) obtained in Examples 1 to 11 can sufficiently fix the amorphous organic adherend at room temperature and the melting point of the side chain crystalline polymer or more. At this temperature, it can be easily peeled from the amorphous organic adherend.
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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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| AU1441692A (en) | 1991-02-12 | 1992-09-07 | Landec Corporation | Temperature zone specific pressure-sensitive adhesive compositions, and adhesive assemblies and methods of use associated therewith |
| 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 |
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| JP5358086B2 (en) | 2007-11-15 | 2013-12-04 | ニッタ株式会社 | Temperature sensitive adhesive |
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| 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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