JP7460451B2 - temperature sensitive adhesive - Google Patents
temperature sensitive adhesive Download PDFInfo
- Publication number
- JP7460451B2 JP7460451B2 JP2020099194A JP2020099194A JP7460451B2 JP 7460451 B2 JP7460451 B2 JP 7460451B2 JP 2020099194 A JP2020099194 A JP 2020099194A JP 2020099194 A JP2020099194 A JP 2020099194A JP 7460451 B2 JP7460451 B2 JP 7460451B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- temperature
- crystalline polymer
- chain crystalline
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims description 91
- 230000001070 adhesive effect Effects 0.000 title claims description 91
- 229920000642 polymer Polymers 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 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 claims description 8
- 239000002390 adhesive tape Substances 0.000 claims description 7
- 230000007423 decrease Effects 0.000 claims description 7
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 11
- 150000002222 fluorine compounds Chemical class 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- -1 2-hydroxyhexyl Chemical group 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229940042596 viscoat Drugs 0.000 description 6
- 239000013522 chelant Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-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
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002438 flame photometric detection Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment 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
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 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
- 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000003277 amino group Chemical group 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
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 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
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 230000003111 delayed effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 239000012046 mixed solvent Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- 102220013334 rs368367224 Human genes 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution 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
- 238000010557 suspension polymerization reaction 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Description
本発明は、感温性粘着剤に関する。 The present invention relates to a temperature-sensitive adhesive.
感温性粘着剤は、側鎖結晶性ポリマーを主成分として含有しており、側鎖結晶性ポリマーの融点未満の温度に冷却されると、側鎖結晶性ポリマーが結晶化することによって粘着力が低下する粘着剤である。感温性粘着剤は、シート、テープなどに加工されて、フラットパネルディスプレイ（以下、「ＦＰＤ」ということがある。）などの製造工程において、ガラス、プラスチックなどからなる基板を仮固定するときに使用されている（例えば、特許文献１参照）。このような用途に使用される感温性粘着剤は、工程によっては高温に加熱されることがあるため、被着体の浮き抑制などの耐熱性が要求される。また、高温に加熱された後の剥離性も要求される。 Thermosensitive adhesives contain a side-chain crystalline polymer as the main component, and when cooled to a temperature below the melting point of the side-chain crystalline polymer, the side-chain crystalline polymer crystallizes, causing the adhesive strength to decrease. The thermosensitive adhesives are processed into sheets, tapes, etc., and are used to temporarily fix substrates made of glass, plastic, etc. in the manufacturing process of flat panel displays (hereinafter sometimes referred to as "FPDs") (see, for example, Patent Document 1). Thermosensitive adhesives used for such purposes are sometimes heated to high temperatures in some processes, so they are required to have heat resistance, such as preventing the adherend from lifting. They are also required to have releasability after being heated to high temperatures.
しかし、従来の感温性粘着剤は、高温に加熱されたときに被着体によっては浮きが発生することがあった。この傾向は、シクロオレフィンポリマーフィルム（以下、「ＣＯＰフィルム」ということがある。）のように１３０℃以上に加熱されると変形し易く、変形したときの応力が粘着力よりも大きくなり易い被着体の場合に顕著であった。２００℃で３０分程度のアニール処理を感温性粘着剤に施せば、被着体への粘着力が向上して被着体の浮きの発生を抑制できるが、１工程手間となる。 However, conventional heat-sensitive adhesives could cause lifting depending on the adherend when heated to high temperatures. This tendency was particularly pronounced in the case of adherends such as cycloolefin polymer film (hereinafter sometimes referred to as "COP film"), which is prone to deformation when heated to 130°C or higher and in which the stress generated by deformation tends to be greater than the adhesive strength. Annealing the heat-sensitive adhesive for about 30 minutes at 200°C improves the adhesive strength to the adherend and prevents the adherend from lifting, but this requires an additional step.
本発明の課題は、高温に加熱されたときに被着体の浮きの発生を抑制することができ、高温に加熱された後の剥離性にも優れる感温性粘着剤を提供することである。 An object of the present invention is to provide a temperature-sensitive adhesive that can suppress the occurrence of floating of an adherend when heated to a high temperature and has excellent releasability after being heated to a high temperature. .
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
（１）側鎖結晶性ポリマーを含有し、前記側鎖結晶性ポリマーの融点未満の温度で粘着力が低下する感温性粘着剤であって、２０ｍｇＫＯＨ／ｇ以上の酸価を有する粘着付与剤をさらに含有する、感温性粘着剤。
（２）前記粘着付与剤の含有量が、前記側鎖結晶性ポリマー１００重量部に対して１０～５０重量部である、前記（１）に記載の感温性粘着剤。
（３）前記粘着付与剤が、ロジン系樹脂である、前記（１）または（２）に記載の感温性粘着剤。
（４）前記粘着付与剤の軟化点が、９０～１７５℃である、前記（１）～（３）のいずれかに記載の感温性粘着剤。
（５）５０℃におけるシクロオレフィンポリマーフィルムに対する１８０°剥離強度が、１．０Ｎ／２５ｍｍ以上である、前記（１）～（４）のいずれかに記載の感温性粘着剤。
（６）前記（１）～（５）のいずれかに記載の感温性粘着剤を含む、感温性粘着シート。
（７）フィルム状の基材と、前記基材の少なくとも片面に積層されており前記（１）～（５）のいずれかに記載の感温性粘着剤を含む粘着剤層と、を備える、感温性粘着テープ。
As a result of intensive research to solve the above problems, the present inventors found a solution consisting of the following configuration and completed the present invention.
(1) A temperature-sensitive adhesive that contains a side chain crystalline polymer and whose adhesive strength decreases at a temperature below the melting point of the side chain crystalline polymer, and has an acid value of 20 mgKOH/g or more. A temperature-sensitive adhesive further containing.
(2) The temperature-sensitive adhesive according to (1) above, wherein the content of the tackifier is 10 to 50 parts by weight based on 100 parts by weight of the side chain crystalline polymer.
(3) The temperature-sensitive adhesive according to (1) or (2) above, wherein the tackifier is a rosin resin.
(4) The temperature-sensitive adhesive according to any one of (1) to (3) above, wherein the tackifier has a softening point of 90 to 175°C.
(5) The temperature-sensitive adhesive according to any one of (1) to (4) above, which has a 180° peel strength against a cycloolefin polymer film at 50° C. of 1.0 N/25 mm or more.
(6) A temperature-sensitive adhesive sheet comprising the temperature-sensitive adhesive according to any one of (1) to (5) above.
(7) comprising a film-like base material and an adhesive layer laminated on at least one side of the base material and containing the temperature-sensitive adhesive according to any one of (1) to (5) above; Temperature sensitive adhesive tape.
本発明によれば、高温に加熱されたときに被着体の浮きの発生を抑制することができ、高温に加熱された後の剥離性にも優れるという効果がある。 The present invention has the effect of suppressing the occurrence of lifting of the adherend when heated to a high temperature, and also of providing excellent peelability after being heated to a high temperature.
＜感温性粘着剤＞
以下、本発明の一実施形態に係る感温性粘着剤について詳細に説明する。
<Temperature-sensitive adhesive>
Hereinafter, a temperature-sensitive adhesive according to an embodiment of the present invention will be described in detail.
（側鎖結晶性ポリマー）
本実施形態の感温性粘着剤は、側鎖結晶性ポリマーを含有する。側鎖結晶性ポリマーは、融点を有するポリマーである。融点とは、ある平衡プロセスにより、最初は秩序ある配列に整合されていた重合体の特定部分が無秩序状態になる温度であり、示差熱走査熱量計（ＤＳＣ）を使用して、１０℃／分の測定条件で測定して得られる値のことである。
(Side chain crystalline polymer)
The temperature-sensitive adhesive of this embodiment contains a side chain crystalline polymer. A side chain crystalline polymer is a polymer that has a melting point. The melting point is the temperature at which certain parts of the polymer, initially aligned in an ordered arrangement, become disordered due to some equilibrium process, and is measured using differential scanning calorimetry (DSC) at 10°C/min. This is the value obtained by measuring under the following measurement conditions.
側鎖結晶性ポリマーは、上述した融点未満の温度で結晶化し、且つ、融点以上の温度で相転移して流動性を示す。すなわち、側鎖結晶性ポリマーは、温度変化に対応して結晶状態と流動状態とを可逆的に起こす感温性を有する。 The side chain crystalline polymer crystallizes at a temperature below the above-mentioned melting point, and exhibits fluidity by undergoing a phase transition at a temperature above the melting point. That is, the side chain crystalline polymer has temperature sensitivity that allows it to reversibly change between a crystalline state and a fluid state in response to temperature changes.
本実施形態の感温性粘着剤は、側鎖結晶性ポリマーの融点未満の温度で粘着力が低下する。言い換えれば、本実施形態の感温性粘着剤は、融点未満の温度で側鎖結晶性ポリマーが結晶化したときに粘着力が低下する割合で、側鎖結晶性ポリマーを含有する。つまり、本実施形態の感温性粘着剤は、側鎖結晶性ポリマーを主成分として含有する。したがって、感温性粘着剤から被着体を剥離するときには、感温性粘着剤を側鎖結晶性ポリマーの融点未満の温度に冷却すれば、側鎖結晶性ポリマーが結晶化することによって粘着力が低下する。また、感温性粘着剤を側鎖結晶性ポリマーの融点以上の温度に加熱すれば、側鎖結晶性ポリマーが流動性を示すことによって粘着力が回復するので、繰り返し使用することができる。なお、上述した主成分とは、感温性粘着剤中に重量比で最も多く含まれる成分のことである。 The adhesive strength of the thermosensitive adhesive of this embodiment decreases at a temperature below the melting point of the side chain crystalline polymer. In other words, the thermosensitive adhesive of this embodiment contains the side chain crystalline polymer in a ratio at which the adhesive strength decreases when the side chain crystalline polymer crystallizes at a temperature below the melting point. In other words, the thermosensitive adhesive of this embodiment contains the side chain crystalline polymer as the main component. Therefore, when peeling the adherend from the thermosensitive adhesive, if the thermosensitive adhesive is cooled to a temperature below the melting point of the side chain crystalline polymer, the adhesive strength decreases due to the crystallization of the side chain crystalline polymer. In addition, if the thermosensitive adhesive is heated to a temperature equal to or higher than the melting point of the side chain crystalline polymer, the adhesive strength is restored due to the side chain crystalline polymer exhibiting fluidity, so that the thermosensitive adhesive can be used repeatedly. The main component mentioned above is the component that is contained in the largest amount by weight in the thermosensitive adhesive.
側鎖結晶性ポリマーは、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートをモノマー成分として含む。炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートは、その炭素数１６以上の直鎖状アルキル基が側鎖結晶性ポリマーにおける側鎖結晶性部位として機能する。すなわち、側鎖結晶性ポリマーは、側鎖に炭素数１６以上の直鎖状アルキル基を有する櫛形のポリマーであり、この側鎖が分子間力などによって秩序ある配列に整合されることにより結晶化する。なお、上述した（メタ）アクリレートとは、アクリレートまたはメタクリレートのことである。 The side chain crystalline polymer contains (meth)acrylate having a linear alkyl group having 16 or more carbon atoms as a monomer component. In the (meth)acrylate having a linear alkyl group having 16 or more carbon atoms, the linear alkyl group having 16 or more carbon atoms functions as a side chain crystalline site in a side chain crystalline polymer. In other words, a side chain crystalline polymer is a comb-shaped polymer that has a linear alkyl group having 16 or more carbon atoms in its side chain, and crystallizes when this side chain is aligned into an ordered arrangement by intermolecular forces. do. Note that the above-mentioned (meth)acrylate refers to acrylate or methacrylate.
炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートとしては、例えば、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、エイコシル（メタ）アクリレート、ベヘニル（メタ）アクリレートなどの炭素数１６～２２の線状アルキル基を有する（メタ）アクリレートが挙げられる。例示した（メタ）アクリレートは、１種のみを使用してもよいし、２種以上を併用してもよい。炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートは、側鎖結晶性ポリマーを構成するモノマー成分中に好ましくは１０～９９重量％、より好ましくは２０～９９重量％の割合で含まれる。 Examples of (meth)acrylates having a linear alkyl group with 16 or more carbon atoms include (meth)acrylates having a linear alkyl group with 16 to 22 carbon atoms, such as cetyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, and behenyl (meth)acrylate. The exemplified (meth)acrylates may be used alone or in combination of two or more. The (meth)acrylates having a linear alkyl group with 16 or more carbon atoms are preferably contained in the monomer components constituting the side chain crystalline polymer in a proportion of 10 to 99% by weight, more preferably 20 to 99% by weight.
側鎖結晶性ポリマーを構成するモノマー成分には、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートと共重合し得る他のモノマーが含まれてもよい。他のモノマーとしては、例えば、炭素数１～６のアルキル基を有する（メタ）アクリレート、極性モノマーなどが挙げられる。 The monomer components constituting the side chain crystalline polymer may include other monomers that can be copolymerized with the (meth)acrylate having a linear alkyl group having 16 or more carbon atoms. Examples of other monomers include (meth)acrylates having an alkyl group having 1 to 6 carbon atoms, polar monomers, and the like.
炭素数１～６のアルキル基を有する（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレートなどが挙げられる。例示した（メタ）アクリレートは、１種のみを使用してもよいし、２種以上を併用してもよい。炭素数１～６のアルキル基を有する（メタ）アクリレートは、側鎖結晶性ポリマーを構成するモノマー成分中に好ましくは７０重量％以下、より好ましくは１～７０重量％の割合で含まれる。 Examples of (meth)acrylates having an alkyl group with 1 to 6 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate. The exemplified (meth)acrylates may be used alone or in combination of two or more. The (meth)acrylates having an alkyl group with 1 to 6 carbon atoms are preferably contained in the monomer components constituting the side chain crystalline polymer in an amount of 70% by weight or less, and more preferably 1 to 70% by weight.
極性モノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸などのカルボキシル基を有するエチレン性不飽和単量体；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシヘキシル（メタ）アクリレートなどのヒドロキシル基を有するエチレン性不飽和単量体などが挙げられる。例示した極性モノマーは、１種のみを使用してもよいし、２種以上を併用してもよい。極性モノマーは、側鎖結晶性ポリマーを構成するモノマー成分中に好ましくは１０重量％以下、より好ましくは１～１０重量％の割合で含まれる。 Examples of polar monomers include ethylenically unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxy Examples include ethylenically unsaturated monomers having a hydroxyl group such as propyl (meth)acrylate and 2-hydroxyhexyl (meth)acrylate. The illustrated polar monomers may be used alone or in combination of two or more. The polar monomer is preferably contained in the monomer component constituting the side chain crystalline polymer in a proportion of 10% by weight or less, more preferably 1 to 10% by weight.
側鎖結晶性ポリマーを構成するモノマー成分には、反応性フッ素化合物がさらに含まれてもよい。これにより、感温性粘着剤を側鎖結晶性ポリマーの融点未満の温度に冷却すれば、側鎖結晶性ポリマーが結晶化することによる粘着力の低下に加えて、フッ素化合物に起因する離型性も加わるので、粘着力を大きく低下させることができる。 The monomer component constituting the side chain crystalline polymer may further contain a reactive fluorine compound. As a result, if the temperature-sensitive adhesive is cooled to a temperature below the melting point of the side-chain crystalline polymer, in addition to the decrease in adhesive strength due to crystallization of the side-chain crystalline polymer, mold release caused by fluorine compounds will occur. Since the adhesive strength is also added, the adhesive force can be greatly reduced.
反応性フッ素化合物とは、反応性を示す官能基を有するフッ素化合物のことである。反応性を示す官能基としては、例えば、エポキシ基（グリシジル基およびエポキシシクロアルキル基を含む）、メルカプト基、カルビノール基（メチロール基）、カルボキシル基、シラノール基、フェノール基、アミノ基、水酸基、エチレン性不飽和二重結合を有する基などが挙げられる。エチレン性不飽和二重結合を有する基としては、例えば、ビニル基、アリル基、（メタ）アクリル基、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基などが挙げられる。 A reactive fluorine compound is a fluorine compound having a functional group that exhibits reactivity. Examples of functional groups that exhibit reactivity include epoxy groups (including glycidyl groups and epoxycycloalkyl groups), mercapto groups, carbinol groups (methylol groups), carboxyl groups, silanol groups, phenol groups, amino groups, hydroxyl groups, and groups having an ethylenically unsaturated double bond. Examples of groups having an ethylenically unsaturated double bond include vinyl groups, allyl groups, (meth)acrylic groups, (meth)acryloyl groups, and (meth)acryloyloxy groups.
反応性フッ素化合物の具体例としては、下記一般式（Ｉ）で表される化合物などが挙げられる。 Specific examples of the reactive fluorine compound include compounds represented by the following general formula (I).
Ｒ2が示すアルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基などの炭素数１～６の直鎖または分岐したアルキレン基などが挙げられる。 Examples of the alkylene group represented by R 2 include linear or branched alkylene groups having 1 to 6 carbon atoms, such as methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, and hexamethylene group. can be mentioned.
一般式（Ｉ）で表される化合物の具体例としては、下記式（Ｉａ）で表される２，２，２－トリフルオロエチルアクリレート、式（Ｉｂ）で表される２，２，２－トリフルオロエチルメタクリレートなどが挙げられる。 Specific examples of compounds represented by general formula (I) include 2,2,2-trifluoroethyl acrylate represented by the following formula (Ia) and 2,2,2-trifluoroethyl methacrylate represented by the following formula (Ib).
上述した反応性フッ素化合物は、市販品を使用することができる。市販の反応性フッ素化合物としては、例えば、いずれも大阪有機化学工業社製の「ビスコート３Ｆ」、「ビスコート３ＦＭ」、「ビスコート４Ｆ」、「ビスコート８Ｆ」、「ビスコート８ＦＭ」、共栄社化学社製の「ライトエステルＭ－３Ｆ」などが挙げられる。 The reactive fluorine compounds mentioned above can be commercially available products. Examples of commercially available reactive fluorine compounds include "Viscoat 3F", "Viscoat 3FM", "Viscoat 4F", "Viscoat 8F", and "Viscoat 8FM", all manufactured by Osaka Organic Chemical Industry Co., Ltd., and "Light Ester M-3F" manufactured by Kyoeisha Chemical Co., Ltd.
反応性フッ素化合物は、１種のみを使用してもよいし、２種以上を併用してもよい。反応性フッ素化合物は、モノマー成分中に好ましくは１～２０重量％、より好ましくは１～１０重量％の割合で含まれる。 Only one type of reactive fluorine compound may be used, or two or more types may be used in combination. The reactive fluorine compound is contained in the monomer component preferably in a proportion of 1 to 20% by weight, more preferably 1 to 10% by weight.
側鎖結晶性ポリマーの好ましい組成としては、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートが２５～３０重量％、炭素数１～６のアルキル基を有する（メタ）アクリレートが５０～６５重量％、極性モノマーが５～１０重量％、および反応性フッ素化合物が５～１０重量％である。 The preferred composition of the side-chain crystalline polymer is 25 to 30% by weight of (meth)acrylate with a linear alkyl group having 16 or more carbon atoms, 50 to 65% by weight of (meth)acrylate with an alkyl group having 1 to 6 carbon atoms, 5 to 10% by weight of a polar monomer, and 5 to 10% by weight of a reactive fluorine compound.
モノマー成分の重合方法としては、例えば、溶液重合法、塊状重合法、懸濁重合法、乳化重合法などが挙げられる。溶液重合法を採用する場合には、モノマー成分と溶媒とを混合し、必要に応じて重合開始剤、連鎖移動剤などを添加して、撹拌しながら４０～９０℃程度で２～１０時間程度反応させればよい。 Examples of methods for polymerizing monomer components include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. When using the solution polymerization method, the monomer components and solvent are mixed, a polymerization initiator, a chain transfer agent, etc. are added as necessary, and the mixture is stirred at 40 to 90°C for about 2 to 10 hours. All you have to do is react.
側鎖結晶性ポリマーの重量平均分子量は、好ましくは１０００００以上、より好ましくは３０００００～９０００００、さらに好ましくは４０００００～７０００００である。重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、得られた測定値をポリスチレン換算した値である。 The weight average molecular weight of the side chain crystalline polymer is preferably 100,000 or more, more preferably 300,000 to 900,000, and even more preferably 400,000 to 700,000. The weight average molecular weight is measured by gel permeation chromatography (GPC) and the measured value is converted into a polystyrene equivalent value.
側鎖結晶性ポリマーの融点は、好ましくは０℃以上、より好ましくは１０～６０℃である。融点は、例えば、側鎖結晶性ポリマーを構成するモノマー成分の組成などを変えることによって調整することができる。 The melting point of the side-chain crystalline polymer is preferably 0°C or higher, more preferably 10 to 60°C. The melting point can be adjusted, for example, by changing the composition of the monomer components that make up the side-chain crystalline polymer.
（粘着付与剤）
本実施形態の感温性粘着剤は、上述した側鎖結晶性ポリマーに加えて、２０ｍｇＫＯＨ／ｇ以上の酸価を有する粘着付与剤をさらに含有する。これにより、ＣＯＰフィルムのように１３０℃以上に加熱されると変形し易く、変形したときの応力が粘着力よりも大きくなり易い被着体に対して、高温に加熱されたときに被着体の浮きや剥がれの発生を抑制することができ、高温に加熱された後の剥離性にも優れるという効果が得られる。したがって、本実施形態の感温性粘着剤をＣＯＰフィルムのような被着体を含む製品の製造工程に使用すれば、アニール処理などの手間を必要とせず、歩留りよくスムーズに工程を進めることができる。具体例を挙げると、本実施形態の感温性粘着剤は、ＦＰＤの製造工程における基板の仮固定用として好適に使用することができる。なお、上述した粘着付与剤は、ＣＯＰフィルムのような被着体に対して感温性粘着剤の親和性を向上させて粘着力を高める役割を有すると推察される。
(Tackifier)
The temperature-sensitive adhesive of this embodiment further contains a tackifier having an acid value of 20 mgKOH/g or more in addition to the above-mentioned side chain crystalline polymer. As a result, unlike adherends such as COP film, which easily deform when heated to 130°C or higher, and whose stress when deformed tends to be greater than the adhesive force, it is possible to It is possible to suppress the occurrence of lifting and peeling of the film, and it also has the effect of being excellent in releasability after being heated to a high temperature. Therefore, if the temperature-sensitive adhesive of this embodiment is used in the manufacturing process of a product including an adherend such as a COP film, the process can proceed smoothly with a high yield without the need for labor such as annealing. can. To give a specific example, the temperature-sensitive adhesive of this embodiment can be suitably used for temporarily fixing a substrate in the manufacturing process of an FPD. Note that the above-mentioned tackifier is presumed to have a role of improving the affinity of the temperature-sensitive adhesive to an adherend such as a COP film and increasing the adhesive force.
また、本実施形態の感温性粘着剤によれば、ＣＯＰフィルム以外の他の被着体に対しても、高温に加熱されたときに被着体の浮きや剥がれの発生を抑制することができ、高温に加熱された後の剥離性にも優れるという効果が得られる。したがって、本実施形態の感温性粘着剤は、高い汎用性を発揮することもできる。他の被着体としては、例えば、ポリイミドフィルム、ポリエチレンテレフタレートフィルム、ポリビニルブチラールフィルム、ステンレス鋼（ＳＵＳ）、ガラスなどが挙げられる。 Furthermore, according to the temperature-sensitive adhesive of the present embodiment, it is possible to suppress the occurrence of lifting and peeling of adherends other than COP films when heated to high temperatures. It also has the effect of being excellent in releasability after being heated to a high temperature. Therefore, the temperature-sensitive adhesive of this embodiment can also exhibit high versatility. Examples of other adherends include polyimide films, polyethylene terephthalate films, polyvinyl butyral films, stainless steel (SUS), and glass.
酸価の上限値は、特に限定されないが、３００ｍｇＫＯＨ／ｇ以下であってもよい。酸価は、好ましくは１００～３００ｍｇＫＯＨ／ｇ、より好ましくは１１０～２５５ｍｇＫＯＨ／ｇである。酸価は、ＪＩＳ Ｋ ２５０１に準拠して測定される値である。 The upper limit of the acid value is not particularly limited, but may be 300 mgKOH/g or less. The acid value is preferably 100 to 300 mgKOH/g, more preferably 110 to 255 mgKOH/g. The acid value is a value measured in accordance with JIS K 2501.
粘着付与剤の含有量は、側鎖結晶性ポリマー１００重量部に対して、好ましくは１０～５０重量部、より好ましくは１０～３０重量部である。 The content of the tackifier is preferably 10 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the side chain crystalline polymer.
粘着付与剤は、ロジン系樹脂であってもよい。また、粘着付与剤の軟化点は、好ましくは９０～１７５℃である。軟化点は、ＪＩＳ Ｋ ５９０２に規定される環球法に従って測定される値である。 The tackifier may be a rosin-based resin. The softening point of the tackifier is preferably 90 to 175°C. The softening point is a value measured according to the ring and ball method specified in JIS K 5902.
上述した粘着付与剤は、市販品を使用することができる。市販の粘着付与剤としては、例えば、いずれも荒川化学工業社製の「ＫＥ－６０４」、「ＫＲ－１４０」、「Ｒ－９５」などが挙げられる。 The above-mentioned tackifier can be a commercially available product. Examples of commercially available tackifiers include "KE-604", "KR-140", and "R-95", all manufactured by Arakawa Chemical Industries Co., Ltd.
なお、粘着付与剤は、１種のみを使用してもよいし、２種以上を併用してもよい。２種以上を併用する場合には、混合物が２０ｍｇＫＯＨ／ｇ以上の酸価を有する限り、２０ｍｇＫＯＨ／ｇ未満の酸価を有する粘着付与剤を併用してもよい。例えば、粘着付与剤が、互いに異なる酸価を有する第１粘着付与剤と第２粘着付与剤との混合物であってもよい。これにより、酸価の調整の自由度を向上させることができる。第１粘着付与剤および第２粘着付与剤のうち一方の酸価が、２０ｍｇＫＯＨ／ｇ未満であってもよい。 The tackifier may be used alone or in combination of two or more. When using two or more, a tackifier having an acid value of less than 20 mgKOH/g may be used in combination as long as the mixture has an acid value of 20 mgKOH/g or more. For example, the tackifier may be a mixture of a first tackifier and a second tackifier having different acid values. This improves the freedom to adjust the acid value. The acid value of one of the first tackifier and the second tackifier may be less than 20 mgKOH/g.
感温性粘着剤は、５０℃におけるＣＯＰフィルムに対する１８０°剥離強度が、好ましくは１．０Ｎ／２５ｍｍ以上、より好ましくは２．０Ｎ／２５ｍｍ以上、さらに好ましくは２．５Ｎ／２５ｍｍ以上である。これにより、ＣＯＰフィルムに対して感温性粘着剤が優れた粘着力を有する。５０℃におけるＣＯＰフィルムに対する１８０°剥離強度の上限値は、特に限定されないが、７．０Ｎ／２５ｍｍ以下であってもよい。１８０°剥離強度は、ＪＩＳ Ｚ０２３７に準拠して測定される値である。 The temperature-sensitive adhesive has a 180° peel strength against a COP film at 50°C of preferably 1.0 N/25 mm or more, more preferably 2.0 N/25 mm or more, even more preferably 2.5 N/25 mm or more. As a result, the temperature-sensitive adhesive has excellent adhesion to the COP film. The upper limit of the 180° peel strength for the COP film at 50° C. is not particularly limited, but may be 7.0 N/25 mm or less. The 180° peel strength is a value measured in accordance with JIS Z0237.
感温性粘着剤は、１３０℃を経た後の５℃におけるＣＯＰフィルムに対する１８０°剥離強度が、好ましくは０．２Ｎ／２５ｍｍ以下である。これにより、感温性粘着剤が高温に加熱された後でもＣＯＰフィルムに対して優れた易剥離性を有する。なお、１３０℃を経た後の５℃におけるＣＯＰフィルムに対する１８０°剥離強度の下限値は、特に限定されないが、０．０５Ｎ／２５ｍｍ以上であってもよい。 The 180° peel strength of the heat-sensitive adhesive against a COP film at 5°C after exposure to 130°C is preferably 0.2 N/25 mm or less. This allows the heat-sensitive adhesive to have excellent peelability against a COP film even after being heated to a high temperature. The lower limit of the 180° peel strength against a COP film at 5°C after exposure to 130°C is not particularly limited, but may be 0.05 N/25 mm or more.
（架橋剤）
感温性粘着剤は、架橋剤をさらに含有してもよい。架橋剤としては、例えば、金属キレート化合物、アジリジン化合物、イソシアネート化合物、エポキシ化合物などが挙げられる。
(Crosslinking agent)
The temperature-sensitive adhesive may further contain a crosslinking agent. Examples of the crosslinking agent include metal chelate compounds, aziridine compounds, isocyanate compounds, and epoxy compounds.
架橋剤として金属キレート化合物を採用すると、感温性粘着剤の耐熱性を向上させることができる。金属キレート化合物としては、例えば、多価金属のアセチルアセトン配位化合物、多価金属のアセト酢酸エステル配位化合物などが挙げられる。多価金属としては、例えば、アルミニウム、ニッケル、クロム、鉄、チタン、亜鉛、コバルト、マンガン、ジルコニウムなどが挙げられる。金属キレート化合物は、１種のみを使用してもよいし、２種以上を併用してもよい。これらの中でも、アルミニウムのアセチルアセトン配位化合物またはアセト酢酸エステル配位化合物が好ましく、アルミニウムトリスアセチルアセトナートがより好ましい。 When a metal chelate compound is used as a crosslinking agent, the heat resistance of the temperature-sensitive adhesive can be improved. Examples of the metal chelate compound include acetylacetone coordination compounds of polyvalent metals, acetoacetate coordination compounds of polyvalent metals, and the like. Examples of polyvalent metals include aluminum, nickel, chromium, iron, titanium, zinc, cobalt, manganese, and zirconium. Only one type of metal chelate compound may be used, or two or more types may be used in combination. Among these, aluminum acetylacetone coordination compounds or acetoacetate coordination compounds are preferred, and aluminum trisacetylacetonate is more preferred.
架橋条件としては、加熱温度が９０～１２０℃程度であり、加熱時間が１分～２０分程度である。 The crosslinking conditions include a heating temperature of about 90 to 120°C and a heating time of about 1 to 20 minutes.
架橋剤の含有量は、側鎖結晶性ポリマー１００重量部に対して、好ましくは０．１～１０重量部である。 The content of the crosslinking agent is preferably 0.1 to 10 parts by weight per 100 parts by weight of the side chain crystalline polymer.
（架橋遅延剤）
感温性粘着剤は、架橋遅延剤をさらに含有してもよい。これにより、架橋剤による架橋反応を遅延させて短時間で粘度が高くなるのを抑制し、ポットライフを向上させることができる。架橋遅延剤の添加は、架橋剤の添加前に行うのが好ましい。架橋遅延剤の含有量は、架橋剤の含有量と同じであってもよい。架橋遅延剤としては、例えば、アセチルアセトンなどが挙げられるが、これに限定されない。
(Crosslinking retarder)
The temperature-sensitive adhesive may further contain a crosslinking retarder. Thereby, the crosslinking reaction by the crosslinking agent can be delayed, the viscosity can be prevented from increasing in a short time, and the pot life can be improved. The addition of the crosslinking retarder is preferably carried out before the addition of the crosslinking agent. The content of the crosslinking retarder may be the same as the content of the crosslinking agent. Examples of the crosslinking retarder include, but are not limited to, acetylacetone.
上述した感温性粘着剤の使用形態は、特に限定されず、例えば、そのまま使用してもよいし、下記で説明するように、粘着シート、粘着テープなどの形態で使用してもよい。 The form in which the above-mentioned temperature-sensitive adhesive is used is not particularly limited. For example, it may be used as is, or it may be used in the form of an adhesive sheet, adhesive tape, etc., as described below.
＜感温性粘着シート＞
本実施形態の感温性粘着シートは、上述した感温性粘着剤を含むものであり、基材レスのシート状である。感温性粘着シートの厚さは、好ましくは５～１００μｍ、より好ましくは５～５０μｍである。
<Temperature-sensitive adhesive sheet>
The temperature-sensitive adhesive sheet of this embodiment contains the above-mentioned temperature-sensitive adhesive and is in the form of a sheet without a base material. The thickness of the temperature-sensitive adhesive sheet is preferably 5 to 100 μm, more preferably 5 to 50 μm.
感温性粘着シートの表面には、離型フィルムを積層してもよい。離型フィルムとしては、例えば、ポリエチレンテレフタレート（以下、「ＰＥＴ」ということがある。）などからなるフィルムの表面に、シリコーンなどの離型剤を塗布したものが挙げられる。離型フィルムの厚さは、好ましくは５～５００μｍ、より好ましくは２５～２５０μｍである。離型フィルムは、感温性粘着シートの使用時に剥離される。 A release film may be laminated on the surface of the heat-sensitive adhesive sheet. An example of a release film is one made of polyethylene terephthalate (hereinafter sometimes referred to as "PET"), with a release agent such as silicone applied to the surface. The thickness of the release film is preferably 5 to 500 μm, more preferably 25 to 250 μm. The release film is peeled off when the heat-sensitive adhesive sheet is used.
＜感温性粘着テープ＞
本実施形態の感温性粘着テープは、フィルム状の基材と、基材の少なくとも片面に積層されている粘着剤層とを備えている。フィルム状とは、フィルム状のみに限定されるものではなく、本実施形態の効果を損なわない限りにおいて、フィルム状ないしシート状をも含む概念である。
<Temperature-sensitive adhesive tape>
The temperature-sensitive adhesive tape of this embodiment includes a film-like base material and an adhesive layer laminated on at least one side of the base material. The term "film shape" is not limited to only film shape, but is a concept that includes film shape or sheet shape as long as the effects of this embodiment are not impaired.
基材の構成材料としては、例えば、ポリエチレン、ポリエチレンテレフタレート、ポリプロピレン、ポリエステル、ポリアミド、ポリイミド、ポリカーボネート、エチレン酢酸ビニル共重合体、エチレンエチルアクリレート共重合体、エチレンポリプロピレン共重合体、ポリ塩化ビニルなどの合成樹脂が挙げられる。 Examples of materials that can be used to form the substrate include synthetic resins such as polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-polypropylene copolymer, and polyvinyl chloride.
基材の構造は、単層構造または多層構造のいずれであってもよい。基材の厚さは、好ましくは５～５００μｍ、より好ましくは２５～２５０μｍである。基材は、粘着剤層に対する密着性を高めるうえで、表面処理が施されていてもよい。表面処理としては、例えば、コロナ放電処理、プラズマ処理、ブラスト処理、ケミカルエッチング処理、プライマー処理などが挙げられる。 The structure of the base material may be either a single layer structure or a multilayer structure. The thickness of the base material is preferably 5 to 500 μm, more preferably 25 to 250 μm. The base material may be subjected to surface treatment in order to improve its adhesion to the adhesive layer. Examples of the surface treatment include corona discharge treatment, plasma treatment, blasting treatment, chemical etching treatment, and primer treatment.
基材の少なくとも片面に積層されている粘着剤層は、上述した感温性粘着剤を含んでいる。粘着剤層を基材の少なくとも片面に積層するには、例えば、感温性粘着剤に溶剤を加えて塗布液を調製し、得られた塗布液をコーターなどで基材の片面または両面に塗布して乾燥させればよい。コーターとしては、例えば、ナイフコーター、ロールコーター、カレンダーコーター、コンマコーター、グラビアコーター、ロッドコーターなどが挙げられる。 The adhesive layer laminated on at least one side of the substrate contains the above-mentioned temperature-sensitive adhesive. To laminate the adhesive layer on at least one side of the substrate, for example, a solvent is added to the temperature-sensitive adhesive to prepare a coating liquid, and the resulting coating liquid is applied to one or both sides of the substrate using a coater or the like, and then dried. Examples of coaters include a knife coater, a roll coater, a calendar coater, a comma coater, a gravure coater, and a rod coater.
粘着剤層の厚さは、好ましくは５～１００μｍ、より好ましくは５～５０μｍである。 The thickness of the adhesive layer is preferably 5 to 100 μm, more preferably 5 to 50 μm.
基材の両面に粘着剤層を積層する場合には、片面の粘着剤層と他面の粘着剤層は、互いの厚さ、組成などが、同じであってもよいし、異なっていてもよい。また、片面の粘着剤層が上述した感温性粘着剤を含む限り、他面の粘着剤層は特に限定されない。他面の粘着剤層は、例えば、天然ゴム系粘着剤、合成ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤などで構成することもできる。 When adhesive layers are laminated on both sides of the substrate, the adhesive layer on one side and the adhesive layer on the other side may be the same or different in thickness, composition, etc. Furthermore, as long as the adhesive layer on one side contains the above-mentioned temperature-sensitive adhesive, the adhesive layer on the other side is not particularly limited. The adhesive layer on the other side may be composed of, for example, a natural rubber adhesive, a synthetic rubber adhesive, an acrylic adhesive, a silicone adhesive, a urethane adhesive, etc.
感温性粘着テープの表面には、離型フィルムを積層してもよい。離型フィルムとしては、上述した感温性粘着シートで例示したのと同じものが挙げられる。離型フィルムは感温性粘着テープの使用時に剥離される。 A release film may be laminated on the surface of the temperature-sensitive adhesive tape. As the release film, the same ones as those exemplified for the above-mentioned temperature-sensitive adhesive sheet can be mentioned. The release film is peeled off when using the temperature-sensitive adhesive tape.
以下、合成例および実施例を挙げて本発明を詳細に説明するが、本発明は以下の合成例および実施例のみに限定されるものではない。 Hereinafter, the present invention will be explained in detail with reference to synthesis examples and examples, but the present invention is not limited only to the following synthesis examples and examples.
（合成例：側鎖結晶性ポリマー）
まず、表１に示すモノマーを表１に示す割合で反応容器に加えた。表１に示すモノマーは、以下のとおりである。
Ｃ１８Ａ：ステアリルアクリレート
Ｃ１Ａ：メチルアクリレート
Ｖ－３Ｆ：上述した式（Ｉａ）で表される２，２，２－トリフルオロエチルアクリレートである大阪有機化学工業社製の反応性フッ素化合物「ビスコート３Ｆ」
ＡＡ：アクリル酸
(Synthesis example: side chain crystalline polymer)
First, the monomers shown in Table 1 were added to a reaction vessel in the proportions shown in Table 1. The monomers shown in Table 1 are as follows.
C18A: Stearyl acrylate C1A: Methyl acrylate V-3F: Reactive fluorine compound "Viscoat 3F" manufactured by Osaka Organic Chemical Industry Co., Ltd., which is 2,2,2-trifluoroethyl acrylate represented by the above-mentioned formula (Ia)
AA: Acrylic acid
次に、固形分濃度が３０重量％になるように酢酸エチル：トルエン＝７５：２５（重量比）の混合溶媒を反応容器に加え、混合液を得た。得られた混合液を５５℃で４時間撹拌することによって各モノマーを共重合させ、側鎖結晶性ポリマーを得た。 Next, a mixed solvent of ethyl acetate and toluene (weight ratio: 75:25) was added to the reaction vessel so that the solids concentration was 30% by weight, and a mixed solution was obtained. The resulting mixed solution was stirred at 55°C for 4 hours to copolymerize the monomers and obtain a side-chain crystalline polymer.
得られた側鎖結晶性ポリマーの重量平均分子量および融点を表１に示す。重量平均分子量は、ＧＰＣで測定して得られた測定値をポリスチレン換算した値である。融点は、ＤＳＣを用いて１０℃／分の測定条件で測定した値である。 The weight average molecular weight and melting point of the obtained side chain crystalline polymer are shown in Table 1. The weight average molecular weight is a value obtained by measuring by GPC and converting it into polystyrene. The melting point is a value measured using DSC at 10°C/min.
［実施例１～９および比較例１～７］
＜感温性粘着シートの作製＞
まず、合成例で得られた側鎖結晶性ポリマー１００重量部に対して、表２に示す粘着付与剤を２０重量部の割合で混合した。表２に示す粘着付与剤は、以下のとおりである。
Ａ：酸価が１０～１６ｍｇＫＯＨ／ｇ、軟化点が１５０～１７０℃である荒川化学工業社製のロジンエステル「Ｄ－１６０」
Ｂ：酸価が２～１０ｍｇＫＯＨ／ｇ、軟化点が９５～１０５℃である荒川化学工業社製の特殊ロジンエステル「Ａ－１００」
Ｃ：酸価が２３０～２４５ｍｇＫＯＨ／ｇ、軟化点が１２４～１３４℃である荒川化学工業社製の酸変性超淡色ロジン「ＫＥ－６０４」
Ｄ：酸価が１３０～１６０ｍｇＫＯＨ／ｇ、軟化点が１３０～１５０℃である荒川化学工業社製の超淡色重合ロジン「ＫＲ－１４０」
Ｅ：酸価が１５８～１６８ｍｇＫＯＨ／ｇ、軟化点が９３～１０３℃である荒川化学工業社製の重合ロジン「Ｒ－９５」
Ｆ：ＡとＣの混合物（重量比での混合比率５０：５０）
[Examples 1 to 9 and Comparative Examples 1 to 7]
<Preparation of temperature-sensitive adhesive sheet>
First, 20 parts by weight of the tackifier shown in Table 2 was mixed with 100 parts by weight of the side chain crystalline polymer obtained in the synthesis example. The tackifiers shown in Table 2 are as follows.
A: Rosin ester “D-160” manufactured by Arakawa Chemical Industry Co., Ltd. with an acid value of 10 to 16 mgKOH/g and a softening point of 150 to 170°C
B: Special rosin ester “A-100” manufactured by Arakawa Chemical Industry Co., Ltd. with an acid value of 2 to 10 mgKOH/g and a softening point of 95 to 105°C
C: Acid-modified ultra-light colored rosin “KE-604” manufactured by Arakawa Chemical Industry Co., Ltd. with an acid value of 230 to 245 mgKOH/g and a softening point of 124 to 134°C
D: Ultra-light color polymerized rosin “KR-140” manufactured by Arakawa Chemical Industry Co., Ltd. with an acid value of 130 to 160 mgKOH/g and a softening point of 130 to 150°C
E: Polymerized rosin “R-95” manufactured by Arakawa Chemical Industry Co., Ltd. with an acid value of 158 to 168 mgKOH/g and a softening point of 93 to 103°C
F: Mixture of A and C (mixing ratio by weight 50:50)
次に、側鎖結晶性ポリマー１００重量部に対して、架橋遅延剤を３重量部の割合で混合した後、架橋剤を３重量部の割合でさらに混合し、感温性粘着剤を得た。使用した架橋遅延剤および架橋剤は、以下のとおりである。
架橋遅延剤：アセチルアセトン
架橋剤：金属キレート化合物である川研ファインケミカル社製のアルミニウムトリスアセチルアセトナート
Next, 3 parts by weight of a crosslinking retarder was mixed with 100 parts by weight of the side chain crystalline polymer, and then 3 parts by weight of a crosslinking agent was further mixed therewith to obtain a heat-sensitive adhesive. The crosslinking retarder and crosslinking agent used were as follows:
Crosslinking retarder: Acetylacetone Crosslinking agent: Aluminum tris acetylacetonate, a metal chelate compound manufactured by Kawaken Fine Chemicals Co., Ltd.
次に、得られた感温性粘着剤を酢酸エチルによって固形分濃度が２３重量％となるように調整し、塗布液を得た。そして、得られた塗布液を離型フィルム上に塗布し、１１０℃×３分の条件で架橋反応を行い、厚さ２５μｍの感温性粘着シートを得た。なお、離型フィルムは、表面にシリコーンが塗布された厚さ５０μｍのポリエチレンテレフタレートフィルムを用いた。 Next, the obtained heat-sensitive adhesive was adjusted with ethyl acetate so that the solid content concentration was 23% by weight, and a coating liquid was obtained. The obtained coating liquid was then applied onto a release film, and a crosslinking reaction was carried out under conditions of 110°C x 3 minutes, to obtain a heat-sensitive adhesive sheet with a thickness of 25 μm. The release film used was a polyethylene terephthalate film with a thickness of 50 μm and a silicone coating on the surface.
＜評価＞
実施例１～９および比較例１～７で得られた各感温性粘着シートについて、１８０°剥離強度および高温加熱試験を評価した。各評価方法を以下に示すとともに、その結果を表２に示す。
<Evaluation>
The temperature-sensitive adhesive sheets obtained in Examples 1 to 9 and Comparative Examples 1 to 7 were evaluated for 180° peel strength and high temperature heating test. Each evaluation method is shown below, and the results are shown in Table 2.
（１８０°剥離強度）
［実施例１～３、５、７～９および比較例１～３、５、７］
５０℃および５℃における１８０°剥離強度をＪＩＳ Ｚ０２３７に準拠して測定した。具体的には、まず、５０℃の雰囲気温度において、２ｋｇのゴムローラーを使用して感温性粘着シートの片面をガラス板に貼着した。
(180° peel strength)
[Examples 1 to 3, 5, 7 to 9 and Comparative Examples 1 to 3, 5, 7]
The 180° peel strength at 50°C and 5°C was measured in accordance with JIS Z0237. Specifically, first, one side of the temperature-sensitive adhesive sheet was adhered to a glass plate using a 2 kg rubber roller at an ambient temperature of 50°C.
次に、この雰囲気温度で感温性粘着シートの他面に表２に示す被着体を貼着し、試験片を得た。表２に示す被着体は、以下のとおりである。
ＣＯＰ：厚さが４２μｍである日本ゼオン社製のＣＯＰフィルム「ゼオノアフィルム」
ＰＩ：厚さが２５μｍである東レ・デュポン社製のポリイミドフィルム「カプトン１００Ｈ」
ＰＥＴ：厚さが２５μｍであるユニチカ社製のＰＥＴフィルム「Ｓ－２５」
ＰＶＢ：厚さ１００μｍのＰＥＴからなる基材の片面に、積水化学工業社製のポリビニルブチラール「ＢＬ－Ｓ」を厚さ１０μｍで塗布してフィルム化したＰＶＢフィルム
Next, at this atmospheric temperature, an adherend shown in Table 2 was attached to the other surface of the heat-sensitive adhesive sheet to obtain a test piece. The adherends shown in Table 2 are as follows.
COP: ZeonoaFilm, a COP film manufactured by Zeon Corporation with a thickness of 42 μm
PI: Polyimide film "Kapton 100H" manufactured by Toray DuPont Co., Ltd., having a thickness of 25 μm
PET: 25 μm thick PET film "S-25" manufactured by Unitika Co., Ltd.
PVB: A PVB film made by applying polyvinyl butyral "BL-S" manufactured by Sekisui Chemical Co., Ltd. to a thickness of 10 μm on one side of a substrate made of PET with a thickness of 100 μm.
得られた試験片を以下の条件にした後、ロードセルを用いて３００ｍｍ／分の速度で被着体を感温性粘着シートから１８０°剥離した（ｎ＝３）。 After the obtained test piece was subjected to the following conditions, the adherend was peeled 180° from the temperature-sensitive adhesive sheet using a load cell at a speed of 300 mm/min (n=3).
［５０℃］
試験片を５０℃の雰囲気温度に２０分間静置した後に１８０°剥離した。
[50° C.]
The test piece was allowed to stand at an atmospheric temperature of 50° C. for 20 minutes and then peeled off at an angle of 180°.
［５℃］
試験片を１３０℃の熱風循環オーブン中で９０分間加熱した後、５℃のクールプレート上に２０分間載置してから１８０°剥離した。
[5℃]
The test piece was heated in a hot air circulation oven at 130°C for 90 minutes, placed on a cool plate at 5°C for 20 minutes, and then peeled off at 180°.
［実施例４、６および比較例４、６］
まず、５０℃の雰囲気温度において、感温性粘着シートの片面を厚さ１００μｍのＰＥＴフィルムに貼着した。次に、この雰囲気温度で感温性粘着シートの他面に表２に示す被着体を貼着し、試験片を得た。表２に示す被着体は、以下のとおりである。
ＳＵＳ：厚さが１ｍｍのＳＵＳ３０４
ガラス：厚さが０．７ｍｍであるＣｏｒｎｉｎｇ社製の「ＥＡＧＬＥ ＸＧ」
[Examples 4 and 6 and Comparative Examples 4 and 6]
First, one side of a heat-sensitive adhesive sheet was attached to a PET film having a thickness of 100 μm at an ambient temperature of 50° C. Next, at this ambient temperature, an adherend shown in Table 2 was attached to the other side of the heat-sensitive adhesive sheet to obtain a test piece. The adherends shown in Table 2 are as follows.
SUS: SUS304 with a thickness of 1 mm
Glass: Corning "EAGLE XG" with a thickness of 0.7 mm
そして、ＰＥＴフィルムを感温性粘着シートから１８０°剥離した以外は、実施例１～３、５、７～９と同様にして、５０℃および５℃における１８０°剥離強度を測定した。 Then, the 180° peel strength was measured at 50°C and 5°C in the same manner as in Examples 1 to 3, 5, and 7 to 9, except that the PET film was peeled off from the heat-sensitive adhesive sheet at 180°.
（高温加熱試験）
まず、上述した１８０°剥離強度の評価と同様にして試験片を得た。次に、得られた試験片を５０℃で３分間静置した後、１３０℃の熱風循環オーブン中で９０分間加熱した。そして、試験片の状態を室温（２３℃）で目視観察することによって、被着体の浮きの発生を有無を評価した。評価基準は、以下のように設定した。
〇：被着体に浮きが見られなかった。
×：被着体に浮きが見られた。
(High temperature heating test)
First, a test piece was obtained in the same manner as in the evaluation of 180° peel strength described above. Next, the obtained test piece was left to stand at 50°C for 3 minutes, and then heated in a hot air circulating oven at 130°C for 90 minutes. Then, the condition of the test piece was visually observed at room temperature (23°C) to evaluate whether or not the adherend had lifted off. The evaluation criteria were set as follows:
◯: No lifting was observed on the adherend.
×: Lifting was observed on the adherend.
表２から明らかなように、実施例１～９は、５０℃における１８０°剥離強度の値が高く、１３０℃を経た後の５℃における１８０°剥離強度の値が低いことがわかる。また、実施例１～９は、１３０℃に加熱されたときに被着体の浮きの発生を抑制できていることもわかる。 As is clear from Table 2, Examples 1 to 9 have high values of 180° peel strength at 50°C and low values of 180° peel strength at 5°C after passing through 130°C. It can also be seen that Examples 1 to 9 were able to suppress the occurrence of floating of the adherend when heated to 130°C.
Claims (7)
１００～３００ｍｇＫＯＨ／ｇの酸価を有する粘着付与剤をさらに含有する、感温性粘着剤。 A temperature-sensitive adhesive containing a side-chain crystalline polymer, the adhesive strength of which decreases at a temperature lower than the melting point of the side-chain crystalline polymer,
A temperature-sensitive adhesive further comprising a tackifier having an acid value of 100 to 300 mgKOH/ g .
前記基材の少なくとも片面に積層されており請求項１～５のいずれかに記載の感温性粘着剤を含む粘着剤層と、を備える、感温性粘着テープ。 A film-like base material,
A temperature-sensitive adhesive tape comprising: an adhesive layer laminated on at least one side of the base material and containing the temperature-sensitive adhesive according to any one of claims 1 to 5.
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| JP2012102212A (en) | 2010-11-09 | 2012-05-31 | Nitta Corp | Easily peelable pressure-sensitive adhesive sheet and easily peelable pressure-sensitive adhesive tape |
| JP2016196544A (en) | 2015-04-03 | 2016-11-24 | ニッタ株式会社 | Temperature sensitive adhesive |
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| JP6289960B2 (en) * | 2014-03-27 | 2018-03-07 | ニッタ株式会社 | Temperature sensitive adhesive |
| JP6600954B2 (en) * | 2015-03-20 | 2019-11-06 | 東洋インキＳｃホールディングス株式会社 | Re-peelable pressure-sensitive adhesive and pressure-sensitive adhesive sheet using the same |
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| JP2016196544A (en) | 2015-04-03 | 2016-11-24 | ニッタ株式会社 | Temperature sensitive adhesive |
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