WO2023145567A1 - 粘着テープ - Google Patents
粘着テープ Download PDFInfo
- Publication number
- WO2023145567A1 WO2023145567A1 PCT/JP2023/001309 JP2023001309W WO2023145567A1 WO 2023145567 A1 WO2023145567 A1 WO 2023145567A1 JP 2023001309 W JP2023001309 W JP 2023001309W WO 2023145567 A1 WO2023145567 A1 WO 2023145567A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- weight
- adhesive tape
- adhesive layer
- Prior art date
Links
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 37
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 65
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000098 polyolefin Polymers 0.000 claims abstract description 28
- 230000008961 swelling Effects 0.000 claims abstract description 28
- 239000012790 adhesive layer Substances 0.000 claims abstract description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 142
- 239000010410 layer Substances 0.000 claims description 81
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 52
- 239000000853 adhesive Substances 0.000 claims description 50
- 230000001070 adhesive effect Effects 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 36
- 239000003431 cross linking reagent Substances 0.000 claims description 33
- 239000012948 isocyanate Substances 0.000 claims description 15
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 31
- -1 acryl Chemical group 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 230000009477 glass transition Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 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
- 239000003643 water by type Substances 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 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
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling 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
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002960 margaryl 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])[H] 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000005641 methacryl 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 125000002958 pentadecyl 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])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001228 spectrum Methods 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
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 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 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH 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
- 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
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to adhesive tapes.
- Adhesive tapes are used for assembly in mobile electronic devices such as mobile phones and personal digital assistants (PDAs) (for example, Patent Documents 1 and 2). Adhesive tapes are also used for bonding optical members (for example, Patent Document 3).
- Adhesive tapes used for fixing such members are required to have both resistance to peeling (adhesive strength) and resistance to shear stress (displacement) (holding power).
- adhesive strength In order to improve the adhesive force, it is effective to design the adhesive layer so that it stretches well against the peeling stress, that is, to increase the flexibility of the adhesive layer.
- the holding force In order to improve the holding force, it is effective to design the pressure-sensitive adhesive layer so that it does not deform due to shear stress (displacement), that is, to make the pressure-sensitive adhesive layer hard. Therefore, since adhesive strength and holding power are in a trade-off relationship, it has been very difficult to achieve both at a high level. In particular, it has been difficult to improve the holding power when shear stress (displacement) is applied for a long time at a high temperature (about 70 to 100° C.).
- An object of the present invention is to provide a pressure-sensitive adhesive tape that exhibits excellent adhesive strength and exhibits excellent holding power even when shear stress is applied at high temperatures for a long period of time.
- the present disclosure 1 is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is an olefin polymer having a structural unit derived from a (meth)acrylic acid alkyl ester and a polymerizable unsaturated double bond at the end. wherein the pressure-sensitive adhesive layer has a swelling ratio of 40 or more and 500 or less when immersed in tetrahydrofuran at a temperature of 25°C for 24 hours.
- the present disclosure 2 is the adhesive tape according to the present disclosure 1, wherein the adhesive layer has a gel fraction of 20% by weight or more and 65% by weight or less.
- Present Disclosure 3 is the pressure-sensitive adhesive tape according to Present Disclosure 1 or 2, wherein the acrylic copolymer contains a structural unit derived from a polar group-containing monomer.
- Present Disclosure 4 is the pressure-sensitive adhesive tape according to Present Disclosure 3, wherein the polar group-containing monomer contains a hydroxyl group-containing monomer.
- Present Disclosure 5 is the pressure-sensitive adhesive tape according to Present Disclosure 4, wherein the acrylic copolymer contains 0.01% by weight or more and 2% by weight or less of structural units derived from the hydroxyl group-containing monomer.
- Present Disclosure 6 is the pressure-sensitive adhesive tape according to Present Disclosure 1, 2, 3, 4, or 5, wherein the pressure-sensitive adhesive layer contains a cross-linking agent.
- Present Disclosure 7 is the pressure-sensitive adhesive tape according to Present Disclosure 6, wherein the cross-linking agent is an isocyanate-based cross-linking agent.
- Present Disclosure 8 is the adhesive tape according to Present Disclosure 1, 2, 3, 4, 5, 6, or 7, wherein the acrylic copolymer has a weight average molecular weight (Mw) of 500,000 or more and 1,500,000 or less.
- the present disclosure 9 is the adhesive tape according to the present disclosure 1, 2, 3, 4, 5, 6, 7 or 8, wherein the (meth)acrylic acid alkyl ester is butyl acrylate.
- the present disclosure 10 is the present disclosure 1, 2, 3, 4, wherein the content of the structural unit derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal is 5% by weight or more and 30% by weight or less. 5, 6, 7, 8 or 9 adhesive tapes.
- the present disclosure 11 is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer includes structural units derived from butyl acrylate and structural units derived from an olefin polymer having a polymerizable unsaturated double bond at the end. and the pressure-sensitive adhesive layer is a pressure-sensitive adhesive tape containing an isocyanate-based cross-linking agent.
- This disclosure 12 is the pressure-sensitive adhesive tape according to present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the pressure-sensitive adhesive layer contains a tackifying resin.
- Present Disclosure 13 is the adhesive tape of Present Disclosure 12, wherein the tackifying resin contains a high hydroxyl value tackifying resin having a hydroxyl value of 15 mgKOH/g or more.
- the present disclosure 14 is that the content of the high hydroxyl value tackifying resin having a hydroxyl value of 15 mgKOH/g or more is 20 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the acrylic copolymer.
- 13 is the adhesive tape of Disclosure 13;
- This disclosure 15 is the adhesive tape of this disclosure 12, 13 or 14, wherein said tackifying resin further contains a low hydroxyl value tackifying resin having a hydroxyl value of less than 15 mgKOH/g.
- the present disclosure 16 is that the content of the low hydroxyl value tackifying resin having a hydroxyl value of less than 15 mgKOH/g is 10 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the acrylic copolymer. 15.
- the adhesive tape of Disclosure 15. The present invention will be described in detail below.
- the present inventors have found that in a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer, a structural unit derived from a (meth)acrylic acid alkyl ester and a structural unit derived from an olefin polymer having a polymerizable unsaturated double bond at the terminal are combined. It has been found that the adhesive strength and holding power of the adhesive tape can be improved by using the acrylic copolymer having the following properties. In such an adhesive tape, the present inventors further found that the specific swelling ratio measured for the adhesive layer was adjusted to a specific range, or butyl acrylate was used as a structural unit derived from a (meth)acrylic acid alkyl ester. By containing an isocyanate cross-linking agent while selecting a structural unit derived from, it was found that the holding power can be improved even when shear stress is applied for a long time at high temperature, and the present invention has been completed.
- the adhesive tape of the present invention has an adhesive layer.
- the pressure-sensitive adhesive layer is an acrylic copolymer (hereinafter simply referred to as Also referred to as "acrylic copolymer").
- (meth)acryl means acryl or methacryl.
- the above acrylic copolymer has a structure in which structural units derived from an olefin polymer having a polymerizable unsaturated double bond at the terminal aggregate through interaction to form a pseudo-crosslinking point. Since the acrylic copolymer has such a structure, the pressure-sensitive adhesive layer is hard like a cross-linked pressure-sensitive adhesive layer when the strain is small, and exhibits high holding power.
- the pressure-sensitive adhesive layer exhibits high flexibility.
- the pressure-sensitive adhesive layer containing the acrylic copolymer improves the adhesive strength and holding power of the pressure-sensitive adhesive tape.
- the pressure-sensitive adhesive layer has a swelling ratio of 40 or more and 500 or less when immersed in tetrahydrofuran at a temperature of 25° C. for 24 hours.
- the swelling ratio of the pressure-sensitive adhesive layer is 40 or more, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive tape is improved.
- the swelling ratio of the pressure-sensitive adhesive layer is 500 or less, the holding power of the pressure-sensitive adhesive tape is improved when shear stress is applied for a long time at high temperature.
- the swelling ratio of the adhesive layer is preferably 50 or more and 300 or less, more preferably 150 or less.
- the swelling ratio of the pressure-sensitive adhesive layer can be measured by the following method.
- the pressure-sensitive adhesive layer is immersed in tetrahydrofuran at a temperature of 25° C. for 24 hours, and the weight W3 of the pressure-sensitive adhesive layer after immersion in tetrahydrofuran is measured. Thereafter, the tetrahydrofuran is dried, and the weight W4 of the adhesive layer after the tetrahydrofuran drying is measured.
- the method for adjusting the swelling ratio of the pressure-sensitive adhesive layer within the above range is not particularly limited, but a method for adjusting the composition of the acrylic copolymer is preferred.
- a method of incorporating structural units derived from a polar group-containing monomer in addition to structural units derived from (meth)acrylic acid alkyl esters and structural units derived from an olefin polymer having a polymerizable unsaturated double bond at the terminal is also preferred.
- a method of adjusting the type and amount of the polar group-containing monomer to be contained is also preferred.
- a method of adjusting the weight average molecular weight (Mw) of the acrylic copolymer to an appropriate range is also preferred.
- a method for adjusting the type and amount of the tackifying resin contained in the pressure-sensitive adhesive layer a method for adjusting the type and amount of the cross-linking agent contained in the pressure-sensitive adhesive layer, and an appropriate gel fraction of the pressure-sensitive adhesive layer.
- a range adjustment method is also preferred.
- the gel fraction of the pressure-sensitive adhesive layer is not particularly limited, it is preferably 20% by weight or more and 65% by weight or less. If the gel fraction of the pressure-sensitive adhesive layer is within the above range, it becomes easier to adjust the swelling ratio of the pressure-sensitive adhesive layer to the above range. If the gel fraction of the pressure-sensitive adhesive layer is 20% by weight or more, the holding power of the pressure-sensitive adhesive tape is further improved when shear stress is applied at high temperature for a long time. When the gel fraction of the pressure-sensitive adhesive layer is 65% by weight or less, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive tape is further improved.
- the gel fraction of the adhesive layer is more preferably 35% by weight or more, more preferably 60% by weight or less, and even more preferably 50% by weight or less.
- the pressure-sensitive adhesive layer preferably has a peak loss tangent (tan ⁇ , hereinafter simply referred to as loss tangent) measured at a measurement frequency of 10 Hz using a dynamic viscoelasticity measuring device at 40° C. or lower.
- the loss tangent of the pressure-sensitive adhesive layer having a peak in the above range further improves the pressure-sensitive adhesive strength and holding power of the pressure-sensitive adhesive tape.
- the pressure-sensitive adhesive layer more preferably has a loss tangent peak at 35° C. or lower, and more preferably at 25° C. or lower.
- the peak temperature of the loss tangent can be adjusted by the raw material of the acrylic copolymer.
- the loss tangent is -100 under the conditions of 5° C./min, 10 Hz in low-speed heating shear deformation mode using a viscoelastic spectrometer (manufactured by IT Keisoku Co., Ltd., DVA-200, or equivalent). It can be obtained by measuring dynamic viscoelasticity spectrum from °C to 200 °C.
- the above acrylic copolymer has a structural unit derived from a (meth)acrylic acid alkyl ester and a structural unit derived from an olefin polymer having a polymerizable unsaturated double bond at the terminal.
- the (meth)acrylic acid alkyl ester is not particularly limited, and examples thereof include (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 24 carbon atoms.
- a (meth)acrylic acid alkyl ester having an alkyl group having 4 to 8 carbon atoms is preferable, and butyl acrylate is more preferable, because the glass transition temperature described later is easily satisfied and the adhesive strength of the adhesive tape is further improved. , n-butyl acrylate is more preferred.
- These (meth)acrylic acid alkyl esters may be used alone, or two or more of them may be used in combination.
- the content of the structural unit derived from the (meth)acrylic acid alkyl ester in the acrylic copolymer is not particularly limited, it is preferably 50% by weight or more and 95% by weight or less.
- the content of the structural unit derived from the (meth)acrylic acid alkyl ester is within the above range, the adhesive strength and holding power of the pressure-sensitive adhesive tape are further improved.
- the content of structural units derived from the (meth)acrylic acid alkyl ester is more preferably 60% by weight or more, still more preferably 70% by weight or more, and more preferably 90% by weight or less. , 85% by weight or less.
- the olefin polymer having a polymerizable unsaturated double bond at one end may have a polymerizable unsaturated double bond at one end, or may have a polymerizable unsaturated double bond at both ends. good too.
- an olefin polymer having a polymerizable unsaturated double bond at one end is preferable because chemical cross-linking in the molecule hardly occurs and the swelling ratio of the pressure-sensitive adhesive layer can be easily adjusted within the above range.
- the olefin polymer having a polymerizable unsaturated double bond at the end is not particularly limited, and an ethylene-butylene copolymer, ethylene- Propylene copolymers, ethylene polymers, propylene polymers, butylene polymers and the like can be mentioned.
- the group containing a polymerizable unsaturated double bond is not particularly limited, and examples thereof include (meth)acryloyl groups, vinyl ether groups, styryl groups and the like. Among them, a (meth)acryloyl group is preferable because of its excellent copolymerizability with the (meth)acrylic acid alkyl ester.
- the olefin polymer having a polymerizable unsaturated double bond at one end include an ethylene macromonomer having a (meth)acryloyl group at one end, a propylene macromonomer having a (meth)acryloyl group at one end, Examples thereof include ethylene-butylene macromonomers having a (meth)acryloyl group at one end and ethylene-propylene macromonomers having a (meth)acryloyl group at one end. Among them, it becomes easier to satisfy the glass transition temperature described later, and the adhesive strength of the adhesive tape is further improved.
- Ethylene-propylene macromonomers with These olefin polymers having polymerizable unsaturated double bonds at their terminals may be used alone, or two or more of them may be used in combination.
- the macromonomer here refers to a monomer having a polymerizable functional group with a weight average molecular weight of about 1,000 to 100,000.
- the content of the structural unit derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal in the acrylic copolymer is not particularly limited, it is preferably 5% by weight or more and 30% by weight or less.
- the content of the structural unit derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal is 5% by weight or more, an appropriate number of pseudo-crosslinking points are formed, and the adhesiveness of the adhesive tape is increased. Better strength and holding power.
- the content of the structural unit derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal is 30% by weight or less, cohesive failure of the pressure-sensitive adhesive layer can be further suppressed.
- the content of the structural unit derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal is more preferably 8% by weight or more, further preferably 10% by weight or more, and 27% by weight. is more preferably 25% by weight or less.
- the above acrylic copolymer easily satisfies the glass transition temperature described later, and the adhesive strength of the adhesive tape is further improved.
- the content of structural units derived from monomers containing two or more polymerizable unsaturated double bonds is preferably 0.1% by weight or less.
- the acrylic copolymer is crosslinked when the strain is small because the constituent units derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal form a pseudo crosslink point.
- the pseudo cross-linking points are broken and the adhesive layer does not have a cross-linked structure. Therefore, by reducing the content of the structural unit derived from the monomer containing two or more polymerizable unsaturated double bonds that facilitates the construction of a chemically crosslinked structure, the acrylic copolymer can be formed when the strain increases. Molecules can be more easily stretched, and adhesive strength can be further improved. More preferably, the content of structural units derived from the monomer containing two or more polymerizable unsaturated double bonds is 0%.
- the acrylic copolymer preferably contains a structural unit derived from a polar group-containing monomer.
- the acrylic copolymer contains a structural unit derived from the polar group-containing monomer, the polar groups interact with each other, so that the adhesive strength and holding power of the pressure-sensitive adhesive tape are further improved.
- the acrylic copolymer contains a structural unit derived from the polar group-containing monomer and the pressure-sensitive adhesive layer further contains a cross-linking agent, the intermolecular cross-linking agent of the acrylic copolymer chemically cross-linked via By adjusting the degree of cross-linking at this time, the swelling ratio and gel fraction of the pressure-sensitive adhesive layer can be adjusted to appropriate ranges.
- Examples of the polar group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, (meth)acryloylacetic acid, (meth)acryloylpropionic acid, (meth)acryloylbutyric acid, (meth)acryloylpentanoic acid, and crotonic acid.
- unsaturated monocarboxylic acids such as (meth)acrylic acid, (meth)acryloylacetic acid, (meth)acryloylpropionic acid, (meth)acryloylbutyric acid, (meth)acryloylpentanoic acid, and crotonic acid.
- At least one selected from the group consisting of carboxy group-containing monomers and hydroxyl group-containing monomers is preferable, and hydroxyl group-containing monomers are more preferable, since the swelling ratio of the pressure-sensitive adhesive layer can be easily adjusted within the above range.
- These polar group-containing monomers may be used alone, or two or more of them may be used in combination.
- the content of the structural unit derived from the polar group-containing monomer in the acrylic copolymer is not particularly limited, it is preferably 0.1% by weight or more and 10% by weight or less.
- the content of the structural unit derived from the polar group-containing monomer is 0.1% by weight or more, the interaction between the polar groups can be further enhanced.
- the content of the structural unit derived from the polar group-containing monomer is 10% by weight or less, the acrylic copolymer does not become too hard, and the adhesive strength of the adhesive tape is further improved.
- the content of the structural unit derived from the polar group-containing monomer is more preferably 1% by weight or more, still more preferably 3% by weight or more, more preferably 8% by weight or less, and 6% by weight.
- the content of structural units derived from the hydroxyl group-containing monomer in the acrylic copolymer is preferably 0.01% by weight or more and 2% by weight or less. If the content of the structural unit derived from the hydroxyl group-containing monomer is within the above range, the swelling ratio of the pressure-sensitive adhesive layer can be easily adjusted within the above range, and the adhesive strength and holding power of the pressure-sensitive adhesive tape are further improved. More preferably, the content of structural units derived from the hydroxyl group-containing monomer is 0.05% by weight or more and 1% by weight or less.
- the above acrylic copolymer has a glass transition temperature in the range of -100 to 200°C when measured by differential scanning calorimetry, and all of the above glass transition temperatures are preferably -20°C or lower.
- the acrylic copolymer has a glass transition temperature in the above temperature range, and all of the glass transition temperatures are ⁇ 20° C. or lower, that is, the acrylic copolymer includes a structure having a high glass transition temperature. Since the molecule
- the glass transition temperature can be adjusted depending on the type of monomer that is the material for the acrylic copolymer.
- the glass transition temperature is measured using a differential scanning calorimeter (e.g., 220C manufactured by Seiko Instruments Inc.) under a nitrogen atmosphere (nitrogen flow, flow rate: 50 mL/min), in accordance with JIS K6240: 2011. It can be obtained by measuring at a measurement temperature of -100 to 200°C and a heating rate of 10°C/min.
- the weight average molecular weight (Mw) of the acrylic copolymer is not particularly limited, it is preferably 500,000 or more and 2,000,000 or less. When the weight average molecular weight (Mw) of the acrylic copolymer is 500,000 or more, the swelling ratio of the pressure-sensitive adhesive layer can be easily adjusted within the above range, and the pressure-sensitive adhesive tape has improved adhesive strength and holding power. If the weight average molecular weight (Mw) of the acrylic copolymer is 2,000,000 or less, the adhesive strength of the pressure-sensitive adhesive tape will be higher.
- the weight average molecular weight (Mw) of the acrylic copolymer is more preferably 650,000 or more, more preferably 800,000 or more, more preferably 1,500,000 or less, and 1,200,000 or less. More preferred.
- the molecular weight distribution (weight average molecular weight/number average molecular weight, Mw/Mn) of the acrylic copolymer is not particularly limited, it is preferably 1.0 or more and 6.0 or less. When the molecular weight distribution (Mw/Mn) of the acrylic copolymer is within the above range, the adhesive strength and holding power of the pressure-sensitive adhesive tape are further improved.
- the molecular weight distribution (Mw/Mn) of the acrylic copolymer is more preferably 1.5 or more, and more preferably 4.5 or less.
- the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be determined, for example, by GPC using polystyrene standards.
- the content of the acrylic copolymer in the pressure-sensitive adhesive layer is not particularly limited, but the main component in the polymer components constituting the pressure-sensitive adhesive layer (that is, the component contained in more than 50% by weight of the polymer components) Preferably.
- the pressure-sensitive adhesive layer preferably contains a cross-linking agent. Since the pressure-sensitive adhesive layer contains the cross-linking agent, the molecules of the acrylic copolymer are chemically cross-linked via the cross-linking agent. By adjusting the degree of cross-linking at this time, the swelling ratio and gel fraction of the pressure-sensitive adhesive layer can be adjusted to appropriate ranges. In order for the molecules of the acrylic copolymer to be chemically crosslinked via the crosslinking agent, the acrylic copolymer preferably contains a structural unit derived from the polar group-containing monomer.
- the cross-linking agent is not particularly limited, and examples thereof include epoxy-based cross-linking agents and isocyanate-based cross-linking agents. Among these, an isocyanate-based cross-linking agent is preferable because it facilitates adjustment of the swelling ratio of the pressure-sensitive adhesive layer within the above range and further improves the adhesive strength and holding power of the pressure-sensitive adhesive tape.
- the content of the cross-linking agent in the pressure-sensitive adhesive layer is not particularly limited. When the cross-linking agent is the isocyanate-based cross-linking agent, its content makes it easier to adjust the swelling ratio of the pressure-sensitive adhesive layer to the above range, and the adhesive strength and holding power of the pressure-sensitive adhesive tape are further improved.
- the content is preferably 0.1 parts by weight or more and 5 parts by weight or less, more preferably 0.5 parts by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the acrylic copolymer.
- the acrylic copolymer is a group consisting of a carboxy group-containing monomer and a hydroxyl group-containing monomer. It is preferable that the adhesive layer has a structural unit derived from at least one selected from the above, and the pressure-sensitive adhesive layer contains an isocyanate-based cross-linking agent, and the acrylic copolymer has a structural unit derived from a hydroxyl group-containing monomer. and the pressure-sensitive adhesive layer more preferably contains an isocyanate-based cross-linking agent.
- the pressure-sensitive adhesive layer preferably contains a tackifying resin. This further improves the adhesive strength of the adhesive tape.
- the tackifying resin is not particularly limited, it preferably contains a high hydroxyl value tackifying resin having a hydroxyl value of 15 mgKOH/g or more. Since the high hydroxyl value tackifier resin has a high polarity, it is difficult to be compatible with the constitutional unit derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal, which has a low polarity.
- the hydroxyl value of the high hydroxyl value tackifying resin is more preferably 30 mgKOH/g or more, preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less.
- the high hydroxyl value tackifier resin include terpene phenol resins and polymerized rosin ester resins.
- the content of the high hydroxyl value tackifying resin in the pressure-sensitive adhesive layer is not particularly limited, it is preferably 1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the acrylic copolymer.
- the content of the high hydroxyl value tackifying resin is more preferably 20 parts by weight or more, and more preferably 35 parts by weight or less.
- the tackifying resin may further contain a low hydroxyl value tackifying resin having a hydroxyl value of less than 15 mgKOH/g. Since the low hydroxyl value tackifier resin has low polarity, it is easily compatible with the structural unit derived from the olefin polymer having a polymerizable unsaturated double bond at the terminal. As a result, it is believed that the low hydroxyl value tackifying resin is compatible with the pseudo cross-linking points, thereby moderately softening the pseudo cross-linking points and improving the adhesive strength.
- the decrease in holding power can be reduced by using the high hydroxyl value tackifying resin in combination, and the initial adhesive strength can be improved while holding. Power can also be secured.
- the low hydroxyl value tackifying resin include terpene resins and petroleum resins.
- the content of the low hydroxyl value tackifying resin in the pressure-sensitive adhesive layer is not particularly limited, but is preferably 10 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the acrylic copolymer, and 25 parts by weight. Above, it is more preferable that it is 40 weight parts or less.
- the weight ratio of the content of the low hydroxyl value tackifying resin to the content of the high hydroxyl value tackifying resin in the pressure-sensitive adhesive layer is not particularly limited, From the viewpoint of further improving the adhesive strength to SUS while suppressing cohesive failure, it is preferably 0.3 or more, more preferably 0.8 or more, and preferably 4.0 or less. It is more preferably 5 or less.
- the pressure-sensitive adhesive layer may contain conventionally known fine particles and additives such as inorganic fine particles, conductive fine particles, antioxidants, foaming agents, organic fillers and inorganic fillers, if necessary.
- a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer has a structural unit derived from a (meth)acrylic acid alkyl ester and a polymerizable unsaturated double bond at the terminal. and a structural unit derived from an olefin polymer, and the pressure-sensitive adhesive layer has a swelling ratio of 40 or more and 500 or less when immersed in tetrahydrofuran at a temperature of 25 ° C. for 24 hours.
- the adhesive tape having an adhesive layer, wherein the adhesive layer includes structural units derived from butyl acrylate and structural units derived from an olefin polymer having a polymerizable unsaturated double bond at the end
- a pressure-sensitive adhesive tape containing an acrylic copolymer having and wherein the pressure-sensitive adhesive layer contains an isocyanate-based cross-linking agent is also an aspect of the present invention. That is, instead of the swelling ratio being 40 or more and 500 or less, a structural unit derived from butyl acrylate is selected as a structural unit derived from a (meth)acrylic acid alkyl ester, and an isocyanate-based cross-linking agent is contained.
- a pressure-sensitive adhesive tape that has excellent adhesion and exhibits excellent holding power even when shear stress is applied at high temperatures for a long period of time.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more, preferably 200 ⁇ m or less, and 150 ⁇ m or less. is more preferable, and 100 ⁇ m or less is even more preferable. When the thickness of the pressure-sensitive adhesive layer is within this range, the pressure-sensitive adhesive tape can have excellent adhesive strength, holding power, and handleability.
- the pressure-sensitive adhesive tape of the present invention may be a non-support type having no base material, or a support type pressure-sensitive adhesive layer formed on a base material.
- the pressure-sensitive adhesive tape of the present invention may be a single-sided pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer on one side of a base material, or may be a double-sided pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer on both sides.
- the pressure-sensitive adhesive tape of the present invention preferably has a base material and the pressure-sensitive adhesive layer on at least one surface of the base material because of excellent reworkability.
- the base material is not particularly limited. Examples include an opened sheet.
- the thickness of the substrate is not particularly limited, it is preferably 5 ⁇ m or more and 200 ⁇ m or less. When the thickness of the base material is within this range, the pressure-sensitive adhesive tape can have appropriate stiffness and be excellent in handleability. More preferably, the thickness of the substrate is 10 ⁇ m or more and 150 ⁇ m or less.
- the method for producing the pressure-sensitive adhesive tape of the present invention is not particularly limited, and conventionally known methods can be used. For example, first, the (meth)acrylic acid alkyl ester, the olefin polymer having a polymerizable unsaturated double bond at the terminal, and, if necessary, other monomers are copolymerized by a conventional method to obtain the acrylic copolymer. obtain. Next, a pressure-sensitive adhesive solution containing the obtained acrylic copolymer, and, if necessary, a tackifying resin and other additives is applied on a film that has been subjected to a release treatment, followed by drying. can be done. Moreover, the pressure-sensitive adhesive tape produced by the above method can be used as a pressure-sensitive adhesive layer, and a support-type pressure-sensitive adhesive tape can be obtained by laminating the pressure-sensitive adhesive layer to a base material.
- the application of the adhesive tape of the present invention is not particularly limited. It is preferably used for purposes such as lamination of optical members.
- ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding adhesive force, and can provide the adhesive tape which exhibits the outstanding holding power, even when a long-time shearing stress is applied at high temperature.
- Example 1 Preparation of Acrylic Copolymer A reactor equipped with a thermometer, a stirrer and a cooling tube was prepared. In this reactor, 73.9 parts by weight of n-butyl acrylate, 20 parts by weight of ethylene-butylene macromonomer, 6 parts by weight of acrylic acid, 0.1 part by weight of 4-hydroxybutyl acrylate, and 0.01 part by weight of lauryl mercaptan were added. , and 80 parts by weight of ethyl acetate were added, and then the reactor was heated to initiate reflux.
- an ethyl acetate solution of an acrylic copolymer having a solid content of 55% by weight was obtained.
- the weight average molecular weight and molecular weight distribution of the obtained acrylic copolymer were measured using 2690 Separations Module (manufactured by Waters) as a measuring instrument, GPC KF-806L (manufactured by Showa Denko) as a column, ethyl acetate as a solvent, and sample flow rate. Measurement was performed under conditions of 1 mL/min and a column temperature of 40°C.
- Ethylene-butylene macromonomer (olefin polymer having a methacryloyl group at one end, manufactured by Kraton Polymer Japan, HPVM-L1253, weight average molecular weight 7000, glass transition temperature -68°C)
- the details of the tackifying resin and the cross-linking agent are as follows.
- G150 (YS Polyster G150) (terpene phenol resin, manufactured by Yasuhara Chemical Co., hydroxyl value 140 mgKOH/g)
- U115 (YS Polyster U115) (terpene phenol resin, manufactured by Yasuhara Chemical Co., Ltd., hydroxyl value 20 mgKOH/g)
- PX1150 (YS resin PX1150) (terpene resin, manufactured by Yasuhara Chemical Co., hydroxyl value 0 mgKOH/g)
- PX800 (YS resin PX800) (terpene resin, manufactured by Yasuhara Chemical Co., hydroxyl value 0 mgKOH/g)
- Coronate L-45 isocyanate cross-linking agent, manufactured by Tosoh Corporation
- Coronate HX isocyanate-based cross-linking agent, manufactured by Tosoh Corporation
- Aluminum trisacetylacetonate metallic cross
- Examples 2-31, Comparative Examples 1-4 and 6-9 A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1, except for the changes shown in Tables 1 and 2.
- the double-sided pressure-sensitive adhesive tape obtained in Comparative Example 3 has an uncrosslinked pressure-sensitive adhesive layer. 4 were both 0, so the swelling ratio could not be defined (* in Table 2).
- Example 5 A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1, except that the amount of lauryl mercaptan was changed to 0.2 parts by weight to obtain an acrylic copolymer and that the composition was changed as shown in Table 2.
- test piece was prepared by cutting the double-sided adhesive tape into a width of 25 mm. Then, the obtained test piece was attached to a SUS plate and crimped by reciprocating once with a 1 kg rubber roller. After that, it was cured at 23°C for 24 hours, and the obtained measurement sample was subjected to a 180° peel test at a tensile speed of 300 mm/min according to JIS Z 0237: 2009, and the adhesive strength (N/inch) at 23°C was measured. bottom.
- the double-sided pressure-sensitive adhesive tapes obtained in Examples 22 and 23 had an adhesive force of 50 N/inch or more, but the pressure-sensitive adhesive layer was broken (cohesive failure) (** in Table 2).
- Adhesive strength is 50 N / inch or more
- Adhesive strength is 43 N / inch or more and less than 50 N / inch
- Adhesive strength is 40 N / inch or more and less than 43 N / inch
- Adhesive strength is less than 40 N / inch
- FIG. 1 shows a diagram schematically showing a shear holding force evaluation method.
- a test piece 6 was prepared by cutting a double-sided adhesive tape into a width of 25 mm and a length of 60 mm.
- One side of the test piece 6 was backed with a polyethylene terephthalate (PET) film 5 .
- PET polyethylene terephthalate
- the other surface of the test piece 6 was bonded to a cold-rolled stainless steel plate (SUS304 plate) 7 having a thickness of 2.0 mm, a width of 50 mm, and a length of 75 mm at 23 ° C., and the length of adhesion was 25 mm.
- SUS304 plate cold-rolled stainless steel plate
- a 2-kg roller was reciprocated once to press-bond to prepare a measurement sample.
- a weight 8 of 1 kg was attached to the measurement sample in an environment of 85° C. so as to apply a load in the shear direction. From the amount of displacement of the test piece 6 24 hours after the load was applied by the weight 8, the holding force was evaluated according to the following criteria.
- ⁇ The amount of deviation is 0.5 mm or less
- ⁇ The amount of deviation is greater than 0.5 mm and 1.0 mm or less
- the amount of deviation is greater than 1.0 mm ⁇ : The test piece fell
- ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding adhesive force, and can provide the adhesive tape which exhibits the outstanding holding power, even when a long-time shearing stress is applied at high temperature.
- PET polyethylene terephthalate
- SUS304 plate weight (1 kg)
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Abstract
Description
本開示2は、前記粘着剤層は、ゲル分率が20重量%以上、65重量%以下である、本開示1の粘着テープである。
本開示3は、前記アクリル共重合体は、極性基含有モノマーに由来する構成単位を含有する、本開示1又は2の粘着テープである。
本開示4は、前記極性基含有モノマーは、水酸基含有モノマーを含有する、本開示3の粘着テープである。
本開示5は、前記アクリル共重合体は、前記水酸基含有モノマーに由来する構成単位の含有量が0.01重量%以上、2重量%以下である、本開示4の粘着テープである。
本開示6は、前記粘着剤層は、架橋剤を含有する、本開示1、2、3、4又は5の粘着テープである。
本開示7は、前記架橋剤は、イソシアネート系架橋剤である、本開示6の粘着テープである。
本開示8は、前記アクリル共重合体は、重量平均分子量(Mw)が50万以上、150万以下である、本開示1、2、3、4、5、6又は7の粘着テープである。
本開示9は、前記(メタ)アクリル酸アルキルエステルはブチルアクレートである、本開示1、2、3、4、5、6、7又は8の粘着テープである。
本開示10は、前記末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位の含有量が5重量%以上30重量%以下である、本開示1、2、3、4、5、6、7、8又は9の粘着テープである。
本開示11は、粘着剤層を有する粘着テープであって、前記粘着剤層は、ブチルアクリレートに由来する構成単位と、末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位とを有するアクリル共重合体を含有し、前記粘着剤層は、イソシアネート系架橋剤を含有する粘着テープである。
本開示12は、前記粘着剤層は、粘着付与樹脂を含有する、本開示1、2、3、4、5、6、7、8、9、10又は11の粘着テープである。
本開示13は、前記粘着付与樹脂は、水酸基価が15mgKOH/g以上である高水酸基価粘着付与樹脂を含有する、本開示12の粘着テープである。
本開示14は、前記水酸基価が15mgKOH/g以上である高水酸基価粘着付与樹脂の含有量が、前記アクリル共重合体100重量部に対して20重量部以上、40重量部以下である、本開示13の粘着テープである。
本開示15は、前記粘着付与樹脂は、更に、水酸基価が15mgKOH/g未満である低水酸基価粘着付与樹脂を含有する、本開示12、13又は14の粘着テープである。
本開示16は、前記水酸基価が15mgKOH/g未満である低水酸基価粘着付与樹脂の含有量が、前記アクリル共重合体100重量部に対して10重量部以上、60重量部以下である、本開示15の粘着テープである。
以下、本発明を詳述する。
上記粘着剤層は、(メタ)アクリル酸アルキルエステルに由来する構成単位と、末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位とを有するアクリル共重合体(以下、単に「アクリル共重合体」ともいう)を含有する。なお、本明細書中において(メタ)アクリルとは、アクリル又はメタクリルを意味する。
上記アクリル共重合体は、末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位が相互作用によって凝集し、擬似的な架橋点を形成した構造となっている。上記アクリル共重合体がこのような構造を取ることで、上記粘着剤層は、ひずみが小さいときは架橋された粘着剤層のように固く、保持力が高い性質を示す。一方、剥離応力がかかってひずみが大きくなったときは、上記擬似的な架橋点が切れて、上記アクリル共重合体の分子が伸びることから、上記粘着剤層は、柔軟性が高い性質を示す。つまり、上記粘着剤層が上記アクリル共重合体を含有することで、粘着テープの粘着力と保持力とが向上する。
上記粘着剤層の膨潤比が40以上であれば、粘着テープの粘着力が向上する。上記粘着剤層の膨潤比が500以下であれば、高温において長時間のせん断応力がかかった場合の粘着テープの保持力が向上する。上記粘着剤層の膨潤比は50以上、300以下であることが好ましく、150以下であることがより好ましい。
なお、上記粘着剤層の膨潤比は、以下の方法で測定することができる。
まず、粘着剤層をテトラヒドロフランに温度25℃で24時間浸漬し、テトラヒドロフラン浸漬後の粘着剤層の重量W3を測定する。その後、テトラヒドロフランを乾燥させ、テトラヒドロフラン乾燥後の粘着剤層の重量W4を測定する。下記式(2)を用いて粘着剤層の膨潤比を算出する。
膨潤比=W3/W4 (2)
上記粘着剤層のゲル分率が20重量%以上であれば、高温において長時間のせん断応力がかかった場合の粘着テープの保持力がより向上する。上記粘着剤層のゲル分率が65重量%以下であれば、粘着テープの粘着力がより向上する。上記粘着剤層のゲル分率は35重量%以上であることがより好ましく、60重量%以下であることがより好ましく、50重量%以下であることがさらに好ましい。
なお、上記粘着剤層のゲル分率は、以下の方法で測定することができる。
まず、粘着剤層の粘着剤を0.1gこそぎ取ってテトラヒドロフラン50mL中に浸漬し、振とう機で温度23℃、200rpmの条件で24時間振とうする。振とう後、金属メッシュ(目開き#200メッシュ)を用いて、テトラヒドロフランとテトラヒドロフランを吸収し膨潤した粘着剤を分離する。分離後の粘着剤を110℃の条件下で1時間乾燥させる。乾燥後の金属メッシュを含む粘着剤の重量を測定し、下記式(1)を用いてゲル分率を算出する。
ゲル分率(重量%)=100×(W1-W2)/W0 (1)
(W0:初期粘着剤重量、W1:乾燥後の金属メッシュを含む粘着剤重量、W2:金属メッシュの初期重量)
上記粘着剤層の損失正接が上記範囲にピークを有することで、粘着テープの粘着力と保持力とがより向上する。上記粘着剤層は、損失正接のピークを35℃以下に有することがより好ましく、25℃以下に有することが更に好ましい。上記損失正接のピークの温度は上記アクリル共重合体の原料によって調節することができる。
なお、上記損失正接は、粘弾性スペクトロメーター(アイティー計測制御社製、DVA-200、又はその同等品)を用い、低速昇温せん断変形モードの5℃/分、10Hzの条件で、-100℃~200℃の動的粘弾性スペクトルを測定することで得ることができる。
上記(メタ)アクリル酸アルキルエステルは特に限定されず、例えば、直鎖状又は分岐鎖状の炭素数1~24のアルキル基を有する(メタ)アクリル酸アルキルエステルが挙げられる。具体的には、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、s-ブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、n-ペンチル(メタ)アクリレート、イソペンチル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、イシヘキシル(メタ)アクリレート、n-ヘプチル(メタ)アクリレート、イソヘプチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、n-ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、n-デシル(メタ)アクリレート、イソデシル(メタ)アクリレート、n-ドデシル(メタ)アクリレート、n-トリデシル(メタ)アクリレート、n-テトラデシル(メタ)アクリレート、ペンタデシル(メタ)アクリレート、ヘキサデシル(メタ)アクリレート、ヘプタデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート等が挙げられる。なかでも、後述するガラス転移温度を満たしやすくなり、粘着テープの粘着力がより向上することから、アルキル基の炭素数が4~8の(メタ)アクリル酸アルキルエステルが好ましく、ブチルアクリレートがより好ましく、n-ブチルアクリレートが更に好ましい。なお、これらの(メタ)アクリル酸アルキルエステルは単独で用いてもよく、2種以上を併用してもよい。
上記末端に重合性不飽和二重結合を有するオレフィン重合体として、具体的には、片末端に(メタ)アクリロイル基を有するエチレンマクロモノマー、片末端に(メタ)アクリロイル基を有するプロピレンマクロモノマー、片末端に(メタ)アクリロイル基を有するエチレン-ブチレンマクロモノマー、片末端に(メタ)アクリロイル基を有するエチレン-プロピレンマクロモノマー等が挙げられる。なかでも、後述するガラス転移温度を満たしやすくなり、粘着テープの粘着力がより向上することから、片末端に(メタ)アクリロイル基を有するエチレン-ブチレンマクロモノマー、片末端に(メタ)アクリロイル基を有するエチレン-プロピレンマクロモノマーが好ましい。なお、これらの末端に重合性不飽和二重結合を有するオレフィン重合体は単独で用いてもよく、2種以上を併用してもよい。また、ここでマクロモノマーとは、重量平均分子量1000~10万程度の重合可能な官能基を有するモノマーを指す。
上述のように、上記アクリル共重合体は上記末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位が擬似的な架橋点を形成することで、ひずみが小さいときは架橋された粘着剤層のような性質を示す一方、ひずみが大きくなると擬似的な架橋点が切れて架橋構造を有さない粘着剤層のような性質を示す。よって、化学架橋構造を構築しやすい上記重合性不飽和二重結合を2つ以上含むモノマーに由来する構成単位の含有量を少なくすることで、ひずみが大きくなったときに上記アクリル共重合体の分子をより伸びやすくすることができ、粘着力をより向上させることができる。上記重合性不飽和二重結合を2つ以上含むモノマーに由来する構成単位の含有量は0%であることがより好ましい。
上記アクリル共重合体が上記極性基含有モノマーに由来する構成単位を含有することで、極性基同士が相互作用するため、粘着テープの粘着力と保持力とがより向上する。また、上記アクリル共重合体が上記極性基含有モノマーに由来する構成単位を含有することで、上記粘着剤層が更に架橋剤を含有する場合には、上記アクリル共重合体の分子間が架橋剤を介して化学架橋される。このときの架橋度を調整することにより、上記粘着剤層の膨潤比及びゲル分率を適切な範囲に調整することができる。
上記極性基含有モノマーとしては、例えば、(メタ)アクリル酸、(メタ)アクリロイル酢酸、(メタ)アクリロイルプロピオン酸、(メタ)アクリロイル酪酸、(メタ)アクリロイルペンタン酸、クロトン酸等の不飽和モノカルボン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、N-ビニル-2-ピロリドン、(メタ)アクリロイルモルフォリン、(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート等が挙げられる。また、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート等の水酸基含有モノマーも挙げられる。なかでも、上記粘着剤層の膨潤比を上記範囲に調整しやすいことから、カルボキシ基含有モノマー及び水酸基含有モノマーからなる群より選択される少なくとも1種が好ましく、水酸基含有モノマーがより好ましい。なお、これらの極性基含有モノマーは単独で用いてもよく、2種以上を併用してもよい。
なかでも、上記アクリル共重合体における上記水酸基含有モノマーに由来する構成単位の含有量は、0.01重量%以上、2重量%以下であることが好ましい。上記水酸基含有モノマーに由来する構成単位の含有量が上記範囲内であれば、上記粘着剤層の膨潤比を上記範囲に調整しやすくなり、粘着テープの粘着力と保持力とがより向上する。上記水酸基含有モノマーに由来する構成単位の含有量は、0.05重量%以上、1重量%以下であることがより好ましい。
上記アクリル共重合体が上記温度範囲にガラス転移温度を有し、かつ、その全てのガラス転移温度が-20℃以下である、つまり、上記アクリル共重合体が高いガラス転移温度を有する構造を含まないことで、上記アクリル共重合体の分子が伸びやすくなるため、粘着テープの粘着力がより向上する。全ての上記ガラス転移温度が-30℃以下であることがより好ましく、-35℃以下であることが更に好ましい。上記ガラス転移温度は上記アクリル共重合体の材料となるモノマーの種類によって調節することができる。
なお、上記ガラス転移温度は、窒素雰囲気下(窒素フロー、流量50mL/分)、示差走査熱量計(例えば、セイコーインスツル社製の220C等)を用いて、JIS K6240:2011に準拠した方法で測定温度-100~200℃、昇温速度10℃/分の条件下で測定を行うことにより求めることができる。
なお、上記重量平均分子量(Mw)及び上記数平均分子量(Mn)は、例えばGPC法によりポリスチレン標準で求めることができる。具体的には、例えば、測定機器としてWaters社製「2690 Separations Module」、カラムとして昭和電工社製「GPC KF-806L」、溶媒として酢酸エチルを用い、サンプル流量1mL/min、カラム温度40℃の条件で測定することができる。
上記粘着剤層が上記架橋剤を含有することで、上記アクリル共重合体の分子間が上記架橋剤を介して化学架橋される。このときの架橋度を調整することにより、上記粘着剤層の膨潤比及びゲル分率を適切な範囲に調整することができる。なお、上記アクリル共重合体の分子間が上記架橋剤を介して化学架橋されるためには、上記アクリル共重合体が上記極性基含有モノマーに由来する構成単位を含有することが好ましい。
上記粘着剤層における上記架橋剤の含有量は特に限定されない。上記架橋剤が上記イソシアネート系架橋剤である場合、その含有量は、上記粘着剤層の膨潤比を上記範囲に調整しやすくなり、粘着テープの粘着力と保持力とがより向上することから、上記アクリル共重合体100重量部に対して0.1重量部以上、5重量部以下であることが好ましく、0.5重量部以上、3重量部以下であることがより好ましい。
上記粘着付与樹脂は特に限定されないが、水酸基価が15mgKOH/g以上である高水酸基価粘着付与樹脂を含有することが好ましい。
上記高水酸基価粘着付与樹脂は極性が高いことから、極性の低い上記末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位と相溶しがたい。その結果、極性の低い上記末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位同士の相互作用による擬似的な架橋点の形成を阻害することなく、粘着力をより向上させることができる。
上記高水酸基価粘着付与樹脂の水酸基価は30mgKOH/g以上であることがより好ましく、200mgKOH/g以下であることが好ましく、150mgKOH/g以下であることがより好ましい。上記高水酸基価粘着付与樹脂としては、例えば、テルペンフェノール樹脂、重合ロジンエステル樹脂等が挙げられる。
上記低水酸基価粘着付与樹脂は極性が低いため、上記末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位と相溶しやすい。その結果、上記低水酸基価粘着付与樹脂が擬似的な架橋点に相溶することで、擬似的な架橋点が適度に柔軟化し、粘着力が向上すると考えられる。また、上記低水酸基価粘着付与樹脂の含有量が多くなった場合であっても、上記高水酸基価粘着付与樹脂を併用することで保持力の低下を低減でき、初期粘着力を向上させつつ保持力も確保できると考えられる。上記低水酸基価粘着付与樹脂としては、例えば、テルペン樹脂、石油樹脂等が挙げられる。
上記基材は特に限定されず、例えば、アクリル、オレフィン、ポリカーボネート、塩化ビニル、ABS、ポリエチレンテレフタレート(PET)、ナイロン、ウレタン、ポリイミド等の樹脂からなるシート、網目状の構造を有するシート、孔が開けられたシート等が挙げられる。
(1)アクリル共重合体の調製
温度計、攪拌機、冷却管を備えた反応器を用意した。この反応器内に、n-ブチルアクリレート73.9重量部、エチレン-ブチレンマクロモノマー20重量部、アクリル酸6重量部、4-ヒドロキシブチルアクリレート0.1重量部、ラウリルメルカプタン0.01重量部と、酢酸エチル80重量部を加えた後、反応器を加熱して還流を開始した。続いて、上記反応器内に、重合開始剤として1,1-ビス(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサン0.01重量部を添加し、還流下で重合を開始させた。次に、重合開始から1時間後及び2時間後にも、1,1-ビス(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサンを0.01重量部ずつ添加し、更に、重合開始から4時間後にt-ヘキシルパーオキシピバレートを0.05重量部添加して重合反応を継続させた。そして、重合開始から8時間後に、固形分55重量%のアクリル共重合体の酢酸エチル溶液を得た。
得られたアクリル共重合体の重量平均分子量及び分子量分布を、測定機器として2690 Separations Module(Waters社製)、カラムとしてGPC KF-806L(昭和電工社製)、溶媒として酢酸エチルを用い、サンプル流量1mL/min、カラム温度40℃の条件で測定した。
エチレン-ブチレンマクロモノマー(片末端にメタクリロイル基を有するオレフィン重合体、クレイトン・ポリマージャパン社製、HPVM-L1253、重量平均分子量7000、ガラス転移温度-68℃)
アクリル共重合体の酢酸エチル溶液の固形分100重量部に対して、粘着付与樹脂としてG150(YSポリスターG150)を25重量部、PX1150を30重量部、イソシアネート系架橋剤を0.2重量部加えて混合することで粘着剤溶液を得た。片面に離型処理を施した50μmのポリエチレンテレフタレート(PET)フィルムの離型処理面上に、得られた粘着剤溶液を乾燥皮膜の厚さが40μmとなるようにドクターナイフで塗工し、110℃、5分間加熱して塗工溶液を乾燥させることで両面粘着テープを得た。
G150(YSポリスターG150)(テルペンフェノール樹脂、ヤスハラケミカル社製、水酸基価140mgKOH/g)
U115(YSポリスターU115)(テルペンフェノール樹脂、ヤスハラケミカル社製、水酸基価20mgKOH/g)
PX1150(YSレジンPX1150)(テルペン樹脂、ヤスハラケミカル社製、水酸基価0mgKOH/g)
PX800(YSレジンPX800)(テルペン樹脂、ヤスハラケミカル社製、水酸基価0mgKOH/g)
コロネートL-45(イソシアネート系架橋剤、東ソー社製)
コロネートHX(イソシアネート系架橋剤、東ソー社製)
アルミニウムトリスアセチルアセトネート(金属系架橋剤、マツモトファインケミカル社製)
トリメチロールプロパン-トリ-β-アジリジニルプロピオネート(アジリジン系架橋剤、東京化成工業社製)
パーロイルL(有機過酸化物系架橋剤、日油社製)
まず、粘着剤層をテトラヒドロフランに温度25℃で24時間浸漬し、テトラヒドロフラン浸漬後の粘着剤層の重量W3を測定した。その後、テトラヒドロフランを乾燥させ、テトラヒドロフラン乾燥後の粘着剤層の重量W4を測定した。下記式(2)を用いて粘着剤層の膨潤比を算出した。
膨潤比=W3/W4 (2)
まず、粘着剤層の粘着剤を0.1gこそぎ取ってテトラヒドロフラン50mL中に浸漬し、振とう機で温度23℃、200rpmの条件で24時間振とうした。振とう後、金属メッシュ(目開き#200メッシュ)を用いて、テトラヒドロフランとテトラヒドロフランを吸収し膨潤した粘着剤を分離した。分離後の粘着剤を110℃の条件下で1時間乾燥させた。乾燥後の金属メッシュを含む粘着剤の重量を測定し、下記式(1)を用いてゲル分率を算出した。
ゲル分率(重量%)=100×(W1-W2)/W0 (1)
(W0:初期粘着剤重量、W1:乾燥後の金属メッシュを含む粘着剤重量、W2:金属メッシュの初期重量)
表1~2に示すように変更したこと以外は実施例1と同様にして両面粘着テープを得た。
なお、比較例3で得られた両面粘着テープは、粘着剤層が未架橋であり、膨潤比の測定においてテトラヒドロフラン浸漬後の粘着剤層の重量W3及びテトラヒドロフラン乾燥後の粘着剤層の重量W4がいずれも0となったため、膨潤比を定義できなかった(表2中の*)。
ラウリルメルカプタンを0.2重量部に変更してアクリル共重合体を得たこと及び表2に示すように変更したこと以外は実施例1と同様にして両面粘着テープを得た。
実施例及び比較例で得られた両面粘着テープについて以下の評価を行った。結果を表1~2に示した。
両面粘着テープを25mm幅に裁断して試験片を作製した。次いで、得られた試験片をSUS板に貼り、1kgのゴムローラーで1往復することによって圧着した。その後、23℃において24時間養生し、得られた測定サンプルについてJIS Z 0237:2009に従い、引張速度300mm/minの条件で180°ピール試験を行い、23℃における粘着力(N/inch)を測定した。
なお、実施例22及び23で得られた両面粘着テープについては、粘着力は50N/inch以上であったが、粘着剤層で破壊(凝集破壊)が生じた(表2中の**)。実施例22及び23以外の実施例及び比較例で得られた両面粘着テープは界面破壊であった。
◎:粘着力が50N/inch以上
○:粘着力が43N/inch以上50N/inch未満
△:粘着力が40N/inch以上43N/inch未満
×:粘着力が40N/inch未満
図1にせん断保持力評価方法を模式的に示す図を示す。
まず、JIS Z-1528に準じ、両面粘着テープを幅25mm、長さ60mmに裁断して試験片6を作製した。試験片6の一方の面をポリエチレンテレフタレート(PET)フィルム5でバッキングした。試験片6の他方の面を23℃で厚み2.0mm、幅50mm、長さ75mmの冷間圧延ステンレス鋼板(SUS304板)7に接着長さが25mmとなり、試験片6がSUS304板7の端部からはみ出すように、長さ方向においてずらして貼り合わせた後、2kgローラーを1往復させて圧着し、測定サンプルを作製した。測定サンプルを23℃、50%RHの雰囲気下に20分間放置した後、85℃の環境下、測定サンプルに対してせん断方向に負荷がかかるように1kgの錘8を取り付けた。錘8により負荷をかけてから24時間後の試験片6のずれ量から、下記基準で保持力を評価した。
◎:ずれ量が0.5mm以下
○:ずれ量が0.5mmより大きく1.0mm以下
△:ずれ量が1.0mmより大きい
×:試験片が落下した
6 試験片
7 SUS304板
8 錘(1kg)
Claims (16)
- 粘着剤層を有する粘着テープであって、
前記粘着剤層は、(メタ)アクリル酸アルキルエステルに由来する構成単位と、末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位とを有するアクリル共重合体を含有し、
前記粘着剤層は、テトラヒドロフランに温度25℃で24時間浸漬したときの膨潤比が40以上、500以下である
ことを特徴とする粘着テープ。 - 前記粘着剤層は、ゲル分率が20重量%以上、65重量%以下である、請求項1記載の粘着テープ。
- 前記アクリル共重合体は、極性基含有モノマーに由来する構成単位を含有する、請求項1又は2記載の粘着テープ。
- 前記極性基含有モノマーは、水酸基含有モノマーを含有する、請求項3記載の粘着テープ。
- 前記アクリル共重合体は、前記水酸基含有モノマーに由来する構成単位の含有量が0.01重量%以上、2重量%以下である、請求項4記載の粘着テープ。
- 前記粘着剤層は、架橋剤を含有する、請求項1、2、3、4又は5記載の粘着テープ。
- 前記架橋剤は、イソシアネート系架橋剤である、請求項6記載の粘着テープ。
- 前記アクリル共重合体は、重量平均分子量(Mw)が50万以上、150万以下である、請求項1、2、3、4、5、6又は7記載の粘着テープ。
- 前記(メタ)アクリル酸アルキルエステルはブチルアクレートである、請求項1、2、3、4、5、6、7又は8記載の粘着テープ。
- 前記末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位の含有量が5重量%以上30重量%以下である、請求項1、2、3、4、5、6、7、8又は9記載の粘着テープ。
- 粘着剤層を有する粘着テープであって、
前記粘着剤層は、ブチルアクリレートに由来する構成単位と、末端に重合性不飽和二重結合を有するオレフィン重合体に由来する構成単位とを有するアクリル共重合体を含有し、
前記粘着剤層は、イソシアネート系架橋剤を含有する
ことを特徴とする粘着テープ。 - 前記粘着剤層は、粘着付与樹脂を含有する、請求項1、2、3、4、5、6、7、8、9、10又は11記載の粘着テープ。
- 前記粘着付与樹脂は、水酸基価が15mgKOH/g以上である高水酸基価粘着付与樹脂を含有する、請求項12記載の粘着テープ。
- 前記水酸基価が15mgKOH/g以上である高水酸基価粘着付与樹脂の含有量が、前記アクリル共重合体100重量部に対して20重量部以上、40重量部以下である、請求項13記載の粘着テープ。
- 前記粘着付与樹脂は、更に、水酸基価が15mgKOH/g未満である低水酸基価粘着付与樹脂を含有する、請求項12、13又は14記載の粘着テープ。
- 前記水酸基価が15mgKOH/g未満である低水酸基価粘着付与樹脂の含有量が、前記アクリル共重合体100重量部に対して10重量部以上、60重量部以下である、請求項15記載の粘着テープ。
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JP2001131250A (ja) * | 1999-11-04 | 2001-05-15 | Sekisui Chem Co Ltd | アクリル系共重合体、アクリル系粘着剤組成物、アクリル系粘着テープもしくはシート及びアクリル系接着剤組成物 |
JP2003013028A (ja) * | 2001-06-29 | 2003-01-15 | Sekisui Chem Co Ltd | アクリル系粘着剤組成物及び粘着テープ |
JP2003013027A (ja) * | 2001-06-28 | 2003-01-15 | Sekisui Chem Co Ltd | アクリル系粘着剤組成物及び粘着テープ |
JP2003253225A (ja) * | 2002-02-27 | 2003-09-10 | Sekisui Chem Co Ltd | 粘着フィルムの製造方法及び粘着剤用液状組成物 |
JP2009242541A (ja) | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | 衝撃吸収テープ |
JP2009258274A (ja) | 2008-04-15 | 2009-11-05 | Sekisui Chem Co Ltd | 表示装置前板用粘着シート |
JP2012214544A (ja) | 2011-03-31 | 2012-11-08 | Lintec Corp | 粘着剤および粘着シート |
WO2022230935A1 (ja) * | 2021-04-30 | 2022-11-03 | 積水化学工業株式会社 | 粘着テープ |
WO2022230936A1 (ja) * | 2021-04-30 | 2022-11-03 | 積水化学工業株式会社 | 粘着テープ及び粘着剤組成物 |
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- 2023-01-18 CN CN202380014230.0A patent/CN118202014A/zh active Pending
- 2023-01-18 KR KR1020247012441A patent/KR20240136307A/ko unknown
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JP2001131250A (ja) * | 1999-11-04 | 2001-05-15 | Sekisui Chem Co Ltd | アクリル系共重合体、アクリル系粘着剤組成物、アクリル系粘着テープもしくはシート及びアクリル系接着剤組成物 |
JP2003013027A (ja) * | 2001-06-28 | 2003-01-15 | Sekisui Chem Co Ltd | アクリル系粘着剤組成物及び粘着テープ |
JP2003013028A (ja) * | 2001-06-29 | 2003-01-15 | Sekisui Chem Co Ltd | アクリル系粘着剤組成物及び粘着テープ |
JP2003253225A (ja) * | 2002-02-27 | 2003-09-10 | Sekisui Chem Co Ltd | 粘着フィルムの製造方法及び粘着剤用液状組成物 |
JP2009242541A (ja) | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | 衝撃吸収テープ |
JP2009258274A (ja) | 2008-04-15 | 2009-11-05 | Sekisui Chem Co Ltd | 表示装置前板用粘着シート |
JP2012214544A (ja) | 2011-03-31 | 2012-11-08 | Lintec Corp | 粘着剤および粘着シート |
WO2022230935A1 (ja) * | 2021-04-30 | 2022-11-03 | 積水化学工業株式会社 | 粘着テープ |
WO2022230936A1 (ja) * | 2021-04-30 | 2022-11-03 | 積水化学工業株式会社 | 粘着テープ及び粘着剤組成物 |
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