CN115141551A - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- CN115141551A CN115141551A CN202210320651.3A CN202210320651A CN115141551A CN 115141551 A CN115141551 A CN 115141551A CN 202210320651 A CN202210320651 A CN 202210320651A CN 115141551 A CN115141551 A CN 115141551A
- Authority
- CN
- China
- Prior art keywords
- adhesive
- active energy
- component
- meth
- pressure
- 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.)
- Pending
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 165
- 239000000853 adhesive Substances 0.000 title claims abstract description 164
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 101
- 239000000178 monomer Substances 0.000 claims abstract description 79
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 61
- 239000010410 layer Substances 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 239000012790 adhesive layer Substances 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 229920005601 base polymer Polymers 0.000 claims abstract description 17
- -1 polyethylene terephthalate Polymers 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 79
- 239000000758 substrate Substances 0.000 description 36
- 125000000217 alkyl group Chemical group 0.000 description 26
- 238000000034 method Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- MAIIXYUYRNFKPL-OWOJBTEDSA-N (e)-4-(2-hydroxyethoxy)-4-oxobut-2-enoic acid Chemical compound OCCOC(=O)\C=C\C(O)=O MAIIXYUYRNFKPL-OWOJBTEDSA-N 0.000 description 1
- MAIIXYUYRNFKPL-UPHRSURJSA-N (z)-4-(2-hydroxyethoxy)-4-oxobut-2-enoic acid Chemical compound OCCOC(=O)\C=C/C(O)=O MAIIXYUYRNFKPL-UPHRSURJSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- NTINFTOOVNKGIU-UHFFFAOYSA-N 2-(2-hydroxyethoxycarbonyl)benzoic acid Chemical compound OCCOC(=O)C1=CC=CC=C1C(O)=O NTINFTOOVNKGIU-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
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- LYGZOGDWCOYSGJ-UHFFFAOYSA-N 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropanoyl)phenoxy]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1OC1=CC=C(C(=O)C(C)(C)O)C=C1 LYGZOGDWCOYSGJ-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SBHBXEGSFJXBTA-UHFFFAOYSA-N 3-methoxysilylpropyl prop-2-enoate Chemical compound CO[SiH2]CCCOC(=O)C=C SBHBXEGSFJXBTA-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- YYTFQDRGDZTBEV-UHFFFAOYSA-N 4-ethenoxy-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(OC=C)CCC2OC21 YYTFQDRGDZTBEV-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-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
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000013522 chelant 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
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- SINKOGOPEQSHQD-UHFFFAOYSA-N cyclopentadienide Chemical compound C=1C=C[CH-]C=1 SINKOGOPEQSHQD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 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
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical class N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
An active energy ray-peelable pressure-sensitive adhesive sheet is provided which can be preferably used in a step under high-temperature conditions, and which, when irradiated with active energy rays after use in the step, can be easily peeled off with the pressure-sensitive adhesive layer having sufficiently reduced adhesiveness and without leaving adhesive residue on an adherend. The adhesive sheet has an adhesive layer with reduced adhesive strength when irradiated with active energy rays. The adhesive layer is composed of an active energy ray-curable adhesive. The active energy ray-curable adhesive is formed from a heat-cured product of an adhesive composition and contains heat-reactive substances (A) and (C). The adhesive composition contains at least (A) an adhesive base polymer having a hydroxyl group, (B) an active energy ray-reactive monomer having 3 or more radical-reactive groups in one molecule, (C) a crosslinking agent, and (D) an alpha-hydroxyalkylphenone-based photopolymerization initiator, and has a composition comprising, relative to the ratio of (A): the mass ratio of (B) in (1) is more than 0.1 and not more than 2.0.
Description
Technical Field
The present invention relates to an active energy ray-peelable pressure-sensitive adhesive sheet that can be easily peeled off by being irradiated with active energy rays from the outside.
Background
In a process for manufacturing a substrate such as a thin electronic circuit board, a resin film is used as a one-sided adhesive sheet on a base material, and the one-sided adhesive sheet is bonded and fixed to the substrate, whereby components are mounted on the substrate and parts are processed. The substrate after the mounting of parts and the processing of parts are completed and the adhesive sheet are separated from each other. When temporarily fixing a substrate by such an adhesive sheet, sufficient adhesive force is required during mounting and processing, but if the load applied to the substrate when peeling the adhesive sheet is large, the substrate may be damaged. Therefore, the adhesive force of the adhesive sheet at the time of peeling needs to be as low as possible.
In recent years, electronic components and semiconductor components are required to have higher heat resistance than ever before, mainly for vehicle-mounted applications. Meanwhile, materials constituting the above-mentioned components, for example, sealing resins for chips in semiconductor packages, are also required to have higher heat resistance. Resins having high heat resistance generally require higher heating temperatures for curing. Therefore, the adhesive sheet used in the process of curing such a high heat-resistant resin is also required to have high heat resistance.
A pressure-sensitive adhesive sheet for the above-mentioned applications is known, for example, the pressure-sensitive adhesive sheet in patent document 1, which has sufficient adhesiveness during use, but after use, is subjected to some external stimulus such as ultraviolet irradiation, and the adhesiveness is significantly reduced.
Documents of the prior art
Patent document 1: japanese patent laid-open No. 2010-106283
Disclosure of Invention
Problems to be solved by the invention
The pressure-sensitive adhesive sheet disclosed in patent document 1 is obtained by providing a pressure-sensitive adhesive layer made of an ultraviolet-ray-releasable pressure-sensitive adhesive on a substrate that is transparent to ultraviolet rays, and the pressure-sensitive adhesive layer is crosslinked and cured by irradiation with ultraviolet rays, thereby reducing the adhesive strength. The pressure-sensitive adhesive sheet maintains sufficient adhesive force with an adherend during use, and at the same time, the pressure-sensitive adhesive is crosslinked and cured by irradiating ultraviolet rays from the substrate side to reduce the adhesive force of the adhesive layer, thereby facilitating peeling of the adherend.
However, in the pressure-sensitive adhesive sheet disclosed in patent document 1, since the pressure-sensitive adhesive component in the pressure-sensitive adhesive layer is easily affected by heat, the adhesive strength of the pressure-sensitive adhesive layer cannot be sufficiently reduced if ultraviolet light is irradiated after the step under high temperature conditions of 180 ℃ and 20 minutes, for example. Therefore, when the pressure-sensitive adhesive sheet is peeled off, adhesive residue is generated on the adherend, that is, when the pressure-sensitive adhesive sheet is heated at a high temperature before the ultraviolet irradiation, the adhesive strength after the ultraviolet irradiation is not good. Further, since the initial adhesion at the time of bonding is small, it tends to be difficult to hold the adherend at normal temperature, that is, the initial tack is small, and the initial adhesion at the time of bonding at normal temperature is poor.
In view of the above circumstances, an object of the present invention is to provide an active energy ray-peelable pressure-sensitive adhesive sheet which can be used by being attached to an adherend in various production steps including the production step of the substrate and the production steps of the electronic component and the semiconductor component, and which can be preferably used in a step under a high temperature condition of, for example, 180 ℃ for 20 minutes, and when the pressure-sensitive adhesive sheet is irradiated with an active energy ray after being used in the step, the pressure-sensitive adhesive layer is sufficiently reduced in adhesiveness, can be easily peeled off, and does not leave adhesive residues on the adherend.
Means for solving the problems
As a result of intensive studies, the inventors of the present invention have found that when a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer whose adhesive force is reduced by irradiation with active energy rays satisfies the following conditions, thermal degradation of a pressure-sensitive adhesive component when used in a process under high temperature conditions is suppressed, and the pressure-sensitive adhesive sheet is effective in both easy peelability and adhesive residue property when irradiated with active energy rays.
Use is made of an adhesive base polymer having hydroxyl groups, i.e. a specific base polymer, and a crosslinking agent is included.
As the active energy ray-reactive compound, a compound having a predetermined number or more of radical-reactive groups and a small molecular weight, that is, a specific active energy ray-reactive monomer is used.
Use of a-hydroxyacetophenone-based photopolymerization initiator, i.e., a specific photopolymerization initiator.
The blending amount of the above-mentioned specific active energy ray-reactive monomer with respect to the above-mentioned specific base polymer is within a specific range.
The pressure-sensitive adhesive layer is formed from a heat-cured product of a pressure-sensitive adhesive composition containing the above-mentioned components. That is, the adhesive layer comprises the thermal reactants of the particular base polymer and crosslinker.
The present inventors have completed the invention provided below based on these new findings and solved the problems described above.
The following (a) is an adhesive base polymer having a hydroxyl group, (B) is an active energy ray-reactive monomer having 3 or more radical-reactive groups in one molecule, (C) is a crosslinking agent, and (D) is an α -hydroxyalkylphenone-based photopolymerization initiator. Further, (A1) is an acrylic resin having a hydroxyl group, the component a is a (meth) acrylate polymer having a glass transition temperature of-10 ℃ or higher, and the component b is a (meth) acrylate polymer having a glass transition temperature of-30 ℃ or lower.
According to the present invention, there is provided an adhesive sheet having an adhesive layer whose adhesive force is reduced by irradiation with active energy rays,
the pressure-sensitive adhesive layer is formed from a cured product of a pressure-sensitive adhesive composition and is composed of an active energy ray-curable pressure-sensitive adhesive containing a thermal reaction product of (A) and (C),
the adhesive composition comprises at least (A), (B), (C) and (D), and, with respect to (A): the mass ratio of (B) in (1) is more than 0.1 and not more than 2.0.
The adhesive sheet may have the following configurations.
- (A) may include (A1).
The glass transition temperature of- (A1) may be in the range of-70 ℃ or higher and 40 ℃ or lower.
The component (A1) may contain a component (a) and a component (b) as constituent components.
Component a relative to component b: the mass ratio of 1 may be greater than 1.0 and less than 9.0.
The (B) may contain an active energy ray-reactive monomer having 5 or more radical-reactive groups in one molecule.
- (D) may include oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).
The component (D) may be contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the component (B).
The initial adhesion to the adhesive layer of polyethylene terephthalate at 23 ℃ Xl may be 0.5 (N/25 mm) or more.
After heating at 180 ℃ for 20 minutes and further irradiation with active energy rays, the adhesive force X3 after heating and irradiation of the adhesive layer of polyethylene terephthalate at 23 ℃ may be 0.3 (N/25 mm) or less.
Effects of the invention
The active energy ray-peelable pressure-sensitive adhesive sheet according to the present invention is formed from a thermally cured product of a pressure-sensitive adhesive composition, has a pressure-sensitive adhesive layer whose adhesive strength is reduced by irradiation with active energy rays, and contains a crosslinking agent and a specific photopolymerization initiator, wherein the amount of a specific active energy ray-reactive monomer to be mixed with respect to a specific base polymer in the pressure-sensitive adhesive composition is within a specific range. Since the adhesive layer is formed from a thermoset of the adhesive composition, thermal reactants of the particular base polymer and crosslinker are present in the adhesive layer. According to the structure of the pressure-sensitive adhesive layer, even in a step under a high temperature condition of, for example, 180 ℃ and 20 minutes, a decrease in cohesive force due to thermal deterioration of the pressure-sensitive adhesive component is suppressed, and as a result, the pressure-sensitive adhesive layer is sufficiently decreased in adhesiveness by irradiation with active energy rays after the step, and an active energy ray-peelable pressure-sensitive adhesive sheet in which adhesive residue is less likely to occur on an adherend can be provided.
With the above configuration, the pressure-sensitive adhesive sheet is suitably used in a high-temperature environment of, for example, 150 ℃ or higher, preferably 170 ℃ or higher.
Detailed Description
The following describes preferred embodiments of the present invention, but the present invention is not limited to the following embodiments, and appropriate changes, modifications, and the like to the following embodiments based on the general knowledge of those skilled in the art are also within the scope of the present invention.
In the numerical ranges described in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.
In the present specification, when a plurality of substances corresponding to each component are present in a composition, unless otherwise specified, the content ratio or content amount of each component in the composition means the content ratio or content amount of the total of the plurality of substances present in the composition.
In the present specification, "(meth) acrylic acid" means both or either of acrylic acid and methacrylic acid. The same applies to other similar terms. The term "copolymer" is also included in "polymer".
In the present specification, the number average molecular weights (Mn 1, mn 2) and the mass average molecular weights (Mw 1, mw 2) are standard polystyrene converted values measured by a Gel Permeation Chromatography (GPC) method. The glass transition temperatures (Tg 1, tg 2) can be measured by a Differential Scanning Calorimeter (DSC).
In the present specification, unless otherwise specified, "adhesive layer" means an adhesive layer before the adhesive force is reduced, that is, before the irradiation of active energy rays. The "active energy ray-curable adhesive agent" is a releasable adhesive agent, and the "adhesive sheet" is a removable adhesive sheet, that is, a removable adhesive sheet. "removability" refers to the ability to be reattached to an adherend.
< adhesive sheet >
The pressure-sensitive adhesive sheet according to an embodiment of the present invention has a pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet may be composed of only the pressure-sensitive adhesive layer, that is, without a substrate, or may be composed of a substrate and a pressure-sensitive adhesive layer laminated on the substrate. The substrate may be a polymer film such as a PET film. In the case where there is no substrate, a release sheet, that is, a double-sided release sheet may be provided on both surfaces of the adhesive sheet, that is, the adhesive layer. In the case of the above-mentioned substrate, a release sheet, that is, a single-sided release sheet may be provided on the surface of the pressure-sensitive adhesive layer opposite to the substrate.
Examples of the release sheet include: a releasable laminate sheet having a release sheet substrate and a release agent layer provided on one surface of the release sheet substrate, or a polyolefin film as a polar substrate such as a polyethylene film, a polypropylene film, or the like.
The release sheet substrate may be paper or a polymer film. Examples of the release agent constituting the release agent layer include general-purpose addition-type or condensation-type silicone release agents and long-chain alkyl group-containing compounds. In particular, addition type silicone release agents having high reactivity are preferably used.
When the pressure-sensitive adhesive sheet is in the form of a double-sided release sheet having no substrate, that is, composed of only the pressure-sensitive adhesive layer, it is preferable to have a pair of release sheets having mutually different release forces on both surfaces of the pressure-sensitive adhesive sheet, that is, the pressure-sensitive adhesive layer. That is, in order to facilitate peeling, it is preferable that the peeling sheets have different peelability from one side of the peeling sheets to the other side of the peeling sheets. When the releasability of one side is different from that of the other side, it is easy to peel only the release sheet having a high releasability first, thereby improving the processability.
< adhesive base layer >
The adhesive layer is composed of an active energy ray-curable adhesive, and refers to the adhesive sheet itself when the adhesive sheet has no substrate, as follows. When an active energy ray-curable pressure-sensitive adhesive is used, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer which has low elasticity and high flexibility at the time of application and is excellent in handling properties and which can be reduced in adhesive strength by irradiation with active energy rays when peeling is required can be obtained.
The "active energy ray-curable adhesive" is an adhesive which is cured by irradiation with an active energy ray and has a reduced adhesive force, and which has a predetermined adhesive force before the irradiation with the active energy ray. The "adhesive force" has the same meaning as a peeling force, i.e., a force required to peel from an adhesive object. The "active energy ray" refers to an electromagnetic wave or a charged particle ray having an energy quantum. Examples thereof include ultraviolet rays, electron rays, visible rays, X-rays, and ion rays. Among them, from the viewpoint of general versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
The active energy ray-curable pressure-sensitive adhesive is formed from a heat-cured product of a pressure-sensitive adhesive composition having a specific composition according to an embodiment of the present invention.
2-1.< adhesive composition >
The pressure-sensitive adhesive composition according to an embodiment, hereinafter also simply referred to as "composition", contains a base polymer, an active energy ray-reactive compound, (C) a crosslinking agent, and a photopolymerization initiator. The base polymer, the active energy ray-reactive compound and the photopolymerization initiator each contain 95% by mass or more, preferably 100% by mass, of (A) an adhesive base polymer having a hydroxyl group, (B) an active energy ray-reactive monomer and (D) an α -hydroxyalkylphenone-based photopolymerization initiator. The base polymer, the active energy ray-reactive compound, and the photopolymerization initiator may contain components other than (a), (B), and (D), respectively. That is, the composition according to one embodiment contains at least (a), (B), (C), and (D). Hereinafter, each component will be described in detail.
2-1-1. (base polymer)
In the composition according to one embodiment, a composition having a hydroxyl group is used as the base polymer, specifically, (a) an adhesive base polymer having a hydroxyl group is used. The component (a) for forming the composition serves as a matrix of the active energy ray-curable adhesive constituting the adhesive layer. (A) The material is not particularly limited as long as it has a hydroxyl group. In view of suppressing the decrease in cohesive force due to the thermal deterioration of the pressure-sensitive adhesive component even in the step under a high temperature condition of 180 ℃ for 20 minutes, for example, it is preferable to use (A1) an acrylic resin having a hydroxyl group, because the pressure-sensitive adhesive layer is sufficiently decreased in adhesiveness by irradiation with an active energy ray after the step, and an active energy ray-peelable pressure-sensitive adhesive sheet in which an adherend is less likely to have adhesive residue can be easily obtained.
One kind may be used alone, or two or more kinds may be used in combination.
The content of (a) in the composition, that is, the total amount is not particularly limited, but considering the blending ratio with other components, it is preferably 30 mass% or more, more preferably 40 mass% or more, further preferably 90 mass% or less, and further preferably 80 mass% or less, based on 100 mass% of the total solid content of the composition.
(A1) Acrylic resin having hydroxyl group
When (a) is composed of (A1), (A1) preferably contains a component a for exhibiting high-temperature peeling force and elastic modulus properties, that is, A1 st (meth) acrylate polymer, and a component b for exhibiting peeling force properties, that is, a 2 nd (meth) acrylate polymer. More preferably, component a has a higher glass transition temperature (Tg 1) than the glass transition temperature (Tg 2) of component b, i.e., tg1 > Tg2.
(A1) The total content of these components a and b is preferably 90% by mass or more, more preferably 95% by mass or more. The upper limit is 100 mass%. Further, if the mass average molecular weights (Mw 1, mw 2) of the component a and the component b are too low, the cohesive force is insufficient, and the peeling force is likely to increase and a state of residual gum is likely to occur when the composition is irradiated with an active energy ray after processing under high temperature conditions. Therefore, in addition to satisfying the above conditions (Tg 1 > Tg 2), it is preferable to use as the component a and the component b a resin having appropriately high mass average molecular weights (Mw 1, mw 2), that is, mw1 and Mw2 of 100,000 or more.
(A1) The hydroxyl value of (b), i.e., the solid content, is preferably at least 1 (mgKOH/g), more preferably at least 3 (mgKOH/g), more preferably at most 20 (mgKOH/g), more preferably at most 15 (mgKOH/g). By adjusting the hydroxyl value of (A1) within the above range, the (A1) is crosslinked to a crosslinking density suitable for imparting an appropriate adhesive force to the adhesive layer, and as a result, high heat resistance is easily obtained and sufficient adhesiveness is obtained in use.
Component a-
As the component a, for example, those having a mass average molecular weight (Mw 1) of 10 ten thousand or more, preferably 20 ten thousand or more, and a glass transition temperature (Tg 1) of-10 ℃ or more, preferably-5 ℃ or more are used. If Mw1 is less than 10 ten thousand, there is a problem that the peeling force at the time of adhesive residue and re-peeling becomes large, whereas if Tg1 is less than-10 ℃, the peeling force and elastic modulus at high temperature are lowered, and therefore both are not preferable. Further, if Mw1 is too high, a problem of poor compatibility tends to occur, and if Tg1 is too high, a problem of difficulty in adhesion to an adherend tends to occur. Therefore, as the component a, it is preferable to satisfy the above conditions, that is, mw1 is 10 ten thousand or more and Tg1 is-10 ℃ or more, and further, mw1 is 200 ten thousand or less, preferably 100 ten thousand or less and/or Tg1 is 40 ℃ or less, preferably 30 ℃ or less.
The dispersity (Mw 1/Mn 1) of the component a represented by the ratio of Mw1 to the number average molecular weight (Mn 1) is not particularly limited, and is preferably from 1 to 30 or so from the viewpoint of adhesiveness.
The component a contains a hydroxyl group-containing monomer which is a monomer having a hydroxyl group in the molecule as a monomer unit constituting the polymer. Since the composition according to one embodiment contains (C) a crosslinking agent, the hydroxyl group of the hydroxyl group-containing monomer reacts with (C), and the cohesive force of the resulting adhesive can be easily controlled. Therefore, the resulting adhesive layer easily exerts desired adhesive force.
Examples of the hydroxyl group-containing monomer include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate (HEMA, HEA), 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. Among these, the hydroxyl group-containing monomer is preferably 2-hydroxyethyl (meth) acrylate, and more preferably 2-hydroxyethyl methacrylate (HEMA) from the viewpoints of good compatibility with other monomers and copolymerization properties during the synthesis of the component a, and particularly good crosslinking reaction with the crosslinking agent (C). These may be used alone or in combination of two or more.
Component a preferably contains 0.5 mass% or more, more preferably 1 mass% or more of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. By setting the lower limit of the content, which is the ratio of the hydroxyl group-containing monomer, to the above value, high cohesive force and heat resistance can be obtained. The component a preferably contains 5% by mass or less, more preferably 3% by mass or less of a hydroxyl group-containing monomer as a monomer unit constituting the polymer. By setting the upper limit of the content of the hydroxyl group-containing monomer to the above value, an appropriate adhesive force can be obtained.
The component a is a monomer unit constituting the polymer, and has a hydroxyl group-containing monomer, preferably an alkyl (meth) acrylate having 1 to 20 carbon atoms and an alkyl group, from the viewpoint of easily developing a desired adhesive force.
Examples of the alkyl (meth) acrylate in which the alkyl group has 1 to 20 carbon atoms include: methyl (meth) acrylate (MMA, MA), (ethyl (meth) acrylate (EMA, EA), (propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (EHMA, EHA), (isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
Among them, the alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms is preferably one or more (meth) acrylates having an alkyl group with 1 to 8 carbon atoms from the viewpoint of further improving the adhesiveness. The (meth) acrylate having an alkyl group with 1 to 8 carbon atoms preferably contains one or more of ethyl (meth) acrylate (EMA, EA), and more preferably Ethyl Acrylate (EA) and Ethyl Methacrylate (EMA), from the viewpoint of adjusting Tg. These may be used alone or in combination of two or more.
The component a is an alkyl (meth) acrylate having an alkyl group and having 1 to 20 carbon atoms, and is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 98% by mass or less, and further preferably 95% by mass or less, as a monomer unit constituting the polymer. When the content of the alkyl (meth) acrylate is within the above range, tg can be adjusted to an appropriate range, and an appropriate adhesive force at room temperature can be obtained.
The component a may contain a hydroxyl group-containing monomer and a monomer other than the alkyl (meth) acrylate as a monomer unit constituting the polymer within a range in which the effects of the present invention are exhibited. In this case, the content ratio, which is the total ratio of the constituent unit derived from the hydroxyl group-containing monomer and the constituent unit derived from the alkyl (meth) acrylate, is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more, based on 100% by mass of the total constituent monomer units of the component a.
The other monomer is not particularly limited as long as it can be copolymerized with the hydroxyl group-containing monomer and the alkyl (meth) acrylate. Examples of the other monomers include: (meth) acrylates having a cyclic group such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; aromatic monovinyl groups such as styrene, α -methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene and toluylene; ethylene cyanides such as Acrylonitrile (AN) and methacrylonitrile; vinyl esters such as vinyl formate, vinyl Acetate (VA), vinyl propionate, and vinyl versatate; examples of the monomer include monomers having a functional group other than a hydroxyl group, such as a carboxyl group, a glycidyl group, an amide group, an N-substituted amide group, and a tertiary amino group. These may be used alone or in combination of two or more.
Examples of the monomer having a carboxyl group include: acrylic Acid (AA), methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, lauric acid, 2- (meth) acryloyloxyethyl succinate, monohydroxyethyl maleate (meth) acrylate, monohydroxyethyl fumarate (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 1, 2-cyclohexanedicarboxylic acid monohydroxyethyl (meth) acrylate, (meth) acrylic acid dimer, and ω -carboxy-polycaprolactone mono (meth) acrylate, and the like.
Examples of the monomer having a glycidyl group include: glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, 3, 4-epoxycyclohexyl vinyl ether, (meth) allyl glycidyl ether, and 3, 4-epoxycyclohexyl (meth) allyl ether.
Examples of the monomer having an amide group or an N-substituted amide group include: acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-t-butylacrylamide, N-octylacrylamide, diacetone acrylamide, and the like.
Examples of the monomer having a tertiary amino group include: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and the like.
The hydroxyl value of component a, i.e., the solid content, is preferably 1 (mgKOH/g) or more, more preferably 3 (mgKOH/g) or more, further preferably 20 (mgKOH/g) or less, and further preferably 15 (mgKOH/g) or less. When the hydroxyl value of the component a is adjusted to be within the above range, both appropriate adhesive force and heat resistance can be easily achieved.
The hydroxyl value of the component a can be calculated by the following formula. In the case where a plurality of hydroxyl group-containing monomers are contained, the hydroxyl value of each monomer having a hydroxyl group is calculated by the following formula, and the total value is defined as the hydroxyl value of the component a.
(calculation formula 1)
Hydroxyl value (mgKOH/g) = { (A1/100) ÷ B1 }. Times.C 1 × D1 × 1000
In the above-mentioned formula 1, the,
a1 is a hydroxyl group-containing monomer used in the component a, and the content (mass%) of all monomers used in the component a.
B1 is the molecular weight of the hydroxyl group-containing monomer used in component a.
C1 is the number of hydroxyl groups in one molecule of the hydroxyl group-containing monomer.
D1 is the molecular weight of potassium hydroxide (KOH).
The polymerization method of the component a is not particularly limited. As the polymerization method, known methods such as solution polymerization, emulsion polymerization, suspension polymerization, block polymerization, and the like can be used. Solution polymerization is preferred. In the solution polymerization, a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as needed are generally charged into a polymerization tank, and a heating reaction is carried out for several hours while stirring in a nitrogen gas flow or at the reflux temperature of the organic solvent. In this case, at least a part of the organic solvent, the monomer and the polymerization initiator may be added in this order.
Component b-
As the component b, for example, those having a mass average molecular weight (Mw 2) of 10 ten thousand or more, preferably 20 ten thousand or more, and a glass transition temperature (Tg 2) of-30 ℃ or less, preferably-35 ℃ or less are used. When Mw2 is less than 20 ten thousand, there is a problem that the peeling force at the time of adhesive residue and re-peeling becomes large, and the reason why Tg2 is set to-30 ℃ or less is that the adhesive force starts to be expressed when the glass transition temperature (Tg) of the adhesive is increased by 30 ℃, that is, (Tg +30 ℃). Further, if Mw2 is too high, a problem of an abnormal compatibility is likely to occur. Therefore, as component b, it is preferable to satisfy the above conditions, i.e., mw2 of 10 ten thousand or more and Tg2 of-30 ℃ or less, and further satisfy the conditions that Mw2 is 200 ten thousand or less, preferably 100 ten thousand or less, and/or Tg2 is-70 ℃ or more, preferably-60 ℃ or more.
The dispersity (Mw 2/Mn 2) of the component b represented by the ratio of Mw2 to the number average molecular weight (Mn 2) is not particularly limited, and is preferably from 1 to 30 from the viewpoint of adhesiveness.
The component b has a hydroxyl group-containing monomer as a monomer unit constituting the polymer, similarly to the component a. As the hydroxyl group-containing monomer, those explained in the above-mentioned component a can be cited. These may be used alone or in combination of two or more.
The hydroxyl group-containing monomer is preferably contained in the component b in an amount of 0.5 mass% or more, more preferably 1 mass% or more, as a monomer unit constituting the polymer. By setting the lower limit of the content ratio, which is the ratio of the hydroxyl group-containing monomer, to the above value, the pressure-sensitive adhesive layer can be appropriately hardened, and as a result, an appropriate cohesive force can be easily obtained. The component b preferably contains a hydroxyl group-containing monomer in an amount of 5% by mass or less, more preferably 3% by mass or less, as a monomer unit constituting the polymer. By setting the upper limit of the content of the hydroxyl group-containing monomer to the above value, the pressure-sensitive adhesive layer can be softened appropriately, and an advantage of an appropriate adhesive force can be obtained.
The component b is the same as the component a in that the monomer unit constituting the polymer is a hydroxyl group-containing monomer, preferably an alkyl (meth) acrylate having 1 to 20 carbon atoms and an alkyl group, from the viewpoint of easily developing a desired adhesive force.
As the alkyl (meth) acrylate in which the alkyl group has 1 to 20 carbon atoms, those described in the above-mentioned component a can be cited. Among them, from the viewpoint of further improving the adhesion, one or more (meth) acrylates having an alkyl group and having 1 to 8 carbon atoms are preferable. The (meth) acrylate having an alkyl group with 1 to 8 carbon atoms preferably contains one or more of 2-ethylhexyl (meth) acrylate (EHMA, EHA), and more preferably 2-ethylhexyl acrylate (EHA), from the viewpoint of facilitating both hardness and softness. These may be used alone or in combination of two or more.
The component b is an alkyl (meth) acrylate having an alkyl group and having 1 to 20 carbon atoms, and is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or less, and further preferably 65% by mass or less, as a monomer unit constituting the polymer. When the content of the alkyl (meth) acrylate is within the above range, the pressure-sensitive adhesive layer can be provided with sufficient adhesive force to prevent the pressure-sensitive adhesive layer from being easily detached from an adherend while maintaining excellent peelability.
The component b may contain a hydroxyl group-containing monomer and a monomer other than the alkyl (meth) acrylate as a monomer unit constituting the polymer in the same range as the component a in which the effect of the present invention is exhibited. In this case, the content ratio, which is the total ratio of the constituent unit derived from the hydroxyl group-containing monomer and the constituent unit derived from the alkyl (meth) acrylate, is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more, based on 100% by mass of the total constituent monomer units of the component b.
Examples of the other monomer include the components described in the above-mentioned component a. These may be used alone or in combination of two or more.
The hydroxyl value of component b, i.e., the solid content, is preferably 1 (mgKOH/g) or more, more preferably 3 (mgKOH/g) or more, further preferably 20 (mgKOH/g) or less, and further preferably 15 (mgKOH/g) or less. By adjusting the hydroxyl value of the component b within the above range, it is possible to easily achieve both appropriate adhesive force and heat resistance. The hydroxyl value of component b can be calculated by the above-mentioned calculation method for component a.
The polymerization method of the component b is not particularly limited, as in the component a. Solution polymerization is preferred.
The mixing ratio of component a and component b-
(A1) The mass ratio of component a to component b:1, preferably more than 1.0, more preferably 1.5 or more, and further preferably 2.0 or more. By setting the lower limit of the mass ratio of the component a to the above value, advantages of high cohesive force and sufficient film forming performance of the coating film can be enjoyed. On the other hand, the mass ratio of component a to component b:1 is preferably less than 9.0, more preferably 4.0 or less, and still more preferably 2.5 or less. By setting the upper limit of the mass ratio of the component a to the above value, the advantage of appropriate adhesive force can be enjoyed.
The difference in glass transition temperatures (Tg 1-Tg 2) between component a and component b-
When the component a and the component b are selected from the viewpoint of the cohesive force, the adhesive property and the compatibility, the difference between Tg1 and Tg2, i.e., tg1-Tg2, is preferably 10 ℃ or more, more preferably 30 ℃ or more. Thus, the adhesive sheet has high heat resistance and also has an appropriate adhesive property.
In addition to or in addition to this, when the component a and the component b are selected, mw1/Mw2, which is the ratio of Mw1 to Mw2, is, for example, 0.05 to 20, preferably 0.2 to 5. This makes it possible to form a pressure-sensitive adhesive layer that is less likely to cause adhesive residue while ensuring compatibility.
Polymerization mode-
The polymerization system of the component a and the component b may be a random copolymer or a block copolymer. Further, the polymer may be used singly or in combination of two or more.
2-1-2. (active energy ray-reactive compound)
The active energy ray-reactive compound used for forming the composition is a material which is polymerized and cured by irradiation with active energy rays (described above) in the presence of a photopolymerization initiator. In the composition according to one embodiment, the active energy ray-reactive compound is required to be in the form of a monomer, specifically, (B) an active energy ray-reactive monomer having 3 or more radical-reactive groups in one molecule. (B) May be ultraviolet curable which is cured by irradiation with ultraviolet light. Since the pressure-sensitive adhesive layer contains (B), the pressure-sensitive adhesive layer can be cured by polymerization of (B) by irradiation with active energy rays after the pressure-sensitive adhesive layer is used for bonding to an adherend, and the adhesive strength of the pressure-sensitive adhesive layer is lowered, so that the pressure-sensitive adhesive sheet can be easily peeled from the adherend.
Even if there are 3 or more radical-reactive groups in one molecule, if it is an active energy ray-reactive oligomer or polymer having a large molecular weight, there arises a problem of incompatibility with (A). Even in the case of an active energy ray-reactive monomer, if the radical-reactive group is a bifunctional or monofunctional monomer having less than 2, there is a problem that the peeling force is not sufficiently reduced when the active energy ray is irradiated.
Since (B) is a trifunctional or higher active energy ray-reactive monomer having three or more radical-reactive groups, the crosslinking reaction proceeds during the polymerization of (B), and the adhesive layer can be effectively cured to reduce the adhesive force. The number of the reactive groups contained in (B) is preferably 4 or more, more preferably 5 or more, from the viewpoint of more effectively curing the adhesive layer to reduce the adhesive force. From the viewpoint of more effectively curing the pressure-sensitive adhesive layer to lower the adhesive force, the amount of the active energy ray-reactive monomer having 5 or more radical-reactive groups in one molecule is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass, relative to 100% by mass which is the total amount of (B).
Radical reactive group means a functional group that reacts and cures by a radical. Examples of the solvent include, but are not limited to: acrylate, methacrylate, vinyl, allyl, thiol, and the like. The radical-reactive group is preferably an acrylate group or a methacrylate group, and more preferably an acrylate group, from the viewpoint of the curing speed when the active energy ray is irradiated. (meth) acrylate refers to both acrylate and methacrylate. The same applies to other similar terms.
Examples of the active energy ray-reactive monomer having three or more functions include: trifunctional types such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, epoxypropylene-modified trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, and e-caprolactone-modified tris (2- (meth) acryloyloxyethyl) isocyanurate; tetrafunctional types such as diglycerin tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate; pentafunctional types such as propionic acid-modified dipentaerythritol penta (meth) acrylate; hexafunctional types such as dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among these, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane tri (meth) acrylate are preferable from the viewpoint of improving the compatibility with (a), and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferable.
One kind may be used alone, or two or more kinds may be used in combination.
(B) The molecular weight of (b) is preferably from 200 to 1500, more preferably from 250 to 1000, still more preferably from 400 to 700. (B) The viscosity of (A) is about 300 to 10000 mPas, preferably 5000 to 8000 mPas, at 25 ℃.
The mass ratio of (B) in the composition relative to (A): 1, more than 0.1 is preferable, and 0.2 or more is preferable, 0.4 or more is more preferable, and 0.5 or more is particularly preferable. By setting the lower limit of the mass ratio of (B) to the above value, the advantage of reducing the peeling force when the active energy ray is irradiated can be enjoyed. (B) The mass ratio of (A) to (A) is preferably 2.0 or less, more preferably 1.0 or less, still more preferably 0.8 or less, particularly preferably 0.6 or less. By setting the upper limit of the mass ratio of (B) to the above value, the advantage of sufficient film forming performance can be enjoyed.
2-1-3. (crosslinking agent)
The crosslinking agent (C) used for forming the composition means a substance capable of crosslinking (A) to form a crosslinked polymer. By forming the crosslinked polymer, advantages can be enjoyed such that thermal deterioration of the binder component is suppressed when the crosslinked polymer is used in a process under high-temperature conditions, and the crosslinked polymer is easily peeled off when irradiated with active energy rays.
Examples of (C) include: isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents and amine crosslinking agents. Among them, isocyanate-based crosslinking agents are preferable.
Examples of the isocyanate-based crosslinking agent include: lower aliphatic polyisocyanates such as tetramethylene diisocyanate (BDI) and hexamethylene diisocyanate (also known as HDI); alicyclic isocyanates such as cyclopentadienide, cyclohexanediisocyanate, and isophorone diisocyanate; aromatic isocyanates such as 2, 4-tolylene diisocyanate (also known as 2, 4-TDI), 4' -diphenylmethane diisocyanate, and xylylene diisocyanate; and isocyanate adducts such as trimethylolpropane/hexamethylene diisocyanate trimer adduct having a product name of "Coronate L", manufactured by Nippon polyurethane industries, trimethylolpropane/hexamethylene diisocyanate trimer adduct having a product name of "Coronate HL", manufactured by Nippon polyurethane industries, isocyanurate of hexamethylene diisocyanate having a product name of "Cornate HX", manufactured by Nippon polyurethane industries, and the like.
The content of (C), i.e., the total amount, in the composition is not particularly limited, since it varies depending on the kind of the crosslinking agent, the number of functional groups, and the like, but is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, more preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, relative to 100 parts by mass of (a). By setting the content of (C), there are advantages in preventing residual gum and in easily adjusting the adhesive force.
2-1-4. (photopolymerization initiator)
The photopolymerization initiator used for forming the composition initiates the polymerization of (B) by irradiation with active energy rays (described above). In the composition according to one embodiment, it is necessary to use a specific, specifically, (D) α -hydroxyacetophenone-based photopolymerization initiator as the photopolymerization initiator. Since, when a photopolymerization initiator other than the α -hydroxyacetophenone type, for example, a benzylketal type photopolymerization initiator (for example, 2-dimethoxy-1, 2-diphenylethan-1-one) is used, the present inventors have found that, although the mechanism is not clear, when used in a process under high temperature conditions, troubles such as thermal deterioration of the binder component are likely to occur.
Examples of (D) include: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -phenyl } -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like. Among them, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) is preferable.
(D) One kind may be used alone, or two or more kinds may be used in combination.
As (D), a suitably synthesized product may be used, or a commercially available product may be used. Examples of commercially available products include: 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, "OMNIRAD659" from IGM RESINS; oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), "ESACURE ONE" or "ESACURE KIP160" from IGM RESINS, and the like.
The content of (D), i.e., the total amount, in the composition is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, further preferably 20 parts by mass or less, and further preferably 15 parts by mass or less, relative to 100 parts by mass of (B). When the content of (D) is within the above range, thermal deterioration of the adhesive component during use in the step under high temperature conditions is suppressed, and curing by active energy rays is sufficiently performed, whereby an adhesive layer having suitably reduced adhesive strength can be easily obtained.
2-1-5. (optional ingredients)
The composition according to one embodiment may contain any component (E) other than the above components (a), (B), (C), and (D) within a range not to impair the effects of the present invention. Examples of the component (E) include components known as additives for adhesives. For example, light stabilizers such as plasticizers, antioxidants, antistatic agents, leveling agents, metal corrosion inhibitors, silane coupling agents, ultraviolet absorbers, hindered amine compounds, and the like can be selected as necessary. In addition, dyes and pigments may also be added for coloring purposes.
As the plasticizer, for example, a non-functional acrylic polymer can be used. As the non-functional acrylic polymer, there may be mentioned: a polymer composed of only acrylic monomer units having no functional group other than an acrylate group, and a polymer composed of acrylic monomer units having no functional group other than an acrylate group and non-acrylic monomer units having no functional group. Since the non-functional acrylic polymer is not crosslinked, the adhesion is not affected.
As the antioxidant, there may be mentioned: a phenol type antioxidant (preferably a hindered phenol type antioxidant), an amine type antioxidant, a lactone type antioxidant, a phosphorus type antioxidant, a sulfur type antioxidant, and the like. When an antioxidant is mixed, a phenol-based antioxidant is preferably used from the viewpoint of durability such as heat resistance and weather resistance of the cured film. These antioxidants may be used singly or in combination of two or more.
As the metal corrosion inhibitor, from the viewpoint of compatibility and effectiveness of the binder, benzotriazole-based resins are cited as preferable examples.
Examples of the silane coupling agent include: mercaptoalkoxysilane compounds such as mercapto-substituted alkoxy oligomers, (meth) acryloyloxypropylmethoxysilane, and the like. Examples of the ultraviolet absorber include: benzotriazole compounds, benzophenone compounds, triazine compounds, and the like.
The composition according to one embodiment can be prepared or produced by mixing the components (a), (B), (C), and (D) and, if necessary, adding (E). The order of mixing the components is not particularly limited as long as the components are uniformly mixed.
2-2.< thermoset >
The active energy ray-curable adhesive is formed from a thermoset of the coating liquid, which is the composition. Since the pressure-sensitive adhesive layer is composed of the active energy ray-curable pressure-sensitive adhesive, the production of the pressure-sensitive adhesive layer includes a heating step.
By forming the pressure-sensitive adhesive layer composed of the active energy ray-curable pressure-sensitive adhesive from the heat-cured product of the composition, the heat-cured products of (a) and (C) are present in the pressure-sensitive adhesive layer in addition to (B) and (D), and according to this structure, even in a step under a high temperature condition of, for example, 180 ℃ for 20 minutes, a decrease in cohesive force due to heat deterioration of the pressure-sensitive adhesive component can be suppressed. As a result, the adhesive property of the pressure-sensitive adhesive layer can be sufficiently reduced by irradiation with active energy rays after the step under high temperature conditions, and adhesive residue is less likely to occur on the adherend. This finding is the first finding of the present inventors.
The composition may contain a solvent. In this case, the solvent is used to improve the coatability of the above composition. Examples of the solvent include: hydrocarbons such as toluene; halogenated hydrocarbons; alcohols; ethers; ketones such as methyl isobutyl ketone; esters; polyhydric alcohols such as ethylene glycol monomethyl ether and derivatives thereof.
When the composition contains a solvent, the composition is heated to remove the solvent and form a pressure-sensitive adhesive layer composed of an active energy ray-curable pressure-sensitive adhesive.
< production example of adhesive sheet >
An example of manufacturing the pressure-sensitive adhesive sheet according to an embodiment is as follows. First, the composition according to an embodiment is applied to one surface of a release sheet (in the case of no substrate) or a substrate (in the case of a substrate) to form a coating layer having the composition. The coating method may be a known method, and examples thereof include: roll coating, twin roll coating (comma coater), slit coating (die coater), reverse coating, screen printing, gravure coating, and the like.
Subsequently, the coating layer is dried and cured by heating, thereby forming an adhesive layer of an active energy ray-curable adhesive formed of a thermally cured product of the composition. The conditions for heating and drying may be appropriately adjusted depending on the thickness of the coating layer, the heat resistance of the release sheet or the substrate to be coated, and the like. For example, the temperature is preferably from 100 ℃ to 200 ℃ for from 0.5 minutes to 10 minutes, more preferably from 120 ℃ to 180 ℃ for from 1 minute to 5 minutes.
In one embodiment, a thermoset product of the composition obtained after heat drying and curing may be stored, i.e., left to stand for a predetermined time. That is, the production of the pressure-sensitive adhesive layer may include a maintenance step in addition to the heating step. By maintaining the pressure-sensitive adhesive layer after heating and drying, even if the uncrosslinked portions of (a) and (C) remain, the crosslinking reaction can be completed, and this contributes to stabilization of the performance of the pressure-sensitive adhesive layer. The maintenance conditions are, for example, 20 ℃ to 60 ℃ inclusive and 3 days to 2 weeks inclusive.
The thickness of the pressure-sensitive adhesive layer, that is, the thickness after heat drying, is not particularly limited and may be appropriately set according to the application, and is preferably 5 μm to 200 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, the extrusion and sticking of the pressure-sensitive adhesive can be suppressed while maintaining the pressure-sensitive adhesive performance, and the processability can be improved. After the adhesive layer is formed, a release sheet may be affixed to the exposed surface of the adhesive layer by a known method as needed.
< example of Using pressure-sensitive adhesive sheet >
An example of use of the adhesive sheet according to an embodiment is as follows. First, the adhesive sheet is attached to the surface of an adherend so as to face the exposed surface of the adhesive layer. Next, the pressure-sensitive adhesive sheet attached to the surface of the adherend is irradiated with active energy rays, so that the adhesive strength of the pressure-sensitive adhesive layer is reduced. Various conditions such as the irradiation intensity (mJ/cm 2) of the active energy ray to be irradiated and the irradiation time (sec) are not particularly limited, and can be set as needed. Finally, the pressure-sensitive adhesive sheet with reduced adhesive strength is removed from the adherend.
As described above, the composition according to one embodiment contains the above (B), which is a specific active energy ray-reactive compound, and the above (D), which is a specific photopolymerization initiator. Therefore, the adhesive layer of the active energy ray-curable adhesive formed from the heat-cured product of the composition is polymerized and cured by irradiation with active energy rays, and as a result, the adhesive strength after irradiation is effectively reduced compared to that before irradiation with active energy rays.
The pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet according to one embodiment has an appropriate adhesive force to an adherend before being irradiated with an active energy ray, and can be adhered to the adherend with an adhesive force that is not easily peeled off in various production steps including: a process for producing a substrate such as a thin electronic circuit board, which includes mounting of components and processing of members; manufacturing process of electronic component and semiconductor component. On the other hand, after irradiation with active energy rays, the adhesive layer is effectively reduced in adhesive strength by polymerization of the above (B), and can be easily peeled from an adherend.
< adhesive force of adhesive layer >
The adhesive force of the adhesive layer provided in the adhesive sheet according to one embodiment before and after irradiation with active energy rays and the rate of decrease in the adhesive force after irradiation with active energy rays before and after irradiation with active energy rays can be appropriately designed according to the application and the use conditions. In particular, when used in various manufacturing processes (described above), the following design is preferable in order to withstand the process under high temperature conditions.
The adhesive force 1 of the pressure-sensitive adhesive layer to polyethylene terephthalate at 23 ℃, i.e., the initial adhesive force X1, is preferably 0.5 (N/25 mm) or more, more preferably 2.0 (N/25 mm) or more. If X1 is less than 0.5 (N/25 mm), the adhesive force is insufficient, the adhesiveness to the adherend is deteriorated, and there is a possibility that the workability is deteriorated.
The adhesive force 2 of the pressure-sensitive adhesive layer to polyethylene terephthalate at 23 ℃ after irradiation with active energy rays, i.e., the adhesion force X2 after irradiation, is preferably 0.2 (N/25 mm) or less, more preferably 0.05 (N/25 mm) or less. If X2 exceeds 0.2 (N/25 mm), peeling from the adherend becomes difficult, which may cause troubles such as a decrease in workability.
The adhesive force 2/adhesive force 1, which is the reduction rate of the adhesive force of the adhesive layer, is not particularly limited, but is preferably 0.6 or less, and more preferably 0.4 or less.
After heating at 180 ℃ for 20 minutes and irradiation with active energy rays, the adhesive force 3 of the adhesive layer to polyethylene terephthalate at 23 ℃, i.e., the adhesive force X3 after heating and irradiation, is preferably 0.3 (N/25 mm) or less, more preferably 0.1 (N/25 mm) or less. If X3 exceeds 0.3 (N/25 mm), peeling from the adherend becomes difficult, and there is a possibility that the workability is deteriorated.
The "adhesive force to polyethylene terephthalate" refers to an adhesive force measured by bonding (bonding condition: 2kg roller 1 reciprocating) an adhesive layer of an adhesive sheet (width: 25 mm. Times.100 mm) to a polyethylene terephthalate film (thickness: 50 μm), leaving the adhesive sheet in an environment of 23 ℃ and humidity 65% for 20 minutes, and then subjecting the adhesive sheet to a tensile test (peeling speed: 300mm/min, peeling angle: 180 ℃ C.) on the polyethylene terephthalate film.
< uses of adhesive sheets >
As described above, the adhesive sheet according to one embodiment of the present invention includes a process for manufacturing a substrate such as a thin electronic circuit board, and includes a process for mounting components and processing members, and a process for manufacturing electronic components and semiconductor components. Can be used in various production processes, including, for example, a process under a high temperature condition of 180 ℃ for 20 minutes.
Examples
Hereinafter, the present invention will be specifically described based on experimental examples including examples and comparative examples, but the present invention is not limited to these experimental examples. In the following description, "part" means "part by mass" and "%" means "% by mass".
[ Components of the composition ]
The following base polymers were prepared.
A1a: acrylic resin having hydroxyl group
(glass transition temperature: 0 ℃ C., mass-average molecular weight: 30 ten thousand)
A1b: acrylic resin having hydroxyl group
(glass transition temperature: -42 ℃ C., mass average molecular weight 39 ten thousand)
A1c: acrylic resin having no hydroxyl group
(glass transition temperature: -7 ℃ C., mass average molecular weight 15 ten thousand)
In addition, the "A1a" is a copolymer of Ethyl Methacrylate (EMA), ethyl Acrylate (EA), acrylonitrile (AN), and 2-hydroxyethyl methacrylate (HEMA), and the mass ratio is EMA: EA: AN: HEMA =46:47:5:2.
the "A1b" is a copolymer of 2-ethylhexyl acrylate (EHA), vinyl Acetate (VA), and 2-hydroxyethyl methacrylate (HEMA), and the mass ratio of EHA: VA: HEMA = 63.7.
The "A1c" is a copolymer of 2-ethylhexyl acrylate (EHA), methyl Acrylate (MA), acrylic Acid (AA), and the mass ratio is EHA: MA: AA = 25.
The following active energy ray-reactive compounds were prepared.
B1: active energy ray reactive monomer
(dipentaerythritol hexaacrylate, 6 acrylate groups)
B2: active energy ray reactive monomer
(alkoxy polyalkylene glycol acrylate, 1 acrylate group)
B4: active energy ray reactive oligomer
(urethane acrylate, 9 acrylate groups, mass average molecular weight 0.2 ten thousand)
The following crosslinking agents were prepared.
C1: cross-linker 1 (HDI series, hexamethylene diisocyanate trimer)
The following photopolymerization initiators were prepared.
D1: alpha-hydroxyalkyl-benzophenone photopolymerization initiator
(oligo [ 2-hydroxy-2-methyl- [1- (methylvinyl) phenyl ] propanone ])
D2: benzyl ketal photopolymerization initiator
(2, 2-dimethoxy-1, 2-diphenylethan-1-one)
The following were prepared as arbitrary components.
E1: antioxidant (hindered phenols)
(pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ])
E4: solvent (mixed solvent of toluene and methyl isobutyl ketone)
[ Experimental examples 1 to 22]
1. Preparation of the composition
The above-described components were uniformly mixed and dissolved in the solid content ratios (in terms of mass) shown in tables 1 and 2, to prepare adhesive compositions (coating liquids). The total solid content of each coating liquid was adjusted to 30% by mass.
2. Production of adhesive sheet
The coating liquids obtained in the respective experimental examples were applied to one surface of a substrate (PET film having a thickness of 12 μm) by means of a baker's type applicator so that the thickness of the formed pressure-sensitive adhesive layer was about 10 μm, and then subjected to heat treatment at 160 ℃ for 2 minutes to crosslink, i.e., to form a cured product, thereby forming a pressure-sensitive adhesive layer on one surface of the substrate film. Then, a separator (a PET film having a thickness of 25 μm and having one surface subjected to a release treatment) was bonded to the surface of the pressure-sensitive adhesive layer, and the release-treated surface was brought into contact with the surface. Then, the adhesive sheets (substrate/adhesive layer/separator) of the respective experimental examples were stored at 40 ℃ and 50% rh for 5 days, i.e., maintained to terminate the crosslinking reaction.
3. Evaluation of
For the adhesive sheets obtained in the respective experimental examples, the physical properties of the adhesive layer were evaluated or measured by the following methods. The results are shown in tables 1 and 2.
(2-1) initial adhesion force (X1)
The pressure-sensitive adhesive sheet obtained in each experimental example was cut into a size of 25mm in width × 100mm in length, and the separator was peeled from the obtained sheet as a test piece (substrate/pressure-sensitive adhesive layer). A polyethylene terephthalate film (LUMIRROR S10, thickness 50 μm, width 30mm, manufactured by Toray corporation) was attached to the entire surface of the adhesive layer of the test piece, and the roller was reciprocated 1 time at 23 ℃ and 65% humidity by 2 kg. The evaluation samples obtained as above were subjected to a tensile test. After the sample for evaluation was set in a tensile tester, it was left to stand in an environment of 23 ℃ and 65% humidity for 20 minutes, and then, a tensile test was started. The conditions of the tensile test were peel angle 180 ° and peel speed (pull rate): 300mm/min. The load when the PET film was peeled from the adhesive sheet was measured, and the maximum load at that time was used as the initial adhesive force X1 of the adhesive sheet, and evaluated according to the following criteria.
Very good: 2.0 (N/25 mm) or more (excellent in adhesiveness)
O: less than 2.0 (N/25 mm) and not less than 0.5 (N/25 mm) (good adhesiveness)
X: less than 0.5 (N/25 mm) (insufficient adhesiveness)
(2-2) adhesive force after irradiation (X2)
The evaluation sample obtained by the same procedure as in (2-1) was irradiated with ultraviolet rays (irradiation intensity: 220mW/cm2, integrated light amount: 190mJ/cm 2) from the substrate side in the same atmosphere (temperature 23 ℃ C., humidity 65%), and then subjected to a tensile test in the same manner as in (2-1). Then, the load at the time of peeling the PET film from the adhesive sheet was measured, and the maximum load at this time was taken as the adhesive force X2 after irradiation of the adhesive sheet, and evaluated according to the following criteria.
Very good: 0.05 (N/25 mm) or less (excellent in peelability)
O: greater than 0.05 (N/25 mm) and not greater than 0.2 (N/25 mm) (good peelability)
X: greater than 0.2 (N/25 mm) (insufficient peeling)
(2-3) adhesive force after heating and irradiation (X3)
The sample for evaluation obtained by the same procedure as in (2-1) above was heated at 180 ℃ for 20 minutes and then cooled in the same environment (temperature 23 ℃, humidity 65%). Then, in the same manner as in (2-2), a tensile test was performed after irradiation of ultraviolet light from the substrate side. Then, the load at the time of peeling the PET film from the adhesive sheet was measured, and the maximum load at this time was evaluated as the adhesive force X3 after heating and irradiation of the adhesive sheet according to the following criteria.
Very good: 0.1 (N/25 mm) or less (excellent in peelability)
O: more than 0.1 (N/25 mm) and not more than 0.3 (N/25 mm) (good peelability)
X: greater than 0.3 (N/25 mm) (insufficient peeling)
(2-4) cull (X4)
In (2-3) above, the adhesive sheet-bonded surface of the PET film from which the adhesive sheet was peeled was observed with a microscope (magnification 150 times), and the presence or absence of the adhesive residue X4, which is an adhesive layer component remaining adhered to the PET film, was examined, specifically, the number of adhered matters having a particle diameter (length of the longest side in the case of irregular shape) of 1000 μm or more was counted and evaluated according to the following criteria.
O: the number of attachments is less than 5 (no adhesive residue)
X: the number of attachments is more than 5 (with adhesive residue)
(2-5) film Forming Property (adhesion to substrate)
The adhesion between the pressure-sensitive adhesive layer and the base material was visually observed for the test piece obtained by the same procedure as in (2-1) above, and evaluated according to the following criteria.
O: with peeling (good sealing)
X: no peeling (sealing property deficiency)
4. Investigation of
As shown in tables 1 and 2, when (a) does not contain a substance having a hydroxyl group in the liquid formulation (experimental example 12), one or more of the adhesive force (X1, X2, X3), the residual gum (X4), and the film forming property of the film cannot be satisfied.
Even if (a) contains a substance having a hydroxyl group, if (B) is not contained (experimental example 13), or if (B) is contained, the ratio of (a): when the mass ratio of (B) in 1 is 0.1 or less (experimental example 1) or more than 2.0 (experimental example 10), one or more of the adhesive force (X1, X2, X3), the residual gum (X4) and the film forming property of the film cannot be satisfied.
Even if (A) contains a substance having a hydroxyl group, and the ratio of (A): the mass ratio range of (B) of 1 is suitably more than 0.1 and 2.0 or less, but if (B) contained is less than trifunctional (experimental example 14), or (B) is trifunctional or more but not a monomer (experimental example 15), or (C) is not contained (experimental example 18), or (D) is not contained (experimental example 16), or (D) is contained but not an α -hydroxyalkylbenzone (experimental example 17), one or more of the adhesive force (X1, X2, X3), the residual gum (X4), and the film forming property cannot be satisfied.
In contrast, in the case where (a) contains a substance having a hydroxyl group, the ratio of (a): when the mass ratio of (B) in 1 is more than 0.1 and 2.0 or less, and (B) is a trifunctional or higher monomer, and (C) and (D) contain an α -hydroxyalkylbenzone (experimental examples 2 to 9 and 11), the adhesive force (X1, X2 and X3), the residual gum (X4) and the film forming property of the film can be satisfied.
In addition, (a) is composed of acrylic resin (A1) having hydroxyl group, and (A1) is composed of substance (A1 a) corresponding to component a and substance (A1 b) corresponding to component b (experimental examples 4, 19 to 22), when the mass ratio of (A1 b) to (A1 a): 1 is centered on 2.3 (experimental example 4), and the value is increased to 9.0 (experimental example 22, reference example), the evaluation result itself of the adhesive force (X1) is good (good), but when a large force is applied at the time of peeling, the sheet is deformed (zipping), and the peeling force tends to be weak. On the other hand, when the value is reduced to 1.0 (experimental example 19, reference example), the adhesive force (X3) and film forming property of the film tend to deteriorate. In contrast, when the mass ratio of (A1 b) to (A1 a) is appropriate, that is, more than 1.0 and less than 9.0 (experimental examples 4, 20, and 21), the above-described problem does not occur, and satisfactory performance can be obtained.
Claims (8)
1. An adhesive sheet having an adhesive layer whose adhesive force is reduced by irradiation with active energy rays, wherein,
the adhesive layer is formed of a thermosetting adhesive composition and is composed of an active energy ray-curable adhesive containing a thermal reaction product of (A) and (C),
the adhesive composition comprises at least (A), (B), (C) and (D), and, with respect to (A): the mass ratio of (B) in (1) is more than 0.1 and not more than 2.0,
(A) An adhesive base polymer having a hydroxyl group,
(B) An active energy ray-reactive monomer having 3 or more radical-reactive groups in one molecule,
(C) Is a cross-linking agent,
(D) An alpha-hydroxyalkylphenone-based photopolymerization initiator.
2. The adhesive sheet according to claim 1, wherein,
(A) Comprises (A1) of a polymer,
(A1) Is an acrylic resin having hydroxyl groups.
3. The adhesive sheet according to claim 2, wherein,
(A1) Has a glass transition temperature in the range of-70 ℃ to 40 ℃ inclusive, and contains, as constituent components, a component a and a component b, the ratio of component a to component b being: the mass ratio of 1 is more than 1.0 and less than 9.0,
the component a is a (meth) acrylate polymer having a glass transition temperature of-10 ℃ or higher,
The component b is a (meth) acrylate polymer having a glass transition temperature of-30 ℃ or lower.
4. The adhesive sheet according to any one of claims 1 to 3,
(B) Contains an active energy ray-reactive monomer having 5 or more radical-reactive groups in one molecule.
5. The adhesive sheet according to any one of claims 1 to 3,
(D) Containing oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).
6. The adhesive sheet according to any one of claims 1 to 3,
(D) The amount of the (B) is 0.1 to 20 parts by mass based on 100 parts by mass of the (B).
7. The adhesive sheet according to any one of claims 1 to 3,
the adhesive force of the pressure-sensitive adhesive layer to polyethylene terephthalate at 23 ℃, that is, the initial adhesive force Xl, is 0.5 (N/25 mm) or more, and after heating at 180 ℃ for 20 minutes and further irradiation with active energy rays, the adhesive force to polyethylene terephthalate at 23 ℃, that is, the adhesive force X3 after heating and irradiation, is 0.3 (N/25 mm) or less.
8. The adhesive sheet according to any one of claims 1 to 3,
it is suitable for use in high temperature environment of 150 deg.c.
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| JP2021055428A JP7466487B2 (en) | 2021-03-29 | 2021-03-29 | Adhesive sheet |
| JP2021-055428 | 2021-03-29 |
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| CN115141551A true CN115141551A (en) | 2022-10-04 |
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| TW (1) | TW202300606A (en) |
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| Publication number | Publication date |
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| TW202300606A (en) | 2023-01-01 |
| JP7466487B2 (en) | 2024-04-12 |
| JP2022152600A (en) | 2022-10-12 |
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