WO2023276944A1 - Pressure-sensitive adhesive composition and protective sheet - Google Patents
Pressure-sensitive adhesive composition and protective sheet Download PDFInfo
- Publication number
- WO2023276944A1 WO2023276944A1 PCT/JP2022/025552 JP2022025552W WO2023276944A1 WO 2023276944 A1 WO2023276944 A1 WO 2023276944A1 JP 2022025552 W JP2022025552 W JP 2022025552W WO 2023276944 A1 WO2023276944 A1 WO 2023276944A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylenically unsaturated
- group
- meth
- unsaturated group
- polyisocyanate
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 76
- 230000001681 protective effect Effects 0.000 title claims description 78
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 111
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 111
- 229920000642 polymer Polymers 0.000 claims abstract description 107
- 150000001875 compounds Chemical class 0.000 claims abstract description 91
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims abstract description 56
- 150000003077 polyols Chemical class 0.000 claims abstract description 51
- 229920005862 polyol Polymers 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 132
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 79
- 239000000047 product Substances 0.000 claims description 48
- 239000000853 adhesive Substances 0.000 claims description 47
- 230000001070 adhesive effect Effects 0.000 claims description 47
- 239000012790 adhesive layer Substances 0.000 claims description 37
- 239000004014 plasticizer Substances 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- -1 a1 Chemical class 0.000 description 93
- 238000000034 method Methods 0.000 description 30
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 29
- 230000008859 change Effects 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229920002799 BoPET Polymers 0.000 description 15
- 238000011109 contamination Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 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 6
- 238000011282 treatment Methods 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 2
- XRBWKWGATZNBFW-UHFFFAOYSA-N 2-[2-(2-ethenoxyethoxy)ethoxy]ethanol Chemical compound OCCOCCOCCOC=C XRBWKWGATZNBFW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- FXPHJTKVWZVEGA-UHFFFAOYSA-N ethenyl hydrogen carbonate Chemical class OC(=O)OC=C FXPHJTKVWZVEGA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-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
- ATIAIEWDRRJGSL-UHFFFAOYSA-N 1,3-bis(2-hydroxyethyl)-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(CCO)C(=O)N(CCO)C1=O ATIAIEWDRRJGSL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 1
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- ONCICIKBSHQJTB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]propan-1-one Chemical compound CCC(=O)C1=CC=C(N(C)C)C=C1 ONCICIKBSHQJTB-UHFFFAOYSA-N 0.000 description 1
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- OPJWPPVYCOPDCM-UHFFFAOYSA-N 2-ethylhexyl octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CC)CCCC OPJWPPVYCOPDCM-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-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
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 1
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- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
Definitions
- the present invention relates to a protective sheet having a pressure-sensitive adhesive composition and a cured product of the pressure-sensitive adhesive composition.
- optical films are used for optical parts such as liquid crystal displays and touch panels for smartphones, personal computers, and televisions.
- a protective sheet is generally laminated on the surface of these optical films for the purpose of preventing contamination and damage during transportation, manufacturing, and inspection processes. This protective sheet is peeled off in a process after each of the processes described above.
- the protective sheet is required to have no so-called adhesive residue (removability), in which part of the adhesive layer constituting the protective sheet remains on the surface of the product (adherend) after peeling (Patent Document 1).
- adhesive residue removability
- the required performance has become stricter year by year.
- Various adhesives have been proposed to solve this problem.
- Patent Document 2 discloses a pressure-sensitive adhesive containing a urethane prepolymer having a hydroxyl group and a nonionic sulfonic acid ester, which satisfies removability and resistance to adherend contamination under high temperature and high humidity conditions.
- Patent Document 3 discloses a pressure-sensitive adhesive composition containing a base polymer and a silicone-based additive and/or a fluorine-based additive. It is described that the contamination of the adherend surface is sufficiently low.
- the present invention was made to solve the above problems, and an object thereof is to provide a protective sheet that is less likely to contaminate adherends. Another object of the present invention is to provide a pressure-sensitive adhesive composition suitable for providing the protective sheet. More specifically, the object is to provide a pressure-sensitive adhesive composition capable of suppressing change in the gel fraction of a cured product even under high-temperature and high-humidity conditions.
- the present invention includes the following aspects.
- the ethylenically unsaturated group-containing urethane polymer (A) is a polyoxyalkylene polyol (a1); a polyisocyanate (a2); A reaction product with a hydroxy group-containing ethylenically unsaturated compound (a3-1) or an isocyanato group-containing ethylenically unsaturated compound (a3-2),
- a pressure-sensitive adhesive composition wherein the polyisocyanate (a2) comprises an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group-free polyisocyanate (a2-2).
- the ethylenically unsaturated group-containing urethane polymer (A) is the polyoxyalkylene polyol (a1); and The hydroxy group-containing ethylenically unsaturated compound (a3-1) or the isocyanato group-containing ethylenically unsaturated compound (a3-2) is added to the end of the urethane prepolymer that is the reaction product of the polyisocyanate (a2).
- the pressure-sensitive adhesive composition according to [1] which is a urethane polymer.
- the polyoxyalkylene polyol (a1) is a compound having two hydroxy groups
- the ethylenically unsaturated group-containing urethane polymer (A) is a (meth)acryloyloxy group-containing urethane polymer
- the ethylenically unsaturated group-containing polyisocyanate (a2-1) is a (meth)acryloyloxy group-containing polyisocyanate
- the hydroxy group-containing ethylenically unsaturated compound (a3-1) is a hydroxy group-containing (meth)acrylate
- the pressure-sensitive adhesive composition according to any one of [1] to [3], wherein the isocyanato group-containing ethylenically unsaturated compound (a3-2) is an isocyanato group-containing (meth)acrylate.
- the ethylenically unsaturated group-containing urethane polymer (A) comprises the polyoxyalkylene polyol (a1), the polyisocyanate (a2), and the hydroxy group-containing ethylenically unsaturated compound (a3-1).
- the total amount of isocyanato groups in the polyisocyanate (a2) is 1.1 to 1.5 mol per 1 mol of the total amount of hydroxy groups in the polyoxyalkylene polyol (a1)
- the content ratio (molar ratio (a2-1)/(a2-2)) of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2) is The pressure-sensitive adhesive composition according to any one of [1] to [7], which is 0.03 to 0.8.
- the ethylenically unsaturated group-containing urethane polymer (A) comprises the polyoxyalkylene polyol (a1), the polyisocyanate (a2), and the isocyanato group-containing ethylenically unsaturated compound (a3-2).
- the pressure-sensitive adhesive composition is a reactant of The total amount of hydroxy groups in the polyoxyalkylene polyol (a1) is 1.1 to 1.5 mol per 1 mol of the total amount of isocyanato groups in the polyisocyanate (a2),
- the content ratio (molar ratio (a2-2)/(a2-1)) of the ethylenically unsaturated group-free polyisocyanate (a2-2) and the ethylenically unsaturated group-containing polyisocyanate (a2-1) is The pressure-sensitive adhesive composition according to any one of [1] to [8], which is 0.03 to 0.8.
- the polyfunctional (meth)acrylate (B2) is a tri- to hexa-functional (meth)acrylate.
- [13] 30 of the ethylenically unsaturated group-containing urethane polymer (A) is added to a total of 100% by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B) ⁇ 70 wt%, the pressure-sensitive adhesive composition according to any one of [1] to [12], wherein the ethylenically unsaturated group-containing monomer (B) is 30 to 70 parts by mass.
- Monofunctional (meth)acrylate (B1) is 25 to 60% by mass with respect to a total of 100% by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B) % and the polyfunctional (meth)acrylate (B2) is 1 to 30% by mass.
- the photopolymerization initiator (C) is 0.05 to 5 Parts by mass, the pressure-sensitive adhesive composition according to [15], wherein the plasticizer (D) is 1 to 30 parts by mass.
- a pressure-sensitive adhesive composition that can suppress changes in the gel fraction of the cured product even under high-temperature and high-humidity conditions. Therefore, it is possible to provide a protective sheet that has an adhesive layer that is a cured product of the adhesive composition and that does not easily stain an adherend.
- the (meth)acryloyl group is one or more selected from a group represented by the chemical formula CH 2 ⁇ CH—CO— and a group represented by the chemical formula CH 2 ⁇ C(CH 3 )—CO—.
- An allyl group means a group represented by the chemical formula CH 2 ⁇ CH—CH 2 —.
- the pressure-sensitive adhesive composition of the present embodiment comprises an ethylenically unsaturated group-containing urethane polymer (A) (hereinafter simply referred to as “(A) component”) and an ethylenically unsaturated group-containing monomer (B) (hereinafter simply Also referred to as “component (B)”) and a photopolymerization initiator (C) (hereinafter also simply referred to as “component (C)”).
- the pressure-sensitive adhesive composition may contain (D) a plasticizer (hereinafter also simply referred to as "component (D)”), if necessary.
- the ethylenically unsaturated group-containing urethane polymer (A) used in the present embodiment comprises a polyoxyalkylene polyol (a1), a polyisocyanate (a2), and a hydroxy group-containing ethylenically unsaturated compound (a3-1) or an isocyanato group. It is a reaction product with the containing ethylenically unsaturated compound (a3-2). Since the adhesive composition of the present embodiment contains the ethylenically unsaturated group-containing urethane polymer (A), even if the cured product of the adhesive composition is placed under high temperature and high humidity conditions, the cured product change in gel fraction can be suppressed.
- the ethylenically unsaturated group-containing urethane polymer (A) of the present embodiment includes, as the polyisocyanate (a2), an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group-free polyisocyanate (a2-1) described later. Since two types of isocyanate (a2-2) are used, these compounds are incorporated into the polymer chain in a mixed manner.
- the hydroxy group-containing ethylenically unsaturated compound (a3-1) or the isocyanato group-containing ethylenically unsaturated compound (a3-2) is used. Since the ethylenically unsaturated group-containing urethane polymer (A) has a complicated structure, it is difficult to unambiguously define it by a structural formula or the like.
- the ethylenically unsaturated group-containing urethane polymer (A) is preferably at least one of a vinyl group-containing urethane polymer, an allyl group-containing urethane polymer, and a (meth)acryloyloxy group-containing urethane polymer. More preferably, the ethylenically unsaturated group-containing urethane polymer (A) is a (meth)acryloyloxy group-containing urethane polymer.
- Examples of the ethylenically unsaturated group-containing urethane polymer (A) include the below-described first ethylenically unsaturated group-containing urethane polymer (A-1) or second ethylenically unsaturated group-containing urethane polymer (A-2).
- the first ethylenically unsaturated group-containing urethane polymer (A-1) used in the present embodiment comprises a polyoxyalkylene polyol (a1), a polyisocyanate (a2), and a hydroxy group-containing ethylenically unsaturated compound (a3-1 ).
- the first ethylenically unsaturated group-containing urethane polymer (A-1) is a urethane prepolymer that is a reaction product of a polyoxyalkylene polyol (a1) and a polyisocyanate (a2), and has hydroxyl groups at the terminals.
- the first ethylenically unsaturated group-containing urethane polymer (A-1) is preferably a (meth)acryloyloxy group-containing urethane polymer.
- the polyoxyalkylene polyol (a1) is not particularly limited as long as it is a compound having a polyoxyalkylene chain, no isocyanato group, and two or more hydroxy groups, and a compound having two hydroxy groups.
- the number of carbon atoms in the alkylene chain constituting the polyoxyalkylene chain is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4. Specific examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol and the like.
- the first ethylenically unsaturated group-containing urethane polymer (A-1) has a polyoxyalkylene chain, thereby keeping the glass transition temperature (Tg) low and the wettability of the adhesive layer constituting the protective sheet to the adherend. can be improved.
- the polyoxyalkylene polyol (a1) has two or more hydroxy groups, and is preferably a glycol having two hydroxy groups. Specific examples include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like. Among them, polyethylene glycol and polypropylene glycol are preferable from the viewpoint of availability, and polypropylene glycol is more preferable from the viewpoint of flexibility of the first ethylenically unsaturated group-containing urethane polymer (A-1).
- One of the polyoxyalkylene polyols (a1) may be used alone, or two or more thereof may be used in combination. A copolymer of two or more polyoxyalkylene polyols may also be used as the polyoxyalkylene polyol (a1).
- the number average molecular weight of the polyoxyalkylene polyol (a1) is preferably from 500 to 5,000, more preferably from 800 to 4,000, even more preferably from 1,000 to 3,000.
- the number average molecular weight is 500 or more, sufficient adhesive strength can be obtained when used as a protective sheet.
- the number average molecular weight is 5000 or less, the number of urethane bonds in the first ethylenically unsaturated group-containing urethane polymer (A-1) can be sufficiently secured, so that the cohesive force of the adhesive layer constituting the protective sheet is sufficient. improves.
- the hydroxyl value of the polyoxyalkylene polyol (a1) is preferably 30-300 mgKOH/g, more preferably 40-200 mgKOH/g, even more preferably 50-150 mgKOH/g.
- the hydroxyl value is 30 mgKOH/g or more, there is an advantage in low staining property after the durability test.
- the hydroxyl value is 300 mgKOH/g or less, there is an advantage that a cured product having moderate adhesion can be obtained.
- the hydroxyl value is measured by a method conforming to the B method of JIS K1557-1.
- the polyisocyanate (a2) used in the present embodiment is a compound having no hydroxy group and two or more isocyanato groups, and an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group Contains non-containing polyisocyanate (a2-2).
- the number of isocyanate groups possessed by the polyisocyanate (a2) is preferably two from the viewpoint of suppression of gelation during synthesis and uniform elongation of the polymer.
- the ethylenically unsaturated group-containing polyisocyanate (a2-1) is not particularly limited as long as it is a compound having two or more isocyanato groups and one or more ethylenically unsaturated groups.
- ethylenically unsaturated group-containing polyisocyanates (a2-1) may be used alone or in combination of two or more.
- ethylenically unsaturated group-containing polyisocyanate (a2-1) ethylenically unsaturated groups are introduced into portions other than the terminals (inside the molecular chain) of the ethylenically unsaturated group-containing urethane polymer (A). be. Therefore, the number of cross-linking points increases when the pressure-sensitive adhesive composition is cured, and the gel fraction of the cured product is less likely to change even when placed under high-temperature and high-humidity conditions.
- the ethylenically unsaturated group-containing polyisocyanate (a2-1) is preferably at least one of vinyl group-containing polyisocyanate, allyl group-containing polyisocyanate, and (meth)acryloyloxy group-containing polyisocyanate. More preferably, the ethylenically unsaturated group-containing polyisocyanate (a2-1) is a (meth)acryloyloxy group-containing polyisocyanate.
- (Meth)acryloyloxy group-containing polyisocyanates include, for example, reaction products of hydroxy group-containing (meth)acrylates and polyisocyanates.
- (Meth) acryloyloxy group-containing polyisocyanate is synthesized as a compound having an allophanate bond by performing urethanization and allophanatization according to the methods described in JP-A-2002-533542 and JP-A-2012-111851.
- examples of the hydroxy group-containing (meth)acrylate include those similar to the compound (a3-1) described later.
- Examples of the polyisocyanate include those similar to the compound (a2-2) described later.
- an allophanate bond-containing compound obtained by reacting a hydroxy group-containing (meth) acrylate and a diisocyanate with an excess diisocyanate is preferable, and an allophanate bond-containing compound obtained by reacting a hydroxyalkyl (meth) acrylate and an alkylene diisocyanate with an excess of an alkylene diisocyanate is more preferable.
- an allophanate bond-containing compound obtained by reacting a hydroxyalkyl (meth) acrylate and an alkylene diisocyanate with an excess of an alkylene diisocyanate is more preferable.
- one or more selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate one or more selected from hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Allophanatized reactants are more preferred.
- the ethylenically unsaturated group-containing polyisocyanate (a2-1) is preferably two isocyanate groups, an average of 1.1 to 2.0 (meth) acryloyloxy groups, and 1 to 3 allophanate bonds. including.
- the ethylenically unsaturated group-containing polyisocyanate (a2-1) is more preferable, two isocyanate groups, an average of 1.2 to 1.6 (meth) acryloyloxy groups, and 1 to 2 allophanate bonds including.
- the (meth)acryloyloxy group-containing polyisocyanate may be a commercially available product, such as BASF's Laromer (registered trademark) PR9000, which is a reaction product of 2-hydroxyethyl acrylate and hexamethylene diisocyanate and contains allophanate linkages. is mentioned.
- These (meth)acryloyloxy group-containing polyisocyanates may be used alone or in combination of two or more.
- the (meth)acryloyloxy group-containing polyisocyanate (a2-1) the (meth)acryloyloxy group in the portion (in the molecular chain) other than the terminal of the (meth)acryloyloxy group-containing urethane polymer (A) is introduced. Therefore, the number of cross-linking points increases when the pressure-sensitive adhesive composition is cured, and the gel fraction of the cured product is less likely to change even when placed under high-temperature and high-humidity conditions.
- the ethylenically unsaturated group-free polyisocyanate (a2-2) is not particularly limited as long as it is a compound having two or more isocyanato groups and no ethylenically unsaturated groups.
- tolylene diisocyanate and its hydrogenated products xylylene diisocyanate and its hydrogenated products, diphenylmethane diisocyanate and its hydrogenated products, 1,5-naphthylene diisocyanate and its hydrogenated products, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, norbornane diisocyanate and the like.
- polyisocyanate having a cyclic hydrocarbon structure is preferred, and isophorone diisocyanate is preferred from the viewpoint of ease of reaction control when synthesizing the ethylenically unsaturated group-containing urethane polymer (A) and light resistance as a cured product.
- 4,4′-dicyclohexyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and norbornane diisocyanate are more preferred, and isophorone diisocyanate is even more preferred.
- These ethylenically unsaturated group-free polyisocyanates may be used alone or in combination of two or more.
- the content ratio (molar ratio (a2-1)/(a2-2)) of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2) is It is preferably 0.03 to 0.8, more preferably 0.08 to 0.7, even more preferably 0.1 to 0.6, and 0.4 to 0.6 is particularly preferred.
- the hydroxy group-containing ethylenically unsaturated compound (a3-1) is not particularly limited as long as it does not have an isocyanato group and has a hydroxy group and an ethylenically unsaturated group.
- the ethylenically unsaturated group is preferably at least one selected from the group consisting of a vinyl group, an allyl group, and a (meth)acryloyloxy group. Preferably.
- the hydroxy group-containing ethylenically unsaturated compound (a3-1) of this embodiment is preferably a hydroxy group-containing (meth)acrylate.
- the hydroxy group-containing (meth)acrylate is not particularly limited as long as it is a compound that does not have an isocyanato group and has a hydroxy group and a (meth)acryloyloxy group.
- Hydroxyalkyl (meth)acrylates such as, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; 1,3-butanediol mono(meth)acrylate, 1 , 6-hexanediol mono(meth)acrylate, 3-methylpentanediol mono(meth)acrylate and other polyol-derived (meth)acryloyl group-containing monools.
- hydroxyalkyl (meth)acrylates are preferable, and hydroxyalkyl (meth)acrylates having an alkyl group having 2 to 6 carbon atoms (meth) ) acrylate, more preferably 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. These may be used individually by 1 type, and may use 2 or more types together.
- an ethylenically unsaturated group can be introduced into the molecular chain terminal portion of the first ethylenically unsaturated group-containing urethane polymer (A-1). can.
- the adhesive composition is photocured, the ethylenically unsaturated group derived from the hydroxy group-containing ethylenically unsaturated compound (a3-1), the ethylenically unsaturated group-containing polyisocyanate (a2-1) derived and the ethylenically unsaturated groups of component (B), which will be described later, are polymerized to make the gel fraction less likely to change. Therefore, when the protective sheet is peeled off, the adherend is less likely to be contaminated.
- the hydroxy group-containing ethylenically unsaturated compound (a3-1) of this embodiment may be a compound having a hydroxy group and a vinyl group.
- Compounds having a hydroxy group and a vinyl group include polyalkylene glycol monovinyl ethers, hydroxyalkyl vinyl ethers, hydroxycarboxylic acid vinyl esters, hydroxyalkyl vinyl esters, and the like.
- Polyalkylene glycol monovinyl ether includes diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and the like.
- Hydroxyalkyl vinyl ethers include 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether and the like.
- Hydroxycarboxylic acid vinyl esters include vinyl hydroxyacetate, vinyl hydroxypropanoate, vinyl hydroxybutanoate, vinyl hydroxyhexanoate, and vinyl 4-hydroxycyclohexyl acetate.
- Hydroxyalkylvinyl esters include vinyl hydroxycyclohexylcarboxylate and the like.
- the hydroxy group-containing ethylenically unsaturated compound (a3-1) of this embodiment may be a compound having no isocyanato group and having a hydroxy group and an allyl group.
- Compounds having a hydroxy group and an allyl group include hydroxyalkyl allyl ethers, hydroxycarboxylic acid allyl esters, hydroxyalkyl allyl esters, and the like.
- Hydroxyalkyl allyl ethers include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, 4-hydroxycyclohexyl allyl ether and the like.
- hydroxycarboxylic acid allyl esters include allyl hydroxyacetate, allyl hydroxypropanoate, allyl hydroxybutanoate, allyl hydroxyhexanoate, and allyl 4-hydroxycyclohexylacetate.
- the proportion of the hydroxy group-containing ethylenically unsaturated compound (a3-1) is such that the total amount of hydroxy groups in compound (a1) and compound (a3-1) is equivalent to the total amount of isocyanato groups in compound (a2).
- is preferably set to “Equivalent” means that the difference in the number of moles between the two is preferably 0.05 mol or less, more preferably 0.01 mol or less. If the molar difference between the two is 0.05 mol or less, the amount of unreacted compounds (a1) to (a3-1) can be sufficiently reduced, and the amounts of unreacted hydroxy groups and isocyanato groups can also be sufficiently reduced. Therefore, change in gel fraction over time can be suppressed even when cured.
- the weight average molecular weight of the first ethylenically unsaturated group-containing urethane polymer (A-1) is preferably 30,000 to 250,000, more preferably 30,000 to 200,000, further preferably 40,000 to 150,000, and 4.3. ⁇ 150,000 is particularly preferable.
- the weight-average molecular weight is 30,000 or more, the cured product of the pressure-sensitive adhesive composition has sufficient flexibility, and the protective sheet having this cured product as the adhesive layer has sufficient lamination properties.
- the weight-average molecular weight is 250,000 or less, handling as an adhesive composition is easy, and workability is improved.
- the second ethylenically unsaturated group-containing urethane polymer (A-2) used in the present embodiment comprises a polyoxyalkylene polyol (a1), a polyisocyanate (a2), and an isocyanato group-containing ethylenically unsaturated compound (a3-2 ).
- the second ethylenically unsaturated group-containing urethane polymer (A-2) is preferably a (meth)acryloyloxy group-containing urethane polymer.
- the total amount of hydroxy groups in the polyoxyalkylene polyol (a1) is preferably 1.1 to 1.5 mol, preferably 1.15 to 1.5 mol, per 1 mol of the total amount of isocyanato groups in the polyisocyanate (a2). It is more preferably 1.4, and even more preferably 1.2 to 1.3.
- the weight-average molecular weight of the second ethylenically unsaturated group-containing urethane polymer (A-2) is in an appropriate range, and the isocyanato group-containing ethylenically unsaturated compound (a3-2 ) can be sufficiently secured.
- the content ratio (molar ratio (a2-1)/(a2-2)) of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2) is It is preferably 0.03 to 0.8, more preferably 0.08 to 0.7, even more preferably 0.1 to 0.6, and 0.4 to 0.6 is particularly preferred.
- isocyanatoalkyl (meth)acrylates such as 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 6-isocyanatohexyl (meth)acrylate etc.
- isocyanatosialkyl (meth)acrylates having an alkyl group having 2 to 6 carbon atoms are preferred.
- -isocyanatoethyl (meth)acrylate and 4-isocyanatobutyl (meth)acrylate are more preferred. These may be used individually by 1 type, and may use 2 or more types together.
- an ethylenically unsaturated group can be introduced into the molecular chain terminal portion of the second ethylenically unsaturated group-containing urethane polymer (A-2). can.
- the ratio of the isocyanato group-containing ethylenically unsaturated compound (a3-2) is such that the total amount of isocyanato groups in compound (a2) and isocyanato groups in compound (a3-2) is equivalent to the total amount of hydroxy groups in compound (a1). It is preferable to set such that “Equivalent” means that the difference in the number of moles between the two is preferably 0.05 mol or less, more preferably 0.01 mol or less. If the molar difference between the two is 0.05 mol or less, the amount of unreacted compounds (a1) to (a3-2) can be sufficiently reduced, and the amounts of unreacted hydroxy groups and isocyanato groups can also be sufficiently reduced. Therefore, change in gel fraction over time can be suppressed even when cured.
- the weight average molecular weight of the second ethylenically unsaturated group-containing urethane polymer (A-2) is preferably 30,000 to 250,000, more preferably 30,000 to 200,000, further preferably 40,000 to 150,000, and 4.3. ⁇ 150,000 is particularly preferable.
- the weight-average molecular weight is 20,000 or more, the cured product of the pressure-sensitive adhesive composition has sufficient flexibility, and the protective sheet having this cured product as the adhesive layer has sufficient lamination properties.
- the weight-average molecular weight is 250,000 or less, handling as an adhesive composition is easy, and workability is improved.
- “Monofunctional” means having only one (meth)acryloyloxy group
- “polyfunctional” means having a plurality of (meth)acryloyloxy groups.
- the monofunctional (meth)acrylate (B1) the cohesive force of the cured product of the pressure-sensitive adhesive composition can be suppressed, the pressure-sensitive adhesive layer can be made flexible, and the wettability to the adherend can be improved.
- the polyfunctional (meth)acrylate (B2) the cohesive force of the cured product of the pressure-sensitive adhesive composition is improved, and the pressure-sensitive adhesive layer maintains an appropriate hardness and adheres to the pressure-sensitive adhesive surface (between the pressure-sensitive adhesive layer and the adherend). ) can be suppressed from entrapment of air bubbles.
- the components (B1) and (B2) together the peel strength when the protective sheet is peeled off can be adjusted.
- Monofunctional (meth)acrylates (B1) include, for example, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, alkoxy (poly)alkylene glycol (meth)acrylates, and hydroxy group-containing (meth)acrylates. ) acrylates, carboxy group-containing (meth)acrylates, fluorinated alkyl (meth)acrylates, dialkylaminoalkyl (meth)acrylates, (meth)acrylamides, epoxy group-containing (meth)acrylates, and the like.
- alkyl (meth)acrylates examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, Acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate, isooctyl (meth)acrylate, isostearyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, etc. mentioned.
- cyclic alkyl (meth)acrylates include cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, norbornanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ) acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, and the like.
- Alkoxyalkyl (meth)acrylates include, for example, ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-ethoxyethoxyethyl (meth)acrylate, acrylates and the like.
- Alkoxy (poly) alkylene glycol (meth) acrylates include, for example, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, and the like.
- hydroxy group-containing (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,3-butanediol (meth)acrylate, 1,4-butanediol (meth)acrylate, 1,6-hexanediol (meth)acrylate, 3-methylpentanediol (meth)acrylate and the like.
- Carboxy group-containing (meth)acrylates include, for example, (meth)acrylic acid and ⁇ -carboxyethyl (meth)acrylate.
- fluorinated alkyl (meth)acrylates examples include octafluoropentyl (meth)acrylate.
- dialkylaminoalkyl (meth)acrylates examples include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate.
- (Meth)acrylamides include, for example, (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropylacrylamide, N-hexyl(meth)acrylamide , N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, (meth)acryloylmorpholine, diacetoneacrylamide and the like.
- epoxy group-containing (meth)acrylates examples include glycidyl (meth)acrylate and the like.
- alkyl (meth)acrylates are preferred, and have 6 to 18 carbon atoms.
- a chain alkyl (meth)acrylate is more preferred. More specifically, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isooctyl (meth)acrylate, isostearyl (meth)acrylate, and isobornyl (meth)acrylate are preferred, and 2-ethylhexyl (meth)acrylate is more preferred. preferable.
- the monofunctional (meth)acrylate (B1) may consist of one type of compound, or may consist of two or more types of compounds.
- the polyfunctional (meth)acrylate (B2) is preferably an ester compound of a polyol compound and (meth)acrylic acid, more preferably a tri- to hexa-functional (meth)acrylate.
- the reaction between the hydroxy group and the isocyanato group was carried out in the presence of an organic solvent inert to the isocyanato group in any step using urethane such as dibutyltin dilaurate, dibutyltin diethylhexoate, and dioctyltin dilaurate. conversion catalyst.
- urethane such as dibutyltin dilaurate, dibutyltin diethylhexoate, and dioctyltin dilaurate.
- the reaction is preferably carried out at 30-100° C. for 1-5 hours.
- the amount of the urethanization catalyst used is preferably 50 to 500 ppm by mass relative to the total mass of the reactants.
- the polyoxyalkylene polyol (a1) and the polyisocyanate (a2) are determined so that the isocyanato group amount (number basis, hereinafter the same) of the polyisocyanate (a2) is the hydroxy group amount (number basis) of the polyoxyalkylene polyol (a1) , the same applies hereinafter) are added and reacted to synthesize a urethane prepolymer having terminal isocyanato groups.
- the isocyanate group content of the polyisocyanate (a2) is the total isocyanate group content of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2).
- Specific examples of the polyoxyalkylene polyol (a1) and polyisocyanate (a2) are as exemplified in the section on polyurethane (A).
- an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group-free polyisocyanate (a2-2) are used as the polyisocyanate (a2). They may be added, and the order of addition may be either.
- the introduction position of the ethylenically unsaturated group in the main chain of the first ethylenically unsaturated group-containing urethane polymer (A-1) is the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group non-
- the order in which the contained polyisocyanate (a2-2) is added can also be adjusted.
- an ethylenically unsaturated group is also introduced near the center of the main chain of the first ethylenically unsaturated group-containing urethane polymer (A-1). This is because the polymerization of the ethylenically unsaturated groups shortens the distance between the cross-linking points of the first ethylenically unsaturated group-containing urethane polymer (A-1), thereby suppressing changes in the gel fraction of the cured product. .
- the ethylenically unsaturated group-containing polyisocyanate (a2-1) is added first, or the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group
- the non-containing polyisocyanate (a2-2) is added at the same time, and it is more preferable to add the ethylenically unsaturated group-containing polyisocyanate (a2-1) first.
- an isocyanato group-containing urethane prepolymer and a hydroxyl group-containing ethylenically unsaturated compound (a3-1) are reacted to obtain a first ethylenically unsaturated group in which an ethylenically unsaturated group is introduced at the molecular chain end.
- a containing urethane polymer (A-1) is synthesized.
- it is preferable that 90 to 100% of the terminal of the polyurethane contained in the first ethylenically unsaturated group-containing urethane polymer (A-1) is introduced with an ethylenically unsaturated group, and 95 to 100% is More preferably, 100% is even more preferable.
- the introduction amount of the ethylenically unsaturated groups is 90% or more on the number basis with respect to the isocyanato groups, the cohesive force of the adhesive layer obtained by curing the adhesive composition can be sufficiently obtained.
- the ratio of the number of terminals introduced with ethylenically unsaturated groups to the number of terminals of all polyurethane molecular chains can be measured by IR, NMR, or the like.
- the isocyanate group content of the polyisocyanate (a2) is the total isocyanate group content of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2).
- Specific examples of the polyoxyalkylene polyol (a1) and polyisocyanate (a2) are as exemplified in the section on polyurethane (A).
- all the components may be added and mixed at once, or the addition and mixing may be repeated in multiple batches for each component. If there is a component that is solid at room temperature, it can be dissolved in a solvent, dispersed in a dispersion medium, added, or melted by heating. It becomes easy to mix with high uniformity in the pressure-sensitive adhesive composition.
- an adhesive layer containing a cured product of the adhesive composition is formed on one side of a base material.
- the thickness of the adhesive layer is preferably 3 to 150 ⁇ m, more preferably 5 to 130 ⁇ m, even more preferably 10 to 100 ⁇ m.
- the thickness of the adhesive layer is 3 ⁇ m or more, the strength of the adhesive layer is sufficient, and when the thickness is 150 ⁇ m or less, the thickness of the adhesive layer can be easily controlled.
- the thickness of the adhesive layer is preferably 50 ⁇ m or more.
- the material of the base material can be appropriately selected according to the application of the protective sheet, and an example is a resin film.
- the substrate is transparent when the protective sheet is laminated.
- transparent substrates include polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and cellulose.
- the method of applying the adhesive composition to the substrate is not particularly limited and can be selected as appropriate.
- various coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, bar coaters, knife coaters, spray coaters, comma coaters, and direct coaters can be used as a method of applying the adhesive composition to a substrate.
- the method used, the screen printing method, etc. are mentioned.
- Light sources for photocuring the pressure-sensitive adhesive composition include black lights, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and xenon lamps.
- the irradiation intensity of the light is sufficient as long as the pressure-sensitive adhesive composition can be sufficiently cured, and is preferably, for example, 50 to 3000 mW/cm 2 . If the irradiation intensity of light is low, it takes a long time for curing, resulting in a decrease in productivity.
- the protective sheet may be suitably used for the purpose of protecting the surface of a plastic film used as an optical component.
- the optical components include polarizing plates, wave plates, retardation plates, optical compensation films, reflective sheets, brightness enhancement films, and the like. These optical components are used, for example, in liquid crystal displays of smartphones, personal computers, televisions, and the like.
- the protective sheet according to the present embodiment is used as such a protective sheet, the protective sheet is required to cause little contamination of adherends.
- the change in the gel fraction of the adhesive layer constituting the protective sheet and the change in the water contact angle on the surface of the adherend between before attachment of the protective sheet and after peeling of the protective sheet are small.
- a specific method for measuring contamination of the adherend surface by the adhesive layer of the protective sheet will be described later in Examples.
- the protective sheet according to the present embodiment when used as the protective sheet as described above, the protective sheet must have a minimum peel strength in order to prevent it from peeling off from the product or part during handling such as transportation. become.
- the peel strength needs to be low in order to facilitate the peeling work or to prevent the product or parts from being deformed or damaged during peeling.
- the peel strength of the protective sheet when the peel speed is 2.4 m/min, is preferably 1 to 50 gf/25 mm, depending on the thickness of the substrate and the adhesive layer, and 2 to 45 gf. /25 mm, more preferably 2 to 40 gf/25 mm. A specific method for measuring the peel strength of the protective sheet will be described later in Examples.
- the weight average molecular weight of the obtained ethylenically unsaturated group-containing urethane polymer (A) was determined by gel permeation chromatography (Showa Denko Co., Ltd. Shodex (registered trademark) GPC-101, hereinafter, It is a value converted to polystyrene measured by GPC.
- the measurement conditions of GPC are as follows. Column: LF-804 manufactured by Showa Denko K.K.
- PR9000 is Laromer (registered trademark) PR9000, which is a compound represented by the following formula (1).
- n 0.32-0.45.
- a protective sheet having an optical PET film substrate on one side was produced in the same manner as in Examples 1 to 11 and Comparative Examples 1 to 8.
- the adjusted adhesive composition is applied on a 75 ⁇ m thick optical PET film (A4300 manufactured by Toyobo Co., Ltd.), and a 75 ⁇ m thick film is applied from above the applied adhesive composition. It was covered with a release PET film (E7006 manufactured by Toyobo Co., Ltd.).
- the sheet covered with the release PET film is irradiated with ultraviolet rays from the surface on the release PET film side, and the adhesive is removed.
- the composition was photocured.
- the ultraviolet irradiation distance is 25 cm
- the lamp moving speed is 1.0 m/min
- the irradiation amount is 1000 mJ/cm 2 .
- the thickness of the adhesive layer after curing is calculated by measuring the thickness of the protective sheet using a dial gauge and then subtracting the 75 ⁇ m thickness of the optical PET film and the 75 ⁇ m thickness of the release PET film from this measured value. did.
- the measuring surface of the dial gauge was a circular plane with a diameter of 5 mm, and the measuring force was 0.8N.
- the thickness of the adhesive layer was 75 ⁇ m.
- EHA compound name (2-ethylhexyl acrylate, manufactured by Toagosei Co., Ltd.)
- LA compound name (lauryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
- TMPTA compound name (trimethylolpropane triacrylate M-309, manufactured by Toagosei Co., Ltd.)
- Irg-184 compound name (1-Hydroxycyclohexyl Phenyl Ketone, manufactured by Tokyo Chemical Industry Co., Ltd.)
- IPM compound name (Exepar IPM, manufactured by Kao Corporation)
- the adhesive composition on the release PET film was covered with a release PET film (E7006 manufactured by Toyobo Co., Ltd.) having a thickness of 75 ⁇ m.
- a release PET film E7006 manufactured by Toyobo Co., Ltd.
- UV irradiation device manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp
- the pressure-sensitive adhesive composition was photo-cured by irradiating with ultraviolet rays.
- the ultraviolet irradiation distance is 25 cm
- the lamp moving speed is 1.0 m/min
- the irradiation amount is 1000 mJ/cm 2 .
- the prepared sheet was cut into strips of 150 mm x 80 mm, and the release PET films on both sides were peeled off from the cured product of the pressure-sensitive adhesive composition to obtain a sample for measurement.
- This measurement sample was immersed in 50 ml of tetrahydrofuran at 25° C. for 24 hours and then dried at 80° C. for 5 hours. rate was calculated. The results are shown in Tables 2-3.
- test plate consisting of a glass plate was soaked in 3% semi-clean L.I. G. It was immersed overnight in an alkaline cleaning solution, which is an aqueous solution of L (Yokohama Jushi Co., Ltd.), and cleaned with an ultrasonic cleaner for 1 hour. After that, the test plate was immersed in deionized water, washed twice for 30 minutes with an ultrasonic cleaner, and dried at 150° C. in the air for 2 hours. The water contact angle on the surface of the dried test plate was measured at 5 points per sample using a contact angle meter (DMO-601, manufactured by Kyowa Interface Science Co., Ltd.), and the average value was used as a blank. Pure water was used as the water.
- DMO-601 manufactured by Kyowa Interface Science Co., Ltd.
- ⁇ Peel strength of protective sheet> The prepared protective sheet was cut into a size of 25 mm ⁇ 150 mm, and the release PET film was peeled off. Next, the exposed adhesive surface was attached to a glass plate, and a 2 kg rubber roller (width: about 50 mm) was reciprocated once to prepare a sample for measurement. Thirty minutes after the pressure bonding, a tensile test in the direction of 180° was performed at a peel rate of 2.4 m/min to measure the peel strength (g/25 mm) of the protective sheet to the glass plate according to JISZ0237.
- a large change in the water contact angle suggests that the surface of the glass test plate is contaminated with the adhesive layer of the protective sheet, and that this affects the properties of the surface of the test plate.
- large contamination of the glass test plate was visually observed, and due to hydrolysis and oxidative deterioration of the adhesive layer, the solvent-soluble components that cause contamination of the test plate surface increase. This is not desirable because it suggests that Further, a large change in the gel fraction means a change in properties of the adhesive layer of the protective sheet, that is, deterioration, which is also undesirable.
Abstract
Description
本願は、2021年6月30日に、日本に出願された特願2021-108809号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a protective sheet having a pressure-sensitive adhesive composition and a cured product of the pressure-sensitive adhesive composition.
This application claims priority based on Japanese Patent Application No. 2021-108809 filed in Japan on June 30, 2021, the contents of which are incorporated herein.
[1] エチレン性不飽和基含有ウレタンポリマー(A)と、
エチレン性不飽和基含有モノマー(B)と、
光重合開始剤(C)と
を含有し、
前記エチレン性不飽和基含有ウレタンポリマー(A)が、
ポリオキシアルキレンポリオール(a1)と、
ポリイソシアネート(a2)と、
ヒドロキシ基含有エチレン性不飽和化合物(a3-1)又はイソシアナト基含有エチレン性不飽和化合物(a3-2)と
の反応物であり、
前記ポリイソシアネート(a2)が、エチレン性不飽和基含有ポリイソシアネート(a2-1)およびエチレン性不飽和基非含有ポリイソシアネート(a2-2)を含有することを特徴とする粘着剤組成物。
[2] 前記エチレン性不飽和基含有ウレタンポリマー(A)が、
前記ポリオキシアルキレンポリオール(a1)と、
前記ポリイソシアネート(a2)と、の反応物であるウレタンプレポリマーの末端に 前記ヒドロキシ基含有エチレン性不飽和化合物(a3-1)又は前記イソシアナト基含有エチレン性不飽和化合物(a3-2)が付加したウレタンポリマーである[1]に記載の粘着剤組成物。
[3] 前記ポリオキシアルキレンポリオール(a1)が2個のヒドロキシ基を有する化合物であり、
前記ポリイソシアネート(a2)が2個のイソシアナト基を有する化合物である[1]または[2]に記載の粘着剤組成物。
[4] 前記エチレン性不飽和基含有ウレタンポリマー(A)が、(メタ)アクリロイルオキシ基含有ウレタンポリマーであり、
前記エチレン性不飽和基含有ポリイソシアネート(a2-1)が、(メタ)アクリロイルオキシ基含有ポリイソシアネートであり、
前記ヒドロキシ基含有エチレン性不飽和化合物(a3-1)が、ヒドロキシ基含有(メタ)アクリレートであり、
前記イソシアナト基含有エチレン性不飽和化合物(a3-2)が、イソシアナト基含有(メタ)アクリレートである[1]~[3]のいずれかに記載の粘着剤組成物。
[5] 前記エチレン性不飽和基含有モノマー(B)が、単官能(メタ)アクリレート(B1)および多官能(メタ)アクリレート(B2)を含有する[1]~[4]のいずれかに記載の粘着剤組成物。
[6] 前記エチレン性不飽和基含有ウレタンポリマー(A)の重量平均分子量が、3万~25万である[1]~[5]のいずれかに記載の粘着剤組成物。
[7] 前記ポリオキシアルキレンポリオール(a1)の数平均分子量が、500~5,000である[1]~[6]のいずれかに記載の粘着剤組成物。
[8] 前記エチレン性不飽和基含有ウレタンポリマー(A)が、前記ポリオキシアルキレンポリオール(a1)と、前記ポリイソシアネート(a2)と、前記ヒドロキシ基含有エチレン性不飽和化合物(a3-1)との反応物であり、
前記ポリイソシアネート(a2)のイソシアナト基の総量が、前記ポリオキシアルキレンポリオール(a1)のヒドロキシ基の総量1モルに対して、1.1~1.5モルであり、
前記エチレン性不飽和基含有ポリイソシアネート(a2-1)および前記エチレン性不飽和基非含有ポリイソシアネート(a2-2)の含有割合(モル比(a2-1)/(a2-2))が、0.03~0.8である[1]~[7]のいずれかに記載の粘着剤組成物。
[9] 前記エチレン性不飽和基含有ウレタンポリマー(A)が、前記ポリオキシアルキレンポリオール(a1)と、前記ポリイソシアネート(a2)と、前記イソシアナト基含有エチレン性不飽和化合物(a3-2)との反応物であり、
前記ポリオキシアルキレンポリオール(a1)のヒドロキシ基の総量が、前記ポリイソシアネート(a2)のイソシアナト基の総量1モルに対して、1.1~1.5モルであり、
前記エチレン性不飽和基非含有ポリイソシアネート(a2-2)および前記エチレン性不飽和基含有ポリイソシアネート(a2-1)の含有割合(モル比(a2-2)/(a2-1))が、0.03~0.8である[1]~[8]のいずれかに記載の粘着剤組成物。
[10] 前記エチレン性不飽和基含有ポリイソシアネート(a2-1)が、ヒドロキシ基含有エチレン性不飽和化合物及びジイソシアネートの反応物である[1]~[9]のいずれかに記載の粘着剤組成物。
[11] 前記単官能(メタ)アクリレート(B1)が、炭素数6~18の鎖状アルキル(メタ)アクリレートである[5]~[10]のいずれかに記載の粘着剤組成物。
[12] 前記多官能(メタ)アクリレート(B2)が、3~6官能の(メタ)アクリレートである[5]~[11]のいずれかに記載の粘着剤組成物。
[13] 前記エチレン性不飽和基含有ウレタンポリマー(A)および前記エチレン性不飽和基含有モノマー(B)の合計100質量%に対して、前記エチレン性不飽和基含有ウレタンポリマー(A)が30~70質量%、エチレン性不飽和基含有モノマー(B)が30~70質量部である[1]~[12]のいずれかに記載の粘着剤組成物。
[14] 前記エチレン性不飽和基含有ウレタンポリマー(A)および前記エチレン性不飽和基含有モノマー(B)の合計100質量%に対して、単官能(メタ)アクリレート(B1)が25~60質量%、多官能(メタ)アクリレート(B2)が1~30質量%である[3]~[13]のいずれかに記載の粘着剤組成物。
[15] 可塑剤(D)をさらに含有する[1]~[14]のいずれかに記載の粘着剤組成物。
[16] 前記エチレン性不飽和基含有ウレタンポリマー(A)および前記エチレン性不飽和基含有モノマー(B)の合計100質量部に対して、前記光重合開始剤(C)が0.05~5質量部、前記可塑剤(D)が1~30質量部である[15]に記載の粘着剤組成物。
[17] [1]~[16]のいずれかに記載の粘着剤組成物の硬化物である粘着層を基材の片面に有する保護シート。 The present invention includes the following aspects.
[1] an ethylenically unsaturated group-containing urethane polymer (A);
an ethylenically unsaturated group-containing monomer (B);
containing a photopolymerization initiator (C),
The ethylenically unsaturated group-containing urethane polymer (A) is
a polyoxyalkylene polyol (a1);
a polyisocyanate (a2);
A reaction product with a hydroxy group-containing ethylenically unsaturated compound (a3-1) or an isocyanato group-containing ethylenically unsaturated compound (a3-2),
A pressure-sensitive adhesive composition, wherein the polyisocyanate (a2) comprises an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group-free polyisocyanate (a2-2).
[2] The ethylenically unsaturated group-containing urethane polymer (A) is
the polyoxyalkylene polyol (a1); and
The hydroxy group-containing ethylenically unsaturated compound (a3-1) or the isocyanato group-containing ethylenically unsaturated compound (a3-2) is added to the end of the urethane prepolymer that is the reaction product of the polyisocyanate (a2). The pressure-sensitive adhesive composition according to [1], which is a urethane polymer.
[3] the polyoxyalkylene polyol (a1) is a compound having two hydroxy groups,
The pressure-sensitive adhesive composition according to [1] or [2], wherein the polyisocyanate (a2) is a compound having two isocyanato groups.
[4] The ethylenically unsaturated group-containing urethane polymer (A) is a (meth)acryloyloxy group-containing urethane polymer,
The ethylenically unsaturated group-containing polyisocyanate (a2-1) is a (meth)acryloyloxy group-containing polyisocyanate,
The hydroxy group-containing ethylenically unsaturated compound (a3-1) is a hydroxy group-containing (meth)acrylate,
The pressure-sensitive adhesive composition according to any one of [1] to [3], wherein the isocyanato group-containing ethylenically unsaturated compound (a3-2) is an isocyanato group-containing (meth)acrylate.
[5] Any one of [1] to [4], wherein the ethylenically unsaturated group-containing monomer (B) contains a monofunctional (meth)acrylate (B1) and a polyfunctional (meth)acrylate (B2) adhesive composition.
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], wherein the ethylenically unsaturated group-containing urethane polymer (A) has a weight average molecular weight of 30,000 to 250,000.
[7] The adhesive composition according to any one of [1] to [6], wherein the polyoxyalkylene polyol (a1) has a number average molecular weight of 500 to 5,000.
[8] The ethylenically unsaturated group-containing urethane polymer (A) comprises the polyoxyalkylene polyol (a1), the polyisocyanate (a2), and the hydroxy group-containing ethylenically unsaturated compound (a3-1). is a reactant of
The total amount of isocyanato groups in the polyisocyanate (a2) is 1.1 to 1.5 mol per 1 mol of the total amount of hydroxy groups in the polyoxyalkylene polyol (a1),
The content ratio (molar ratio (a2-1)/(a2-2)) of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2) is The pressure-sensitive adhesive composition according to any one of [1] to [7], which is 0.03 to 0.8.
[9] The ethylenically unsaturated group-containing urethane polymer (A) comprises the polyoxyalkylene polyol (a1), the polyisocyanate (a2), and the isocyanato group-containing ethylenically unsaturated compound (a3-2). is a reactant of
The total amount of hydroxy groups in the polyoxyalkylene polyol (a1) is 1.1 to 1.5 mol per 1 mol of the total amount of isocyanato groups in the polyisocyanate (a2),
The content ratio (molar ratio (a2-2)/(a2-1)) of the ethylenically unsaturated group-free polyisocyanate (a2-2) and the ethylenically unsaturated group-containing polyisocyanate (a2-1) is The pressure-sensitive adhesive composition according to any one of [1] to [8], which is 0.03 to 0.8.
[10] The pressure-sensitive adhesive composition according to any one of [1] to [9], wherein the ethylenically unsaturated group-containing polyisocyanate (a2-1) is a reaction product of a hydroxy group-containing ethylenically unsaturated compound and a diisocyanate. thing.
[11] The pressure-sensitive adhesive composition according to any one of [5] to [10], wherein the monofunctional (meth)acrylate (B1) is a chain alkyl (meth)acrylate having 6 to 18 carbon atoms.
[12] The pressure-sensitive adhesive composition according to any one of [5] to [11], wherein the polyfunctional (meth)acrylate (B2) is a tri- to hexa-functional (meth)acrylate.
[13] 30 of the ethylenically unsaturated group-containing urethane polymer (A) is added to a total of 100% by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B) ~70 wt%, the pressure-sensitive adhesive composition according to any one of [1] to [12], wherein the ethylenically unsaturated group-containing monomer (B) is 30 to 70 parts by mass.
[14] Monofunctional (meth)acrylate (B1) is 25 to 60% by mass with respect to a total of 100% by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B) % and the polyfunctional (meth)acrylate (B2) is 1 to 30% by mass.
[15] The adhesive composition according to any one of [1] to [14], further containing a plasticizer (D).
[16] With respect to a total of 100 parts by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B), the photopolymerization initiator (C) is 0.05 to 5 Parts by mass, the pressure-sensitive adhesive composition according to [15], wherein the plasticizer (D) is 1 to 30 parts by mass.
[17] A protective sheet having an adhesive layer, which is a cured product of the adhesive composition according to any one of [1] to [16], on one side of a substrate.
本実施形態の粘着剤組成物は、エチレン性不飽和基含有ウレタンポリマー(A)(以下、単に「(A)成分」とも言う)と、エチレン性不飽和基含有モノマー(B)(以下、単に「(B)成分」とも言う)と、光重合開始剤(C)(以下、単に「(C)成分」とも言う)とを含有する。前記粘着剤組成物は、必要に応じて、(D)可塑剤(以下、単に「(D)成分」とも言う)を含有しても良い。 (Adhesive composition)
The pressure-sensitive adhesive composition of the present embodiment comprises an ethylenically unsaturated group-containing urethane polymer (A) (hereinafter simply referred to as "(A) component") and an ethylenically unsaturated group-containing monomer (B) (hereinafter simply Also referred to as "component (B)") and a photopolymerization initiator (C) (hereinafter also simply referred to as "component (C)"). The pressure-sensitive adhesive composition may contain (D) a plasticizer (hereinafter also simply referred to as "component (D)"), if necessary.
なお、本実施形態のエチレン性不飽和基含有ウレタンポリマー(A)は、ポリイソシアネート(a2)として、後述するエチレン性不飽和基含有ポリイソシアネート(a2-1)およびエチレン性不飽和基非含有ポリイソシアネート(a2-2)の2種類を用いるため、これらの化合物がポリマー鎖中に混在して取り込まれる。また、ポリオキシアルキレンポリオール(a1)及びポリイソシアネート(a2)の割合によって、ヒドロキシ基含有エチレン性不飽和化合物(a3-1)又はイソシアナト基含有エチレン性不飽和化合物(a3-2)のいずれを用いるかが決まるなど、エチレン性不飽和基含有ウレタンポリマー(A)が複雑構造を有するため、一義的に構造式等で定義することが困難である。
前記エチレン性不飽和基含有ウレタンポリマー(A)は、ビニル基含有ウレタンポリマー、アリル基含有ウレタンポリマー、及び(メタ)アクリロイルオキシ基含有ウレタンポリマーからなる少なくとも1種であることが好ましい。前記エチレン性不飽和基含有ウレタンポリマー(A)は、(メタ)アクリロイルオキシ基含有ウレタンポリマーであることがより好ましい。 The ethylenically unsaturated group-containing urethane polymer (A) used in the present embodiment comprises a polyoxyalkylene polyol (a1), a polyisocyanate (a2), and a hydroxy group-containing ethylenically unsaturated compound (a3-1) or an isocyanato group. It is a reaction product with the containing ethylenically unsaturated compound (a3-2). Since the adhesive composition of the present embodiment contains the ethylenically unsaturated group-containing urethane polymer (A), even if the cured product of the adhesive composition is placed under high temperature and high humidity conditions, the cured product change in gel fraction can be suppressed. Therefore, the protective sheet having the cured product as an adhesive layer is less likely to stain the adherend when peeled off from the adherend.
The ethylenically unsaturated group-containing urethane polymer (A) of the present embodiment includes, as the polyisocyanate (a2), an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group-free polyisocyanate (a2-1) described later. Since two types of isocyanate (a2-2) are used, these compounds are incorporated into the polymer chain in a mixed manner. Also, depending on the ratio of the polyoxyalkylene polyol (a1) and the polyisocyanate (a2), either the hydroxy group-containing ethylenically unsaturated compound (a3-1) or the isocyanato group-containing ethylenically unsaturated compound (a3-2) is used. Since the ethylenically unsaturated group-containing urethane polymer (A) has a complicated structure, it is difficult to unambiguously define it by a structural formula or the like.
The ethylenically unsaturated group-containing urethane polymer (A) is preferably at least one of a vinyl group-containing urethane polymer, an allyl group-containing urethane polymer, and a (meth)acryloyloxy group-containing urethane polymer. More preferably, the ethylenically unsaturated group-containing urethane polymer (A) is a (meth)acryloyloxy group-containing urethane polymer.
本実施形態に用いる第1エチレン性不飽和基含有ウレタンポリマー(A-1)は、ポリオキシアルキレンポリオール(a1)と、ポリイソシアネート(a2)と、ヒドロキシ基含有エチレン性不飽和化合物(a3-1)との反応物である。好ましくは、第1エチレン性不飽和基含有ウレタンポリマー(A-1)は、ポリオキシアルキレンポリオール(a1)と、ポリイソシアネート(a2)と、の反応物であるウレタンプレポリマーの末端にヒドロキシ基含有エチレン性不飽和化合物(a3-1)が付加したウレタンポリマーである。前記第1のエチレン性不飽和基含有ウレタンポリマー(A-1)が、(メタ)アクリロイルオキシ基含有ウレタンポリマーであることが好ましい。 [First ethylenically unsaturated group-containing urethane polymer (A-1)]
The first ethylenically unsaturated group-containing urethane polymer (A-1) used in the present embodiment comprises a polyoxyalkylene polyol (a1), a polyisocyanate (a2), and a hydroxy group-containing ethylenically unsaturated compound (a3-1 ). Preferably, the first ethylenically unsaturated group-containing urethane polymer (A-1) is a urethane prepolymer that is a reaction product of a polyoxyalkylene polyol (a1) and a polyisocyanate (a2), and has hydroxyl groups at the terminals. It is a urethane polymer to which an ethylenically unsaturated compound (a3-1) is added. The first ethylenically unsaturated group-containing urethane polymer (A-1) is preferably a (meth)acryloyloxy group-containing urethane polymer.
ポリオキシアルキレンポリオール(a1)は、ポリオキシアルキレン鎖を有し、イソシアナト基を有さず、2個以上のヒドロキシ基を有する化合物であれば特に限定されなく、2個のヒドロキシ基を有する化合物であることが好ましい。前記ポリオキシアルキレン鎖を構成するアルキレン鎖の炭素数は、2~8であることが好ましく、2~6であることがより好ましく、2~4であることがさらに好ましい。具体例としては、ポリオキシエチレンポリオール、ポリオキシプロピレンポリオール、ポリオキシブチレンポリオール等が挙げられる。第1エチレン性不飽和基含有ウレタンポリマー(A-1)が、ポリオキシアルキレン鎖を有することにより、ガラス転移温度(Tg)を低く抑え、保護シートを構成する粘着層の被着体に対する濡れ性を向上させることができる。 [Polyoxyalkylene polyol (a1)]
The polyoxyalkylene polyol (a1) is not particularly limited as long as it is a compound having a polyoxyalkylene chain, no isocyanato group, and two or more hydroxy groups, and a compound having two hydroxy groups. Preferably. The number of carbon atoms in the alkylene chain constituting the polyoxyalkylene chain is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4. Specific examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol and the like. The first ethylenically unsaturated group-containing urethane polymer (A-1) has a polyoxyalkylene chain, thereby keeping the glass transition temperature (Tg) low and the wettability of the adhesive layer constituting the protective sheet to the adherend. can be improved.
前記ポリオキシアルキレンポリオール(a1)は、1種を単独で用いてもよく、2種以上を併用しても良い。また、2種以上のポリオキシアルキレンポリオールの共重合体をポリオキシアルキレンポリオール(a1)として用いても良い。 The polyoxyalkylene polyol (a1) has two or more hydroxy groups, and is preferably a glycol having two hydroxy groups. Specific examples include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like. Among them, polyethylene glycol and polypropylene glycol are preferable from the viewpoint of availability, and polypropylene glycol is more preferable from the viewpoint of flexibility of the first ethylenically unsaturated group-containing urethane polymer (A-1).
One of the polyoxyalkylene polyols (a1) may be used alone, or two or more thereof may be used in combination. A copolymer of two or more polyoxyalkylene polyols may also be used as the polyoxyalkylene polyol (a1).
本実施形態に用いるポリイソシアネート(a2)は、ヒドロキシ基を有さず、2個以上のイソシアナト基を有する化合物であり、エチレン性不飽和基含有ポリイソシアネート(a2-1)およびエチレン性不飽和基非含有ポリイソシアネート(a2-2)を含有する。ポリイソシアネート(a2)が有するイソシアナト基数は、合成時のゲル化の抑制や、ポリマーを均一に伸長させることができる点から、2個であることが好ましい。 [Polyisocyanate (a2)]
The polyisocyanate (a2) used in the present embodiment is a compound having no hydroxy group and two or more isocyanato groups, and an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group Contains non-containing polyisocyanate (a2-2). The number of isocyanate groups possessed by the polyisocyanate (a2) is preferably two from the viewpoint of suppression of gelation during synthesis and uniform elongation of the polymer.
前記エチレン性不飽和基含有ポリイソシアネート(a2-1)が、好ましく、2つのイソシアネート基と、平均1.1~2.0個の(メタ)アクリロイルオキシ基と、1~3個のアロファネート結合とを含む。前記エチレン性不飽和基含有ポリイソシアネート(a2-1)が、より好ましく、2つのイソシアネート基と、平均1.2~1.6個の(メタ)アクリロイルオキシ基と、1~2個のアロファネート結合とを含む。 (Meth)acryloyloxy group-containing polyisocyanates include, for example, reaction products of hydroxy group-containing (meth)acrylates and polyisocyanates. (Meth) acryloyloxy group-containing polyisocyanate is synthesized as a compound having an allophanate bond by performing urethanization and allophanatization according to the methods described in JP-A-2002-533542 and JP-A-2012-111851. can be obtained by Specifically, examples of the hydroxy group-containing (meth)acrylate include those similar to the compound (a3-1) described later. Examples of the polyisocyanate include those similar to the compound (a2-2) described later. Among them, an allophanate bond-containing compound obtained by reacting a hydroxy group-containing (meth) acrylate and a diisocyanate with an excess diisocyanate is preferable, and an allophanate bond-containing compound obtained by reacting a hydroxyalkyl (meth) acrylate and an alkylene diisocyanate with an excess of an alkylene diisocyanate is more preferable. one or more selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate; one or more selected from hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Allophanatized reactants are more preferred.
The ethylenically unsaturated group-containing polyisocyanate (a2-1) is preferably two isocyanate groups, an average of 1.1 to 2.0 (meth) acryloyloxy groups, and 1 to 3 allophanate bonds. including. The ethylenically unsaturated group-containing polyisocyanate (a2-1) is more preferable, two isocyanate groups, an average of 1.2 to 1.6 (meth) acryloyloxy groups, and 1 to 2 allophanate bonds including.
これらの(メタ)アクリロイルオキシ基含有ポリイソシアネートは、一種を単独で使用してもよく、2種以上を併用しても良い。(メタ)アクリロイルオキシ基含有ポリイソシアネート(a2-1)を使用することにより、(メタ)アクリロイルオキシ基含有ウレタンポリマー(A)の末端以外(分子鎖中)の部分にも(メタ)アクリロイルオキシ基が導入される。そのため、粘着剤組成物を硬化物とした際の架橋点が増加し、高温高湿条件下に置かれた場合でも、硬化物のゲル分率が変化しにくくなる。 The (meth)acryloyloxy group-containing polyisocyanate may be a commercially available product, such as BASF's Laromer (registered trademark) PR9000, which is a reaction product of 2-hydroxyethyl acrylate and hexamethylene diisocyanate and contains allophanate linkages. is mentioned.
These (meth)acryloyloxy group-containing polyisocyanates may be used alone or in combination of two or more. By using the (meth)acryloyloxy group-containing polyisocyanate (a2-1), the (meth)acryloyloxy group in the portion (in the molecular chain) other than the terminal of the (meth)acryloyloxy group-containing urethane polymer (A) is introduced. Therefore, the number of cross-linking points increases when the pressure-sensitive adhesive composition is cured, and the gel fraction of the cured product is less likely to change even when placed under high-temperature and high-humidity conditions.
ヒドロキシ基含有エチレン性不飽和化合物(a3-1)は、イソシアナト基を有さず、ヒドロキシ基とエチレン性不飽和基とを有する化合物であれば特に限定されない。硬化性の観点からは、エチレン性不飽和基は、ビニル基、アリル基、及び(メタ)アクリロイルオキシ基からなる群から選択される少なくとも1種であることが好ましく、(メタ)アクリロイルオキシ基であることが好ましい。 [Hydroxy group-containing ethylenically unsaturated compound (a3-1)]
The hydroxy group-containing ethylenically unsaturated compound (a3-1) is not particularly limited as long as it does not have an isocyanato group and has a hydroxy group and an ethylenically unsaturated group. From the viewpoint of curability, the ethylenically unsaturated group is preferably at least one selected from the group consisting of a vinyl group, an allyl group, and a (meth)acryloyloxy group. Preferably.
本実施態様のヒドロキシ基含有エチレン性不飽和化合物(a3-1)は、ヒドロキシ基含有(メタ)アクリレートであることが好ましい。ヒドロキシ基含有(メタ)アクリレートとしては、イソシアナト基を有さず、ヒドロキシ基と(メタ)アクリロイルオキシ基を有する化合物であれば特に限定されない。例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート;1,3-ブタンジオールモノ(メタ)アクリレート、1,6-ヘキサンジオールモノ(メタ)アクリレート、3-メチルペンタンジオールモノ(メタ)アクリレート等の各種ポリオール由来の(メタ)アクリロイル基を有するモノオール等が挙げられる。ポリイソシアネート(a2)のイソシアナト基との反応性、粘着剤組成物としての光硬化性の観点からは、ヒドロキシアルキル(メタ)アクリレートが好ましく、炭素数2~6のアルキル基を有するヒドロキシアルキル(メタ)アクリレートがより好ましく、2-ヒドロキシエチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートがより好ましい。これらは、一種を単独で使用してもよく、2種以上を併用しても良い。
ヒドロキシ基含有エチレン性不飽和化合物(a3-1)を使用することにより、第1エチレン性不飽和基含有ウレタンポリマー(A-1)の分子鎖末端部分にエチレン性不飽和基を導入することができる。その結果、粘着剤組成物を光硬化させた際に、ヒドロキシ基含有エチレン性不飽和化合物(a3-1)由来のエチレン性不飽和基、エチレン性不飽和基含有ポリイソシアネート(a2-1)由来のエチレン性不飽和基、及び後述する(B)成分のエチレン性不飽和基等が重合して、ゲル分率が変化しにくくなる。そのため、保護シートとして剥離した際の被着体の汚染が生じにくくなる。 <Hydroxy group-containing (meth)acrylate>
The hydroxy group-containing ethylenically unsaturated compound (a3-1) of this embodiment is preferably a hydroxy group-containing (meth)acrylate. The hydroxy group-containing (meth)acrylate is not particularly limited as long as it is a compound that does not have an isocyanato group and has a hydroxy group and a (meth)acryloyloxy group. Hydroxyalkyl (meth)acrylates such as, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; 1,3-butanediol mono(meth)acrylate, 1 , 6-hexanediol mono(meth)acrylate, 3-methylpentanediol mono(meth)acrylate and other polyol-derived (meth)acryloyl group-containing monools. From the viewpoint of reactivity with the isocyanato groups of the polyisocyanate (a2) and photocurability as a pressure-sensitive adhesive composition, hydroxyalkyl (meth)acrylates are preferable, and hydroxyalkyl (meth)acrylates having an alkyl group having 2 to 6 carbon atoms (meth) ) acrylate, more preferably 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. These may be used individually by 1 type, and may use 2 or more types together.
By using the hydroxy group-containing ethylenically unsaturated compound (a3-1), an ethylenically unsaturated group can be introduced into the molecular chain terminal portion of the first ethylenically unsaturated group-containing urethane polymer (A-1). can. As a result, when the adhesive composition is photocured, the ethylenically unsaturated group derived from the hydroxy group-containing ethylenically unsaturated compound (a3-1), the ethylenically unsaturated group-containing polyisocyanate (a2-1) derived and the ethylenically unsaturated groups of component (B), which will be described later, are polymerized to make the gel fraction less likely to change. Therefore, when the protective sheet is peeled off, the adherend is less likely to be contaminated.
本実施態様のヒドロキシ基含有エチレン性不飽和化合物(a3-1)は、ヒドロキシ基とビニル基を有する化合物であってもよい。ヒドロキシ基とビニル基を有する化合物としては、ポリアルキレングリコールモノビニルエーテル、ヒドロキシアルキルビニルエーテル、ヒドロキシカルボン酸ビニルエステル、ヒドロキシアルキルビニルエステルなどが挙げられる。 <Compound having a hydroxy group and a vinyl group>
The hydroxy group-containing ethylenically unsaturated compound (a3-1) of this embodiment may be a compound having a hydroxy group and a vinyl group. Compounds having a hydroxy group and a vinyl group include polyalkylene glycol monovinyl ethers, hydroxyalkyl vinyl ethers, hydroxycarboxylic acid vinyl esters, hydroxyalkyl vinyl esters, and the like.
ヒドロキシアルキルビニルエーテルとしては、4-ヒドロキシブチルビニルエーテル、4-ヒドロキシシクロヘキシルビニルエーテル等が挙げられる。
ヒドロキシカルボン酸ビニルエステルとしては、ヒドロキシ酢酸ビニル、ヒドロキシプロパン酸ビニル、ヒドロキシブタン酸ビニル、ヒドロキシヘキサン酸ビニル、4-ヒドロキシシクロヘキシル酢酸ビニル等が挙げられる。
ヒドロキシアルキルビニルエステルとしては、ヒドロキシシクロヘキシルカルボン酸ビニル等が挙げられる。 Polyalkylene glycol monovinyl ether includes diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and the like.
Hydroxyalkyl vinyl ethers include 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether and the like.
Hydroxycarboxylic acid vinyl esters include vinyl hydroxyacetate, vinyl hydroxypropanoate, vinyl hydroxybutanoate, vinyl hydroxyhexanoate, and vinyl 4-hydroxycyclohexyl acetate.
Hydroxyalkylvinyl esters include vinyl hydroxycyclohexylcarboxylate and the like.
本実施態様のヒドロキシ基含有エチレン性不飽和化合物(a3-1)は、イソシアナト基を有さず、ヒドロキシ基とアリル基を有する化合物であってもよい。ヒドロキシ基とアリル基を有する化合物としては、ヒドロキシアルキルアリルエーテル、ヒドロキシカルボン酸アリルエステル、ヒドロキシアルキルアリルエステル等が挙げられる。 <Compound having a hydroxy group and an allyl group>
The hydroxy group-containing ethylenically unsaturated compound (a3-1) of this embodiment may be a compound having no isocyanato group and having a hydroxy group and an allyl group. Compounds having a hydroxy group and an allyl group include hydroxyalkyl allyl ethers, hydroxycarboxylic acid allyl esters, hydroxyalkyl allyl esters, and the like.
ヒドロキシカルボン酸アリルエステルとしては、ヒドロキシ酢酸アリル、ヒドロキシプロパン酸アリル、ヒドロキシブタン酸アリル、ヒドロキシヘキサン酸アリル、4-ヒドロキシシクロヘキシル酢酸アリル等が挙げられる。
ヒドロキシアルキルアリルエステルとしては、ヒドロキシエチルアリルエステル、ヒドロキシプロピルアリルエステル、ヒドロキシブチルアリルエステル、ヒドロキシイソブチルアリルエステル、ヒドロキシシクロヘキシルアリルエステル等が挙げられる。 Hydroxyalkyl allyl ethers include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, 4-hydroxycyclohexyl allyl ether and the like.
Examples of hydroxycarboxylic acid allyl esters include allyl hydroxyacetate, allyl hydroxypropanoate, allyl hydroxybutanoate, allyl hydroxyhexanoate, and allyl 4-hydroxycyclohexylacetate.
Hydroxyalkyl allyl esters include hydroxyethyl allyl ester, hydroxypropyl allyl ester, hydroxybutyl allyl ester, hydroxyisobutyl allyl ester, hydroxycyclohexyl allyl ester and the like.
本実施形態に用いる第2エチレン性不飽和基含有ウレタンポリマー(A-2)は、ポリオキシアルキレンポリオール(a1)と、ポリイソシアネート(a2)と、イソシアナト基含有エチレン性不飽和化合物(a3-2)との反応物である。前記第2エチレン性不飽和基含有ウレタンポリマー(A-2)が、(メタ)アクリロイルオキシ基含有ウレタンポリマーであることが好ましい。 [Second ethylenically unsaturated group-containing urethane polymer (A-2)]
The second ethylenically unsaturated group-containing urethane polymer (A-2) used in the present embodiment comprises a polyoxyalkylene polyol (a1), a polyisocyanate (a2), and an isocyanato group-containing ethylenically unsaturated compound (a3-2 ). The second ethylenically unsaturated group-containing urethane polymer (A-2) is preferably a (meth)acryloyloxy group-containing urethane polymer.
第2エチレン性不飽和基含有ウレタンポリマー(A―2)に用いるポリオキシアルキレンポリオール(a1)は、前述の本実施形態の第1エチレン性不飽和基含有ウレタンポリマー(A―1)に用いるポリオキシアルキレンポリオール(a1)又はそれらの好ましい例を用いることができる。 [Polyoxyalkylene polyol (a1)]
The polyoxyalkylene polyol (a1) used in the second ethylenically unsaturated group-containing urethane polymer (A-2) is the polyoxyalkylene polyol (a1) used in the first ethylenically unsaturated group-containing urethane polymer (A-1) of the present embodiment described above. Oxyalkylene polyol (a1) or preferred examples thereof can be used.
第2エチレン性不飽和基含有ウレタンポリマー(A―2)に用いるポリイソシアネート(a2)は、前述の本実施形態の第1エチレン性不飽和基含有ウレタンポリマー(A―1)に用いるポリイソシアネート(a2)又はそれらの好ましい例を用いることができる。 [Polyisocyanate (a2)]
The polyisocyanate (a2) used for the second ethylenically unsaturated group-containing urethane polymer (A-2) is the polyisocyanate (a2) used for the first ethylenically unsaturated group-containing urethane polymer (A-1) of the present embodiment. a2) or preferred examples thereof can be used.
イソシアナト基含有エチレン性不飽和化合物(a3-2)としては、ヒドロキシ基を有さず、イソシアナト基とエチレン性不飽和基を有する化合物であれば特に限定されない。イソシアナト基含有エチレン性不飽和化合物(a3-2)がイソシアナト基含有(メタ)アクリレートであることが好ましい。例えば、2-イソシアナトエチル(メタ)アクリレート、2-イソシアナトプロピル(メタ)アクリレート、4-イソシアナトブチル(メタ)アクリレート、6-イソシアナトヘキシル(メタ)アクリレート等のイソシアナトアルキル(メタ)アクリレート等が挙げられる。ポリオキシアルキレンポリオール(a1)のヒドロキシ基との反応性、粘着剤組成物としての光硬化性の観点からは、炭素数2~6のアルキル基を有するイソシアナトシアルキル(メタ)アクリレートが好ましく、2-イソシアナトエチル(メタ)アクリレート、4-イソシアナトブチル(メタ)アクリレートがより好ましい。これらは、一種を単独で使用してもよく、2種以上を併用しても良い。 イソシアナト基含有エチレン性不飽和化合物(a3-2)を使用することにより、第2エチレン性不飽和基含有ウレタンポリマー(A-2)の分子鎖末端部分にエチレン性不飽和基を導入することができる。その結果、粘着剤組成物を光硬化させた際に、イソシアナト基含有エチレン性不飽和化合物(a3-2)由来のエチレン性不飽和基、エチレン性不飽和基含有ポリイソシアネート(a2-1)由来のエチレン性不飽和基、及び後述する(B)成分のエチレン性不飽和基等が重合して、ゲル分率が変化しにくくなる。そのため、保護シートとして剥離した際の被着体の汚染が生じにくくなる。 [Isocyanato group-containing ethylenically unsaturated compound (a3-2)]
The isocyanato group-containing ethylenically unsaturated compound (a3-2) is not particularly limited as long as it is a compound having no hydroxy group and having an isocyanato group and an ethylenically unsaturated group. The isocyanato group-containing ethylenically unsaturated compound (a3-2) is preferably an isocyanato group-containing (meth)acrylate. For example, isocyanatoalkyl (meth)acrylates such as 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 6-isocyanatohexyl (meth)acrylate etc. From the viewpoint of reactivity with hydroxy groups of the polyoxyalkylene polyol (a1) and photocurability as a pressure-sensitive adhesive composition, isocyanatosialkyl (meth)acrylates having an alkyl group having 2 to 6 carbon atoms are preferred. -isocyanatoethyl (meth)acrylate and 4-isocyanatobutyl (meth)acrylate are more preferred. These may be used individually by 1 type, and may use 2 or more types together. By using the isocyanato group-containing ethylenically unsaturated compound (a3-2), an ethylenically unsaturated group can be introduced into the molecular chain terminal portion of the second ethylenically unsaturated group-containing urethane polymer (A-2). can. As a result, when the adhesive composition is photocured, the ethylenically unsaturated group derived from the isocyanato group-containing ethylenically unsaturated compound (a3-2), the ethylenically unsaturated group-containing polyisocyanate (a2-1) derived and the ethylenically unsaturated groups of component (B), which will be described later, are polymerized to make the gel fraction less likely to change. Therefore, when the protective sheet is peeled off, the adherend is less likely to be contaminated.
エチレン性不飽和基含有モノマー(B)は、エチレン性不飽和基を有する単量体であれば特に限定されない。硬化性の観点からは、ビニル基又は(メタ)アクリロイル基を有することが好ましく、(メタ)アクリロイル基を有することがより好ましい。中でも、粘着剤組成物の希釈性、低粘着性、保護シートの打ち抜き加工性などの観点から、エチレン性不飽和基含有モノマー(B)は、単官能(メタ)アクリレート(B1)および/または多官能(メタ)アクリレート(B2)であることが好ましい。「単官能」とは、(メタ)アクリロイルオキシ基を1つのみ有することを意味し、「多官能」とは、複数の(メタ)アクリロイルオキシ基を有することを意味する。単官能(メタ)アクリレート(B1)を用いることにより、粘着剤組成物の硬化物の凝集力を押さえ、粘着層を柔軟にして、被着体に対する濡れ性を向上させることができる。多官能(メタ)アクリレート(B2)を用いることにより、粘着剤組成物の硬化物の凝集力が向上し、粘着層の適度な硬さを維持して粘着面(粘着層と被着体の間)への気泡の挟み込みを抑制することができる。(B1)(B2)成分を併用することにより、保護シートを剥離する際の剥離強度を調整することができる。 [Ethylenically unsaturated group-containing monomer (B)]
The ethylenically unsaturated group-containing monomer (B) is not particularly limited as long as it is a monomer having an ethylenically unsaturated group. From the viewpoint of curability, it preferably has a vinyl group or a (meth)acryloyl group, and more preferably has a (meth)acryloyl group. Among them, the ethylenically unsaturated group-containing monomer (B) is a monofunctional (meth)acrylate (B1) and/or multi It is preferably a functional (meth)acrylate (B2). "Monofunctional" means having only one (meth)acryloyloxy group, and "polyfunctional" means having a plurality of (meth)acryloyloxy groups. By using the monofunctional (meth)acrylate (B1), the cohesive force of the cured product of the pressure-sensitive adhesive composition can be suppressed, the pressure-sensitive adhesive layer can be made flexible, and the wettability to the adherend can be improved. By using the polyfunctional (meth)acrylate (B2), the cohesive force of the cured product of the pressure-sensitive adhesive composition is improved, and the pressure-sensitive adhesive layer maintains an appropriate hardness and adheres to the pressure-sensitive adhesive surface (between the pressure-sensitive adhesive layer and the adherend). ) can be suppressed from entrapment of air bubbles. By using the components (B1) and (B2) together, the peel strength when the protective sheet is peeled off can be adjusted.
光重合開始剤(C)は、光照射によりラジカルを発生する重合開始剤であれば特に限定されないが、カルボニル系光重合開始剤、スルフィド系光重合開始剤、アシルホスフィンオキサイド類、キノン系光重合開始剤、スルホクロリド系光重合開始剤、チオキサントン系光重合開始剤等が挙げられる。 [Photoinitiator (C)]
The photopolymerization initiator (C) is not particularly limited as long as it is a polymerization initiator that generates radicals upon irradiation with light. initiators, sulfochloride-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.
可塑剤(D)は、公知の物を特に制限なく使用することができる。例えば、脂肪酸エステルを好ましく使用することができる。可塑剤(D)は、保護シートのラミネート性(濡れ性)、泡抜け性(貼合時に挟み込んだ気泡の抜けやすさ)を向上させることができる。 [Plasticizer (D)]
A known plasticizer (D) can be used without particular limitation. For example, fatty acid esters can be preferably used. The plasticizer (D) can improve the lamination property (wettability) of the protective sheet and the bubble removal property (easiness of removal of air bubbles sandwiched during lamination).
粘着剤組成物は、低分子量成分として、エチレン性不飽和基含有モノマー(B)を含んでいるため、溶媒を加えなくとも塗布可能な粘度に調整することができる。すなわち、粘着剤組成物は、溶媒を実質に含まなくても良い。その場合、保護シートを製造する際、溶媒を加熱乾燥する工程が省略することができ、生産性が高くなる。特に、50μmを超える膜厚の保護シートを製造する際に、粘着剤組成物がその溶媒を実質に含まないことが好ましい。本発明の「実質に含まない」の意味は、本発明の粘着剤組成物における前記溶媒の含有量が0~1質量%であり、好ましく0~0.5質量%以下であり、より好ましく0~0.1質量%以下である。
粘着剤組成物は、塗工時の粘度調整を目的として溶媒を添加してもよい。溶媒は粘着剤組成物に含まれるその他の成分等によって適宜選択可能であるが、有機溶媒が好ましい。用いられる有機溶媒としては、特に限定されないが、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサノン、n-へキサン、トルエン、キシレン、n-プロパノール、イソプロパノール等が挙げられる。これらの有機溶媒は単独で使用してもよく、また2種以上を混合して用いてもよい。溶媒は、粘着剤組成物を基材等に塗布した後、乾燥することにより除去し、その後に光硬化を行うことが好ましい。 [solvent]
Since the pressure-sensitive adhesive composition contains the ethylenically unsaturated group-containing monomer (B) as a low-molecular-weight component, the viscosity can be adjusted so that it can be applied without adding a solvent. That is, the pressure-sensitive adhesive composition may be substantially free of solvent. In that case, the step of heating and drying the solvent can be omitted when manufacturing the protective sheet, resulting in high productivity. In particular, when producing a protective sheet with a film thickness exceeding 50 μm, it is preferred that the pressure-sensitive adhesive composition does not substantially contain the solvent. The meaning of "substantially not contained" in the present invention is that the content of the solvent in the adhesive composition of the present invention is 0 to 1% by mass, preferably 0 to 0.5% by mass or less, more preferably 0 ~0.1% by mass or less.
A solvent may be added to the pressure-sensitive adhesive composition for the purpose of adjusting the viscosity during coating. The solvent can be appropriately selected depending on other components contained in the pressure-sensitive adhesive composition, but organic solvents are preferred. The organic solvent used is not particularly limited, but includes methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol and isopropanol. These organic solvents may be used alone or in combination of two or more. It is preferable that the solvent is removed by drying after coating the pressure-sensitive adhesive composition on a substrate or the like, and then photocuring.
エチレン性不飽和基含有ウレタンポリマー(A)の含有量は、(A)成分及び(B)成分の合計100質量%に対して、30~70質量%が好ましく、40~60質量%がより好ましく、50~60質量%がさらに好ましい。含有量が30質量%以上であると、粘着剤組成物の硬化物の凝集力を向上させることができ、適度な硬さを有した粘着層となるため、保護シートの粘着面(粘着層と被着体の間)への気泡の挟み込みを抑制することができる。含有量が70質量%以下であると、粘着剤組成物の硬化物の凝集力を抑え、粘着層が柔軟になり、粘着層の被着体に対する濡れ性を向上することができる。 [Blending ratio of adhesive composition]
The content of the ethylenically unsaturated group-containing urethane polymer (A) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, based on the total 100% by mass of components (A) and (B). , 50 to 60 mass % is more preferable. When the content is 30% by mass or more, the cohesive force of the cured product of the adhesive composition can be improved, and the adhesive layer has an appropriate hardness. It is possible to suppress entrapment of air bubbles between adherends. When the content is 70% by mass or less, the cohesive force of the cured product of the pressure-sensitive adhesive composition can be suppressed, the pressure-sensitive adhesive layer becomes flexible, and the wettability of the pressure-sensitive adhesive layer to the adherend can be improved.
エチレン性不飽和基含有モノマー(B)が、単官能(メタ)アクリレート(B1)および多官能(メタ)アクリレート(B2)を含有する場合には、単官能(メタ)アクリレート(B1)の含有量は、20~60質量%が好ましく、25~55質量%がより好ましく、35~50質量%がさらに好ましい。単官能(メタ)アクリレート(B1)の含有量が20質量%以上であると、粘着剤組成物の硬化物の凝集力を押さえ、柔軟な硬化物が得られるため、被着体に対する粘着層の濡れ性を向上させることができる。単官能(メタ)アクリレート(B1)の含有量が60質量%以下であると、粘着剤組成物の硬化物の凝集力を向上させることができ、適度な硬さを有した粘着層となるため、保護シートの粘着面(粘着層と被着体の間)への気泡の挟み込みを抑制することができる。
多官能(メタ)アクリレート(B2)の含有量は、(A)成分及び(B)成分の合計100質量%に対して、1~30質量%が好ましく、3~20質量%がより好ましく、5~15質量%がさらに好ましい。多官能(メタ)アクリレート(B2)の含有量が1質量%以上であると、保護シートを剥離する際の剥離強度を抑えることができる。多官能(メタ)アクリレート(B2)の含有量が30質量%以下であると、粘着剤組成物の硬化物の柔軟性を維持することができ、ヘイズも低く抑えることができる。 The content of the ethylenically unsaturated group-containing monomer (B) is preferably 30 to 70% by mass, more preferably 40 to 65% by mass, based on the total 100% by mass of components (A) and (B). 50 to 60% by mass is more preferable.
When the ethylenically unsaturated group-containing monomer (B) contains a monofunctional (meth)acrylate (B1) and a polyfunctional (meth)acrylate (B2), the content of the monofunctional (meth)acrylate (B1) is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, even more preferably 35 to 50% by mass. When the content of the monofunctional (meth)acrylate (B1) is 20% by mass or more, the cohesive force of the cured product of the pressure-sensitive adhesive composition is suppressed, and a flexible cured product is obtained. Wettability can be improved. When the content of the monofunctional (meth)acrylate (B1) is 60% by mass or less, the cohesive force of the cured product of the adhesive composition can be improved, and the adhesive layer has an appropriate hardness. , the entrapment of air bubbles in the adhesive surface of the protective sheet (between the adhesive layer and the adherend) can be suppressed.
The content of the polyfunctional (meth)acrylate (B2) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total 100% by mass of the components (A) and (B). ~15% by mass is more preferred. When the content of the polyfunctional (meth)acrylate (B2) is 1% by mass or more, the peel strength when peeling the protective sheet can be suppressed. When the content of the polyfunctional (meth)acrylate (B2) is 30% by mass or less, the flexibility of the cured product of the pressure-sensitive adhesive composition can be maintained, and the haze can be kept low.
以下、本実施形態の粘着剤組成物に含まれるエチレン性不飽和基含有ウレタンポリマー(A)の好ましい合成方法の一例について説明するが、エチレン性不飽和基含有ウレタンポリマー(A)の合成方法はこれに限られず、合成に用いる原料や設備等の条件によって適宜変更可能である。また、この例においては、ヒドロキシ基とイソシアナト基の反応は、いずれの工程においても、イソシアナト基に不活性な有機溶媒の存在下で、ジブチルスズジラウレート、ジブチルスズジエチルヘキソエート、ジオクチルスズジラウレート等のウレタン化触媒を用いて行われる。反応は、30~100℃で1~5時間継続して行われることが好ましい。ウレタン化触媒の使用量は、反応物の総質量に対して、50~500質量ppmであることが好ましい。 [Method for synthesizing ethylenically unsaturated group-containing urethane polymer (A)]
An example of a preferred method for synthesizing the ethylenically unsaturated group-containing urethane polymer (A) contained in the pressure-sensitive adhesive composition of the present embodiment will be described below. It is not limited to this, and can be appropriately changed depending on conditions such as raw materials and equipment used for synthesis. Further, in this example, the reaction between the hydroxy group and the isocyanato group was carried out in the presence of an organic solvent inert to the isocyanato group in any step using urethane such as dibutyltin dilaurate, dibutyltin diethylhexoate, and dioctyltin dilaurate. conversion catalyst. The reaction is preferably carried out at 30-100° C. for 1-5 hours. The amount of the urethanization catalyst used is preferably 50 to 500 ppm by mass relative to the total mass of the reactants.
まず、ポリオキシアルキレンポリオール(a1)とポリイソシアネート(a2)とを、ポリイソシアネート(a2)のイソシアナト基量(数基準、以下同じ)が、ポリオキシアルキレンポリオール(a1)のヒドロキシ基量(数基準、以下同じ)より多くなる割合で仕込み、これらを反応させて末端にイソシアナト基を有するウレタンプレポリマーを合成する。ポリイソシアネート(a2)のイソシアナト基量が、エチレン性不飽和基含有ポリイソシアネート(a2-1)およびエチレン性不飽和基非含有ポリイソシアネート(a2-2)の合計のイソシアナト基量である。ポリオキシアルキレンポリオール(a1)及びポリイソシアネート(a2)の具体的な例は、ポリウレタン(A)の項で例示したとおりである。 [Method for synthesizing first ethylenically unsaturated group-containing urethane polymer (A-1)]
First, the polyoxyalkylene polyol (a1) and the polyisocyanate (a2) are determined so that the isocyanato group amount (number basis, hereinafter the same) of the polyisocyanate (a2) is the hydroxy group amount (number basis) of the polyoxyalkylene polyol (a1) , the same applies hereinafter) are added and reacted to synthesize a urethane prepolymer having terminal isocyanato groups. The isocyanate group content of the polyisocyanate (a2) is the total isocyanate group content of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2). Specific examples of the polyoxyalkylene polyol (a1) and polyisocyanate (a2) are as exemplified in the section on polyurethane (A).
数基準で、第1エチレン性不飽和基含有ウレタンポリマー(A-1)に含まれるポリウレタンの末端の90~100%にエチレン性不飽和基が導入されていることが好ましく、95~100%がより好ましく、100%がさらに好ましい。エチレン性不飽和基の導入量が、イソシアナト基に対して、数基準で90%以上であれば、粘着剤組成物を硬化して得られる粘着層の凝集力が十分に得られる。全てのポリウレタン分子鎖の末端の数に対するエチレン性不飽和基が導入されている末端の数の割合は、IR、NMR等により測定することができる。 Next, an isocyanato group-containing urethane prepolymer and a hydroxyl group-containing ethylenically unsaturated compound (a3-1) are reacted to obtain a first ethylenically unsaturated group in which an ethylenically unsaturated group is introduced at the molecular chain end. A containing urethane polymer (A-1) is synthesized.
On a numerical basis, it is preferable that 90 to 100% of the terminal of the polyurethane contained in the first ethylenically unsaturated group-containing urethane polymer (A-1) is introduced with an ethylenically unsaturated group, and 95 to 100% is More preferably, 100% is even more preferable. If the introduction amount of the ethylenically unsaturated groups is 90% or more on the number basis with respect to the isocyanato groups, the cohesive force of the adhesive layer obtained by curing the adhesive composition can be sufficiently obtained. The ratio of the number of terminals introduced with ethylenically unsaturated groups to the number of terminals of all polyurethane molecular chains can be measured by IR, NMR, or the like.
まず、ポリオキシアルキレンポリオール(a1)とポリイソシアネート(a2)とを、ポリオキシアルキレンポリオール(a1)のヒドロキシ基量(数基準、以下同じ)がポリイソシアネート(a2)のイソシアナト基量(数基準、以下同じ)より多くなる割合で仕込み、これらを反応させて末端にヒドロキシ基を有するウレタンプレポリマーを合成する。ポリイソシアネート(a2)のイソシアナト基量が、エチレン性不飽和基含有ポリイソシアネート(a2-1)およびエチレン性不飽和基非含有ポリイソシアネート(a2-2)の合計のイソシアナト基量である。ポリオキシアルキレンポリオール(a1)及びポリイソシアネート(a2)の具体的な例は、ポリウレタン(A)の項で例示したとおりである。 [Method for synthesizing second ethylenically unsaturated group-containing urethane polymer (A-2)]
First, the polyoxyalkylene polyol (a1) and the polyisocyanate (a2) are separated so that the amount of hydroxy groups (number basis, hereinafter the same) of the polyoxyalkylene polyol (a1) is equal to the amount of isocyanato groups (number basis, hereinafter the same) of the polyisocyanate (a2) The same applies hereinafter), and reacted to synthesize a urethane prepolymer having terminal hydroxy groups. The isocyanate group content of the polyisocyanate (a2) is the total isocyanate group content of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2). Specific examples of the polyoxyalkylene polyol (a1) and polyisocyanate (a2) are as exemplified in the section on polyurethane (A).
数基準で、第2エチレン性不飽和基含有ウレタンポリマー(A-2)に含まれるポリウレタンの末端の90~100%にエチレン性不飽和基が導入されていることが好ましく、95~100%がより好ましく、100%がさらに好ましい。エチレン性不飽和基の導入量が、ヒドロキシ基に対して、数基準で90%以上であれば、粘着剤組成物を硬化して得られる粘着層の凝集力が十分に得られる。全てのポリウレタン分子鎖の末端の数に対するエチレン性不飽和基が導入されている末端の数の割合は、IR、NMR等により測定することができる。 Next, a hydroxy group-containing urethane prepolymer and an isocyanato group-containing ethylenically unsaturated compound (a3-2) are reacted to obtain a second ethylenically unsaturated group in which an ethylenically unsaturated group is introduced at the molecular chain end. A containing urethane polymer (A-2) is synthesized.
On a numerical basis, it is preferable that 90 to 100% of the terminal polyurethanes contained in the second ethylenically unsaturated group-containing urethane polymer (A-2) are introduced with ethylenically unsaturated groups, and 95 to 100% are More preferably, 100% is even more preferable. If the introduction amount of the ethylenically unsaturated groups is 90% or more on the number basis with respect to the hydroxyl groups, the cohesive strength of the adhesive layer obtained by curing the adhesive composition can be sufficiently obtained. The ratio of the number of terminals introduced with ethylenically unsaturated groups to the number of terminals of all polyurethane molecular chains can be measured by IR, NMR, or the like.
エチレン性不飽和基含有ウレタンポリマー(A)と、エチレン性不飽和基含有モノマー(B)と、光重合開始剤(C)と、必要に応じて、可塑剤(D)と、その他の添加剤、及び有機溶媒とを混合することで、粘着剤組成物を製造される。混合方法は、特に限定されないが、例えば、ホモディスパー、パドル翼等の攪拌翼を取り付けた攪拌装置を用いて行うことができる。 [Method for producing pressure-sensitive adhesive composition]
An ethylenically unsaturated group-containing urethane polymer (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and optionally a plasticizer (D) and other additives , and an organic solvent to produce a pressure-sensitive adhesive composition. The mixing method is not particularly limited, but for example, it can be carried out using a stirring device equipped with stirring blades such as Homodisper and paddle blades.
[保護シートの構成]
本実施形態にかかる保護シートは、基材の片面に、上記粘着剤組成物の硬化物を含む粘着層が形成されている。粘着層の厚みは、3~150μmであることが好ましく、5~130μmであることがより好ましく、10~100μmであることがさらに好ましい。粘着層の膜厚が3μm以上であれば粘着層の強度が十分であり、膜厚が150μm以下であれば粘着層の膜厚の制御が容易である。
さらに、被着体を衝撃から守る機能(耐衝撃性)を保護シートに付与させたい場合には、粘着層の膜厚は50μm以上であることが好ましい。 (protection sheet)
[Configuration of protection sheet]
In the protective sheet according to this embodiment, an adhesive layer containing a cured product of the adhesive composition is formed on one side of a base material. The thickness of the adhesive layer is preferably 3 to 150 μm, more preferably 5 to 130 μm, even more preferably 10 to 100 μm. When the thickness of the adhesive layer is 3 μm or more, the strength of the adhesive layer is sufficient, and when the thickness is 150 μm or less, the thickness of the adhesive layer can be easily controlled.
Furthermore, when the protection sheet is to have a function of protecting the adherend from impact (impact resistance), the thickness of the adhesive layer is preferably 50 μm or more.
本実施形態にかかる保護シートの製造方法は、例えば、基材に粘着剤組成物を塗布し、塗布した粘着剤組成物に紫外線を照射して光硬化させることにより得ることができる。 [Method for manufacturing protective sheet]
The method for producing a protective sheet according to the present embodiment can be obtained, for example, by applying an adhesive composition to a substrate and irradiating the applied adhesive composition with ultraviolet rays to photocure it.
検査工程においては、製品または部品に保護シートがラミネートされた状態で、製品または部品の細かい異物や傷を十分に発見、あるいは検出できることが要求されることがある。また、保護シートは、光学部品として用いられるプラスチックフィルムの表面を保護する目的で好適に用いられることもある。前記光学部品としては、例えば、偏光板、波長板、位相差板、光学補償フィルム、反射シート、輝度向上フィルム等が挙げられる。これらの光学部品は、例えば、スマートフォン、パソコン、テレビ等の液晶ディスプレイなどに用いられるものである。 [Usage and Required Performance of Protective Sheet]
In the inspection process, it may be required to be able to sufficiently discover or detect small foreign matter and flaws on the product or part with a protective sheet laminated on the product or part. Also, the protective sheet may be suitably used for the purpose of protecting the surface of a plastic film used as an optical component. Examples of the optical components include polarizing plates, wave plates, retardation plates, optical compensation films, reflective sheets, brightness enhancement films, and the like. These optical components are used, for example, in liquid crystal displays of smartphones, personal computers, televisions, and the like.
以下の実施例において、得られたエチレン性不飽和基含有ウレタンポリマー(A)の重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー(昭和電工株式会社製Shodex(登録商標) GPC-101、以下、GPCとする。)により測定されたポリスチレン換算の値である。GPCの測定条件は以下のとおりである。
カラム:昭和電工株式会社製LF-804
カラム温度:40℃
試料:ポリウレタン(A)の0.2質量%テトラヒドロフラン溶液
流量:1ml/分
溶離液:テトラヒドロフラン
検出器:RI検出器(示差屈折率検出器) (Measurement of weight average molecular weight)
In the following examples, the weight average molecular weight of the obtained ethylenically unsaturated group-containing urethane polymer (A) was determined by gel permeation chromatography (Showa Denko Co., Ltd. Shodex (registered trademark) GPC-101, hereinafter, It is a value converted to polystyrene measured by GPC. The measurement conditions of GPC are as follows.
Column: LF-804 manufactured by Showa Denko K.K.
Column temperature: 40°C
Sample: 0.2% by weight tetrahydrofuran solution of polyurethane (A) Flow rate: 1 ml/min Eluent: Tetrahydrofuran Detector: RI detector (differential refractive index detector)
(合成例1)
温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコに、Laromer(登録商標) PR9000(BASF製)を1mol、及び水酸基価が56mgKOH/gのヒドロキシ基を末端に有するポリプロピレングリコールD-2000(三井化学製、数平均分子量2000)を5mol仕込んだ。その後、この四つ口フラスコを80℃まで昇温して2時間反応させた。次いで、イソホロンジイソシアネート(デスモジュールI、住化コベストロウレタン製)を5mol仕込み、80℃で6時間反応させ、イソシアナト基を両末端に有するウレタンプレポリマーを得た。 <Synthesis of ethylenically unsaturated group-containing urethane polymer (A)>
(Synthesis example 1)
In a four-necked flask equipped with a thermometer, stirrer, dropping funnel, condenser with drying tube, 1 mol of Laromer® PR9000 (manufactured by BASF) and a hydroxyl group with a hydroxyl value of 56 mgKOH/g are terminated. 5 mol of polypropylene glycol D-2000 (manufactured by Mitsui Chemicals, number average molecular weight 2000) was charged. Thereafter, the four-necked flask was heated to 80° C. and reacted for 2 hours. Next, 5 mol of isophorone diisocyanate (Desmodur I, manufactured by Sumika Covestro Urethane) was charged and reacted at 80° C. for 6 hours to obtain a urethane prepolymer having isocyanato groups at both ends.
Laromer(登録商標) PR9000を2mol、及びイソホロンジイソシアネートを4molに変えたこと以外は(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-i)の合成法と同様にして、アクリロイルオキシ基を末端に有する(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-ii)を得た。得られた(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-ii)の重量平均分子量は、130,000であった。表1に示す。 (Synthesis example 2)
Acryloyloxy group-terminated urethane polymer (Ai) was synthesized in the same manner as the (meth)acryloyloxy group-containing urethane polymer (Ai), except that 2 mol of Laromer (registered trademark) PR9000 and 4 mol of isophorone diisocyanate were used. A meth)acryloyloxy group-containing urethane polymer (A-ii) was obtained. The weight average molecular weight of the obtained (meth)acryloyloxy group-containing urethane polymer (A-ii) was 130,000. Table 1 shows.
水酸基価が56mgKOH/gのヒドロキシ基を末端に有するポリプロピレングリコールD-2000に代えて水酸基価が111mgKOH/gのヒドロキシ基を末端に有するポリプロピレングリコールD-1000(三井化学製、数平均分子量1000)を用いること以外は(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-i)の合成法と同様にして、アクリロイルオキシ基を末端に有するポリウレタン(A-iii)を得た。得られた(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-iii)の重量平均分子量は、90,000であった。表1に示す。 (Synthesis Example 3)
Polypropylene glycol D-1000 (manufactured by Mitsui Chemicals, number average molecular weight 1000) having a hydroxyl group at the end with a hydroxyl value of 111 mgKOH/g instead of polypropylene glycol D-2000 having a hydroxyl group at the end with a hydroxyl value of 56 mgKOH/g. Polyurethane (A-iii) having an acryloyloxy group at its end was obtained in the same manner as in the synthesis method of (meth)acryloyloxy group-containing urethane polymer (Ai), except that it was used. The obtained (meth)acryloyloxy group-containing urethane polymer (A-iii) had a weight average molecular weight of 90,000. Table 1 shows.
2-ヒドロキシエチルアクリレート2molに代えて4-ヒドロキシブチルビニルエーテル2molを用いること以外は(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-i)の合成法と同様にして、アクリロイルオキシ基を末端に有するポリウレタン(A-iv)を得た。得られた(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-iv)の重量平均分子量は、45,000であった。表1に示す。 (Synthesis Example 4)
A polyurethane having an acryloyloxy group at its terminal was prepared in the same manner as in the method for synthesizing the (meth)acryloyloxy group-containing urethane polymer (Ai), except that 2 mol of 4-hydroxybutyl vinyl ether was used instead of 2 mol of 2-hydroxyethyl acrylate. (A-iv) was obtained. The obtained (meth)acryloyloxy group-containing urethane polymer (A-iv) had a weight average molecular weight of 45,000. Table 1 shows.
Laromer(登録商標) PR9000を0mol、及びイソホロンジイソシアネートを6molに変えたこと以外は(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-i)の合成法と同様にして、アクリロイルオキシ基を末端に有するウレタンポリマー(cA-i)を得た。得られたウレタンポリマー(cA-i)の重量平均分子量は、42,000であった。表1に示す。 (Comparative Synthesis Example 1)
Acryloyloxy-terminated urethane was prepared in the same manner as in the method for synthesizing (meth)acryloyloxy group-containing urethane polymer (Ai), except that Laromer (registered trademark) PR9000 was changed to 0 mol and isophorone diisocyanate was changed to 6 mol. Polymer (cA-i) was obtained. The weight average molecular weight of the obtained urethane polymer (cA-i) was 42,000. Table 1 shows.
各成分と配合量を表1に記載のものに変えたこと以外は(メタ)アクリロイルオキシ基含有ウレタンポリマー(A-i)の合成法と同様にして、アクリロイルオキシ基を末端に有するウレタンポリマー(cA-ii)を得た。得られたウレタンポリマー(cA-ii)の重量平均分子量は、20,000であった。表1に示す。 (Comparative Synthesis Example 2)
A urethane polymer having an acryloyloxy group at its terminal (Ai) was synthesized in the same manner as the (meth)acryloyloxy group-containing urethane polymer (Ai), except that each component and the blending amount were changed to those shown in Table 1. cA-ii) was obtained. The weight average molecular weight of the resulting urethane polymer (cA-ii) was 20,000. Table 1 shows.
エチレン性不飽和基含有ウレタンポリマー(A)、エチレン性不飽和基含有モノマー(B)、光重合開始剤(C)、及び可塑剤(D)を、表2~3に記載の組成で配合し、25℃でディスパーを用いて混合した。実施例1~11、比較例1~8にかかる粘着剤組成物を調製した。 <Preparation of adhesive composition>
An ethylenically unsaturated group-containing urethane polymer (A), an ethylenically unsaturated group-containing monomer (B), a photopolymerization initiator (C), and a plasticizer (D) are blended according to the composition shown in Tables 2 and 3. , and mixed with a disper at 25°C. PSA compositions for Examples 1 to 11 and Comparative Examples 1 to 8 were prepared.
実施例1~11及び比較例1~8について同じ方法で、片面に光学用PETフィルムの基材を有する保護シートを作製した。まず、アプリケーターを用いて、調整した粘着剤組成物を、厚さ75μmの光学用PETフィルム(東洋紡株式会社製A4300)上に塗布し、塗布された粘着剤組成物の上から、厚さ75μmの剥離PETフィルム(東洋紡株式会社製E7006)で覆った。次に、紫外線照射装置(アイグラフィックス株式会社製、UV照射装置3kW、高圧水銀ランプ)を用い、剥離PETフィルムで覆われたシートを、剥離PETフィルム側の面から紫外線を照射して粘着剤組成物を光硬化させた。紫外線の照射距離は25cm、ランプ移動速度は1.0m/分、照射量は1000mJ/cm2である。硬化後の粘着層の厚さはダイヤルゲージを用いて、保護シートの厚さを測定した後、この測定値から光学用PETフィルムの厚さ75μmと剥離PETフィルムの厚さ75μmとを引いて算出した。ダイヤルゲージの測定面は、直径5mmの円形の平面で、測定力は0.8Nとした。実施例1~11、比較例1~8のいずれにおいても粘着層の厚さは75μmであった。 <Production of protective sheet>
A protective sheet having an optical PET film substrate on one side was produced in the same manner as in Examples 1 to 11 and Comparative Examples 1 to 8. First, using an applicator, the adjusted adhesive composition is applied on a 75 μm thick optical PET film (A4300 manufactured by Toyobo Co., Ltd.), and a 75 μm thick film is applied from above the applied adhesive composition. It was covered with a release PET film (E7006 manufactured by Toyobo Co., Ltd.). Next, using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UV irradiation device 3 kW, high-pressure mercury lamp), the sheet covered with the release PET film is irradiated with ultraviolet rays from the surface on the release PET film side, and the adhesive is removed. The composition was photocured. The ultraviolet irradiation distance is 25 cm, the lamp moving speed is 1.0 m/min, and the irradiation amount is 1000 mJ/cm 2 . The thickness of the adhesive layer after curing is calculated by measuring the thickness of the protective sheet using a dial gauge and then subtracting the 75 μm thickness of the optical PET film and the 75 μm thickness of the release PET film from this measured value. did. The measuring surface of the dial gauge was a circular plane with a diameter of 5 mm, and the measuring force was 0.8N. In each of Examples 1-11 and Comparative Examples 1-8, the thickness of the adhesive layer was 75 μm.
EHA:化合物名(2-エチルヘキシルアクリレート、東亜合成株式会社製)
LA:化合物名(ラウリルアクリレート、大阪有機化学工業株式会社製)
TMPTA:化合物名(トリメチロールプロパントリアクリレートM-309、東亜合成株式会社製)
Irg-184:化合物名(1-Hydroxycyclohexyl Phenyl Ketone、東京化成工業株式会社製)
IPM:化合物名(エキセパールIPM、花王株式会社製) The following compounds were used in the table.
EHA: compound name (2-ethylhexyl acrylate, manufactured by Toagosei Co., Ltd.)
LA: compound name (lauryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
TMPTA: compound name (trimethylolpropane triacrylate M-309, manufactured by Toagosei Co., Ltd.)
Irg-184: compound name (1-Hydroxycyclohexyl Phenyl Ketone, manufactured by Tokyo Chemical Industry Co., Ltd.)
IPM: compound name (Exepar IPM, manufactured by Kao Corporation)
実施例1~11及び比較例1~8にかかる粘着剤組成物及び保護シートについて、初期条件下及び高温高湿条件下放置後のゲル分率変化、水接触角変化を以下に記載する方法により評価した。また、高温高湿条件下放置後に保護シートを剥離した後の被着体のガラス試験板の汚染の有無を以下に記載する方法により評価した。結果を表2~3に示した。 <Evaluation of adhesive composition and protective sheet>
Regarding the adhesive compositions and protective sheets according to Examples 1 to 11 and Comparative Examples 1 to 8, changes in gel fraction and changes in water contact angle after being left under initial conditions and under high temperature and high humidity conditions were measured by the methods described below. evaluated. In addition, the presence or absence of contamination of the adherend glass test plate after peeling off the protective sheet after being left under high-temperature and high-humidity conditions was evaluated by the method described below. The results are shown in Tables 2-3.
まず、アプリケーターを用いて、実施例1~11及び比較例1~8のそれぞれにかかる粘着剤組成物を、硬化後の粘着層の厚さが75μmとなるように50μm厚の剥離PETフィルム(東山フィルム株式会社製HY-S10)に塗布した。なお、粘着層の厚さの確認方法は、保護シートの作製の項で上記した測定方法と同様である。 (Gel fraction)
First, using an applicator, the adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 8 were applied to a 50 μm thick release PET film (Higashiyama HY-S10 manufactured by Film Co., Ltd.). The method for confirming the thickness of the adhesive layer is the same as the measurement method described above in the section on preparation of the protective sheet.
B:測定用サンプルのテトラヒドロフラン浸漬前の質量 A: Dry mass of measurement sample after immersion in tetrahydrofuran (excluding mass of tetrahydrofuran)
B: Mass of measurement sample before immersion in tetrahydrofuran
B:高温高湿条件下放置後のゲル分率 A: Gel fraction under initial conditions B: Gel fraction after standing under high temperature and high humidity conditions
ガラス板からなる試験板を3%セミクリーンL.G.L(横浜樹脂製)水溶液であるアルカリ洗浄液に一晩漬け、超音波洗浄機で1時間洗浄した。その後、試験板をイオン交換水につけ、超音波洗浄機で30分洗浄を2回繰り返し、空気中温度150℃で2時間乾燥させた。乾燥後の試験板の表面の水接触角を、接触角計(DMо―601、協和界面科学株式会社製)で1サンプルにつき5か所測定し、この平均値をブランクとした。水は純水を用いた。 実施例1~11及び比較例1~8のそれぞれで作製した保護シートを25mm×150mmの短冊状に切り取り、剥離PETフィルムを剥離した。露出した粘着剤層の全面を、洗浄および乾燥させた試験板にラミネートしてゴムローラーを1往復させて、測定用サンプルを作製した。この測定用サンプルについて、空気中温度85℃、相対湿度85%の環境下で250時間放置した。その後、測定用サンプルから保護シートを剥がした後に前記ブランクと同様の手順で、高温高湿条件下放置後のガラス板からなる試験板表面の水接触角を測定した。 (water contact angle)
A test plate consisting of a glass plate was soaked in 3% semi-clean L.I. G. It was immersed overnight in an alkaline cleaning solution, which is an aqueous solution of L (Yokohama Jushi Co., Ltd.), and cleaned with an ultrasonic cleaner for 1 hour. After that, the test plate was immersed in deionized water, washed twice for 30 minutes with an ultrasonic cleaner, and dried at 150° C. in the air for 2 hours. The water contact angle on the surface of the dried test plate was measured at 5 points per sample using a contact angle meter (DMO-601, manufactured by Kyowa Interface Science Co., Ltd.), and the average value was used as a blank. Pure water was used as the water. The protective sheets prepared in Examples 1 to 11 and Comparative Examples 1 to 8 were cut into strips of 25 mm×150 mm, and the release PET film was peeled off. The entire surface of the exposed pressure-sensitive adhesive layer was laminated on a washed and dried test plate, and a rubber roller was reciprocated once to prepare a sample for measurement. This measurement sample was allowed to stand for 250 hours in an environment with an air temperature of 85° C. and a relative humidity of 85%. Thereafter, after peeling off the protective sheet from the measurement sample, the water contact angle on the surface of the test plate made of a glass plate after being left under high temperature and high humidity conditions was measured in the same procedure as for the blank.
B:高温高湿条件下放置後の水接触角(°) A: blank water contact angle (°)
B: Water contact angle (°) after being left under high temperature and high humidity conditions
水接触角の試験と同様にして、測定用サンプルを空気中温度85℃、相対湿度85%の環境下で250時間放置した。次いで、測定用サンプルから保護シートを剥がした後に、ガラス試験板の表面をデジタル光学顕微鏡(株式会社ハイロックス社製、RH-2000)により倍率400倍で観察し、ガラス試験板の汚染の有無を観察した。 (Contamination of glass test plate)
In the same manner as in the water contact angle test, the measurement sample was allowed to stand for 250 hours in an environment with an air temperature of 85° C. and a relative humidity of 85%. Next, after peeling off the protective sheet from the measurement sample, the surface of the glass test plate was observed with a digital optical microscope (RH-2000, manufactured by Hylox Co., Ltd.) at a magnification of 400 times to check for contamination of the glass test plate. Observed.
作製した保護シートを25mm×150mmの大きさに切り取り、剥離PETフィルムを剥がした。次に、露出した粘着面をガラス板に貼合し、2kgのゴムローラー(幅:約50mm)を1往復させて、測定用サンプルを作製した。
圧着から30分後に剥離速度2.4m/minで180°方向の引張試験を行って、保護シートのガラス板に対する剥離強度(g/25mm)を、JISZ0237に準じて、測定した。 <Peel strength of protective sheet>
The prepared protective sheet was cut into a size of 25 mm×150 mm, and the release PET film was peeled off. Next, the exposed adhesive surface was attached to a glass plate, and a 2 kg rubber roller (width: about 50 mm) was reciprocated once to prepare a sample for measurement.
Thirty minutes after the pressure bonding, a tensile test in the direction of 180° was performed at a peel rate of 2.4 m/min to measure the peel strength (g/25 mm) of the protective sheet to the glass plate according to JISZ0237.
一方、表3に示す通り、比較例2~8は、ゲル分率変化、水接触角変化のいずれかが高く、またガラス試験板への汚染が視認されたことから、保護シートとして求められる性能が不十分であることが分かった。水接触角変化が大きいものについては、ガラス試験板表面が保護シートの粘着層により汚染され、この影響で試験板表面の性状が変化していることが示唆される。ゲル分率変化が大きいものについては、ガラス試験板への大きな汚染が視認されており、粘着層の加水分解や酸化劣化等により、試験板表面の汚染の原因となる溶媒易溶成分が増加することを示唆しており好ましくない。また、ゲル分率変化が大きいことは保護シートの粘着層の性状変化、すなわち劣化を意味している点からも好ましくない。
比較例1については、高温高湿条件下に放置している間に保護シートの剥離強度が低下してガラス板から剥離してしまい、水接触角変化の測定ができなかった。すなわち、保護シートとして使用できるレベルのものではなかった。 As shown in Table 2, it was found that in all of Examples 1 to 11, changes in the gel fraction of the cured product of the pressure-sensitive adhesive composition were suppressed even when left under high-temperature and high-humidity conditions. In addition, in the evaluation of the surface of the glass test plate from which the protective sheet was peeled off after being left under high-temperature and high-humidity conditions, no visible contamination was observed, the change in water contact angle was kept low, and contamination by the protective sheet was suppressed to a high level. I found out.
On the other hand, as shown in Table 3, in Comparative Examples 2 to 8, either the gel fraction change or the water contact angle change was high, and contamination on the glass test plate was visually observed, so the performance required as a protective sheet was found to be insufficient. A large change in the water contact angle suggests that the surface of the glass test plate is contaminated with the adhesive layer of the protective sheet, and that this affects the properties of the surface of the test plate. For those with large gel fraction changes, large contamination of the glass test plate was visually observed, and due to hydrolysis and oxidative deterioration of the adhesive layer, the solvent-soluble components that cause contamination of the test plate surface increase. This is not desirable because it suggests that Further, a large change in the gel fraction means a change in properties of the adhesive layer of the protective sheet, that is, deterioration, which is also undesirable.
With respect to Comparative Example 1, the peel strength of the protective sheet decreased and the protective sheet was peeled off from the glass plate while the protective sheet was left under high-temperature and high-humidity conditions, making it impossible to measure the change in contact angle with water. In other words, it was not of a level that could be used as a protective sheet.
Claims (17)
- エチレン性不飽和基含有ウレタンポリマー(A)と、
エチレン性不飽和基含有モノマー(B)と、
光重合開始剤(C)と
を含有し、
前記エチレン性不飽和基含有ウレタンポリマー(A)が、
ポリオキシアルキレンポリオール(a1)と、
ポリイソシアネート(a2)と、
ヒドロキシ基含有エチレン性不飽和化合物(a3-1)又はイソシアナト基含有エチレン性不飽和化合物(a3-2)と
の反応物であり、
前記ポリイソシアネート(a2)が、エチレン性不飽和基含有ポリイソシアネート(a2-1)およびエチレン性不飽和基非含有ポリイソシアネート(a2-2)を含有することを特徴とする粘着剤組成物。 an ethylenically unsaturated group-containing urethane polymer (A);
an ethylenically unsaturated group-containing monomer (B);
containing a photopolymerization initiator (C),
The ethylenically unsaturated group-containing urethane polymer (A) is
a polyoxyalkylene polyol (a1);
a polyisocyanate (a2);
A reaction product with a hydroxy group-containing ethylenically unsaturated compound (a3-1) or an isocyanato group-containing ethylenically unsaturated compound (a3-2),
A pressure-sensitive adhesive composition, wherein the polyisocyanate (a2) comprises an ethylenically unsaturated group-containing polyisocyanate (a2-1) and an ethylenically unsaturated group-free polyisocyanate (a2-2). - 前記エチレン性不飽和基含有ウレタンポリマー(A)が、
前記ポリオキシアルキレンポリオール(a1)と、
前記ポリイソシアネート(a2)と、の反応物であるウレタンプレポリマーの末端に
前記ヒドロキシ基含有エチレン性不飽和化合物(a3-1)又は前記イソシアナト基含有エチレン性不飽和化合物(a3-2)が付加したウレタンポリマーである請求項1に記載の粘着剤組成物。 The ethylenically unsaturated group-containing urethane polymer (A) is
the polyoxyalkylene polyol (a1); and
The hydroxy group-containing ethylenically unsaturated compound (a3-1) or the isocyanato group-containing ethylenically unsaturated compound (a3-2) is added to the end of the urethane prepolymer that is the reaction product of the polyisocyanate (a2). 2. The pressure-sensitive adhesive composition according to claim 1, which is a urethane polymer. - 前記ポリオキシアルキレンポリオール(a1)が2個のヒドロキシ基を有する化合物であり、
前記ポリイソシアネート(a2)が2個のイソシアナト基を有する化合物である請求項1または2に記載の粘着剤組成物。 The polyoxyalkylene polyol (a1) is a compound having two hydroxy groups,
3. The pressure-sensitive adhesive composition according to claim 1, wherein the polyisocyanate (a2) is a compound having two isocyanato groups. - 前記エチレン性不飽和基含有ウレタンポリマー(A)が、(メタ)アクリロイルオキシ基含有ウレタンポリマーであり、
前記エチレン性不飽和基含有ポリイソシアネート(a2-1)が、(メタ)アクリロイルオキシ基含有ポリイソシアネートであり、
前記ヒドロキシ基含有エチレン性不飽和化合物(a3-1)が、ヒドロキシ基含有(メタ)アクリレートであり、
前記イソシアナト基含有エチレン性不飽和化合物(a3-2)が、イソシアナト基含有(メタ)アクリレートである請求項1~3のいずれか一項に記載の粘着剤組成物。 The ethylenically unsaturated group-containing urethane polymer (A) is a (meth)acryloyloxy group-containing urethane polymer,
The ethylenically unsaturated group-containing polyisocyanate (a2-1) is a (meth)acryloyloxy group-containing polyisocyanate,
The hydroxy group-containing ethylenically unsaturated compound (a3-1) is a hydroxy group-containing (meth)acrylate,
The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the isocyanato group-containing ethylenically unsaturated compound (a3-2) is an isocyanato group-containing (meth)acrylate. - 前記エチレン性不飽和基含有モノマー(B)が、単官能(メタ)アクリレート(B1)および多官能(メタ)アクリレート(B2)を含有する請求項1~4のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the ethylenically unsaturated group-containing monomer (B) contains a monofunctional (meth) acrylate (B1) and a polyfunctional (meth) acrylate (B2). Composition.
- 前記エチレン性不飽和基含有ウレタンポリマー(A)の重量平均分子量が、3万~25万である請求項1~5のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the ethylenically unsaturated group-containing urethane polymer (A) has a weight average molecular weight of 30,000 to 250,000.
- 前記ポリオキシアルキレンポリオール(a1)の数平均分子量が、500~5,000である請求項1~6のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the polyoxyalkylene polyol (a1) has a number average molecular weight of 500 to 5,000.
- 前記エチレン性不飽和基含有ウレタンポリマー(A)が、前記ポリオキシアルキレンポリオール(a1)と、前記ポリイソシアネート(a2)と、前記ヒドロキシ基含有エチレン性不飽和化合物(a3-1)との反応物であり、
前記ポリイソシアネート(a2)のイソシアナト基の総量が、前記ポリオキシアルキレンポリオール(a1)のヒドロキシ基の総量1モルに対して、1.1~1.5モルであり、
前記エチレン性不飽和基含有ポリイソシアネート(a2-1)および前記エチレン性不飽和基非含有ポリイソシアネート(a2-2)の含有割合(モル比(a2-1)/(a2-2))が、0.03~0.8である請求項1~7のいずれか一項に記載の粘着剤組成物。 The ethylenically unsaturated group-containing urethane polymer (A) is a reaction product of the polyoxyalkylene polyol (a1), the polyisocyanate (a2), and the hydroxy group-containing ethylenically unsaturated compound (a3-1). and
The total amount of isocyanato groups in the polyisocyanate (a2) is 1.1 to 1.5 mol per 1 mol of the total amount of hydroxy groups in the polyoxyalkylene polyol (a1),
The content ratio (molar ratio (a2-1)/(a2-2)) of the ethylenically unsaturated group-containing polyisocyanate (a2-1) and the ethylenically unsaturated group-free polyisocyanate (a2-2) is The pressure-sensitive adhesive composition according to any one of claims 1 to 7, which is 0.03 to 0.8. - 前記エチレン性不飽和基含有ウレタンポリマー(A)が、前記ポリオキシアルキレンポリオール(a1)と、前記ポリイソシアネート(a2)と、前記イソシアナト基含有エチレン性不飽和化合物(a3-2)との反応物であり、
前記ポリオキシアルキレンポリオール(a1)のヒドロキシ基の総量が、前記ポリイソシアネート(a2)のイソシアナト基の総量1モルに対して、1.1~1.5モルであり、
前記エチレン性不飽和基非含有ポリイソシアネート(a2-2)および前記エチレン性不飽和基含有ポリイソシアネート(a2-1)の含有割合(モル比(a2-2)/(a2-1))が、0.03~0.8である請求項1~8のいずれか一項に記載の粘着剤組成物。 The ethylenically unsaturated group-containing urethane polymer (A) is a reaction product of the polyoxyalkylene polyol (a1), the polyisocyanate (a2), and the isocyanato group-containing ethylenically unsaturated compound (a3-2). and
The total amount of hydroxy groups in the polyoxyalkylene polyol (a1) is 1.1 to 1.5 mol per 1 mol of the total amount of isocyanato groups in the polyisocyanate (a2),
The content ratio (molar ratio (a2-2)/(a2-1)) of the ethylenically unsaturated group-free polyisocyanate (a2-2) and the ethylenically unsaturated group-containing polyisocyanate (a2-1) is The pressure-sensitive adhesive composition according to any one of claims 1 to 8, which is 0.03 to 0.8. - 前記エチレン性不飽和基含有ポリイソシアネート(a2-1)が、ヒドロキシ基含有エチレン性不飽和化合物及びジイソシアネートの反応物である請求項1~9のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 9, wherein the ethylenically unsaturated group-containing polyisocyanate (a2-1) is a reaction product of a hydroxy group-containing ethylenically unsaturated compound and a diisocyanate.
- 前記単官能(メタ)アクリレート(B1)が、炭素数6~18の鎖状アルキル(メタ)アクリレートである請求項5~10のいずれか一項に記載の粘着剤組成物。 The adhesive composition according to any one of claims 5 to 10, wherein the monofunctional (meth)acrylate (B1) is a chain alkyl (meth)acrylate having 6 to 18 carbon atoms.
- 前記多官能(メタ)アクリレート(B2)が、3~6官能の(メタ)アクリレートである請求項5~11のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 5 to 11, wherein the polyfunctional (meth)acrylate (B2) is a tri- to hexa-functional (meth)acrylate.
- 前記エチレン性不飽和基含有ウレタンポリマー(A)および前記エチレン性不飽和基含有モノマー(B)の合計100質量%に対して、前記エチレン性不飽和基含有ウレタンポリマー(A)が30~70質量%、エチレン性不飽和基含有モノマー(B)が30~70質量%である請求項1~12のいずれか一項に記載の粘着剤組成物。 The ethylenically unsaturated group-containing urethane polymer (A) is 30 to 70 mass% with respect to the total 100% by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B). %, the pressure-sensitive adhesive composition according to any one of claims 1 to 12, wherein the ethylenically unsaturated group-containing monomer (B) is 30 to 70% by mass.
- 前記エチレン性不飽和基含有ウレタンポリマー(A)および前記エチレン性不飽和基含有モノマー(B)の合計100質量%に対して、単官能(メタ)アクリレート(B1)が25~60質量%、多官能(メタ)アクリレート(B2)が1~30質量%である請求項3~13のいずれか一項に記載の粘着剤組成物。 With respect to the total 100% by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B), the monofunctional (meth)acrylate (B1) is 25 to 60% by mass. The adhesive composition according to any one of claims 3 to 13, wherein the functional (meth)acrylate (B2) is 1 to 30% by weight.
- 可塑剤(D)をさらに含有する請求項1~14のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 14, further comprising a plasticizer (D).
- 前記エチレン性不飽和基含有ウレタンポリマー(A)および前記エチレン性不飽和基含有モノマー(B)の合計100質量部に対して、前記光重合開始剤(C)が0.05~5質量部、前記可塑剤(D)が1~30質量部である請求項15に記載の粘着剤組成物。 0.05 to 5 parts by mass of the photopolymerization initiator (C) with respect to a total of 100 parts by mass of the ethylenically unsaturated group-containing urethane polymer (A) and the ethylenically unsaturated group-containing monomer (B); The pressure-sensitive adhesive composition according to claim 15, wherein the plasticizer (D) is 1 to 30 parts by mass.
- 請求項1~16のいずれか一項に記載の粘着剤組成物の硬化物である粘着層を基材の片面に有する保護シート。 A protective sheet having an adhesive layer, which is a cured product of the adhesive composition according to any one of claims 1 to 16, on one side of a substrate.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003183615A (en) * | 2001-12-21 | 2003-07-03 | Nippon Synthetic Chem Ind Co Ltd:The | Tacky adhesive composition curable by actinic energy ray |
JP2016020477A (en) * | 2014-06-18 | 2016-02-04 | 昭和電工株式会社 | Photocurable composition for transparent adhesive sheet, and transparent adhesive sheet |
JP2017193609A (en) * | 2016-04-19 | 2017-10-26 | Dic株式会社 | Adhesive composition and adhesive sheet |
JP2017206654A (en) * | 2016-05-20 | 2017-11-24 | 昭和電工株式会社 | Adhesive composition, adhesive sheet, touch panel, and image display device |
JP2018076456A (en) * | 2016-11-10 | 2018-05-17 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
JP2018095770A (en) * | 2016-12-15 | 2018-06-21 | 昭和電工株式会社 | Photocurable composition, and adhesive sheet |
WO2019069746A1 (en) * | 2017-10-05 | 2019-04-11 | 昭和電工株式会社 | Adhesive composition and adhesive sheet |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003183615A (en) * | 2001-12-21 | 2003-07-03 | Nippon Synthetic Chem Ind Co Ltd:The | Tacky adhesive composition curable by actinic energy ray |
JP2016020477A (en) * | 2014-06-18 | 2016-02-04 | 昭和電工株式会社 | Photocurable composition for transparent adhesive sheet, and transparent adhesive sheet |
JP2017193609A (en) * | 2016-04-19 | 2017-10-26 | Dic株式会社 | Adhesive composition and adhesive sheet |
JP2017206654A (en) * | 2016-05-20 | 2017-11-24 | 昭和電工株式会社 | Adhesive composition, adhesive sheet, touch panel, and image display device |
JP2018076456A (en) * | 2016-11-10 | 2018-05-17 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
JP2018095770A (en) * | 2016-12-15 | 2018-06-21 | 昭和電工株式会社 | Photocurable composition, and adhesive sheet |
WO2019069746A1 (en) * | 2017-10-05 | 2019-04-11 | 昭和電工株式会社 | Adhesive composition and adhesive sheet |
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