CN114410231A - Photocurable composition, adhesive sheet laminate, laminate for image display device construction, and image display device - Google Patents
Photocurable composition, adhesive sheet laminate, laminate for image display device construction, and image display device Download PDFInfo
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- CN114410231A CN114410231A CN202210166287.XA CN202210166287A CN114410231A CN 114410231 A CN114410231 A CN 114410231A CN 202210166287 A CN202210166287 A CN 202210166287A CN 114410231 A CN114410231 A CN 114410231A
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- Prior art keywords
- meth
- acrylate
- photocurable composition
- acrylic copolymer
- macromonomer
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- 239000000203 mixture Substances 0.000 title claims abstract description 174
- 239000000853 adhesive Substances 0.000 title claims description 106
- 230000001070 adhesive effect Effects 0.000 title claims description 104
- 238000010276 construction Methods 0.000 title description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 113
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 60
- 239000003999 initiator Substances 0.000 claims abstract description 47
- 238000004132 cross linking Methods 0.000 claims abstract description 35
- 238000000235 small-angle X-ray scattering Methods 0.000 claims abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 213
- 239000000178 monomer Substances 0.000 claims description 129
- 238000005259 measurement Methods 0.000 claims description 33
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 20
- 238000000016 photochemical curing Methods 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 230000002209 hydrophobic effect Effects 0.000 claims description 13
- 230000001186 cumulative effect Effects 0.000 claims description 11
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 25
- 238000004026 adhesive bonding Methods 0.000 abstract 1
- -1 acrylate ester Chemical class 0.000 description 80
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 60
- 125000000524 functional group Chemical group 0.000 description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 27
- 229920000578 graft copolymer Polymers 0.000 description 26
- 229920001577 copolymer Polymers 0.000 description 22
- 230000009477 glass transition Effects 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 20
- 238000007334 copolymerization reaction Methods 0.000 description 18
- 238000005191 phase separation Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010410 layer Substances 0.000 description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 12
- 230000000740 bleeding effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 10
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920001400 block copolymer Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 206010040844 Skin exfoliation Diseases 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000005361 soda-lime glass Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 125000002704 decyl 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])* 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 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 4
- 238000005187 foaming Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229940119545 isobornyl methacrylate Drugs 0.000 description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 4
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- TURIFVBTZSEGBT-SREVYHEPSA-N (Z)-2-(3-prop-2-enoyloxypropyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCCOC(=O)C=C TURIFVBTZSEGBT-SREVYHEPSA-N 0.000 description 3
- MMEJYPZZFYTVLJ-WAYWQWQTSA-N (z)-2-(2-prop-2-enoyloxyethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCOC(=O)C=C MMEJYPZZFYTVLJ-WAYWQWQTSA-N 0.000 description 3
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 3
- PWMLMBQHHBLIQM-UHFFFAOYSA-N 1-(3-prop-2-enoyloxypropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCCOC(=O)C=C)C(O)=O PWMLMBQHHBLIQM-UHFFFAOYSA-N 0.000 description 3
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- WLIVGKZSWFDOQX-UHFFFAOYSA-N 2-(3-prop-2-enoyloxypropyl)butanedioic acid Chemical compound C(C=C)(=O)OCCCC(C(=O)O)CC(=O)O WLIVGKZSWFDOQX-UHFFFAOYSA-N 0.000 description 3
- 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 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 3
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 3
- UOCXAYCXGRZSHW-UHFFFAOYSA-N 3-(3-prop-2-enoyloxypropyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCCOC(=O)C=C)=C1C(O)=O UOCXAYCXGRZSHW-UHFFFAOYSA-N 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 3
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000035945 sensitivity Effects 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- DSTUKHPLWATFCG-UHFFFAOYSA-N (2-benzoylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C(=O)C1=CC=CC=C1 DSTUKHPLWATFCG-UHFFFAOYSA-N 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 2
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
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Classifications
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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
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- C08F290/04—Polymers provided for in subclasses C08C or C08F
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- 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
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- 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
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- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Macromonomer-Based Addition Polymer (AREA)
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- Laminated Bodies (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Provides a method for filling the bonding surface with the concave-convex parts when heated to a heat-fusible temperature, and further firms the adherends after photocuringA novel photocurable composition for adhesive bonding. A photocurable composition is provided, which is characterized by comprising: a (meth) acrylic copolymer (A) containing a macromonomer as a copolymerizable component, a crosslinking agent (B), and a crosslinking initiator (C), and the photocurable composition has a half-value width X1 (nm) of a one-dimensional scattering curve in a small-angle X-ray scattering measurement‑1) Is 0.05<X1<0.30。
Description
The present application is a divisional application of patent application No. 201780074699.8, application date 2017, 11/28/h, entitled "photocurable composition, pressure-sensitive adhesive sheet laminate, cured product, laminate for image display device configuration, and image display device".
Technical Field
The present invention relates to a photocurable composition using a (meth) acrylic copolymer containing a macromonomer as a structural unit, and an adhesive sheet, an adhesive sheet laminate, a cured product, a laminate for image display device construction, and an image display device using the photocurable composition.
Background
Macromonomers are high molecular weight monomers having functional groups capable of bonding. The macromonomer can easily synthesize a graft copolymer by addition or copolymerization with other monomers. Further, when a graft copolymer is synthesized using a macromonomer, resins having different physical properties can be separately incorporated into a branch component and a dry component in a simple and convenient manner with good purity, and therefore, various adhesive compositions using such a macromonomer have been proposed in the field of adhesive adhesives.
For example, patent document 1 discloses a resin composition for an adhesive agent having excellent adhesiveness such as adhesiveness, adhesive strength, and cohesive strength, which contains a graft copolymer obtained by radical polymerization of a macromonomer having a number average molecular weight of 1000 to 100000 and a glass transition temperature of-20 ℃ or lower, a radically polymerizable monomer having a hydroxyl group or a carboxyl group, and other monomers, and the glass transition temperature of a dry polymer of the resin composition for an adhesive agent is higher than the glass transition temperature of a branched polymer.
Patent document 2 discloses, as a method for improving durability and removability under high temperature and high humidity conditions, an adhesive using a copolymer (having a weight average molecular weight of 50 to 200 ten thousand) of 0.2 to 3 parts by mass of a (meth) acryloyl group-containing macromonomer having a glass transition temperature of 40 ℃ or higher and a number average molecular weight of 2000 to 20000, 57 to 98.8 parts by mass of an alkyl (meth) acrylate, 1 to 20 parts by mass of a functional group-containing monomer, and 0 to 20 parts by mass of another monomer copolymerizable with at least the alkyl (meth) acrylate.
Patent document 3 discloses a curable adhesive composition that can be easily bonded to various adherends, can exhibit adhesive strength as an adhesive by curing after bonding, is less likely to cause bleeding of the adhesive from cut surfaces during cutting, and is less likely to cause adhesion between cut surfaces, the curable adhesive composition including: an acrylic adhesive polymer obtained by copolymerizing an alkyl (meth) acrylate monomer with a macromonomer having a number average molecular weight Mn of 1000 to 200000 and a glass transition point Tg of 30 to 150 ℃ in an amount of 1 to 30 mass% based on the total monomer components, a photocationic polymerizable compound, and a photocationic photopolymerization initiator.
Patent document 4 proposes a pressure-sensitive adhesive which is excellent in adhesiveness even when a filler is contained in a high content in an adhesive layer of an adhesive tape and maintains adhesiveness even when exposed to high temperature, the pressure-sensitive adhesive being characterized by containing: a (meth) acrylic graft copolymer having a (meth) acrylic copolymer as a dry polymer and a (meth) acrylic macromonomer as a graft polymer; a crosslinking agent; and a filler.
Patent document 5 discloses that the adhesive has a degree of adhesiveness (referred to as "tackiness") that can be peeled off in a normal state, that is, a room temperature state, and when the adhesive is heated to a heat-fusible temperatureDisclosed is a pressure-sensitive adhesive resin composition which has fluidity, can be filled into each corner following a level difference portion of a bonding surface, and can finally firmly bond adherends to each other, the pressure-sensitive adhesive resin composition being characterized by containing: 100 parts by mass of an acrylic copolymer (A), 0.5 to 20 parts by mass of a crosslinking agent (B), and 0.1 to 5 parts by mass of a crosslinking initiator (C), wherein the acrylic copolymer (A) has a weight-average molecular weight of 5.0X 104～5.0×105The adhesive resin composition contains a repeating unit derived from a (meth) acrylate ester as a dry component of the graft copolymer, and contains a repeating unit derived from a (meth) acrylate ester and having a number average molecular weight of 5.0X 102Above and below 6.0X 103The graft copolymer (A) contains a repeating unit derived from the macromonomer in an amount of 0.1 to 3 mol% in the acrylic copolymer (A).
Patent document 6 discloses an adhesive composition containing a (meth) acrylic copolymer (a) having a weight average molecular weight of 5 to 100 ten thousand, which is obtained by polymerizing a monomer mixture containing a macromonomer (a) having a number average molecular weight of 500 or more and less than 6000 and a vinyl monomer (b), and an adhesive sheet using the adhesive composition.
Patent document 7 discloses a method for producing a novel laminate for image display device components, which can maintain a sheet-like shape at room temperature, has a sufficient degree of adhesiveness to be peelable, is flowable by heat fusion, and can be finally crosslinked to firmly bond image display device components to each other.
Patent document 8 discloses a photocurable adhesive sheet that can be photocured even in a portion that is difficult to reach by light, such as a printed masking portion, and that can cure the entire sheet even in an adhesive sheet having a certain thickness.
Patent document 9 discloses a method of recycling an optical device constituting member by peeling 2 optical device constituting members from an optical device constituting laminate in which 2 optical device constituting members are temporarily bonded to each other via a transparent adhesive material.
Patent document 10 discloses an adhesive sheet laminate which can suppress the mixing of foreign matters at the interface between an adhesive layer and a release layer and the transfer and transfer of the release agent to the adhesive layer during the bonding of image display device constituent members, and which is excellent in durability after the bonding.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 1-203412
Patent document 2: japanese laid-open patent publication No. 8-209095
Patent document 3: japanese laid-open patent publication No. 11-158450
Patent document 4: japanese patent laid-open publication No. 2011-
Patent document 5: japanese laid-open patent publication No. 2015-105296
Patent document 6: international publication No. 2015/080244A1
Patent document 7: international publication No. 2015/137178A1
Patent document 8: international publication No. 2016/024618A1
Patent document 9: international publication No. 2016/002763A1
Patent document 10: international publication No. 2016/088697A1
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a novel photocurable composition which can be heated to a heat-fusible temperature to fill the corners of the bonded surface following the uneven portions of the bonded surface and can further firmly bond adherends to each other after photocuring, by further improving the above-described previously disclosed photocurable composition, that is, a photocurable composition having a (meth) acrylic copolymer containing a macromonomer as a structural unit and a crosslinking agent.
Means for solving the problems
The present invention provides a photocurable composition, characterized by comprising: a (meth) acrylic copolymer (A) containing a macromonomer as a structural unit, a crosslinking agent (B), and a crosslinking initiator (C), and the photocurable composition has a half-value width X1 (nm) of a one-dimensional scattering curve in a small-angle X-ray scattering measurement-1) Is 0.05<X1<0.30。
ADVANTAGEOUS EFFECTS OF INVENTION
The photocurable composition of the present invention can maintain a sheet shape at room temperature and exhibit self-adhesiveness (referred to as "tackiness"), and when heated in an uncrosslinked state, it softens or flows, and when heated to a temperature equal to or higher than the glass transition temperature of the macromonomer, for example, it softens or flows, and it follows the irregularities of the bonding surface and fills the corners. Further, by performing photocuring, excellent cohesive force can be exerted, and therefore, adherends can be firmly attached to each other.
Detailed Description
An example of an embodiment of the present invention will be described below. However, the present invention is not limited to the following embodiments.
[ Photocurable composition ]
An example of the composition according to an embodiment of the present invention (referred to as "the present photocurable composition") is a photocurable composition comprising: a (meth) acrylic copolymer (A) containing a macromonomer as a structural unit, a crosslinking agent (B), and a crosslinking initiator (C), and the photocurable composition has a half-value width X1 (nm) of a one-dimensional scattering curve in a small-angle X-ray scattering measurement-1) Is 0.05<X1<0.30。
The above-mentioned "containing a macromonomer as a structural unit" means a case where the macromonomer is contained as a copolymer component of the (meth) acrylic copolymer (a), and also includes a case where the macromonomer is contained as an addition bonding component of the (meth) acrylic copolymer (a), and the macromonomer is contained as a structural unit other than the copolymer component.
The photocurable composition preferably has a structure in which at least either one of the crosslinking agent (B) and the crosslinking initiator (C) is bonded to the (meth) acrylic copolymer (a).
When at least either one of the crosslinking agent (B) and the crosslinking initiator (C) is bonded to the (meth) acrylic copolymer (a), bleeding of the bonded crosslinking agent (B) and crosslinking initiator (C) can be suppressed. Further, by bonding at least either one of the crosslinking agent (B) and the crosslinking initiator (C) to the (meth) acrylic copolymer (a), the reaction efficiency of the photocrosslinking reaction is promoted, and therefore, a photocured product having a higher cohesive force can be obtained.
Further, when at least either one of the crosslinking agent (B) and the crosslinking initiator (C) is bonded to the (meth) acrylic copolymer (a), the site at which the (meth) acrylic copolymer (a) is crosslinked can be intentionally designed, and therefore, the half-value width of the one-dimensional scattering curve in the small-angle X-ray scattering measurement defined in the present invention can be easily controlled.
Here, the above "bonding to the (meth) acrylic copolymer (a)" means a state in which the crosslinking agent (B) or the crosslinking initiator (C) is bonded to the (meth) acrylic copolymer (a) through a chemical bond including a covalent bond, an ionic bond, and a metallic bond.
The photocurable composition is characterized in that the half-value width X1 (nm) of the one-dimensional scattering curve in the small-angle X-ray scattering measurement is as described above-1) Is 0.05<X1<0.30。
The small-angle X-ray scattering measurement is a method for obtaining structural information on a nanometer scale (1 to 100nm) by observing scattered X-rays having a scattering angle of several degrees or less (specifically, 10 ° or less, for example).
Therefore, a composition in which a one-dimensional scattering curve can be observed in a small-angle X-ray scattering measurement is a composition in which a one-dimensional scattering curve is not observed in a small-angle X-ray scattering measurement. The shape and state of the photocurable composition are not limited as long as a one-dimensional scattering curve can be observed in the small-angle X-ray scattering measurement.
The (meth) acrylic copolymer (a) in the photocurable composition is a copolymer containing a macromonomer as a structural unit. Copolymers having macromonomers as structural units usually form graft copolymers or block copolymers. When the polymerizable group of the macromonomer is 1, a graft copolymer is usually formed by addition, condensation or copolymerization with another monomer. When the number of polymerizable groups of the macromonomer is 2, a block copolymer is usually formed by addition, condensation or copolymerization with another monomer. It is known that graft copolymers, block copolymers in general form (micro) phase-separated structures.
The specification of the half-value width of the one-dimensional scattering curve in the measurement of small-angle X-ray scattering of the photocurable composition can be considered as a measure of the "phase separation state" of the (micro) phase separation structure formed by the composition containing the (meth) acrylic copolymer (a) as described above. That is, for example, the dry component and the branch component in the graft copolymer or the respective block components in the block copolymer are in a state of being finely separated in the form of different "phases".
Here, the case where the half-value width of the one-dimensional scattering curve in the small-angle X-ray scattering measurement is large (wide) means that the peak is wide, and means that the density difference of each phase in phase separation is small and the phase separation structure is not uniform, compared with the case where the half-value width is small.
On the other hand, the smaller (narrower) half-value width indicates a sharper peak, which means that the density difference of the respective phases in phase separation is more clear and the phase separation structure is more uniform than the case where the half-value width is large.
Therefore, in the photocurable composition, by controlling the half-value width to be within a specific range, each phase subjected to microphase separation can exhibit different adhesion characteristics.
Therefore, it is considered that the resin composition can have both properties which are generally difficult to satisfy.
In the following description, terms such as "branched component" and "dry component" are sometimes used, and the term "graft copolymer" may be used instead of "each block component" (for example, "block component a" and "block component B").
From the above-described viewpoints, the half-value width X1 of the one-dimensional scattering curve in the small-angle X-ray scattering measurement of the photocurable composition can be defined as: the (micro) phase separation structure formed by the branch component and the dry component formed by the macromonomer in the copolymer polymer containing the macromonomer as a structural unit is changed depending on the prescribed crosslinking agent and photoinitiator, and then the state is indicated.
Therefore, by setting 0.05< X1<0.30 in the photocurable composition of the present invention, it is possible to achieve both adhesion and shape stability, which are contradictory physical properties, at a higher level than the previously disclosed photocurable composition as described above, that is, the conventional photocurable composition having a (meth) acrylic copolymer containing a macromonomer as a structural unit and a crosslinking agent, and to obtain an effect of improving handling properties.
From the above-mentioned viewpoints, the half-value width X1 of the one-dimensional scattering curve in the small-angle X-ray scattering measurement is preferably 0.05< X1<0.30, more preferably 0.06< X1 or X1<0.27, particularly 0.08< X1 or X1<0.25, and particularly 0.11< X1 or X1. ltoreq.0.23 in the present photocurable composition.
According to the above, the half-value width X1 is preferably any one of 0.05< X1<0.30, 0.05< X1<0.27, 0.05< X1<0.25, or 0.05< X1 ≦ 0.23, more preferably any one of 0.06< X1<0.30, 0.06< X1<0.27, 0.06< X1<0.25, or 0.06< X1 ≦ 0.23, further preferably any one of 0.08< X1<0.30, 0.08< X1<0.27, 0.08< X1<0.25, or 0.08< X1 ≦ 0.23, and most preferably any one of 0.11< X1<0.30, 0.11< X1<0.27, 0.11< X1<0.25, or 0.05< X68538 < X3923.
The photocurable composition may be prepared by adjusting the structure, composition, molecular weight, etc. of the (meth) acrylic copolymer (a) as a base polymer and adjusting or selecting the type and amount of the crosslinking agent (B) and the crosslinking initiator (C), as a main means for adjusting the half-value width X1 of the one-dimensional scattering curve in the small-angle X-ray scattering measurement. However, the present invention is not limited to such a means. The "base polymer" refers to a main component contained in the photocurable composition, and the "main component" refers to a component contained in an amount exceeding 40% by mass of the photocurable composition.
Here, as the structure of the (meth) acrylic copolymer (a), for example, a graft copolymer or a block copolymer is selected.
The composition of the (meth) acrylic copolymer (a) can be adjusted by adjusting the composition of the dry component and the branched component (each block component in the case of a block copolymer).
Specifically, the half width can be controlled by adjusting the glass transition temperature (Tg) of the phase based on the branched component and the phase based on the dry component of the (meth) acrylic copolymer (a), optimizing the balance between compatibility parameters of the branched component and the dry component, or optimizing the balance between hydrophilicity and hydrophobicity of the branched component and the dry component. For example, the half width can be controlled by forming a phase having a high Tg from a branched component and a phase having a low Tg from a dry component.
As described above, by using the graft polymer, the balance between the compatibility of the branch component and the dry component is optimized, and the half-value width can be controlled to form an optimum phase separation state, thereby achieving both adhesiveness and hot-melt property.
Examples of the adjustment of the kinds of the crosslinking agent (B) and the crosslinking initiator (C) include adjustment of compatibility with a hydrophilic component constituting the (meth) acrylic copolymer (a). The phase separation state, that is, the half-value width of the one-dimensional scattering curve can be controlled by adjusting the compatibility between the dry component formed from the (meth) acrylic copolymer (a) and the branched component (each block component in the case of a block copolymer) by using a component having high compatibility with either or both of the dry component and the branched component (each block component in the case of a block copolymer) formed from the (meth) acrylic copolymer (a) or by adjusting the amount of addition of the component (C).
Among these, as a method for adjusting the half-value width X1 of the photocurable composition, as described later, it is effective to optimize the (meth) acrylic copolymer (a) by optimizing the type and content ratio of the functional groups of the monomers constituting the dry component and the branch component, optimizing the molecular weight of the branch component, and the like, and to adjust the type and amount of the crosslinking agent (B) and the crosslinking initiator (C).
Further, in order to adjust the half-value width X1 to a preferable range, the photocurable composition preferably contains, for example, (1) a (meth) acrylic monomer or a vinyl monomer having 5 or more carbon atoms, particularly 8 or more carbon atoms, particularly 9 or more carbon atoms, and particularly 10 or more carbon atoms, as a main copolymerization component (dry component) of the (meth) acrylic copolymer (a), as will be described later. Specifically, it is preferably selected from the monomers contained in the dry component of the acrylic copolymer (a1) described later.
In addition, (2a) preferably uses a hydrophilic component as the copolymerizable component (dry component) other than the (meth) acrylic monomer or the vinyl monomer. Specifically, it is preferably selected from the hydrophilic monomers contained in the dry component of the acrylic copolymer (a1) described later. Further, it is more preferable that (2b) the hydrophilic component is contained in a mass ratio of 0.1 to 20 relative to the copolymerization component (dry component) 100 to improve the hydrophilicity of the dry component.
Further, (3a) preferably comprises a (meth) acrylic monomer or vinyl monomer component having 4 or less carbon atoms as a branched component of the (meth) acrylic copolymer (a) in a mass ratio of 1 to 100 relative to the dry component 100, and the microphase separation state of the phase of the dry component and the phase of the branched component is adjusted. Preferably, (3b) a (meth) acrylic monomer or vinyl monomer component having a cyclic structure is blended as a branched component of the (meth) acrylic copolymer (a) so as to be in a mass ratio of 1 to 100 relative to the dry component 100, and a microphase separation state of the phase of the dry component and the phase of the branched component is adjusted.
Further, (4a) preferably uses a hydroxyl group-containing compound or the like having high compatibility with the hydrophilic component as the crosslinking agent (B). Specifically, it is preferably selected from the examples of the crosslinking agent (B) described later. Further, it is more preferable that (4B) the crosslinking agent (B) is added in an amount of 0.05 to 30 parts by mass based on 100 parts by mass of the (meth) acrylic copolymer, and the polarity of the phase formed from the dry component is appropriately adjusted.
As described above, by appropriately selecting the above (1) to (4b) independently from each other, it is possible to adjust the phase separation structure of the dry component and the branch component. Among these methods (1) to (4b), the combination of (1) with (2a) and/or (2b) and the combination of (1) with (3a) and/or (3b) are preferable, the combination of (1) with (3a) and/or (3b) with (4a) and/or (4b) is more preferable, and all of the methods (1) to (4b) are most preferably used. However, the method is not limited thereto.
Since the optimum phase separation state can be achieved by optimizing the balance between the compatibility of the branched component and the dry component by using the graft polymer as described above, the half-value width X1 can be controlled by using, for example, a hydrophobic component as the main copolymerizable component (dry component) of the copolymer (a) and a hydrophilic component as the branched component of the copolymer (B) in addition to the above.
The photocurable composition is more preferably irradiated at 4000mJ/m in cumulative light irradiation2Half-value Width X2 (nm) of one-dimensional scattering Curve in Small-Angle X-ray Scattering measurement at light time of (1)-1) Is 0.05<X2<0.25。
The present photocurable composition was cured by irradiating the composition at 4000mJ/m in cumulative light irradiation2The one-dimensional scattering curve at the time of irradiation with light, i.e., the half-value width X2 (nm) of the one-dimensional scattering curve of the photocurable composition after irradiation with light-1) Is 0.05<X2<0.25, not only the effect obtained when X1 is in the predetermined range, but also the effect that the composition after photocuring attains a high cohesive force can be obtained. The wavelength of the irradiation light is preferably a wavelength which is sensitive to a crosslinking initiator (C) described later.
From the above viewpoint, the present photocurable composition has a cumulative irradiation dose of 4000mJ/m2Half-value Width X2 (nm) of one-dimensional scattering Curve in Small-Angle X-ray Scattering measurement at light time of (1)-1) Preferably 0.05<X2<0.25, more preferably 0.06<X2 or X2<0.24, particularly preferably 0.08<X2 or X2<0.22, more preferably 0.10<X2 or X2<0.20。
According to the above, the half-value width X2 is preferably any one of 0.05< X2<0.25, 0.05< X2<0.24, 0.05< X2<0.22, or 0.05< X2<0.20, more preferably any one of 0.06< X2<0.25, 0.06< X2<0.24, 0.06< X2<0.22, or 0.06< X2<0.20, further preferably any one of 0.08< X2<0.25, 0.08< X2<0.24, 0.08< X2<0.22, or 0.08< X2<0.20, further preferably any one of 0.10< X2<0.25, 0.10< X2<0.24, 0.10< X2<0.22, or 0.10< X2.
For the present photocurable composition, the irradiation was adjusted to 4000mJ/m in cumulative light irradiation2Half-value Width X2 (nm) of one-dimensional scattering Curve in Small-Angle X-ray Scattering measurement at light time of (1)-1) The same means as those for adjusting the half-value width X1 are used. For example, there is a method of adjusting the structure, composition, molecular weight, and the like of the (meth) acrylic copolymer (a) as a base polymer and adjusting or selecting the kinds and amounts of the crosslinking agent (B) and the crosslinking initiator (C). However, the present invention is not limited to such a means.
Further, in order to adjust the half-value width X2 to a preferable range, it is preferable that (1) a (meth) acrylic monomer or a vinyl monomer having 5 or more, particularly 8 or more, particularly 9 or more, and particularly 10 or more carbon atoms is used as a main copolymerization component (dry component) of the (meth) acrylic copolymer (a), as described later in detail. Specifically, it is preferably selected from the monomers contained in the dry component of the acrylic copolymer (a1) described later.
In addition, (2a) preferably uses a hydrophilic component as the copolymerization component (dry component) other than the (meth) acrylic monomer or the vinyl monomer. Specifically, it is preferably selected from the hydrophilic monomers contained in the dry component of the acrylic copolymer (a1) described later. Further, it is more preferable that (2b) the hydrophilic component is contained in a mass ratio of 0.1 to 20 relative to the copolymerization component (dry component) 100 to improve the hydrophilicity of the dry component.
Further, (3a) preferably comprises a (meth) acrylic monomer or vinyl monomer component having 4 or less carbon atoms as a branched component of the (meth) acrylic copolymer (a) in a mass ratio of 1 to 100 relative to the dry component 100, and the microphase separation state of the phase of the dry component and the phase of the branched component is adjusted. Preferably, (3b) a (meth) acrylic monomer or vinyl monomer component having a cyclic structure is blended as a branched component of the (meth) acrylic copolymer (a) so as to be in a mass ratio of 1 to 100 relative to the dry component 100, and a microphase separation state of the phase of the dry component and the phase of the branched component is adjusted.
Further, (4a) preferably uses a hydroxyl group-containing compound or the like having high compatibility with the hydrophilic component as the crosslinking agent (B). Specifically, it is preferably selected from the examples of the crosslinking agent (B) described later. Further, it is more preferable that (4B) the crosslinking agent (B) is added in an amount of 0.05 to 30 parts by mass based on 100 parts by mass of the (meth) acrylic copolymer, and the polarity of the phase formed from the dry component is appropriately adjusted.
As described above, by appropriately selecting the above (1) to (4b) independently from each other, it is possible to adjust the phase separation structure of the dry component and the branch component. Among these methods (1) to (4b), the combination of (1) with (2a) and/or (2b) and the combination of (1) with (3a) and/or (3b) are preferable, the combination of (1) with (3a) and/or (3b) with (4a) and/or (4b) is more preferable, and all of the methods (1) to (4b) are most preferably used. However, the method is not limited thereto.
Since the optimum phase separation state can be achieved by optimizing the balance between the compatibility of the branched component and the dry component by using the graft polymer as described above, the half-value width X2 can be controlled by using, for example, a hydrophobic component as the main copolymerizable component (dry component) of the copolymer (a) and a hydrophilic component as the branched component of the copolymer (B) in addition to the above.
As described above, the shape and state of the photocurable composition are not limited. 4000mJ/m as described above2When the photocurable composition is not uniformly irradiated with the light of (4), the determination may be made based on the case where the photocurable composition is formed into a sheet having a thickness of 150 μm (measurement object).
The photocurable composition preferably has the properties of exhibiting adhesiveness at 20 ℃ and softening or fluidizing at 50-100 ℃.
As described above, the photocurable composition can have such properties by using the (meth) acrylic copolymer (a1) described later as a base resin.
[ meth (acrylic) copolymer (A) >
As the (meth) acrylic copolymer (a) containing a macromonomer as a structural unit, a (meth) acrylic copolymer (a1) containing a graft copolymer having a macromonomer as a branching component can be exemplified.
Since the photocurable composition is crosslinked by the action of the crosslinking agent (B) and the crosslinking initiator (C), it is preferable that the (meth) acrylic copolymer (a) is a graft copolymer in view of efficiency.
When the photocurable composition is produced using the (meth) acrylic copolymer (a1) as a base resin, the half-value width of the one-dimensional scattering curve in the small-angle X-ray scattering measurement defined in the present invention can be easily controlled. That is, this half width is one mode of the means for achieving the range. Therefore, the photocurable composition can maintain a predetermined shape, for example, a sheet shape at room temperature, exhibits self-adhesiveness (self-adhesiveness), has a hot-melt property that softens or flows when heated in an uncrosslinked state, can be further photocured, and can be bonded by exhibiting excellent cohesive force after photocuring.
Therefore, when the (meth) acrylic copolymer (a1) is used as the base polymer of the photocurable composition, the composition can exhibit adhesiveness at room temperature (20 ℃) even in an uncrosslinked state and can have a property of softening or fluidizing when heated to a temperature of 50 to 90 ℃, more preferably 60 ℃ or higher or 80 ℃ or lower.
(Dry ingredients)
The glass transition temperature of the (co) polymer constituting the dry component of the (meth) acrylic copolymer (A1) is preferably-70 to 0 ℃.
In this case, the glass transition temperature of the (co) polymer component constituting the dry component means the glass transition temperature of a polymer obtained by polymerizing only the monomer component constituting the dry component of the (meth) acrylic copolymer (a 1). Specifically, it is a value calculated from the glass transition temperature and the composition ratio of a polymer obtained from a homopolymer of each component of the (co) polymer by means of the Fox calculation formula. The polymer containing only the dry component may be a homopolymer or a copolymer.
The formula for Fox calculation is the following formula, and can be determined using the values described in polymer handbook [ polymer handbook, j. brandrup, Interscience, 1989 ].
1/(273+Tg)＝Σ(Wi/(273+Tgi))
[ in the formula, Wi represents the weight fraction of the monomer i, and Tgi represents the Tg (. degree. C.) of the homopolymer of the monomer i. ]
Since the glass transition temperature of the (co) polymer constituting the dry component of the (meth) acrylic copolymer (a1) affects the flexibility of the photocurable composition in a room temperature state and the wettability of the photocurable composition to an adherend, that is, the adhesiveness, the glass transition temperature of the photocurable composition is preferably-70 ℃ to 0 ℃, particularly-65 ℃ or more or-5 ℃ or less, and particularly preferably-60 ℃ or more or-10 ℃ or less, in order to obtain a proper adhesiveness (tackiness) in a room temperature state.
However, even if the glass transition temperature of the (co) polymer is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. The dry ingredients may be made softer, for example, by reducing their molecular weight.
Examples of the monomer contained in the dry component of the (meth) acrylic copolymer (A1) include (meth) acrylic ester monomers, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, tert-butyl acrylate, and mixtures thereof, Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3,5, 5-trimethylcyclohexane acrylate, p-cumylphenol ethylene oxide-modified (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, and the like.
In addition, hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glyceryl (meth) acrylate to which a hydrophilic group is bonded to these (meth) acrylate monomers may also be used.
In addition, carboxyl group-containing monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate may be used.
Further, monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride; epoxy group-containing monomers such as glycidyl (meth) acrylate, glycidyl α -ethacrylate, and 3, 4-epoxybutyl (meth) acrylate, amino group-containing (meth) acrylate monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; acrylamide monomers such as (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxyethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide-chloromethane salt, (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, and the like; amide group-containing monomers such as maleic acid amide and maleimide; heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole; isocyanate group-containing or blocked isocyanate group-containing monomers such as 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 2- (0- [ 1' -methylpropylideneamino ] carboxyamino) ethyl (meth) acrylate, and 2- [ (3, 5-dimethylpyrazolyl) carbonylamino ] ethyl (meth) acrylate; and ultraviolet-absorbing group-containing monomers such as 2- [ 2-hydroxy-5- [2- ((meth) acryloyloxy) ethyl ] phenyl ] -2H-benzotriazole.
In addition, various vinyl monomers copolymerizable with the above acrylic monomers and methacrylic monomers, such as styrene, t-butylstyrene, α -methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, and alkyl vinyl monomer, can also be suitably used.
The dry component of the (meth) acrylic copolymer (a1) preferably contains a hydrophobic monomer and a hydrophilic monomer as constituent units.
Since the tendency of whitening due to moist heat is observed when the dry component of the (meth) acrylic copolymer (a1) is composed of only hydrophobic monomers, it is preferable to prevent whitening due to moist heat by introducing hydrophilic monomers also into the dry component.
Specifically, as the dry component of the (meth) acrylic copolymer (a1), a copolymer component obtained by randomly copolymerizing a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the end of a macromonomer can be mentioned.
Examples of the hydrophobic (meth) acrylate monomer include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, and mixtures thereof, Lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methyl methacrylate.
Examples of the hydrophobic vinyl monomer include alkyl vinyl esters such as vinyl acetate, styrene, t-butyl styrene, α -methyl styrene, vinyl toluene, and alkyl vinyl monomers.
Among them, alkyl (meth) acrylates having 5 or more carbon atoms, particularly 8 or more carbon atoms, particularly 9 or more carbon atoms, and particularly 10 or more carbon atoms are preferable from the viewpoint of easily forming a suitable phase separation structure with compatibility with a branch component described later and from the viewpoint of imparting a suitable adhesiveness (tackiness) to the photocurable composition.
For example, when the photocurable composition is used for a member having a touch sensor function, the photocurable composition having a low relative dielectric constant may be required in order to absorb a change in touch detection sensitivity and suppress the generation of noise in a detection signal. In this case, from the viewpoint of adjusting the relative dielectric constant of the photocurable composition and/or a cured product obtained by photocuring the photocurable composition to be low, it is preferable to use an alkyl (meth) acrylate having 5 or more, particularly 8 or more, particularly 9 or more, and particularly 10 or more carbon atoms as the hydrophobic monomer.
Examples of the alkyl (meth) acrylate having 8 or more carbon atoms include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
Examples of the hydrophilic monomer include hydroxyl-containing (meth) acrylates such as methyl acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2- (meth) acrylate, hydroxy (meth) acrylate, hydroxy (meth) acrylate, hydroxy (meth) acrylate, hydroxy (meth) acrylate, as the monomer other than the carboxyl group-containing monomers such as crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate and monomethyl itaconate, the anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, the epoxy group-containing monomers such as glycidyl (meth) acrylate, glycidyl α -ethylacrylate and 3, 4-epoxybutyl (meth) acrylate, and the alkoxy polyalkylene glycol (meth) acrylates such as methoxypolyethylene glycol (meth) acrylate, there may be used (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxyethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, phenyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-butyl (meth) acrylate, N-butyl acrylate, N-butyl (meth) acrylate, N-butyl acrylate, N-butyl acrylate, N-acrylate, N-butyl acrylate, N, and one, N, (meth) acrylamide monomers such as N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide and the like.
Among the above, from the viewpoint of preventing whitening by moist heat of the photocurable composition and improving adhesion to an adherend, the hydrophilic monomer is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride group-containing monomer, or a (meth) acrylamide monomer.
On the other hand, when the photocurable composition is used for a member having corrosiveness such as a metal or a metal oxide, it is preferable to use a hydrophilic component containing no carboxyl group or acid anhydride having high acidity in order to prevent the corrosion deterioration of an adherend by the photocurable composition and/or a cured product obtained by photocuring the photocurable composition. From the above-mentioned viewpoint, as the hydrophilic monomer, for example, (meth) acrylamide monomers such as hydroxyl group-containing (meth) acrylates including hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glyceryl (meth) acrylate, (meth) acrylamides, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxyethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, phenyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and diacetone (meth) acrylamide are preferably used.
(Branch component: macromonomer)
The (meth) acrylic copolymer (A1) preferably incorporates a macromonomer as a branching component of the graft copolymer, containing the macromonomer as a structural unit.
The macromonomer is a macromolecular monomer having a polymerizable functional group at the end and a high molecular weight skeleton component.
The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the above (meth) acrylic copolymer (a 1).
Specifically, the glass transition temperature (Tg) of the macromonomer affects the heating melting temperature (hot melt temperature) of the photocurable composition, and is preferably from 30 ℃ to 120 ℃, more preferably from 40 ℃ or higher to 110 ℃ or lower, particularly preferably from 50 ℃ or higher to 100 ℃ or lower.
When the macromonomer has such a glass transition temperature (Tg), it can be adjusted to a temperature close to 50 to 80 ℃ while maintaining excellent processability and storage stability by adjusting the molecular weight.
The glass transition temperature of the macromonomer is the glass transition temperature of the macromonomer itself, and can be measured by a Differential Scanning Calorimeter (DSC).
Further, it is also preferable to adjust the molecular weight and content of the macromonomer so that the branched components attract each other at room temperature to maintain a state in which physical crosslinking is performed as a binder composition, and the physical crosslinking can be released by heating to an appropriate temperature to obtain fluidity.
From the above viewpoint, the macromonomer is preferably contained in the (meth) acrylic copolymer (a1) at a ratio of 5 to 30% by mass, particularly preferably 6% by mass or more or 25% by mass or less, and particularly preferably 8% by mass or more or 20% by mass or less.
The number average molecular weight of the macromonomer is preferably 500 to 10 ten thousand, more preferably less than 8000, still more preferably 800 or more and less than 7500, particularly 1000 or more and less than 7000.
As the macromonomer, a conventionally produced macromonomer (for example, a macromonomer manufactured by Toyo Synthesis Co., Ltd.) can be suitably used.
The high molecular weight backbone component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
Examples of the high-molecular-weight skeleton component of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, and mixtures thereof, Lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3,5, 5-trimethylcyclohexane acrylate, p-cumylphenol ethylene oxide-modified (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, hydroxyalkyl (meth) acrylate, meth) acrylic acid, glycidyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxy polyalkylene glycol (meth) acrylate, and other (meth) acrylate monomers, styrene, poly (meth) acrylate, poly (vinyl (meth) acrylate, poly (meth) acrylate, poly (meth), T-butylstyrene, α -methylstyrene, vinyltoluene, an alkyl vinyl monomer, an alkyl vinyl ester, an alkyl vinyl ether, a hydroxyalkyl vinyl ether, (meth) acrylonitrile, (meth) acrylamide, an N-substituted (meth) acrylamide, and other various vinyl monomers, and these may be used alone or in combination of 2 or more.
The macromonomer has a radical polymerizable group or a polymerizable functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, or a mercapto group. The macromonomer preferably has a radical polymerizable group copolymerizable with other monomers. The radical polymerizable group may contain one or more than two, and among them, one is particularly preferable. When the macromonomer has a functional group, the functional group may contain one or more, and among them, one is particularly preferable. The radical polymerizable group and the functional group may be contained in either one or both of them. When both the radically polymerizable group and the functional group are contained, the number of the functional group or the radically polymerizable group other than any of the functional group added to the polymer unit composed of another monomer or the radically polymerizable group copolymerized with another monomer may be two or more.
Therefore, examples of the terminal functional group of the macromonomer include a functional group such as a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an amino group, an amide group, and a mercapto group, in addition to a radical polymerizable group such as a methacryloyl group, an acryloyl group, and a vinyl group.
Among these, the terminal functional group of the macromonomer preferably has a radical polymerizable group copolymerizable with other monomers. In this case, the radical polymerizable group may contain one or two or more, and among them, one is particularly preferable.
When the macromonomer has a functional group, it may have one or more functional groups, and among them, one is particularly preferable.
The radical polymerizable group and the functional group may be contained in either one or both of them. When both the radically polymerizable group and the functional group are contained, the number of the functional group or the radically polymerizable group other than any of the functional group added to the polymer unit composed of another monomer or the radically polymerizable group copolymerized with another monomer may be two or more.
The macromonomer can be produced by a known method. Examples of the method for producing the macromonomer include a method of producing the macromonomer using a cobalt chain transfer agent, a method of using an α -substituted unsaturated compound such as α -methylstyrene dimer as a chain transfer agent, a method of chemically bonding polymerizable groups, and a method of utilizing thermal decomposition. Among these, as a method for producing a macromonomer, a method for producing a macromonomer using a cobalt chain transfer agent is preferred in terms of a small number of production steps and the use of a catalyst having a high chain transfer constant.
(production method)
The acrylic copolymer (a1) can be obtained by, for example, adding a polymer composed of the specific macromonomer (a) and the vinyl monomer (b), or by polymerizing a monomer mixture containing the specific macromonomer (a) and the vinyl monomer (b).
< crosslinking agent (B) >
The crosslinking agent (B) in the photocurable composition has a function as a control agent for a (micro) phase separation structure formed as a composition containing the (meth) acrylic copolymer (a), in other words, a control agent for adjusting flexibility and cohesion of the photocurable composition.
Examples of the crosslinking agent (B) include crosslinking agents having at least 1 crosslinkable functional group selected from a (meth) acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a carbodiimide group, an oxazoline group, an aziridine group, a vinyl group, an amino group, an imino group, an amide group, an N-substituted (meth) acrylamide group, and an alkoxysilyl group, and 1 kind or a combination of 2 or more kinds may be used.
The crosslinkable functional group may be protected by a protective group which can be deprotected.
Among them, polyfunctional (meth) acrylates are preferable from the viewpoint of ease of control of the crosslinking reaction.
Examples of such polyfunctional (meth) acrylates include 1, 4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol glycidyl ether di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polyalkoxy di (meth) acrylate, bisphenol F polyalkoxy di (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxethyl (meth) acrylate, epsilon-caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and the like, Pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, di (meth) acrylate of the epsilon-caprolactone adduct of hydroxypivalic acid neopentyl glycol, mixtures thereof, and mixtures thereof, Examples of the ultraviolet-curable polyfunctional monomer include ultraviolet-curable polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, alkoxylated trimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, and also polyfunctional acrylic oligomers such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and polyether (meth) acrylate, and polyfunctional acrylamides.
In the above-mentioned examples, from the viewpoint of improving the adhesion to an adherend and the effect of suppressing whitening by moist heat, among the polyfunctional (meth) acrylate monomers, a polyfunctional monomer or oligomer containing a polar functional group such as a hydroxyl group, a carboxyl group, an amino group, or an amide group is preferable. Among them, polyfunctional (meth) acrylates having a hydroxyl group or an amide group are preferably used.
From the viewpoint of preventing whitening by moist heat, the (meth) acrylate copolymer (a1), i.e., the graft copolymer, preferably contains a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as dry components, and further, a polyfunctional (meth) acrylate having a hydroxyl group is preferably used as the crosslinking agent (B).
In addition, a monofunctional or polyfunctional (meth) acrylate which reacts with the crosslinking agent (B) may be added for adjusting the effects of adhesion, moist heat resistance, and the like.
Examples of the crosslinking agent having 2 or more crosslinkable functional groups include monomers containing an isocyanate group or a blocked isocyanate group such as an epoxy group-containing monomer (e.g., glycidyl (meth) acrylate, glycidyl α -ethacrylate, 3, 4-epoxybutyl (meth) acrylate, 4-hydroxybutyl glycidyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, 2- (0- [ 1' -methylpropylideneamino ] carboxyamino) ethyl (meth) acrylate, 2- [ (3, 5-dimethylpyrazolyl) carbonylamino ] ethyl (meth) acrylate, vinyltrimethoxysilane, vinyltoluene-co-xylene, vinyltoluene-co-xylene, vinyltoluene-xylene-ethylene-propylene-based xylene, vinyltoluene-propylene-ethylene-based xylene, vinyltoluene-propylene-based xylene-containing xylene-based xylene-ethylene-based xylene-ethylene-based xylene-ethylene-based xylene-based, Various silane coupling agents such as vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-isocyanatopropyltriethoxysilane.
The crosslinking agent having 2 or more crosslinkable functional groups may have a structure in which one crosslinkable functional group is reacted with the (meth) acrylic copolymer to bond the (meth) acrylic copolymer (a).
By bonding the crosslinking agent (B) to the (meth) acrylic copolymer (a), bleeding of the crosslinking agent (B) can be suppressed, and unintended plasticization of the adhesive composition can be suppressed. Further, by bonding the crosslinking agent (B) to the (meth) acrylic copolymer (a), the reaction efficiency of the photocrosslinking reaction is promoted, and thus a cured product having a higher cohesive force can be obtained.
The content of the crosslinking agent (B) is preferably 0.05 parts by mass or 30 parts by mass, more preferably 0.1 parts by mass or 20 parts by mass, even more preferably 0.5 parts by mass or more or 15 parts by mass, and particularly preferably 1 part by mass or more or 13 parts by mass, based on 100 parts by mass of the (meth) acrylic copolymer (a), from the viewpoint of maintaining a proper phase separation structure by adjusting the half-value width of a one-dimensional scattering curve in the small-angle X-ray scattering measurement to a proper range and balancing flexibility and cohesion of the photocurable composition.
The photocurable composition may further contain a monofunctional monomer that reacts with the crosslinkable functional group of the crosslinking agent (B). By containing the monofunctional monomer, the half-value width X1 of the one-dimensional scattering curve in the small-angle X-ray scattering measurement of the photocurable composition can be increased, or the fluidity at the time of hot-melting can be improved, and the adhesion to an adherend and the effect of suppressing whitening due to moist heat can be improved.
Examples of such monofunctional monomers include hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, and polyalkylene glycol (meth) acrylate in addition to alkyl (meth) acrylates such as methyl acrylate; carboxyl group-containing monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate; anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; ether group-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and methoxypolyethylene glycol (meth) acrylate; (meth) acrylamide monomers such as (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxyethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, phenyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and diacetone (meth) acrylamide.
Among them, hydroxyl group-containing (meth) acrylates and (meth) acrylamide monomers are preferably used from the viewpoint of improving the adhesion to an adherend and the effect of suppressing whitening due to moist heat.
< crosslinking initiator (C) >
The crosslinking initiator (C) used in the photocurable composition functions as a reaction initiation aid in the crosslinking reaction of the crosslinking agent (B).
The crosslinking initiator can be suitably used in the conventional known crosslinking initiator. Among them, from the viewpoint of ease of control of the crosslinking reaction, a photopolymerization initiator which is sensitive to ultraviolet rays having a wavelength of 380nm or less is preferable.
On the other hand, a photopolymerization initiator which is sensitive to light having a wavelength longer than 380nm is preferable in terms of obtaining high photoreactivity and in terms of easily reaching the deep part of the sheet when the photocurable composition is formed into a sheet.
Photopolymerization initiators are roughly classified into 2 types according to the mechanism of radical generation, and roughly classified into cleavage type photopolymerization initiators capable of generating radicals by cleaving and decomposing single bonds of the photopolymerization initiators themselves; and a hydrogen abstraction type photopolymerization initiator which forms an excited complex with a hydrogen donor in the system by the photo-excited initiator and is capable of transferring hydrogen of the hydrogen donor.
Among these, the cleavage type photopolymerization initiators decompose to form other compounds when radical is generated by light irradiation, and do not function as a crosslinking initiator when excited. Therefore, it is preferable that the active species do not remain in the adhesive material after the completion of the crosslinking reaction, and there is no possibility of unexpected light deterioration or the like being given to the adhesive material.
On the other hand, the hydrogen abstraction photopolymerization initiator does not generate a decomposition product such as a cleavage photopolymerization initiator when a radical reaction is caused by irradiation of an active energy ray such as an ultraviolet ray, and therefore, it is difficult to form a volatile component after the reaction is completed, and damage to an adherend can be reduced, and this is useful in this respect.
Examples of the cleavage type photopolymerization initiator include 2, 2-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) benzyl } phenyl ] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) Methyl phenylglyoxylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone, {1- [4- (phenylthio) -2- (O-benzoyloxime) ] }1, 2-octanedione, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, (2,4, 6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) 2,4, 4-trimethylpentylphosphine oxide, derivatives thereof and the like.
Examples of the hydrogen abstraction-type photopolymerization initiator include benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, 4-phenylbenzophenone, 3 '-dimethyl-4-methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, 4- [2- ((meth) acryloyloxy) ethoxy ] benzophenone, 4- (meth) acryloyloxy-4' -methoxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2-phenyl-2-oxoacetic acid) oxydiene, 4- (1, 3-acryloyl-1, 4,7,10, 13-pentaoxatridecyl) benzophenone, and mixtures thereof, Thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2, 4-dimethylthioxanthone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, camphorquinone, derivatives thereof, and the like.
However, the photopolymerization initiator is not limited to the above-mentioned ones. Any one of the photopolymerization initiators mentioned above or a derivative thereof may be used, or two or more kinds thereof may be used in combination.
Among them, acylphosphine oxide-based photopolymerization initiators such as bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, (2,4, 6-trimethylbenzoyl) ethoxyphenylphosphine oxide, and bis (2, 6-dimethoxybenzoyl) 2,4, 4-trimethylpentylphosphine oxide are preferable in terms of high sensitivity to light, and discoloration due to the fact that the resultant is decomposed after the reaction.
In addition, from the viewpoint of easiness of reaction control and compatibility with an acrylic copolymer including a graft copolymer having a macromonomer as a branch component, benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, 4-phenylbenzophenone, 3 '-dimethyl-4-methoxybenzophenone, 4- (meth) acryloyloxybenzophenone, 4- [2- ((meth) acryloyloxy) ethoxy ] benzophenone, 4- (meth) acryloyloxy-4' -methoxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate and the like are preferably used as the crosslinking initiator (C).
The content of the crosslinking initiator (C) is not particularly limited. The acrylic copolymer (A) is preferably contained in an amount of 0.1 to 10 parts by mass, particularly 0.5 part by mass or more and 5 parts by mass or less, particularly 1 part by mass or more and 3 parts by mass or less, based on 100 parts by mass of the acrylic copolymer (A).
By setting the content of the crosslinking initiator (C) in the above range, appropriate reaction sensitivity to active energy rays can be obtained.
Further, a sensitizer may be used in addition to the crosslinking initiator (C) component.
The sensitizer is not particularly limited, and may be used without any problem as long as it is a sensitizer used in a photopolymerization initiator. Examples thereof include aromatic amines, anthracene derivatives, anthraquinone derivatives, coumarin derivatives, thioxanthone derivatives, phthalocyanine derivatives, and the like, aromatic ketones such as benzophenone, xanthone, thioxanthone, mie ketone, 9, 10-phenanthrenequinone, and derivatives thereof.
< other ingredients >
The photocurable composition may contain known components blended in a general adhesive composition as components other than those described above. For example, various additives such as a tackifier resin, an antioxidant, a light stabilizer, a metal deactivator, a rust inhibitor, an aging inhibitor, a moisture absorbent, a hydrolysis inhibitor, an antistatic agent, an antifoaming agent, and inorganic particles can be suitably contained.
Further, if necessary, a reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.) may be appropriately contained.
< present pressure-sensitive adhesive sheet >
A pressure-sensitive adhesive sheet (referred to as "the present pressure-sensitive adhesive sheet") can be produced from the photocurable composition.
The adhesive sheet may be a sheet formed of a single layer, or may be a multilayer sheet in which 2 or more layers are laminated.
When the adhesive sheet is a 3-layer or more adhesive sheet, for example, when a laminated adhesive sheet including an intermediate layer and an outermost layer is formed, the outermost layer is preferably formed from the photocurable composition.
When the adhesive sheet is formed into an adhesive sheet having a laminated structure including an intermediate layer and outermost layers, the ratio of the thickness of each outermost layer to the thickness of the intermediate layer is preferably 1: 1-1: 20. among them, 1: 2-1: 10.
when the thickness of the intermediate layer is within the above range, it is preferable that the contribution to the thickness of the adhesive material layer in the laminate is not excessive, and the intermediate layer is not excessively flexible and does not deteriorate the workability of cutting and retrieving.
When the outermost layer is in the above range, the adhesion to an adherend and the wettability can be maintained without deteriorating the conformability to uneven and curved surfaces, which is preferable.
(thickness of the adhesive sheet)
The thickness of the present adhesive sheet can be reduced by reducing the thickness of the sheet, and on the other hand, if the thickness of the sheet is excessively reduced, for example, if the surface to be bonded has irregularities, the adhesive sheet cannot sufficiently follow the irregularities and cannot exhibit sufficient adhesive strength.
From the above viewpoint, the thickness of the adhesive sheet is preferably 20 μm to 500 μm, particularly 25 μm or more or 350 μm or less, and particularly preferably 50 μm or more or 250 μm or less.
(adhesive force of the adhesive sheet)
The adhesive sheet was attached to glass and irradiated at 4000mJ/m in cumulative light exposure2The 180 ° peel strength to glass in the case of light, that is, the 180 ° peel strength of the present adhesive sheet after light irradiation is preferably 3N/cm or more.
When the 180 ° peel strength to glass is 3N/cm or more, excellent cohesive force can be exerted, and therefore, adherends can be firmly adhered to each other. Therefore, the image display constituent members described later can be more firmly attached to each other.
From the above-mentioned viewpoint, the 180 ° peel strength of the adhesive sheet against glass upon light irradiation is preferably 3N/cm or more, more preferably 5N/cm or more, particularly 10N/cm or more, as described above.
(method of Using the adhesive sheet)
The present adhesive sheet may be used alone as it is. Further, the laminate may be used in a state of being laminated with another member.
< pressure-sensitive adhesive sheet laminate >
The present adhesive sheet laminate may have any structure as long as it is a laminate including the adhesive sheet in the layer structure. For example, a release film may be laminated on one side or both sides of the present adhesive sheet to form an adhesive sheet laminate.
As the release film, a film known in the art can be used as desired.
The thickness of the release film is not particularly limited. Among them, for example, from the viewpoint of processability and handleability, it is preferably 25 to 500. mu.m, more preferably 38 to 250 μm, particularly 50 to 200 μm.
< the present cured product >
By curing the photocurable composition by irradiation with light (referred to as "photocuring"), a half-value width X3 (nm) of a one-dimensional scattering curve characteristic of a small-angle X-ray scattering measurement can be obtained-1) Is 0.05<X3<0.25 cured product (referred to as "the present cured product").
Here, the cured product is obtained by curing the photocurable composition by irradiation with light, and the form thereof is arbitrary. Therefore, the sheet-like shape may or may not be a sheet-like shape.
In the cured product, the half-value width X3 (nm) of the one-dimensional scattering curve in the small-angle X-ray scattering measurement was measured-1) Is 0.05<X3<0.25, a cured product having high cohesive force and high reliability can be obtained.
From the above-mentioned viewpoints, the half-value width X3 (nm) of the one-dimensional scattering curve in the measurement of small-angle X-ray scattering in the present cured product-1) From the same viewpoint as the above-mentioned photocurable composition, it is preferably 0.05<X3<0.25, more preferably 0.06<X3 or X3<0.24, in particular 0.08<X3 or X3<0.22, in particular 0.10<X3 or X3<0.20。
According to the above, the half-value width X3 is preferably any one of 0.05< X3<0.25, 0.05< X3<0.24, 0.05< X3<0.22, or 0.05< X3<0.20, more preferably any one of 0.06< X3<0.25, 0.06< X3<0.24, 0.06< X3<0.22, or 0.06< X3<0.20, further preferably any one of 0.08< X3<0.25, 0.08< X3<0.24, 0.08< X3<0.22, or 0.08< X3<0.20, further preferably any one of 0.10< X3<0.25, 0.10< X3<0.24, 0.10< X3<0.22, or 0.10< X3.
The half width X3 of the cured product was adjusted by adjusting the half width X1 (nm)-1) The same applies to the above-mentioned means. For example, there is a method of adjusting the structure, composition, molecular weight, and the like of the (meth) acrylic copolymer (a) as a base polymer and adjusting or selecting the kinds and amounts of the crosslinking agent (B) and the crosslinking initiator (C). However, the method is not limited to these means.
Further, in order to adjust the half-value width X3 to a preferable range, it is preferable to use (1) a (meth) acrylic monomer or a vinyl monomer having 5 or more, particularly 8 or more, particularly 9 or more, particularly 10 or more carbon atoms as a main copolymerization component (dry component) of the (meth) acrylic copolymer, as described above. Specifically, it is preferably selected from the monomers contained in the dry component of the acrylic copolymer (a 1).
In addition, (2a) preferably uses a hydrophilic component as the copolymerizable component (dry component) other than the (meth) acrylic monomer or the vinyl monomer. Specifically, it is preferably selected from the hydrophilic monomers contained in the dry component of the acrylic copolymer (a1) described later. Further, it is more preferable that (2b) the hydrophilic component is contained in a mass ratio of 0.1 to 20 relative to the copolymerization component (dry component) 100 to improve the hydrophilicity of the dry component.
Further, (3a) preferably comprises a (meth) acrylic monomer or vinyl monomer component having 4 or less carbon atoms as a branched component of the (meth) acrylic copolymer (a) in a mass ratio of 1 to 100 relative to the dry component 100, and the microphase separation state of the phase of the dry component and the phase of the branched component is adjusted. Preferably, (3b) a (meth) acrylic monomer or vinyl monomer component having a cyclic structure is blended as a branched component of the (meth) acrylic copolymer (a) so as to be in a mass ratio of 1 to 100 relative to the dry component 100, and a microphase separation state of the phase of the dry component and the phase of the branched component is adjusted.
Further, (4a) preferably uses a hydroxyl group-containing compound or the like having high compatibility with the hydrophilic component as the crosslinking agent (B). Specifically, it is preferably selected from the examples of the crosslinking agent (B) described above. Further, it is more preferable that (4B) the crosslinking agent (B) is contained in an amount of 0.05 to 30 parts by mass per 100 parts by mass of the (meth) acrylic copolymer, and the polarity of the dry component is appropriately adjusted.
As described above, by appropriately selecting the above (1) to (4) independently from each other, it is possible to adjust the phase separation structure of the trunk component and the branch component. Among these methods (1) to (4b), the combination of (1) with (2a) and/or (2b) and the combination of (1) with (3a) and/or (3b) are preferable, the combination of (1) with (3a) and/or (3b) with (4a) and/or (4b) is more preferable, and all of the methods (1) to (4b) are most preferably used. However, the method is not limited thereto.
Since the optimum phase separation state can be achieved by optimizing the balance between the compatibility of the branched component and the dry component by using the graft polymer as described above, the half-value width X3 can be controlled by using, for example, a hydrophobic component as the main copolymerizable component (dry component) of the copolymer (a) and a hydrophilic component as the branched component of the copolymer (B) in addition to the above.
< laminate for constituting image display device >
The laminate for constituting an image display device (referred to as "laminate for constituting an image display device" herein) can be formed by laminating 2 members constituting an image display device with the photocurable composition or the adhesive sheet or the cured product interposed therebetween.
In this case, the 2 image display device components include any one of the group consisting of a touch sensor, an image display panel, a surface protection panel, and a polarizing film, or a combination of 2 or more kinds.
Specific examples of the laminate for constituting the present image display device include a release sheet/the present photocurable composition or the present adhesive sheet or the present cured product/touch panel, a release sheet/the present photocurable composition or the present adhesive sheet or the present cured product/protective panel, a release sheet/the present photocurable composition or the present adhesive sheet or the present cured product/image display panel, an image display panel/the present photocurable composition or the present adhesive sheet or the present cured product/touch panel, an image display panel/the present photocurable composition or the present adhesive sheet or the present cured product/protective panel, an image display panel/the present photocurable composition or the present adhesive sheet or the present cured product/touch panel/the present photocurable composition or the present adhesive sheet or the present cured product/protective panel, a pressure sensitive adhesive sheet, A polarizing film/the present photocurable composition or the present adhesive sheet or the present cured product/touch panel, a polarizing film/the present photocurable composition or the present adhesive sheet or the present cured product/touch panel/the present photocurable composition or the present adhesive sheet or the present cured product/protective panel, and the like. However, the present invention is not limited to these examples.
The touch panel also includes a structure for protecting the touch panel function in the panel and a structure for providing the touch panel function in the image display panel.
< present image display apparatus >
An image display device (referred to as "the present image display device") can be configured by using the laminate for configuring the present image display device as described above.
The present image display device may be, for example, an image display device such as a liquid crystal display, an organic EL display, an inorganic EL display, electronic paper, a plasma display, or a Micro Electro Mechanical System (MEMS) display.
< description of sentence >
In the case where "X to Y" (X, Y is an arbitrary number) is described in the present specification, unless otherwise specified, the meaning of "preferably greater than X" or "preferably less than Y" is also included together with the meaning of "X or more and Y or less".
In addition, the description of "X or more" or "X ≦" (X is an arbitrary number), also includes the meaning of "preferably greater than X".
In addition, the term "preferably less than Y" is also included in the case where "Y" is not more than Y "or" Y ≧ "(Y is an arbitrary number).
In general, the boundary between a sheet and a film is not clear, and it is not necessary to distinguish them in the present invention in terms of expression, and therefore, in the present invention, "sheet" is included when it is referred to as "film" and "film" is included when it is referred to as "sheet".
Examples
The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.
[ example 1]
To 1kg of an acrylic copolymer (A-1, mass average molecular weight: 20 ten thousand) obtained by random copolymerization of 15 parts by mass of a polymethyl methacrylate macromonomer having a number average molecular weight of 2500, 81 parts by mass of butyl acrylate and 4 parts by mass of acrylic acid as a (meth) acrylic copolymer (A), 50g of propoxylated pentaerythritol triacrylate (NK ESTER ATM-4PL, manufactured by Ninghamu chemical Co., Ltd.) (B-1) as a crosslinking agent (B) and 15g of ESACURE TZT (manufactured by IGM Co., Ltd.) (C-1) as a photoinitiator (C) were added and uniformly mixed to obtain a photocurable composition 1.
Then, the photocurable composition 1 was formed into a sheet-like shape with a thickness of 150 μm on a polyethylene terephthalate film (made by Mitsubishi resin corporation, Diafil MRV, thickness 100 μm) whose surface was subjected to a peeling treatment, and the surface was covered with the polyethylene terephthalate film (made by Mitsubishi resin corporation, Diafil MRQ, thickness 75 μm) whose surface was subjected to a peeling treatment, thereby producing an adhesive sheet laminate 1.
[ example 2]
To 1kg of an acrylic copolymer (A-2, mass average molecular weight: 15 ten thousand) obtained by random copolymerization of 15 parts by mass of a polymethyl methacrylate macromonomer (number average molecular weight 3000) having a methacryloyl group as a terminal functional group, 81 parts by mass of butyl acrylate, and 4 parts by mass of acrylic acid as a (meth) acrylic copolymer (A), 110g of propoxylated pentaerythritol triacrylate (NK ESTER ATM-4PL, manufactured by Nippon Kogyo Co., Ltd.) (B-1) as a crosslinking agent (B) and 15g of ESACURE TZTT (manufactured by IGM Co., Ltd.) (C-1) as a photoinitiator (C) were added and uniformly mixed to obtain a photocurable composition 2.
A pressure-sensitive adhesive sheet laminate 2 was produced from the photocurable composition 2 in the same manner as in example 1.
[ example 3]
1kg of an acrylic copolymer (A-3, mass average molecular weight: 4.6 ten thousand) obtained by random copolymerization of 15 parts by mass of a polymethyl methacrylate macromonomer (number average molecular weight 6700) having a terminal functional group of a methacryloyl group, 81 parts by mass of butyl acrylate, and 4 parts by mass of acrylic acid as a (meth) acrylic copolymer (A), 5g of nonanediol diacrylate (Viscoat 260, manufactured by Osaka organic industries, Ltd.) (B-2) as a crosslinking agent (B), and 15g of ESACURE TZT (manufactured by IGM) as a photoinitiator (C) were added and mixed uniformly to obtain a photocurable composition 3.
A pressure-sensitive adhesive sheet laminate 3 was produced from the photocurable composition 3 in the same manner as in example 1.
[ example 4]
2-isocyanatoethyl methacrylate (Karenz MOI) (B-3) was mixed as a crosslinking agent (B) in an amount of 27g per 1kg of an acrylic copolymer (A-4, mass-average molecular weight: 11 ten thousand) obtained by random copolymerization of 30 parts by mass of a polymethyl methacrylate macromonomer (number-average molecular weight 2500) having a methacryloyl group as a terminal functional group, 66 parts by mass of butyl acrylate and 4 parts by mass of acrylic acid as a (meth) acrylic copolymer (A). The carboxyl group of the (meth) acrylic copolymer (A-4) was reacted with the isocyanate group of the crosslinking agent (B-3) by heating at 80 ℃ for 4 hours. Subsequently, 15g of ESACURE TZT (manufactured by IGM Co.) (C-1) and 100g of hydroxybutyl acrylate were added as photoinitiators (C) and mixed uniformly to obtain a photocurable composition 4.
A pressure-sensitive adhesive sheet laminate 4 was produced from the photocurable composition 4 in the same manner as in example 1.
[ example 5]
36g of 2-isocyanatoethyl methacrylate (Karenz MOI, product of Showa Denko K.K.) (B-3) as a crosslinking agent (B) was mixed with 1kg of the acrylic copolymer (A-2, mass-average molecular weight: 15 ten thousand) used in example 2 as the (meth) acrylic copolymer (A). The carboxyl group of the (meth) acrylic copolymer (A-4) was reacted with the isocyanate group of the crosslinking agent (B-3) by heating at 80 ℃ for 4 hours. Subsequently, 15g of ESACURE KTO46 (manufactured by IGM Co., Ltd.) (C-2) was added as a photoinitiator (C) and uniformly mixed to obtain a photocurable composition 5.
A pressure-sensitive adhesive sheet laminate 5 was produced from the photocurable composition 5 in the same manner as in example 1.
[ example 6]
To 1kg of an acrylic copolymer (A-5, mass average molecular weight: 7.4 ten thousand) obtained by random copolymerization of 11 parts by mass of a polymethyl methacrylate macromonomer (number average molecular weight 2500) having a number average molecular weight 2500 in which a terminal functional group is a methacryloyl group, 86 parts by mass of 2-ethylhexyl acrylate, and 3 parts by mass of acrylic acid as a (meth) acrylic copolymer (A), 90g of propoxylated pentaerythritol triacrylate (NK ESTER ATM-4PL, manufactured by Nippon Korea chemical Co., Ltd.) (B-1) and 15g of ESACURE TZT (manufactured by IGM Co., Ltd.) (C-1) as a crosslinking agent (B) were added and uniformly mixed to obtain a photocurable composition 6.
A pressure-sensitive adhesive sheet laminate 6 was produced from the photocurable composition 6 in the same manner as in example 1.
[ example 7]
With respect to the (meth) acrylic copolymer (a) to be obtained by mixing a monomer comprising isobornyl methacrylate: methyl methacrylate ═ 1: 1.5 parts by mass of a macromonomer (number average molecular weight 3000) having a terminal functional group of a methacryloyl group, 43.7 parts by mass of lauryl acrylate, 40 parts by mass of 2-ethylhexyl acrylate, and 2.8 parts by mass of acrylamide were randomly copolymerized to obtain 1kg of an acrylic graft copolymer (A-6, mass average molecular weight: 16 ten thousand) and 50g of propoxylated pentaerythritol triacrylate (NK ESTER ATM-4PL, manufactured by Newzhou chemical Co., Ltd.) (B-1) as a crosslinking agent (B) and 15g of methyl benzoylformate (Speedcure MBF, manufactured by Lambson corporation) (C-3) as a photoinitiator (C) were added and mixed uniformly to obtain a photocurable composition 7.
A pressure-sensitive adhesive sheet laminate 7 was produced from the photocurable composition 7 in the same manner as in example 1.
[ example 8]
With respect to the (meth) acrylic copolymer (a) to be obtained by mixing a monomer comprising isobornyl methacrylate: methyl methacrylate ═ 1: 1.1.1 kg of an acrylic graft copolymer (A-7, mass average molecular weight: 7.9 ten thousand) obtained by random copolymerization of 30 parts by mass of a macromonomer (number average molecular weight 3000) having a terminal functional group of a methacryloyl group, 33 parts by mass of lauryl acrylate, 34 parts by mass of 2-ethylhexyl acrylate, and 3 parts by mass of acrylamide, 200g of tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Mikamura chemical Co., Ltd.) (B-4) as a crosslinking agent (B), and 15g of ESACURE TZT (manufactured by IGM Co., Ltd.) (C-1) as a photoinitiator (C) were added and mixed uniformly to obtain a photocurable composition 8.
A pressure-sensitive adhesive sheet laminate 8 was produced from the photocurable composition 8 in the same manner as in example 1.
[ example 9]
With respect to the (meth) acrylic copolymer (a) to be obtained by mixing a monomer comprising isobornyl methacrylate: methyl methacrylate ═ 1: 1.5 parts by mass of a macromonomer (number-average molecular weight 8800) having a terminal functional group of a methacryloyl group, 43.7 parts by mass of lauryl acrylate, 40 parts by mass of 2-ethylhexyl acrylate, and 2.8 parts by mass of acrylamide were randomly copolymerized to obtain 1kg of an acrylic graft copolymer (A-8, mass-average molecular weight: 11 ten thousand), and 90g of propoxylated pentaerythritol triacrylate (NK ESTER ATM-4PL, manufactured by Ninghamu chemical Co., Ltd.) (B-1) as a crosslinking agent (B) and 15g of ESACURE TZT (manufactured by IGM Co., Ltd.) (C-1) as a photoinitiator (C) were added and mixed uniformly to obtain a photocurable composition 9.
A pressure-sensitive adhesive sheet laminate 9 was produced from the photocurable composition 9 in the same manner as in example 1.
Comparative example 1
A photocurable composition 10 was obtained by uniformly mixing 1kg of an MMA-BA-MMA triblock copolymer (KURARARAAY CO., LTD, KURARITY LA2140e) (A-9, mass average molecular weight: 7.4 ten thousand) containing butyl acrylate and methyl methacrylate as a (meth) acrylic copolymer (A) with 110g of propoxylated pentaerythritol triacrylate (NK ESTER ATM-4PL, manufactured by Newzhou chemical Co., Ltd.) (B-1) as a crosslinking agent (B) and 15g of ESACURE TZTT (IGM) (C-1) as a photoinitiator (C).
A pressure-sensitive adhesive sheet laminate 10 was produced from the photocurable composition 10 in the same manner as in example 1.
Comparative example 2
To 1kg of an acrylic copolymer (A-10, mass average molecular weight: 50 ten thousand) containing 24 parts by mass of 2-ethylhexyl acrylate, 74 parts by mass of butyl acrylate and 2 parts by mass of acrylic acid as a (meth) acrylic copolymer (A) were added 5.5g of nonanediol diacrylate (Viscoat 260, manufactured by Osaka Seiko Co., Ltd.) (B-2) as a crosslinking agent (B) and 9.5g of ESACURE ZTT (C-1) (manufactured by IGM) as a photocrosslinking initiator (C), and the mixture was uniformly mixed to obtain a photocurable composition 11. The (meth) acrylic copolymer (a-10) is a copolymer containing no macromonomer component.
A pressure-sensitive adhesive sheet laminate 11 was produced from the photocurable composition 11 in the same manner as in example 1.
Comparative example 3
With respect to the (meth) acrylic copolymer (a) to be obtained by mixing a monomer comprising isobornyl methacrylate: methyl methacrylate ═ 1: 1.5 parts by mass of a macromonomer (number average molecular weight 3000) having a terminal functional group of a methacryloyl group, 43.7 parts by mass of lauryl acrylate, 40 parts by mass of 2-ethylhexyl acrylate, and 2.8 parts by mass of acrylamide were randomly copolymerized to obtain 1kg of an acrylic graft copolymer (A-11, mass average molecular weight: 4.9 ten thousand) and 90g of propoxylated pentaerythritol triacrylate (NK ESTER ATM-4PL, manufactured by Ninghamu chemical Co., Ltd.) (B-1) as a crosslinking agent (B) and 15g of ESACURE TZT (C-1) (manufactured by IGM) as a photoinitiator (C) were added and mixed uniformly to obtain a photocurable composition 12.
A pressure-sensitive adhesive sheet laminate 12 was produced from the photocurable composition 12 in the same manner as in example 1.
The photocurable composition 12 is a viscous liquid at room temperature because the (meth) acrylic polymer (a-11) has a low molecular weight and high fluidity.
< evaluation >
Next, a method for evaluating the photocurable composition, the adhesive sheet, or the adhesive sheet laminate obtained in the above examples and comparative examples will be described.
[ Small-Angle X-ray Scattering ]
For small-angle X-ray scattering measurements, BL03XU (advanced Soft Material development, science Association Beam line) from SPring-8 used as a large-scale radiation light facility was performed.
The photocurable compositions before photocuring, which were the adhesive sheet laminates produced in examples and comparative examples, were peeled from the release films on both sides, and the adhesive sheets were set in a jig for a sample.
The beam shape of the X-ray was adjusted to 120 μm in the vertical direction and 120 μm in the horizontal direction. The X-ray wavelength is set to
The detector used a CCD (Hamamatsu Photonics V7739P + ORCA R2). The camera length was set to about 4m, and calibration was performed using a standard sample (collagen). The type, thickness, and exposure time of the attenuator (attenuation plate) are adjusted so that strong X-rays do not damage the detector, and then the sample is irradiated with X-rays to obtain a two-dimensional scatter image of the sample.
And correcting the background according to the two-dimensional scattering image of the sample obtained in the previous step. Specifically, a two-dimensional scattering Image of the background, which was subjected to the same operation as in the above-described step in a state where no sample was present, was acquired, and the two-dimensional scattering Image of the background was subtracted from the two-dimensional scattering Image of the sample using Image processing software (Image-J), thereby obtaining a two-dimensional scattering Image for analysis. In the two-dimensional scattering image for analysis, annular scattering was observed. Then, the two-dimensional scattering image for analysis is converted into a one-dimensional scattering curve. Specifically, a two-dimensional scattering image for analysis is read in by X-ray data processing software (Fit2d), and integrated over an omnidirectional angle and in a range of q 0.04 to 0.4, thereby obtaining a horizontal axis q [ nm ]-1]And the vertical axis is a one-dimensional scattering curve of scattering intensity.
And (4) calculating the half-value width X and the peak position Y of the peak according to the obtained one-dimensional scattering curve. In the one-dimensional scattering curve, the following is the case: a case where q is a minimum value near 0.1 and the scattering intensity increases toward the origin; and a case where the scattering intensity becomes smaller toward the origin after passing through an inflection point near q 0.1. When q is a minimum value near 0.1 and the scattering intensity increases toward the origin, a region larger than q of the minimum value is an analysis target. When the scattering intensity becomes smaller toward the origin after passing through an inflection point near q 0.1, a region larger than q at the inflection point is an object of analysis. Next, as baseline correction, the minimum value of the scattering intensity of the analysis target region is obtained, and the minimum value is subtracted from the entire region to perform baseline correction. The obtained corrected one-dimensional scattering curve was fitted with a gaussian function and a lorentzian function, and the half-value width of the obtained synthesis function was X1, and the peak position was Y1. Waveform separation software (Fityk) was used in the fitting.
Further, the inter-domain distance Z1 of the phase-separated structure of the photocurable composition was calculated from Z1 ═ 2 pi/Y1. In the case where no peak was detected from the obtained one-dimensional scattering curve, it is shown as (ND) in the table.
The adhesive sheet laminates prepared in examples and comparative examples were irradiated from one release film side with a high pressure mercury lamp to reach a cumulative light amount of 4000mJ/cm at a wavelength of 365nm2The photocurable composition is cured by irradiating light in the manner as described above. The cured product, which was the photocurable composition after photocuring, was subjected to the same operation as the photocurable composition before photocuring described above, and the peak half-value width (X2) and the peak position (Y2) of the one-dimensional scattering curve in the small-angle X-ray scattering measurement were obtained, and the inter-domain distance (Z2) was calculated from the peak position (Y2).
[ holding force ]
The pressure-sensitive adhesive sheet laminates prepared in examples and comparative examples were cut to 40 mm. times.50 mm, the release film on one side was peeled off, and a polyethylene terephthalate film for mounting (Diafil S-100, thickness 38 μm, manufactured by Mitsubishi resin corporation) was backed up by a hand roller and then cut into a long shape having a width of 25 mm. times.100 mm in length to prepare test pieces.
Then, the remaining release film was peeled off, and the SUS plate (120 mm. times.50 mm. times.1.2 mm in thickness) was attached to the SUS plate with a hand press roll so that the attached area became 25 mm. times.20 mm.
Thereafter, the test piece was aged at 40 ℃ for 15 minutes in an atmosphere, and then a weight of 500gf (4.9N) was attached to the test piece in the vertical direction and left to stand, and then the falling time (minutes) of the weight was measured. For those that did not fall within 30 minutes, the length (mm) of downward deviation of the position of attachment of the SUS to the test piece, i.e., the amount of deviation, was measured.
In the table, "< 0.2 mm" means a state where the amount of shift is less than 0.2mm and there is almost no shift.
[ glass adhesion ]
< measurement of adhesion before curing >
One of the release films of the pressure-sensitive adhesive sheet laminates prepared in examples and comparative examples was peeled off, and a polyethylene terephthalate film (product of Toyo Boseki Kabushiki Kaisha, trade name "COSMOSHINE A4300", thickness 100 μm) as a backing film was pressed against the release film by a hand press roll. The sheet was cut into a strip shape of 10mm in width × 100mm in length, and the remaining release film was peeled off and the exposed adhesive face roll was attached to soda-lime glass by a hand pressure roll. Autoclave treatment (70 ℃ C., gauge pressure 0.2MPa, 20 minutes) was performed to carry out final adhesion, and a glass adhesion measurement sample before photocuring was prepared. The adhesive sheet was peeled from the glass while the mount film was stretched at an angle of 180 ° at a peeling speed of 60 mm/min, and the tensile strength was measured with a load cell to measure the 180 ° peel strength (N/cm) of the adhesive sheet before photocuring from the glass.
< measurement of adhesion after curing >
One of the release films of the pressure-sensitive adhesive sheet laminates prepared in examples and comparative examples was peeled off, and a polyethylene terephthalate film (product of Toyo Boseki Kabushiki Kaisha, trade name "COSMOSHINE A4300", thickness 100 μm) as a backing film was pressed against the release film by a hand press roll. The sheet was cut into a strip shape of 10mm in width × 100mm in length, and the remaining release film was peeled off and the exposed adhesive face roll was attached to soda-lime glass by a hand pressure roll. Autoclave treatment (70 ℃ C., gauge pressure 0.2MPa, 20 minutes) was carried out, and after final application, the cumulative light quantity at a wavelength of 365nm from the mounting film side was 4000mJ/cm using a high-pressure mercury lamp2The pressure-sensitive adhesive sheet was irradiated with light to prepare a sample for measuring glass adhesion after photocuring. The adhesive sheet was peeled from the glass while the mount film was stretched at an angle of 180 ° at a peeling speed of 60 mm/min, the tensile strength was measured with a load cell, and the 180 ° peel strength (N/cm) of the photo-cured adhesive sheet from the glass was measured.
In the table, "< 0.5" indicates a state in which the peel strength was too small to be measured.
[ relative dielectric constant ]
The adhesive sheet laminates prepared in examples and comparative examples were prepared fromOne release film side, the cumulative quantity of light at a wavelength of 365nm using a high-pressure mercury lamp was 4000mJ/cm2The photocurable composition is cured by irradiating light in the manner as described above. Thereafter, the release film was peeled off in this order and attached to an electrode (manufactured by KEYCOM corporation, DPT-009). The relative dielectric constant at 23 ℃ and 50% RH and at a frequency of 100kHz was measured by an LCR measuring instrument (manufactured by Agilent Technologies, E4980A) in accordance with JIS K6911.
The case where the relative dielectric constant at a frequency of 100kHz was 3.5 or more was evaluated as "x (pore)", and the case where the relative dielectric constant was less than 3.5 was evaluated as "O (good)".
[ Corrosion resistance of Metal ]
On a glass substrate (60 mm. times.45 mm), 10.5 reciprocations were made with a line width of 70 μm, a line length of 46mm and a line interval of 30 μm to form 5 pieces of thickness
And forming a 2mm square of ITO pattern (length of about 97cm) at both ends of the round-trip line to form an ITO pattern, thereby producing an ITO glass substrate for evaluating metal corrosion resistance.
The release films on one side of the pressure-sensitive adhesive sheets produced in examples and comparative examples were peeled off, and a PET film (tomobo co., ltd., COSMOSHINE a4100, 125 μm) was attached to the exposed surface thereof by a hand-press roll. Next, after the adhesive sheet was cut out to 52mm × 45mm, the remaining release film was peeled off, and the adhesive sheet was attached to an ITO glass substrate for evaluation of metal corrosion resistance by a hand pressure roller so as to cover 5 round-trip lines of ITO. Autoclave treatment (70 ℃ C., gauge pressure 0.2MPa, 20 minutes) was carried out, and after final application, the accumulated light amount at a wavelength of 365nm from the PET film side by a high-pressure mercury lamp was 4000mJ/cm2In the method (1), the adhesive sheet was irradiated with light to prepare a sample for evaluating metal corrosion resistance (ITO wiring with adhesive sheet).
For 5 ITO wirings in the sample for evaluating reliability against metal corrosion (ITO wiring with adhesive sheet), the resistance values at room temperature were measured, and the average value (Ω 0) of the initial wiring resistance values was obtained.
The corrosion resistance reliability evaluation sample (ITO wiring with adhesive sheet) was stored at 65 ℃ under 90% RH for 800 hours. After storage, the resistance value of the ITO wiring in the sample for evaluating metal corrosion resistance (ITO wiring with adhesive sheet) was measured in the same manner, and the average value (Ω) of the wiring resistance values after the environmental test was obtained.
Then, the ITO resistance value, that is, the rate of change in resistance value (%) between line ends [ ((Ω/Ω 0) -1) × 100], was calculated and shown as "resistance value change" in the table.
When the change in the resistance value is less than 5%, it is determined as "very good", when 5% or more and less than 10% are determined as "good", and when 10% or more are determined as "x (poor)".
[ shape stability ]
The adhesive sheet laminates prepared in examples and comparative examples were each half-cut (half cut) into a square shape of 30mm × 30mm from one release film (made by mitsubishi resin corporation, diafil MRQ, thickness 75 μm) side so as not to penetrate the other release film (made by mitsubishi resin corporation, diafil MRV, thickness 100 μm).
One cut release film (made by Mitsubishi resin corporation, Diafil MRQ, thickness 75 μm) was peeled off, and the exposed adhesive surface was covered with a polyethylene terephthalate film (made by Mitsubishi resin corporation, Diafil MRT, thickness 50 μm) which had been peeled off. The peeled films on both sides were cut into 50mm × 50mm, and a sample for evaluation of shape stability before photocuring was prepared.
The sample for evaluation of shape stability was cured at 40 ℃ and 90% humidity for 300 hours, and the amount of adhesive oozing out from the edge face of the cured adhesive sheet was observed. Regarding the amount of bleeding of the adhesive material, the bleeding distance of the adhesive material at the center of each side of the cured adhesive sheet after cutting was measured, and the average distance of 4 sides was taken as the amount of bleeding (mm) of the adhesive material.
When the adhesive sheet was crushed after aging and the amount of adhesive bleeding was 2mm or more, the sheet was judged as "x (hole)", when adhesive bleeding was observed but 1mm or more and less than 2mm was judged as "good", and the sheet less than 1mm was judged as "very good".
In the table, "< 0.1 mm" means that the amount of bleeding of the adhesive material was less than 0.1mm and the state of substantially no bleeding of the adhesive material, and "> 2.0 mm" means that the amount of bleeding of the adhesive material was more significant and the amount of bleeding was more than 2.0 mm.
[ differential height absorbency ]
A glass plate with a printing height difference of 52mm x 80mm in the center recess was prepared by printing a glass plate having a thickness of 40 to 50 μm on the peripheral edge (3 mm on the long side and 15mm on the short side) of 58mm x 110mm x 0.8mm thick.
The release films on one side of the adhesive sheet laminates produced in examples and comparative examples were peeled off, and the adhesive sheet laminates were rolled on the entire surface of soda-lime glass (54mm × 82mm × 0.5mm in thickness). The remaining release film was peeled off, and an adhesive sheet was applied to the frame-like printing height difference of the glass plate with the printing height difference, and pressure-bonded by a vacuum press (absolute pressure 5kPa, temperature 70 ℃, pressure 0.04MPa) to prepare an evaluation sample.
Regarding the level difference absorbency of the above-described evaluation sample, after autoclave treatment was carried out for 30 minutes under the conditions of 60 ℃ and 0.3MPa, the appearance of the adhered evaluation sample was confirmed, and the case where bubbles were observed in the vicinity of the printed level difference was judged as "x (hole)", and the case where no bubbles were observed was judged as "o (good)".
[ reliability of resistance to foaming ]
A polarizing plate with an adhesive layer (VLC 2-1518AGD2SF4, size 54 mm. times.82 mm, manufactured by SANRITZ CORPORATION) was attached to soda-lime glass 54 mm. times.82 mm. times.0.5 mm thick by a hand pressure roller, and autoclave treatment (25 ℃ C., gauge pressure 0.2MPa, 20 minutes) was performed to prepare a polarizing plate substrate.
The release film on one surface of the adhesive sheet laminates produced in examples and comparative examples was peeled off, and soda lime glass of 54mm × 82mm × 0.5mm in thickness was stuck to the exposed surface thereof by a hand pressure roller. Next, the remaining release film of the adhesive sheet laminate was peeled off, and the polarizing plate surface of the polarizing plate base material was attached to the exposed surface thereof by a hand press roller. Autoclave treatment (temperature 60 ℃, air pressure 0.4MPa, 30 minutes) was carried out, and after final application, sodium calcium carbonate was removed by a high-pressure mercury lampThe cumulative light quantity of the glass surface at a wavelength of 365nm is 4000mJ/cm2The adhesive sheet was irradiated with light to prepare a sample for evaluating reliability against foaming.
The evaluation sample was aged at 95 ℃ for 100 hours, and the sample was judged as "good" when no change in appearance was observed such as no foaming, and "x (color)" when foaming and peeling were observed.
[ Table 1]
The photocurable compositions prepared in the examples have a half-value width of a predetermined range as determined by small-angle X-ray scattering measurement, and therefore achieve both appropriate cohesive strength and adhesion, and are excellent in storage stability and adhesion reliability.
The result was that the holding power was particularly high for the photocurable composition having a half-value width of 0.08 or more before and after photocuring.
Further, the photocurable compositions 6 to 9 using a hydrophobic monomer having 5 or more carbon atoms as the main copolymerization component of the (meth) acrylic copolymer (a) have a low relative dielectric constant of 3.5 or less at a frequency of 100kHz, and are more suitable for use in touch sensors.
Further, the photocurable compositions 7 to 9 used no carboxyl group-containing monomer having a high acidity or acid anhydride group-containing monomer as a copolymerization component of the (meth) acrylic copolymer (a), and acrylamide as a hydrophilic component. Therefore, the photocurable compositions 7 to 9 are particularly excellent in metal corrosion resistance and are also suitable for adherends having corrosion properties such as metals and metal oxides.
On the other hand, the photocurable composition prepared in comparative example 1 had a half-value width X1 of less than 0.05, which was determined by small-angle X-ray scattering measurement, and exceeded the specification of the present invention, and therefore, the cohesive force was too strong, the adhesiveness was insufficient, and the level difference absorption was poor.
The photocurable composition prepared in comparative example 2 did not show a one-dimensional scattering curve based on the small-angle X-ray scattering measurement. Therefore, the cohesive force of the photocurable composition is insufficient, and the storage stability before photocuring and the reliability of foam resistance after bonding are poor.
The photocurable composition prepared in comparative example 3 used a (meth) acrylic polymer containing a macromonomer as a structural unit, but was viscous liquid at room temperature, and no one-dimensional scattering curve in the small-angle X-ray scattering measurement was observed in the photocurable composition. Therefore, the photocurable composition lacks cohesive force, and storage stability before photocuring and reliability of foam resistance after bonding are poor.
Claims (18)
1. A photocurable composition, comprising: a (meth) acrylic copolymer (A), a crosslinking agent (B), and a crosslinking initiator (C),
the (meth) acrylic copolymer (A) is a (meth) acrylic copolymer (A1) containing a macromonomer as a structural unit, the dry component of the (meth) acrylic copolymer (A1) contains a hydrophobic monomer containing an alkyl (meth) acrylate having 5 or more carbon atoms and a hydrophilic monomer as structural units,
half-value Width X1 (nm) of one-dimensional scattering Curve in the Small-Angle X-ray Scattering measurement of the photocurable composition-1) Is 0.05<X1<0.30。
2. The photocurable composition according to claim 1, wherein the irradiation is 4000mJ/m in cumulative light exposure2Half-value Width X2 (nm) of one-dimensional scattering Curve in Small-Angle X-ray Scattering measurement at light time of (1)-1) Is 0.05<X2<0.25。
3. The photocurable composition according to claim 1, wherein the (meth) acrylic copolymer (A) is obtained by polymerizing monomers comprising a macromonomer (a), an alkyl (meth) acrylate having 5 or more carbon atoms, and a vinyl monomer (b).
4. The photocurable composition according to claim 2, wherein the (meth) acrylic copolymer (a) is obtained by polymerizing monomers comprising a macromonomer (a), an alkyl (meth) acrylate having 5 or more carbon atoms, and a vinyl monomer (b).
5. The photocurable composition according to claim 3, wherein the number average molecular weight of the macromonomer (a) is 500 to 10 ten thousand.
6. The photocurable composition according to claim 4, wherein the number average molecular weight of the macromonomer (a) is 500 to 10 ten thousand.
7. The photocurable composition according to any one of claims 1 to 6, wherein at least either one of the crosslinking agent (B) and the crosslinking initiator (C) is bonded to the (meth) acrylic copolymer (A).
8. The photocurable composition according to any one of claims 1 to 6, characterized in that it exhibits adhesiveness at 20 ℃ and softens or fluidizes at 50 to 100 ℃.
9. The photocurable composition according to claim 7, wherein the composition exhibits adhesiveness at 20 ℃ and softens or fluidizes at 50 to 100 ℃.
10. An adhesive sheet comprising the photocurable composition according to any one of claims 1 to 9.
11. The adhesive sheet according to claim 10, wherein the adhesive sheet is attached to glass and irradiated with 4000mJ/m in cumulative light exposure2The 180 DEG peel strength to glass in the light-emitting state of (1) is 3N/cm or more.
12. A pressure-sensitive adhesive sheet laminate comprising the pressure-sensitive adhesive sheet according to claim 10 or 11 and a release film laminated thereon.
13. A laminate for an image display device, comprising 2 image display device-constituting members and the photocurable composition according to any one of claims 1 to 9 interposed therebetween.
14. A cured product obtained by photocuring a photocurable composition, the photocurable composition comprising: a (meth) acrylic copolymer (A), a crosslinking agent (B), and a crosslinking initiator (C),
the (meth) acrylic copolymer (A) is a (meth) acrylic copolymer (A1) containing a macromonomer as a structural unit, the dry component of the (meth) acrylic copolymer (A1) contains a hydrophobic monomer containing an alkyl (meth) acrylate having 5 or more carbon atoms and a hydrophilic monomer as structural units,
half-value Width X3 (nm) of one-dimensional scattering Curve in Small-Angle X-ray Scattering measurement of the cured product-1) Is 0.05<X3<0.25。
15. The cured product according to claim 14, wherein the (meth) acrylic copolymer (A) is obtained by polymerizing monomers comprising a macromonomer (a), an alkyl (meth) acrylate having 5 or more carbon atoms, and a vinyl monomer (b).
16. A laminate for image display devices, which comprises 2 image display device-constituting members and the cured product according to claim 14 or 15 interposed therebetween.
17. The laminate for image display device according to claim 13 or 16, wherein the constituent member for image display device comprises any 2 or more combinations selected from the group consisting of a touch sensor, an image display panel, a surface protection panel, a polarizing film, and a retardation film.
18. An image display device comprising the laminate for image display device formation according to claim 13, 16 or 17.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016234672 | 2016-12-02 | ||
| JP2016-234672 | 2016-12-02 | ||
| CN201780074699.8A CN110023357A (en) | 2016-12-02 | 2017-11-28 | Photocurable composition, bonding sheet, bonding laminate, solidfied material, image display device constitute and use laminated body and image display device |
| PCT/JP2017/042596 WO2018101252A1 (en) | 2016-12-02 | 2017-11-28 | Photocurable composition, pressure-sensitive adhesive sheet, pressure-sensitive adhesive sheet laminate, cured product, laminate for forming image display device, and image display device |
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| CN201780074699.8A Division CN110023357A (en) | 2016-12-02 | 2017-11-28 | Photocurable composition, bonding sheet, bonding laminate, solidfied material, image display device constitute and use laminated body and image display device |
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| CN202210166287.XA Pending CN114410231A (en) | 2016-12-02 | 2017-11-28 | Photocurable composition, adhesive sheet laminate, laminate for image display device construction, and image display device |
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| JP (2) | JP7024726B2 (en) |
| KR (1) | KR102407621B1 (en) |
| CN (2) | CN110023357A (en) |
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| KR102566973B1 (en) * | 2017-08-08 | 2023-08-14 | 미쯔비시 케미컬 주식회사 | Photocurable pressure-sensitive adhesive sheet, photocurable pressure-sensitive adhesive sheet laminate, production method for photocurable pressure-sensitive adhesive sheet laminate, and production method for image display panel laminate |
| JP2020012098A (en) * | 2018-07-10 | 2020-01-23 | 三菱ケミカル株式会社 | Adhesive composition, and adhesive including the same, adhesive for polarizing plate, and image display device |
| CN112384587B (en) * | 2018-08-06 | 2023-04-14 | 三菱化学株式会社 | Photocurable adhesive sheet, adhesive sheet laminate, laminate for image display device, and image display device |
| JP6590269B1 (en) * | 2018-09-27 | 2019-10-16 | パナソニックＩｐマネジメント株式会社 | UV curable resin composition for sealing organic EL element, method for producing organic EL light emitting device, organic EL light emitting device, and touch panel |
| EP3902887A4 (en) * | 2018-12-28 | 2022-11-02 | Saint-Gobain Performance Plastics Corporation | Adhesive composition and methods of forming the same |
| CN114051521A (en) * | 2019-06-28 | 2022-02-15 | 日东电工株式会社 | Adhesive sheet and use thereof |
| JP7563081B2 (en) | 2019-10-01 | 2024-10-08 | 三菱ケミカル株式会社 | POLARIZING FILM WITH ADHESIVE LAYER, ADHESIVE SHEET, LAMINATED MEMBER, AND IMAGE DISPLAY DEVICE |
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| KR102473023B1 (en) * | 2019-11-01 | 2022-12-01 | 코제노벨머티얼리스코리아 주식회사 | Pressure-sensitive adhesive film |
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| KR102530142B1 (en) * | 2021-04-02 | 2023-05-10 | 솔루스첨단소재 주식회사 | Compound for encapsulating organic light emitting diode and organic light emitting display device comprising the same |
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| KR102407621B1 (en) | 2022-06-10 |
| TW201833283A (en) | 2018-09-16 |
| WO2018101252A1 (en) | 2018-06-07 |
| JP7259916B2 (en) | 2023-04-18 |
| JP2022033767A (en) | 2022-03-02 |
| JP7024726B2 (en) | 2022-02-24 |
| CN110023357A (en) | 2019-07-16 |
| TWI752127B (en) | 2022-01-11 |
| JPWO2018101252A1 (en) | 2019-10-24 |
| KR20190089049A (en) | 2019-07-29 |
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