JP7385168B2 - Photocurable adhesive composition - Google Patents
Photocurable adhesive composition Download PDFInfo
- Publication number
- JP7385168B2 JP7385168B2 JP2019047384A JP2019047384A JP7385168B2 JP 7385168 B2 JP7385168 B2 JP 7385168B2 JP 2019047384 A JP2019047384 A JP 2019047384A JP 2019047384 A JP2019047384 A JP 2019047384A JP 7385168 B2 JP7385168 B2 JP 7385168B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- polymer block
- adherend
- adhesive composition
- acrylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000001070 adhesive effect Effects 0.000 title claims description 36
- 239000000853 adhesive Substances 0.000 title claims description 33
- 239000000203 mixture Substances 0.000 title claims description 27
- 229920000642 polymer Polymers 0.000 claims description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 36
- 229920001400 block copolymer Polymers 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 125000004437 phosphorous atom Chemical group 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229920002799 BoPET Polymers 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- -1 ethylhexyl Chemical group 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 239000002390 adhesive tape Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 5
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- YENKRZXDJWBUIY-UHFFFAOYSA-N 1-phosphonooxypropan-2-yl 2-methylprop-2-enoate Chemical compound OP(=O)(O)OCC(C)OC(=O)C(C)=C YENKRZXDJWBUIY-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- OGWZVZSVQQBXJD-UHFFFAOYSA-N 2-[ethoxy(hydroxy)phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CCOP(O)(=O)OCCOC(=O)C(C)=C OGWZVZSVQQBXJD-UHFFFAOYSA-N 0.000 description 1
- PQCQUHTVHDSFDH-UHFFFAOYSA-N 2-[ethoxy(hydroxy)phosphoryl]oxyethyl prop-2-enoate Chemical compound CCOP(O)(=O)OCCOC(=O)C=C PQCQUHTVHDSFDH-UHFFFAOYSA-N 0.000 description 1
- DLRWTPMKTXWFNM-UHFFFAOYSA-N 2-[hydroxy(2-methylpropoxy)phosphoryl]oxyethyl prop-2-enoate Chemical compound CC(C)COP(O)(=O)OCCOC(=O)C=C DLRWTPMKTXWFNM-UHFFFAOYSA-N 0.000 description 1
- WAJJFPMYKWCDNI-UHFFFAOYSA-N 2-[hydroxy(2-prop-2-enoyloxyethoxy)phosphoryl]oxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOP(=O)(O)OCCOC(=O)C=C WAJJFPMYKWCDNI-UHFFFAOYSA-N 0.000 description 1
- YWLLQUWZWIKQKV-UHFFFAOYSA-N 2-[hydroxy(methoxy)phosphoryl]oxyethyl prop-2-enoate Chemical compound COP(O)(=O)OCCOC(=O)C=C YWLLQUWZWIKQKV-UHFFFAOYSA-N 0.000 description 1
- SILWEVCKWYUWDG-UHFFFAOYSA-N 2-[hydroxy(octan-3-yloxy)phosphoryl]oxyethyl prop-2-enoate Chemical compound CCCCCC(CC)OP(O)(=O)OCCOC(=O)C=C SILWEVCKWYUWDG-UHFFFAOYSA-N 0.000 description 1
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical group COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- KVPYIEPKUGXISR-UHFFFAOYSA-N 2-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCC(C)OC1=CC=CC=C1 KVPYIEPKUGXISR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000012958 Amine synergist Substances 0.000 description 1
- DWSLZXIVLWVGRD-UHFFFAOYSA-N CC(=C)C(=O)OCCP(O)=O Chemical compound CC(=C)C(=O)OCCP(O)=O DWSLZXIVLWVGRD-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- AGIABBZIYOGTGE-UHFFFAOYSA-N bis(prop-2-enyl)phosphinic acid Chemical compound C=CCP(=O)(O)CC=C AGIABBZIYOGTGE-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 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 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- YOTGRUGZMVCBLS-UHFFFAOYSA-N pentadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C(C)=C YOTGRUGZMVCBLS-UHFFFAOYSA-N 0.000 description 1
- GOZDOXXUTWHSKU-UHFFFAOYSA-N pentadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C=C GOZDOXXUTWHSKU-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、光硬化性粘着剤組成物に関する。 The present invention relates to a photocurable adhesive composition.
画像表示装置又は入力装置を搭載した携帯電子機器(例えば、携帯電話、携帯情報端末等)や車載用電子機器においては、組み立てのために両面粘着テープやシートが用いられている。例えば、携帯電子機器の表面を保護するためのカバーパネルをタッチパネルモジュール又はディスプレイパネルモジュールに接着したり、タッチパネルモジュールとディスプレイパネルモジュールとを接着したりするために両面粘着テープやシートが用いられている。このような両面粘着テープやシートは、例えば、額縁状等の形状に打ち抜かれ、表示画面の周辺に配置されるようにして用いられる(例えば、特許文献1、2)。また、車両部品(例えば、車載用パネル)を車両本体に固定する用途にも両面粘着テープやシートが用いられている。 2. Description of the Related Art Double-sided adhesive tapes and sheets are used for assembly in portable electronic devices (for example, mobile phones, personal digital assistants, etc.) and in-vehicle electronic devices equipped with image display devices or input devices. For example, double-sided adhesive tapes and sheets are used to adhere a cover panel to a touch panel module or display panel module to protect the surface of a portable electronic device, or to adhere a touch panel module and a display panel module. . Such double-sided adhesive tapes and sheets are, for example, punched out into a frame-like shape and used so as to be placed around a display screen (for example, Patent Documents 1 and 2). Further, double-sided adhesive tapes and sheets are also used for fixing vehicle parts (for example, vehicle panels) to the vehicle body.
近年の大型の携帯電子機器における部品の接着固定、車両部品の接着固定等の用途においては、重量の大きな部品又は部材を貼り合わせる必要があり、両面粘着テープやシートにかかる負荷が大きくなっている。また、近年の携帯電子機器では、表示画面の周辺を狭くしてより広い画面を確保する、いわゆる狭額縁化が進んでおり、狭額縁化した携帯電子機器では画面の周辺部の幅が極めて狭いため、接着面積が狭くとも確実に部材を固定できる高い粘着力が求められている。更に、車両部品の接着固定では、夏場の車内において高温にさらされた場合にも剥離しない高い高温保持力が求められている。 In recent years, in applications such as adhesive fixing of parts in large portable electronic devices and adhesive fixing of vehicle parts, it is necessary to bond heavy parts or members together, and the load on double-sided adhesive tapes and sheets is increasing. . In addition, in recent years, mobile electronic devices have become increasingly narrow-framed, in which the periphery of the display screen is narrowed to ensure a wider screen. Therefore, there is a need for high adhesive strength that can securely fix components even if the bonding area is small. Furthermore, when bonding and fixing vehicle parts, there is a demand for a high temperature retention ability that will not peel off even when exposed to high temperatures inside a car in the summer.
このように、電子機器部品の固定や車両部品の固定に用いられる両面粘着テープやシートには、従来以上に高い粘着力、高温保持力が求められるようになってきている。 As described above, double-sided adhesive tapes and sheets used for fixing electronic device parts and vehicle parts are required to have higher adhesive strength and high temperature holding power than ever before.
このような粘着テープやシートの粘着層として、透明性や耐候性、耐久性に優れることから、アクリル系粘着剤が広く用いられている。またアクリル系粘着剤としては、塗工性や粘着物性の観点から、(メタ)アクリル系ブロック共重合体からなる粘着剤が提案され、(例えば、特許文献3、4)このような粘着剤は高温保持力に優れることが開示されている。 Acrylic adhesives are widely used as adhesive layers for such adhesive tapes and sheets because of their excellent transparency, weather resistance, and durability. In addition, as an acrylic adhesive, from the viewpoint of coating properties and adhesive properties, an adhesive made of a (meth)acrylic block copolymer has been proposed (for example, Patent Documents 3 and 4). It is disclosed that it has excellent high-temperature holding power.
一方、粘着剤として、環境問題の高まりから有機溶剤を使用しない組成物への移行が進んでおり、(メタ)アクリル酸エステルと光重合開始剤による活性エネルギー線硬化型粘着剤が提案されている。特許文献5や特許文献6には(メタ)アクリル系ブロック共重合体を使用する活性エネルギー線硬化型粘着剤が開示されている。 On the other hand, due to increasing environmental concerns, there is a shift toward adhesive compositions that do not use organic solvents, and active energy ray-curable adhesives using (meth)acrylic acid esters and photopolymerization initiators have been proposed. . Patent Document 5 and Patent Document 6 disclose active energy ray-curable adhesives using (meth)acrylic block copolymers.
本発明が解決しようとする課題は(メタ)アクリル系ブロック共重合体を使用する光硬化性粘着剤組成物であって、特許文献3や特許文献4とは別異の熱間クリープ性に優れる粘着剤を提供することにある。 The problem to be solved by the present invention is a photocurable adhesive composition using a (meth)acrylic block copolymer, which has excellent hot creep properties different from those of Patent Document 3 and Patent Document 4. Our goal is to provide adhesives.
本発明者らは特定の(メタ)アクリル系ブロック共重合体と、リン原子を含む置換基を有する(メタ)アクリレートモノマーを併用すると、熱間クリープ性に優れる粘着剤を製造できることを見出した。すなわち、本発明は次の粘着剤に関する。 The present inventors have discovered that when a specific (meth)acrylic block copolymer and a (meth)acrylate monomer having a substituent containing a phosphorus atom are used in combination, an adhesive with excellent hot creep properties can be produced. That is, the present invention relates to the following adhesive.
(1)(A)ガラス転移温度が50℃以上である(メタ)アクリル酸エステル重合体ブロック(a)5~45質量%及びガラス転移温度が20℃以下である(メタ)アクリル酸エステル重合体ブロック(b)55~95質量%を含有する(メタ)アクリル系ブロック共重合体と、(B)前記(A)(メタ)アクリル系ブロック共重合体を溶解し、光重合可能である溶媒と、(C)光重合開始剤と、(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーとを含有する光硬化性粘着剤組成物。
(2)前記(A)(メタ)アクリル系ブロック共重合体が、式(a1)-(b)-(a2)で表されるトリブロック共重合体である、(1)に記載の光硬化性粘着剤組成物。(重合体ブロック(a1)、重合体ブロック(a2)は前記重合体ブロック(a)と同一の(メタ)アクリル酸エステル重合体ブロックであり、重合体ブロック(a1)、重合体ブロック(a2)は同一であっても異なっていてもよい。)
(3)前記(A)(メタ)アクリル系ブロック共重合体が、メチルメタクリレートをモノマー単位として含む重合体ブロック(a)、ブチルアクリレートをモノマー単位として含む重合体ブロック(b)を含有する(メタ)アクリル系ブロック共重合体である、(1)または(2)に記載の光硬化性粘着剤組成物。
(4)前記(B)反応性の溶媒が、酸素または窒素原子を含む置換基を有する単官能(メタ)アクリレートモノマーである、(1)~(3)のいずれか1つに記載の光硬化性粘着剤組成物。
(1) (A) (meth)acrylic acid ester polymer block having a glass transition temperature of 50°C or higher (a) 5 to 45% by mass and a (meth)acrylic acid ester polymer having a glass transition temperature of 20°C or lower block (b) a (meth)acrylic block copolymer containing 55 to 95% by mass, and (B) a solvent capable of dissolving and photopolymerizing the (meth)acrylic block copolymer (A); , (C) a photopolymerization initiator, and (D) a (meth)acrylate monomer having a substituent containing a phosphorus atom.
(2) Photocuring according to (1), wherein the (meth)acrylic block copolymer (A) is a triblock copolymer represented by formula (a1)-(b)-(a2). adhesive composition. (The polymer block (a1) and the polymer block (a2) are the same (meth)acrylic acid ester polymer blocks as the polymer block (a), and the polymer block (a1) and the polymer block (a2) may be the same or different.)
(3) The (A) (meth)acrylic block copolymer contains a polymer block (a) containing methyl methacrylate as a monomer unit and a polymer block (b) containing butyl acrylate as a monomer unit (meth). ) The photocurable adhesive composition according to (1) or (2), which is an acrylic block copolymer.
(4) Photocuring according to any one of (1) to (3), wherein the reactive solvent (B) is a monofunctional (meth)acrylate monomer having a substituent containing oxygen or nitrogen atom. adhesive composition.
本発明に係る光硬化性粘着剤組成物は、高温環境下でも優れた熱間クリープ性を有する粘着剤であり、幅広い温度域での使用に耐えうる。なお、本発明において「高温」とは、常温を超える温度であって、例えば80℃程度の温度を指す。 The photocurable pressure-sensitive adhesive composition according to the present invention is a pressure-sensitive adhesive that has excellent hot creep properties even in a high-temperature environment, and can withstand use in a wide temperature range. Note that in the present invention, "high temperature" refers to a temperature exceeding normal temperature, for example, a temperature of about 80°C.
以下に、本発明の実施形態について詳細に説明する。 Embodiments of the present invention will be described in detail below.
本発明に使用される(A)(メタ)アクリル系ブロック共重合体は、粘着剤層に柔軟性とともに適度な硬度を付与するベース樹脂である。該樹脂を粘着剤に用いると、温度変化によって適切な凝集力と応力緩和性が得られ、耐久信頼性が優秀に維持される。 The (meth)acrylic block copolymer (A) used in the present invention is a base resin that imparts flexibility and appropriate hardness to the adhesive layer. When this resin is used in a pressure-sensitive adhesive, appropriate cohesive force and stress relaxation properties can be obtained depending on temperature changes, and excellent durability and reliability can be maintained.
前記(A)(メタ)アクリル系ブロック共重合体は、ガラス転移温度が50℃以上である(メタ)アクリル酸エステル重合体ブロック(a)5~45質量%及びガラス転移温度が20℃以下である(メタ)アクリル酸エステル重合体ブロック(b)55~95質量%を含有する。 The (meth)acrylic block copolymer (A) comprises 5 to 45% by mass of (meth)acrylic acid ester polymer block (a) having a glass transition temperature of 50°C or higher and a glass transition temperature of 20°C or lower. Contains 55 to 95% by mass of a certain (meth)acrylic acid ester polymer block (b).
本発明における重合体ブロック(a)および重合体ブロック(b)のガラス転移温度は、(A)(メタ)アクリル系ブロック共重合体を示差走査熱量計(以後、DSCと略することがある)で測定して得られた曲線において認められる重合体ブロック(a)および重合体ブロック(b)の転移領域の外挿開始温度(Tgi;転移前の基線の直線部分と転移領域の変曲点の接線とを外挿して得られる交点の温度;例えば、齋藤安俊著「物質科学のための熱分析の基礎」(1990年12月15日共立出版株式会社発行)第126頁等参照)である。本発明における(A)(メタ)アクリル系ブロック共重合体のDSC測定による曲線に基づけば、重合体ブロック(a)のガラス転移温度、重合体ブロック(b)のガラス転移温度等の複数のガラス転移温度が求められるが、その中の重合体ブロック(a)に由来するガラス転移温度は、重合体ブロック(a)と同様の化学構造(モノマー組成、立体規則性等)を有する重合体のDSC測定による曲線のガラス転移温度と同一であるか、またはそれに近い温度であるので、容易に判定することができ、重合体ブロック(b)についても同様である。なお、重合体ブロック(a)と同様の化学構造を有する重合体は、重合体ブロック(a)を1H-NMR、13C-NMR等の手段で分析することにより重合体ブロック(a)のモノマー組成、立体規則性等の化学構造が判明するので、その化学構造が再現されるように適宜、重合を行うことにより容易に製造することができ、重合体ブロック(b)についても同様である。また、本発明の(A)(メタ)アクリル系ブロック共重合体を製造する際、最初の重合工程が重合体ブロック(a)の形成工程である場合には、その工程で形成された重合体ブロック(a)の一部をそのまま、重合体ブロック(a)と同様の化学構造を有する重合体のDSC測定用試料として利用するのが簡便であり、重合体ブロック(b)についても同様である。 The glass transition temperature of the polymer block (a) and the polymer block (b) in the present invention is determined by measuring the (A) (meth)acrylic block copolymer using a differential scanning calorimeter (hereinafter sometimes abbreviated as DSC). The extrapolation onset temperature (Tgi) of the transition region of polymer block (a) and polymer block (b) observed in the curves obtained by measuring Temperature at the intersection obtained by extrapolating the tangent; see, for example, Yasutoshi Saito, "Fundamentals of Thermal Analysis for Materials Science" (published by Kyoritsu Shuppan Co., Ltd., December 15, 1990, p. 126). Based on the curve obtained by DSC measurement of the (A) (meth)acrylic block copolymer in the present invention, the glass transition temperature of the polymer block (a), the glass transition temperature of the polymer block (b), etc. The glass transition temperature derived from polymer block (a) is determined by DSC of a polymer having the same chemical structure (monomer composition, stereoregularity, etc.) as polymer block (a). Since it is the same as or close to the glass transition temperature of the measured curve, it can be easily determined, and the same applies to polymer block (b). In addition, the polymer having the same chemical structure as the polymer block (a) can be determined by analyzing the polymer block (a) by 1 H-NMR, 13 C-NMR, etc. Since the chemical structure such as the monomer composition and stereoregularity is known, it can be easily produced by conducting appropriate polymerization so that the chemical structure is reproduced, and the same applies to the polymer block (b). . In addition, when producing the (meth)acrylic block copolymer (A) of the present invention, if the first polymerization step is the step of forming the polymer block (a), the polymer formed in that step It is convenient to use part of block (a) as it is as a sample for DSC measurement of a polymer having the same chemical structure as polymer block (a), and the same applies to polymer block (b). .
前記(A)(メタ)アクリル系ブロック共重合体は、重合体ブロック(a)及び重合体ブロック(b)を少なくとも1つずつ含み、好ましくは式(a1)-(b)-(a2)で表されるトリブロック共重合体である。重合体ブロック(a1)、重合体ブロック(a2)は重合体ブロック(a)と同一の(メタ)アクリル酸エステル重合体ブロックであり、重合体ブロック(a1)、重合体ブロック(a2)を構成する(メタ)アクリル酸エステルモノマーの種類や分子量等については、同一であっても異なっていてもよい。 The (meth)acrylic block copolymer (A) contains at least one polymer block (a) and one polymer block (b), and preferably has the formula (a1)-(b)-(a2). It is a triblock copolymer represented by: Polymer block (a1) and polymer block (a2) are the same (meth)acrylic acid ester polymer blocks as polymer block (a), and constitute polymer block (a1) and polymer block (a2). The type, molecular weight, etc. of the (meth)acrylic acid ester monomers used may be the same or different.
重合体ブロック(a)を構成する(メタ)アクリル酸エステルモノマーとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸イソブチル、メタクリル酸sec-ブチル、メタクリル酸tert-ブチル、メタクリル酸シクロヘキシル、メタクリル酸イソボルニル、メタクリル酸フェニル、メタクリル酸2-ヒドロキシエチル等のメタクリル酸エステル;アクリル酸tert-ブチル、アクリル酸シクロヘキシル、アクリル酸イソボルニル、アクリル酸フェニル、アクリル酸2-ヒドロキシエチル等のアクリル酸エステルが挙げられる。これらは単独で用いてもよいし、2種以上を併用してもよい。これらの中でも接着層の成形性および粘接着性の点からメタクリル酸メチルが好ましい。 Examples of the (meth)acrylic acid ester monomer constituting the polymer block (a) include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and methacrylic acid. Methacrylic acid esters such as cyclohexyl, isobornyl methacrylate, phenyl methacrylate, and 2-hydroxyethyl methacrylate; Acrylic acids such as tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, phenyl acrylate, and 2-hydroxyethyl acrylate Examples include esters. These may be used alone or in combination of two or more. Among these, methyl methacrylate is preferred from the viewpoint of moldability and adhesive properties of the adhesive layer.
重合体ブロック(b)を構成する(メタ)アクリル酸エステルモノマーとしては、例えばメタクリル酸n-プロピル、メタクリル酸n-ブチル、メタクリル酸アミル、メタクリル酸イソアミル、メタクリル酸n-ヘキシル、メタクリル酸2-エチルヘキシル、メタクリル酸ペンタデシル、メタクリル酸ドデシル、メタクリル酸フェノキシエチル、メタクリル酸2-メトキシエチル等のメタクリル酸エステル;アクリル酸メチル、アクリル酸エチル、アクリル酸n-プロピル、アクリル酸イソプロピル、アクリル酸n-ブチル、アクリル酸イソブチル、アクリル酸sec-ブチル、アクリル酸アミル、アクリル酸イソアミル、アクリル酸n-ヘキシル、アクリル酸2-エチルヘキシル、アクリル酸ペンタデシル、アクリル酸ドデシル、アクリル酸ベンジル、アクリル酸フェノキシエチル、アクリル酸2-メトキシエチル等のアクリル酸エステルが挙げられる。これらは単独で用いてもよいし、2種以上を併用してもよい。これらの中でも、接着層の粘接着性の観点から、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸n-ブチル、アクリル酸2-エチルヘキシル、アクリル酸ドデシル、アクリル酸フェノキシエチル、アクリル酸2-メトキシエチルが好ましい。 Examples of the (meth)acrylic acid ester monomer constituting the polymer block (b) include n-propyl methacrylate, n-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, and 2-methacrylate. Methacrylic acid esters such as ethylhexyl, pentadecyl methacrylate, dodecyl methacrylate, phenoxyethyl methacrylate, 2-methoxyethyl methacrylate; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate , isobutyl acrylate, sec-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, benzyl acrylate, phenoxyethyl acrylate, acrylic acid Examples include acrylic esters such as 2-methoxyethyl. These may be used alone or in combination of two or more. Among these, from the viewpoint of adhesive properties of the adhesive layer, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, phenoxyethyl acrylate, acrylic acid 2-methoxyethyl is preferred.
(A)(メタ)アクリル系ブロック共重合体は、(メタ)アクリル酸エステル重合体ブロック(a)および(メタ)アクリル酸エステル重合体ブロック(b)の他に、他の重合体ブロックを有してもよい。他の重合体ブロックとしては、例えばメタクリル酸、アクリル酸、スチレン、α-メチルスチレン、p-メチルスチレン、m-メチルスチレン、アクリロニトリル、メタクリロニトリル、エチレン、プロピレン、イソブテン、ブタジエン、イソプレン、オクテン、酢酸ビニル、無水マレイン酸、塩化ビニル、塩化ビニリデン等の単量体単位から構成される(共)重合体ブロックおよび/またはこれらの水素添加物;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリ乳酸、ポリウレタン、ポリジメチルシロキサンからなる重合体ブロック等が挙げられる。 (A) The (meth)acrylic block copolymer has other polymer blocks in addition to the (meth)acrylic ester polymer block (a) and the (meth)acrylic ester polymer block (b). You may. Examples of other polymer blocks include methacrylic acid, acrylic acid, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, (Co)polymer blocks composed of monomer units such as vinyl acetate, maleic anhydride, vinyl chloride, vinylidene chloride and/or hydrogenated products thereof; polyethylene terephthalate, polybutylene terephthalate, polylactic acid, polyurethane, polyester Examples include polymer blocks made of dimethylsiloxane.
本発明に係る(A)(メタ)アクリル系ブロック共重合体は、原料モノマーを重合することにより合成しても良いし、市販されているものを用いても良い。重合方法としては特に制限されるものではないが、例えば、アニオン重合法、原子移動ラジカル重合法(ATRP)等を用いることができる。各重合法の詳細な説明はここでは省略するが、アニオン重合法としては、例えば、有機アルカリ金属化合物を重合開始剤としてアルカリ金属又はアルカリ土類金属の塩等の鉱酸塩の存在下でアニオン重合する方法、有機アルカリ金属化合物を重合開始剤として有機アルミニウム化合物の存在下でアニオン重合する方法、有機希土類金属錯体を重合開始剤としてアニオン重合する方法等の公知の方法を用いることができ、ATRPとしては、例えば、有機ハロゲン化物またはハロゲン化スルホニル化合物を開始剤として、遷移金属化合物、含窒素化合物の存在下で重合する方法等の公知の方法を用いることができる。市販品としては、例えば、(株)クラレ製の「クラリティ(登録商標)」シリーズ等が挙げられる。 The (meth)acrylic block copolymer (A) according to the present invention may be synthesized by polymerizing raw material monomers, or a commercially available one may be used. Although the polymerization method is not particularly limited, for example, anionic polymerization method, atom transfer radical polymerization method (ATRP), etc. can be used. A detailed explanation of each polymerization method is omitted here, but as an anionic polymerization method, for example, anionic polymerization is performed using an organic alkali metal compound as a polymerization initiator in the presence of a mineral acid salt such as an alkali metal or alkaline earth metal salt. Known methods such as polymerization, anionic polymerization in the presence of an organic aluminum compound using an organic alkali metal compound as a polymerization initiator, and anionic polymerization using an organic rare earth metal complex as a polymerization initiator can be used. For example, a known method such as a method of polymerizing in the presence of a transition metal compound or a nitrogen-containing compound using an organic halide or a halogenated sulfonyl compound as an initiator can be used. Examples of commercially available products include the "Clarity (registered trademark)" series manufactured by Kuraray Co., Ltd.
本発明に使用される(B)光重合可能である反応性の溶媒は、(A)(メタ)アクリル系ブロック共重合体を溶解する反応性の溶媒であると同時に粘着剤の粘度を調整し、また粘着層に硬度を付与する役割を担う。そのため(B)光重合可能である反応性の溶媒は(A)(メタ)アクリル系ブロック共重合体の良溶媒であり、かつ低粘度であることが好ましく、ヒドロキシル基やアミド基、フェノキシ基等の極性基を含有するアクリレートモノマーが好適である。 The photopolymerizable reactive solvent (B) used in the present invention is a reactive solvent that dissolves the (A) (meth)acrylic block copolymer and at the same time adjusts the viscosity of the adhesive. , also plays a role in imparting hardness to the adhesive layer. Therefore, (B) a photopolymerizable reactive solvent is preferably a good solvent for (A) (meth)acrylic block copolymer and has a low viscosity, such as hydroxyl group, amide group, phenoxy group, etc. Acrylate monomers containing polar groups are preferred.
具体的にはヒドロキシル基を有するモノマーとして、ヒドロキシエチル(メタ)アクリレート、2‐ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2‐ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等があり、またアミド基を有するモノマーとしては、アクリルアミド、N,N‐ジメチルアクリルアミド、N,N‐ジエチルアクリルアミド、N-イソプロピルアクリルアミド、アクリルロイルモルホリン等があり、更にフェノキシ基を有するモノマーとして、フェノキシエチルアクリレート、2-ヒドロキシ-3-フェノキシプロピルアクリレート、メチルフェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、フェノキシポリエチレングリコールアクリレート等がある。これらを単独で用いてもよいし2種以上を併用してもよい。 Specifically, monomers having a hydroxyl group include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl ( meth)acrylate, and monomers having an amide group include acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, acrylylmorpholine, and monomers having a phenoxy group. Examples include phenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, methylphenoxyethyl acrylate, phenoxydiethylene glycol acrylate, and phenoxypolyethylene glycol acrylate. These may be used alone or in combination of two or more.
前記(B)光重合可能である反応性の溶媒の添加量は、(A)(メタ)アクリル系ブロック共重合体を完全に溶解する量であり、かつ本光硬化性粘着剤組成物が粘着剤として機能する範囲であれば特に限定されないが、例えば(A)(メタ)アクリル系ブロック共重合体100質量部に対し、30質量部以上300質量部以下であることが好ましい。 The amount of the photopolymerizable reactive solvent (B) added is such that it completely dissolves the (A) (meth)acrylic block copolymer and that the photocurable pressure-sensitive adhesive composition is adhesive. The amount is not particularly limited as long as it functions as an agent, but it is preferably 30 parts by mass or more and 300 parts by mass or less, for example, with respect to 100 parts by mass of the (meth)acrylic block copolymer (A).
本発明に使用される(C)光重合開始剤は、紫外線や電子線などの照射でラジカルを生じ、そのラジカルが重合反応のきっかけとなるもので、汎用の光重合開始剤で良い。具体的には、ベンゾインエチルエーテル、ベンゾインブチルエーテル及びベンゾインイソプロピルエーテル等のベンゾインエーテル類;4,4’-ビスジメチルアミノベンゾフェノン及び4,4’-ビスジエチルアミノベンゾフェノン等のベンゾフェノン類;アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル-]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン、2-メチル-1-〔4-(メチルチオ)フェニル〕-2-モルホリノ-プロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-ジメチルアミノ-2-(4-メチルベンジル)-1-(4-モルホリン-4-イル-フェニル)-ブタン-1-オン、及びN,N-ジメチルアミノアセトフェノン等のアセトフェノン類;2,4-ジエチルチオキサントン、2-クロロチオキサントン及び2-イソプロピルチオキサントン等のチオキサントン類;ベンジルジメチルケタール、アセトフェノンジメチルケタール等のケタール類;2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド等のフォスフィンオキサイド類;エチル-p-ジメチルアミノベンゾエート、(2-ジメチルアミノ)エチルベンゾエート、ビス-4,4’-ジメチルアミノベンゾフェノン等のアミン相乗剤等が挙げられる。 The photopolymerization initiator (C) used in the present invention generates radicals upon irradiation with ultraviolet rays, electron beams, etc., and the radicals trigger a polymerization reaction, and may be any general-purpose photopolymerization initiator. Specifically, benzoin ethers such as benzoin ethyl ether, benzoin butyl ether and benzoin isopropyl ether; benzophenones such as 4,4'-bisdimethylaminobenzophenone and 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 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, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl- 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1- 2, Phosphine oxides such as 4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; ethyl-p-dimethylaminobenzoate, (2-dimethylamino)ethylbenzoate , amine synergists such as bis-4,4'-dimethylaminobenzophenone, and the like.
前記(C)光重合開始剤は、1種単独で用いてもよく、2種以上を任意の割合で組み合わせて用いてもよい。光開始剤は、その添加量は特に制限はないが、添加量が少ないと硬化が深部まで進行せず、硬化不良が生じる場合があるので、(A)(メタ)アクリル系ブロック共重合体100重量部に対して、0.05重量部以上が好ましく、0.1重量部以上がより好ましく、1重量部以上が更に好ましい。また、開始剤が多いと開始剤が残存し、硬化物性に悪影響が生じる場合があるので、添加量は(A)(メタ)アクリル系ブロック共重合体100重量部に対して、30重量部以下が好ましく、20重量部以下がより好ましく、10重量部以下が更に好ましい。 The photopolymerization initiator (C) may be used alone or in combination of two or more in any proportion. There is no particular restriction on the amount of the photoinitiator added, but if the amount added is too small, curing may not proceed to the deep part, resulting in poor curing, so (A) (meth)acrylic block copolymer 100 It is preferably at least 0.05 part by weight, more preferably at least 0.1 part by weight, and even more preferably at least 1 part by weight. In addition, if too much initiator is used, the initiator may remain and adversely affect the cured properties, so the amount added should be 30 parts by weight or less per 100 parts by weight of (A) (meth)acrylic block copolymer. is preferable, 20 parts by weight or less is more preferable, and even more preferably 10 parts by weight or less.
本発明に使用される(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーは、(メタ)アクリレート部位により光硬化の際架橋に取り込まれると共に、リン原子を含む置換基により光硬化後の粘着層形成後に貼り付ける部材に対しての密着性の向上が期待できる。 (D) The (meth)acrylate monomer having a substituent containing a phosphorus atom used in the present invention is incorporated into crosslinking during photocuring by the (meth)acrylate moiety, and after photocuring by the substituent containing a phosphorus atom. After forming the adhesive layer, it is expected that the adhesion to the member to which it is attached will be improved.
前記(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーとしては、例えば、リン酸2-メタクリロイルオキシエチル、リン酸ビス-(2-メタクリロイルオキシエチル)、リン酸2-アクリロイルオキシエチル、リン酸ビス-(2-アクリロイルオキシエチル)、リン酸メチル-(2-メタクリロイルオキシエチル)、リン酸エチルメタクリロイルオキシエチル、リン酸メチルアクリロイルオキシエチル、リン酸エチルアクリロイルオキシエチル、リン酸プロピルアクリロイルオキシエチル、リン酸イソブチルアクリロイルオキシエチル、リン酸エチルヘキシルアクリロイルオキシエチル、リン酸ハロプロピルアクリロイルオキシエチル、リン酸ハロイソブチルアクリロイルオキシエチル、又はリン酸ハロエチルヘキシルアクリロイルオキシエチル、ビニルホスホン酸、アリルホスホン酸、アリルホスフィン酸、β-メタクリロイルオキシエチルホスフィン酸、ジアリルホスフィン酸、β-メタクリロイルオキシエチル)ホスフィン酸、及びアリルメタクリロイルオキシエチルホスフィン酸が挙げられ、特にリン酸2-メタクリロイルオキシエチルもしくはリン酸ビス-(2-メタクリロイルオキシエチル)が好ましい。 Examples of the (meth)acrylate monomer having a substituent containing a phosphorus atom (D) include 2-methacryloyloxyethyl phosphate, bis-(2-methacryloyloxyethyl) phosphate, 2-acryloyloxyethyl phosphate, Bis-(2-acryloyloxyethyl) phosphate, Methyl-(2-methacryloyloxyethyl) phosphate, Ethyl methacryloyloxyethyl phosphate, Methyl acryloyloxyethyl phosphate, Ethyl acryloyloxyethyl phosphate, Propyl acryloyloxy phosphate Ethyl, isobutyl acryloyloxyethyl phosphate, ethylhexyl acryloyloxyethyl phosphate, halopropyl acryloyloxyethyl phosphate, haloisobutyl acryloyloxyethyl phosphate, or haloethylhexyl acryloyloxyethyl phosphate, vinylphosphonic acid, allylphosphonic acid, allyl Mention may be made of phosphinic acid, β-methacryloyloxyethylphosphinic acid, diallylphosphinic acid, β-methacryloyloxyethyl)phosphinic acid, and allylmethacryloyloxyethylphosphinic acid, especially 2-methacryloyloxyethyl phosphate or bis-(2 -methacryloyloxyethyl) is preferred.
前記(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーの添加量は、1種単独で用いてもよく、2種以上を任意の割合で組み合わせて用いてもよい。(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーは、本発明の組成物に熱間クリープ性を向上させる化合物であるため、添加量が少ないと該効果の発現が乏しくなる。したがって、(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーの添加量は0.01部質量部以上であることが好ましく、1部以上がさらに好ましい。また、添加量が多いと本発明の粘着剤としての性質に悪影響が出ることがあるので、(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーの添加量は30質量部以下であることが好ましい。 The amount of the (D) (meth)acrylate monomer having a substituent containing a phosphorus atom may be used alone or in combination of two or more in any proportion. (D) The (meth)acrylate monomer having a substituent containing a phosphorus atom is a compound that improves the hot creep property of the composition of the present invention, so if the amount added is small, the effect will be poorly expressed. Therefore, the amount of the (D) (meth)acrylate monomer having a substituent containing a phosphorus atom added is preferably 0.01 part by mass or more, more preferably 1 part or more. Furthermore, if the amount added is too large, the properties as an adhesive of the present invention may be adversely affected, so the amount of (D) (meth)acrylate monomer having a substituent containing a phosphorus atom added is 30 parts by mass or less. It is preferable.
本発明の粘着剤組成物には、性能を損なわない範囲で、必要により、(B)成分及び(D)成分以外の(メタ)アクリレートモノマー、粘着付与剤、可塑剤、酸化防止剤及び濡れ性調整剤等の各種添加剤が含まれていても良い。 The pressure-sensitive adhesive composition of the present invention may optionally include (meth)acrylate monomers other than component (B) and component (D), a tackifier, a plasticizer, an antioxidant, and a wettability agent to the extent that performance is not impaired. Various additives such as regulators may be included.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの記載に何ら制限を受けるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these descriptions in any way.
(実施例1~7、比較例1)
表1記載の成分を均一に溶解するまで撹拌し、実施例1~7、比較例1の光硬化性粘着剤組成物を調整した。配合は下記表1に記載の通りである。
(Examples 1 to 7, Comparative Example 1)
The components listed in Table 1 were stirred until uniformly dissolved to prepare photocurable adhesive compositions of Examples 1 to 7 and Comparative Example 1. The formulation is as shown in Table 1 below.
表1において、各配合物質の配合量はgで示され、各配合物質の詳細は下記の通りである。
※1 LK9243: (メタ)アクリル系トリブロック共重合体(製品名「クラリティ LK9243」、重合体ブロック(a)にメチルメタクリレートを用い、重合体ブロック(b)にブチルアクリレート及び2-エチルヘキシルアクリレートを用いた(メタ)アクリル系ブロック共重合体、(株)クラレ製)
※2 LA2140:(メタ)アクリル系トリブロック共重合体(製品名「クラリティ LA2140」、重合体ブロック(a)にメチルメタクリレートを用い、重合体ブロック(b)にブチルアクリレートを用いた(メタ)アクリル系ブロック共重合体、(株)クラレ製)
※3 4HBA:4-ヒドロキシブチルアクリレート
※4 IrgTPO:2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(製品名「IRGACURETPO」、BASF社製)
※5 P-2M:2-メタクロイロキシエチルアシッドホスフェート(製品名「ライトエステルP-2M」、共栄社化学(株)製)
※6 LA:ラウリルアクリレート
※7 K125:テルペンフェノール樹脂(製品名「YSポリスターK125」、ヤスハラケミカル(株)製)
In Table 1, the amount of each compounded substance is shown in g, and the details of each compounded substance are as follows.
*1 LK9243: (Meth)acrylic triblock copolymer (product name "Clarity LK9243", polymer block (a) uses methyl methacrylate, polymer block (b) uses butyl acrylate and 2-ethylhexyl acrylate. (meth)acrylic block copolymer, manufactured by Kuraray Co., Ltd.)
*2 LA2140: (meth)acrylic triblock copolymer (product name "Clarity LA2140", (meth)acrylic using methyl methacrylate for the polymer block (a) and butyl acrylate for the polymer block (b) block copolymer, manufactured by Kuraray Co., Ltd.)
*3 4HBA: 4-hydroxybutyl acrylate *4 IrgTPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name "IRGACURETPO", manufactured by BASF)
*5 P-2M: 2-Methachloroyloxyethyl acid phosphate (product name "Light Ester P-2M", manufactured by Kyoeisha Chemical Co., Ltd.)
*6 LA: Lauryl acrylate *7 K125: Terpene phenol resin (product name "YS Polystar K125", manufactured by Yasuhara Chemical Co., Ltd.)
評価方法は以下の通りとした。
熱間クリープ試験:
第1の被着体としてPETフィルム1枚、第2の被着体として一端に穴の開いたSUS板1枚を用意し、第1の被着体についてはイソプロピルアルコールにより表面を脱脂し、第2の被着体についてはアセトンにより表面を脱脂した。脱脂した第1の被着体表面に、厚さが100μm、塗布面積が25×25mm2になるように実施例1に係る光硬化性粘着剤組成物を均一に塗布した。次に、第1の被着体に塗布された実施例1に係る光硬化性粘着剤組成物に紫外線(UV)を照射し[照射条件:UV-LEDランプ(波長365nm、照度:1000mW/cm2)、積算光量:3000mJ/cm2]、硬化させた。硬化後速やかに、脱脂済みの第2の被着体の穴の開いた一端とは逆側の部分を、UV光照射により硬化した光硬化性粘着剤組成物を挟むように第1の被着体に貼り合わせ、2kgローラ2往復にて圧締し、試験片を作成した。続いて、この試験片を23℃50%RHの環境下で24時間養生した。養生後、試験片のSUS板の穴にS字フックを取り付け、SUS板側が上になるよう試験片を鉛直に吊り下げた。続いて、PETフィルムの端部に1kgの重りを取り付け、試験片のせん断方向、すなわち鉛直方向に荷重を加えた。荷重をかけた試験片を、80℃に設定した熱風乾燥器(佐竹化学機械工業株式会社製熱風循環恒温乾燥器:41-S4)の天井に前記S字フックを介して取り付け、24時間静置し、熱間クリープ試験を実施した。ほぼずれが生じなかったもの(1.0mm未満)を◎、ずれが小さかったもの(1.0mm以上1.5mm未満)を○、ずれが大きかったもの(1.5mm以上25mm未満)を△、PETフィルムとSUS板が剥がれ重りが落下したものを×として評価した。
The evaluation method was as follows.
Hot creep test:
One PET film was prepared as the first adherend, and one SUS board with a hole at one end was prepared as the second adherend.The surface of the first adherend was degreased with isopropyl alcohol, and the The surface of No. 2 adherend was degreased with acetone. The photocurable adhesive composition according to Example 1 was uniformly applied to the degreased surface of the first adherend so that the thickness was 100 μm and the application area was 25×25 mm 2 . Next, the photocurable adhesive composition according to Example 1 applied to the first adherend was irradiated with ultraviolet rays (UV) [Irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW/cm 2 ), integrated light amount: 3000 mJ/cm 2 ], and was cured. Immediately after curing, the portion of the degreased second adherend opposite to the holed end is coated with the first adherend so as to sandwich the photocurable adhesive composition cured by UV light irradiation. A test piece was prepared by attaching the test piece to the body and pressing it with a 2 kg roller twice. Subsequently, this test piece was cured for 24 hours in an environment of 23° C. and 50% RH. After curing, an S-shaped hook was attached to the hole in the SUS plate of the test piece, and the test piece was hung vertically with the SUS plate side facing upward. Subsequently, a 1 kg weight was attached to the end of the PET film, and a load was applied in the shear direction of the test piece, that is, in the vertical direction. The loaded test piece was attached to the ceiling of a hot air dryer (hot air circulation constant temperature dryer: 41-S4 manufactured by Satake Kagaku Kikai Co., Ltd.) set at 80°C via the S-shaped hook, and left undisturbed for 24 hours. Then, a hot creep test was conducted. ◎ for almost no deviation (less than 1.0 mm), ○ for small deviation (1.0 mm or more and less than 1.5 mm), △ for large deviation (1.5 mm or more and less than 25 mm). Those in which the PET film and the SUS plate were peeled off and the weight fell were evaluated as ×.
表1からわかるように、リン原子を含む置換基を有する(メタ)アクリレートモノマーを含有する粘着剤組成物は熱間クリープ性に優れていた。 As can be seen from Table 1, the adhesive composition containing the (meth)acrylate monomer having a substituent containing a phosphorus atom had excellent hot creep properties.
本発明に係る光硬化性粘着剤組成物は、高温環境下でも優れた接着強さを有する粘着剤であり、幅広い温度域での使用に耐えうる。
The photocurable pressure-sensitive adhesive composition according to the present invention is a pressure-sensitive adhesive that has excellent adhesive strength even in a high-temperature environment, and can withstand use in a wide temperature range.
Claims (3)
(A)ガラス転移温度が50℃以上である(メタ)アクリル酸エステル重合体ブロック(a)5~45質量%、及びガラス転移温度が20℃以下である(メタ)アクリル酸エステル重合体ブロック(b)55~95質量%を含有する(メタ)アクリル系ブロック共重合体と、
(B)前記(A)(メタ)アクリル系ブロック共重合体を溶解し、光重合可能である反応性の溶媒と、
(C)光重合開始剤と、
(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーと、
を含有し、
前記(A)(メタ)アクリル系ブロック共重合体が、式(a1)-(b)-(a2)で表されるトリブロック共重合体であり(重合体ブロック(a1)、重合体ブロック(a2)は前記重合体ブロック(a)と同一の(メタ)アクリル酸エステル重合体ブロックであり、重合体ブロック(a1)、重合体ブロック(a2)は同一であっても異なっていてもよい。)、
前記(D)リン原子を含む置換基を有する(メタ)アクリレートモノマーの添加量が、0.01質量部以上30質量部以下であり、
前記熱間クリープ特性の試験が、イソプロピルアルコールで表面を脱脂した第1の被着体としてのPETフィルムと、アセトンで表面を脱脂した第2の被着体としての一端に穴を有するSUS板とを用意し、前記第1の被着体表面に厚さが100μm、塗布面積が25×25mm 2 になるように前記光硬化性粘着剤組成物を均一に塗布し、紫外線(UV)を前記光硬化性粘着剤組成物に照射し[照射条件:UV-LEDランプ(波長365nm、照度:1000mW/cm 2 )、積算光量:3000mJ/cm 2 ]て硬化後速やかに、前記第2の被着体の前記穴を有する前記一端とは逆側の部分を前記硬化した前記光硬化性粘着剤組成物を挟むように前記第1の被着体に貼り合わせ、2kgローラ2往復にて圧締して作成した試験片を23℃50%RHの環境下で24時間養生した後、前記試験片の前記第2の被着体の前記穴にS字フックを取り付け、前記第2の被着体側が上になるように前記試験片を鉛直に吊り下げ、前記第1の被着体の端部に1kgの重りを取り付け、前記試験片のせん断方向に荷重をかけて80℃に設定した熱風乾燥器の天井に前記S字フックを介して前記試験片取り付けて24時間静置して実施された場合、前記第1の被着体と前記第2の被着体とのずれが1.5mm未満である光硬化性粘着剤組成物。 A photocurable adhesive composition having excellent hot creep properties,
(A) (meth)acrylic acid ester polymer block (a) 5 to 45% by mass having a glass transition temperature of 50°C or higher; and (meth)acrylic acid ester polymer block (meth)acrylic acid ester polymer block having a glass transition temperature of 20°C or lower ( b) a (meth)acrylic block copolymer containing 55 to 95% by mass;
(B) a reactive solvent that dissolves the (meth)acrylic block copolymer (A) and is photopolymerizable;
(C) a photopolymerization initiator;
(D) a (meth)acrylate monomer having a substituent containing a phosphorus atom;
Contains
The (meth)acrylic block copolymer (A) is a triblock copolymer represented by the formula (a1)-(b)-(a2) (polymer block (a1), polymer block ( a2) is the same (meth)acrylic acid ester polymer block as the polymer block (a), and the polymer block (a1) and the polymer block (a2) may be the same or different. ),
The amount of the (meth)acrylate monomer having a substituent containing a phosphorus atom (D) added is 0.01 parts by mass or more and 30 parts by mass or less,
The hot creep property test was conducted using a PET film as a first adherend whose surface was degreased with isopropyl alcohol, and a SUS plate having a hole at one end as a second adherend whose surface was degreased with acetone. was prepared, the photocurable adhesive composition was uniformly applied to the surface of the first adherend to a thickness of 100 μm and a coating area of 25 x 25 mm2, and ultraviolet (UV) light was applied to the surface of the first adherend . Immediately after curing by irradiating the curable adhesive composition [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW/cm 2 ), cumulative light amount: 3000 mJ/cm 2 ], the second adherend is cured. The part opposite to the one end having the hole is pasted to the first adherend so as to sandwich the cured photocurable adhesive composition, and pressed with two reciprocations of a 2 kg roller. After curing the prepared test piece in an environment of 23°C and 50% RH for 24 hours, an S-shaped hook was attached to the hole of the second adherend of the test piece, and the second adherend side was facing upward. The test piece was hung vertically so that When the test piece is attached to the ceiling via the S-shaped hook and left undisturbed for 24 hours, the deviation between the first adherend and the second adherend is less than 1.5 mm. Photocurable adhesive composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019047384A JP7385168B2 (en) | 2019-03-14 | 2019-03-14 | Photocurable adhesive composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019047384A JP7385168B2 (en) | 2019-03-14 | 2019-03-14 | Photocurable adhesive composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2020147698A JP2020147698A (en) | 2020-09-17 |
JP7385168B2 true JP7385168B2 (en) | 2023-11-22 |
Family
ID=72432202
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019047384A Active JP7385168B2 (en) | 2019-03-14 | 2019-03-14 | Photocurable adhesive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP7385168B2 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003301147A (en) | 2002-04-09 | 2003-10-21 | Nitto Denko Corp | Radiation-curable pressure-sensitive adhesive sheet |
WO2009107537A1 (en) | 2008-02-29 | 2009-09-03 | 株式会社カネカ | Curable composition |
JP2011026551A (en) | 2009-05-21 | 2011-02-10 | Kaneka Corp | Ultraviolet-curing type pressure-sensitive adhesive composition |
JP2014156585A (en) | 2013-01-16 | 2014-08-28 | Cemedine Co Ltd | Photocurable composition |
JP2017036368A (en) | 2015-08-07 | 2017-02-16 | アイカ工業株式会社 | Photosetting adhesive composition |
JP2017165807A (en) | 2016-03-14 | 2017-09-21 | アイカ工業株式会社 | Photocurable resin composition for tape |
JP2019505617A (en) | 2015-12-15 | 2019-02-28 | スリーエム イノベイティブ プロパティズ カンパニー | Curable composition, pressure sensitive adhesive, adhesive tape, bonded product |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3262607B2 (en) * | 1992-11-09 | 2002-03-04 | 日本カーバイド工業株式会社 | Active energy ray-curable adhesive composition and tape |
-
2019
- 2019-03-14 JP JP2019047384A patent/JP7385168B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003301147A (en) | 2002-04-09 | 2003-10-21 | Nitto Denko Corp | Radiation-curable pressure-sensitive adhesive sheet |
WO2009107537A1 (en) | 2008-02-29 | 2009-09-03 | 株式会社カネカ | Curable composition |
JP2011026551A (en) | 2009-05-21 | 2011-02-10 | Kaneka Corp | Ultraviolet-curing type pressure-sensitive adhesive composition |
JP2014156585A (en) | 2013-01-16 | 2014-08-28 | Cemedine Co Ltd | Photocurable composition |
JP2017036368A (en) | 2015-08-07 | 2017-02-16 | アイカ工業株式会社 | Photosetting adhesive composition |
JP2019505617A (en) | 2015-12-15 | 2019-02-28 | スリーエム イノベイティブ プロパティズ カンパニー | Curable composition, pressure sensitive adhesive, adhesive tape, bonded product |
JP2017165807A (en) | 2016-03-14 | 2017-09-21 | アイカ工業株式会社 | Photocurable resin composition for tape |
Also Published As
Publication number | Publication date |
---|---|
JP2020147698A (en) | 2020-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5801514B1 (en) | Photocurable pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and laminate | |
TWI830400B (en) | Use of double-sided adhesive sheets, laminated bodies containing components for forming image display devices, laminated body forming sets, and double-sided adhesive sheets | |
JP6767113B2 (en) | Adhesive composition and adhesive sheet | |
JP6361121B2 (en) | Adhesive resin composition | |
KR101991996B1 (en) | Adhesive composition, adhesive film, optical member, adhesive sheet and image display apparatus | |
KR102008181B1 (en) | Adhesive composition, adhesive film, and image display device | |
JP6260278B2 (en) | Photocurable adhesive composition and display panel | |
JP5738795B2 (en) | Photocurable adhesive composition and adhesive sheet using the same | |
JP5008870B2 (en) | Adhesive composition and adhesive sheet containing the same | |
JP6825963B2 (en) | Photo-curable adhesive composition | |
JP2009299037A (en) | Adhesive | |
US8034849B2 (en) | Adhesive composition and adhesive sheet | |
JP6947665B2 (en) | Photocurable adhesive resin composition | |
JP2018127638A (en) | Adhesive resin composition | |
JP7385168B2 (en) | Photocurable adhesive composition | |
WO2022130339A1 (en) | Composition including an acrylic monomer with a carboxylic acid group, an acrylic monomer with a hydroxyl group, an alkyl (meth)acrylate monomer and crosslinker, and related articles and methods | |
US20240076523A1 (en) | Free-radically polymerizable crosslinker, curable composition, and adhesive therefrom | |
JP2016224327A (en) | Polarizing plate | |
JP2007197694A (en) | Emulsion type adhesive and adhesive sheet | |
JP7329347B2 (en) | Photocurable resin composition | |
US20240343951A1 (en) | Composition including monomer with a carboxylic acid group, monomer with a hydroxyl group, an alkyl monomer, and crosslinker and related article and method | |
WO2024214759A1 (en) | Adhesive sheet, laminate, and release sheet-attached adhesive sheet | |
JP2024126071A (en) | Adhesive composition, adhesive, and adhesive sheet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20200108 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220310 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20221213 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230117 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20230303 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230509 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230801 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230829 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20231011 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20231024 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7385168 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |