JPWO2012046810A1 - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JPWO2012046810A1 JPWO2012046810A1 JP2012537761A JP2012537761A JPWO2012046810A1 JP WO2012046810 A1 JPWO2012046810 A1 JP WO2012046810A1 JP 2012537761 A JP2012537761 A JP 2012537761A JP 2012537761 A JP2012537761 A JP 2012537761A JP WO2012046810 A1 JPWO2012046810 A1 JP WO2012046810A1
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- resin composition
- hydroxyl group
- composition according
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 80
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 45
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 17
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- -1 2-hydroxypropyl Chemical group 0.000 description 22
- 238000012360 testing method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 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 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 239000004593 Epoxy Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-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
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- HZHPOJPIGFWDTD-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C=C HZHPOJPIGFWDTD-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920013646 Hycar Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000017284 Pometia pinnata Nutrition 0.000 description 1
- 240000007653 Pometia tomentosa Species 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001186 cumulative effect Effects 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
- 238000013461 design Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 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 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3885—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Abstract
本発明は、透明性、鉛筆硬度、接着性が大きい樹脂組成物の提供することを課題として、水酸基を有する(メタ)アクリル酸エステル単量体(A)と水酸基を有する光重合開始剤(B)とイソシアネート基を有するイソシアネート(C)とを反応させて得られるウレタンアクリレート(D)、重合可能な(メタ)アクリレート(E)、シランカップリング剤(F)を含有する樹脂組成物を提供し、この樹脂組成物は接着剤やハードコート剤として使用され、さらにはタッチパネル積層体や液晶パネル積層体の製造に好適に使用できる。An object of the present invention is to provide a resin composition having high transparency, pencil hardness and adhesiveness, and a (meth) acrylic acid ester monomer (A) having a hydroxyl group and a photopolymerization initiator having a hydroxyl group (B ) And an isocyanate group having an isocyanate group (C), a urethane acrylate (D), a polymerizable (meth) acrylate (E), and a resin composition containing a silane coupling agent (F) are provided. The resin composition is used as an adhesive or a hard coat agent, and can be suitably used for manufacturing a touch panel laminate or a liquid crystal panel laminate.
Description
本発明は、樹脂組成物に関する。本発明は、例えば、接着剤、ハードコート剤とそれを用いた電子デバイスに関する。 The present invention relates to a resin composition. The present invention relates to, for example, an adhesive, a hard coat agent, and an electronic device using the same.
LCD等の表示体の上に搭載するタッチパネルには、抵抗膜式、静電容量式、電磁誘導式、光学式等がある。これらのタッチパネルの上には、化粧板やアイコンシートを貼り合わせる場合がある。化粧板は、見た目のデザイン性を良くするために使用する。アイコンシートは、タッチする位置を指定するために使用する。静電容量式タッチパネルは、透明基板の上に透明電極を形成し、その透明電極の上に透明板を貼り合わせた構造を有している。 Examples of touch panels mounted on a display body such as an LCD include a resistance film type, a capacitance type, an electromagnetic induction type, and an optical type. A decorative board or an icon sheet may be pasted on these touch panels. The decorative board is used to improve the visual design. The icon sheet is used to specify a touch position. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate, and a transparent plate is bonded to the transparent electrode.
従来は、上記の化粧板とタッチパネルとの貼り合わせ、アイコンシートとタッチパネルとの貼り合わせ、静電容量式タッチパネルにおける透明電極を形成した透明基板と透明板との貼り合わせを、シート状の両面粘着シートを用いて行うか、被着体の片面に粘着加工するかして、行っていた。このような粘着剤を使用する技術では、接着が不十分であったり、貼り合わせ面に気泡が混入したりするという問題があった。特に、貼り合わせ面に印刷加工がしてあると、印刷のあるところとないところの段差部分に気泡が残りやすいという問題があった。 Conventionally, bonding of the decorative plate and the touch panel, bonding of the icon sheet and the touch panel, and bonding of the transparent substrate on which the transparent electrode is formed in the capacitive touch panel and the transparent plate are performed by sheet-like double-sided adhesive. This is done by using a sheet or by performing adhesive processing on one side of the adherend. In the technique using such a pressure-sensitive adhesive, there is a problem that adhesion is insufficient or bubbles are mixed into the bonding surface. In particular, when printing is performed on the bonding surface, there is a problem that bubbles are likely to remain in the stepped portions where printing is performed and where printing is not performed.
近年、LCD等の表示体のガラスの厚さが薄くなってきている。ガラスが薄くなると外部応力でLCDが変形しやすくなる。この薄いガラスのLCD等の表示体と、アクリル板やポリカーボネート板等の光学機能材料とを貼り合わせる場合、ガラスとアクリル等の線膨張の違いや、アクリル板やポリカーボネート等のプラスチック成型材の成型時の歪みにより、耐熱試験や耐湿試験において成型歪みの緩和や吸湿・乾燥が起こり、寸法変化や反り等の面精度変化が起きる。従来の接着剤(例えば、特許文献1〜2)でこの変形を抑えようとした場合、接着面が剥がれたり、LCDが割れたり、LCDが表示ムラになったりするという問題点があった。 In recent years, the thickness of glass of display bodies such as LCDs has been reduced. When the glass becomes thinner, the LCD is easily deformed by external stress. When this thin glass LCD or other optical display material is bonded to an optical functional material such as an acrylic plate or a polycarbonate plate, the difference in linear expansion between the glass and acrylic or the molding of a plastic molding material such as an acrylic plate or polycarbonate Due to this distortion, mold distortion is relaxed and moisture absorption / drying occurs in the heat resistance test and moisture resistance test, and surface accuracy changes such as dimensional changes and warpage occur. When trying to suppress this deformation with a conventional adhesive (for example, Patent Documents 1 and 2), there are problems that the adhesive surface is peeled off, the LCD is cracked, or the LCD becomes uneven in display.
上記のような問題点の解決策として、特許文献3のようなUV硬化型樹脂がある。これはイソボルニル(メタ)アクリレートのような剛直な骨格モノマーをベースとした高弾性樹脂であるが故に、高温信頼性試験において被着体の膨張収縮に耐えることができず剥がれを生じてしまう可能性があった。 As a solution to the above problems, there is a UV curable resin as in Patent Document 3. Because this is a highly elastic resin based on a rigid skeletal monomer such as isobornyl (meth) acrylate, it cannot withstand the expansion and contraction of the adherend in a high-temperature reliability test and may cause peeling. was there.
本発明は、例えば、タッチパネル等の表示体に使用される化粧板やアイコンシートを貼り合わせる場合や、静電容量タッチパネルにおける透明電極を形成した透明基板と透明基板とを貼り合わせる場合に、十分な接着性を付与し、気泡を含まずに貼り合わせることが困難であるという従来技術の問題点を解決する接着剤、ハードコート剤の提供である。本発明は、例えば、表示体と光学機能材料とを貼り合わせた場合に、接着面が剥がれたり、表示体のガラスが割れたりする従来技術の問題点を解決する接着剤、ハードコート剤の提供である。 The present invention is sufficient when, for example, a decorative plate or icon sheet used for a display body such as a touch panel is bonded, or when a transparent substrate on which a transparent electrode is formed in a capacitive touch panel is bonded to a transparent substrate. The present invention provides an adhesive and a hard coat agent that imparts adhesiveness and solves the problems of the prior art that it is difficult to bond without containing bubbles. The present invention provides, for example, an adhesive and a hard coat agent that solve the problems of the prior art in which, when a display body and an optical functional material are bonded together, the adhesive surface peels off or the glass of the display body is broken. It is.
即ち、一つの側面から、本発明は樹脂組成物を提供する。この樹脂組成物は、水酸基を有する(メタ)アクリル酸エステル単量体(A)と水酸基を有する光重合開始剤(B)とイソシアネート基を有するイソシアネート(C)とを反応させて得られるウレタンアクリレート(D);重合可能な(メタ)アクリレート(E);およびシランカップリング剤(F)を含有する樹脂組成物である。
この樹脂組成物の一実施形態においては、水酸基を有する(メタ)アクリル酸エステル単量体(A)が、(メタ)アクリロイル基を2個以上有する化合物である。更に別の一実施形態においては、水酸基を有する光重合開始剤(B)が、水酸基を2個以上有する。That is, from one aspect, the present invention provides a resin composition. This resin composition is a urethane acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester monomer (A), a hydroxyl group-containing photopolymerization initiator (B) and an isocyanate group-containing isocyanate (C). (D) A resin composition containing a polymerizable (meth) acrylate (E); and a silane coupling agent (F).
In one embodiment of this resin composition, the (meth) acrylic acid ester monomer (A) having a hydroxyl group is a compound having two or more (meth) acryloyl groups. In still another embodiment, the photopolymerization initiator (B) having a hydroxyl group has two or more hydroxyl groups.
別の側面からの本発明はこの樹脂組成物の硬化体を提供する。
更に別の側面から本発明は、本発明は、該硬化体により被着体が被覆又は接合された複合体を提供する。
この複合体の一実施形態においては、該複合体の被着体がトリアセチルセルロース、フッ素系ポリマー、ポリエステル、ポリカーボネート、ポリオレフィン、ガラス、金属からなる群から選ばれる1種以上である。The present invention from another aspect provides a cured product of this resin composition.
From still another aspect, the present invention provides a composite in which an adherend is coated or bonded with the cured body.
In one embodiment of this composite, the adherend of the composite is at least one selected from the group consisting of triacetylcellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal.
別の側面から、本発明は該樹脂組成物で被着体が貼り合わされたタッチパネル積層体を提供し、さらに本発明はこのタッチパネル積層体を用いたディスプレイを提供する。 From another aspect, the present invention provides a touch panel laminate in which an adherend is bonded with the resin composition, and the present invention further provides a display using the touch panel laminate.
さらに別の観点から、本発明は該樹脂組成物で被着体が貼り合わされた液晶パネル積層体を提供し、さらに本発明は該液晶パネル積層体を用いたディスプレイを提供する。 From still another aspect, the present invention provides a liquid crystal panel laminate in which an adherend is bonded with the resin composition, and the present invention further provides a display using the liquid crystal panel laminate.
別の観点から、本発明は前記の樹脂組成物からなる接着剤を提供する。また、別の観点から、本発明は該樹脂組成物からなるハードコート剤を提供する。 From another viewpoint, the present invention provides an adhesive comprising the above resin composition. Moreover, from another viewpoint, this invention provides the hard-coat agent which consists of this resin composition.
本発明の樹脂組成物は、透明性が大きい、鉛筆硬度が大きい、接着性が大きい、といった効果を有する。 The resin composition of the present invention has effects such as high transparency, high pencil hardness, and high adhesion.
光重合開始剤を有するウレタンアクリレート(D)は、水酸基を有する(メタ)アクリル酸エステル単量体(A)と水酸基を有する光重合開始剤(B)と2個以上のイソシアネート基を有するイソシアネート(C)とを反応させて得られるものである。 The urethane acrylate (D) having a photopolymerization initiator includes a (meth) acrylic acid ester monomer (A) having a hydroxyl group, a photopolymerization initiator (B) having a hydroxyl group, and an isocyanate having two or more isocyanate groups ( And C).
水酸基を有する(メタ)アクリル酸エステル単量体(A)は、少なくとも1個の(メタ)アクリレート基と水酸基を有するものである。1個の(メタ)アクリレート基と水酸基を有する(メタ)アクリレートとしては、例えば、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、及びプロピレングリコール(メタ)アクリレート等が挙げられる。2個以上の(メタ)アクリレート基と水酸基を有する(メタ)アクリレート化合物としては、例えば、グリセリンジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ヒドロキシプロピル化トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールヒドロキシペンタ(メタ)アクリレート、ビス(ペンタエリスリトール)テトラ(メタ)アクリレート、テトラメチロールメタン−トリ(メタ)アクリレート、2−ヒドロキシ−3−(メタ)アクリロイロキシプロピルメタクリレート等が挙げられる。水酸基を有する(メタ)アクリル酸エステル単量体(A)の(メタ)アクリレート基の数は、2個以上が好ましく、3個以上がより好ましい。水酸基を有する(メタ)アクリル酸エステル単量体(A)の水酸基の数は、2個以上が好ましい。 The (meth) acrylic acid ester monomer (A) having a hydroxyl group has at least one (meth) acrylate group and a hydroxyl group. Examples of the (meth) acrylate having one (meth) acrylate group and a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and propylene. Examples include glycol (meth) acrylate. Examples of the (meth) acrylate compound having two or more (meth) acrylate groups and a hydroxyl group include glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, hydroxypropylated trimethylolpropane tri (meth) acrylate, Examples include dipentaerythritol hydroxypenta (meth) acrylate, bis (pentaerythritol) tetra (meth) acrylate, tetramethylolmethane-tri (meth) acrylate, and 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate. The number of (meth) acrylate groups in the (meth) acrylic acid ester monomer (A) having a hydroxyl group is preferably 2 or more, and more preferably 3 or more. The number of hydroxyl groups in the (meth) acrylic acid ester monomer (A) having a hydroxyl group is preferably 2 or more.
水酸基を有する光重合開始剤(B)は、少なくとも1個の水酸基を有するものである。1個の水酸基を有する光重合開始剤としては、例えば、2−ヒドロキシ−メチル−1−フェニル−プロパン−1−オン(チバ・ジャパン社製、製品名Darocur1173)、1−ヒドロキシ−シクロヘキシル−フェニル−ケトン(チバ・ジャパン社製、製品名Irgacure184)等が挙げられる。2個以上の水酸基を有する光重合開始剤としては、例えば、1−[4−(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(チバ・ジャパン社製、製品名Irgacure2959)、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(チバ・ジャパン社製、製品名Irgacure127)等が挙げられる。水酸基を有する光重合開始剤(B)の水酸基の数は、2個以上が好ましい。2個以上有することで、放射線照射後に開裂した光開始剤が(メタ)アクリル酸エステル単量体(A)のアクリロイル基の反応系に取り込むことができるため、マイグレーションが抑制できるためである。なお、水酸基の数の上限については特に限定するものではない。 The photopolymerization initiator (B) having a hydroxyl group has at least one hydroxyl group. Examples of the photopolymerization initiator having one hydroxyl group include 2-hydroxy-methyl-1-phenyl-propan-1-one (manufactured by Ciba Japan, product name Darocur 1173), 1-hydroxy-cyclohexyl-phenyl- Examples include ketones (product name Irgacure 184, manufactured by Ciba Japan). Examples of the photopolymerization initiator having two or more hydroxyl groups include 1- [4- (hydroxyethoxy) -phenyl] -2-hydroxy-2methyl-1-propan-1-one (manufactured by Ciba Japan, Product name Irgacure 2959), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (manufactured by Ciba Japan) Product name Irgacure 127) and the like. The number of hydroxyl groups in the photopolymerization initiator (B) having a hydroxyl group is preferably 2 or more. By having two or more, the photoinitiator cleaved after irradiation can be taken into the reaction system of the acryloyl group of the (meth) acrylate monomer (A), and thus migration can be suppressed. In addition, the upper limit of the number of hydroxyl groups is not particularly limited.
イソシアネート基を有するイソシアネート(C)は、イソシアネート基を2個以上有することが好ましい。2個以上のイソシアネート基を有するイソシアネート(C)は、例えば、芳香族ジイソシアネート、脂環族ジイソシアネート、及び脂肪族ジイソシアネート等が挙げられ、芳香族イソシアネート又は脂環族イソシアネートが好適に用いられる。イソシアネート化合物の形態としては単量体、二量体、及び三量体があり、三量体が好適に用いられる。 The isocyanate (C) having an isocyanate group preferably has two or more isocyanate groups. Examples of the isocyanate (C) having two or more isocyanate groups include aromatic diisocyanate, alicyclic diisocyanate, and aliphatic diisocyanate, and aromatic isocyanate or alicyclic isocyanate is preferably used. As the form of the isocyanate compound, there are a monomer, a dimer, and a trimer, and a trimer is preferably used.
芳香族ジイソシアネートとしては、例えば、トリレンジイソシアネート、4,4−ジフェニルメタンジイソシアネート、及びキシリレンジイソシアネート等が挙げられる。 Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, and xylylene diisocyanate.
脂環族ジイソシアネートとしては、例えば、イソホロンジイソシアネート、メチレンビス(4−シクロヘキシルイソシアネート)等が挙げられる。 Examples of the alicyclic diisocyanate include isophorone diisocyanate and methylene bis (4-cyclohexyl isocyanate).
脂肪族ジイソシアネートとしては、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等が挙げられる。 Examples of the aliphatic diisocyanate include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
上記ジイソシアネートのトリメチロールプロパンアダクト体、水と反応したビュウレット体、イソシアヌレート環を有する3量体等も好適に用いられる。 A trimethylolpropane adduct of the above diisocyanate, a burette reacted with water, a trimer having an isocyanurate ring, and the like are also preferably used.
前記水酸基を有する(メタ)アクリル酸エステル単量体(A)のモル数と、前記水酸基を有する光重合開始剤(B)の水酸基のモル数の合計(A)+(B)=10とした場合に、(A)は6以上が好ましく、9以上がより好ましい。(A)は9.9以下が好ましく、9.8以下がより好ましい。 The total number of moles of the hydroxyl group-containing (meth) acrylic acid ester monomer (A) and the hydroxyl group of the hydroxyl group-containing photopolymerization initiator (B) (A) + (B) = 10. In such a case, (A) is preferably 6 or more, more preferably 9 or more. (A) is preferably 9.9 or less, and more preferably 9.8 or less.
前記水酸基を有する(メタ)アクリル酸エステル単量体(A)の水酸基のモル数と、前記水酸基を有する光重合開始剤(B)の水酸基のモル数の合計(A)+(B)=10とした場合に、2個以上のイソシアネート基を有するイソシアネート(C)のイソシアネート基のモル数は、8〜12が好ましく、9〜11がより好ましい。 Total (A) + (B) = 10 of the number of moles of hydroxyl group of the (meth) acrylic acid ester monomer (A) having the hydroxyl group and the number of moles of hydroxyl group of the photopolymerization initiator (B) having the hydroxyl group. In this case, the number of moles of the isocyanate group of the isocyanate (C) having two or more isocyanate groups is preferably 8 to 12, and more preferably 9 to 11.
前記光重合開始剤を有するウレタンアクリレート(D)の製造方法は特に限定するものではない。前記光重合開始剤を有するウレタンアクリレート(D)は、例えば、水酸基を有する(メタ)アクリル酸エステル単量体(A)と水酸基を有する光重合開始剤(B)とを酢酸エチル等の溶媒中で攪拌しながら40℃に加温した後、2個以上のイソシアネート基を有するイソシアネート(C)を2時間かけて連続的に添加し、更に6時間攪拌することにより得ることができる。 The manufacturing method of urethane acrylate (D) which has the said photoinitiator is not specifically limited. In the urethane acrylate (D) having the photopolymerization initiator, for example, the (meth) acrylic acid ester monomer (A) having a hydroxyl group and the photopolymerization initiator (B) having a hydroxyl group are mixed in a solvent such as ethyl acetate. The mixture can be heated to 40 ° C. with stirring, and then the isocyanate (C) having two or more isocyanate groups can be continuously added over 2 hours and further stirred for 6 hours.
重合可能な(メタ)アクリレート(E)は、重合可能な(メタ)アクリル系組成物で、ラジカル重合可能であればいかなるものでも良く、その例を示せば次の通りである。ここで、(メタ)アクリル系組成物とは、メタクリル酸エステルとアクリル酸エステルの総記(以下、〜(メタ)アクレートのように記す。)である。重合可能な(メタ)アクリレート(E)としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、イソオクチル(メタ)アクリレート、イソデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリアクリレート、フェニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、イソボルニル(メタ)アクリレート、メトキシ化シクロトリエン(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、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、4−ヒドロキシブチル(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、アルキルオキシポリプロピレングリコール(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、2−ヒドロキシ−3−フェノキシプロピル(メタ)アクリレート、グリシジル(メタ)アクリレート、カプロラクトン変成テトラフルフリル(メタ)アクリレート、エトキシカルボニルメチル(メタ)アクリレート、フェノールエチレンオキシド変成(メタ)アクリレート、パラクミルフェノールエチレンオキシ変成(メタ)アクリレート、ノニルフェノールエチレンオキシド変成(メタ)アクリレート、ノニルフェノールポリプロピレンオキシド変成(メタ)アクリレート、2−エチルヘキシルカルビトール(メタ)アクリレート、ポリグリセロールジ(メタ)アクリレート、ポリブチレングリコールジ(メタ)アクリレート、1,4ブタンジオール(メタ)アクリレート、1,6ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、エポキシ(メタ)アクリレート(大阪有機化学社製、「ビスコート#540」)、ポリエステル(メタ)アクリレート(東亜合成社製、「アロニックスM−6100」、共栄化学社製、「エポキシエステル3000M」)、ウレタン(メタ)アクリレート(東亞合成社製、「アロニックスM−1100」)、ポリエチレングリコールウレタン変成ジ(メタ)アクリレート、ポリプロピレングリコールウレタン変成ジ(メタ)アクリレート、エポキシ(メタ)アクリレート(東亞合成社製、「アロニックスM−5710」)、ポリブタジエンジ(メタ)アクリレート(日本曹達社製、「TE−2000」)、アクリルニトリルブタジェン(メタ)アクリレート(宇部興産社製、「HyCAr VTBNX」)、ベンジル(メタ)アクリレート、グリセロール(メタ)アクリレート、グリセロールジ(メタ)アクリレート、フェノキシジエチレングリコール(メタ)アクリレート、2,2−ビス(4−(メタ)アクリロキシフェニル)プロパン、2,2−ビス(4−(メタ)アクリロキシジエトキシフェニル)プロパン、2,2−ビス(4−(メタ)アクリロキシエトキシフェニル)プロパン、2,2−ビス(4−(メタ)アクリロキシプロポキシフェニル)プロパン、2,2−ビス(4−(メタ)アクリロキシテトラエトキシフェニル)プロパン、2,2−ビス[4−((メタ)アクリロキシポリエトキシ)フェニル]プロパン、ペンタエリストールテトラ(メタ)アクリレート、ジペンタエリストールヘキサ(メタ)アクリレート等が挙げられる。 The polymerizable (meth) acrylate (E) may be any polymerizable (meth) acrylic composition as long as it is capable of radical polymerization, and examples thereof are as follows. Here, the (meth) acrylic composition is a general description of methacrylic acid ester and acrylic acid ester (hereinafter referred to as ~ (meth) acrylate). Examples of the polymerizable (meth) acrylate (E) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Isobornyl (meth) acrylate, methoxylated cyclotriene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Droxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, alkyloxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone modified tetrafurfuryl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethyleneoxy Modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol polypropylene Oxide modified (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, polyglycerol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,4 butanediol (meth) acrylate, 1,6 hexanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, epoxy (meth) acrylate (manufactured by Osaka Organic Chemical Co., Ltd., “Biscoat # 540”), polyester (meth) acrylate (Toagosei) "Aronix M-6100", manufactured by Kyoei Chemical Co., Ltd., "epoxy ester 3000M"), urethane (meth) acrylate (manufactured by Toagosei Co., Ltd., "Aronix M-1100"), polyethylene glycol urethane modified di (Meth) acrylate, polypropylene glycol urethane modified di (meth) acrylate, epoxy (meth) acrylate (manufactured by Toagosei Co., Ltd., “Aronix M-5710”), polybutadiene di (meth) acrylate (manufactured by Nippon Soda Co., Ltd., “TE-2000” )), Acrylonitrile butadiene (meth) acrylate (manufactured by Ube Industries, “HyCAr VTBNX”), benzyl (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2 , 2-bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) )propane 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, 2,2-bis [4-((meth) acrylic) Roxypolyethoxy) phenyl] propane, pentaerythritol tetra (meth) acrylate, dipentaerystol hexa (meth) acrylate and the like.
上記の(E)成分は、1種又は2種以上使用することができるが、イソボルニル(メタ)アクリレート、ジシクロペンテニルジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレートからなる群のうちの1種以上であることが望ましい。これは、高温高湿試験、耐候性試験をはじめとする耐久性試験にて、高い保持率を示す点で、有利である。 The above component (E) can be used alone or in combination of two or more thereof, and is selected from the group consisting of isobornyl (meth) acrylate, dicyclopentenyl di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. One or more types are desirable. This is advantageous in that it exhibits a high retention rate in durability tests such as a high temperature and high humidity test and a weather resistance test.
本発明ではガラス乃至プラスチックへの密着力を向上させる目的で、(F)成分として、シランカップリング剤を含有することができる。シランカップリング剤としては、例えば、γ−クロロプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニル−トリス(β−メトキシエトキシ)シラン、γ−(メタ)アクリロキシプロピルトリメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、N−β−(アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−β−(アミノエチル)−γ−アミノプロピルメチルジメトキシシラン、γ−ユレイドプロピルトリエトキシシラン等が挙げられる。これらの中では、ガラス等への密着性の点で、γ−グリシドキシプロピルトリメトキシシラン及び/又はγ−(メタ)アクリロキシプロピルトリメトキシシランが好ましく、γ−グリシドキシプロピルトリメトキシシランがより好ましい。 In the present invention, a silane coupling agent can be contained as the component (F) for the purpose of improving the adhesion to glass or plastic. Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, and γ- (meth) acryloxypropyl. Trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- ( Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, and the like. Among these, γ-glycidoxypropyltrimethoxysilane and / or γ- (meth) acryloxypropyltrimethoxysilane are preferable from the viewpoint of adhesion to glass or the like, and γ-glycidoxypropyltrimethoxysilane is preferable. Is more preferable.
本発明の樹脂組成物において、(D)成分、(E)成分の合計100質量部中、(D)成分を5〜95質量部、(E)成分を5〜95質量部を含有することが好ましく、(D)成分を10〜90質量部、(E)成分を10〜90質量部を含有することがより好ましく、(D)成分を30〜80質量部、(E)成分を20〜70質量部を含有することが最も好ましい。 The resin composition of the present invention may contain 5 to 95 parts by mass of the (D) component and 5 to 95 parts by mass of the (E) component in a total of 100 parts by mass of the (D) component and the (E) component. Preferably, the component (D) contains 10 to 90 parts by mass, the component (E) contains 10 to 90 parts by mass, the component (D) 30 to 80 parts by mass, and the component (E) 20 to 70 parts. Most preferably, it contains parts by mass.
(F)成分の使用量は、(D)成分、(E)成分の合計100質量部に対して、0.01〜10質量部を含有する場合が、組成物の被着体に対するに対する接着性が特段に高くなり、且つ、硬化性が良好となる点で、好ましく、0.1〜5質量部を含有する場合が、より好ましい。 (F) The usage-amount of a component contains 0.01-10 mass parts with respect to a total of 100 mass parts of (D) component and (E) component, but the adhesiveness with respect to the to-be-adhered body of a composition. Is particularly high and the curability is favorable, and the case of containing 0.1 to 5 parts by mass is more preferable.
貯蔵安定性を維持する目的で、重合禁止剤を含む市販の酸化防止剤等を使用することができる。 For the purpose of maintaining storage stability, a commercially available antioxidant containing a polymerization inhibitor can be used.
これらの他にも所望により可塑剤、充填剤、着色剤又は防錆剤等の既に知られている物質を使用することもできる。 In addition to these, known substances such as plasticizers, fillers, colorants, and rust preventives may be used as desired.
本発明は、樹脂組成物に可視光線又は紫外線を照射し、組成物を硬化し、接着する。 In the present invention, the resin composition is irradiated with visible light or ultraviolet light to cure and bond the composition.
可視光線又は紫外線の積算光量は、365nmにおいて100〜40000mJ/cm2が好ましく、500〜4000mJ/cm2がより好ましい。Cumulative amount of the visible light or ultraviolet is preferably 100~40000mJ / cm 2 at 365nm, 500~4000mJ / cm 2 is more preferable.
本発明の樹脂組成物は、タッチパネルにおける透明電極を形成した透明基板上の透明基板の代わりとしての保護基材となる。本発明の樹脂組成物は、気泡を含まずに貼り合わせるものであり、且つ十分な接着性を確保するものである。本発明の樹脂組成物は、接着剤、ハードコート剤として使用できる。 The resin composition of the present invention serves as a protective base material in place of the transparent substrate on the transparent substrate on which the transparent electrode in the touch panel is formed. The resin composition of the present invention is bonded without containing bubbles and ensures sufficient adhesiveness. The resin composition of the present invention can be used as an adhesive or a hard coat agent.
本発明では、樹脂組成物の硬化体によって、被着体を接合又は被覆して複合体を作製することができる。被着体の各種材料については、トリアセチルセルロース、フッ素系ポリマー、ポリエステル、ポリカーボネート、シクロオレフィンポリマー等のポリオレフィン、ガラス、金属からなる群から選ばれる1種以上が好ましく、ポリエステル、ポリカーボネート、ガラスからなる群から選ばれる1種以上がより好ましい。 In the present invention, a composite can be produced by bonding or covering an adherend with a cured body of the resin composition. About various materials of a to-be-adhered body, 1 or more types chosen from the group which consists of polyolefin, glass, a metal, such as triacetylcellulose, a fluorine-type polymer, polyester, a polycarbonate, a cycloolefin polymer, is preferable, and consists of polyester, a polycarbonate, and glass. One or more selected from the group is more preferred.
本発明の樹脂組成物で被着体を貼り合わせることにより、積層体を作製できる。積層体としては、タッチパネル積層体や液晶パネル積層体等の電子デバイスが挙げられる。タッチパネル積層体や液晶パネル積層体等は、ディスプレイに使用できる。 A laminate can be produced by laminating the adherend with the resin composition of the present invention. Examples of the laminate include electronic devices such as a touch panel laminate and a liquid crystal panel laminate. A touch panel laminated body, a liquid crystal panel laminated body, etc. can be used for a display.
以下、本発明を表1〜3を用いて説明する。本発明はこれらに限定されるものではない。表1は、光重合開始剤を有するウレタンアクリレート(D)に用いる化合物の配合を表したものであり、表2及び表3は、組成物の配合及びその評価をまとめたものである。 Hereinafter, this invention is demonstrated using Tables 1-3. The present invention is not limited to these. Table 1 shows the composition of the compounds used for the urethane acrylate (D) having a photopolymerization initiator, and Tables 2 and 3 summarize the composition of the composition and its evaluation.
<実験材料の調製>
実施例に係る接着剤乃至ハードコート剤は下記の処方で製造した。<Preparation of experimental materials>
The adhesives or hard coat agents according to the examples were produced according to the following formulation.
表1中に記載した各化合物は、以下のものである。
水酸基を有する(メタ)アクリル酸エステル単量体(A)−イ:2−ヒドロキシエチルメタクリレート;
水酸基を有する(メタ)アクリル酸エステル単量体(A)−ロ:ペンタエリスリトールトリアクリレート(大阪有機化学社製、製品名V#300);
水酸基を有する(メタ)アクリル酸エステル単量体(A)−ハ:グリセリンジメタクリレート(共栄社化学社製、製品名ライトエステルG−101P);
水酸基を有する光重合開始剤(B)−イ:1−ヒドロキシ−シクロヘキシル−フェニル−ケトン(チバ・ジャパン社製、製品名Irgacure184);
水酸基を有する光重合開始剤(B)−ロ: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(チバ・ジャパン社製、製品名Irgacure127);
水酸基を有する光重合開始剤(B)−ハ:1−[4−(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(チバ・ジャパン社製、製品名Irgacure2959);
2個以上のイソシアネート基を有するイソシアネート(C)−イ:ヘキサメチレンジイソシアネートの3量体(旭化成ケミカルズ社製、製品名デュネラート TPA−100);
2個以上のイソシアネート基を有するイソシアネート(C)−ロ:トリレンジイソシアネート;
重合可能な(メタ)アクリレート(E)−イ:ジシクロペンテニルジアクリレート;
重合可能な(メタ)アクリレート(E)−ロ:トリメチロールプロパントリアクリレート;
シランカップリング剤(F)−イ:γ−メタクリロキシプロピルトリメトキシシラン;
シランカップリング剤(F)−ロ:γ−グリシドキシプロピルトリメトキシシランEach compound described in Table 1 is as follows.
(Meth) acrylic acid ester monomer having a hydroxyl group (A) -i: 2-hydroxyethyl methacrylate;
(Meth) acrylic acid ester monomer having a hydroxyl group (A) -B: pentaerythritol triacrylate (manufactured by Osaka Organic Chemicals, product name V # 300);
(Meth) acrylic acid ester monomer having a hydroxyl group (A) -ha: glycerin dimethacrylate (manufactured by Kyoeisha Chemical Co., product name Light Ester G-101P);
Photopolymerization initiator having a hydroxyl group (B) -i: 1-hydroxy-cyclohexyl-phenyl-ketone (product name Irgacure 184, manufactured by Ciba Japan);
Photopolymerization initiator having a hydroxyl group (B) -ro: 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1 -ON (Ciba Japan, product name Irgacure 127);
Photopolymerization initiator (B) -ha having a hydroxyl group: 1- [4- (hydroxyethoxy) -phenyl] -2-hydroxy-2methyl-1-propan-1-one (product name Irgacure 2959, manufactured by Ciba Japan) );
Isocyanate (C) -i having two or more isocyanate groups: trimer of hexamethylene diisocyanate (manufactured by Asahi Kasei Chemicals Co., Ltd., product name Dunerato TPA-100);
Isocyanate (C) -ro: tolylene diisocyanate having two or more isocyanate groups;
Polymerizable (meth) acrylate (E) -i: dicyclopentenyl diacrylate;
Polymerizable (meth) acrylate (E) -b: trimethylolpropane triacrylate;
Silane coupling agent (F) -i: γ-methacryloxypropyltrimethoxysilane;
Silane coupling agent (F) -b: γ-glycidoxypropyltrimethoxysilane
光重合開始剤を有するウレタンアクリレート(D)は、遮光条件下で、水酸基を有する(メタ)アクリル酸エステル単量体(A)と水酸基を有する光重合開始剤(B)とを酢酸エチル中で攪拌しながら40℃に加温した後、2個以上のイソシアネート基を有するイソシアネート(C)を2時間かけて連続的に添加し、更に6時間攪拌することにより得たものである。 The urethane acrylate (D) having a photopolymerization initiator is prepared by combining a (meth) acrylic acid ester monomer (A) having a hydroxyl group and a photopolymerization initiator (B) having a hydroxyl group in ethyl acetate under light-shielding conditions. After heating to 40 ° C. with stirring, an isocyanate (C) having two or more isocyanate groups was continuously added over 2 hours, and the mixture was further stirred for 6 hours.
(実施例及び比較例)
各実施例及び比較例に対応する接着剤乃至ハードコート剤の主な成分とその配合量は、表1〜3に示す通りである。調製にあたっては、これらの表1に示した成分に加えて、上述の(E)成分及び(F)成分を配合したものである。
比較例1〜2においては、光重合開始剤を有するウレタンアクリレート(D)の代わりに、ウレタンアクリレートオリゴマ(根上工業社製、製品名UN−3320HS)50〜100質量部と光重合開始剤(チバ・ジャパン社製、製品名Irugacure651)3質量部を配合したものを用いて組成物を調製した。(Examples and Comparative Examples)
The main components of the adhesives or hard coat agents corresponding to the respective Examples and Comparative Examples and their blending amounts are as shown in Tables 1-3. In preparation, in addition to the components shown in Table 1, the components (E) and (F) described above are blended.
In Comparative Examples 1 and 2, instead of urethane acrylate (D) having a photopolymerization initiator, 50 to 100 parts by mass of urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., product name UN-3320HS) and a photopolymerization initiator (Ciba -The composition was prepared using what mix | blended 3 mass parts with the Japan company make and product name Irugacure 651).
各種物性は、次のように測定した。 Various physical properties were measured as follows.
〔光硬化性〕
温度23℃で測定した。光硬化性に関しては、テンパックスガラス(25mm×25mm×2mm)の表面に硬化性樹脂組成物を厚み0.1mmになるように塗布した。その後、無電極放電ランプを使用したフュージョン社製硬化装置を用い、波長365nmのUV光を積算光量2000mJ/cm2の条件にて照射し、硬化させた。光硬化性として、硬化率を記載した。硬化率は、FT−IRを使用し、以下の式により算出した。
(硬化率)=[100−((硬化後の、炭素と炭素の二重結合の吸収スペクトルの強度)/(硬化前の、炭素と炭素の二重結合の吸収スペクトルの強度))]×100(%)
光硬化性の評価は次の通り。
○:表面にタック無し(FT−IRから算出した硬化率:90%以上)、△:表面の一部にタック有り(FT−IRから算出した硬化率:50%−89%)、×:表面全体にタック有り(FT−IRから算出した硬化率:0−49%)。[Photocurability]
Measurement was performed at a temperature of 23 ° C. Regarding photocurability, the curable resin composition was applied to the surface of Tempax glass (25 mm × 25 mm × 2 mm) so as to have a thickness of 0.1 mm. Thereafter, using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, UV light having a wavelength of 365 nm was irradiated and cured under the condition of an integrated light quantity of 2000 mJ / cm 2 . Curing rate was described as photocurability. The curing rate was calculated by the following formula using FT-IR.
(Curing rate) = [100-((intensity of absorption spectrum of carbon-carbon double bond after curing) / (intensity of absorption spectrum of carbon-carbon double bond before curing))] × 100 (%)
Evaluation of photocurability is as follows.
○: There is no tack on the surface (curing rate calculated from FT-IR: 90% or more), Δ: There is tack on a part of the surface (curing rate calculated from FT-IR: 50% -89%), x: surface There is tack on the whole (curing rate calculated from FT-IR: 0-49%).
(評価用部材製造方法:実施例比較例共通)
得られた組成物を、膜厚が10μmとなる様に、バーコーターにてテンパックスガラス(25mm×25mm×2mmt)上に塗布し、〔光硬化性〕に従い硬化後、組成物の皮膜を形成した。(Evaluation member manufacturing method: common to comparative examples)
The resulting composition was applied onto Tempax glass (25 mm x 25 mm x 2 mmt) with a bar coater so that the film thickness was 10 µm, and cured according to [photocurability] to form a film of the composition did.
得られた各フィルムの全光線透過率、ヘーズ、鉛筆硬度の結果及び耐光性試験の結果の値を表1〜3に一括して示す。 Tables 1 to 3 collectively show the values of the total light transmittance, haze, pencil hardness, and light resistance test of each film obtained.
性能試験方法は下記の通りである。 The performance test method is as follows.
(全光線透過率及びヘーズ)
ヘーズメーター(スガ試験機社製)を使用し、JIS K7361及びJIS K7136に準拠して測定した。(Total light transmittance and haze)
Using a haze meter (manufactured by Suga Test Instruments Co., Ltd.), the measurement was performed according to JIS K7361 and JIS K7136.
(鉛筆硬度)
スクラッチ試験機(KASAI社製)を使用し、JIS K5600−5−4に準拠し、荷重1kgで測定した。(Pencil hardness)
A scratch tester (manufactured by KASAI) was used, and measurement was performed at a load of 1 kg in accordance with JIS K5600-5-4.
(耐光性試験)
サンシャインウエザーメーター(スガ試験機社製)を用い、サンプルのコーティング面側に紫外線を照射し、200時間暴露した(水噴霧なし)。暴露後のサンプルについて、鉛筆硬度を測定した。(Light resistance test)
Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the coated surface side of the sample was irradiated with ultraviolet rays and exposed for 200 hours (no water spray). About the sample after exposure, pencil hardness was measured.
(ガラスへの引張せん断接着強さ(接着強さ、ガラス))
JIS K 6850に従い測定した。被着材としてテンパックスガラス(25mm×25mm×2mm)を用いた。接着部位を8mmφ(接着部位を8mmφとは、接着部位が直径8mmの円であることをいう)として、樹脂組成物を用い、2枚のテンパックスガラスを貼り合わせた。無電極放電ランプを使用したフュージョン社製硬化装置により、365nmの波長の積算光量2000mJ/cm2の条件にて硬化させ、引張せん断接着強さ試験片を作製した。試験片は、万能試験機を使用して、温度23℃、湿度50%の環境下、引張速度10mm/minで引張せん断接着強さを測定した。(Tensile shear adhesion strength to glass (adhesion strength, glass))
It measured according to JIS K 6850. Tempax glass (25 mm × 25 mm × 2 mm) was used as the adherend. The bonded part was 8 mmφ (the bonded part is 8 mmφ means that the bonded part is a circle having a diameter of 8 mm), and two Tempax glasses were bonded together using the resin composition. A tensile shear bond strength test piece was prepared by curing with a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp under conditions of an integrated light quantity of 2000 mJ / cm 2 with a wavelength of 365 nm. The test piece was measured for tensile shear bond strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
(ポリエステルへの接着強さ(接着強さ、ポリエステル))
被着材としてPETフィルム(10mm×50mm×185μm)を用いた。接着部位を10mm×30mmとして、樹脂組成物を用い、2枚のPETフィルムを貼り合わせた。無電極放電ランプを使用したフュージョン社製硬化装置により、365nmの波長の積算光量2000mJ/cm2の条件にて硬化させ、剥離接着強さ試験片を作製した。試験片は、万能試験機を使用して、温度23℃、湿度50%の環境下、引張速度50mm/minで剥離接着強さを測定した。(Adhesive strength to polyester (adhesive strength, polyester))
A PET film (10 mm × 50 mm × 185 μm) was used as the adherend. Two PET films were bonded together by using a resin composition with an adhesion site of 10 mm × 30 mm. A peel adhesive strength test piece was prepared by curing under a condition of an integrated light amount of 2000 mJ / cm 2 with a wavelength of 365 nm by a fusion device using an electrodeless discharge lamp. The test piece was measured for peel adhesion strength at a tensile speed of 50 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
(ポリカーボネートへの引張せん断接着強さ(接着強さ、ポリカーボネート))
JIS K 6850に従い測定した。被着材としてポリカーボネート板(25mm×25mm×2mm)を用いた。接着部位を8mmφ(接着部位を8mmφとは、接着部位が直径8mmの円であることをいう)として、樹脂組成物を用い、2枚のポリカーボネート板を貼り合わせた。無電極放電ランプを使用したフュージョン社製硬化装置により、365nmの波長の積算光量2000mJ/cm2の条件にて硬化させ、引張せん断接着強さ試験片を作製した。試験片は、万能試験機を使用して、温度23℃、湿度50%の環境下、引張速度10mm/minで引張せん断接着強さを測定した。(Tensile shear bond strength to polycarbonate (bond strength, polycarbonate))
It measured according to JIS K 6850. A polycarbonate plate (25 mm × 25 mm × 2 mm) was used as the adherend. The adhesive part was 8 mmφ (the adhesive part is 8 mmφ means that the adhesive part is a circle having a diameter of 8 mm), and two polycarbonate plates were bonded together using the resin composition. A tensile shear bond strength test piece was prepared by curing with a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp under conditions of an integrated light quantity of 2000 mJ / cm 2 with a wavelength of 365 nm. The test piece was measured for tensile shear bond strength at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% using a universal testing machine.
表より、本発明の樹脂組成物は、以下の特徴を有することが判る。
(1)本発明の樹脂組成物は、気泡を含まずに貼り合わせることができ、透明性が大きい。本発明の樹脂組成物は、透明基板の保護基材となる。
(2)本発明の樹脂組成物は、鉛筆硬度、特に耐光性試験後の鉛筆硬度が大きい。本発明の樹脂組成物は、光暴露の環境下で使用しても傷が付きにくいハードコート剤を提供できる。
(3)本発明の樹脂組成物は、十分な接着性を確保する。本発明の樹脂組成物は、接着剤として使用できる。From the table, it can be seen that the resin composition of the present invention has the following characteristics.
(1) The resin composition of the present invention can be bonded without containing bubbles, and has high transparency. The resin composition of this invention becomes a protective base material of a transparent substrate.
(2) The resin composition of the present invention has a high pencil hardness, particularly after the light resistance test. The resin composition of the present invention can provide a hard coat agent that is hardly damaged even when used in an environment exposed to light.
(3) The resin composition of the present invention ensures sufficient adhesion. The resin composition of the present invention can be used as an adhesive.
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KR102184587B1 (en) * | 2019-02-28 | 2020-12-01 | 주식회사 케이씨씨 | Adhesive Composition |
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