JP6270145B2 - UV curable adhesive composition for optics, the cured layer and optical member - Google Patents
UV curable adhesive composition for optics, the cured layer and optical member Download PDFInfo
- Publication number
- JP6270145B2 JP6270145B2 JP2014093277A JP2014093277A JP6270145B2 JP 6270145 B2 JP6270145 B2 JP 6270145B2 JP 2014093277 A JP2014093277 A JP 2014093277A JP 2014093277 A JP2014093277 A JP 2014093277A JP 6270145 B2 JP6270145 B2 JP 6270145B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- acrylate
- meth
- optical
- 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
- 239000000203 mixture Substances 0.000 title claims description 88
- 230000001070 adhesive effect Effects 0.000 title claims description 47
- 239000000853 adhesive Substances 0.000 title claims description 46
- 230000003287 optical effect Effects 0.000 title claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 44
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000005062 Polybutadiene Substances 0.000 claims description 16
- 229920002857 polybutadiene Polymers 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229920005749 polyurethane resin Polymers 0.000 claims description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000011521 glass Substances 0.000 description 17
- -1 2-hydroxypropyl Chemical group 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000002087 whitening effect Effects 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000004383 yellowing Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000035939 shock Effects 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 4
- 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 4
- 230000003139 buffering effect Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 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 3
- 238000010030 laminating Methods 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000037303 wrinkles Effects 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
- QASBHTCRFDZQAM-UHFFFAOYSA-N (2-isocyanato-2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)N=C=O QASBHTCRFDZQAM-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-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
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-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
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-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=C(C)C=C1 PUBNJSZGANKUGX-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
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-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
- GNDOBZLRZOCGAS-JTQLQIEISA-N 2-isocyanatoethyl (2s)-2,6-diisocyanatohexanoate Chemical compound O=C=NCCCC[C@H](N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-JTQLQIEISA-N 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- ACMIJDVJWLMBCX-PXAZEXFGSA-N 4-[(3ar,6ar)-2,3,3a,4,6,6a-hexahydro-1h-pyrrolo[2,3-c]pyrrol-5-yl]-6-fluoro-n-methyl-2-(2-methylpyrimidin-5-yl)oxy-9h-pyrimido[4,5-b]indol-8-amine Chemical compound CNC1=CC(F)=CC(C2=C(N3C[C@@H]4NCC[C@@H]4C3)N=3)=C1NC2=NC=3OC1=CN=C(C)N=C1 ACMIJDVJWLMBCX-PXAZEXFGSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- HZRPIZSSEMKEEW-UHFFFAOYSA-N C1CO1.O=C1NC(=O)NC(=O)N1 Chemical compound C1CO1.O=C1NC(=O)NC(=O)N1 HZRPIZSSEMKEEW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 1
- 206010052128 Glare Diseases 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-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
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine 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
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、光学用紫外線硬化型接着剤組成物、該硬化層および光学部材に関する。より詳しくは、種々の光学機器等における光学部材・部品の接着に好適な光学用紫外線硬化型接着剤組成物、該組成物からなる硬化層、および該硬化層を含んでなる光学部材に関する。 The present invention relates to an optical ultraviolet curable adhesive composition, the cured layer, and an optical member. More specifically, the present invention relates to an optical ultraviolet curable adhesive composition suitable for bonding optical members and components in various optical devices, a cured layer made of the composition, and an optical member comprising the cured layer.
近年、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ等の表示装置とタッチパッドのような位置入力装置を組み合わせたタッチパネルが広く利用されている。これらのタッチパネルは、表示装置と、透明電極が形成されたガラス板又は樹脂製フィルムと、透明保護板（ガラス又は樹脂製）とを貼り合わせた構造を有している。該タッチパネルでは、外的な衝撃が表示パネルに伝わらないように、表示パネルとそれを保護する透明保護板との間に一定の間隙が設けられている。 In recent years, a touch panel in which a display device such as a liquid crystal display, a plasma display, or an organic EL display is combined with a position input device such as a touch pad has been widely used. These touch panels have a structure in which a display device, a glass plate or a resin film on which a transparent electrode is formed, and a transparent protective plate (made of glass or resin) are bonded together. In the touch panel, a certain gap is provided between the display panel and the transparent protective plate for protecting the display panel so that an external impact is not transmitted to the display panel.
この間隙が空気層である場合は、上記の表示パネルや保護板の構成材料と空気層との屈折率差に起因して光の反射損失が大きくなり、良好な視認性が得られないため、この間隙に透明物質を介在させるようになっている。該透明物質としては、透明樹脂シート、粘着性透明ゲル、硬化性粘着性樹脂組成物などの使用態様が提案されている。 When this gap is an air layer, the light reflection loss increases due to the difference in refractive index between the constituent material of the display panel or the protective plate and the air layer, and good visibility cannot be obtained. A transparent substance is interposed in the gap. As the transparent substance, use forms such as a transparent resin sheet, an adhesive transparent gel, and a curable adhesive resin composition have been proposed.
前記透明物質には、光学用途で求められる各種の性能（可視光透過性等）に加え、長期間使用しても表示不良等を発生させない、耐熱性、耐湿熱性などの高い耐久性が求められる。例えば、高温高湿度下での耐久性に優れた粘着性透明シート用組成物が提案されている（特許文献１）。 The transparent material is required to have high durability such as heat resistance and heat-and-moisture resistance, in addition to various performances required for optical applications (visible light transmittance, etc.), and does not cause defective display even after long-term use. . For example, a composition for an adhesive transparent sheet excellent in durability under high temperature and high humidity has been proposed (Patent Document 1).
表示装置の組み立てに際しては、透明樹脂シートは、粘着性透明ゲルなどに比べて扱いやすく、また、ポリマーの主要構成単位として（メタ）アクリル系モノマーを用いた透明シートでは、シリコーンゲルと比べて接着性に優れ、またウレタンゲルと比較して耐久性に優れるという利点がある。 When assembling a display device, transparent resin sheets are easier to handle than sticky transparent gels, and transparent sheets that use (meth) acrylic monomers as the main structural unit of the polymer are more adhesive than silicone gels. There is an advantage that it is excellent in durability and superior in durability compared with urethane gel.
しかし、画面の大型化に伴って、用いられる透明シートも大判化しなければならないが、該大判シートの取り扱いは容易ではない。例えば、（１）該シートと表示パネルや保護板との界面で、皺や気泡が生じないように貼着させる必要があるため、大判の透明樹脂シートでは高度な貼着技術が求められる、（２）特に表示装置の薄型化に伴い、一層熟練した貼着技術が求められる、（３）表示パネルや保護板へのアンチグレア処理や、液晶画面を見やすくするための黒色印刷層の形成（保護板の裏面（シートと接触する側の面）の外周縁部に施される）に伴う凹凸（印刷部による段差）への追従性が求められる、（４）貼着時に生じた皺や気泡を修復するため、該シートに対する剥離・再貼着性（リペア性）が求められるなど、益々高度の取り扱い技術が要求されている。 However, as the screen becomes larger, the transparent sheet to be used has to be enlarged, but the handling of the large sheet is not easy. For example, (1) since it is necessary to adhere so that wrinkles and bubbles do not occur at the interface between the sheet and the display panel or the protective plate, a large transparent resin sheet requires a high degree of adhesion technology. 2) With the thinning of the display device in particular, more skilled sticking techniques are required. (3) Anti-glare treatment on the display panel and the protective plate, and formation of a black print layer to make the liquid crystal screen easy to see (protective plate) (4) Restoration of wrinkles and bubbles generated at the time of sticking is required. (4) Repair of irregularities (steps caused by printed parts) associated with the outer peripheral edge of the back surface (the surface on the side in contact with the sheet) Therefore, more advanced handling techniques are required, such as peelability (repairability) to the sheet.
一方、液状の硬化性樹脂組成物を前記間隙に充填する方法が知られている。具体的には、液晶表示パネルの表面に貼り付けられた偏光板の周囲にスペーサを配置し、このスペーサの上部に表面保護ガラスを載せるとともに、偏光板と表面保護ガラスの間に気泡が入らないように接着剤を充填し、液晶表示パネル上に前記表面保護ガラスを取り付ける方法等が提案されている（特許文献２）。該使用態様では、粘着シートの貼着作業に比べて取り扱いが一般的に容易であり、表示画面の仕様変更（大型化、間隙幅の変更、段差追従など）に伴う各種要求に対応しやすいという利点があるが、該接着剤として紫外線硬化型樹脂を使用しており、硬化収縮が大きいため、硬化後の歪や応力による表示不良が問題となることがある。 On the other hand, a method of filling the gap with a liquid curable resin composition is known. Specifically, a spacer is arranged around the polarizing plate attached to the surface of the liquid crystal display panel, and a surface protective glass is placed on the upper portion of the spacer, and air bubbles do not enter between the polarizing plate and the surface protective glass. Thus, a method of filling the surface protective glass on the liquid crystal display panel by filling the adhesive is proposed (Patent Document 2). In this mode of use, handling is generally easier than adhesion work of adhesive sheets, and it is easy to respond to various demands associated with display screen specification changes (upsizing, gap width changes, step following, etc.). Although there is an advantage, since an ultraviolet curable resin is used as the adhesive and curing shrinkage is large, display defects due to distortion and stress after curing may be a problem.
さらに、硬化物には外部からの衝撃やヒートサイクル等による熱衝撃を緩和して、画像表示パネルへの影響を抑えることが求められるが、硬化物の弾性率が高過ぎる場合は、耐衝撃性が低下するという問題があった。 Furthermore, cured products are required to mitigate external impacts and thermal shocks caused by heat cycles, etc., and to suppress the impact on the image display panel, but if the cured product has an excessively high elastic modulus, impact resistance There was a problem that decreased.
上記の収縮率および弾性率を改善するためにロジン系化合物や石油樹脂系の可塑剤が検討されている（特許文献３参照）。これらの可塑剤は、収縮率や弾性率を改善する以外に接着性を向上させる効果も発現しうる。 In order to improve the shrinkage and elastic modulus, rosin compounds and petroleum resin plasticizers have been studied (see Patent Document 3). These plasticizers can also exhibit the effect of improving adhesiveness in addition to improving the shrinkage rate and elastic modulus.
しかし、上記可塑剤のみで収縮率や弾性率の改善を行うと、各種特性の低下、特に高温高湿度下での耐白化性および高温下での耐黄変性が低下するため、収縮率および弾性率の改善と耐白化性および耐黄変性の両立が課題となっている。 However, if the shrinkage rate and elastic modulus are improved using only the above plasticizer, various properties, particularly whitening resistance under high temperature and high humidity and yellowing resistance under high temperature, decrease. The improvement of the rate, the whitening resistance, and the yellowing resistance are compatible.
また近年、タッチパネル製品の多様化により、高い耐久性（耐熱性、耐湿熱性）が光学用接着剤組成物、該組成物からなる硬化層、および該硬化層を含んでなる光学部材に求められており、該粘着組成物から得られる接着層は、前記の要求諸特性を必ずしも満足し得ないものであり、改良の余地がある。 In recent years, due to the diversification of touch panel products, high durability (heat resistance, moist heat resistance) has been demanded of optical adhesive compositions, cured layers made of the compositions, and optical members comprising the cured layers. In addition, the adhesive layer obtained from the pressure-sensitive adhesive composition does not necessarily satisfy the above-mentioned required characteristics, and there is room for improvement.
本発明は、硬化収縮が小さく、特定範囲の弾性率を有し、さらに高温高湿下での耐白化性および高温下での耐黄変性に優れる接着硬化層を付与しうる、光学用紫外線硬化型接着剤組成物を提供することを目的とする。 The present invention has an optical ultraviolet curing that has a small curing shrinkage, has an elastic modulus in a specific range, and can provide an adhesive cured layer excellent in whitening resistance under high temperature and high humidity and yellowing resistance under high temperature. An object of the present invention is to provide a mold adhesive composition.
本発明者は、前記課題に鑑み、該接着剤の組成・配合につき鋭意検討した結果、意外にも、特定の粘着付与剤などを含有する特定の紫外線硬化型接着剤組成物により該課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies on the composition and blending of the adhesive in view of the above problems, the present inventor unexpectedly solved the problem with a specific ultraviolet curable adhesive composition containing a specific tackifier and the like. The present inventors have found that this can be done and have completed the present invention.
すなわち本発明は、水素添加ポリブタジエンジオール（Ａ）２０〜４０重量％、水素添加ポリブタジエン系ウレタンアクリレート（Ｂ）２０〜４０重量％、アルキル基の炭素数が８〜１０である単官能アルキル（メタ）アクリレート（Ｃ）５〜４０重量％、アルキル基の炭素数が２〜４である単官能ヒドロキシアルキル（メタ）アクリレート（Ｄ）１〜１０重量％、光重合開始剤（Ｅ）０．５〜５重量％、およびガードナー色数が２以下、軟化点が８０〜１２０℃、アニリン点が５０〜１００℃の範囲にある石油樹脂（Ｆ）１０〜３０重量％（各成分の合計量を１００重量％とする）を含み、２５℃における粘度が１，０００〜５０，０００ｍＰａ・ｓであり、かつ該硬化物の弾性率が１．０×１０４〜１．０×１０５Ｐａとなることを特徴とする光学用紫外線硬化型接着剤組成物に関する。 That is, the present invention is a monofunctional alkyl (meth) in which hydrogenated polybutadiene diol (A) is 20 to 40% by weight, hydrogenated polybutadiene urethane acrylate (B) is 20 to 40% by weight, and the alkyl group has 8 to 10 carbon atoms. Acrylate (C) 5 to 40% by weight, monofunctional hydroxyalkyl (meth) acrylate (D) 1 to 10% by weight of alkyl group having 2 to 4 carbon atoms, photopolymerization initiator (E) 0.5 to 5 10% to 30% by weight of a petroleum resin (F) having a weight percentage of 2 or less, a Gardner color number of 2 or less, a softening point of 80 to 120 ° C., and an aniline point of 50 to 100 ° C. (the total amount of each component is 100% by weight) include that), especially that the viscosity at 25 ° C. is 1,000 to 50,000 mPa · s, and the elastic modulus of the cured product is 1.0 × 10 4 ~1.0 × 10 5 Pa An optical ultraviolet-curable adhesive composition according to.
また本発明は、前記の光学用紫外線硬化型接着剤組成物を紫外線硬化させて得られることを特徴とする光学用紫外線硬化接着層に関する。 The present invention also relates to an optical ultraviolet curable adhesive layer obtained by ultraviolet curing the optical ultraviolet curable adhesive composition.
更に本発明は、前記の光学用紫外線硬化接着層を含んでなることを特徴とする光学部材に関する。 Furthermore, the present invention relates to an optical member comprising the optical ultraviolet curing adhesive layer described above.
本発明の光学用紫外線硬化型接着剤組成物は、硬化収縮が小さいため、硬化後の歪が少ない。また該硬化物は透明性に優れるとともに、特定範囲の弾性率を持つことから、本発明の光学用紫外線硬化型接着剤組成物を使用した表示パネルは、熱衝撃および外部衝撃に対する緩衝性に優れる。さらに、高温高湿下での耐白化性および高温下での耐黄変性に優れるため、光学用部品等として有用である。 Since the optical ultraviolet curable adhesive composition of the present invention has a small curing shrinkage, the distortion after curing is small. In addition, since the cured product is excellent in transparency and has a specific range of elastic modulus, the display panel using the optical ultraviolet curable adhesive composition of the present invention is excellent in buffering against thermal shock and external impact. . Further, since it is excellent in whitening resistance under high temperature and high humidity and yellowing resistance under high temperature, it is useful as an optical component.
本発明の光学用紫外線硬化型接着剤組成物（以下、本組成物という）は、前記のように、水素添加ポリブタジエンジオール（Ａ）２０〜４０重量％、水素添加ポリブタジエン系ウレタンアクリレート（Ｂ）２０〜４０重量％、アルキル基の炭素数が８〜１０である単官能アルキル（メタ）アクリレート（Ｃ）５〜４０重量％、アルキル基の炭素数が２〜４である単官能ヒドロキシアルキル（メタ）アクリレート（Ｄ）１〜１０重量％、光重合開始剤（Ｅ）０．５〜５重量％、およびガードナー色数が２以下、軟化点が８０〜１２０℃、アニリン点が５０〜１００℃の範囲にある石油樹脂（Ｆ）１０〜３０重量％（各成分の合計量を１００重量％とする）を含み、２５℃における粘度が１，０００〜５０，０００ｍＰａ・ｓであり、かつ該硬化物の弾性率が１．０×１０４〜１．０×１０５Ｐａとなることを特徴とする組成物である。 As described above, the optical ultraviolet curable adhesive composition for optical use of the present invention (hereinafter referred to as the present composition) is hydrogenated polybutadiene diol (A) 20 to 40% by weight, hydrogenated polybutadiene urethane acrylate (B) 20 ˜40 wt%, monofunctional alkyl (meth) acrylate (C) having 8 to 10 carbon atoms in the alkyl group 5 to 40 wt%, monofunctional hydroxyalkyl (meth) having 2 to 4 carbon atoms in the alkyl group Acrylate (D) 1 to 10% by weight, photopolymerization initiator (E) 0.5 to 5% by weight, Gardner color number is 2 or less, softening point is 80 to 120 ° C., aniline point is 50 to 100 ° C. 10 to 30% by weight of petroleum resin (F) (the total amount of each component is 100% by weight), the viscosity at 25 ° C. is 1,000 to 50,000 mPa · s, and the curing A composition elastic modulus is characterized by comprising a 1.0 × 10 4 ~1.0 × 10 5 Pa.
なお、本明細書において、簡略便宜上、本組成物から得られる紫外線硬化層を本硬化層といい、また本硬化層を含んでなる光学部材を本部材と称する。 In the present specification, for the sake of brevity, an ultraviolet curable layer obtained from the composition is referred to as a main cured layer, and an optical member including the main cured layer is referred to as a main member.
本組成物における（Ａ）成分は、ポリブタジエンジオールを水素添加して得られるものである。（Ａ）成分を用いることにより、接着力・耐久性に優れた本組成物および本硬化層が得られる。（Ａ）成分の数平均分子量（ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値）は、特に限定されないが、接着力の点より１，０００〜５，０００であるのが好ましい。（Ａ）成分のヨウ素価は、特に限定されないが、通常５０以下であり、耐久性の点より２５以下であるのが好ましく、また水酸基価は、通常１０〜２００の範囲であり、接着性の点より２０〜１００であるのが好ましい。なお、（Ａ）成分に該当する市販品としては、例えば、日本曹達（株）製「ＮＩＳＳＯ−ＰＢ ＧＩ−１０００」、「ＮＩＳＳＯ−ＰＢ ＧＩ−２０００」、「ＮＩＳＳＯ−ＰＢ ＧＩ−３０００」、ＣＲＡＹ ＶＡＬＬＥＹ社製「Ｋｒａｓｏｌ ＨＬＢＨ−Ｐ２０００」、「Ｋｒａｓｏｌ ＨＬＢＨ−Ｐ３０００」などが挙げられる。 The component (A) in the present composition is obtained by hydrogenating polybutadiene diol. By using the component (A), the present composition and the present cured layer excellent in adhesive strength and durability can be obtained. The number average molecular weight (polystyrene conversion value by gel permeation chromatography) of the component (A) is not particularly limited, but is preferably 1,000 to 5,000 from the viewpoint of adhesive strength. The iodine value of the component (A) is not particularly limited, but is usually 50 or less, preferably 25 or less from the viewpoint of durability. The hydroxyl value is usually in the range of 10 to 200, and has an adhesive property. It is preferable that it is 20-100 from a point. In addition, as a commercial item applicable to (A) component, Nippon Soda Co., Ltd. product "NISSO-PBGI-1000", "NISSO-PBGI-2000", "NISSO-PBGI-3000", CRAY, for example. Examples thereof include “Krasol HLBH-P2000”, “Krasol HLBH-P3000” manufactured by VALLEY.
（Ａ）成分の使用量は、本組成物１００重量部中、２０〜４０重量％である必要があり、２５〜３５重量％であるのが好ましい。（Ａ）成分の割合を２０重量％以上にすることで、本組成物・本硬化層の熱衝撃および外部衝撃に対する緩衝性を向上でき、また（Ａ）成分の割合を４０重量％以下にすることで、本組成物の耐熱性が向上する。 (A) The usage-amount of a component needs to be 20-40 weight% in 100 weight part of this composition, and it is preferable that it is 25-35 weight%. By setting the proportion of the component (A) to 20% by weight or more, the buffering property against thermal shock and external impact of the composition / cured layer can be improved, and the proportion of the component (A) is made 40% by weight or less. Thereby, the heat resistance of this composition improves.
本組成物における（Ｂ）成分は、水素添加ポリブタジエンポリオール（以下、（ｂ１）成分という）、１分子中にイソシアネート基を２個以上有する脂肪族または／および脂環式ポリイソシアネート（以下、（ｂ２）成分という）を反応させて得られるイソシアネート基含有ポリウレタン樹脂（以下、（ｂ３）成分という）、または水酸基含有ポリウレタン樹脂（以下、（ｂ４）成分という）を、水酸基含有（メタ）アクリレート（以下、（ｂ５）成分という）またはイソシアネート基含有（メタ）アクリレート（以下、（ｂ６）成分という）と反応させて得られる生成物である。なお、（ｂ１）成分は、前記（Ａ）成分に相当するものである。 The component (B) in the composition is a hydrogenated polybutadiene polyol (hereinafter referred to as the component (b1)), an aliphatic or / and alicyclic polyisocyanate (hereinafter referred to as (b2) having two or more isocyanate groups in one molecule. ) Component) is reacted with an isocyanate group-containing polyurethane resin (hereinafter referred to as component (b3)) or a hydroxyl group-containing polyurethane resin (hereinafter referred to as component (b4)), and a hydroxyl group-containing (meth) acrylate (hereinafter referred to as component). (B5) component) or a product obtained by reacting with an isocyanate group-containing (meth) acrylate (hereinafter referred to as component (b6)). The component (b1) corresponds to the component (A).
（Ｂ）成分は、以下の２つの方法で合成可能である。第一の方法としては、（ｂ１）成分と（ｂ２）成分をイソシアネート基量が水酸基量より多くなる割合で反応させて、鎖延長させた（ｂ３）成分を合成する。この時、（ｂ１）成分の水酸基量と（ｂ２）成分のイソシアネート基量の調整により、（ｂ３）成分の分子量を調整できる。イソシアネート基に対する水酸基量が大きくなるほど、得られる（ｂ３）成分の分子量は大きくなり、イソシアネート基に対する水酸基量が小さくなるほど、該分子量は小さくなる。得られた（ｂ３）成分に（ｂ５）成分（１個の水酸基を残して、各種ポリオールを（メタ）アクリレート化したもの）を反応させて、残存するイソシアネート基を（メタ）アクリロイル基に転換することにより（Ｂ）成分が得られる。 The component (B) can be synthesized by the following two methods. As a first method, the component (b3) in which the chain is extended is synthesized by reacting the component (b1) and the component (b2) at a ratio in which the amount of isocyanate groups is larger than the amount of hydroxyl groups. At this time, the molecular weight of the component (b3) can be adjusted by adjusting the amount of the hydroxyl group of the component (b1) and the amount of the isocyanate group of the component (b2). The molecular weight of the obtained component (b3) increases as the amount of hydroxyl groups relative to the isocyanate group increases, and the molecular weight decreases as the amount of hydroxyl groups relative to the isocyanate group decreases. The resulting (b3) component is reacted with the (b5) component (one of the hydroxyl groups and various polyols that have been (meth) acrylated) to convert the remaining isocyanate groups into (meth) acryloyl groups. Thus, the component (B) is obtained.
第二の方法としては、（ｂ１）成分と（ｂ２）成分を水酸基量がイソシアネート基量より多くなる割合で反応させて、鎖延長させた（ｂ４）成分を合成する。この時、（ｂ１）成分の水酸基量と（ｂ２）成分のイソシアネート基量の調整により、（ｂ４）成分の分子量を調整できる。イソシアネート基に対する水酸基量が大きくなるほど、得られる（ｂ４）成分の分子量は大きくなり、イソシアネート基に対する水酸基量が小さくなるほど、該分子量は小さくなる。得られた（ｂ４）成分に（ｂ６）成分を反応させることにより（Ｂ）成分が得られる。 As a second method, the (b1) component and the (b2) component are reacted at a ratio in which the amount of hydroxyl groups is larger than the amount of isocyanate groups to synthesize a component (b4) having a chain extended. At this time, the molecular weight of the component (b4) can be adjusted by adjusting the amount of the hydroxyl group of the component (b1) and the amount of the isocyanate group of the component (b2). The molecular weight of the component (b4) obtained increases as the amount of hydroxyl groups relative to the isocyanate group increases, and the molecular weight decreases as the amount of hydroxyl groups relative to the isocyanate group decreases. The component (B) is obtained by reacting the component (b4) with the component (b6).
上記２つの反応は、いずれも、水酸基とイソシアネート基との反応であり、イソシアネート基に不活性な有機溶媒の存在下、ジブチル錫ジラウレートやジブチル錫ジエチルヘキソエートのような一般的なウレタン化触媒を用いて、撹拌下に通常３０〜１００℃で、１〜５時間程度の条件で行われる。ウレタン化触媒の使用量は反応に供される原料の合計重量基準で、通常５０〜５００ｐｐｍである。 The above two reactions are both a reaction between a hydroxyl group and an isocyanate group. In the presence of an organic solvent inert to the isocyanate group, a general urethanization catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate is used. Is usually performed at 30 to 100 ° C. with stirring for about 1 to 5 hours. The amount of the urethanization catalyst used is usually 50 to 500 ppm, based on the total weight of the raw materials used for the reaction.
（ｂ２）成分としては、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、リジンジイソシアネート、リジントリイソシアネート等の脂肪族ポリイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化キシリレンジイソシアネート類、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン等の脂環式ポリイソシアネート類、これらの２〜６量体などが挙げられ、これらは単独、組み合わせのいずれでも使用できる。（ｂ２）成分を用いることにより、接着力・耐久性に優れた本硬化層を提供できる。 Examples of the component (b2) include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate. And alicyclic polyisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane, dimer or hexamer thereof, and the like can be used either alone or in combination. By using the component (b2), a fully cured layer having excellent adhesive strength and durability can be provided.
（ｂ５）成分としては、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、４−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシシクロヘキシル（メタ）アクリレート、５−ヒドロキシシクロオクチル（メタ）アクリレート、１，３−ブタンジオール（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（メタ）アクリレート、３−メチルペンタンジオール（メタ）アクリレートなどが挙げられ、これらは単独、組み合わせのいずれでも使用できる。 Examples of the component (b5) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, and 5-hydroxycyclooctyl. (Meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth) acrylate, etc. These can be used either alone or in combination.
（ｂ６）成分としては、例えば、２−イソシアネートエチル（メタ）アクリレート、１，１−ビス（アクロイルオキシメチル）エチルイソシアネート等などが挙げられる。中でも、水酸基との反応性、及び光硬化性の点から、２−イソシアネートエチルアクリレートが好ましい。 Examples of the component (b6) include 2-isocyanatoethyl (meth) acrylate and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Among these, 2-isocyanatoethyl acrylate is preferable from the viewpoint of reactivity with a hydroxyl group and photocurability.
（Ｂ）成分は、前記のように、（ｂ１）成分と（ｂ２）成分とを反応させて（ｂ３）成分または（ｂ４）成分を得た後、該（ｂ３）成分と（ｂ５）成分とを反応させ、または該（ｂ４）成分と（ｂ６）成分とを反応させることにより製造できる。（Ｂ）成分の製造では、（ｂ１）成分、（ｂ２）成分および（ｂ５）成分を一括反応、または（ｂ１）成分、（ｂ２）成分および（ｂ６）成分を一括反応させる方法も採用できるが、（Ｂ）成分の重量平均分子量を制御しやすい点から前記方法を採用するのが好ましい。 As described above, the component (B) reacts with the component (b1) and the component (b2) to obtain the component (b3) or the component (b4), and then the component (b3) and the component (b5) Or by reacting the component (b4) and the component (b6). In the production of the component (B), it is possible to adopt a method in which the components (b1), (b2) and (b5) are collectively reacted, or the components (b1), (b2) and (b6) are collectively reacted. It is preferable to employ the above method from the viewpoint of easily controlling the weight average molecular weight of the component (B).
（Ｂ）成分の重量平均分子量（ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値）は、格別限定されないが、得られる本組成物・本硬化層の接着性および耐久性の点から、５，０００〜５０，０００であるのが好ましい。 (B) Although the weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of a component is not specifically limited, From the point of the adhesiveness and durability of this composition and this hardened layer which are obtained, 5,000-50 1,000 is preferred.
なお、（Ｂ）成分の平均官能基数は、格別限定されないが、得られる本硬化層の耐久性の点から、１．５〜３．０であるのが好ましく、より好ましくは１．８〜２．２である。なお、該平均官能基数とは、（Ｂ）成分の１分子中に存在する（メタ）アクリロイル基の平均個数を意味する。 In addition, although the average functional group number of (B) component is not exceptionally limited, it is preferable that it is 1.5-3.0 from the point of durability of this hardened layer obtained, More preferably, it is 1.8-2. .2. The average number of functional groups means the average number of (meth) acryloyl groups present in one molecule of the component (B).
（Ｂ）成分の使用量は、本組成物１００重量部中、２０〜４０重量％である必要があり、２５〜３５重量％の範囲が好ましい。（Ｂ）成分の割合を２０重量％以上にすることで、本組成物の高温下、高温高湿下における耐久性を向上でき、また（Ｂ）成分の割合を４０重量％以下にすることで、本組成物の熱衝撃および外部衝撃に対する緩衝性を向上させることができる。 (B) The usage-amount of a component needs to be 20-40 weight% in 100 weight part of this composition, and the range of 25-35 weight% is preferable. By making the proportion of the component (B) 20% by weight or more, the durability of the present composition under high temperature and high temperature and high humidity can be improved, and by making the proportion of the component (B) 40% by weight or less. In addition, the buffer property against thermal shock and external shock of the composition can be improved.
（Ｃ）成分は、本組成物の粘度を低下させて取り扱い性を向上させる観点から、必須成分として用いられる。（Ｃ）成分の具体例としては、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレートが挙げられ、これらは１種単独で、または２種以上を適宜に組み合わせて使用できる。 (C) A component is used as an essential component from a viewpoint of reducing the viscosity of this composition and improving handleability. Specific examples of the component (C) include octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth) acrylate. Can be used singly or in appropriate combination of two or more.
（Ｃ）成分の使用量は、本組成物１００重量部中、５〜４０重量％である必要があり、１０〜３０重量％の範囲が好ましい。（Ｃ）成分の割合を５重量％以上にすることで、本組成物の取り扱い性を向上でき、また（Ｃ）成分の割合を４０重量％以下にすることで、本組成物の硬化性を向上させることができる。 (C) The usage-amount of a component needs to be 5-40 weight% in 100 weight part of this composition, and the range of 10-30 weight% is preferable. By making the proportion of the component (C) 5% by weight or more, the handleability of the composition can be improved, and by making the proportion of the component (C) 40% by weight or less, the curability of the composition can be improved. Can be improved.
（Ｄ）成分は、本組成物の耐湿熱性の点から必須成分として用いられる。（Ｄ）成分の具体例としては、２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートが挙げられ、これらは１種単独で、または２種以上を適宜に組み合わせて使用できる。 (D) component is used as an essential component from the point of the heat-and-moisture resistance of this composition. Specific examples of the component (D) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. These may be used alone or in combination. The above can be used in appropriate combinations.
（Ｄ）成分の使用量は、本組成物１００重量部中、１〜１０重量％である必要があり、３〜６重量％の範囲が好ましい。（Ｄ）成分の割合を１重量％以上にすることで、本組成物の耐白化性を向上でき、また（Ｄ）成分の割合を１０重量％以下にすることで、本組成物の硬化性を向上させることができる。 (D) The usage-amount of a component needs to be 1-10 weight% in 100 weight part of this composition, and the range of 3-6 weight% is preferable. By making the proportion of the component (D) 1% by weight or more, the whitening resistance of the composition can be improved, and by making the proportion of the component (D) 10% by weight or less, the curability of the composition. Can be improved.
（Ｅ）成分は、紫外線照射により分解しラジカルを発生する光重合開始剤であれば、各種公知のものを格別限定なく使用できる。具体的には、ベンゾイン化合物、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、チタノセン化合物、チオキサントン化合物、オキシムエステル化合物等の光重合開始剤、アミンやキノン等の光増感剤等が挙げられ、具体的には、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、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−モルフォリノプロパン−１−オン、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン、２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウム、１，２−オクタンジオン１−［４−（フェニルチオ）−２−（ｏ−ベンゾイルオキシム）］、エタノン１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（ｏ−アセチルオキシム）等が挙げられ、１種を単独で使用しても、２種以上を併用してもよい。これらの中でも、１−ヒドロキシシクロヘキシルフェニルケトン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイドが、本組成物の硬化性を一層向上しうるため好適である。 As the component (E), various known compounds can be used without any particular limitation as long as they are photopolymerization initiators that decompose upon irradiation with ultraviolet rays to generate radicals. Specific examples include photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and oxime ester compounds, and photosensitizers such as amines and quinones. Are 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 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-methylthiophenyl) -2- Rufolinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6- Trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η 5 -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octanedione 1- [4- (phenylthio) -2- (o-benzoyloxime)], ethanone 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime) and the like. It may be used in combination. Among these, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable because the curability of the composition can be further improved.
（Ｅ）成分の使用量は、本組成物１００重量部中、０．５〜５重量％である必要があり、１〜３重量％であるのが好ましい。（Ｅ）成分の割合を０．５重量％以上にすることで、紫外線照射による硬化重合のばらつきを防止でき、また５重量％以下にすることで、（Ｅ）成分の分解物に起因する臭気発生を低減でき、かつ硬化層の着色を防止できる。 (E) The usage-amount of a component needs to be 0.5-5 weight% in 100 weight part of this composition, and it is preferable that it is 1-3 weight%. By setting the ratio of the component (E) to 0.5% by weight or more, variation in curing polymerization due to ultraviolet irradiation can be prevented, and by setting the ratio to 5% by weight or less, the odor caused by the decomposition product of the component (E) Generation | occurrence | production can be reduced and coloring of a hardened layer can be prevented.
（Ｆ）成分は、粘着付与樹脂として用いられるが、得られる本組成物の色調、透明性、紫外線硬化性、粘着性、耐久性などの要求性能を考慮して、各種公知の粘着付与樹脂のうちから選定されたものである。すなわち、（Ｆ）成分は、ガードナー色数が２以下、軟化点が８０〜１２０℃、アニリン点（ＪＩＳ Ｋ ２２５６準拠）が５０〜１００℃の範囲にある石油樹脂である。（Ｆ）成分の好ましい性状としては、ガードナー色数が１以下、軟化点が８５〜１１０℃、アニリン点が６０〜１００℃である。（Ｆ）成分に相当する市販品としては、荒川化学工業（株）製のアルコンＭ−９０、Ｍ−１００、Ｍ−１１５、出光興産（株）製のアイマーブＳ−１００、エクソンモービル社製のエスコレッツ５６９０、イーストマンケミカル社製のリガライト５１００などが挙げられる。 The component (F) is used as a tackifying resin, but in consideration of required performance such as color tone, transparency, ultraviolet curable property, tackiness, and durability of the obtained composition, various known tackifying resins are used. It was selected from our house. That is, the component (F) is a petroleum resin having a Gardner color number of 2 or less, a softening point of 80 to 120 ° C., and an aniline point (according to JIS K 2256) of 50 to 100 ° C. (F) As a preferable property of a component, the Gardner color number is 1 or less, a softening point is 85-110 degreeC, and an aniline point is 60-100 degreeC. Commercially available products corresponding to the component (F) include Arcon M-90, M-100, M-115 manufactured by Arakawa Chemical Industries, Imabe S-100 manufactured by Idemitsu Kosan Co., Ltd., manufactured by ExxonMobil Corporation. Examples include Escorez 5690, Rigalite 5100 manufactured by Eastman Chemical Co., Ltd.
（Ｆ）成分の使用量は、本組成物１００重量部中、１０〜３０重量％である必要があり、１５〜２５重量％の範囲が好ましい。（Ｆ）成分の割合を１０重量％以上にすることで、本組成物の粘着性を向上でき、また（Ｆ）成分の割合を３０重量％以下にすることで、本組成物の耐熱性を向上させることができる。 Component (F) should be used in an amount of 10 to 30% by weight, preferably 15 to 25% by weight, in 100 parts by weight of the present composition. By making the proportion of the component (F) 10% by weight or more, the tackiness of the composition can be improved, and by making the proportion of the component (F) 30% by weight or less, the heat resistance of the composition can be improved. Can be improved.
本組成物の製造は、前記（Ａ）〜（Ｆ）成分を前記特定の割合で混合することによって行われる。各成分の混合方法および添加順序については、特段の限定はされない。 The composition is produced by mixing the components (A) to (F) at the specific ratio. There are no particular limitations on the mixing method and order of addition of the components.
また、本組成物には、必要に応じて、本発明の効果を損なわない範囲で、種々の添加剤を含有させることができる。例えば、多官能モノマー、表面調整剤、界面活性剤、紫外線吸収剤、酸化防止剤、無機フィラー、シランカップリング剤、コロイダルシリカ、消泡剤、湿潤剤、防錆剤、安定化剤等の添加剤を含有させることができる。 Moreover, various additives can be contained in this composition in the range which does not impair the effect of this invention as needed. For example, addition of polyfunctional monomers, surface conditioners, surfactants, UV absorbers, antioxidants, inorganic fillers, silane coupling agents, colloidal silica, antifoaming agents, wetting agents, rust inhibitors, stabilizers, etc. An agent can be included.
上記多官能モノマーの具体例としては、１，４−ブタンジオールジ（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、１，６−ヘキサンジオール（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート等脂肪族構造を有するジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、トリシクロデカンジ（メタ）アクリレート等の脂環式構造を有するジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド変性ジ（メタ）アクリレート、ビスフェノールＦエチレンオキサイド変性ジ（メタ）アクリレート等の芳香族構造を有するジ（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、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート等の３官能以上の多官能（メタ）アクリレートが挙げられる。 Specific examples of the polyfunctional monomer include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol di ( Di (meth) acrylate having an alicyclic structure such as di (meth) acrylate having an aliphatic structure such as (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricyclodecane di (meth) acrylate, bisphenol A ethylene oxide Di (meth) acrylate having an aromatic structure such as modified di (meth) acrylate, bisphenol F ethylene oxide modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate Over DOO, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and a polyfunctional (meth) acrylate having three or more functional such as dipentaerythritol hexaacrylate.
本組成物の粘度については、前記のような光学部材間隙への充填性の点から、２５℃における粘度が１，０００〜５０，０００ｍＰａ・ｓであることが必要であり、２，０００〜２０，０００ｍＰａ・ｓであるのが好ましい。粘度を１，０００ｍＰａ・ｓ以上にすることで、貼り合わせ工程における液のはみ出しを低減でき、５０，０００ｍＰａ・ｓ以下にすることで、貼り合わせ工程における気泡の混入を防止することができる。 About the viscosity of this composition, the viscosity in 25 degreeC needs to be 1,000-50,000 mPa * s from the point of the filling property to the above optical member gaps, and 2,000-20 1,000 mPa · s is preferable. By setting the viscosity to 1,000 mPa · s or more, it is possible to reduce the protrusion of the liquid in the bonding process, and by setting the viscosity to 50,000 mPa · s or less, it is possible to prevent air bubbles from being mixed in the bonding process.
本組成物の硬化体積収縮率は、格別の限定はされないが、３．０％以下とすることが好ましい。該収縮率を３．０％以下にすることで、硬化後の歪や応力を緩和させることができる。 The cured volume shrinkage of the composition is not particularly limited, but is preferably 3.0% or less. By setting the shrinkage rate to 3.0% or less, strain and stress after curing can be relaxed.
本硬化物における弾性率は、１．０×１０４〜１．０×１０５Ｐａの範囲とする必要があり、２．０×１０４〜７．０×１０４Ｐａの範囲であるのが好ましい。弾性率を１．０×１０４Ｐａ以上にすることで、本硬化物の機械的強度を向上させることができ、１．０×１０５Ｐａ以下にすることで、熱衝撃および外部衝撃に対しての緩衝性を向上させることができる。 The elastic modulus in the cured product needs to be in the range of 1.0 × 10 4 to 1.0 × 10 5 Pa, and is in the range of 2.0 × 10 4 to 7.0 × 10 4 Pa. preferable. By setting the elastic modulus to 1.0 × 10 4 Pa or more, the mechanical strength of the cured product can be improved. By setting the elastic modulus to 1.0 × 10 5 Pa or less, against thermal shock and external impact. All buffering properties can be improved.
本組成物は、表示パネルと化粧板やアイコンシートとの貼合や、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合、また表示体と光学機能材料との貼合など、各種の光学機器や光学部材のための接着材用途で好適に用いられる。前記部材の材質としては、ポリエチレンテレフタレート、ポリカーボネート、ガラス、ポリカーボネート、アクリル樹脂などが挙げられる。表示体としては、ガラスに偏光板を貼り付けてある液晶ディスプレイ、ＥＬディスプレイ、ＥＬ照明、電子ペーパーやプラズマディスプレイ等の表示素子が挙げられる。光学機能材料としては、視認性向上や外部衝撃から表示素子の割れ防止を目的とするアクリル板（片面または両面ハードコート処理や反射防止コート処理してあってもよい）、ポリカーボネート板、ポリエチレンテレフタレート板、ポリエチレンナフタレート板等の透明プラスチック板、強化ガラス（飛散防止フィルムが付いていてもよい）およびタッチパネル入力センサー等が挙げられる。 This composition includes various types of bonding, such as bonding between a display panel and a decorative plate or an icon sheet, bonding between a transparent substrate on which a transparent electrode is formed on a touch panel and a transparent plate, and bonding between a display body and an optical functional material. It is suitably used for adhesive materials for optical devices and optical members. Examples of the material of the member include polyethylene terephthalate, polycarbonate, glass, polycarbonate, and acrylic resin. As a display body, display elements, such as a liquid crystal display which stuck the polarizing plate on glass, EL display, EL illumination, electronic paper, and a plasma display, are mentioned. Examples of optical functional materials include acrylic plates (which may be treated with a single-sided or double-sided hard coating or antireflection coating), polycarbonate plates, polyethylene terephthalate plates for the purpose of improving visibility and preventing cracking of display elements from external impacts. And a transparent plastic plate such as a polyethylene naphthalate plate, tempered glass (which may have an anti-scattering film), and a touch panel input sensor.
本組成物の硬化に使用する紫外線の光源としては、キセノンランプ、高圧水銀灯、メタルハライドランプを有する紫外線照射装置が挙げられる。また、光量、光源、搬送速度等の条件は適宜調整すればよく、光量が通常８０〜１６０Ｗ／ｃｍ程度、搬送速度が通常５〜５０ｍ／分程度である。なお、積算光量としては、１００〜５０００ｍＪ／ｃｍ２であることが好ましく、５００〜３０００ｍＪ／ｃｍ２であることがより好ましい。上記範囲内であれば、適切な硬化反応を担保でき、目的とする諸性能を有する本硬化層を得ることができる。 Examples of the ultraviolet light source used for curing the composition include an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. Moreover, what is necessary is just to adjust conditions, such as a light quantity, a light source, and a conveyance speed suitably, and a light quantity is about 80-160 W / cm normally, and a conveyance speed is about about 5-50 m / min normally. As integrated light quantity is preferably 100~5000mJ / cm 2, more preferably 500~3000mJ / cm 2. If it is in the said range, an appropriate hardening reaction can be ensured and the hardened layer which has the target various performance can be obtained.
本組成物の硬化に際しては、貼り合わせ工程における液のはみ出しを一層低減する観点から、塗工後に予備的に硬化させた後に貼り合わせを行い、貼り合わせ後に完全硬化させるのが好ましい。本組成物をスリットコーター等で透明電極が形成されたガラス板もしくは樹脂製フィルム、または透明保護板（ガラス又は樹脂製）等に塗工後、積算光量で１００〜１０００ｍＪ／ｃｍ２の紫外線を照射して予備的に硬化させる。その後、表示装置等と真空注で貼り合わせを行い、積算光量で５００〜３０００ｍＪ／ｃｍ２の紫外線を照射し、本組成物を完全硬化させることで、貼り合わせを行うことができる。塗工後に予備的に硬化させることで、本組成物の流動性が失われるため、貼り合わせ工程における液のはみ出しを一層低減することができる。 When the present composition is cured, it is preferable to perform pre-curing after the coating and then laminating and then completely curing after the laminating from the viewpoint of further reducing the protrusion of the liquid in the laminating step. The composition is applied to a glass plate or resin film on which a transparent electrode is formed by a slit coater or the like, or a transparent protective plate (glass or resin), etc., and then irradiated with ultraviolet rays of 100 to 1000 mJ / cm 2 in terms of integrated light quantity. And pre-cured. Then, it can bond together by vacuum-casting with a display apparatus etc., irradiating 500-3000 mJ / cm < 2 > of ultraviolet rays with an integrated light quantity, and hardening this composition completely. By preliminarily curing after coating, the fluidity of the present composition is lost, so that liquid protrusion in the bonding step can be further reduced.
前記のようにして得られた本硬化層の厚みは特に限定されないが、通常平均１０〜１０００μｍ程度、好ましくは２５〜５００μｍである。厚膜をこの範囲とすることで、光学部材・モジュールの耐衝撃性を向上させることができる。 The thickness of the main cured layer obtained as described above is not particularly limited, but is usually about 10 to 1000 μm on average, and preferably 25 to 500 μm. By making the thick film within this range, the impact resistance of the optical member / module can be improved.
以下に本発明を合成例、実施例などにより更に具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to these examples.
合成例１〔（Ｂ）成分の合成〕
冷却菅と撹拌機を備えた反応装置に、重量平均分子量３，０００の水素添加ポリブタジエンジオール（日本曹達（株）製、商品名「ＮＩＳＳＯ−ＰＢ ＧＩ−３０００」、水酸基価２５ｍｇＫＯＨ／ｇ）を９モル、イソホロンジイソシアネート１０モル、およびオクチル酸スズ０．０２重量％（各成分合計量を１００重量％とする）を加え、撹拌下に８０℃まで昇温して２時間保温した後、ＮＣＯ測定にて反応完結を確認し、中間体であるイソシアネート基含有ポリウレタン樹脂を得た。ついで、２−ヒドロキシエチルアクリレート２モルを加え、撹拌下８０℃で２時間保温し、ＮＣＯ測定にて反応完結を確認することにより、重量平均分子量４６，０００、平均官能基数２．０の水素添加ポリブタジエン系ウレタンアクリレート（以下、（Ｂ１）成分という）を得た。なお、当該重量平均分子量は、ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値であり、該測定条件は以下のとおりである〔測定装置本体（製品名「ＨＬＣ−８２２０ＧＰＣ」、東ソー（株）製）、カラム（製品名「ＴＳＫＧｅｌ Ｇ１０００Ｈ」、「ＴＳＫＧｅｌ Ｇ２０００Ｈ」、東ソー（株）製）、展開溶媒（テトラヒドロフラン）〕。（以下同様）
Synthesis Example 1 [Synthesis of component (B)]
A hydrogenated polybutadiene diol having a weight average molecular weight of 3,000 (manufactured by Nippon Soda Co., Ltd., trade name “NISSO-PB GI-3000”, hydroxyl value 25 mgKOH / g) was added to a reactor equipped with a cooling tank and a stirrer. Mole, 10 moles of isophorone diisocyanate, and 0.02% by weight of tin octylate (the total amount of each component is 100% by weight), heated to 80 ° C. with stirring and kept warm for 2 hours. The completion of the reaction was confirmed to obtain an isocyanate group-containing polyurethane resin as an intermediate. Next, 2 mol of 2-hydroxyethyl acrylate was added, and the mixture was kept at 80 ° C. for 2 hours with stirring, and the completion of the reaction was confirmed by NCO measurement. A polybutadiene-based urethane acrylate (hereinafter referred to as “component (B1)”) was obtained. In addition, the said weight average molecular weight is the polystyrene conversion value by a gel permeation chromatography, and this measurement condition is as follows [a measuring apparatus main body (product name "HLC-8220GPC", the Tosoh Corporation make), column. (Product names “TSKGel G1000H”, “TSKGel G2000H”, manufactured by Tosoh Corporation), developing solvent (tetrahydrofuran)]. (The same applies hereinafter)
合成例２〔（Ｂ）成分の合成〕
合成例１と同様の反応装置に、合成例１で用いたと同一の水素添加ポリブタジエンジオール１モル、イソホロンジイソシアネート２モル、およびオクチル酸スズ０．０２重量％を加え、撹拌下に８０℃まで昇温して２時間保温した後、ＮＣＯ測定にて反応完結を確認し、中間体であるイソシアネート基含有ポリウレタン樹脂を得た。ついで、２−ヒドロキシエチルアクリレート２モルを加え、撹拌下８０℃で２時間保温し、ＮＣＯ測定にて反応完結を確認することにより、重量平均分子量７，０００、平均官能基数２．０の水素添加ポリブタジエン系ウレタンアクリレート（以下、（Ｂ２）成分という）を得た。
Synthesis Example 2 [Synthesis of component (B)]
To the same reactor as in Synthesis Example 1, 1 mol of the same hydrogenated polybutadiene diol as used in Synthesis Example 1, 2 mol of isophorone diisocyanate, and 0.02% by weight of tin octylate were added, and the temperature was raised to 80 ° C. with stirring. Then, after keeping the temperature for 2 hours, the completion of the reaction was confirmed by NCO measurement, and an isocyanate group-containing polyurethane resin as an intermediate was obtained. Next, 2 mol of 2-hydroxyethyl acrylate was added, and the mixture was kept at 80 ° C. for 2 hours with stirring, and the completion of the reaction was confirmed by NCO measurement. A polybutadiene-based urethane acrylate (hereinafter referred to as (B2) component) was obtained.
＜接着剤組成物の調製＞
実施例１
（Ａ）成分として水素添加ポリブタジエンジオール（日本曹達（株）製、商品名「ＮＩＳＳＯ−ＰＢ ＧＩ−２０００」）２５部、（Ｂ）成分として合成例１で得られた（Ｂ１）成分２５部、（Ｃ）成分としてｎ−オクチルアクリレート（ＢＡＳＦ社製）２２部、（Ｄ）成分として２−ヒドロキシエチルアクリレート（ＢＡＳＦ社製）５部、（Ｅ）成分として１−ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製、商品名「イルガキュア１８４」）３部、および（Ｆ）成分として石油樹脂（荒川化学工業（株）製、商品名「アルコンＭ−９０」；ガードナー色数１以下、軟化点９０℃、アニリン点８２．９℃）２０部を、いずれも純分換算で配合し、接着剤組成物を調製した（表１参照）。また、該組成物のガードナー色数、粘度、溶剤含有率および相溶性を評価し、結果を表２に示した（以下同様）。
<Preparation of adhesive composition>
Example 1
(A) 25 parts hydrogenated polybutadiene diol (manufactured by Nippon Soda Co., Ltd., trade name “NISSO-PB GI-2000”) as component, 25 parts (B1) component obtained in Synthesis Example 1 as component (B), As component (C), 22 parts of n-octyl acrylate (manufactured by BASF), as component (D), 5 parts of 2-hydroxyethyl acrylate (manufactured by BASF), and as component (E), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF) , Trade name “Irgacure 184”) and 3 parts of petroleum resin (Arakawa Chemical Industries, trade name “Arcon M-90” as component (F); Gardner color number 1 or less, softening point 90 ° C., aniline point (82.9 ° C.) 20 parts were blended in terms of pure matter to prepare an adhesive composition (see Table 1). Moreover, the Gardner color number, viscosity, solvent content and compatibility of the composition were evaluated, and the results are shown in Table 2 (the same applies hereinafter).
実施例２〜９
表１に示すように、各成分の種類および使用量のいずれかを変更して、実施例１と同様の方法に従い、接着剤組成物を調製した。
Examples 2-9
As shown in Table 1, an adhesive composition was prepared according to the same method as in Example 1 except that either the type or amount of each component was changed.
比較例１
表１に示すように、（Ａ）成分および（Ｆ）成分を使用しなかった他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 1
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the components (A) and (F) were not used.
比較例２
表１に示すように、（Ａ）成分を使用しなかった他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 2
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the component (A) was not used.
比較例３
表１に示すように、（Ａ）成分の種類を変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 3
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the type of the component (A) was changed.
比較例４
表１に示すように、（Ｆ）成分を使用しなかった他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 4
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the component (F) was not used.
比較例５
表１に示すように、（Ｃ）成分の種類を変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 5
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the type of the component (C) was changed.
比較例６
表１に示すように、（Ｄ）成分の種類を変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 6
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the type of component (D) was changed.
比較例７
表１に示すように、（Ｄ）成分を使用しなかった他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 7
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the component (D) was not used.
比較例８〜１１
表１に示すように、（Ｆ）成分の種類を変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Examples 8-11
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the type of the component (F) was changed.
比較例１２
表１に示すように、（Ｃ）成分の使用量を５重量％以下に変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 12
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the amount of component (C) used was changed to 5% by weight or less.
比較例１３
表１に示すように、（Ｆ）成分の使用量を３０重量％以上に変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 13
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the amount of the component (F) was changed to 30% by weight or more.
比較例１４
表１に示すように、（Ａ）成分の使用量を４０重量％以上に変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 14
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the amount of component (A) used was changed to 40% by weight or more.
比較例１５
表１に示すように、（Ｂ）成分の使用量を４０重量％以上に変更した他は、実施例１と同様の方法に従い、接着剤組成物を調製した。
Comparative Example 15
As shown in Table 1, an adhesive composition was prepared in the same manner as in Example 1 except that the amount of component (B) used was changed to 40% by weight or more.
表１中の各記号は以下を示す。
Ａ ： 水素添加ポリブタジエンジオール（日本曹達（株）製 、商品名「ＮＩＳＳＯ−ＰＢ ＧＩ−２０００」）
Ａ’ ： 水素添加ポリブタジエン（日本曹達（株）製、商品名「ＮＩＳＳＯ−ＰＢ ＢＩ−２０００」
Ｃ ： ｎ−オクチルアクリレート（大阪有機化学工業（株）製）
Ｃ’ ：ステアリルアクリレート（ＢＡＳＦ社製、商品名「ステアリルアクリレート」）
Ｄ ： ２−ヒドロキシエチルアクリレート（ＢＡＳＦ社製、商品名「ヒドロキシエチルアクリレート」）
Ｄ’ ： ２−ヒドロキシ−３−フェノキシプロピルアクリレート（共栄社化学（株）製、商品名「エポキシエステルＭ−６００Ａ」）
Ｅ ： １−ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製、商品名「イルガキュア１８４」）
Ｍ９０： 水添Ｃ９系石油樹脂（荒川化学工業（株）製、商品名「アルコンＭ−９０」；ガードナー色数１以下、軟化点９０℃、アニリン点８２．９℃）
Ｍ１００：水添Ｃ９系石油樹脂（荒川化学工業（株）製、商品名「アルコンＭ−１００」；ガードナー色数１以下、軟化点１００℃、アニリン点８１．８℃）
Ｆ’１： ロジンエステル（荒川化学工業（株）製、商品名「ＫＥ−３１１」；ガードナー色数１以下、軟化点９０〜１００℃、アニリン点５０℃未満（５０℃まで下げても曇らない））
Ｆ’２： ロジン含有ジオール（荒川化学工業（株）製、商品名「パインクリスタルＤ−６０１１」；ガードナー色数８以下、軟化点８４−９９℃）、アニリン点５０℃未満（５０℃まで下げても曇らない））
Ｆ’３： 水添Ｃ９系石油樹脂（荒川化学工業（株）製、商品名「アルコンＰ−９０」；ガードナー色数１以下、軟化点９０℃、アニリン点１１６．５℃）
Ｆ’４： 水添Ｃ９系石油樹脂（荒川化学工業（株）製、商品名「アルコンＰ−１００」；ガードナー色数１以下、軟化点１００℃、アニリン点１１９．０℃）
Each symbol in Table 1 indicates the following.
A: Hydrogenated polybutadiene diol (manufactured by Nippon Soda Co., Ltd., trade name “NISSO-PB GI-2000”)
A ′: Hydrogenated polybutadiene (manufactured by Nippon Soda Co., Ltd., trade name “NISSO-PB BI-2000”)
C: n-octyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
C ′: Stearyl acrylate (manufactured by BASF, trade name “stearyl acrylate”)
D: 2-hydroxyethyl acrylate (manufactured by BASF, trade name “hydroxyethyl acrylate”)
D ′: 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name “epoxy ester M-600A”)
E: 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by BASF AG)
M90: hydrogenated C9 petroleum resin (Arakawa Chemical Industries, Ltd., trade name "Arkon M90"; Gardner color number of less than 1, a softening point of 90 ° C., aniline point 82.9 ° C.)
M100: Hydrogenated C9 petroleum resin (Arakawa Chemical Industries, trade name “Arcon M-100”; Gardner color number 1 or less , softening point 100 ° C., aniline point 81.8 ° C.)
F′1: Rosin ester (Arakawa Chemical Industries, trade name “KE-311”; Gardner color number 1 or less, softening point 90-100 ° C., aniline point less than 50 ° C. ))
F′2: Rosin-containing diol (Arakawa Chemical Industries, trade name “Pine Crystal D-6011”; Gardner color number 8 or less, softening point 84-99 ° C.), aniline point less than 50 ° C. (down to 50 ° C.) It will not cloud)
F′3: Hydrogenated C9 petroleum resin (Arakawa Chemical Industries, trade name “Arcon P-90”; Gardner color number 1 or less, softening point 90 ° C., aniline point 116.5 ° C.)
F′4: Hydrogenated C9 petroleum resin (Arakawa Chemical Industries, trade name “Arcon P-100”; Gardner color number 1 or less, softening point 100 ° C., aniline point 119.0 ° C.)
実施例１〜９および比較例１〜１５で得られた接着剤組成物の特性（粘度、相溶性）を以下の方法で評価した。結果を表２に示す。 The properties (viscosity and compatibility) of the adhesive compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 15 were evaluated by the following methods. The results are shown in Table 2.
＜粘度＞
ＢＨ型粘度計（東機産業（株）製）により２５℃、３分の条件で測定した。
<Viscosity>
It measured on 25 degreeC and 3-minute conditions with the BH type | mold viscosity meter (made by Toki Sangyo Co., Ltd.).
＜相溶性＞
得られた接着剤組成物を目視で観察し、以下の基準で判断した。
○：均一完全透明
×：白濁、沈降物、不溶解物もしくは液層分離のいずれかを確認
<Compatibility>
The obtained adhesive composition was visually observed and judged according to the following criteria.
○: Uniform and completely transparent ×: Confirmation of white turbidity, sediment, insoluble matter or liquid layer separation
（試験片の作製）
実施例１に係る組成物を、スリットコーターで０．５ｍｍ厚のガラス板に塗工し、０．５ｍｍ厚のガラス板と０．５ｍｍ厚のガラス板の間に、１００μｍの膜厚になるよう貼り合わせた。その後、メタルハライドランプを用いて、照度１５０ｍＪ/ｃｍ２で積算光量が３,０００ｍＪ／ｃｍ２となるように紫外線を照射して、試験片を作成した。実施例２〜９、及び比較例１〜１５に係る組成物についても同様にして、試験片を作製した。
(Preparation of test piece)
The composition according to Example 1 was applied to a 0.5 mm-thick glass plate with a slit coater and bonded to a thickness of 100 μm between the 0.5 mm-thick glass plate and the 0.5 mm-thick glass plate. It was. Thereafter, using a metal halide lamp, a test piece was prepared by irradiating with ultraviolet rays such that the illuminance was 150 mJ / cm 2 and the integrated light quantity was 3000 mJ / cm 2 . Test pieces were prepared in the same manner for the compositions according to Examples 2 to 9 and Comparative Examples 1 to 15.
（接着層の各種評価）
評価例１〜９、比較評価例１〜１５
前記試験片を用いて、以下の試験を実施した。
(Various evaluation of adhesive layer)
Evaluation Examples 1-9, Comparative Evaluation Examples 1-15
The following test was implemented using the said test piece.
＜可視光透過率＞
前記試験片の透過率を、分光光度計（商品名：Ｕ−４１００、（株）日立ハイテクノロジーズ製）を用いて測定した。結果を表３に示す。なお、各透過率は基材であるガラスの値を含めた数値である。
<Visible light transmittance>
The transmittance of the test piece was measured using a spectrophotometer (trade name: U-4100, manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 3. In addition, each transmittance | permeability is a numerical value including the value of the glass which is a base material.
＜貼り合わせ工程での液のはみ出し＞
前記試験片の貼り合わせ工程における液のはみ出しを以下の基準で評価した。結果を表３に示す。
○：試験片側面より液のはみ出しがない場合
×：試験片側面より液のはみ出しがある場合
<Extruding liquid in the bonding process>
The protrusion of the liquid in the test piece bonding step was evaluated according to the following criteria. The results are shown in Table 3.
○: When there is no protrusion of liquid from the side of the test piece ×: When there is protrusion of liquid from the side of the test specimen
＜気泡の混入＞
前記試験片の貼り合わせ工程における気泡の混入を以下の基準で評価した。結果を表３に示す。
○：気泡の巻き込みによる混入がない場合
×：気泡の巻き込みによる混入がある場合
<Bubble contamination>
The mixing of bubbles in the test piece bonding step was evaluated according to the following criteria. The results are shown in Table 3.
○: When there is no contamination due to entrainment of bubbles ×: When there is contamination due to entrainment of bubbles
＜硬化物の硬度＞
実施例１に係る組成物を内径５５．０ｍｍ、高さ１０ｍｍのガラス製の容器に１５ｇ流し込み、照度１５０ｍＪ/ｃｍ２で積算光量が３，０００ｍＪ／ｃｍ２となるように紫外線を照射して硬化させた。得られた硬化物は２５℃で２４時間保管後、ゴム硬度計（商品名：アスカーゴム硬度計Ｃ２型 高分子計器（株）製）を用いて硬度を測定した。実施例２〜９、及び比較例１〜１５に係る組成物についても同様にして、試験片を作製し、硬度を測定した。結果を表３に示す。
<Hardness of cured product>
Composition an inner diameter 55.0mm according to Example 1, poured 15g in a glass container height 10 mm, hardened integrated quantity of light at an intensity 150 mJ / cm 2 was irradiated with ultraviolet rays so that the 3,000 mJ / cm 2 I let you. After the obtained cured product was stored at 25 ° C. for 24 hours, the hardness was measured using a rubber hardness meter (trade name: Asker Rubber Hardness Meter Model C2 manufactured by Kobunshi Keiki Co., Ltd.). Test pieces were prepared in the same manner for the compositions according to Examples 2 to 9 and Comparative Examples 1 to 15, and the hardness was measured. The results are shown in Table 3.
＜硬化物の弾性率＞
実施例１に係る組成物を厚さ２ｍｍとなるようガラス製の容器に流し込み、メタルハライドランプを用いて、照度１５０ｍＪ/ｃｍ２で積算光量が３，０００ｍＪ／ｃｍ２となるように紫外線を照射して硬化させた。得られた硬化物について、ＪＩＳ Ｋ ７３１２で定める成型物の物理試験方法に準拠して評価した。試験片は２号形ダンベル試験片として、精密万能試験機（(株）島津製作所製 オートグラフ ＡＧＳ−Ｘ)を用いて引張速度５００ｍｍ／分で弾性率を測定した。実施例２〜９、及び比較例１〜１５に係る組成物についても同様にして、試験片を作製し、弾性率を測定した。結果を表３に示す。
<Elastic modulus of cured product>
Poured into a glass container such that a thickness of 2mm the composition according to Example 1, by using a metal halide lamp, the integrated quantity of light at an intensity 150 mJ / cm 2 was irradiated with ultraviolet rays so that the 3,000 mJ / cm 2 And cured. About the obtained hardened | cured material, it evaluated based on the physical test method of the molding defined by JISK7312. The test piece was a No. 2 dumbbell test piece, and the elastic modulus was measured at a tensile speed of 500 mm / min using a precision universal testing machine (Autograph AGS-X, manufactured by Shimadzu Corporation). Test pieces were prepared in the same manner for the compositions according to Examples 2 to 9 and Comparative Examples 1 to 15, and the elastic modulus was measured. The results are shown in Table 3.
＜体積収縮率（成型収縮率法）＞
実施例１に係る組成物を内径６６．０ｍｍ、高さ８ｍｍのガラス製の容器に１０ｇ流し込み、照度１５０ｍＪ/ｃｍ２で積算光量が３，０００ｍＪ／ｃｍ２となるように紫外線を照射して硬化させた。硬化物は２５℃で２４時間保管後にアルキメデス法により体積の測定を行った。実施例２〜９、及び比較例１〜１５に係る組成物についても同様にして、試験片を作製し、体積収縮率を測定した。結果を表３に示す。なお、該収縮率は以下の式１を用いて算出した。
（式１）｛（硬化物の体積−硬化前の液状物の体積）／硬化前の液状物の体積｝×１００
<Volume shrinkage (molding shrinkage method)>
Composition an inner diameter 66.0mm according to Example 1, poured 10g in a glass container height 8 mm, hardened integrated quantity of light at an intensity 150 mJ / cm 2 was irradiated with ultraviolet rays so that the 3,000 mJ / cm 2 I let you. The volume of the cured product was measured by Archimedes method after being stored at 25 ° C. for 24 hours. Test pieces were prepared in the same manner for the compositions according to Examples 2 to 9 and Comparative Examples 1 to 15, and the volume shrinkage was measured. The results are shown in Table 3. The shrinkage was calculated using the following formula 1.
(Formula 1) {(Volume of cured product−Volume of liquid before curing) / Volume of liquid before curing} × 100
（積層体の信頼性評価）
＜耐熱試験＞
前記試験片を温度９５℃の恒温恒湿槽中に５００時間静置した後、透過率を前記と同様の方法で測定し、併せて耐久性および耐黄変性について以下の基準で評価した。これらの結果を表４に示す。なお、各透過率は基材であるガラスの値を含めた数値である。
・耐久性の評価基準
○：剥がれなし、接着層浸み出しなし、気泡および破損なし
×：剥がれあり、接着層浸み出しあり、気泡および破損あり
・耐黄変性の評価基準
○：黄変なし ×：黄変あり
(Reliability evaluation of laminates)
<Heat resistance test>
The test piece was allowed to stand in a constant temperature and humidity chamber at a temperature of 95 ° C. for 500 hours, and then the transmittance was measured by the same method as described above, and durability and yellowing resistance were evaluated according to the following criteria. These results are shown in Table 4. In addition, each transmittance | permeability is a numerical value including the value of the glass which is a base material.
Durability evaluation criteria ○: No peeling, no adhesion layer oozing, no bubbles and damage ×: Peeling, adhesion layer oozing, bubbles and damage · Yellowing resistance evaluation criteria ○: No yellowing ×: yellowing
＜耐湿熱試験＞
前記試験片を温度８５℃、湿度８５％の恒温恒湿槽中に５００時間静置した後、透過率を前記と同様の方法で測定し、併せて耐久性および耐白化性について以下の基準で評価した。これらの結果を表４に示す。
・耐久性の評価基準
○：剥がれなし、粘着層浸み出しなし、気泡および破損なし
×：剥がれあり、粘着層浸み出しあり、気泡および破損あり
・耐白化性の評価基準
○：白化なし ×：白化あり
<Moisture and heat resistance test>
After leaving the test piece in a constant temperature and humidity chamber having a temperature of 85 ° C. and a humidity of 85% for 500 hours, the transmittance was measured by the same method as described above, and the durability and whitening resistance were measured according to the following criteria. evaluated. These results are shown in Table 4.
・ Evaluation criteria for durability ○: No peeling, no adhesion layer leaching, no bubbles and damage ×: Peeling, adhesion layer leaching, bubbles and damage ・ Whitening resistance evaluation criteria ○: No whitening × : Whitening
＜ヒートサイクル試験＞
前記試験片を−４０℃と８５℃（各３０分）で５００サイクル繰返した後、透過率を前記と同様の方法で測定し、併せて耐久性について以下の基準で評価した。これらの結果を表４に示す。
・耐久性の評価基準
○：剥がれなし、接着層浸み出しなし、気泡および破損なし
×：剥がれあり、接着層浸み出しあり、気泡および破損あり
<Heat cycle test>
After the test piece was repeated 500 cycles at −40 ° C. and 85 ° C. (each 30 minutes), the transmittance was measured by the same method as above, and the durability was evaluated according to the following criteria. These results are shown in Table 4.
Durability evaluation criteria ○: No peeling, no adhesion layer oozing, no bubbles and damage ×: peeling, adhesion layer oozing, bubbles and damage
表３および表４の評価結果より、本発明に係る各実施例は、各比較例と対比して有意に優れることが分かる。すなわち、各実施例においては、（Ａ）成分、（Ｄ）成分、および（Ｆ）成分を組み合わせることにより耐白化性が向上すること、また（Ａ）成分と（Ｆ）成分は、熱衝撃および外部衝撃に対する緩衝性を向上させること、更に（Ｂ）、（Ｃ）、（Ｅ）成分と組み合わせることで高温下、高温高湿下の耐久性、耐黄変性、耐白化性、緩衝性に優れる光学用紫外線硬化型接着剤組成物が得られることを、それぞれ確認した。
From the evaluation results in Table 3 and Table 4, it can be seen that each Example according to the present invention is significantly superior to each Comparative Example. That is, in each example, the whitening resistance is improved by combining the (A) component, the (D) component, and the (F) component, and the (A) component and the (F) component Improves shock-absorbing properties against external impacts, and in combination with components (B), (C), and (E), excels in durability at high temperatures, high temperatures and high humidity, yellowing resistance, whitening resistance, and buffering properties. It was confirmed that an ultraviolet curable adhesive composition for optics was obtained.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014093277A JP6270145B2 (en) | 2014-04-30 | 2014-04-30 | UV curable adhesive composition for optics, the cured layer and optical member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014093277A JP6270145B2 (en) | 2014-04-30 | 2014-04-30 | UV curable adhesive composition for optics, the cured layer and optical member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015209520A JP2015209520A (en) | 2015-11-24 |
| JP6270145B2 true JP6270145B2 (en) | 2018-01-31 |
Family
ID=54611980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014093277A Active JP6270145B2 (en) | 2014-04-30 | 2014-04-30 | UV curable adhesive composition for optics, the cured layer and optical member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6270145B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6471527B2 (en) * | 2015-02-17 | 2019-02-20 | 協立化学産業株式会社 | Manufacturing method of laminate |
| JP6712459B2 (en) * | 2015-11-19 | 2020-06-24 | アイカ工業株式会社 | Photocurable resin composition |
| CN108137762A (en) * | 2015-12-22 | 2018-06-08 | 日本合成化学工业株式会社 | Actinic energy ray curable resion composition and its manufacturing method |
| JP6825815B2 (en) * | 2016-02-29 | 2021-02-03 | アイカ工業株式会社 | Visibility-enhancing resin composition |
| JP6697306B2 (en) * | 2016-03-31 | 2020-05-20 | ハリマ化成株式会社 | Photocurable composition with moisture curing, conformal coating agent and cured product |
| WO2019016963A1 (en) * | 2017-07-21 | 2019-01-24 | 日本化薬株式会社 | Ultraviolet curable adhesive, and lamination method and article using same |
| WO2019093157A1 (en) * | 2017-11-13 | 2019-05-16 | 日本化薬株式会社 | Ultraviolet-curable adhesive composition, cured product thereof, and method for producing optical member using ultraviolet-curable adhesive composition |
| JPWO2019208517A1 (en) * | 2018-04-23 | 2021-05-20 | 日本化薬株式会社 | A method for manufacturing an ultraviolet curable adhesive composition, a cured product thereof, and an optical member. |
| JP2021192094A (en) * | 2020-06-02 | 2021-12-16 | 住友化学株式会社 | Curable composition and polarization plate |
| KR20230140387A (en) | 2022-03-29 | 2023-10-06 | 아라까와 가가꾸 고교 가부시끼가이샤 | Active energy ray-curable adhesive composition, cured product and adhesive sheet |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0625214B2 (en) * | 1987-07-30 | 1994-04-06 | 丸善石油化学株式会社 | Manufacturing method of hydrogenated petroleum resin |
| JPH05275842A (en) * | 1992-03-30 | 1993-10-22 | Techno Sunstar Kk | Method for temporarily bonding surface mounting component |
| JP2006008947A (en) * | 2004-06-29 | 2006-01-12 | Sekisui Chem Co Ltd | Hot melt adhesive |
| JP5647091B2 (en) * | 2011-10-27 | 2014-12-24 | 電気化学工業株式会社 | Curable composition for surface protection |
| TWI484013B (en) * | 2012-03-12 | 2015-05-11 | Showa Denko Kk | A polymerizable composition, a polymer, an image display device, and a method for manufacturing the same |
| TWI510550B (en) * | 2012-06-15 | 2015-12-01 | Showa Denko Kk | Polymerizable composition, polymer, optical adhesive sheet, image display device, and manufacturing method thereof |
-
2014
- 2014-04-30 JP JP2014093277A patent/JP6270145B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015209520A (en) | 2015-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6270145B2 (en) | UV curable adhesive composition for optics, the cured layer and optical member | |
| JP6414479B2 (en) | UV curable adhesive composition for optics, the cured layer and optical member | |
| TWI512075B (en) | Composition of photohardenable transparent adhesive sheet | |
| JP6820705B2 (en) | Adhesive sheets, display bodies and their manufacturing methods | |
| JP2017075281A (en) | Adhesive sheet and display body | |
| JP2017122213A (en) | Acrylate-terminated urethane polybutadienes from low-monomer 1:1 monoadducts from reactive olefinic compounds and diisocyanates and hydroxy-terminated polybutadienes for liquid optically clear adhesives (locas) | |
| JP5847724B2 (en) | adhesive | |
| JP6660710B2 (en) | Solventless pressure-sensitive adhesive composition, pressure-sensitive adhesive, pressure-sensitive adhesive sheet and display | |
| JP6620092B2 (en) | UV curable resin composition for touch panel, laminating method and article using the same | |
| TWI577770B (en) | An ultraviolet hardening type transparent adhesive | |
| JP2018076456A (en) | Adhesive composition and adhesive sheet | |
| JP6722584B2 (en) | Ultraviolet curable resin composition for touch panel, bonding method and article using the same | |
| JP6625534B2 (en) | UV curable adhesive composition for touch panel and article | |
| JP2018127561A (en) | Adhesive sheet | |
| WO2015190552A1 (en) | Uv-curable resin composition for use in touchscreen, and bonding method and article using said uv-curable resin | |
| JP6712459B2 (en) | Photocurable resin composition | |
| JP6805014B2 (en) | Adhesive sheet | |
| JP2015218324A (en) | Acrylic adhesive composition for optically functional material, adhesive, adhesive sheet, display device, and method for producing the device | |
| JP6894686B2 (en) | Adhesive Compositions, Adhesives, Adhesive Sheets and Labels | |
| TWI793226B (en) | Adhesives, Adhesive Sheets and Displays | |
| JP2016199663A (en) | Ultraviolet-curable adhesive composition and adhesive sheet | |
| TW202012567A (en) | Photocurable adhesive sheet, adhesive sheet laminate, laminate for image display device, and image display device | |
| JP2021098869A (en) | Active energy ray-curable adhesive sheet and laminate | |
| JPWO2015190571A1 (en) | UV curable resin composition for touch panel, laminating method and article using the same | |
| WO2023100866A1 (en) | Adhesive sheet and method for manufacturing adhesive sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20170124 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170201 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20170125 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170306 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20171006 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171012 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171129 |
|
| 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: 20171208 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171221 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6270145 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |