JPWO2013183532A1 - Resin composition for coating material - Google Patents
Resin composition for coating material Download PDFInfo
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- JPWO2013183532A1 JPWO2013183532A1 JP2014519956A JP2014519956A JPWO2013183532A1 JP WO2013183532 A1 JPWO2013183532 A1 JP WO2013183532A1 JP 2014519956 A JP2014519956 A JP 2014519956A JP 2014519956 A JP2014519956 A JP 2014519956A JP WO2013183532 A1 JPWO2013183532 A1 JP WO2013183532A1
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- group
- resin composition
- meth
- component
- atom
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- 239000011342 resin composition Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 45
- -1 dinaphthothiophene compound Chemical class 0.000 claims abstract description 37
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- 125000004429 atom Chemical group 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- LVJFCQSYEZPHJO-UHFFFAOYSA-N 12-thiapentacyclo[11.8.0.02,11.03,8.014,19]henicosa-1(13),2(11),3(8),4,6,9,14,16,18,20-decaen-4-ylmethyl prop-2-enoate Chemical compound C(C=C)(=O)OCC1=CC=CC=2C=CC3=C(C4=C(S3)C=3C=CC=CC3C=C4)C12 LVJFCQSYEZPHJO-UHFFFAOYSA-N 0.000 claims description 6
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- MJDOQXICWBBRJC-UHFFFAOYSA-N 2-(12-thiapentacyclo[11.8.0.02,11.03,8.014,19]henicosa-1(13),2(11),3(8),4,6,9,14,16,18,20-decaen-4-yl)ethyl prop-2-enoate Chemical compound C(C=C)(=O)OCCC1=CC=CC=2C=CC3=C(C4=C(S3)C=3C=CC=CC=3C=C4)C1=2 MJDOQXICWBBRJC-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 229930192474 thiophene Natural products 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000007870 radical polymerization initiator Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- SYXXZXWLYNODHL-UHFFFAOYSA-N dinaphthothiophene Chemical group C1=CC=CC2=C(C3=C(C4=CC=CC=C4C=C3)S3)C3=CC=C21 SYXXZXWLYNODHL-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 241000511976 Hoya Species 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- SQWIEBKHVLRDRG-UHFFFAOYSA-N (2,6-dimethylphenyl)-diphenylphosphorylmethanone Chemical compound CC1=CC=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 SQWIEBKHVLRDRG-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- YTWSMYGVWSAPGB-UHFFFAOYSA-N 10-ethenyl-12-thiapentacyclo[11.8.0.02,11.03,8.014,19]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaene Chemical compound C(=C)C1=CC=2C=CC=CC=2C=2C3=C(SC=21)C=1C=CC=CC=1C=C3 YTWSMYGVWSAPGB-UHFFFAOYSA-N 0.000 description 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 238000000018 DNA microarray Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- IEWRMZSVIVEQCP-UHFFFAOYSA-N [methoxy(phenyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(OC)C(=O)C1=C(C)C=C(C)C=C1C IEWRMZSVIVEQCP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000919 ceramic Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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 1
- KWVVOKMSNYUZCL-UHFFFAOYSA-N (2,4-dimethylbenzoyl)-phenylphosphinic acid Chemical compound CC1=CC(C)=CC=C1C(=O)P(O)(=O)C1=CC=CC=C1 KWVVOKMSNYUZCL-UHFFFAOYSA-N 0.000 description 1
- QAWHMCKOUTZPAL-UHFFFAOYSA-N (2,6-dibromophenyl)-diphenylphosphorylmethanone Chemical compound BrC1=CC=CC(Br)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 QAWHMCKOUTZPAL-UHFFFAOYSA-N 0.000 description 1
- JLLAWIKMLAQZCZ-UHFFFAOYSA-N (2,6-dichlorophenyl)-diphenylphosphorylmethanone Chemical compound ClC1=CC=CC(Cl)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 JLLAWIKMLAQZCZ-UHFFFAOYSA-N 0.000 description 1
- PYIMUNFRJFKRDE-UHFFFAOYSA-N (2,6-dimethoxyphenyl)-[methoxy(phenyl)phosphoryl]methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(OC)C1=CC=CC=C1 PYIMUNFRJFKRDE-UHFFFAOYSA-N 0.000 description 1
- ZTESOBUXHNQNGT-UHFFFAOYSA-N (2,6-dimethylphenyl)-diphenylphosphanylmethanone Chemical compound CC1=CC=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 ZTESOBUXHNQNGT-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- QWHUYUGHATYPGB-UHFFFAOYSA-N 1-[methoxy(methyl)phosphoryl]-2-methylpropan-1-one Chemical compound COP(C)(=O)C(=O)C(C)C QWHUYUGHATYPGB-UHFFFAOYSA-N 0.000 description 1
- MFULLOGPOIYABI-UHFFFAOYSA-N 1-[methoxy(phenyl)phosphoryl]-2-methylpropan-1-one Chemical compound CC(C)C(=O)P(=O)(OC)C1=CC=CC=C1 MFULLOGPOIYABI-UHFFFAOYSA-N 0.000 description 1
- QTFWVMNQFWUOOH-UHFFFAOYSA-N 1-diphenylphosphoryl-2,2-dimethylheptan-1-one Chemical compound C=1C=CC=CC=1P(=O)(C(=O)C(C)(C)CCCCC)C1=CC=CC=C1 QTFWVMNQFWUOOH-UHFFFAOYSA-N 0.000 description 1
- PIOUPIXFXCOVGD-UHFFFAOYSA-N 1-diphenylphosphoryl-2-ethylhexan-1-one Chemical compound C=1C=CC=CC=1P(=O)(C(=O)C(CC)CCCC)C1=CC=CC=C1 PIOUPIXFXCOVGD-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-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
- XXHDHAPOSIFMIG-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCC(O)OC1=CC=CC=C1 XXHDHAPOSIFMIG-UHFFFAOYSA-N 0.000 description 1
- OBFOSROPNNOGQF-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCCOCCOCC(O)OC1=CC=CC=C1 OBFOSROPNNOGQF-UHFFFAOYSA-N 0.000 description 1
- YCPMSWJCWKUXRH-UHFFFAOYSA-N 2-[4-[9-[4-(2-prop-2-enoyloxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethyl prop-2-enoate Chemical compound C1=CC(OCCOC(=O)C=C)=CC=C1C1(C=2C=CC(OCCOC(=O)C=C)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YCPMSWJCWKUXRH-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- PGJKTKAYCLVULZ-UHFFFAOYSA-N 2-methylbut-2-enoic acid prop-2-enoic acid Chemical compound OC(=O)C=C.CC=C(C)C(O)=O PGJKTKAYCLVULZ-UHFFFAOYSA-N 0.000 description 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PMGJMVAMSUFURL-UHFFFAOYSA-N 5,20-bis(ethenyl)-12-thiapentacyclo[11.8.0.02,11.03,8.014,19]henicosa-1(13),2(11),3(8),4,6,9,14,16,18,20-decaene Chemical compound C(=C)C=1C=CC=2C=CC3=C(C4=C(S3)C=3C=CC=CC=3C(=C4)C=C)C=2C=1 PMGJMVAMSUFURL-UHFFFAOYSA-N 0.000 description 1
- VEHGWOMBMHXNOH-UHFFFAOYSA-N 6,18-bis(ethenyl)-12-thiapentacyclo[11.8.0.02,11.03,8.014,19]henicosa-1(13),2(11),3(8),4,6,9,14,16,18,20-decaene Chemical compound C(=C)C1=CC=2C=CC3=C(C4=C(S3)C=3C=CC=C(C=3C=C4)C=C)C=2C=C1 VEHGWOMBMHXNOH-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SRDIKKIBPZKIOO-UHFFFAOYSA-N C(=C)C1=CC2=C(C3=C(S2)C=2C=C(C=CC=2C=C3)C=C)C=2C=CC=CC1=2 Chemical compound C(=C)C1=CC2=C(C3=C(S2)C=2C=C(C=CC=2C=C3)C=C)C=2C=CC=CC1=2 SRDIKKIBPZKIOO-UHFFFAOYSA-N 0.000 description 1
- VVKBLKAHEULGSW-UHFFFAOYSA-N C(=C)OC1=CC=2C=CC3=C(C4=C(S3)C=3C=CC=C(C=3C=C4)OC=C)C=2C=C1 Chemical compound C(=C)OC1=CC=2C=CC3=C(C4=C(S3)C=3C=CC=C(C=3C=C4)OC=C)C=2C=C1 VVKBLKAHEULGSW-UHFFFAOYSA-N 0.000 description 1
- XPOTZJLKYZYZQX-UHFFFAOYSA-N C(C(=C)C)(=O)OCC1=CC=2C=CC=CC=2C=2C3=C(SC=21)C=1C=CC=CC=1C=C3 Chemical compound C(C(=C)C)(=O)OCC1=CC=2C=CC=CC=2C=2C3=C(SC=21)C=1C=CC=CC=1C=C3 XPOTZJLKYZYZQX-UHFFFAOYSA-N 0.000 description 1
- DMTLQBISMSUAEG-UHFFFAOYSA-N C(C(=C)C)(=O)OCCC1=CC=2C=CC=CC2C=2C3=C(SC21)C=2C=CC=CC2C=C3 Chemical compound C(C(=C)C)(=O)OCCC1=CC=2C=CC=CC2C=2C3=C(SC21)C=2C=CC=CC2C=C3 DMTLQBISMSUAEG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/38—Esters containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/06—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 a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F28/00—Homopolymers and 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 a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F28/06—Homopolymers and 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 a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
Abstract
高い屈折率と高い透明性を有し且つ溶剤の使用が不要である被覆材用樹脂組成物を提供する。本発明によれば、（１）（Ａ）成分として、エチレン性不飽和二重結合を有する重合性官能基を１つ以上有する特定のジナフトチオフェン系化合物、（Ｂ）成分として、１つ以上の芳香環を含有する単官能（メタ）アクリレート、（Ｃ）成分として、光ラジカル重合開始剤、を含有し、前記（Ａ）成分の含有割合が１５〜６０質量部の範囲であり、前記（Ｂ）成分の含有割合が４０〜８５質量部の範囲であることを特徴とする被覆材用樹脂組成物が提供される。Provided is a resin composition for a coating material which has a high refractive index and high transparency and does not require the use of a solvent. According to the present invention, (1) a specific dinaphthothiophene compound having one or more polymerizable functional groups having an ethylenically unsaturated double bond as component (A), and one or more as component (B) A monofunctional (meth) acrylate containing an aromatic ring, a photo-radical polymerization initiator as the component (C), the content ratio of the component (A) being in the range of 15 to 60 parts by mass, B) The resin composition for coating | covering materials characterized by the content rate of a component being the range of 40-85 mass parts is provided.
Description
本発明は、各種センサー素子、表示素子等に用いられる被覆材用樹脂組成物に関し、さらには反射防止膜や光導波路膜の高屈折率層に用いられる高屈折率樹脂組成物に関する。 The present invention relates to a resin composition for a coating material used for various sensor elements, display elements and the like, and further relates to a high refractive index resin composition used for a high refractive index layer of an antireflection film or an optical waveguide film.
従来、ＣＣＤ、ＣＭＯＳ等のセンサー素子や、ディスプレイ等の表示素子に用いられるガラス、フィルムおよびシートの表面には、表面を保護する目的で、無機物又は有機物からなる被覆層が設けられる。さらに、近年では、前記の表面保護層に、反射防止や光導波等の機能を付与する目的で高屈折率層と低屈折率層を交互に積層した被覆層等が用いられている。この高屈折率層には、チタニア、ジルコニアおよびアルミナといったセラミックスを蒸着等により形成した高屈折率無機膜や、ビスフェノールＡ型エポキシ（メタ）アクリレートやウレタン（メタ）アクリレート等のラジカル重合性モノマーを配合し、塗布後に紫外線等のエネルギー線を照射して硬化膜とする高屈折率有機膜とが目的に応じて用いられているが、前者の無機膜では基材がフィルムやシートの場合に、密着性が不足したり、膜が脆く、フィルムを曲げた際に割れてしまったりする等の課題があり、近年ではラジカル重合性モノマーを配合した光硬化型の高屈折率有機膜が広く使用されるようになっている。 Conventionally, on the surfaces of glass, films and sheets used for sensor elements such as CCD and CMOS, and display elements such as displays, a coating layer made of an inorganic substance or an organic substance is provided for the purpose of protecting the surface. Furthermore, in recent years, a covering layer in which high refractive index layers and low refractive index layers are alternately stacked is used for the purpose of imparting functions such as antireflection and optical waveguide to the surface protective layer. This high refractive index layer contains a high refractive index inorganic film formed by vapor deposition of ceramics such as titania, zirconia and alumina, and radical polymerizable monomers such as bisphenol A type epoxy (meth) acrylate and urethane (meth) acrylate. However, the high-refractive-index organic film that is cured by irradiating energy rays such as ultraviolet rays after coating is used according to the purpose, but the former inorganic film is in close contact when the substrate is a film or sheet. In recent years, photocurable high-refractive-index organic films blended with radically polymerizable monomers have been widely used. It is like that.
反射防止膜や光導波路膜に用いられる高屈折率層に適用可能な高屈折率を有する樹脂組成物としては、例えば特許文献１〜３には、硫黄含有（メタ）アクリレートを用いた樹脂組成物および光硬化性樹脂組成物が公知である。また例えば特許文献４には、ジフェニルスルフォン構造を有するウレタン（メタ）アクリレートを用いた活性エネルギー線硬化性組成物が開示されている。 As a resin composition having a high refractive index applicable to a high refractive index layer used for an antireflection film or an optical waveguide film, for example, in Patent Documents 1 to 3, a resin composition using a sulfur-containing (meth) acrylate is used. Also known are photocurable resin compositions. Further, for example, Patent Document 4 discloses an active energy ray-curable composition using urethane (meth) acrylate having a diphenyl sulfone structure.
しかしながら、前記の特許文献に記載の主成分である、硫黄含有（メタ）アクリレートや、ジフェニルスルフォン構造を有するウレタン（メタ）アクリレートでは、４，４'−ジメルカプトジフェニルサルファイドジメタクリレートは、ビスフェノールＡ型エポキシ（メタ）アクリレート等の芳香環を有する化合物よりは高い屈折率を有してはいるものの、これら化合物は一般に波長４５０ｎｍ以下の光を吸収するため、黄色く着色し透明性が低下しやすい、フィルムと密着しにくいという課題があった。 However, in the case of sulfur-containing (meth) acrylate and urethane (meth) acrylate having a diphenylsulfone structure, which are the main components described in the above-mentioned patent documents, 4,4′-dimercaptodiphenyl sulfide dimethacrylate is a bisphenol A type. Although it has a higher refractive index than a compound having an aromatic ring such as epoxy (meth) acrylate, these compounds generally absorb light with a wavelength of 450 nm or less, so they are colored yellow and the transparency tends to decrease. There was a problem that it was difficult to adhere to.
前記の様な課題に対して高い屈折率と高い透明性を有する化合物として特許文献５にジナフトチオフェン骨格を有する化合物および重合体が開示されている。特許文献５の実施例では、エチレン性不飽和二重結合を有するジナフトチオフェンを用いた光重合性組成物を、酢酸エチル等の溶剤を用いて希釈して作成した光硬化膜が開示されている（段落番号[０１４３]）。しかしながら、残存溶剤の影響で強度の低下や、アウトガス発生の要因となり、良好な信頼性を得ることができなかったり、あるいは長時間保存した場合等に結晶性の成分が組成物中に析出しやすく、屈折率が変動したり、塗布できなくなったりするといった欠点があった。 As a compound having a high refractive index and high transparency with respect to the above problems, Patent Document 5 discloses a compound and a polymer having a dinaphthothiophene skeleton. In Examples of Patent Document 5, a photocured film prepared by diluting a photopolymerizable composition using dinaphthothiophene having an ethylenically unsaturated double bond with a solvent such as ethyl acetate is disclosed. (Paragraph number [0143]). However, due to the influence of the residual solvent, it may cause a decrease in strength and outgassing, and good reliability cannot be obtained, or crystalline components tend to precipitate in the composition when stored for a long time. , The refractive index fluctuates and the coating cannot be performed.
本発明はこのような事情に鑑みてなされたものであり、高い屈折率と高い透明性を有し且つ溶剤の使用が不要である被覆材用樹脂組成物を提供するものである。 This invention is made | formed in view of such a situation, and provides the resin composition for coating | covering materials which has a high refractive index and high transparency, and does not require the use of a solvent.
本発明によれば、
（１）（Ａ）成分として、下記一般式（１）で表されるエチレン性不飽和二重結合を有する重合性官能基を１つ以上有するジナフトチオフェン系化合物、
（Ｂ）成分として、１つ以上の芳香環を含有する単官能（メタ）アクリレート、
（Ｃ）成分として、光ラジカル重合開始剤、
を含有し、組成物の総量に対して、前記（Ａ）成分の含有割合は１５〜６０質量部の範囲であり、前記（Ｂ）成分の含有割合は４０〜８５質量部の範囲であることを特徴とする被覆材用樹脂組成物が提供される。According to the present invention,
(1) As a component (A), a dinaphthothiophene compound having one or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1):
(B) As a component, a monofunctional (meth) acrylate containing one or more aromatic rings,
(C) As a component, radical photopolymerization initiator,
The content ratio of the component (A) is in the range of 15 to 60 parts by mass, and the content ratio of the component (B) is in the range of 40 to 85 parts by mass with respect to the total amount of the composition. A resin composition for a coating material is provided.
本発明者らは、被覆材用樹脂組成物に適した組成物を得るべく鋭意検討を行なっていたところ、上記一般式（１）に示すようなジナフトチオフェン系化合物は、溶媒を用いずに、特許文献５の［０１４３］に記載のような多官能エポキシアクリレート及び光ラジカル重合開始剤と混合すると、しばらく静置した後に、容易に溶解しない析出物が発生し、被覆材用樹脂組成物として利用することが難しいことが分かった（比較例２）。そこで、このような問題を解決すべく、さらに検討を進めたところ、多官能エポキシアクリレートの代わりに、１つ以上の芳香環を含有する単官能（メタ）アクリレートを用いた場合には、このような析出物や分離物が発生しないか、発生しても容易に溶解可能であることが分かった。さらに、芳香環を含有する単官能（メタ）アクリレートの代わりに、芳香環を有するが（メタ）アクリレートではない化合物を用いた場合（比較例３）、光照射を行なっても十分に硬化が起こらず、被覆材用樹脂組成物としての利用が困難であることが分かった。さらに、芳香環を有さない単官能（メタ）アクリレートを用いた場合（比較例４）、容易に溶解しない析出物が発生してしまった。
また、重合性官能基を有するジナフトチオフェン系化合物の代わりに、このような官能基を有さないジナフトチオフェン系化合物を用いた場合（比較例５）、容易に溶解しない析出物が発生してしまった。さらに、ジナフトチオフェン系化合物を用いなかった場合（比較例１）、屈折率が低くなってしまった。
以上より、重合性官能基を有するジナフトチオフェン系化合物と、芳香環を含有する単官能（メタ）アクリレートと、光ラジカル重合開始剤との組み合わせによる相乗効果によって、高い屈折率と高い透明性を有し且つ溶剤の使用が不要である被覆材用樹脂組成物が得られることが分かった。The present inventors have intensively studied to obtain a composition suitable for the resin composition for a coating material. As a result, the dinaphthothiophene compound as shown in the general formula (1) does not use a solvent. When mixed with a polyfunctional epoxy acrylate and a radical photopolymerization initiator as described in [0143] of Patent Document 5, a precipitate that does not easily dissolve is generated after standing for a while, as a resin composition for a coating material. It was found that it was difficult to use (Comparative Example 2). Accordingly, further investigations have been made to solve such problems. When a monofunctional (meth) acrylate containing one or more aromatic rings is used in place of the polyfunctional epoxy acrylate, this is the case. It was found that no precipitates or separations were generated, or even if generated, they could be easily dissolved. Further, when a compound having an aromatic ring but not (meth) acrylate is used instead of a monofunctional (meth) acrylate containing an aromatic ring (Comparative Example 3), sufficient curing occurs even when light irradiation is performed. Therefore, it was found that it was difficult to use as a resin composition for a coating material. Furthermore, when a monofunctional (meth) acrylate having no aromatic ring was used (Comparative Example 4), a precipitate that was not easily dissolved was generated.
Further, when a dinaphthothiophene compound having no functional group is used instead of the dinaphthothiophene compound having a polymerizable functional group (Comparative Example 5), a precipitate that does not easily dissolve is generated. I have. Furthermore, when a dinaphthothiophene compound was not used (Comparative Example 1), the refractive index was low.
From the above, high refractive index and high transparency are achieved by the synergistic effect of the combination of a dinaphthothiophene compound having a polymerizable functional group, a monofunctional (meth) acrylate containing an aromatic ring, and a photo radical polymerization initiator. It has been found that a resin composition for a coating material that has a solvent and does not require the use of a solvent is obtained.
好ましくは、前記（Ｂ）成分は、１つの芳香環を含有する単官能（メタ）アクリレートである。
好ましくは、前記（Ｂ）成分が、ベンジル（メタ）アクリレート及びフェノキシエチル（メタ）アクリレートから選ばれる１つ以上を含む。
好ましくは、前記重合性官能基は、（メタ）アクリロイル基又はアリルエーテル基である。
好ましくは、前記一般式（１）において、ａ＝ｂ＝ｃ＝０であり、ｄ＝１である。
好ましくは、前記（Ａ）成分は、６−（メタ）アクリロイルメチルジナフトチオフェン、６−（メタ）アクリロイルエチルジナフトチオフェン、２，１２−ジアリルエーテルジナフトチオフェン、及び３，１１−ジアリルエーテルジナフトチオフェンから選ばれる１つ以上を含む。
好ましくは、前記（Ｃ）成分の含有割合は、組成物の総量に対して、０．２〜１０質量部である。Preferably, the component (B) is a monofunctional (meth) acrylate containing one aromatic ring.
Preferably, the component (B) includes one or more selected from benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
Preferably, the polymerizable functional group is a (meth) acryloyl group or an allyl ether group.
Preferably, in the general formula (1), a = b = c = 0 and d = 1.
Preferably, the component (A) is 6- (meth) acryloylmethyldinaphthothiophene, 6- (meth) acryloylethyldinaphthothiophene, 2,12-diallyl ether dinaphthothiophene, and 3,11-diallyl etherdi. Including one or more selected from naphthothiophene.
Preferably, the content ratio of the component (C) is 0.2 to 10 parts by mass with respect to the total amount of the composition.
また、本発明の別の観点によれば、上記記載の被覆材用樹脂組成物からなることを特徴とする被覆材、及びこの被覆材を形成した基材(例：ガラス、フィルム又はシート）が提供される。 According to another aspect of the present invention, there is provided a covering material comprising the above-described resin composition for a covering material, and a base material (eg, glass, film or sheet) on which the covering material is formed. Provided.
また、本発明のさらに別の観点によれば、上記記載の被覆材用樹脂組成物からなる層を基板上に形成したのちに、前記の被覆材用樹脂組成物より低い屈折率を有する層を形成してなること特徴とする膜（例：反射防止膜又は光導波路膜）、このような膜を有する基材、及びこのような基材を有する素子（例：センサー素子又は表示素子）が提供される。 According to still another aspect of the present invention, a layer having a refractive index lower than that of the above-mentioned resin composition for a coating material is formed after a layer made of the above-described resin composition for a coating material is formed on a substrate. Provided is a film formed by being formed (eg, an antireflection film or an optical waveguide film), a base material having such a film, and an element (eg, sensor element or display element) having such a base material Is done.
本発明の樹脂組成物は、重合性官能基を有するジナフトチオフェン系化合物、芳香環を有する単官能（メタ）アクリレート、ラジカル重合開始剤を特定の割合で含有する被覆材用樹脂組成物からなるので、センサー素子、表示素子等の表面保護や、反射防止膜、光導波路膜等に求められる高い屈折率と透明性、および優れた密着性を有するという特徴を有している。また、本発明の被覆材用樹脂組成物は、溶媒を使用する必要がないため、残存溶剤の影響による強度低下や、アウトガス発生の問題を回避することができる。 The resin composition of the present invention comprises a resin composition for a coating material containing a dinaphthothiophene compound having a polymerizable functional group, a monofunctional (meth) acrylate having an aromatic ring, and a radical polymerization initiator in a specific ratio. Therefore, it has characteristics such as high refractive index and transparency required for surface protection of sensor elements, display elements, antireflection films, optical waveguide films, and the like, and excellent adhesion. Moreover, since the resin composition for coating | covering material of this invention does not need to use a solvent, the strength fall by the influence of a residual solvent and the problem of outgas generation | occurrence | production can be avoided.
＜用語の説明＞
本明細書において、被覆材とは、ガラス基板、プラスチックフィルム、プラスチックシート等の基材上を、表面保護、意匠性を付与、および反射防止や光導波といった機能性を付与することを目的に被覆する材料を意味する。<Explanation of terms>
In this specification, a coating material is a coating on a substrate such as a glass substrate, a plastic film, or a plastic sheet for the purpose of imparting surface protection, designability, and functionality such as antireflection and optical waveguide. Means the material to be.
本実施形態に係る樹脂組成物の成分について説明する。 The components of the resin composition according to this embodiment will be described.
本実施形態に係るエネルギー線硬化性樹脂組成物は、（Ａ）成分として、下記一般式（１）式で表されるエチレン性不飽和二重結合を有する重合性官能基を１つ以上有するジナフトチオフェン系化合物を有する。
上記重合性官能基としては、ビニル基、スチリル基、ビニルエーテル基、アリル基、アリルエーテル基、（メタ）アクリロイル基、（メタ）アクリロニトリル基等が例示できるが、透明性、基材との密着性の点で、（メタ）アクリロイル基又はアリルエーテル基が好ましく、（メタ）アクリロイル基が特に好ましい。 Examples of the polymerizable functional group include a vinyl group, a styryl group, a vinyl ether group, an allyl group, an allyl ether group, a (meth) acryloyl group, a (meth) acrylonitrile group, etc., but transparency and adhesion to a substrate. In this respect, a (meth) acryloyl group or an allyl ether group is preferable, and a (meth) acryloyl group is particularly preferable.
上記ジナフトチオフェン系化合物の具体例としては、６−ビニルジナフトチオフェン、６−（メタ）アクリロイルオキシメチルジナフトチオフェン、６−（メタ）アクリロイルオキシエチルジナフトチオフェン、６−ビニルエーテルジナフトチオフェン、６−アリルジナフトチオフェン、６−アリルオキシジナフトチオフェン、２，１２−ジビニルジナフトチオフェン、３，１１−ジビニルジナフトチオフェン、５，９−ジビニルジナフトチオフェン、２，１２−ジ（メタ）アクリロイルオキシメチルジナフトチオフェン、３，１１−ジ（メタ）アクリロイルオキシメチルジナフトチオフェン、２，１２−ジアリルオキシメチルジナフトチオフェン、３，１１−ジアリルオキシジナフトチオフェン、２，１２−ジビニルオキシメチルジナフトチオフェン、３，１１−ジビニルオキシジナフトチオフェン等が挙げられるが、透明性の点で、６−（メタ）アクリロイルオキシメチルジナフトチオフェン、６−（メタ）アクリロイルオキシエチルジナフトチオフェン、２，１２−ジアリルオキシジナフトチオフェン、及び３，１１−ジアリルオキシジナフトチオフェンが好ましく、６−（メタ）アクリロイルオキシメチルジナフトチオフェンが特に好ましい。 Specific examples of the dinaphthothiophene compound include 6-vinyldinaphthothiophene, 6- (meth) acryloyloxymethyldinaphthothiophene, 6- (meth) acryloyloxyethyl dinaphthothiophene, 6-vinyl ether dinaphthothiophene, 6-allyldinaphthothiophene, 6-allyloxydinaphthothiophene, 2,12-divinyldinaphthothiophene, 3,11-divinyldinaphthothiophene, 5,9-divinyldinaphthothiophene, 2,12-di (meth) Acryloyloxymethyldinaphthothiophene, 3,11-di (meth) acryloyloxymethyldinaphthothiophene, 2,12-diallyloxymethyldinaphthothiophene, 3,11-diallyloxydinaphthothiophene, 2,12-divinyloxymethyl Ginaft Ofene, 3,11-divinyloxydinaphthothiophene and the like can be mentioned, but in terms of transparency, 6- (meth) acryloyloxymethyldinaphthothiophene, 6- (meth) acryloyloxyethyl dinaphthothiophene, 2,12 -Diallyloxydinaphthothiophene and 3,11-diallyloxydinaphthothiophene are preferred, and 6- (meth) acryloyloxymethyldinaphthothiophene is particularly preferred.
（Ａ）成分の含有割合は、樹脂組成物の総量に対して１５〜６０質量部であることが好ましく、特に屈折率、透明性、基材との密着性、（Ｂ）成分との相溶性の点で、１５〜５０質量部がより好ましく、１７〜５０質量部がさらに好ましく、２０〜４０質量部が最も好ましい。ここで、樹脂組成物の総量とは、（Ａ）成分と（Ｂ）成分の合計１００質量部であることが好ましい。 The content ratio of the component (A) is preferably 15 to 60 parts by mass with respect to the total amount of the resin composition. Particularly, the refractive index, transparency, adhesion to the substrate, and compatibility with the component (B). In this respect, 15 to 50 parts by mass is more preferable, 17 to 50 parts by mass is further preferable, and 20 to 40 parts by mass is most preferable. Here, the total amount of the resin composition is preferably 100 parts by mass in total of the component (A) and the component (B).
上記ジナフトチオフェン系化合物は、特開２０１１−１７８９８５号公報（上記特許文献５）、特開２０１２−１３６５７６（上記特許文献６）に例示される製造方法をもって製造することができるが、この方法に限らずいかなる製造方法によって製造されたものでも使用できる。 The dinaphthothiophene compound can be produced by a production method exemplified in JP2011-178985A (above Patent Literature 5) and JP2012-136576A (above Patent Literature 6). A product manufactured by any manufacturing method is not limited.
＜（Ｂ）成分：単官能（メタ）アクリレート＞
本発明の樹脂組成物は（Ｂ）成分として、１つ以上の芳香環を有する単官能（メタ）アクリレートを含有する。芳香環の数は、例えば、１，２，３であり、好ましくは、１つである。<(B) component: monofunctional (meth) acrylate>
The resin composition of the present invention contains a monofunctional (meth) acrylate having one or more aromatic rings as the component (B). The number of aromatic rings is, for example, 1, 2, 3, and preferably one.
上記単官能（メタ）アクリレートの具体例としては、ベンジル（メタ）アクリレート、フェノキシエチル（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、フェノキシテトラエチレングリコール（メタ）アクリレート、フェノキシヘキサエチレングリコール（メタ）アクリレート、ノニルフェニル（メタ）アクリレート、エチレンオキサイド変性ノニルフェニル（メタ）アクリレート、フタル酸変性（メタ）アクリレート、ナフチル（メタ）アクリレート、ビスフェニルフルオレン（メタ）アクリレート、２−（ｏ−フェニルフェノキシ）エチル（メタ）アクリレート等が例示できるが、（Ａ）成分との相溶性、屈折率、透明性の点から、ベンジル（メタ）アクリレートおよび／またはフェノキシエチル（メタ）アクリレートが特に好ましい。 Specific examples of the monofunctional (meth) acrylate include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, and phenoxyhexaethylene glycol (meth) acrylate. , Nonylphenyl (meth) acrylate, ethylene oxide modified nonylphenyl (meth) acrylate, phthalic acid modified (meth) acrylate, naphthyl (meth) acrylate, bisphenylfluorene (meth) acrylate, 2- (o-phenylphenoxy) ethyl ( Examples include meth) acrylate, but benzyl (meth) acrylate and / or phenoxyethyl (meth) from the viewpoint of compatibility with component (A), refractive index, and transparency. Acrylate is particularly preferred.
（Ｂ）成分の含有割合は、樹脂組成物の総量に対して４０〜８５質量部であることが好ましく、特に屈折率、透明性、基材との密着性、（Ａ）成分との相溶性の点で、５０〜８５質量部がより好ましく、５０〜８３質量部がさらに好ましく、６０〜８０質量部が最も好ましい。 The content ratio of the component (B) is preferably 40 to 85 parts by mass with respect to the total amount of the resin composition, and particularly the refractive index, transparency, adhesion to the substrate, and compatibility with the component (A). In this respect, 50 to 85 parts by mass is more preferable, 50 to 83 parts by mass is more preferable, and 60 to 80 parts by mass is most preferable.
本発明の樹脂組成物には、発明の効果を損なわない範囲で、芳香環を有さない単官能（メタ）アクリレート化合物や、多官能の（メタ）アクリレートを含有しても良い。 The resin composition of the present invention may contain a monofunctional (meth) acrylate compound having no aromatic ring or a polyfunctional (meth) acrylate as long as the effects of the invention are not impaired.
＜（Ｃ）成分：光ラジカル重合開始剤＞
本実施の樹脂組成物は、（Ｃ）光ラジカル重合開始剤を含有する。光ラジカル重合開始剤は、エネルギー線を照射することによりラジカルが発生する化合物であれば、特に制限されない。<(C) component: radical photopolymerization initiator>
The resin composition of the present embodiment contains (C) a radical photopolymerization initiator. The radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals when irradiated with energy rays.
上記光ラジカル重合開始剤としては、ベンジル、ベンゾイン、ベンゾイン安息香酸、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン誘導体、ベンゾフェノン、４−フェニルベンゾフェノン等のベンゾフェノン誘導体、２，２−ジエトキシアセトフェノン、ベンジルジメチルケタール等のアルキルアセトフェノン誘導体、１−ヒドロキシシクロヘキシルフェニルケトン、１−（４−イソプロピルフェニル）２−ヒドロキシ−２−メチルプロパン−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−２−メチル−１−フェニルプロパン−１−オン等のα−ヒドロキシアセトフェノン誘導体、ビスジエチルアミノベンゾフェノン、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−ベンジル−２-ジメチルアミノ−1−（４−モルフォリノフェニル）−１−ブタノン−１等のα−アミノアルキルアセトフェノン誘導体、イソブチリル−メチルフォスフィン酸メチルエステル、イソブチリル−フェニルフォスフィン酸メチルエステル、ピバロイル−フェニルフォスフィン酸メチルエステル、２−エチルヘキサノイル−フェニルフォスフィン酸メチルエステル、ピバロイル−フェニルフォスフィン酸イソプロピルエステル、ｐ−トルイル−フェニルフォスフィン酸メチルエステル、ｏ−トルイル−フェニルフォスフィン酸メチルエステル、２，４−ジメチルベンゾイル−フェニルフォスフィン酸メチルエステル、ｐ−３級ブチルベンゾイル−フェニルフォスフィン酸イソプロピルエステル、ビバロイル−（４−メチルフェニル）−フォスフィン酸メチルエステル、ピバロイル−フェニルフォスフィン酸ビニルエステル、（メタ）アクリロイル−フェニルフォスフィン酸メチルエステル、イソブチリル−ジフェニルフォスフィンオキサイド、ピバロイル−ジフェニルフォスフィンオキサイド、１−メチル−１−シクロヘキサノイル−ジフェニルフォスフィンオキサイド、２−エチルヘキサノイル−ジフェニルフォスフィンオキサイド、ｐ−トルイル−ジフェニルフォスフィンオキサイド、ｏ−トルイル−ジフェニルフォスフィンオキサイド、ｐ−３級ブチルベンゾイル−ジフェニルフォスフィンオキサイド、（メタ）アクリロイルジフェニルフォスフィンオキサイド、ベンゾイル−ジフェニルフォスフィンオキサイド、２，２−ジメチル−ヘプタノイル−ジフェニルフォスフィンオキサイド、テレフタロイル−ビス−ジフェニルフォスフィンオキサイド、アジポイル−ビス−ジフェニルフォスフィンオキサイド、２，６−ジメチルベンゾイル−ジフェニルフォスフィンオキサイド、２，６−ジメトキシベンゾイル−フェニルフォスフィン酸メチルエステル、２，６−ジメチルベンゾイル−ジフェニルフォスフィンオキサイド、２，６−ジメトキシベンゾイル−ジフォスフィンオキサイド、２，４，６−トリメチルベンゾイル−フェニルフォスフィン酸メチルエステル、２，４，６−トリメチルベンゾイル−ジフェニルフォスフィンオキサイド、２，３，６−トリメチルベンゾイル−ジフェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイル−トリフォスフィン酸メチルエステル、２，４，６−トリメトキシベンゾイル−ジフェニルフォスフィンオキサイド、２，６−ジクロルベンゾイル−フェニルフォスフィン酸エステル、２，６−ジクロルベンゾイル−ジフェニルフォスフィンオキサイド、２，３，４，６−テトラメチルベンゾイル−ジフェニルフォスフィンオキサイド、２，６−ジブロムベンゾイル−ジフェニルフォスフィンオキサイド、２，６−ジメチルベンゾイルジフェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイル−フェニルフォスフィン酸メチルエステル、２，６−ジクロルベンゾイル−若しくは２，６−ジメトキシベンゾイル−ジフェニルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルフォスフィンオキサイド等のアシルフォスフィンオキサイド誘導体、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)等のオキシムエステル化合物が挙げられる。これらの中では、アルキルアセトフェノン誘導体、α−ヒドロキシアセトフェノン類、ホスフィンオキサイド類からなる１種以上が、反応性、透明性に優れる点で、好ましい。これらは１種又は２種以上組み合わせて用いることができる。 Examples of the photo radical polymerization initiator include benzyl derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzophenone derivatives such as benzophenone and 4-phenylbenzophenone, and 2,2-diethoxy. Alkylacetophenone derivatives such as acetophenone and benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -Phenyl) -2-hydroxy-2-methyl-1-propan-1-one, α-hydroxyacetophenone derivatives such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, Sudiethylaminobenzophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Α-Aminoalkylacetophenone derivatives such as butanone-1, isobutyryl-methylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid methyl ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester Ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenylphosphinic acid Tilester, p-3 tertiary butylbenzoyl-phenylphosphinic acid isopropyl ester, bivaloyl- (4-methylphenyl) -phosphinic acid methyl ester, pivaloyl-phenylphosphinic acid vinyl ester, (meth) acryloyl-phenylphosphinic acid methyl ester Isobutyryl-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, 1-methyl-1-cyclohexanoyl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, o-Toluyl-diphenylphosphine oxide, p-3 tertiary butylbenzoyl-diphenylphosphine oxide, (meth) acryloyldipheny Ruphosphine oxide, benzoyl-diphenylphosphine oxide, 2,2-dimethyl-heptanoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, adipoyl-bis-diphenylphosphine oxide, 2,6-dimethylbenzoyl-diphenyl Phosphine oxide, 2,6-dimethoxybenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphosphine oxide, 2,4,6-trimethylbenzoyl -Phenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl Diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-triphosphinic acid methyl ester, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-phenylphosphinic acid ester, 2 , 6-Dichlorobenzoyl-diphenylphosphine oxide, 2,3,4,6-tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine Fin oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl- or , 6-Dimethoxybenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide Acylphosphine oxide derivatives such as 1,2-octanedione, 1-[-4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methyl) And oxime ester compounds such as benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime). In these, 1 or more types which consist of an alkyl acetophenone derivative, (alpha) -hydroxy acetophenone, and phosphine oxides are preferable at the point which is excellent in reactivity and transparency. These can be used alone or in combination of two or more.
（Ｃ）成分の含有割合は、樹脂組成物の総量に対して、０．１〜１０質量部の割合で含有させることが好ましく、特に０．５〜５質量部がより好ましい。０．１〜１０質量部の範囲にあれば硬化性が悪くなることもないし、透明性も低下させることもない。 (C) It is preferable to make the content rate of a component contain in the ratio of 0.1-10 mass parts with respect to the total amount of a resin composition, and 0.5-5 mass parts is especially more preferable. If it exists in the range of 0.1-10 mass parts, sclerosis | hardenability will not worsen and transparency will not fall.
＜その他の添加剤＞
本実施形態の目的を損なわない範囲で、酸化防止剤、シランカップリング剤、アクリルゴム、ウレタンゴム等の各種エラストマー、光増感剤、光安定剤、溶剤、増量材、充填剤、補強材、可塑剤、増粘剤、染料、顔料、難燃剤及び界面活性剤等の添加剤を含有しても良い。<Other additives>
As long as the purpose of the present embodiment is not impaired, an antioxidant, a silane coupling agent, various elastomers such as an acrylic rubber and a urethane rubber, a photosensitizer, a light stabilizer, a solvent, an extender, a filler, a reinforcing material, You may contain additives, such as a plasticizer, a thickener, a dye, a pigment, a flame retardant, and surfactant.
本実施形態に係る樹脂組成物の製造方法については、上記の材料を十分に混合できれば特に制限はない。材料の混合方法としては、特に限定されないが、プロペラの回転に伴う撹拌力を利用する撹拌法、自転公転による遊星式撹拌機等の通常の分散機を利用する方法等が挙げられる。これらの混合方法は、低コストで、安定した混合を行えるので好ましい。 About the manufacturing method of the resin composition which concerns on this embodiment, there will be no restriction | limiting in particular if said material can fully be mixed. The mixing method of the material is not particularly limited, and examples thereof include a stirring method using a stirring force accompanying rotation of a propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable because stable mixing can be performed at low cost.
上記の混合を行った後、下記の光源を用いたエネルギー線の照射により、樹脂組成物の硬化を行うことができる。 After performing the above mixing, the resin composition can be cured by irradiation with energy rays using the following light source.
本実施形態において、樹脂組成物の硬化に用いられる光源としては、特に限定されないが、ハロゲンランプ、メタルハライドランプ、ハイパワーメタルハライドランプ（インジウム等を含有する）、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、キセノンエキシマランプ、キセノンフラッシュランプ、ライトエミッティングダイオード（以下、ＬＥＤという）等が挙げられる。これらの光源は、それぞれの光ラジカル重合開始剤の反応波長に対応したエネルギー線の照射を効率よく行える点で、好ましい。 In the present embodiment, the light source used for curing the resin composition is not particularly limited, but is a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium or the like), a low-pressure mercury lamp, a high-pressure mercury lamp, or an ultra-high pressure. Examples thereof include a mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, and a light emitting diode (hereinafter referred to as LED). These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelengths of the respective radical photopolymerization initiators.
上記光源は、各々放射波長、エネルギー分布が異なる。そのため、上記光源は光重合開始剤の反応波長等により適宜選択される。又、自然光（太陽光）も反応開始光源になり得る。 Each of the light sources has a different emission wavelength and energy distribution. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photopolymerization initiator. Natural light (sunlight) can also be a reaction initiation light source.
上記光源は、直接照射、反射鏡等による集光照射、ファイバー等による集光照射を行ってもよい。低波長カットフィルター、熱線カットフィルター、コールドミラー等も用いることもできる。 The light source may perform direct irradiation, condensing irradiation using a reflecting mirror, or condensing irradiation using a fiber or the like. A low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.
上記構成からなる樹脂組成物は、エネルギー線の照射により速やかに硬化するため、高透明性、高屈折率等の光学特性に優れた硬化体を提供することができる。 Since the resin composition having the above-described structure is quickly cured by irradiation with energy rays, a cured product having excellent optical characteristics such as high transparency and high refractive index can be provided.
また、上記構成からなる樹脂組成物は、高透明性、高屈折率などの光学特性が優れ、ガラス、プラスチックフィルム、プラスチックシート等の基材への密着性が優れるため、これら基材の被覆材として提供することができる。 In addition, the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and has excellent adhesion to substrates such as glass, plastic film, and plastic sheet. Can be offered as.
さらに、上記構成からなる樹脂組成物は、高透明性、高屈折率など光学特性に優れるため、反射防止膜や光導波膜の高屈折率層として用いることができ、そのため優れた反射防止膜や光導波路膜を提供できる。 Furthermore, since the resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, it can be used as a high refractive index layer of an antireflection film or an optical waveguide film. An optical waveguide film can be provided.
反射防止膜、および光導波路膜は、ガラス、プラスチックフィルム、プラスチックシート等の各種基材の上に、本発明の樹脂組成物からなる層（以下、高屈折率層という）を塗布、エネルギー線照射により形成した後、高屈折率層上に、高屈折率層より低い屈折率を有する層（以下、低屈折率層という）を形成することで作製される。 The antireflection film and optical waveguide film are coated with a layer made of the resin composition of the present invention (hereinafter referred to as a high refractive index layer) on various substrates such as glass, plastic film, plastic sheet, etc., and irradiated with energy rays. Then, a layer having a lower refractive index than the high refractive index layer (hereinafter referred to as a low refractive index layer) is formed on the high refractive index layer.
基材としては、無アルカリガラス、アルカリガラス、硼珪酸ガラス、石英等のガラス基材や、シリカ、アルミナ、窒化珪素等のセラミックス基材、シリコーン、アルミ、ステンレス、鉄、銅、銀等の金属基材、アクリル系樹脂、スチレン系樹脂、カーボネート系樹脂、オレフィン系樹脂、ポリエステル系樹脂、ポリイミド系樹脂、ポリアミド系樹脂、エポキシ系樹脂、シリコーン系樹脂、フッ素系樹脂、セルロース系樹脂等の樹脂からなるフィルム基材、シート基材などを用いることができる。 Base materials include glass base materials such as alkali-free glass, alkali glass, borosilicate glass, and quartz, ceramic base materials such as silica, alumina, and silicon nitride, and metals such as silicone, aluminum, stainless steel, iron, copper, and silver. From resins such as base materials, acrylic resins, styrene resins, carbonate resins, olefin resins, polyester resins, polyimide resins, polyamide resins, epoxy resins, silicone resins, fluorine resins, and cellulose resins A film base material, a sheet base material, and the like can be used.
低屈折率層としては、無機膜としてはフッ化マグネシウム、フッ化カリウム等のアルカリ金属のフッ化物や、シリカ等が例示でき、有機膜としてはポリパーフルオロエチレン、パーフルオロシクロオレフィン等のフッ素樹脂、ポリエチレングリコール等のポリエーテル樹脂、シリコーン樹脂、アクリル樹脂、エポキシ樹脂、ウレタン樹脂およびそれらのフッ素変性樹脂などを用いることができる。 Examples of the low refractive index layer include inorganic films such as alkali metal fluorides such as magnesium fluoride and potassium fluoride, silica, and the like, and organic films such as fluoropolymers such as polyperfluoroethylene and perfluorocycloolefin. Polyether resins such as polyethylene glycol, silicone resins, acrylic resins, epoxy resins, urethane resins and their fluorine-modified resins can be used.
上記構成からなる樹脂組成物は、高透明性、高屈折率など光学特性に優れるため、高液晶パネル、有機エレクトロルミネッセンスパネル、タッチパネル、プロジェクター、スマートフォン、携帯電話、デジタルカメラ、デジタルムービーの表示素子や、ＣＣＤ、ＣＭＯＳ、バイオチップ等の各種センサー部品、フラッシュメモリー、ＤＲＡＭ、半導体レーザー等の半導体素子に用いられる被覆材、さらには反射防止膜や光導波膜の高屈折率層として用いることができる。 The resin composition having the above structure is excellent in optical properties such as high transparency and high refractive index, and therefore has a high liquid crystal panel, an organic electroluminescence panel, a touch panel, a projector, a smartphone, a mobile phone, a digital camera, a digital movie display element, It can be used as a coating material used for various sensor parts such as CCD, CMOS, and biochip, semiconductor elements such as flash memory, DRAM, and semiconductor laser, and also as a high refractive index layer of an antireflection film or an optical waveguide film.
以下に、実施例及び比較例を挙げて、本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例では、以下の化合物を使用した。 In the examples, the following compounds were used.
（Ａ）ジナフトチオフェン化合物
ジナフトチオフェン化合物は、特開２０１１−１７８９８５（上記特許文献５）に記載の合成方法（［実施例］［０１０６］〜［０１２１］）にて製造したものを用いた。
（Ａ−１）６−メタクリロイルオキシメチルジナフトチオフェン（略号：ＤＮＴＭＡ）
（Ａ−２）６−ビニルジナフトチオフェン（略号：ＶＤＮＴ）
（Ａ−３）６−メタクリロイルオキシエチルジナフトチオフェン（略号：ＥＤＮＴＭＡ）
（Ａ−４）２，１２−ジアリルオキシジナフトチオフェン（略号：ＤＡＯＤＮＴ）
（Ａ−５）３，１１−ジアリルオキシジナフトチオフェン（略号：ｉ−ＤＡＯＤＮＴ）
（Ａ−６）ジナフトチオフェン（略号：ＤＮＴ）(A) Dinaphthothiophene compound The dinaphthothiophene compound used what was manufactured with the synthesis method ([Example] [0106]-[0121]) of Unexamined-Japanese-Patent No. 2011-178985 (the said patent document 5). .
(A-1) 6-methacryloyloxymethyldinaphthothiophene (abbreviation: DNTMA)
(A-2) 6-vinyldinaphthothiophene (abbreviation: VDNT)
(A-3) 6-methacryloyloxyethyl dinaphthothiophene (abbreviation: EDNTMA)
(A-4) 2,12-diallyloxydinaphthothiophene (abbreviation: DAODNT)
(A-5) 3,11-diallyloxydinaphthothiophene (abbreviation: i-DAODNT)
(A-6) Dinaphthothiophene (abbreviation: DNT)
（Ｂ）芳香環を有する単官能（メタ）アクリレート
（Ｂ−１）ベンジルメタクリレート（共栄社化学社製「ライトエステルＢＺ」）
（Ｂ−２）ベンジルアクリレート（大阪有機化学工業社製「ビスコート＃１６０」）
（Ｂ−３）フェノキシエチルメタクリレート（共栄社化学社製「ライトエステルＰＯ」）
（Ｂ−４）フェノキシエチルアクリレート（共栄社化学社製「ライトアクリレートＰＯ−Ａ」）
（Ｂ−５）２−（ｏ−フェニルフェノキシ）エチルアクリレート（新中村化学工業社製「ＮＫエステルＡ−ＬＥＮ−１０」）(B) Monofunctional (meth) acrylate (B-1) benzyl methacrylate having an aromatic ring (“Light Ester BZ” manufactured by Kyoeisha Chemical Co., Ltd.)
(B-2) Benzyl acrylate (“Biscoat # 160” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(B-3) Phenoxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester PO”)
(B-4) Phenoxyethyl acrylate (Kyoeisha Chemical Co., Ltd. “Light acrylate PO-A”)
(B-5) 2- (o-phenylphenoxy) ethyl acrylate (“NK Ester A-LEN-10” manufactured by Shin-Nakamura Chemical Co., Ltd.)
（Ｃ）光ラジカル重合開始剤
（Ｃ−１）ベンジルジメチルケタール（ＢＡＳＦ社製「イルガキュアー６５１」）
（Ｃ−２）１−ヒドロキシ−シクロヘキシルフェニルケトン（ＢＡＳＦ社製「イルガキュアー１８４」）
（Ｃ−３）ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド（ＢＡＳＦ社製「イルガキュアー８１９」）(C) Photoradical polymerization initiator (C-1) Benzyldimethyl ketal ("Irgacure 651" manufactured by BASF)
(C-2) 1-hydroxy-cyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF)
(C-3) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure 819” manufactured by BASF)
その他の化合物として、下記を用いた。
（Ｄ−１）ビスフェノールＡ型エポキシアクリレート（共栄社化学社製「エポキシエステル３００２Ｍ」）
（Ｄ−２）スチレン（和光純薬工業社製「スチレン」）
（Ｄ−３）メチルメタクリレート（三菱ガス化学社製「ＭＭＡ」）
（Ｄ−４）９，９−ビス［４−（２−アクリロイルオキシエトキシ）フェニル］フルオレン（大阪ガスケミカル社製「ＢＰＦＥＡ」）The following were used as other compounds.
(D-1) Bisphenol A type epoxy acrylate (“Epoxy ester 3002M” manufactured by Kyoeisha Chemical Co., Ltd.)
(D-2) Styrene (“Styrene” manufactured by Wako Pure Chemical Industries, Ltd.)
(D-3) Methyl methacrylate ("MMA" manufactured by Mitsubishi Gas Chemical Company)
(D-4) 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (“BPFEA” manufactured by Osaka Gas Chemical Company)
（実施例１〜１８、比較例１〜６）
表１〜表３に示す種類の原材料を、表１〜表３に示す組成割合（単位は質量部）で混合し、被覆材用樹脂組成物を調製し、後述の評価を実施した。溶媒は用いなかった。各種評価結果を表１〜表３に示す。特記しない限り、２３℃、湿度５０％の環境下で実施した。(Examples 1-18, Comparative Examples 1-6)
The raw materials of the types shown in Tables 1 to 3 were mixed at the composition ratios (units are parts by mass) shown in Tables 1 to 3 to prepare a resin composition for a coating material, and evaluation described below was performed. No solvent was used. Various evaluation results are shown in Tables 1 to 3. Unless otherwise specified, the test was carried out in an environment of 23 ° C. and 50% humidity.
〔液安定性評価〕
３０ｍｌのバイアル瓶に樹脂組成物１０ｍｌを入れ密封したサンプルを準備し、サンプルを温度２３℃の雰囲気中に２４時間静置し、２４時間後の液の状態を目視で確認し、以下の基準で評価した。
○：静置前と変化がなかった
△：析出物や分離物がみられるが５０℃加温により再溶解した
×：析出物や分離物がみられ５０℃加温でも再溶解しなかった
尚、混合後の液の状態を目視で確認し、析出物や分離物がみられた試料については続く評価は実施しなかった。(Liquid stability evaluation)
Prepare a sealed sample by placing 10 ml of the resin composition in a 30 ml vial, leave the sample in an atmosphere at a temperature of 23 ° C. for 24 hours, visually check the liquid state after 24 hours, and use the following criteria: evaluated.
◯: No change from before standing Δ: Precipitates and isolates were seen but redissolved by heating at 50 ° C. x: Precipitates and isolates were seen and did not dissolve again even at 50 ° C. The state of the liquid after mixing was visually confirmed, and subsequent evaluation was not carried out for the sample in which precipitates and separated matters were observed.
〔屈折率の評価〕
（１）液屈折率
液屈折率の評価は、多波長アッベ屈折率計（アタゴ社製「ＤＲ−Ｍ２」）を用いて、温度２５℃、波長５８９ｎｍにおける屈折率を測定した。
（２）硬化物屈折率
樹脂組成物を容積１５ｍｍ×１５ｍｍ×１．０ｍｍのシリコーンゴム製の型枠に流し込み、超高圧水銀ランプ搭載装置（ＨＯＹＡ社製「ＵＬ−７５０」）にて、３６５ｎｍの波長の照射強度３０ｍＷ／ｃｍ２、積算光量３０，０００ｍＪ／ｃｍ２の条件にて硬化した硬化物試験片を作成し、屈折率を評価した。屈折率の評価は、分光プリズムカプラ屈折率測定装置（メトリコン社製「ＭＯＤＥＬ ２０１０ ＰＲＩＳＭ ＣＯＵＰＬＥＲ」）を用いて、波長６３３ｎｍにおける屈折率を測定した。(Evaluation of refractive index)
(1) Liquid Refractive Index The liquid refractive index was evaluated by measuring the refractive index at a temperature of 25 ° C. and a wavelength of 589 nm using a multiwavelength Abbe refractometer (“DR-M2” manufactured by Atago Co., Ltd.).
(2) Cured Product Refractive Index The resin composition was poured into a silicone rubber mold having a volume of 15 mm × 15 mm × 1.0 mm, and the film thickness was 365 nm with an ultra-high pressure mercury lamp mounting device (“UL-750” manufactured by HOYA). A cured product test piece cured under conditions of an irradiation intensity of a wavelength of 30 mW / cm 2 and an integrated light amount of 30,000 mJ / cm 2 was prepared, and a refractive index was evaluated. The refractive index was evaluated by measuring the refractive index at a wavelength of 633 nm using a spectroscopic prism coupler refractive index measuring device ("MODEL 2010 PRISM COUPLER" manufactured by Metricon).
〔分光透過率測定〕
樹脂組成物を耐熱ガラス（商品名「耐熱パイレックス（登録商標）ガラス」、２５ｍｍ×２５ｍｍ×２．０ｍｍ）上に膜厚３０μｍで塗布した後に、超高圧水銀ランプ搭載装置（ＨＯＹＡ社製「ＵＬ−７５０」）にて、３６５ｎｍの波長の照射強度５０ｍＷ／ｃｍ２、積算光量３０，０００ｍＪ／ｃｍ２の条件にて硬化した試験片を作成し、紫外−可視分光光度計（島津製作所社製「ＵＶ−２５５０」）、リファレンスを耐熱ガラスとして、４５０ｎｍの透過率を測定した。(Spectral transmittance measurement)
After coating the resin composition on heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, 25 mm × 25 mm × 2.0 mm) with a film thickness of 30 μm, an ultra-high pressure mercury lamp mounting device (“UL-” manufactured by HOYA) 750 "), a test piece cured under the conditions of an irradiation intensity of a wavelength of 365 nm of 50 mW / cm 2 and an integrated light quantity of 30,000 mJ / cm 2 was prepared, and an ultraviolet-visible spectrophotometer (Shimadzu Corporation" UV " -2550 "), and the transmittance was measured at 450 nm using a heat resistant glass as a reference.
〔密着性評価（クロスカット試験）〕
１２５μｍ厚のポリエステルフィルム（東洋紡社製「コスモシャインＡ４１００」）上に、樹脂組成物を超高圧水銀ランプ搭載装置（ＨＯＹＡ社製「ＵＬ−７５０」）にて、３６５ｎｍの波長の照射強度５０ｍＷ／ｃｍ２、積算光量３０，０００ｍＪ／ｃｍ２、窒素雰囲気下の条件にて硬化して形状が２０ｍｍ×２０ｍｍ×８０μｍの樹脂組成物の硬化膜を形成した試験片を作製した。
このようにして得られた各試験片に対して、温度２３℃、相対湿度５０％の環境下で、硬化膜に縦２ｍｍ×横２ｍｍ×２５マスになるようにカットラインを入れた後、セロファンテープ（ニチバン社製型式ＣＴ−４０５ＡＰ：幅２４ｍｍ、粘着力２３Ｎ／１０ｍｍ）を貼り付けて１８０°剥離を実施した。１８０°剥離後に残ったマスの数を数え、以下の基準で評価した。その他、特に明示のない条件はＪＩＳ Ｋ ５６００−５−６に従った。
○：２５枚全て残った
△：１５枚以上２４枚以下残った
×：１４枚未満であった[Adhesion evaluation (cross cut test)]
On a polyester film of 125 μm thickness (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.), the resin composition was irradiated with an ultra-high pressure mercury lamp (“UL-750” manufactured by HOYA) with an irradiation intensity of a wavelength of 365 nm of 50 mW / cm. 2. A test piece was prepared in which a cured film of a resin composition having a shape of 20 mm × 20 mm × 80 μm was formed by curing under the condition of an integrated light quantity of 30,000 mJ / cm 2 and a nitrogen atmosphere.
For each test piece obtained in this manner, a cut line was placed in the cured film so as to be 2 mm long × 2 mm wide × 25 squares in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then cellophane. The tape (Nichiban Co., Ltd. model CT-405AP: width 24mm, adhesive strength 23N / 10mm) was affixed and 180 degree peeling was implemented. The number of cells remaining after 180 ° peeling was counted and evaluated according to the following criteria. Other conditions not specified in particular were in accordance with JIS K 5600-5-6.
○: All 25 sheets remained Δ: 15 or more and 24 or less remained x: Less than 14 sheets
＜考察＞
実施例１〜１８では、何れも液安定性・屈折率・分光透過率・密着性の点で優れた結果が得られた。但し、実施例１では、ジナフトチオフェン系化合物の配合割合が少ないため、屈折率が若干低かった。実施例６では、ジナフトチオフェン系化合物の配合割合が多いため、液安定性及び密着性が若干悪化した。また、ビニル基を有するジナフトチオフェン系化合物を用いた実施例１０では、（メタ）アクリロイル基又はアリルエーテル基を有するジナフトチオフェン系化合物を用いた実施例１〜９、実施例１１〜１４に比べて、液安定性、分光透過率及び密着性が好ましくなかった。この結果は、（メタ）アクリロイル基又はアリルエーテル基を有するジナフトチオフェン系化合物を用いることの優位性を示している。さらに、実施例３と実施例１１〜１３を比較すると、実施例３のようにＤＮＴＭＡを用いた場合、屈折率及び分光透過率が特に高くなることが分かった。さらに、実施例１４のように、（Ｂ）成分として芳香環を２つ有するアクリレートを用いたところ、液安定性、分光透過率及び密着性が悪化した。<Discussion>
In Examples 1 to 18, excellent results were obtained in terms of liquid stability, refractive index, spectral transmittance, and adhesion. However, in Example 1, since the blending ratio of the dinaphthothiophene compound was small, the refractive index was slightly low. In Example 6, since the compounding ratio of the dinaphthothiophene compound was large, the liquid stability and adhesion were slightly deteriorated. In Example 10 using a dinaphthothiophene compound having a vinyl group, Examples 1 to 9 and Examples 11 to 14 using a dinaphthothiophene compound having a (meth) acryloyl group or an allyl ether group were used. In comparison, liquid stability, spectral transmittance and adhesion were not preferred. This result shows the advantage of using a dinaphthothiophene compound having a (meth) acryloyl group or an allyl ether group. Furthermore, when Example 3 and Examples 11-13 were compared, when DNTMA was used like Example 3, it turned out that a refractive index and spectral transmittance become especially high. Furthermore, as in Example 14, when an acrylate having two aromatic rings was used as the component (B), the liquid stability, spectral transmittance, and adhesion were deteriorated.
また、比較例１では、ジナフトチオフェン系化合物を用いなかったため、屈折率が十分でなかった。比較例２では、多官能アクリレート（ビスフェノールＡ型エポキシアクリレート）を用いたため、液安定性が非常に悪く、屈折率・分光透過率評価のための試験片を作成することができなかった。比較例３では、（Ｂ）成分の代わりに、芳香環を有するが（メタ）アクリレートではない化合物（スチレン）を用いたため、光照射を行なっても十分に硬化が起こらなかった。比較例４では、（Ｂ）成分の代わりに、芳香環を有さない単官能（メタ）アクリレート（メチルメタクリレート）を用いたため、液安定性が悪く、容易に溶解しない析出物が発生してしまった。比較例５では、官能基を有さないジナフトチオフェン系化合物（ジナフトチオフェン）を用いたため、液安定性が悪く、容易に溶解しない析出物が発生してしまった。比較例６では、（Ｂ）成分が少なすぎたために、液安定性が悪く、容易に溶解しない析出物が発生してしまった。 In Comparative Example 1, since the dinaphthothiophene compound was not used, the refractive index was not sufficient. In Comparative Example 2, since polyfunctional acrylate (bisphenol A type epoxy acrylate) was used, the liquid stability was very poor, and a test piece for evaluation of refractive index and spectral transmittance could not be prepared. In Comparative Example 3, since a compound (styrene) having an aromatic ring but not (meth) acrylate was used instead of the component (B), curing did not occur sufficiently even when light irradiation was performed. In Comparative Example 4, since monofunctional (meth) acrylate (methyl methacrylate) having no aromatic ring was used instead of component (B), the liquid stability was poor and precipitates that did not dissolve easily were generated. It was. In Comparative Example 5, since a dinaphthothiophene compound (dinaphthothiophene) having no functional group was used, the liquid stability was poor and precipitates that were not easily dissolved were generated. In Comparative Example 6, since there was too little (B) component, the liquid stability was bad and the precipitate which does not melt | dissolve easily occurred.
本発明の樹脂組成物は、高透明性、高屈折率など光学特性に優れるため、高液晶パネル、有機エレクトロルミネッセンスパネル、タッチパネル、プロジェクター、スマートフォン、携帯電話、デジタルカメラ、デジタルムービーの表示素子や、ＣＣＤ、ＣＭＯＳ、バイオチップ等の各種センサー部品のセンサー素子、フラッシュメモリー、ＤＲＡＭ、半導体レーザー等の半導体素子に用いられる被覆材、さらには反射防止膜や光導波膜の高屈折率層として好適に用いることができ、産業上非常に有用である。
Since the resin composition of the present invention is excellent in optical properties such as high transparency and high refractive index, a high liquid crystal panel, organic electroluminescence panel, touch panel, projector, smartphone, mobile phone, digital camera, digital movie display element, Suitable for use as sensor elements for various sensor components such as CCD, CMOS, biochip, coating materials used for semiconductor elements such as flash memory, DRAM, and semiconductor laser, and as a high refractive index layer for antireflection films and optical waveguide films. Can be very useful in industry.
Claims (12)
（Ｂ）成分として、１つ以上の芳香環を含有する単官能（メタ）アクリレート、
（Ｃ）成分として、光ラジカル重合開始剤、
を含有し、組成物の総量に対して、前記（Ａ）成分の含有割合は１５〜６０質量部の範囲であり、前記（Ｂ）成分の含有割合は４０〜８５質量部の範囲であることを特徴とする被覆材用樹脂組成物。As the component (A), a dinaphthothiophene compound having one or more polymerizable functional groups having an ethylenically unsaturated double bond represented by the following general formula (1):
(B) As a component, a monofunctional (meth) acrylate containing one or more aromatic rings,
(C) As a component, radical photopolymerization initiator,
The content ratio of the component (A) is in the range of 15 to 60 parts by mass, and the content ratio of the component (B) is in the range of 40 to 85 parts by mass with respect to the total amount of the composition. A resin composition for a coating material.
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI574978B (en) | 2017-03-21 |
| CN104350111B (en) | 2017-10-10 |
| JP6105574B2 (en) | 2017-03-29 |
| TW201404787A (en) | 2014-02-01 |
| KR20150024319A (en) | 2015-03-06 |
| WO2013183532A1 (en) | 2013-12-12 |
| KR102135467B1 (en) | 2020-07-17 |
| CN104350111A (en) | 2015-02-11 |
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