JP5336161B2 - Metal oxide fine particle-containing curable resin composition, cured product thereof, and light diffusing material - Google Patents
Metal oxide fine particle-containing curable resin composition, cured product thereof, and light diffusing material Download PDFInfo
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- JP5336161B2 JP5336161B2 JP2008315330A JP2008315330A JP5336161B2 JP 5336161 B2 JP5336161 B2 JP 5336161B2 JP 2008315330 A JP2008315330 A JP 2008315330A JP 2008315330 A JP2008315330 A JP 2008315330A JP 5336161 B2 JP5336161 B2 JP 5336161B2
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- oxide fine
- metal oxide
- compound
- resin composition
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- 239000010419 fine particle Substances 0.000 title claims description 92
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 49
- 150000004706 metal oxides Chemical class 0.000 title claims description 49
- 239000011342 resin composition Substances 0.000 title claims description 25
- 239000000463 material Substances 0.000 title claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 84
- -1 3,3,3-trifluoropropyl Chemical group 0.000 claims description 55
- 150000002894 organic compounds Chemical class 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000011787 zinc oxide Substances 0.000 claims description 34
- 229910000077 silane Inorganic materials 0.000 claims description 20
- 239000003607 modifier Substances 0.000 claims description 18
- 150000003377 silicon compounds Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000000962 organic group Chemical group 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 230000009257 reactivity Effects 0.000 claims description 12
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 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 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 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 claims description 4
- 125000005375 organosiloxane group Chemical group 0.000 claims description 4
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 150000004756 silanes Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 5
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 229920001795 coordination polymer Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 2
- KTRQRAQRHBLCSQ-UHFFFAOYSA-N 1,2,4-tris(ethenyl)cyclohexane Chemical compound C=CC1CCC(C=C)C(C=C)C1 KTRQRAQRHBLCSQ-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000003544 oxime group Chemical group 0.000 description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- UIEXFJVOIMVETD-UHFFFAOYSA-N P([O-])([O-])[O-].[Pt+3] Chemical class P([O-])([O-])[O-].[Pt+3] UIEXFJVOIMVETD-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- LDKSTCHEYCNPDS-UHFFFAOYSA-L carbon monoxide;dichloroplatinum Chemical compound O=C=[Pt](Cl)(Cl)=C=O LDKSTCHEYCNPDS-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- CYQKXQIXVAOBJJ-UHFFFAOYSA-N cyclohexylmethyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1CCCCC1 CYQKXQIXVAOBJJ-UHFFFAOYSA-N 0.000 description 1
- IBUKRVCWZGCWPB-UHFFFAOYSA-N cyclohexylmethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1CCCCC1 IBUKRVCWZGCWPB-UHFFFAOYSA-N 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 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 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical class P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- ZHOVAWFVVBWEGQ-UHFFFAOYSA-N tripropylsilane Chemical compound CCC[SiH](CCC)CCC ZHOVAWFVVBWEGQ-UHFFFAOYSA-N 0.000 description 1
- XAASNKQYFKTYTR-UHFFFAOYSA-N tris(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)O[Si](C)(C)C XAASNKQYFKTYTR-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
- Overhead Projectors And Projection Screens (AREA)
- Optical Elements Other Than Lenses (AREA)
Description
本発明は、金属酸化物微粒子を含有する硬化性樹脂組成物、その硬化物、及び光拡散材に関するものであり、更に詳しくは光拡散材料、または透明高屈折率材料に関する。 The present invention relates to a curable resin composition containing metal oxide fine particles, a cured product thereof, and a light diffusing material, and more particularly to a light diffusing material or a transparent high refractive index material.
近年、液晶テレビやＤＭＤ（デジタルマイクロミラーデバイス）などの画面が広く普及している。しかし、これらの画面にはシンチレーションと呼ばれる画質の低下が起きることがある。これは小さな光源から出射された光が充分に拡散しないために起きる現象である。 In recent years, screens such as liquid crystal televisions and DMDs (digital micromirror devices) have become widespread. However, image quality degradation called scintillation may occur on these screens. This is a phenomenon that occurs because light emitted from a small light source is not sufficiently diffused.
このシンチレーションを抑えるために、スクリーン用材料に、コロイダルシリカ、酸化チタン、酸化亜鉛、酸化ジルコニウム等の微粒子を添加した、光拡散材料が知られている。中でも酸化亜鉛は透明性が高く、こうした光拡散材料用の光拡散性微粒子として使用されている。一般にこれらの光拡散性微粒子ではその微粒子の二次粒径を１００ｎｍ以上にしなければ光拡散が起こりにくいことが知られており、このような二次粒径とするために、光拡散性微粒子を一定程度凝集させることが必要である。 In order to suppress this scintillation, a light diffusing material is known in which fine particles such as colloidal silica, titanium oxide, zinc oxide, and zirconium oxide are added to a screen material. Among them, zinc oxide has high transparency and is used as light diffusing fine particles for such a light diffusing material. In general, it is known that in these light diffusing fine particles, light diffusion is difficult to occur unless the secondary particle size of the fine particles is set to 100 nm or more. It is necessary to agglomerate to a certain extent.
しかし、このような凝集を制御することは一般に非常に困難であり、凝集し過ぎてしまうと、保存や硬化作業中に金属微粒子が沈殿してしまうため、樹脂中に均一に分散することが非常に困難であるという問題があった。 However, it is generally very difficult to control such agglomeration, and if it agglomerates too much, metal fine particles will precipitate during storage and curing operations, so it is very difficult to uniformly disperse in the resin. There was a problem that it was difficult.
一方、白色発光ダイオード（ＬＥＤ）が、従来の白熱電球の１／３〜１／１０の消費電力、１０倍近い長寿命を達成できることから、次世代の照明として注目されており、携帯電話やパソコンなどのバックライトとしても非常に身近なものとなっている。このようなＬＥＤからの光の取り出しについては、更にその取り出し効率を向上させることが重要であるが、一般にＬＥＤ封止剤として使用されるエポキシ樹脂やシリコーン樹脂は、その屈折率が１．４〜１．５前後と、一般に高屈折率材料からなるＬＥＤの発光領域と比べて低いため、ＬＥＤの光がこれらの界面で全反射してしまい、外部への光取り出し効率が悪くなるという問題がある。 On the other hand, white light-emitting diodes (LEDs) are attracting attention as next-generation lighting because they can achieve a power consumption that is 1/3 to 1/10 that of conventional incandescent bulbs and nearly 10 times longer lifespan. It has become very familiar as a backlight. Regarding the extraction of light from such LEDs, it is important to further improve the extraction efficiency, but epoxy resins and silicone resins generally used as LED sealants have a refractive index of 1.4 to 1.4. Since it is lower than the light emitting region of an LED generally made of a high refractive index material, the light from the LED is totally reflected at these interfaces, and the light extraction efficiency to the outside is deteriorated. .
こうしたことから、簡便に、これらの封止樹脂の透明性、耐光性等の樹脂特性を維持しつつ屈折率を高くする技術の開発が望まれており、そのひとつとして、金属微粒子をこれらの樹脂中に分散する方法が検討されている。例えば、金属酸化物である、酸化ジルコニウムや酸化チタンは屈折率が２．０以上と高く、これらの粒子を２０ｎｍ以下にすることにより、透明性を確保しながら屈折率を上昇させることができると考えられる。 For these reasons, it is desired to develop a technique for easily increasing the refractive index while maintaining the resin properties such as transparency and light resistance of these encapsulating resins. A method of dispersing in is being studied. For example, zirconium oxide and titanium oxide, which are metal oxides, have a high refractive index of 2.0 or more, and by making these particles 20 nm or less, the refractive index can be increased while ensuring transparency. Conceivable.
例えば、特許文献１には、可視光域において、透明、且つ、１．５５以上の屈折率を有するナノ粒子−樹脂複合材料である、シロキサン架橋生成物中に無機ナノ粒子が分散されて成り、無機ナノ粒子は有機化合物で被覆されており、可視光域において透明で１．５５以上の屈折率を有するナノ粒子−樹脂複合材料として、シロキサン架橋生成物は、シロキサン結合（Ｓｉ−Ｏ−Ｓｉ結合）を有し、且つ、反応性官能基を含んだシロキサン化合物の架橋に基づき形成されており、有機化合物は、無機ナノ粒子表面と共有結合あるいはイオン結合を形成する官能基、及び、シロキサン化合物と親和性を示す有機基を有し、分子量が１×１０3以下であるナノ粒子−樹脂複合材料が記載されている。 For example, Patent Document 1 includes inorganic nanoparticles dispersed in a siloxane crosslinked product, which is a nanoparticle-resin composite material that is transparent in the visible light region and has a refractive index of 1.55 or more. The inorganic nanoparticles are coated with an organic compound, and are transparent in the visible light region and have a refractive index of 1.55 or more. As a nanoparticle-resin composite material, a siloxane cross-linked product has a siloxane bond (Si-O-Si bond) And the organic compound is formed of a functional group that forms a covalent bond or an ionic bond with the surface of the inorganic nanoparticles, and a siloxane compound. A nanoparticle-resin composite material having an organic group exhibiting affinity and having a molecular weight of 1 × 10 3 or less is described.
また、例えば、特許文献２には、耐熱性、耐紫外線性、光学的透明性、強靭性、接着性に優れ、高い屈折率で半導体発光素子からの光取り出し効率を向上させた硬化物が得られる、良好な硬化性を有する光関連デバイスの封止用樹脂組成物として、（イ）平均組成式：Ｒ1 a（ＯＸ）bＳｉＯ(4-a-b)/2（式中、Ｒ1は独立に、炭素原子数１〜６のアルキル基、アルケニル基又はアリール基であり、Ｘは独立に、水素原子、炭素原子数１〜６のアルキル基、アルケニル基、アルコキシアルキル基又はアシル基であり、ａは１．００〜１．５の数、ｂは０＜ｂ＜２の数であり、但し、１．００＜ａ＋ｂ＜２である）で表されるポリスチレン換算の重量平均分子量が３×１０3以上のオルガノポリシロキサン、（ロ）アルミニウムキレート化合物、及び（ハ）金属酸化物ゾル微粒子を含有する光関連デバイス封止用樹脂組成物が記載されている。 For example, Patent Document 2 discloses a cured product that has excellent heat resistance, ultraviolet resistance, optical transparency, toughness, and adhesiveness, and has improved light extraction efficiency from a semiconductor light emitting device with a high refractive index. As a resin composition for sealing an optical device having good curability, (a) average composition formula: R 1 a (OX) b SiO (4-ab) / 2 (wherein R 1 is independent Or an alkyl group having 1 to 6 carbon atoms, an alkenyl group or an aryl group, and X is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkoxyalkyl group or an acyl group, a is a number of 1.00 to 1.5, b is a number of 0 <b <2, provided that 1.00 <a + b <2). 3 or more organopolysiloxane, (b) aluminum chelate compound, and Optical devices encapsulating resin composition containing the c) metal oxide sol particles are described.
しかし、上述したように、このような金属酸化物微粒子の凝集を制御することは困難であり、特に、添加した樹脂材料を透明なものとするために、前記２０ｎｍ以下の超微粒子を凝集させることなく、均一に分散させることは非常に困難であるという問題があった。 However, as described above, it is difficult to control the aggregation of the metal oxide fine particles. In particular, in order to make the added resin material transparent, the ultrafine particles of 20 nm or less are aggregated. In addition, there is a problem that it is very difficult to uniformly disperse.
このように金属微粒子は様々な用途に利用できるものの、分散性、粒径、樹脂への親和性の制御が非常に難しいという問題があった。
本発明の目的は、ＳｉＨ基と反応性を有する炭素−炭素二重結合を含有する有機化合物と、１分子中に少なくとも２個のＳｉＨ基を含有するケイ素化合物と、ヒドロシリル化触媒とを含有する硬化性組成物において、粒径、分散性を制御した金属酸化物微粒子を樹脂中に分散させ、光拡散性、または屈折率を向上させた硬化性樹脂組成物を提供することである。 An object of the present invention is to contain an organic compound containing a carbon-carbon double bond reactive with SiH groups, a silicon compound containing at least two SiH groups in one molecule, and a hydrosilylation catalyst. In the curable composition, metal oxide fine particles having a controlled particle size and dispersibility are dispersed in a resin to provide a curable resin composition having improved light diffusibility or refractive index.
上述した課題に鑑み、金属微粒子を含む硬化性樹脂中の、金属微粒子の分散性制御、粒径制御、樹脂への親和性の制御、の各々の改善につき、鋭意検討した。即ち、本発明者らは、ＳｉＨ基と反応性を有する炭素−炭素二重結合を含有する有機化合物（Ａ）、１分子中に少なくとも２個のＳｉＨ基を含有するケイ素化合物（Ｂ）、及びヒドロシリル化触媒を含有する組成物に金属酸化物微粒子（Ｄ）を分散させ、この硬化組成物につき鋭意検討し、当該組成物の硬化物が奏す優れた耐熱性・耐光性を維持しつつ、光拡散性が向上した光拡散材料や、透明高屈折率材料が得られること、を見出し、本発明を完成するに至った。 In view of the above-described problems, the present inventors have intensively studied each improvement in dispersibility control, particle size control, and affinity control for a resin in a curable resin containing metal fine particles. That is, the inventors of the present invention have an organic compound (A) containing a carbon-carbon double bond that is reactive with a SiH group, a silicon compound (B) containing at least two SiH groups in one molecule, and Metal oxide fine particles (D) are dispersed in a composition containing a hydrosilylation catalyst, and the cured composition is studied earnestly, while maintaining the excellent heat resistance and light resistance exhibited by the cured product of the composition. The inventors have found that a light diffusing material with improved diffusibility and a transparent high refractive index material can be obtained, and have completed the present invention.
すなわち、本発明は、ＳｉＨ基との反応性を有する炭素−炭素二重結合を１分子中に２個以上含有する有機化合物（Ａ）、１分子中に２個以上のＳｉＨ基を含有するケイ素化合物（Ｂ）、ヒドロシリル化触媒（Ｃ）、及び、金属酸化物微粒子（Ｄ）を含む金属酸化物微粒子含有硬化性樹脂組成物に関する。 That is, the present invention relates to an organic compound (A) containing two or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, and silicon containing two or more SiH groups in one molecule. The present invention relates to a curable resin composition containing metal oxide fine particles containing a compound (B), a hydrosilylation catalyst (C), and metal oxide fine particles (D).
好ましい実施態様は、前記金属酸化物微粒子（Ｄ）の数平均粒子径を、０．５〜２０ｎｍとすることである。 A preferred embodiment is that the metal oxide fine particles (D) have a number average particle diameter of 0.5 to 20 nm.
好ましい実施態様は、前記金属酸化物微粒子（Ｄ）を、酸化亜鉛とすることである。 A preferred embodiment is that the metal oxide fine particles (D) are zinc oxide.
好ましい実施態様は、前記金属酸化物微粒子（Ｄ）を、加水分解性基含有シラン化合物、カルボキシル基含有化合物、アミノ基含有化合物、ヒドロキシル基含有化合物、メルカプト基含有化合物、リン酸基含有化合物、スルフォン酸基含有化合物、及び配位性高分子からなる群から選ばれる１種以上を含む表面修飾剤（Ｓ）により表面修飾された金属酸化物微粒子（Ｄ）とすることである。 In a preferred embodiment, the metal oxide fine particles (D) are converted into a hydrolyzable group-containing silane compound, a carboxyl group-containing compound, an amino group-containing compound, a hydroxyl group-containing compound, a mercapto group-containing compound, a phosphate group-containing compound, a sulfone. The metal oxide fine particles (D) are surface-modified with a surface modifier (S) containing at least one selected from the group consisting of an acid group-containing compound and a coordination polymer.
好ましい実施態様は、前記表面修飾剤（Ｓ）を、下記一般式１であらわされるＳｉ−Ｏ−Ｓｉ結合を有しない加水分解性基含有シラン化合物（Ｓ−１）、及び下記一般式２であらわされるＳｉ−Ｏ−Ｓｉ結合を有する加水分解性基含有シラン化合物（Ｓ−２）、を含む表面修飾剤（Ｓ）とすることである。 In a preferred embodiment, the surface modifier (S) is represented by the hydrolyzable group-containing silane compound (S-1) having no Si—O—Si bond represented by the following general formula 1 and the following general formula 2. The surface modifying agent (S) includes a hydrolyzable group-containing silane compound (S-2) having a Si—O—Si bond.
好ましい実施態様は、前記表面修飾剤（Ｓ）を、前記金属酸化物微粒子（Ｄ）１モルに対して、前記加水分解性基含有シラン化合物（Ｓ−１）、及び前記加水分解性基含有シラン化合物（Ｓ−２）を併せて０．１〜５モル含むものとすることである。 In a preferred embodiment, the surface modifying agent (S) is mixed with the hydrolyzable group-containing silane compound (S-1) and the hydrolyzable group-containing silane with respect to 1 mol of the metal oxide fine particles (D). It is supposed to contain 0.1 to 5 mol of the compound (S-2).
好ましい実施態様は、前記表面修飾剤（Ｓ）を、前記加水分解性基含有シラン化合物（Ｓ−１）と、前記加水分解性基含有シラン化合物（Ｓ−２）とのモル比が、（Ｓ−１）：（Ｓ−２）＝１：０．０５〜１：２０の範囲含むものとすることである。 In a preferred embodiment, the surface modifier (S) has a molar ratio of the hydrolyzable group-containing silane compound (S-1) and the hydrolyzable group-containing silane compound (S-2) (S -1): (S-2) = 1: 0.05 to 1:20.
好ましい実施態様は、前記加水分解性基含有シラン化合物（Ｓ−１）の炭素数１〜１８の有機基Ｒ１を、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、シクロヘキシルメチル基、ヘキシル基、オクチル基、デシル基、フェニル基、ビニル基、３−メタクリロキシプロピル基、３−イソシアネートプロピル基、３−アクリロキシプロピル基、３−アミノプロピル基、３−グリシドキシプロピル基、２−（３，４−エポキシシクロヘキシル）エチル基、アリル基、３，３，３−トリフルオロプロピル基、及び２−シアノエチル基からなる群より選ばれる１種以上の有機基であるものとすることである。 In a preferred embodiment, the organic group R1 having 1 to 18 carbon atoms of the hydrolyzable group-containing silane compound (S-1) is converted into a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclohexylmethyl group, a hexyl group. Group, octyl group, decyl group, phenyl group, vinyl group, 3-methacryloxypropyl group, 3-isocyanatopropyl group, 3-acryloxypropyl group, 3-aminopropyl group, 3-glycidoxypropyl group, 2- It is to be one or more organic groups selected from the group consisting of (3,4-epoxycyclohexyl) ethyl group, allyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group. .
好ましい実施態様は、前記有機化合物（Ａ）を、脂肪族系化合物、イソシアヌル環含有化合物、及び前記一般式３で示される化合物からなる群より選ばれる１種以上の有機化合物であるものとすることである。 In a preferred embodiment, the organic compound (A) is one or more organic compounds selected from the group consisting of aliphatic compounds, isocyanuric ring-containing compounds, and compounds represented by the general formula 3. It is.
好ましい実施態様は、前記有機化合物（Ａ）の分子量を、２０００以下であるものとすることである。 A preferred embodiment is that the molecular weight of the organic compound (A) is 2000 or less.
好ましい実施態様は、前記オルガノシロキサン（Ｂ）が、下記一般式４で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状オルガノシロキサンであるものとすることである。 A preferred embodiment is that the organosiloxane (B) is a cyclic organosiloxane represented by the following general formula 4 and having at least 3 SiH groups in one molecule.
好ましい実施態様は、前記ケイ素化合物（Ｂ）を、炭素−炭素二重結合を１分子中に１個以上含有する有機化合物（Ｂ−１）と、１分子中に２個以上のＳｉＨ基を有するオルガノシロキサン（Ｂ−２）とのヒドロシリル化反応により得られる化合物とすることである。 In a preferred embodiment, the silicon compound (B) has an organic compound (B-1) containing one or more carbon-carbon double bonds in one molecule and two or more SiH groups in one molecule. This is a compound obtained by a hydrosilylation reaction with an organosiloxane (B-2).
また、本発明は、前記金属酸化物微粒子含有硬化性樹脂組成物を硬化させて得られる硬化物に関する。このような本発明の硬化物は、光拡散材として好適に使用される。 Moreover, this invention relates to the hardened | cured material obtained by hardening the said metal oxide microparticle containing curable resin composition. Such a cured product of the present invention is suitably used as a light diffusing material.
本発明の硬化性組成物は、含有する金属酸化物微粒子の分散性に優れ、粒径制御性にも優れ、樹脂への親和性にも優れた金属酸化物微粒子含有硬化性樹脂組成物なので、光拡散性、または屈折率を向上させた硬化物として利用できる硬化性樹脂組成物となる。 The curable composition of the present invention is a metal oxide fine particle-containing curable resin composition having excellent dispersibility of contained metal oxide fine particles, excellent particle size controllability, and excellent affinity for resin, It becomes a curable resin composition which can be used as a cured product with improved light diffusibility or refractive index.
（金属酸化物微粒子含有硬化性樹脂組成物）
本発明の金属酸化物微粒子含有硬化性樹脂組成物は、ＳｉＨ基との反応性を有する炭素−炭素二重結合を１分子中に２個以上含有する有機化合物（Ａ）、１分子中に２個以上のＳｉＨ基を含有するケイ素化合物（Ｂ）、ヒドロシリル化触媒（Ｃ）、及び、金属酸化物微粒子（Ｄ）を含む金属酸化物微粒子含有硬化性樹脂組成物である。
(Metal oxide fine particle-containing curable resin composition)
The metal oxide fine particle-containing curable resin composition of the present invention includes an organic compound (A) containing two or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, and two in one molecule. A metal oxide fine particle-containing curable resin composition comprising a silicon compound (B) containing at least one SiH group, a hydrosilylation catalyst (C), and metal oxide fine particles (D).
前記有機化合物（Ａ）と前記ケイ素化合物（Ｂ）との混合比率は、必要な強度を失わない限りは特に限定されないが、ケイ素化合物（Ｂ）中のＳｉＨ基の数（Ｙ）の有機化合物（Ａ）中の炭素−炭素二重結合の数（Ｘ）に対する比において、好ましい範囲の下限はＹ／Ｘ≧０．３、より好ましくはＹ／Ｘ≧０．５、さらに好ましくはＹ／Ｘ≧０．７であり、好ましい範囲の上限はＹ／Ｘ≦３、より好ましくはＹ／Ｘ≦２、さらに好ましくはＹ／Ｘ≦１．５である。好ましい範囲からはずれた場合には十分な強度が得られない場合や、熱劣化しやすくなる場合がある。 The mixing ratio of the organic compound (A) and the silicon compound (B) is not particularly limited as long as the necessary strength is not lost, but the organic compound (Y) of SiH groups in the silicon compound (B) ( In the ratio to the number (X) of carbon-carbon double bonds in A), the lower limit of the preferred range is Y / X ≧ 0.3, more preferably Y / X ≧ 0.5, and even more preferably Y / X ≧ The upper limit of the preferable range is Y / X ≦ 3, more preferably Y / X ≦ 2, and still more preferably Y / X ≦ 1.5. If it is out of the preferred range, sufficient strength may not be obtained, or thermal degradation may easily occur.
前記ヒドロシリル化触媒（Ｃ）の量は、十分な硬化性を有し、かつ、硬化性組成物のコストを比較的低く抑えるために、前記ケイ素化合物（Ｂ）成分のＳｉＨ基１モルに対して、好ましい下限は、１０-8モル、より好ましくは１０-6モルであり、好ましい上限は、１０-1モル、より好ましくは１０-2モルである。 The amount of the hydrosilylation catalyst (C) has sufficient curability, and in order to keep the cost of the curable composition relatively low, the amount of the SiH group of the silicon compound (B) component is 1 mol. The preferred lower limit is 10 -8 mol, more preferably 10 -6 mol, and the preferred upper limit is 10 -1 mol, more preferably 10 -2 mol.
本発明の硬化性組成物には、硬化遅延剤、接着性改良剤、熱硬化性樹脂、熱可塑性樹脂、酸化防止剤、紫外線吸収剤、充填材を添加してもよい。 To the curable composition of the present invention, a curing retarder, an adhesion improver, a thermosetting resin, a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a filler may be added.
（硬化物）
本発明の硬化物は、効率的な光拡散材、透明高屈折材として好ましくは利用でき、特に好ましくは光拡散材としての利用である。
(Cured product)
The cured product of the present invention can be preferably used as an efficient light diffusing material and a transparent high refractive material, and particularly preferably used as a light diffusing material.
硬化温度としては種々設定できるが、好ましい温度の下限は３０℃、より好ましくは１００℃であり、好ましい温度の上限は３００℃、より好ましくは２００℃である。反応温度が低いと十分に反応させるための反応時間が長くなり、反応温度が高いと成形加工が困難となりやすい。 Although the curing temperature can be variously set, the lower limit of the preferable temperature is 30 ° C., more preferably 100 ° C., and the upper limit of the preferable temperature is 300 ° C., more preferably 200 ° C. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, molding will tend to be difficult.
硬化は一定の温度で行ってもよいが、必要に応じて多段階あるいは連続的に温度を変化させてもよい。一定の温度で行うより多段階的あるいは連続的に温度を上昇させながら反応させた方が歪のない均一な硬化物が得られやすいという点において好ましい。 Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable to carry out the reaction while raising the temperature in a multistage manner or continuously, as compared with the case where the temperature is constant, in that a uniform cured product without distortion can be easily obtained.
硬化時間も種々設定できるが、高温短時間で反応させるより、比較的低温長時間で反応させた方が歪のない均一な硬化物が得られやすいという点において好ましい。 Although various curing times can be set, it is preferable to react at a relatively low temperature for a long time rather than reacting at a high temperature for a short time because a uniform cured product without distortion can be easily obtained.
（有機化合物（Ａ））
本発明に係る有機化合物（Ａ）は、ＳｉＨ基との反応性を有する炭素−炭素二重結合を１分子中に２個以上含有する有機化合物であり、好ましくは、構成元素としてＣ、Ｈ、Ｎ、Ｏ、Ｓ、及びハロゲンからなる群から選ばれる１種以上の元素のみを含むものである。
(Organic compound (A))
The organic compound (A) according to the present invention is an organic compound containing two or more carbon-carbon double bonds having reactivity with SiH groups in one molecule, and preferably C, H, It contains only one or more elements selected from the group consisting of N, O, S, and halogen.
前記有機化合物（Ａ）は、耐熱性をより向上し得るという観点からは、ＳｉＨ基との反応性を有する炭素−炭素二重結合を、（Ａ）成分１ｇ当たり、０．００１ｍｏｌ以上含有するものが好ましく、０．００５ｍｏｌ以上含有するものがより好ましく、０．００８ｍｏｌ以上含有するものがさらに好ましい。言い換えれば、前記炭素−炭素二重結合の数は、平均して前記有機化合物（Ａ）１分子当たり２個以上あればよいが、力学強度をより向上したい場合には２を越えることが好ましく、３個以上であることがより好ましく、それが１個以下の場合は、本発明に係るケイ素化合物（Ｂ）と反応してもグラフト構造となるのみで架橋構造とならない。 The organic compound (A) contains 0.001 mol or more of a carbon-carbon double bond having reactivity with the SiH group per 1 g of the component (A) from the viewpoint of further improving the heat resistance. Are preferable, those containing 0.005 mol or more are more preferable, and those containing 0.008 mol or more are more preferable. In other words, the number of the carbon-carbon double bonds may be two or more per molecule of the organic compound (A) on average, but it is preferably more than 2 in order to further improve the mechanical strength, It is more preferable that the number is 3 or more, and when it is 1 or less, even if it reacts with the silicon compound (B) according to the present invention, only a graft structure is formed and a crosslinked structure is not formed.
前記有機化合物（Ａ）は、力学的耐熱性が高いという観点、及び原料液の糸引き性が少なく成形性、取扱い性が良好であるという観点からは、分子量が２０００以下であるものが好ましく、９００未満のものがより好ましく、７００未満のものがさらに好ましく、５００未満のものが特に好ましい。 The organic compound (A) is preferably one having a molecular weight of 2000 or less from the viewpoint of high mechanical heat resistance and from the viewpoint that the stringability of the raw material liquid is low and the moldability and handleability are good. Those less than 900 are more preferred, those less than 700 are more preferred, and those less than 500 are particularly preferred.
前記有機化合物（Ａ）は、前記ＳｉＨ基との反応性を有する炭素−炭素二重結合以外の反応性基を有していてもよい。この場合の反応性基としては、エポキシ基、アミノ基、ラジカル重合性不飽和基、カルボキシル基、イソシアネート基、ヒドロキシル基、アルコキシシリル基等が挙げられる。これらの官能基を有している場合には得られる硬化性組成物の接着性が高くなりやすく、得られる硬化物の強度が高くなりやすい。接着性がより高くなりうるという点からは、これらの官能基のうちエポキシ基が好ましい。また、得られる硬化物の耐熱性が高くなりやすいという点においては、反応性基を平均して１分子中に１個以上有していることが好ましい。 The organic compound (A) may have a reactive group other than a carbon-carbon double bond having reactivity with the SiH group. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the resulting curable composition tends to be high, and the strength of the resulting cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, it is preferable to have 1 or more reactive groups in one molecule on average from the point that the heat resistance of the obtained cured product tends to be high.
前記有機化合物（Ａ）は、有機重合体系化合物、及び有機単量体系化合物からなる１種以上であることが好ましい。 The organic compound (A) is preferably at least one of an organic polymer compound and an organic monomer compound.
前記有機重合体系化合物としては例えば、ポリエーテル系、ポリエステル系、ポリアリレート系、ポリカーボネート系、飽和炭化水素系、不飽和炭化水素系、ポリアクリル酸エステル系、ポリアミド系、フェノール−ホルムアルデヒド系（フェノール樹脂系）、ポリイミド系の化合物などが挙げられる。 Examples of the organic polymer compound include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin). Type) and polyimide type compounds.
前記有機化合物（Ａ）の具体的な例としては、得られる硬化物の着色が少なく、光学的透明性が高く、耐光性が高いという観点からは、ビニルシクロヘキセン、ジシクロペンタジエン、トリアリルイソシアヌレート、２，２−ビス（４−ヒドロキシシクロヘキシル）プロパンのジアリルエーテル、１，２，４−トリビニルシクロヘキサンが好ましく、トリアリルイソシアヌレート、２，２−ビス（４−ヒドロキシシクロヘキシル）プロパンのジアリルエーテル、１，２，４−トリビニルシクロヘキサンが特に好ましい。 Specific examples of the organic compound (A) include vinylcyclohexene, dicyclopentadiene, triallyl isocyanurate from the viewpoint that the cured product obtained is less colored, has high optical transparency, and high light resistance. 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinylcyclohexane is preferred, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane diallyl ether, 1,2,4-trivinylcyclohexane is particularly preferred.
最も好ましい前記有機化合物（Ａ）は、耐熱性および透明性が高い前記一般式３で表される化合物である。 The most preferable organic compound (A) is a compound represented by the general formula 3 having high heat resistance and transparency.
前記一般式３のＲ１としては、得られる硬化物の耐熱性がより高くなりうるという観点からは、炭素数１〜２０の一価の有機基であることが好ましく、炭素数１〜１０の一価の有機基であることがより好ましく、炭素数１〜４の一価の有機基であることがさらに好ましい。これらの好ましいＲ１の例としては、メチル基、エチル基、プロピル基、ブチル基、フェニル基、ベンジル基、フェネチル基、ビニル基、アリル基、グリシジル基等が挙げられる。 R1 in the general formula 3 is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be higher, and is preferably 1 to 10 carbon atoms. It is more preferably a valent organic group, and further preferably a monovalent organic group having 1 to 4 carbon atoms. Examples of these preferable R1 include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group and the like.
（ＳｉＨ基との反応性を有する炭素−炭素二重結合）
前記有機化合物（Ａ）中の、ＳｉＨ基との反応性を有する、前記炭素−炭素二重結合の結合位置は、特に限定されず、分子内のどこに存在してもよいが、有機化合物（Ａ）の骨格部分に直接結合していてもよく、２価以上の置換基を介して共有結合することで、側鎖に存在していても良い。
(Carbon-carbon double bond having reactivity with SiH group)
The bonding position of the carbon-carbon double bond having reactivity with the SiH group in the organic compound (A) is not particularly limited and may be present anywhere in the molecule, but the organic compound (A ) May be directly bonded to the skeleton, or may be present in the side chain by covalent bonding via a divalent or higher valent substituent.
原料の入手の容易さからは、下記一般式５、又は、下記一般式６で示される基が好ましく、その中でも下記一般式６で示される基が反応性の観点から特に好ましい。 From the viewpoint of easy availability of the raw material, a group represented by the following general formula 5 or 6 is preferred, and among them, a group represented by the following general formula 6 is particularly preferred from the viewpoint of reactivity.
また、前記ＳｉＨ基との反応性を有する炭素−炭素二重結合としては、下記一般式７又は、下記一般式８で示される部分構造を環内に有する脂環式の基が、硬化物の耐熱性が高いという点から好適である。また、原料の入手の容易さ、反応性の観点からは、下記一般式８で示される脂環式の基が特に好ましい。 Moreover, as a carbon-carbon double bond having reactivity with the SiH group, an alicyclic group having a partial structure represented by the following general formula 7 or the following general formula 8 in the ring is a cured product. This is preferable from the viewpoint of high heat resistance. Further, from the viewpoint of easy availability of raw materials and reactivity, an alicyclic group represented by the following general formula 8 is particularly preferable.
本発明に係るケイ素化合物（Ｂ）は、１分子中に２個以上のＳｉＨ基を含有するケイ素化合物であり、好ましくは、鎖状、及び／又は、環状オルガノポリシロキサンである。 The silicon compound (B) according to the present invention is a silicon compound containing two or more SiH groups in one molecule, and is preferably a linear and / or cyclic organopolysiloxane.
中でも、前記有機化合物（Ａ）との相溶性が良いという観点からは、さらに、前記一般式４で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状オルガノポリシロキサンが好ましく、特に好ましくは、入手容易性の観点からは、１，３，５，７−テトラメチルシクロテトラシロキサンである。 Among these, from the viewpoint of good compatibility with the organic compound (A), a cyclic organopolysiloxane having at least three SiH groups in one molecule represented by the general formula 4 is more preferable. Preferably, from the viewpoint of availability, 1,3,5,7-tetramethylcyclotetrasiloxane.
一般式４中の置換基Ｒ２は、Ｃ、Ｈ、およびＯからなる群から選ばれる元素のみから構成されるものであることが好ましく、炭化水素基であることがより好ましく、メチル基であることがさらに好ましい。 The substituent R2 in the general formula 4 is preferably composed only of an element selected from the group consisting of C, H, and O, more preferably a hydrocarbon group, and a methyl group. Is more preferable.
（Ｂ）成分の分子量は流動性を発現しやすいという観点から、好ましい分子量の下限は５０であり、好ましい分子量の上限は１００，０００、より好ましくは１，０００、さらに好ましくは７００である。 The lower limit of the molecular weight is preferably 50, and the upper limit of the preferable molecular weight is 100,000, more preferably 1,000, and still more preferably 700, from the viewpoint that the molecular weight of the component (B) is easy to develop fluidity.
前記有機化合物（Ａ）と良好な相溶性を有するという観点、およびケイ素化合物（Ｂ）の揮発性が低くなり得られる硬化物からのアウトガスの問題が生じ難いという観点からは、ケイ素化合物（Ｂ）は、ＳｉＨ基との反応性を有する炭素−炭素二重結合を１分子中に１個以上含有する有機化合物（Ｂ−１）と、１分子中に２個以上のＳｉＨ基を有する鎖状、及び／又は、環状のポリオルガノシロキサン（Ｂ−２）を、ヒドロシリル化反応して得ることができる化合物であることが好ましく、このようにして得られた、本発明に係るケイ素化合物（Ｂ）を含む複数の化合物の混合物はそのまま、本発明の硬化性組成物の成分とすることができ、その状態で本発明に係るヒドロシリル化触媒（Ｃ）を含んでいるので特に好ましい。 From the viewpoint of having good compatibility with the organic compound (A) and from the viewpoint that the problem of outgas from a cured product that can be reduced in volatility of the silicon compound (B) is unlikely to occur, the silicon compound (B) Is an organic compound (B-1) containing at least one carbon-carbon double bond having reactivity with a SiH group in one molecule, and a chain having two or more SiH groups in one molecule, And / or the cyclic polyorganosiloxane (B-2) is preferably a compound obtained by a hydrosilylation reaction, and the silicon compound (B) according to the present invention thus obtained is obtained. A mixture of a plurality of compounds to be contained can be used as it is as a component of the curable composition of the present invention, and is particularly preferable because it contains the hydrosilylation catalyst (C) according to the present invention in that state.
このような、有機化合物（Ｂ−１）とポリオルガノシロキサン（Ｂ−２）との反応物であるケイ素化合物（Ｂ）成分の例としては、ビスフェノールＡジアリルエーテルと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、ビニルシクロヘキセンと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、ジビニルベンゼンと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、ジシクロペンタジエンと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、トリアリルイソシアヌレートと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、ジアリルモノグリシジルイソシアヌレートと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、アリルグリシジルエーテルと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、αメチルスチレンと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、モノアリルジグリシジルイソシアヌレートと１，３，５，７−テトラメチルシクロテトラシロキサンとの反応物、等を挙げることができる。 Examples of the silicon compound (B) component that is a reaction product of the organic compound (B-1) and the polyorganosiloxane (B-2) include bisphenol A diallyl ether and 1,3,5,7- Reaction product of tetramethylcyclotetrasiloxane, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane Product, reaction product of dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, diallyl monoglycidyl Reaction product of isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane, allyl glycy A reaction product of ether and 1,3,5,7-tetramethylcyclotetrasiloxane, a reaction product of α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, monoallyl diglycidyl isocyanurate and 1 , 3,5,7-tetramethylcyclotetrasiloxane, and the like.
（有機化合物（Ｂ−１））
有機化合物（Ｂ−１）は、上述の有機化合物（Ａ）と同様であり、即ち、前記有機化合物（Ａ）の好ましい態様は有機化合物（Ｂ−１）についても同様に好ましい。
(Organic compound (B-1))
The organic compound (B-1) is the same as the organic compound (A) described above, that is, the preferred embodiment of the organic compound (A) is also preferred for the organic compound (B-1).
（ヒドロシリル化触媒（Ｃ））
本発明に係るヒドロシリル化触媒（Ｃ）としては、白金化合物の触媒としては、白金の単体、アルミナ、シリカ、カーボンブラック等の担体に固体白金を担持させたもの、塩化白金酸、塩化白金酸とアルコール、アルデヒド、ケトン等との錯体、白金−オレフィン錯体（例えば、Ｐｔ（ＣＨ２＝ＣＨ２）２（ＰＰｈ３）２、Ｐｔ（ＣＨ２＝ＣＨ２）２Ｃｌ２）、白金−ビニルシロキサン錯体（例えば、Ｐｔ（ＶｉＭｅ２ＳｉＯＳｉＭｅ２Ｖｉ）ｎ、Ｐｔ［（ＭｅＶｉＳｉＯ）４］ｍ）、白金−ホスフィン錯体（例えば、Ｐｔ（ＰＰｈ３）４、Ｐｔ（ＰＢｕ３）４）、白金−ホスファイト錯体（例えば、Ｐｔ［Ｐ（ＯＰｈ）３］４、Ｐｔ［Ｐ（ＯＢｕ）３］４）（式中、Ｍｅはメチル基、Ｂｕはブチル基、Ｖｉはビニル基、Ｐｈはフェニル基を表し、ｎ、ｍは、整数を示す。）、ジカルボニルジクロロ白金、カールシュテト（Ｋａｒｓｔｅｄｔ）触媒、また、アシュビー（Ａｓｈｂｙ）らによって開発された白金−炭化水素複合体、ならびにラモロー（Ｌａｍｏｒｅａｕｘ）らによって開発された白金アルコラート触媒、モディック（Ｍｏｄｉｃ）らによって開発された塩化白金−オレフィン複合体等が挙げられ、また、白金化合物以外の触媒としては、ＲｈＣｌ（ＰＰｈ）３、ＲｈＣｌ３、ＲｈＡｌ２Ｏ３、ＲｕＣｌ３、ＩｒＣｌ３、ＦｅＣｌ３、ＡｌＣｌ３、ＰｄＣｌ２・２Ｈ２Ｏ、ＮｉＣｌ２、ＴｉＣｌ４等が挙げられる。
(Hydrosilylation catalyst (C))
As the hydrosilylation catalyst (C) according to the present invention, as a platinum compound catalyst, a platinum simple substance, a support of solid platinum on a support such as alumina, silica, carbon black, chloroplatinic acid, chloroplatinic acid, Complexes with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt (CH2 = CH2) 2 (PPh3) 2, Pt (CH2 = CH2) 2Cl2), platinum-vinylsiloxane complexes (for example, Pt (ViMe2SiOSiMe2Vi)) n, Pt [(MeViSiO) 4] m), platinum-phosphine complexes (eg, Pt (PPh3) 4, Pt (PBu3) 4), platinum-phosphite complexes (eg, Pt [P (OPh) 3] 4, Pt [P (OBu) 3] 4) (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, and Ph represents a phenyl group. N and m are integers.), Dicarbonyldichloroplatinum, Karstedt catalyst, platinum-hydrocarbon complex developed by Ashby et al., And Lamoreaux et al. And platinum chloride-olefin complexes developed by Modic et al., And catalysts other than platinum compounds include RhCl (PPh) 3, RhCl3, RhAl2O3, RuCl3, IrCl3, FeCl 3, AlCl 3, PdCl 2 .2H 2 O, NiCl 2, TiCl 4 and the like can be mentioned.
これらの中で、触媒活性の点から塩化白金酸、白金−オレフィン錯体、白金−ビニルシロキサン錯体が好ましい。また、これらの触媒は単独で使用してもよく、２種以上併用してもよい。 Of these, chloroplatinic acid, platinum-olefin complexes, and platinum-vinylsiloxane complexes are preferred from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.
また、上記触媒には助触媒を併用することが可能であり、例としてトリフェニルホスフィン等のリン系化合物、ジメチルマレエート等の１、２−ジエステル系化合物、２−ヒドロキシ−２−メチル−１−ブチン等のアセチレンアルコール系化合物、単体の硫黄等の硫黄系化合物、トリエチルアミン等のアミン系化合物等が挙げられる。 In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, 2-hydroxy-2-methyl-1 -Acetylene alcohol compounds such as butyne, sulfur compounds such as simple sulfur, amine compounds such as triethylamine, and the like.
（金属酸化物微粒子（Ｄ））
本発明に係る金属酸化物微粒子（Ｄ）としては、実用性に優れる点で、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化チタン、酸化ジルコニウム、酸化鉄、酸化コバルト、酸化ロジウム、酸化ニッケル、酸化パラジウム、酸化銅、酸化亜鉛、酸化カドミウム、酸化アルミニウム、酸化ガリウム、酸化インジウム、酸化ケイ素、酸化ゲルマニウム、酸化スズ、酸化セリウム、酸化ユーロピウム、酸化ディスプロシウム、酸化インジウムスズ、チタン酸バリウム、コバルト酸リチウムから選ばれる１種以上の微粒子が好ましく、紫外線吸収、高屈折率、導電性、高誘電率、光触媒活性などの特性を有する点で酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化カドミウム、酸化スズ、酸化セリウム、酸化インジウムスズ、チタン酸バリウム、コバルト酸リチウムの微粒子がより好ましく、安全性および入手性の点で酸化亜鉛微粒子がもっとも好ましい。これらは単独で使用してもよく、複数を組み合わせて使用してもよい。また他の元素を若干量含む、いわゆるドーピングされた材料の微粒子であってもよい。
(Metal oxide fine particles (D))
As the metal oxide fine particles (D) according to the present invention, magnesium oxide, calcium oxide, strontium oxide, titanium oxide, zirconium oxide, iron oxide, cobalt oxide, rhodium oxide, nickel oxide, palladium oxide are excellent in practicality. , Copper oxide, zinc oxide, cadmium oxide, aluminum oxide, gallium oxide, indium oxide, silicon oxide, germanium oxide, tin oxide, cerium oxide, europium oxide, dysprosium oxide, indium tin oxide, barium titanate, lithium cobaltate One or more fine particles selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, cadmium oxide, tin oxide, and oxidation are preferable in that they have characteristics such as ultraviolet absorption, high refractive index, electrical conductivity, high dielectric constant, and photocatalytic activity. Cerium, indium tin oxide, titanic acid Potassium, more preferably fine particles of lithium cobaltate, zinc oxide fine particles is most preferred in view of safety and availability. These may be used alone or in combination. Further, fine particles of a so-called doped material containing some amount of other elements may be used.
本発明において使用する金属酸化物微粒子（Ｄ）の粒子径は、サイズに由来する量子効果が顕著である点、及び樹脂中に分散させた際の透明性に優れる点で、数平均粒子径で０．５〜２０ｎｍの範囲が好ましく、１〜１０ｎｍの範囲がより好ましい。 The particle diameter of the metal oxide fine particles (D) used in the present invention is a number average particle diameter in that the quantum effect derived from the size is remarkable and the transparency when dispersed in the resin is excellent. The range of 0.5-20 nm is preferable, and the range of 1-10 nm is more preferable.
例えば、酸化亜鉛微粒子の数平均粒子径は、ＴＥＭ観察において９０〜１１０個程度の粒子の直径を測定し、その和を粒子数で除することにより求めることができる。 For example, the number average particle diameter of the zinc oxide fine particles can be obtained by measuring the diameter of about 90 to 110 particles in TEM observation and dividing the sum by the number of particles.
前記金属酸化物微粒子（Ｄ）は、表面修飾剤（Ｓ）、即ち、金属酸化物微粒子表面に化学的・物理的に吸着したり結合したりできる化合物で表面修飾されたものであることが、凝集防止の観点から好ましい。 The metal oxide fine particles (D) are surface-modified with a surface modifier (S), that is, a compound that can be chemically and physically adsorbed or bonded to the surface of the metal oxide fine particles. It is preferable from the viewpoint of preventing aggregation.
（表面修飾剤（Ｓ））
前記表面修飾剤（Ｓ）としては、加水分解性基含有シラン化合物、カルボキシル基含有化合物、アミノ基含有化合物、ヒドロキシル基含有化合物、メルカプト基含有化合物、リン酸基含有化合物、スルフォン酸基含有化合物、及び配位性高分子からなる群から選ばれる１種以上であることが、微粒子の分散性や安定性を確保するという点で好ましい。前記配位性高分子としては、ポリエーテル、ポリビニルピロリドン、ポリアクリル酸等を挙げることができる。これらの中でも、効率が高く強固である点、及び金属酸化物微粒子の表面に起因する物性をコントロールできる点で、加水分解性基含有シラン化合物（以下、シランカップリング剤とも呼ぶ。）が好ましく、樹脂および溶媒への親和性を操作するために、少なくとも１種類以上のシランカップリング剤を併用することが好ましい。
(Surface modifier (S))
Examples of the surface modifier (S) include hydrolyzable group-containing silane compounds, carboxyl group-containing compounds, amino group-containing compounds, hydroxyl group-containing compounds, mercapto group-containing compounds, phosphate group-containing compounds, sulfonic acid group-containing compounds, And at least one selected from the group consisting of coordination polymers is preferable from the viewpoint of ensuring the dispersibility and stability of the fine particles. Examples of the coordination polymer include polyether, polyvinyl pyrrolidone, and polyacrylic acid. Among these, a hydrolyzable group-containing silane compound (hereinafter also referred to as a silane coupling agent) is preferable in that it is highly efficient and strong, and the physical properties resulting from the surface of the metal oxide fine particles can be controlled. In order to manipulate the affinity for the resin and the solvent, it is preferable to use at least one silane coupling agent in combination.
特に好ましい前記表面修飾剤（Ｓ）は、樹脂および溶媒への親和性制御の観点から、前記一般式１であらわされるＳｉ−Ｏ−Ｓｉ結合を有しない加水分解性基含有シラン化合物（Ｓ−１）、及び前記一般式２であらわされるＳｉ−Ｏ−Ｓｉ結合を有する加水分解性基含有シラン化合物（Ｓ−２）、を含むものである。 The particularly preferred surface modifier (S) is a hydrolyzable group-containing silane compound (S-1) having no Si—O—Si bond represented by the general formula 1 from the viewpoint of controlling affinity to a resin and a solvent. And a hydrolyzable group-containing silane compound (S-2) having a Si—O—Si bond represented by the general formula 2.
本発明において、金属酸化物微粒子１モルに対して、加水分解性基含有シラン化合物（Ｓ−１）と（Ｓ−２）とを併せて０．１〜５モル使用することが好ましく、さらに０．２〜２モルの範囲であることがより好ましい。 In the present invention, it is preferable to use 0.1 to 5 moles of the hydrolyzable group-containing silane compounds (S-1) and (S-2) with respect to 1 mole of the metal oxide fine particles. More preferably in the range of 2 to 2 mol.
本発明において、金属酸化物微粒子表面を修飾する加水分解性基含有シラン化合物（Ｓ−１）と（Ｓ−２）とのモル比が、（Ａ）：（Ｂ）＝１：０．０５〜１：２０の範囲であることが好ましい。 In the present invention, the molar ratio of the hydrolyzable group-containing silane compound (S-1) and (S-2) that modifies the surface of the metal oxide fine particles is (A) :( B) = 1: 0.05- A range of 1:20 is preferred.
上記一般式１、又は一般式２のＲ１、又はＲ２は、入手性、及び価格の点で、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、シクロヘキシルメチル基、ヘキシル基、オクチル基、デシル基、フェニル基、ビニル基、３−メタクリロキシプロピル基、３−アクリロキシプロピル基、３−アミノプロピル基、３−グリシドキシプロピル基、２−（３，４−エポキシシクロヘキシル）エチル基、アリル基、３，３，３−トリフルオロプロピル基、及び２−シアノエチル基からなる群から選ばれる１種以上が好ましく、その中でも、メチル基、エチル基、プロピル基、シクロヘキシルメチル基、オクチル基、デシル基、フェニル基、ビニル基、３−メタクリロキシプロピル基、３−アクリロキシプロピル基、アリル基が好ましい。またａが２以上の場合、１分子中の複数のＲは同一でもよく異なっていてもよい。 R1 or R2 in the above general formula 1 or general formula 2 is methyl, ethyl, propyl, isopropyl, butyl, cyclohexylmethyl, hexyl, octyl, in terms of availability and price, Decyl group, phenyl group, vinyl group, 3-methacryloxypropyl group, 3-acryloxypropyl group, 3-aminopropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, One or more selected from the group consisting of an allyl group, a 3,3,3-trifluoropropyl group, and a 2-cyanoethyl group are preferable. Among them, a methyl group, an ethyl group, a propyl group, a cyclohexylmethyl group, an octyl group, A decyl group, a phenyl group, a vinyl group, a 3-methacryloxypropyl group, a 3-acryloxypropyl group, and an allyl group are preferable. When a is 2 or more, a plurality of R in one molecule may be the same or different.
上記一般式１、又は一般式２の加水分解性基Ｘは、アルコキシ基、オキシム基、オキシカルボニル基、ハロゲン原子、水素原子などを挙げることができるが、金属酸化物微粒子表面を修飾する際の反応がマイルドである点で、アルコキシ基、オキシム基、及びオキシカルボニル基から選ばれる１種以上であることが好ましく、その中でも、入手性、及び価格の点で、アルコキシ基がより好ましく、炭素数３以下のアルコキシ基がさらに好ましい。 Examples of the hydrolyzable group X of the general formula 1 or 2 include an alkoxy group, an oxime group, an oxycarbonyl group, a halogen atom, a hydrogen atom, and the like. It is preferably at least one selected from an alkoxy group, an oxime group, and an oxycarbonyl group in that the reaction is mild, and among them, an alkoxy group is more preferable in terms of availability and price, and the number of carbon atoms. 3 or less alkoxy groups are more preferable.
また、上記一般式１、又は一般式２のａは、１、２、又は３であるが、入手性、及び価格の点で、ａは、１、又は２であることが好ましい。 In the general formula 1 or general formula 2, a is 1, 2, or 3. However, a is preferably 1 or 2 in terms of availability and price.
本発明で使用する上記一般式１、又は一般式２であらわされる加水分解性基含有シラン化合物の好ましい例としては、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、シクロヘキシルメチルトリメトキシシラン、シクロヘキシルメチルトリエトキシシラン、デシルトリメトキシシラン、デシルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルメチルジメトキシシラン、ジフェニルジメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジメトキシシラン、ジビニルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、アリルトリメトキシシラン、３，３，３−トリフルオロプロピルトリメトキシシラン等が挙げられる。 Preferred examples of the hydrolyzable group-containing silane compound represented by the above general formula 1 or 2 used in the present invention include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, cyclohexylmethyltrimethoxysilane, cyclohexylmethyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Rumethyldimethoxysilane, divinyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, allyltrimethoxysilane, 3,3,3-trifluoro And propyltrimethoxysilane.
本発明において金属酸化物微粒子と表面修飾剤とを反応させる際、使用する加水分解性基含有シラン化合物（Ｓ−２）は特には限定されないが、金属酸化物微粒子の凝集を防止し、かつＳｉ−Ｏ結合を有する樹脂中に容易に均一分散でき、かつ樹脂による極性や親和性を制御できる点で、トリメトキシシラン、トリエトキシシラン、トリプロピルシラン、ジメトキシメチルシラン、ジエトキシメチルシラン、ペンタメチルジシロキサン、１，１，１，３，５，５，５−ヘプタメチルトリシロキサン、１，１，１，３，５，７，７，−オクタメチルテトラシロキサン、トリス（トリメチルシロキシ）シランからなる群より選ばれる１種類以上のシラン化合物とのヒドロシリル化反応により合成できるものが挙げられる。中でも入手性および価格の点で１，１，１，３，５，５，５−ヘプタメチルトリシロキサンであることが好ましい。 In the present invention, when the metal oxide fine particles and the surface modifier are reacted, the hydrolyzable group-containing silane compound (S-2) used is not particularly limited, but prevents aggregation of the metal oxide fine particles and Si. Trimethoxysilane, triethoxysilane, tripropylsilane, dimethoxymethylsilane, diethoxymethylsilane, and pentamethyl can be easily and uniformly dispersed in a resin having —O bond and the polarity and affinity of the resin can be controlled. Disiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,7,7-octamethyltetrasiloxane, tris (trimethylsiloxy) silane Examples include those that can be synthesized by a hydrosilylation reaction with one or more silane compounds selected from the group. Among these, 1,1,1,3,5,5,5-heptamethyltrisiloxane is preferable in terms of availability and price.
以下に、本発明の実施例および比較例を示すが、本発明は以下によって限定されるものではない。 Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.
（ＢＣ含有合成物の合成）
５Ｌの四つ口フラスコに、攪拌装置、滴下漏斗、及び冷却管をセットした。このフラスコにトルエン１８００ｇ、及び１，３，５，７−テトラメチルシクロテトラシロキサン１４４０ｇを入れ、１２０℃のオイルバス中で加熱、攪拌した。そこに、トリアリルイソシアヌレート２００ｇ、トルエン２００ｇ、及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）１．４４ｍｌの混合液を５０分かけて滴下した。得られた溶液をそのまま６時間加温、攪拌した後、未反応の１，３，５，７−テトラメチルシクロテトラシロキサン、及びトルエンを減圧留去することでＢＣ含有合成物を得た。
(Synthesis of BC-containing compound)
A stirrer, a dropping funnel, and a condenser tube were set in a 5 L four-necked flask. Into this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed and heated and stirred in an oil bath at 120 ° C. A mixed solution of 200 g of triallyl isocyanurate, 200 g of toluene, and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and then unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a BC-containing compound.
バリアン・テクノロジーズ・ジャパン・リミテッド製、３００ＭＨｚ ＮＭＲ装置を用いた１Ｈ−ＮＭＲにより、このＢＣ含有合成物を測定したところ、反応生成物として、１，３，５，７−テトラメチルシクロテトラシロキサンのＳｉＨ基の一部がトリアリルイソシアヌレートと反応したものが生成していることがわかった。 When this BC-containing compound was measured by 1H-NMR using a 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited, the reaction product was SiH of 1,3,5,7-tetramethylcyclotetrasiloxane. It was found that some of the groups reacted with triallyl isocyanurate.
また、このＢＣ含有合成物を重クロロホルムで１％程度まで希釈したものを、ＮＭＲ用チューブに加えて測定し、未反応アリル基由来のメチレン基のピークと、反応アリル基由来のメチレン基のピークから、１，２−ジブロモエタンを内部標準に用いて、1Ｈ−ＮＭＲによりＳｉＨ基の含有量であるジブロモエタン換算の官能基価としてジブロモエタン換算でのＳｉＨ基価（ｍｍｏｌ／ｇ）を求めたところ、８．０８ｍｍｏｌ／ｇのＳｉＨ基を含有していることがわかった。 In addition, a product obtained by diluting this BC-containing compound to about 1% with deuterated chloroform was added to an NMR tube and measured, and a peak of a methylene group derived from an unreacted allyl group and a peak of a methylene group derived from a reacted allyl group were measured. Then, using 1,2-dibromoethane as an internal standard, the SiH group value (mmol / g) in terms of dibromoethane was determined as a functional group value in terms of dibromoethane, which is the content of SiH groups, by 1H-NMR. However, it was found that 8.08 mmol / g SiH group was contained.
上記のように、このＢＣ含有合成物は、混合物であるが、本発明に係る１分子中に２個以上のＳｉＨ基を含有するケイ素化合物（Ｂ）である下記一般式９であらわされる化合物を主成分として含有し、また、本発明に係るヒドロシリル化触媒（Ｃ）である白金ビニルシロキサン錯体を含有している。 As described above, this BC-containing compound is a mixture, but a compound represented by the following general formula 9 is a silicon compound (B) containing two or more SiH groups in one molecule according to the present invention. It contains as a main component and also contains a platinum vinylsiloxane complex which is a hydrosilylation catalyst (C) according to the present invention.
（酸化亜鉛微粒子の合成）
３Ｌの４つ口フラスコに、ＫＯＨ４４．９ｇ、及びメタノール１．６Ｌを入れて攪拌し、完全に溶解させることでＫＯＨのメタノール溶液を得た。別の容器に、酢酸亜鉛二水和物８７．８ｇをとり、メタノール０．４Ｌを加えて溶解させた。この酢酸亜鉛のメタノール溶液をすばやくＫＯＨのメタノール溶液に加え、３５℃で１０分間攪拌することにより透明な酸化亜鉛微粒子メタノール分散液を得た。この分散液中の酸化亜鉛微粒子の濃度は０．２ｍｏｌ／Ｌである。
(Synthesis of zinc oxide fine particles)
In a 3 L four-necked flask, 44.9 g of KOH and 1.6 L of methanol were added and stirred, and dissolved completely to obtain a methanol solution of KOH. In a separate container, 87.8 g of zinc acetate dihydrate was taken and 0.4 L of methanol was added and dissolved. The methanol solution of zinc acetate was quickly added to the methanol solution of KOH and stirred at 35 ° C. for 10 minutes to obtain a transparent zinc oxide fine particle methanol dispersion. The concentration of the zinc oxide fine particles in this dispersion is 0.2 mol / L.
得られた酸化亜鉛微粒子分散液を支持膜に付着、乾燥させた後、そのサンプルにつきＴＥＭ観察したところ、この酸化亜鉛微粒子の数平均粒子径は５ｎｍであった。 After the obtained zinc oxide fine particle dispersion was adhered to the support film and dried, the sample was observed with a TEM. As a result, the number average particle diameter of the zinc oxide fine particles was 5 nm.
（デシルシラン修飾酸化亜鉛微粒子の合成）
前記酸化亜鉛微粒子メタノール分散液２００ｍＬ（酸化亜鉛０．０４モル含有）を５００ｍＬ三口フラスコに入れ、デシルトリメトキシシラン３．８５ｇ（ＬＳ−５２５８；信越化学工業(株)製；酸化亜鉛１モルに対して０．３７モルに相当）を加え、
６０℃で２時間加熱したところ白色沈殿物が生成した。次に、上澄み液を取り除き、この白色沈殿物にヘキサン５０ｍＬを加えたところ、デシル基の導入により溶媒への親和性が向上し、沈殿物は殆ど溶解した。少量の不溶物をろ過により除去した後、このヘキサン溶液から溶媒を留去し、８０℃で１０時間減圧乾燥させることにより、デシルトリメトキシシランで表面修飾された酸化亜鉛微粒子５．３ｇを無色透明液体として得た。
(Synthesis of decylsilane-modified zinc oxide fine particles)
200 mL of the zinc oxide fine particle methanol dispersion (containing 0.04 mol of zinc oxide) is placed in a 500 mL three-necked flask, and 3.85 g of decyltrimethoxysilane (LS-5258; manufactured by Shin-Etsu Chemical Co., Ltd.); Equivalent to 0.37 mol)
When heated at 60 ° C. for 2 hours, a white precipitate was formed. Next, when the supernatant was removed and 50 mL of hexane was added to the white precipitate, the affinity for the solvent was improved by the introduction of the decyl group, and the precipitate was almost dissolved. After removing a small amount of insoluble matter by filtration, the solvent was distilled off from this hexane solution, and dried under reduced pressure at 80 ° C. for 10 hours, so that 5.3 g of zinc oxide fine particles surface-modified with decyltrimethoxysilane were colorless and transparent. Obtained as a liquid.
このデシルシラン修飾酸化亜鉛微粒子の灰分測定を実施した結果、酸化亜鉛の含有量は８０ｗｔ％であり、収率は１００％であった。 As a result of measuring the ash content of the decylsilane-modified zinc oxide fine particles, the zinc oxide content was 80 wt% and the yield was 100%.
（フェニルシラン修飾酸化亜鉛微粒子の合成）
前記酸化亜鉛微粒子メタノール分散液２００ｍＬ（酸化亜鉛０．０４モル含有）を５００ｍＬ三口フラスコに入れ、フェニルトリメトキシシラン２．６２ｇ（Ｇｅｌｅｓｔ社製；酸化亜鉛１モルに対して０．３３モルに相当）を加え、６０℃で２時間加熱したところ白色沈殿物が生成した。次に、上澄み液を取り除き、この白色沈殿物にアセトン５０ｍＬを加えたところ、フェニル基の導入により溶媒への親和性向上し、沈殿物は殆ど溶解した。少量の不溶物をろ過により除去した後、このアセトン溶液から溶媒を留去し、８０℃で１０時間減圧乾燥させることにより、フェニルトリメトキシシランで表面修飾された酸化亜鉛微粒子４．４５ｇを白色固体として得た。
(Synthesis of phenylsilane-modified zinc oxide fine particles)
200 mL of the zinc oxide fine particle methanol dispersion (containing 0.04 mol of zinc oxide) was placed in a 500 mL three-necked flask and 2.62 g of phenyltrimethoxysilane (manufactured by Gelest Co., equivalent to 0.33 mol per 1 mol of zinc oxide) When heated at 60 ° C. for 2 hours, a white precipitate was formed. Next, when the supernatant was removed and 50 mL of acetone was added to the white precipitate, the affinity for the solvent was improved by introduction of the phenyl group, and the precipitate was almost dissolved. After removing a small amount of insoluble matter by filtration, the solvent was distilled off from this acetone solution and dried under reduced pressure at 80 ° C. for 10 hours to obtain 4.45 g of zinc oxide fine particles surface-modified with phenyltrimethoxysilane as a white solid. Got as.
このフェニルシラン表面修飾酸化亜鉛微粒子の灰分測定を実施した結果、酸化亜鉛の含有量は６２ｗｔ％であり、収率は８６％であった。 As a result of measuring the ash content of the phenylsilane surface-modified zinc oxide fine particles, the zinc oxide content was 62 wt% and the yield was 86%.
（ヘキシルシラン修飾酸化亜鉛微粒子の合成）
前記酸化亜鉛微粒子メタノール分散液２００ｍＬ（酸化亜鉛０．０４モル含有）を
５００ｍＬ三口フラスコに入れ、ヘキシルトリメトキシシラン２．９６ｇ（(株)アズマックス製；酸化亜鉛１モルに対して０．３３モルに相当）を加え、６０℃で２時間加熱したところ白色沈殿物が生成した。次に、上澄み液を取り除き、この白色沈殿物にヘキサン５０ｍＬを加えたところ、ヘキシル基の導入により溶媒への親和性向上し、沈殿物は殆ど溶解した。少量の不溶物をろ過により除去した後、このヘキサン溶液から溶媒を留去し、８０℃で１０時間減圧乾燥させることにより、ヘキシルトリメトキシシランで表面修飾された酸化亜鉛微粒子３．５ｇを白色固体として得た。
(Synthesis of hexylsilane-modified zinc oxide fine particles)
200 mL of the zinc oxide fine particle methanol dispersion (containing 0.04 mol of zinc oxide) was placed in a 500 mL three-necked flask, and 2.96 g of hexyltrimethoxysilane (manufactured by Azmax Co., Ltd .; 0.33 mol per 1 mol of zinc oxide) And when heated at 60 ° C. for 2 hours, a white precipitate was formed. Next, when the supernatant was removed and 50 mL of hexane was added to the white precipitate, the affinity for the solvent was improved by the introduction of the hexyl group, and the precipitate was almost dissolved. After removing a small amount of insoluble matter by filtration, the solvent was distilled off from this hexane solution and dried under reduced pressure at 80 ° C. for 10 hours to obtain 3.5 g of zinc oxide fine particles surface-modified with hexyltrimethoxysilane as a white solid. Got as.
このヘキシルシラン修飾酸化亜鉛微粒子の灰分測定を実施した結果、酸化亜鉛の含有量は８０ｗｔ％であり、収率は８７％であった。 As a result of ash measurement of the hexylsilane-modified zinc oxide fine particles, the zinc oxide content was 80 wt% and the yield was 87%.
（表面修飾剤（ＳＳ）の合成）
１００ｍＬの四つ口フラスコに、攪拌装置、滴下漏斗、及び冷却管をセットした。このフラスコにトルエン１０ｍＬ、及び１，１，１，３，５，５，５−ヘプタメチルトリシロキサン１６．３ｍＬを入れ６０℃で攪拌した。そこに、ビニルトリメトキシシラン７．７ｍＬ、トルエン２０ｍＬ、及び白金ビニルシロキサン錯体のキシレン溶液（白金として３ｗｔ％含有）０．７５ｍｌの混合液を２０分かけて滴下した。得られた溶液をそのまま１時間加温、攪拌した後、未反応の１，１，１，３，５，５，５−ヘプタメチルトリシロキサン、ビニルトリメトキシシラン、及びトルエンを減圧留去することで表面修飾剤（ＳＳ）を得た。
(Synthesis of surface modifier (SS))
A stirrer, a dropping funnel, and a condenser tube were set in a 100 mL four-necked flask. To this flask, 10 mL of toluene and 16.3 mL of 1,1,1,3,5,5,5-heptamethyltrisiloxane were added and stirred at 60 ° C. A mixed solution of 7.7 ml of vinyltrimethoxysilane, 20 ml of toluene, and 0.75 ml of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum) was added dropwise over 20 minutes. After heating and stirring the resulting solution as it is for 1 hour, unreacted 1,1,1,3,5,5,5-heptamethyltrisiloxane, vinyltrimethoxysilane, and toluene are distilled off under reduced pressure. A surface modifier (SS) was obtained.
バリアン・テクノロジーズ・ジャパン・リミテッド製、３００ＭＨｚ ＮＭＲ装置を用いた１Ｈ−ＮＭＲにより、この表面修飾剤（ＳＳ）を測定したところ、反応生成物として、１，１，１，３，５，５，５−ヘプタメチルトリシロキサンのＳｉＨ基の一部がビニルトリメトキシシランと反応した、下記一般式１０で表されるものが生成していることが判った。 When this surface modifier (SS) was measured by 1H-NMR using a 300 MHz NMR apparatus manufactured by Varian Technologies Japan Limited, 1,1,1,3,5,5,5 were obtained as reaction products. -It turned out that what is represented by the following general formula 10 which a part of SiH group of heptamethyltrisiloxane reacted with vinyltrimethoxysilane was produced | generated.
（ＳＳ修飾酸化亜鉛微粒子の合成）
前記酸化亜鉛微粒子メタノール分散液２００ｍＬ（酸化亜鉛０．０４モル含有）を４つ口フラスコ（容量５００ｍＬ）に入れ、前記表面修飾剤（ＳＳ）２．３８ｇ（酸化亜鉛１モルに対して０．１６モルに相当）、及びデシルトリメトキシシラン０．４２ｇ（ＬＳ−５２５８；信越化学工業(株)製；酸化亜鉛１モルに対して０．０４モルに相当）を加え、
６０℃で２時間加熱したところ白色沈殿物が生成した。次に、上澄み液を取り除き、得られた白色固体成分を、８０℃で１０時間減圧乾燥させることにより、１，１，１，３，５，５，５ヘプタメチルシロキサン誘導体、及びデシルトリメトキシシランの混合物で表面修飾された酸化亜鉛微粒子としてＳＳ修飾酸化亜鉛微粒子４．０７ｇを白色固体として得た。
(Synthesis of SS-modified zinc oxide fine particles)
200 mL of the zinc oxide fine particle methanol dispersion (containing 0.04 mol of zinc oxide) was placed in a four-necked flask (capacity 500 mL), and 2.38 g of the surface modifier (SS) (0.16 to 1 mol of zinc oxide). And decyltrimethoxysilane 0.42 g (LS-5258; manufactured by Shin-Etsu Chemical Co., Ltd .; equivalent to 0.04 mol with respect to 1 mol of zinc oxide),
When heated at 60 ° C. for 2 hours, a white precipitate was formed. Next, the supernatant liquid is removed, and the obtained white solid component is dried under reduced pressure at 80 ° C. for 10 hours, thereby obtaining 1,1,1,3,5,5,5 heptamethylsiloxane derivative and decyltrimethoxysilane. Thus, 4.07 g of SS-modified zinc oxide fine particles were obtained as a white solid as zinc oxide fine particles surface-modified with the above mixture.
このＳＳ修飾酸化亜鉛微粒子の灰分測定を実施した結果、酸化亜鉛の含有量は８０ｗｔ％であり、収率は１００％であった。 As a result of measuring the ash content of the SS-modified zinc oxide fine particles, the zinc oxide content was 80 wt% and the yield was 100%.
（実施例１：デシルシシラン修飾酸化亜鉛微粒子）
上記デシルシラン修飾酸化亜鉛微粒子０．１３ｇ（４重量部）をトルエン２０ｍＬに分散させたところ、透明な溶液が得られた。この溶液に、前記ＢＣ含有合成物２ｇ、及び有機化合物（Ａ）としてトリアリルイソシアヌレート（エボニック デグサ ジャパン社製、ＴＡＩＣＲＯＳ（登録商標）））１ｇを加え攪拌した。攪拌後４０℃で溶媒を留去し、酸化亜鉛微粒子を微分散させた硬化性樹脂組成物を得た。なおこの有機化合物（Ａ）は、前記一般式３で示される化合物であり、そのＲ１はアリルであり、分子量は２４９である。
Example 1: Decylsilane-modified zinc oxide fine particles
When 0.13 g (4 parts by weight) of the decylsilane-modified zinc oxide fine particles were dispersed in 20 mL of toluene, a transparent solution was obtained. To this solution, 2 g of the BC-containing compound and 1 g of triallyl isocyanurate (manufactured by Evonik Degussa Japan, TAICROS (registered trademark)) as an organic compound (A) were added and stirred. After stirring, the solvent was distilled off at 40 ° C. to obtain a curable resin composition in which zinc oxide fine particles were finely dispersed. In addition, this organic compound (A) is a compound shown by the said General formula 3, The R1 is allyl and the molecular weight is 249.
この硬化性樹脂組成物を、厚さ１ｍｍのスペーサーを入れたガラス板入れ、順に、６０℃／６時間、７０℃／１時間、８０℃／１時間、１２０℃／１時間、１５０℃／１時間で段階的に加熱した後、ガラス板から硬化物を剥がすことで、フィルム状の硬化物サンプルを作製した。作製したサンプル片を、ヘイズメーター（日本電色工業株式会社製 ３００Ａ）によるヘイズ測定、及び紫外可視分光光度計（日本分光株式会社製 Ｖ−５６０）による光線透過率により評価した。尚、本発明の金属酸化物微粒子含有硬化性樹脂組成物を、透明材料や光拡散材料として用いた場合には、吸収光が少ないことが重要なので、全光線透過率が９０％以上を「◎」、８０％以上９０％未満を「○」、８０％未満を「×」と評価した。 This curable resin composition was placed in a glass plate with a spacer having a thickness of 1 mm, and in order, 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C./1 hour, 120 ° C./1 hour, 150 ° C./1. After heating stepwise over time, the cured product was peeled from the glass plate to produce a film-like cured product sample. The produced sample piece was evaluated by haze measurement using a haze meter (Nippon Denshoku Industries Co., Ltd., 300A) and light transmittance using an ultraviolet-visible spectrophotometer (V-560, manufactured by JASCO Corporation). When the curable resin composition containing metal oxide fine particles of the present invention is used as a transparent material or a light diffusing material, it is important that the amount of absorbed light is small, so that the total light transmittance is 90% or more. ”, 80% or more and less than 90% were evaluated as“ ◯ ”, and less than 80% were evaluated as“ x ”.
（実施例２：フェニルシラン修飾酸化亜鉛微粒子）
実施例１において、デシルシラン修飾酸化亜鉛微粒子０．１３ｇに代えて、前記フェニルシラン表面修飾酸化亜鉛微粒子０．１３ｇを、トルエン２０ｍＬに代えて、アセトン２０ｍＬに分散させたこと以外は、実施例１と同様にして、サンプル片を作成し評価した。
(Example 2: Phenylsilane-modified zinc oxide fine particles)
In Example 1, instead of 0.13 g of decylsilane-modified zinc oxide fine particles, 0.13 g of the phenylsilane surface-modified zinc oxide fine particles was replaced with 20 mL of toluene and dispersed in 20 mL of acetone. Similarly, sample pieces were prepared and evaluated.
（実施例３：ヘキシルシラン修飾酸化亜鉛微粒子）
実施例１において、デシルシラン修飾酸化亜鉛微粒子０．１３ｇに代えて、前記ヘキシルシラン表面修飾酸化亜鉛微粒子０．１３ｇを使用したこと以外は、実施例１と同様にして、サンプル片を作成し評価した。
(Example 3: Hexylsilane-modified zinc oxide fine particles)
In Example 1, a sample piece was prepared and evaluated in the same manner as in Example 1 except that 0.13 g of the hexylsilane surface-modified zinc oxide fine particles was used instead of 0.13 g of the decylsilane-modified zinc oxide fine particles. .
（実施例４）
実施例１において、デシルシラン修飾酸化亜鉛微粒子０．１３ｇに代えて、前記ＳＳ修飾酸化亜鉛微粒子０．１３ｇを、トルエン２０ｍＬに代えて、トルエン／イソプロバノール＝５／１で混合した溶媒２０ｍＬに分散させたこと以外は、実施例１と同様に、サンプル片を作成し評価した。
Example 4
In Example 1, instead of 0.13 g of decylsilane-modified zinc oxide fine particles, 0.13 g of the SS-modified zinc oxide fine particles was dispersed in 20 mL of a solvent mixed with toluene / isopropanol = 5/1 instead of 20 mL of toluene. Except that, sample pieces were prepared and evaluated in the same manner as in Example 1.
以上、実施例１〜４の結果を表１にまとめて示す。 The results of Examples 1 to 4 are summarized in Table 1 above.
いずれのサンプルも、９０％以上の全光線透過率を有しつつ、高いヘイズ率を有しており、本発明の金属酸化物微粒子含有硬化性樹脂組成物の硬化物が、効率的な光拡散材料として機能することがわかった。また、金属酸化物微粒子表面の修飾剤の組成を、その微粒子を覆うマトリックスを構成する材料の組成に近づけることにより、さらに透明度の高い複合材料も作成できると考えられることから、透明高屈折材料としての利用も期待できる。 Each sample has a high haze ratio while having a total light transmittance of 90% or more, and the cured product of the curable resin composition containing the metal oxide fine particles of the present invention has an efficient light diffusion. It turns out that it functions as a material. In addition, since it is considered that the composition of the modifier on the surface of the metal oxide fine particles can be made closer to the composition of the material constituting the matrix that covers the fine particles, a composite material with higher transparency can be produced. Can also be expected.
Claims (11)
前記金属酸化物微粒子（Ｄ）が、下記一般式１
であらわされるＳｉ−Ｏ−Ｓｉ結合を有しない加水分解性基含有シラン化合物（Ｓ−１）、を含む表面修飾剤（Ｓ）により表面修飾されたものである、金属酸化物微粒子含有硬化性樹脂組成物。 Organic compound (A) containing two or more carbon-carbon double bonds having reactivity with SiH group in one molecule, silicon compound (B) containing two or more SiH groups in one molecule, hydrosilyl A metal oxide fine particle-containing curable resin composition comprising a oxidization catalyst (C) and a metal oxide fine particle (D) having a number average particle diameter of 0.5 to 20 nm,
The metal oxide fine particles (D) are represented by the following general formula 1
Metal oxide fine particle-containing curable resin, which is surface-modified with a surface modifier (S) containing a hydrolyzable group-containing silane compound (S-1) having no Si—O—Si bond represented by Composition.
であらわされるＳｉ−Ｏ−Ｓｉ結合を有する加水分解性基含有シラン化合物（Ｓ−２）、を含む表面修飾剤（Ｓ）である、請求項１または２に記載の金属酸化物微粒子含有硬化性樹脂組成物。 The surface modifier (S) is further represented by the following general formula 2
The metal oxide fine particle-containing curability according to claim 1, which is a surface modifier (S) containing a hydrolyzable group-containing silane compound (S-2) having a Si—O—Si bond represented by: Resin composition.
で示される化合物からなる群より選ばれる１種以上の有機化合物である、請求項１〜５のいずれかに記載の金属酸化物微粒子含有硬化性樹脂組成物。 The organic compound (A) is an aliphatic compound, an isocyanuric ring-containing compound, and the following general formula 3
The metal oxide fine particle containing curable resin composition in any one of Claims 1-5 which is 1 or more types of organic compounds chosen from the group which consists of a compound shown by these.
で表される、１分子中に少なくとも３個のＳｉＨ基を有する環状オルガノシロキサンである、請求項１〜７のいずれかに記載の金属酸化物微粒子含有硬化性樹脂組成物。 The organosiloxane (B) is represented by the following general formula 4
The metal oxide fine particle-containing curable resin composition according to any one of claims 1 to 7, which is a cyclic organosiloxane having at least three SiH groups in one molecule.
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| CN103288864A (en) * | 2013-05-13 | 2013-09-11 | 东华大学 | Hydrophobic organosilicone surfactant prepared by solid-phase continuous catalytic synthesis and preparation method thereof |
| JP6563383B2 (en) * | 2014-04-14 | 2019-08-21 | 国立大学法人東京工業大学 | Film for transparent screen, method for producing the same, and transparent screen provided with the same |
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| JP6896409B2 (en) * | 2016-12-02 | 2021-06-30 | 三菱瓦斯化学株式会社 | A sheet or film for a transparent screen, and a transparent screen equipped with the sheet or film. |
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