JP5548971B2 - Thermoplastic organic-inorganic hybrid material - Google Patents
Thermoplastic organic-inorganic hybrid material Download PDFInfo
- Publication number
- JP5548971B2 JP5548971B2 JP2008530856A JP2008530856A JP5548971B2 JP 5548971 B2 JP5548971 B2 JP 5548971B2 JP 2008530856 A JP2008530856 A JP 2008530856A JP 2008530856 A JP2008530856 A JP 2008530856A JP 5548971 B2 JP5548971 B2 JP 5548971B2
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- JP
- Japan
- Prior art keywords
- acrylate
- meth
- hybrid material
- group
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims description 77
- 229920001169 thermoplastic Polymers 0.000 title claims description 25
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 95
- 239000010954 inorganic particle Substances 0.000 claims description 47
- 230000004048 modification Effects 0.000 claims description 45
- 238000012986 modification Methods 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 32
- 125000000524 functional group Chemical group 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000008119 colloidal silica Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 55
- 239000000377 silicon dioxide Substances 0.000 description 51
- -1 (meth) acrylic acid halide Chemical class 0.000 description 34
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 15
- 238000002834 transmittance Methods 0.000 description 14
- 238000007334 copolymerization reaction Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000012661 block copolymerization Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 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 2
- 239000013590 bulk material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PGGUSMVPPUCFQR-UHFFFAOYSA-N triethylsilylmethanol Chemical compound CC[Si](CC)(CC)CO PGGUSMVPPUCFQR-UHFFFAOYSA-N 0.000 description 2
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KYEPYBOXOPVJIH-UHFFFAOYSA-N 1-triethylsilylethanol Chemical compound CC[Si](CC)(CC)C(C)O KYEPYBOXOPVJIH-UHFFFAOYSA-N 0.000 description 1
- HHEWUJNOBUFVRY-UHFFFAOYSA-N 1-triphenylsilylethanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C(O)C)C1=CC=CC=C1 HHEWUJNOBUFVRY-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- JSOZORWBKQSQCJ-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C(C)=C JSOZORWBKQSQCJ-UHFFFAOYSA-N 0.000 description 1
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 1
- QURURPFUWRWGSN-UHFFFAOYSA-N 3-sulfanylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCS QURURPFUWRWGSN-UHFFFAOYSA-N 0.000 description 1
- DQSNECNMKBTWCE-UHFFFAOYSA-N 3-sulfanylpropyl prop-2-enoate Chemical compound SCCCOC(=O)C=C DQSNECNMKBTWCE-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AHVOFPQVUVXHNL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C=C AHVOFPQVUVXHNL-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 239000011258 core-shell material Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- ZQKNBDOVPOZPLY-UHFFFAOYSA-N trimethylsilylmethanol Chemical compound C[Si](C)(C)CO ZQKNBDOVPOZPLY-UHFFFAOYSA-N 0.000 description 1
- RZBLAGLYKKRZNL-UHFFFAOYSA-N triphenylsilylmethanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(CO)C1=CC=CC=C1 RZBLAGLYKKRZNL-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Description
本発明は耐熱性、耐熱性、透明性、表面特性(表面硬度)及び機械的強度に優れているのみならず、有機溶媒に可溶で、溶融流動性を有しており、成形性に優れた有機−無機ハイブリッド材料に関する。 The present invention is not only excellent in heat resistance, heat resistance, transparency, surface characteristics (surface hardness) and mechanical strength, but also soluble in organic solvents, has melt flowability, and excellent moldability. And an organic-inorganic hybrid material.
従来から、有機相と無機相とを微細かつ均質に分散させた有機−無機ハイブリッド材料が注目されている。こうした有機−無機ハイブリッド材料は機械的強度が大きく、分散粒子が小さいため光が分散されず透明性を確保できる等、優れた特性をもたせることができる。 Conventionally, an organic-inorganic hybrid material in which an organic phase and an inorganic phase are finely and uniformly dispersed has attracted attention. Such an organic-inorganic hybrid material has excellent mechanical properties such as high mechanical strength and small dispersion particles, so that light is not dispersed and transparency can be secured.
こうした有機−無機ハイブリッド材料の製造方法として、有機高分子共存下において金属アルコキシドを加水分解する方法（以下「ゾル−ゲル法」という）がよく用いられている（例えば非特許文献１）。ゾル−ゲル法で製造された有機−無機ハイブリッド材料は、均質な溶液から析出されるものであるため、有機相と無機相とが分子レベルまで細かく分散されており、極めて均質な材料とすることができる。また、ゾル−ゲル法は高い温度を必要としないため、有機相が熱で変質するおそれも少ない。 As a method for producing such an organic-inorganic hybrid material, a method of hydrolyzing a metal alkoxide in the presence of an organic polymer (hereinafter referred to as “sol-gel method”) is often used (for example, Non-Patent Document 1). Since organic-inorganic hybrid materials produced by the sol-gel method are precipitated from a homogeneous solution, the organic and inorganic phases are finely dispersed to the molecular level, and the material must be extremely homogeneous. Can do. In addition, since the sol-gel method does not require a high temperature, the organic phase is less likely to be altered by heat.
しかし、ゾル−ゲル法によって製造された有機−無機ハイブリッド材料は、ゾル−ゲル反応における脱水縮合によって水が生じ、この水を除去する際に亀裂が生じやすい。このため、無機相の割合を多くして、高弾性率の有機−無機ハイブリッド材料を製造することは困難である。また、金属アルコキシドは高価であるため、製造コストが高騰化するという問題もあった。 However, in the organic-inorganic hybrid material produced by the sol-gel method, water is generated by dehydration condensation in the sol-gel reaction, and cracks are likely to occur when this water is removed. For this reason, it is difficult to produce an organic-inorganic hybrid material having a high elastic modulus by increasing the proportion of the inorganic phase. Moreover, since metal alkoxide is expensive, there also existed a problem that manufacturing cost raised.
このため、アクリル系官能基を有する修飾基がシリカなど表面の水酸基に共有結合した官能基修飾無機粒子と、アクリル系モノマーとが共重合されてなる有機−無機ハイブリッド材料も提案されている（特許文献１）。この有機−無機ハイブリッド材料は、無機物質源としてポリケイ酸を用いるため、無機物質源としての原料コストが極めて安価となり、大量に供給することも可能となる。また、ゾル−ゲル反応を利用していないため、無機相の割合を多くしてもひび割れ等が生じ難く、均質なバルク材を製造することが容易である。さらには、共重合の比率を適亘選択することにより、有機−無機ハイブリッド材料における有機相と無機相との割合をコントロールすることが可能となる。 For this reason, an organic-inorganic hybrid material obtained by copolymerizing a functional group-modified inorganic particle in which a modifying group having an acrylic functional group is covalently bonded to a hydroxyl group on the surface such as silica and an acrylic monomer has been proposed (patent) Reference 1). Since this organic-inorganic hybrid material uses polysilicic acid as the inorganic substance source, the raw material cost as the inorganic substance source is extremely low, and it can be supplied in large quantities. In addition, since the sol-gel reaction is not used, cracks or the like hardly occur even if the proportion of the inorganic phase is increased, and it is easy to produce a homogeneous bulk material. Furthermore, the ratio of the organic phase and the inorganic phase in the organic-inorganic hybrid material can be controlled by appropriately selecting the copolymerization ratio.
一方、無機粒子と有機高分子との間に共有結合を持たない有機−無機ハイブリッド材料（ナノコンポジット）も提案されているが、無機粒子と有機高分子との間に相互作用がないため、無機粒子を高い含有量で有機高分子中に均一に分散させて透明で機械的強度に優れた材料を合成することが困難である（特許文献２）。
上記特許文献１に記載の有機−無機ハイブリッド材料は、透明性や機械的強度において優れたものを提供することはできるが、有機溶媒に溶け難く、溶融流動性を有しないため、溶液のキャスティング法や射出成型の手法を用いて成形することができないという問題を生じていた。このため、成形のためには型内で重合させたり、削り出しによって成形したりしなければならず、成形にコストがかかり、その用途も限られたものとなっていた。 The organic-inorganic hybrid material described in Patent Document 1 can provide a material excellent in transparency and mechanical strength, but is difficult to dissolve in an organic solvent and does not have melt fluidity. And the problem that it cannot be molded using the injection molding technique. For this reason, in order to form, it has to be polymerized in the mold or formed by shaving, and it takes a high cost for forming and its use is limited.
本発明は、上記従来の実情に鑑みてなされたものであり、耐熱性、透明性、表面特性(表面硬度)及び機械的強度に優れているのみならず、有機溶媒に可溶で、溶融流動性を有しており、成形性に優れた有機−無機ハイブリッド材料及びその製造方法を提供することを解決すべき課題とする。 The present invention has been made in view of the above-described conventional circumstances, and is excellent not only in heat resistance, transparency, surface characteristics (surface hardness) and mechanical strength, but also soluble in organic solvents, melt flow It is an object to be solved to provide an organic-inorganic hybrid material having excellent properties and excellent moldability and a method for producing the same.
発明者らは、上記特許文献１に記載の発明の問題点である成形性の問題について解決するために鋭意研究を行った。その結果、無機粒子に存在する水酸基の全てを重合性の官能基を有する修飾基で修飾するのではなく、水酸基の一部についてのみ修飾した無機粒子を用い、これとモノマーとを共重合させることにより、有機溶媒に可溶で、溶融流動性を有し、成形性に優れた熱可塑性有機−無機ハイブリッド材料となることを見出し、本発明をなすに至った。 The inventors have intensively studied to solve the problem of formability, which is a problem of the invention described in Patent Document 1. As a result, instead of modifying all the hydroxyl groups present in the inorganic particles with a modifying group having a polymerizable functional group, use inorganic particles modified only for a part of the hydroxyl groups and copolymerize them with monomers. As a result, the present inventors have found that a thermoplastic organic-inorganic hybrid material that is soluble in an organic solvent, has melt flowability, and has excellent moldability is achieved.
すなわち、本発明の熱可塑性有機−無機ハイブリッド材料は、重合性の官能基を有する修飾基が無機粒子表面の水酸基に共有結合した重合性官能基修飾無機粒子と、重合により熱可塑性ポリマーとなる重合性モノマーとが共重合されてなる熱可塑性有機−無機ハイブリッド材料において、前記重合性官能基修飾無機粒子は、前記無機粒子表面の水酸基の一部にのみ前記重合性の官能基を有する修飾基が共有結合していることを特徴とする。 That is, the thermoplastic organic-inorganic hybrid material of the present invention comprises a polymerizable functional group-modified inorganic particle in which a modifying group having a polymerizable functional group is covalently bonded to a hydroxyl group on the surface of the inorganic particle, and polymerization that becomes a thermoplastic polymer by polymerization. In the thermoplastic organic-inorganic hybrid material obtained by copolymerizing a polymerizable monomer, the polymerizable functional group-modified inorganic particles have a modified group having the polymerizable functional group only on a part of the hydroxyl groups on the surface of the inorganic particles. It is characterized by covalent bonds.
本発明の熱可塑性有機−無機ハイブリッド材料では、無機微粒子ゾルやポリケイ酸等の水酸基を有する無機粒子を無機物質源として用いているため、原料コストが極めて安価となる。また、有機相は無機粒子表面の水酸基に共有結合しているため、有機−無機界面での剥離現象などが生じ難く、耐熱性、透明性、表面特性(表面硬度)
及び機械的強度に優れたものとなる。さらに、ゾル−ゲル反応のような脱水縮合は起こらないため、無機相の割合を多くしてもひび割れ等が生じ難く、均質なバルク材を製造することが容易である。In the thermoplastic organic-inorganic hybrid material of the present invention, since inorganic particles having hydroxyl groups such as inorganic fine particle sol and polysilicic acid are used as the inorganic substance source, the raw material cost is extremely low. In addition, since the organic phase is covalently bonded to the hydroxyl group on the surface of the inorganic particles, the peeling phenomenon at the organic-inorganic interface is unlikely to occur, and heat resistance, transparency, surface characteristics (surface hardness)
In addition, the mechanical strength is excellent. Further, since dehydration condensation as in the sol-gel reaction does not occur, even if the proportion of the inorganic phase is increased, cracks and the like hardly occur, and it is easy to produce a homogeneous bulk material.
さらには、こうした特性に加え、本発明の熱可塑性有機−無機ハイブリッド材料は、有機溶媒に可溶で、溶融流動性を有し、成形性に優れるという特性をも備えている。この理由は次のとおりである。すなわち、本発明の熱可塑性有機−無機ハイブリッド材料は、重合性官能基修飾無機粒子と重合性モノマーとが共重合されてなるが、重合性官能基修飾無機粒子は、無機粒子表面の水酸基の一部にのみ重合性の官能基を有する修飾基が共有結合している（換言すれば、重合性官能基修飾無機粒子には未反応の水酸基が残っている）。このため、無機粒子１つあたりの重合性官能基の数が少なくなり、重合性モノマーと共重合させても３次元網目構造の目が粗くなり、その結果、有機溶媒に可溶で、溶融流動性を有し、射出成型、押出成型等の成形が容易となるのである。 Furthermore, in addition to these characteristics, the thermoplastic organic-inorganic hybrid material of the present invention also has characteristics of being soluble in an organic solvent, having melt flowability, and excellent moldability. The reason for this is as follows. That is, the thermoplastic organic-inorganic hybrid material of the present invention is obtained by copolymerizing a polymerizable functional group-modified inorganic particle and a polymerizable monomer. The polymerizable functional group-modified inorganic particle is a hydroxyl group on the surface of the inorganic particle. A modifying group having a polymerizable functional group is covalently bonded only to the part (in other words, an unreacted hydroxyl group remains in the polymerizable functional group-modified inorganic particle). For this reason, the number of polymerizable functional groups per inorganic particle is reduced, and even when copolymerized with a polymerizable monomer, the three-dimensional network structure becomes rough. As a result, it is soluble in an organic solvent and melt-flowable. Therefore, molding such as injection molding and extrusion molding becomes easy.
重合性官能基修飾無機粒子の、水酸基に対する修飾基の修飾率は1〜９９％、さらに好ましくは５〜８０％であることが好ましい。１％未満では架橋が不十分となり、機械的な強度が小さくなり、透明性も悪くなる。また、９９％を超えた場合には、ゲル化して熱可塑性が不十分なものとなる。 The modification rate of the modifying group with respect to the hydroxyl group of the polymerizable functional group-modified inorganic particles is preferably 1 to 99%, more preferably 5 to 80%. If it is less than 1%, crosslinking is insufficient, the mechanical strength is reduced, and the transparency is also deteriorated. On the other hand, if it exceeds 99%, it gels and the thermoplasticity becomes insufficient.
また、本発明の熱可塑性有機−無機ハイブリッド材料中の重合性官能基修飾無機粒子の含有量は１〜８０重量％、さらに好ましくは３〜７０重量％であることが好ましい。重合性官能基修飾無機粒子の含有量が１重量％未満では耐熱性や硬さの向上効果が小さく、８０重量％を超えると脆くなり、成形性が悪くなる。 The content of the polymerizable functional group-modified inorganic particles in the thermoplastic organic-inorganic hybrid material of the present invention is preferably 1 to 80% by weight, more preferably 3 to 70% by weight. If the content of the polymerizable functional group-modified inorganic particles is less than 1% by weight, the effect of improving heat resistance and hardness is small, and if it exceeds 80% by weight, the material becomes brittle and the moldability deteriorates.
また、熱可塑性に優れた成形性のよい熱可塑性有機−無機ハイブリッド材料とするためには、重合性官能基修飾無機粒子の水酸基に対する修飾基の修飾率と、熱可塑性有機−無機ハイブリッド材料中の重合性官能基修飾無機粒子の含有量との２つ値を考慮することが好ましい。発明者らの試験結果によれば、重合性官能基修飾無機粒子の水酸基に対する修飾基の修飾率が１〜３０％のばあいには、重合性官能基修飾無機粒子の含有量は１〜８０重量％が好ましく、重合性官能基修飾無機粒子の水酸基に対する修飾基の修飾率が３０〜５０％の場合には、重合性官能基修飾無機粒子の含有量は１〜３０重量％が好ましく、重合性官能基修飾無機粒子の水酸基に対する修飾基の修飾率が５０〜８０％の場合には、重合性官能基修飾無機粒子の含有量は１〜１０重量％が好ましくい範囲となる。 In addition, in order to obtain a thermoplastic organic-inorganic hybrid material having excellent thermoplasticity and good moldability, the modification rate of the modifying group with respect to the hydroxyl group of the polymerizable functional group-modified inorganic particles, and the thermoplastic organic-inorganic hybrid material It is preferable to consider two values with the content of the polymerizable functional group-modified inorganic particles. According to the test results of the inventors, when the modification ratio of the modifying group to the hydroxyl group of the polymerizable functional group-modified inorganic particles is 1 to 30%, the content of the polymerizable functional group-modified inorganic particles is 1 to 80. % By weight, and when the modification rate of the modifying group with respect to the hydroxyl group of the polymerizable functional group-modified inorganic particles is 30 to 50%, the content of the polymerizable functional group-modified inorganic particles is preferably 1 to 30% by weight. When the modification ratio of the modifying group to the hydroxyl group of the functional functional group-modified inorganic particles is 50 to 80%, the content of the polymerizable functional group-modified inorganic particles is preferably in the range of 1 to 10% by weight.
無機粒子としては、表面に水酸基が存在するものであれば特に限定はない。こうであれば、重合性の官能基を有する修飾基を無機粒子表面の水酸基に共有結合を介して結合することができる。例えば、シリカ粒子、アルミナ粒子、チタニア粒子、ジルコニア粒子などが挙げられる。この中でも、シリカ粒子は入手が容易で、微細な粒子が得られ易く好適である。さらに好ましいのは、極めて微細な粒子であるコロイダルシリカ粒子である。このようなコロイダルシリカはアルコキシシランを原料にしたゾルゲル法や水ガラスから容易に合成することができる。この他、ケイ酸ナトリウムや水ガラス等を酸によって加水分解したポリケイ酸を用いることもできる。 The inorganic particles are not particularly limited as long as hydroxyl groups exist on the surface. In this case, the modifying group having a polymerizable functional group can be bonded to the hydroxyl group on the surface of the inorganic particle through a covalent bond. Examples thereof include silica particles, alumina particles, titania particles, zirconia particles, and the like. Among these, silica particles are suitable because they are easily available and fine particles are easily obtained. Further preferred are colloidal silica particles which are extremely fine particles. Such colloidal silica can be easily synthesized from a sol-gel method using alkoxysilane as a raw material or water glass. In addition, polysilicic acid obtained by hydrolyzing sodium silicate or water glass with an acid can also be used.
シリカ粒子の粒子径は１〜１００ｎｍであることが好ましく、さらに好ましくは１〜５０ｎｍである。シリカ粒子が１００ｎｍ以下であれば有機相と無機相とが極めて細かく分散されることとなり、極めて均質な材料とすることができる。コロイダルシリカ粒子はこのような粒子径のものが市販されており、容易に入手することができる。 The particle diameter of the silica particles is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the silica particles are 100 nm or less, the organic phase and the inorganic phase are very finely dispersed, and an extremely homogeneous material can be obtained. Colloidal silica particles having such a particle size are commercially available and can be easily obtained.
重合性の官能基を有する修飾基としては、無機粒子表面の水酸基に共有結合が可能な修飾基であれば特に限定はない。このような修飾基を導入できる化合物としては、重合性の官能基を有する酸ハライド類、イソシアネート類、エポキシ類及びチオール類や、重合性の官能基を有する各種のシランカップリング剤等を用いることができる。このような化合物として、例えば、（メタ）アクリル酸ハライド、メタクリロキシプロピルトリメトキシシラン、メタクリロキシプロピルトリエトキシシラン、メタクリロキシプロピルメチルジメトキシシラン、メタクリロキシプロピルジメチルメトキシシラン、メタクリロキシプロピルメチルジエトキシシラン、メタクリロキシプロピルジメチルエトキシシラン、２−メタクリロイルオキシエチルイソシアネート、グリシジルメタクリレート、アリルグリシジルエーテル、ビスフェノールーＡのジグリシジルエーテル、２−アクリロイルオキシエチルイソシアネート、３−メルカプトプロピルメタクリレート、３−メルカプトプロピルアクリレート等が挙げられる。重合性の修飾基はシラノール結合、エステル結合、エーテル結合、ウレタン結合などにより無機粒子表面と共有結合しているとすることができる。このような重合性官能基修飾無機粒子は、無機粒子と重合性の官能基を有する上記化合物とを反応させることによって、容易に得ることができる。
また、無機酸化物表面水酸基の一部を修飾することによって、疎水性を付与することもできる。疎水性を付与する化合物としては、トリメチルシリルメトキシド、トリエチルシリルメトキシド、トリエチルシリルメトキシド、トリエチルシリルエトキシド、トリフェニルシリルメトキシド、トリフェニルシリルエトキシド等のトリアルキルアルコキシドや、トリメチルシリルクロリド、トリエチルシリルクロリド、トリフェニルシリルクロリド等のトリアルキルハライド等が挙げられる。これら疎水性を付与する化合物は、無機粒子と重合性の官能基を有する化合物との反応の前に無機粒子表面の一部の水酸基と反応させても、無機粒子と重合性の官能基を有する化合物との反応後に残った無機粒子表面の水酸基と反応させてもどちらでも良い。The modifying group having a polymerizable functional group is not particularly limited as long as it is a modifying group capable of covalent bonding to the hydroxyl group on the surface of the inorganic particles. As a compound into which such a modifying group can be introduced, acid halides having a polymerizable functional group, isocyanates, epoxies and thiols, various silane coupling agents having a polymerizable functional group, and the like are used. Can do. Examples of such compounds include (meth) acrylic acid halide, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropylmethyldiethoxysilane. , Methacryloxypropyldimethylethoxysilane, 2-methacryloyloxyethyl isocyanate, glycidyl methacrylate, allyl glycidyl ether, diglycidyl ether of bisphenol-A, 2-acryloyloxyethyl isocyanate, 3-mercaptopropyl methacrylate, 3-mercaptopropyl acrylate, etc. Can be mentioned. The polymerizable modifying group can be assumed to be covalently bonded to the surface of the inorganic particles by a silanol bond, an ester bond, an ether bond, a urethane bond, or the like. Such polymerizable functional group-modified inorganic particles can be easily obtained by reacting inorganic particles with the above-mentioned compound having a polymerizable functional group.
Moreover, hydrophobicity can also be imparted by modifying a part of the hydroxyl group on the surface of the inorganic oxide. Examples of compounds that impart hydrophobicity include trialkyl alkoxides such as trimethylsilyl methoxide, triethylsilyl methoxide, triethylsilyl methoxide, triethylsilyl ethoxide, triphenylsilyl methoxide, triphenylsilyl ethoxide, trimethylsilyl chloride, triethyl And trialkyl halides such as silyl chloride and triphenylsilyl chloride. These hydrophobicity-providing compounds have a polymerizable functional group with inorganic particles even if they are reacted with a part of hydroxyl groups on the surface of the inorganic particles before the reaction between the inorganic particles and the compound having a polymerizable functional group. Either of them may be reacted with the hydroxyl group on the surface of the inorganic particles remaining after the reaction with the compound.
重合性の修飾基は（メタ）アクリル基又はビニル基のいずれかを有しており、重合性モノマーは（メタ）アクリル基又はビニル基のいずれかを有していることとすることができる。ここで、（メタ）アクリル基とはアクリル基及びメタクリル基の両方を合わせた概念である。こうであれば、重合開始剤を用いることにより、容易に共重合させることができる。 The polymerizable modifying group may have either a (meth) acryl group or a vinyl group, and the polymerizable monomer may have either a (meth) acryl group or a vinyl group. Here, the (meth) acryl group is a concept that combines both an acrylic group and a methacryl group. If it is like this, it can copolymerize easily by using a polymerization initiator.
こうした重合性モノマーの具体例としては、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の脂環式構造含有（メタ）アクリレート、ベンジル（メタ）アクリレート、４−ブチルシクロヘキシル（メタ）アクリレート、アクリロイルモルホリン等が挙げられる。さらに、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、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、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、エトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、ポリエステル（メタ）アクリレート、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−テトラフルオロプロピル（メタ）アクリレート、１Ｈ,１Ｈ,５Ｈ−オクタフルオロペンチル（メタ）アクリレート、２−（パーフルオロブチル）エチル（メタ）アクリレート、２−（パーフルオロヘキシル）エチル（メタ）アクリレート、２，２，３，３，３−ペンタフルオロプロピル（メタ）アクリレート、３−（パーフルオロブチル）−２−ヒドロキシエチル（メタ）アクリレート、３−（パーフルオロブチル）−２−ヒドロキシプロピル（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、ｔ−オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７−アミノ−３，７−ジメチルオクチル（メタ）アクリレート、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、ヒドロキシブチルビニルエーテル、ラウリルビニルエーテル、セチルビニルエーテル、２−エチルヘキシルビニルエーテル等を挙げることができる。 Specific examples of such polymerizable monomers include alicyclic structure-containing (meth) acrylates such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. , Benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, and the like. Further, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) Acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) Acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( ) Acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meth) acrylate, glycidyl (meth) acrylate, polyester (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl ( (Meth) acrylate, 3- (perfluorobutyl) -2-hydroxyethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) Acrylamide, N, N-dimethyl (Meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) Examples include acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.
また、重合性の修飾基としてのビニル基を有するものとしては、スチレン基、アルキルスチレン基等が挙げられ、ビニル基を有する重合性モノマーとしては、スチレン、p−メチルスチレン、ｐ−ヒドロキシスチレン、（メタ）クリロニトリル、アクリルアミド、塩化ビニル、酢酸ビニル、無水マレイン酸等が挙げられる。 Examples of those having a vinyl group as a polymerizable modifying group include a styrene group and an alkylstyrene group. Examples of the polymerizable monomer having a vinyl group include styrene, p-methylstyrene, p-hydroxystyrene, (Meth) acrylonitrile, acrylamide, vinyl chloride, vinyl acetate, maleic anhydride and the like.
さらには、重合性モノマーは複数種類の重合性モノマーからなり、それら重合性モノマーが共重合されていてもよい。複数種類の重合性モノマーを共重合させることによって、共重合部分の性質を種々に変化させることが可能となり、多種多様な熱可塑性有機−無機ハイブリッド材料とすることができる。また、複数種類の重合性モノマーの共重合としては、ランダム共重合であってもよいし、ブロック共重合であってもよい。いずれの共重合体においても、無機粒子が核（コア）となり、ポリマー層が無機粒子を取り巻くように成長した樹脂層からなるコア−シェル構造をとることができる。 Furthermore, the polymerizable monomer is composed of a plurality of types of polymerizable monomers, and these polymerizable monomers may be copolymerized. By copolymerizing a plurality of types of polymerizable monomers, the properties of the copolymerized moiety can be variously changed, and a wide variety of thermoplastic organic-inorganic hybrid materials can be obtained. The copolymerization of a plurality of types of polymerizable monomers may be random copolymerization or block copolymerization. In any copolymer, a core-shell structure comprising a resin layer grown so that the inorganic particles become nuclei (core) and the polymer layer surrounds the inorganic particles can be taken.
本発明の熱可塑性有機−無機ハイブリッド材料は次のようにして製造することができる。すなわち、本発明の熱可塑性有機−無機ハイブリッド材料の製造方法は、無機粒子表面の水酸基の一部に重合性の官能基を有する修飾基を共有結合させて重合性官能基修飾無機粒子とする表面修飾工程と、該重合性官能基修飾無機粒子と、重合により熱可塑性ポリマーとなる重合性モノマーとを共重合する共重合工程とを備えることを特徴とする。 The thermoplastic organic-inorganic hybrid material of the present invention can be produced as follows. That is, the method for producing a thermoplastic organic-inorganic hybrid material of the present invention is a method in which a modifying group having a polymerizable functional group is covalently bonded to a part of hydroxyl groups on the surface of inorganic particles to form polymerizable functional group-modified inorganic particles. It comprises a modification step, a copolymerization step of copolymerizing the polymerizable functional group-modified inorganic particles and a polymerizable monomer that becomes a thermoplastic polymer by polymerization.
共重合工程における重合方法は特に限定はなく、溶液重合の他、懸濁重合、バルク重合等の手法を用いることができる。また、複数種共重合工程において、複数種類の重合性モノマーを一度に混合してランダム共重合体としたり、複数種類の重合性モノマーを一種類づつ逐次添加してブロック共重合体としたりすることができる。 The polymerization method in the copolymerization step is not particularly limited, and methods such as suspension polymerization and bulk polymerization can be used in addition to solution polymerization. Also, in the multiple-type copolymerization process, multiple types of polymerizable monomers are mixed at once to form a random copolymer, or multiple types of polymerizable monomers are added sequentially one by one to form a block copolymer. Can do.
共重合工程において、複数種類の重合性モノマーを一度に混合してランダム共重合体とする方法や複数種類の重合性モノマーを一種類づつ逐次添加してブロック共重合体とする方法は、諸物性を制御しつつ所望の特性を有する熱可塑性有機−無機ハイブリッド材料とすることが容易であり、好ましい方法である。 In the copolymerization process, multiple types of polymerizable monomers are mixed at once to make a random copolymer, and multiple types of polymerizable monomers are added sequentially one by one to make a block copolymer. It is easy to obtain a thermoplastic organic-inorganic hybrid material having desired characteristics while controlling the temperature, and this is a preferred method.
特に、複数種類の重合性モノマーを一種類づつ逐次添加してブロック共重合体とする方法は、無機粒子が核（コア）となり、種々の特性の異なった樹脂層が無機粒子を取り巻くように成長した複数の樹脂層からなる傾斜型コア−シェル構造をとることが出来、各重合性モノマーから得られる重合物の多種多様な特性を併せ持った機能性有機−無機ハイブリッド材料を合成することが出来る、好ましい方法である。具体的には、例えばアクリルモノマーなどゴム的特性を有する重合性モノマーをブロック共重合させることによって弾性率を制御したり、撥水性や親水性を有する重合性モノマーを表面層近くにブロック共重合させることによって、熱可塑性有機−無機ハイブリッド材料に撥水性や親水性を効果的に付与したりすることができる。このため、複数種類の重合性モノマーをブロック共重合体とすれば、所望の特性を有する多種多様な高機能材料を設計することができる。 In particular, the method of sequentially adding multiple types of polymerizable monomers one by one to make a block copolymer grows so that the inorganic particles become the core (core) and the resin layers with different properties surround the inorganic particles. It is possible to synthesize a functional organic-inorganic hybrid material having a wide variety of characteristics of the polymer obtained from each polymerizable monomer. This is the preferred method. Specifically, for example, the elastic modulus is controlled by block copolymerization of a polymerizable monomer having rubber-like properties such as an acrylic monomer, or a block polymerization of a polymerizable monomer having water repellency and hydrophilicity is made near the surface layer. Thus, water repellency and hydrophilicity can be effectively imparted to the thermoplastic organic-inorganic hybrid material. For this reason, if a plurality of types of polymerizable monomers are used as block copolymers, a wide variety of highly functional materials having desired characteristics can be designed.
以下、本発明を具体化した実施例について、詳細に説明する。
ＰＭＭＡ−シリカハイブリッド材料
＜表面修飾工程＞
３つ口フラスコにメチルエチルケトン分散コロイダルシリカ（日産化学工業（株）製MEK-ST粒子径10〜15nm、シリカ含有量30wt%、）と2-（メタクロイルオキシ）エチルイソシアネート（以下「ＭＯＩ」という）とを種々の割合で加え、触媒としてジラウリル酸ジ-n-ブチルスズ（以下「ＤＢＴＤＬ」という）をコロイダルシリカの重量に対して約650ppm添加し、室温で一日撹拌することにより、MOI修飾コロイダルシリカを得た。Hereinafter, examples embodying the present invention will be described in detail.
PMMA-silica hybrid material <surface modification process>
Methyl ethyl ketone-dispersed colloidal silica (MEK-ST particle size 10-15 nm, silica content 30 wt%, manufactured by Nissan Chemical Industries, Ltd.) and 2- (methacryloyloxy) ethyl isocyanate (hereinafter referred to as “MOI”) in a three-necked flask MOI modified colloidal silica by adding about 650 ppm of dilaurate di-n-butyltin (hereinafter referred to as “DBTDL”) as a catalyst with respect to the weight of the colloidal silica and stirring at room temperature for one day. Got.
＜共重合工程＞
4つ口フラスコに温度計、冷却管及び撹拌羽を取り付け、フラスコ内を窒素置換した後、メチルエチルケトンと過酸化ベンゾイルとMOI修飾コロイダルシリカとを加えた後、油浴中でフラスコを80℃まで加熱した後、約120rpmの速度で撹拌しながら、メタクリル酸メチルを15分かけて滴下し、滴下終了後、さらに6時間撹拌を行った。仕込量はメタクリル酸メチル：メチルエチルケトン＝１：１．２５（重量比）とし、過酸化ベンゾイルはメタクリル酸メチルに対して0.4mol%とした。撹拌終了後、反応溶液を20倍量のメタノール中に滴下し、再沈殿法により白色固体を採取した後、常温で24時間真空乾燥を行い、ＰＭＭＡ−シリカハイブリッド材料を得た。<Copolymerization process>
A four-necked flask was equipped with a thermometer, condenser, and stirring blade, and the atmosphere in the flask was replaced with nitrogen. After adding methyl ethyl ketone, benzoyl peroxide, and MOI-modified colloidal silica, the flask was heated to 80 ° C in an oil bath. After that, methyl methacrylate was added dropwise over 15 minutes while stirring at a speed of about 120 rpm. After completion of the addition, the mixture was further stirred for 6 hours. The amount charged was methyl methacrylate: methyl ethyl ketone = 1: 1.25 (weight ratio), and benzoyl peroxide was 0.4 mol% with respect to methyl methacrylate. After completion of the stirring, the reaction solution was dropped into 20 times the amount of methanol, and a white solid was collected by a reprecipitation method, followed by vacuum drying at room temperature for 24 hours to obtain a PMMA-silica hybrid material.
＜評 価＞
上記のようにして得られたＰＭＭＡ−シリカハイブリッド材料について、有機溶剤への溶解性試験を行った。溶解性試験はPMMA-シリカハイブリッド材料1.0ｇをサンプル瓶に計り取り、有機溶剤（メチルエチルケトン（ＭＥＫ）、テトラヒドロフラン（ＴＨＦ）、アセトン、N’N−ジメチルアセトアミド(ＤＭＡｃ)、ジクロロメタン）
9.0ｇを加えて室温で撹拌し、有機溶剤への溶解性を観察することにより行った。<Evaluation>
The PMMA-silica hybrid material obtained as described above was subjected to a solubility test in an organic solvent. For the solubility test, 1.0 g of PMMA-silica hybrid material was weighed into a sample bottle, and an organic solvent (methyl ethyl ketone (MEK), tetrahydrofuran (THF), acetone, N'N-dimethylacetamide (DMAc), dichloromethane).
9.0 g was added and stirred at room temperature, and the solubility in an organic solvent was observed.
さらに、成形性（熱可塑性）の評価は、熱プレス装置を用い、PMMA-シリカハイブリッド材料を１２０−１３０℃で１０分予熱融解させ、１９０℃、10MPaの圧力でプレスしフィルムを作成することによって行った。 Furthermore, evaluation of formability (thermoplasticity) is performed by preheating and melting PMMA-silica hybrid material at 120-130 ° C. for 10 minutes using a hot press device, and then pressing at 190 ° C. and a pressure of 10 MPa to create a film. went.
また、測定試料（フィルム）はメチルエチルケトンに溶解した後、キャスティング法によって製膜し、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、透過率、表面硬度など諸物性を測定した。測定試料は以下のようにして作製した。すなわち、上記のようにして合成したPMMA−シリカハイブリッド材料をメチルエチルケトンに10wt%となるように加え、超音波洗浄機（SHARP（株）製UT-105HS）を用いて水浴温度約60℃、溶解時間90分の条件下で溶解させた。この溶液をPETシート上にキャスティングし、加熱オーブン中で40℃、4時間乾燥させた。その後、80℃で20時間真空乾燥させることによりPMMA−シリカハイブリッド膜を得た。こうして得られたPMMA−シリカハイブリッド膜について、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、表面硬度及び光透過率を測定した。 A measurement sample (film) was dissolved in methyl ethyl ketone and then formed into a film by a casting method, and various physical properties such as heat resistance, moldability, elongation, tensile strength, Young's modulus, transmittance, and surface hardness were measured. The measurement sample was produced as follows. That is, the PMMA-silica hybrid material synthesized as described above was added to methyl ethyl ketone so that the concentration was 10 wt%, and the water bath temperature was about 60 ° C. and the dissolution time using an ultrasonic cleaner (SHARP UT-105HS). It was dissolved under the condition of 90 minutes. This solution was cast on a PET sheet and dried in a heating oven at 40 ° C. for 4 hours. Thereafter, the PMMA-silica hybrid membrane was obtained by vacuum drying at 80 ° C. for 20 hours. The PMMA-silica hybrid film thus obtained was measured for heat resistance, moldability, elongation rate, tensile strength, Young's modulus, surface hardness and light transmittance.
耐熱性（熱分解温度：Td）は、セイコーインスツル（株）製TG/DTA 6300を用いて熱重量（TG-DTA）測定を行った。アルミ製試料皿にサンプルを約10mg入れ、窒素気流下(流速200ml/min)で、昇温速度10℃/min、温度範囲25℃〜500℃で測定した。得られたTG曲線から熱分解温度を外挿法により算出した。 Heat resistance (thermal decomposition temperature: Td) was measured by thermogravimetry (TG-DTA) using TG / DTA 6300 manufactured by Seiko Instruments Inc. About 10 mg of the sample was placed in an aluminum sample dish, and measured under a nitrogen stream (flow rate 200 ml / min) at a temperature rising rate of 10 ° C./min and a temperature range of 25 ° C. to 500 ° C. The thermal decomposition temperature was calculated from the obtained TG curve by extrapolation.
引張強度は、JTトーシ（株）製卓上型引張試験機リトルセンスター LSC-05/30を用いて行った。測定用サンプルは幅約1cm、長さ約3cmの短冊状に切り出したPMMA−シリカハイブリッドフィルムを、引張強度測定用の台紙に挟むことにより作製した。測定条件はチャック間距離20mm、引張速度5mm/minで行った。各試料の破断時の引張強度、伸び、及び応力−歪曲線の初期勾配からヤング率を求めた。各値とも6〜10回の測定値を平均して決定した。なお、この際、5%以上の誤差を含む試料及び破断位置が不適切な試料は平均値より除外した。また、引張強度の算出に必要なフィルム厚とフィルム幅については、フィルム厚はミツトヨ（株）製膜厚計を用いて0.1μmまで、フィルム幅はミツトヨ（株）製ノギスを用いて0.05mmまでそれぞれ読み取った。また、フィルム表面の表面硬度（鉛筆硬度）を、井本製作所製の鉛筆硬度試験機を用いてJIS-K-5400に準じて測定した。 Tensile strength was measured using a bench type tensile tester Little Senster LSC-05 / 30 manufactured by JT Toshi Co., Ltd. A sample for measurement was prepared by sandwiching a PMMA-silica hybrid film cut into a strip shape having a width of about 1 cm and a length of about 3 cm between mounts for measuring tensile strength. The measurement conditions were a chuck-to-chuck distance of 20 mm and a tensile speed of 5 mm / min. The Young's modulus was determined from the tensile strength at break of each sample, the elongation, and the initial slope of the stress-strain curve. Each value was determined by averaging 6-10 measurements. At this time, samples containing an error of 5% or more and samples with an inappropriate fracture position were excluded from the average value. The film thickness and film width required to calculate the tensile strength can be up to 0.1 μm using a thickness gauge manufactured by Mitutoyo Corp., and the film width can be up to 0.05 mm using calipers manufactured by Mitutoyo Corp. I read each one. The surface hardness (pencil hardness) of the film surface was measured according to JIS-K-5400 using a pencil hardness tester manufactured by Imoto Seisakusho.
光透過率は、JASCO（株）製V-530分光光度計を用いた。測定領域は、紫外−可視光の波長領域（200〜800nm）とした。30mm×10mmに切り出した厚さ約80〜120μmのフィルムを分光光度計用のサンプルホルダーにはさみ、1nmごとの光透過率を測定した。
（結 果）
＜有機溶剤への溶解性及び成形性（熱可塑性）＞
結果を表１に示す。この表から、シリカ表面水酸基のＭＯＩによる修飾率が高いほどゲル化し易く、有機溶剤に対する溶解性および成形性(熱可塑性)が低下するということが分かる。また、ＭＯＩ修飾シリカの含有量が高いほど、ゲル化し易く、有機溶剤に対する溶解性および成形性(熱可塑性)が低下する、ということが分かる。For light transmittance, JASCO Corporation V-530 spectrophotometer was used. The measurement region was an ultraviolet-visible light wavelength region (200 to 800 nm). A film having a thickness of about 80 to 120 μm cut into 30 mm × 10 mm was sandwiched between sample holders for a spectrophotometer, and the light transmittance was measured every 1 nm.
(Result)
<Solubility in organic solvents and moldability (thermoplastic)>
The results are shown in Table 1. From this table, it can be seen that the higher the MOI modification rate of the hydroxyl group on the silica surface, the easier the gelation and the lower the solubility in organic solvents and the moldability (thermoplasticity). Moreover, it turns out that it is easy to gelatinize and the solubility with respect to an organic solvent, and a moldability (thermoplasticity) fall, so that content of MOI modification silica is high.
熱可塑性と溶解性とは相関関係があり、溶解性に優れているほど熱可塑性に優れることが知られている。このため、熱可塑性を備えたＰＭＭＡ−シリカハイブリッド材料とするためには、シリカ表面水酸基のＭＯＩによる修飾率を９９％よりも低くすることが必要となる。ただし、シリカ表面水酸基のＭＯＩによる修飾率が１％未満となると、溶解性（すなわち熱可塑性）は優れたものとなるものの、架橋度が小さくなり機械的強度や透明性の低下などハイブリッド化の効果が十分に現れない。このため、重合性官能基修飾無機粒子の、水酸基に対する修飾基の修飾率は１〜９９％が好ましく、さらに好ましい範囲は５〜８０％である。 There is a correlation between thermoplasticity and solubility, and it is known that the better the solubility, the better the thermoplasticity. For this reason, in order to obtain a PMMA-silica hybrid material having thermoplasticity, it is necessary that the modification rate of the silica surface hydroxyl group by MOI is lower than 99%. However, if the modification rate of MOI on the silica surface hydroxyl group is less than 1%, the solubility (that is, thermoplasticity) will be excellent, but the degree of crosslinking will be reduced and the effect of hybridization such as mechanical strength and transparency will be reduced. Does not appear sufficiently. For this reason, the modification rate of the modifying group with respect to the hydroxyl group of the polymerizable functional group-modified inorganic particles is preferably 1 to 99%, and more preferably 5 to 80%.
また、表１の結果から、溶解性とＭＯＩ修飾シリカ含有量についても相関関係があり、ＭＯＩ修飾シリカ含有量が多いほど、溶解性が悪いことが分かる。ただし、ＭＯＩ修飾シリカ含有量があまり少ないと、耐熱性や表面硬度の向上効果が小さくなる。 Further, from the results of Table 1, it is understood that there is a correlation between the solubility and the MOI-modified silica content, and that the solubility is worse as the MOI-modified silica content is higher. However, if the MOI-modified silica content is too low, the effect of improving heat resistance and surface hardness is reduced.
以上の結果から、成形性が良好で耐熱性や硬さにも優れた熱可塑性有機−無機ハイブリッド材料とするためには、シリカ表面水酸基のＭＯＩによる修飾率と、ＭＯＩ修飾シリカ含有量との２つ値を考慮することが重要であり、表１の結果をふまえ、ＭＯＩによる修飾率が１〜５％の場合にはＭＯＩ修飾シリカ含有量が１〜８０重量％、ＭＯＩによる修飾率が５〜１５％の場合にはＭＯＩ修飾シリカ含有量が１〜６０重量％、ＭＯＩによる修飾率が１５〜３０％の場合にはＭＯＩ修飾シリカ含有量が１〜２５重量％、ＭＯＩによる修飾率が３０〜４５％の場合にはＭＯＩ修飾シリカ含有量が１〜１５重量％、ＭＯＩによる修飾率が４５〜８０％の場合にはＭＯＩ修飾シリカ含有量が１〜５重量％の範囲が好適であるということが分かる。 From the above results, in order to obtain a thermoplastic organic-inorganic hybrid material having good moldability and excellent heat resistance and hardness, the MOI modification rate of the silica surface hydroxyl group and the MOI modified silica content are 2 It is important to take into account the values shown in Table 1. Based on the results shown in Table 1, when the MOI modification rate is 1 to 5%, the MOI-modified silica content is 1 to 80% by weight, and the MOI modification rate is 5 to 5%. When the content is 15%, the MOI-modified silica content is 1 to 60% by weight. When the MOI modification rate is 15 to 30%, the MOI-modified silica content is 1 to 25% by weight and the MOI modification rate is 30 to 30%. In the case of 45%, the MOI-modified silica content is preferably 1 to 15% by weight, and in the case where the MOI modification rate is 45 to 80%, the MOI-modified silica content is preferably in the range of 1 to 5% by weight. I understand.
＜耐熱性、成形性、伸び率、引っ張り強度、ヤング率、表面硬度及び光透過率の測定結果＞
表２に示すように、様々なＭＯＩ修飾率及びＭＯＩ修飾シリカ含量のＰＭＭＡ−シリカハイブリッド材料を調製し（実施例１〜１２、試験例１〜４及び比較例１）、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、透過率、表面硬度など諸物性を測定した。ＰＭＭＡについても同様の測定を行った。<Measurement results of heat resistance, moldability, elongation, tensile strength, Young's modulus, surface hardness and light transmittance>
As shown in Table 2, PMMA-silica hybrid materials having various MOI modification rates and MOI modified silica contents were prepared (Examples 1 to 12, Test Examples 1 to 4 and Comparative Example 1), heat resistance, moldability, Various physical properties such as elongation, tensile strength, Young's modulus, transmittance, and surface hardness were measured. The same measurement was performed for PMMA.
（成形性）
表２から、成形性については、（１）シリカ表面水酸基のＭＯＩによる修飾率が低いほど成形性に優れており、（２）ＭＯＩ修飾シリカの含有量が少ないほど成形性に優れている、ということが分かる。この結果は、上記表1に示した、有機溶剤への溶解性試験から導かれた結果と整合するものである。
（耐熱性）
熱分解温度（Ｔｄ値）は、（１）シリカ表面水酸基のＭＯＩによる修飾率が高いほどＴｄ値が高く、（２）ハイブリッド中のシリカ含有量が高いほどＴｄ値が高い、ということが分かり、ＰＭＭＡとＭＯＩ修飾シリカとの共重合により、耐熱性を高められることが分かった。これはＭＯＩ修飾シリカによってシリカを介した強固な分子間架橋が形成され、またMOI部位に起因する水素結合の形成により、高分子鎖の運動性が強く抑制され
たためと考えられる。
（透過率）
透過率については、いずれもＰＭＭＡとほぼ同等の透過率であり、シリカ粒子がポリマー中で良好に分散し、PMMA特有の高い透明性が維持されることが確認できた。
（ヤング率）
１）シリカ含有量との関係
ＭＯＩ修飾シリカ含有量の増加に伴いヤング率は上昇した。ＰＭＭＡ−シリカ間が共有結合されているために、ポリマー鎖の運動性が強く束縛されることによってヤング率が大幅に上昇したと考えられる。
２）ＭＯＩ修飾率との関係
ＭＯＩ修飾率の増加に伴い、著しく上昇することがわかった。これは、ＭＯＩ修飾率が増加するほど、ＰＭＭＡ−シリカ間の架橋が増し、ポリマーの運動性がより束縛されたためであると考えられる。(Formability)
From Table 2, as for moldability, (1) the lower the MOI modification rate of the hydroxyl group on the silica surface, the better the moldability, and (2) the lower the MOI-modified silica content, the better the moldability. I understand that. This result is consistent with the result derived from the solubility test in organic solvents shown in Table 1 above.
(Heat-resistant)
It can be seen that the thermal decomposition temperature (Td value) is (1) the higher the modification ratio of the silica surface hydroxyl group by MOI, the higher the Td value, and (2) the higher the silica content in the hybrid, the higher the Td value. It was found that heat resistance can be improved by copolymerization of PMMA and MOI-modified silica. This is presumably because the MOI-modified silica formed strong intermolecular bridges via silica, and the formation of hydrogen bonds due to the MOI sites strongly suppressed the polymer chain mobility.
(Transmittance)
As for the transmittance, it was confirmed that the transmittance was almost the same as that of PMMA, the silica particles were well dispersed in the polymer, and the high transparency peculiar to PMMA was maintained.
(Young's modulus)
1) Relationship with silica content The Young's modulus increased with increasing MOI-modified silica content. Since the PMMA-silica bond is covalently bonded, it is thought that the Young's modulus is significantly increased by strongly constraining the mobility of the polymer chain.
2) Relationship with MOI modification rate It was found that the MOI modification rate significantly increased as the MOI modification rate increased. This is considered to be because as the MOI modification rate increases, the cross-linking between PMMA and silica increases, and the mobility of the polymer is more restricted.
以上の結果から、ＭＯＩ修飾率については、低いほど成形性に優れ、高いほどＴｄ値が高くて耐熱性に優れ、ヤング率も大きくなることが分かった。このため、優れた成形性と、優れた耐熱性及びヤング率とを兼ね備えたＰＭＭＡ−シリカハイブリッド材料とするためには、ＭＯＩ修飾率が大きすぎても、小さすぎてもだめであり、１〜９９％、さらに好ましくは５〜８０％とすることが好ましいことが分かる。また、ＭＯＩ修飾シリカ含有量も成形性や耐熱性やヤング率に影響を与えることが分かる。すなわち、成形性が良好で耐熱性や表面硬度にも優れた熱可塑性有機−無機ハイブリッド材料とするためには、シリカ表面水酸基のＭＯＩによる修飾率と、ＭＯＩ修飾シリカ含有量との２つ値を考慮することが重要であり、ＭＯＩによる修飾率が１〜５％の場合にはＭＯＩ修飾シリカ含有量が１〜８０重量％、ＭＯＩによる修飾率が５〜１５％の場合にはＭＯＩ修飾シリカ含有量が１〜６０重量％、ＭＯＩによる修飾率が１５〜３０％の場合にはＭＯＩ修飾シリカ含有量が１〜２５重量％、ＭＯＩによる修飾率が３０〜４５％の場合にはＭＯＩ修飾シリカ含有量が１〜１５重量％、ＭＯＩによる修飾率が４５〜８０％の場合にはＭＯＩ修飾シリカ含有量が１〜５重量％の範囲が好適であるということが分かる。 From the above results, it was found that the lower the MOI modification rate, the better the moldability, and the higher the MOI modification rate, the higher the Td value, the better the heat resistance, and the higher the Young's modulus. For this reason, in order to obtain a PMMA-silica hybrid material having both excellent moldability, excellent heat resistance and Young's modulus, the MOI modification rate is too large or too small. It can be seen that it is preferably 99%, more preferably 5 to 80%. It can also be seen that the MOI-modified silica content also affects the moldability, heat resistance and Young's modulus. That is, in order to obtain a thermoplastic organic-inorganic hybrid material having good moldability and excellent heat resistance and surface hardness, two values of the MOI modification rate of the silica surface hydroxyl group and the MOI modified silica content are set. It is important to consider, when the MOI modification rate is 1 to 5%, the MOI modified silica content is 1 to 80% by weight, and when the MOI modification rate is 5 to 15%, the MOI modified silica content is included. When the amount is 1 to 60% by weight and the MOI modification rate is 15 to 30%, the MOI modified silica content is 1 to 25% by weight. When the MOI modification rate is 30 to 45%, the MOI modified silica content is contained. It can be seen that when the amount is 1 to 15% by weight and the MOI modification rate is 45 to 80%, the MOI-modified silica content is preferably in the range of 1 to 5% by weight.
（ＭＭＡ−メチルアクリレート）ランダム共重合体−シリカハイブリッド材料
重合性モノマーとして、ＭＭＡとメチルアクリレートの２種類の化合物を用い、(ＭＭＡ-ＭＡ)ランダム共重合体−シリカハイブリッド材料を合成した。合成法の詳細を以下に示す。 (MMA-methyl acrylate) random copolymer-silica hybrid material (MMA-MA) random copolymer-silica hybrid material was synthesized using two types of compounds, MMA and methyl acrylate, as polymerizable monomers. Details of the synthesis method are shown below.
＜表面修飾工程＞
上述したＰＭＭＡ−シリカハイブリッド材料の場合と同様の方法により、MOI修飾コロイダルシリカを得た。
＜ランダム共重合工程＞
４つ口フラスコに温度計、冷却管及び攪拌羽を取り付け、フラスコ内を窒素置換した後、後述するモノマー混合物の1.25倍量（重量比）のメチルエチルケトンと、モノマー混合物に対して0.4mol％の過酸化ベンゾイルと、所定量のＭＯＩ修飾コロイダルシリカとを加えた。そして、油浴中で80℃まで加熱した後、約120rpmの速度で攪拌しながら、所定の混合比のメタクリル酸メチルとアクリル酸メチルとの混合物（モノマー混合物）を15分かけて滴下し、滴下終了後6時間反応させた。反応終了後、反応溶液を20倍量のメタノール中に滴下し、再沈殿法により重合物を採取した後、常温で24時間真空乾燥を行い、実施例１３〜実施例１８の（ＭＭＡ−ＭＡ）ランダム共重合体−シリカハイブリッド材料を60〜80%の収率で得た。<Surface modification process>
MOI-modified colloidal silica was obtained by the same method as in the case of the PMMA-silica hybrid material described above.
<Random copolymerization process>
A four-necked flask was equipped with a thermometer, a condenser and a stirring blade, and after the atmosphere in the flask was replaced with nitrogen, 1.25 times (weight ratio) methyl ethyl ketone and 0.4 mol% excess of the monomer mixture described later were added. Benzoyl oxide and a predetermined amount of MOI modified colloidal silica were added. Then, after heating to 80 ° C. in an oil bath, a mixture (monomer mixture) of methyl methacrylate and methyl acrylate having a predetermined mixing ratio was dropped over 15 minutes while stirring at a speed of about 120 rpm. It was made to react for 6 hours after completion | finish. After completion of the reaction, the reaction solution was dropped into 20 times the amount of methanol, and a polymer was collected by a reprecipitation method, followed by vacuum drying at room temperature for 24 hours. (MMA-MA) of Examples 13 to 18 Random copolymer-silica hybrid materials were obtained in 60-80% yield.
（評 価）
こうして得られた（ＭＭＡ−ＭＡ）ランダム共重合体−シリカハイブリッド材料について、上述したＰＭＭＡ−シリカハイブリッド材料の評価方法と同様の方法により、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、透過率、表面硬度など諸物性を測定した。結果を表３に示す。この表から分かるように、重合性モノマーとしてＭＭＡとメチルアクリレートとを混合してランダム共重合を行っても、優れた成形性と、優れた耐熱性及びヤング率とを兼ね備えたハイブリッド材料となることが分かる。
About the (MMA-MA) random copolymer-silica hybrid material thus obtained, the heat resistance, moldability, elongation, tensile strength, Young's modulus, Various physical properties such as transmittance and surface hardness were measured. The results are shown in Table 3. As can be seen from this table, even if MMA and methyl acrylate are mixed as a polymerizable monomer and random copolymerization is performed, a hybrid material having excellent moldability, excellent heat resistance and Young's modulus can be obtained. I understand.
（ＭＭＡ−エチルアクリレート）ランダム共重合体−シリカハイブリッド材料
重合性モノマーとして、ＭＭＡとエチルアクリレートの２種類の化合物を用い、実施例１９〜実施例２１の（ＭＭＡ−ＥＡ）ランダム共重合体−シリカハイブリッド材料を合成した。合成方法は、メチルアクリレートの代わりにエチルアクリレートを用いたこと以外は、上述した（ＭＭＡ−ＭＡ）ランダム共重合体−シリカハイブリッド材料の場合と同様であり、説明を省略する。 (MMA-Ethyl Acrylate) Random Copolymer-Silica Hybrid Material As the polymerizable monomer, two compounds of MMA and ethyl acrylate were used, and (MMA-EA) random copolymer-silica of Examples 19 to 21. A hybrid material was synthesized. The synthesis method is the same as that of the (MMA-MA) random copolymer-silica hybrid material described above except that ethyl acrylate is used instead of methyl acrylate, and the description thereof is omitted.
（評 価）
こうして得られた（ＭＭＡ−エチルアクリレート）ランダム共重合体−シリカハイブリッド材料について、上述したＰＭＭＡ−シリカハイブリッド材料の評価方法と同様の方法により、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、透過率、表面硬度など諸物性を測定した。結果を表４に示す。この表から分かるように、重合性モノマーとしてＭＭＡとエチルアクリレートとを混合してランダム共重合を行っても、優れた成形性と、優れた耐熱性及びヤング率とを兼ね備えたハイブリッド材料となることが分かる。
The (MMA-ethyl acrylate) random copolymer-silica hybrid material thus obtained was subjected to the same heat resistance, moldability, elongation, tensile strength, Young's modulus as in the above-described evaluation method for the PMMA-silica hybrid material. Various physical properties such as transmittance and surface hardness were measured. The results are shown in Table 4. As can be seen from this table, even if MMA and ethyl acrylate are mixed as a polymerizable monomer and random copolymerization is performed, a hybrid material having excellent moldability, excellent heat resistance and Young's modulus can be obtained. I understand.
（ＭＭＡ−ブチルアクリレート）ランダム共重合体−シリカハイブリッド材料
重合性モノマーとして、ＭＭＡとブチルアクリレートの２種類の化合物を用い、実施例２２〜実施例２４の（ＭＭＡ−ＢＡ）ランダム共重合体−シリカハイブリッド材料を合成した。合成方法は、メチルアクリレートの代わりにブチルアクリレートを用いたこと以外は、上述した（ＭＭＡ−メチルアクリレート）ランダム共重合体−シリカハイブリッド材料の場合と同様であり、説明を省略する。 (MMA-butyl acrylate) random copolymer-silica hybrid material (MMA-BA) random copolymer-silica of Examples 22 to 24 using two types of compounds of MMA and butyl acrylate as polymerizable monomers. A hybrid material was synthesized. The synthesis method is the same as that of the (MMA-methyl acrylate) random copolymer-silica hybrid material described above except that butyl acrylate is used instead of methyl acrylate, and the description thereof is omitted.
（評 価）
こうして得られた（ＭＭＡ−ブチルアクリレート）ランダム共重合体−シリカハイブリッド材料について、上述したＰＭＭＡ−シリカハイブリッド材料の評価方法と同様の方法により、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、透過率、表面硬度など諸物性を測定した。結果を表５に示す。この表から分かるように、重合性モノマーとしてＭＭＡとブチルアクリレートとを混合してランダム共重合を行っても、優れた成形性と、優れた耐熱性及びヤング率とを兼ね備えたハイブリッド材料となることが分かる。
With respect to the (MMA-butyl acrylate) random copolymer-silica hybrid material thus obtained, the heat resistance, moldability, elongation rate, tensile strength, Young's modulus were determined in the same manner as the evaluation method for the PMMA-silica hybrid material described above. Various physical properties such as transmittance and surface hardness were measured. The results are shown in Table 5. As can be seen from this table, even if random copolymerization is performed by mixing MMA and butyl acrylate as a polymerizable monomer, it becomes a hybrid material having both excellent moldability, excellent heat resistance and Young's modulus. I understand.
（ＭＭＡ−メチルアクリレート）ブロック共重合体−シリカハイブリッド材料
重合性モノマーとして、ＭＭＡとメチルアクリレートとの混合物を用い、（ＭＭＡ−ＭＡ）ブロック共重合体−シリカハイブリッド材料を合成した。合成法の詳細を以下に示す。 (MMA-methyl acrylate) block copolymer-silica hybrid material As a polymerizable monomer, a mixture of MMA and methyl acrylate was used to synthesize a (MMA-MA) block copolymer-silica hybrid material. Details of the synthesis method are shown below.
＜表面修飾工程＞
上述したＰＭＭＡ−シリカハイブリッド材料の場合と同様の方法により、MOI修飾コロイダルシリカを得た。<Surface modification process>
MOI-modified colloidal silica was obtained by the same method as in the case of the PMMA-silica hybrid material described above.
＜ブロック共重合工程＞
４つ口フラスコに温度計、冷却管及び攪拌羽を取り付け、フラスコ内を窒素置換した後、重合性モノマーの1.25倍量（重量比）のメチルエチルケトンと、重合性モノマーに対して0.4mol％の過酸化ベンゾイルと、所定量のＭＯＩ修飾コロイダルシリカとを加えた。そして、油浴中で80℃まで加熱した後、約120rpmの速度で攪拌しながら、所定量のメチルアクリレートを15分かけて滴下し、滴下終了後１時間反応させた。反応終了後、さらにＭＭＡモノマーを15分かけて滴下し、、滴下終了後6時間反応させた。反応溶液を20倍量のメタノール中に滴下し、再沈殿法により重合物を採取した後、常温で24時間真空乾燥を行い、実施例２５〜実施例２９の（ＭＭＡ−ＭＡ）ブロック共重合体−シリカハイブリッド材料を60〜80%の収率で得た。<Block copolymerization process>
A four-necked flask was equipped with a thermometer, a condenser, and a stirring blade. After the atmosphere in the flask was replaced with nitrogen, 1.25 times (weight ratio) methyl ethyl ketone and 0.4 mol% excess of the polymerizable monomer were added to the polymerizable monomer. Benzoyl oxide and a predetermined amount of MOI modified colloidal silica were added. And after heating to 80 degreeC in an oil bath, predetermined amount methyl acrylate was dripped over 15 minutes, stirring at the speed | rate of about 120 rpm, and it was made to react for 1 hour after completion | finish of dripping. After completion of the reaction, MMA monomer was further added dropwise over 15 minutes, and reacted for 6 hours after completion of the addition. The reaction solution was dropped into 20 times the amount of methanol, and a polymer was collected by a reprecipitation method, followed by vacuum drying at room temperature for 24 hours, and the (MMA-MA) block copolymer of Example 25 to Example 29. -Silica hybrid material was obtained in 60-80% yield.
（評 価）
こうして得られた（ＭＭＡ−ＭＡ）ブロック共重合体−シリカハイブリッド材料について、上述したＰＭＭＡ−シリカハイブリッド材料の評価方法と同様の方法により、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、透過率、表面硬度など諸物性を測定した。結果を表６に示す。この表から分かるように、重合性モノマーとしてＭＭＡとメチルアクリレートとを混合してブロック共重合を行っても、優れた成形性と、優れた耐熱性及びヤン
About the (MMA-MA) block copolymer-silica hybrid material thus obtained, the heat resistance, moldability, elongation, tensile strength, Young's modulus, Various physical properties such as transmittance and surface hardness were measured. The results are shown in Table 6. As can be seen from this table, even when MMA and methyl acrylate are mixed as a polymerizable monomer and block copolymerization is performed, excellent moldability, excellent heat resistance and
（ＭＭＡ−エチルアクリレート）ブロック共重合体−シリカハイブリッド材料
重合性モノマーとして、ＭＭＡとエチルアクリレートの２種類の化合物を用い、実施例３０〜実施例３２の（ＭＭＡ−ＥＡ）ブロック共重合体−シリカハイブリッド材料を合成した。合成方法は、メチルアクリレートの代わりにエチルアクリレートを用いたこと以外は、上述した（ＭＭＡ−メチルアクリレート）ブロック共重合体−シリカハイブリッド材料の場合と同様であり、説明を省略する。 (MMA-ethyl acrylate) block copolymer-silica hybrid material As the polymerizable monomer, two compounds of MMA and ethyl acrylate were used, and (MMA-EA) block copolymer-silica of Examples 30 to 32. A hybrid material was synthesized. The synthesis method is the same as that of the above-described (MMA-methyl acrylate) block copolymer-silica hybrid material except that ethyl acrylate is used instead of methyl acrylate, and the description thereof is omitted.
（評 価）
こうして得られた（ＭＭＡ−ＥＡ）ブロック共重合体−シリカハイブリッド材料について、上述したＰＭＭＡ−シリカハイブリッド材料の評価方法と同様の方法により、耐熱性、成形性、伸び率、引っ張り強度、ヤング率、透過率、表面硬度など諸物性を測定した。結果を表４に示す。この表から分かるように、重合性モノマーとしてＭＭＡとエチルアクリレートとを混合してブロック共重合を行っても、優れた成形性と、優れた耐熱性及びヤング率とを兼ね備えたハイブリッド材料となることが分かる。
With respect to the (MMA-EA) block copolymer-silica hybrid material thus obtained, the heat resistance, moldability, elongation, tensile strength, Young's modulus, Various physical properties such as transmittance and surface hardness were measured. The results are shown in Table 4. As can be seen from this table, even if block copolymerization is performed by mixing MMA and ethyl acrylate as a polymerizable monomer, a hybrid material having both excellent moldability, excellent heat resistance and Young's modulus can be obtained. I understand.
この発明は、上記発明の実施例の説明に何ら限定されるものではない。特許請求の範囲の記載を逸脱せず、当業者が容易に想到できる範囲で種々の変形態様もこの発明に含まれる。 The present invention is not limited to the description of the embodiments of the invention. Various modifications may be included in the present invention as long as those skilled in the art can easily conceive without departing from the description of the scope of claims.
本発明の熱可塑性有機−無機ハイブリッド材料は、耐熱性や透明性に優れ、さらには成形性に優れた機能性材料として、様々な産業分野において利用可能である。 The thermoplastic organic-inorganic hybrid material of the present invention can be used in various industrial fields as a functional material excellent in heat resistance and transparency and further excellent in moldability.
Claims (1)
前記重合性官能基修飾無機微粒子は、前記無機粒子としてコロイダルシリカが用いられ、該コロイダルシリカが有する表面の水酸基の一部のみに前記重合性の官能基を有する修飾基が共有結合し、
前記重合性官能基修飾無機微粒子の前記水酸基に対する修飾基の修飾率は１％以上８０％以下であって、前記修飾率と、前記熱可塑性有機−無機ハイブリッド材料中の前記重合性官能基修飾無機微粒子の含有量との関係は、前記修飾率が１％以上５％以下の場合には前記含有量は１重量％以上８０重量％以下、前記修飾率が５％より上で１５％以下の場合には前記含有量は１重量％以上６０重量％以下、前記修飾率が１５％より上で３０％以下の場合には前記含有量は１重量％以上２５重量％以下、前記修飾率が３０％より上で４５％以下の場合には前記含有量は１重量％以上１５重量％以下、前記修飾率が４５％より上で８０％以下の場合には前記含有量は１重量％以上５重量％以下、であり、
有機溶媒に可溶であることを特徴とする熱可塑性有機−無機ハイブリッド材料。 Polymerizable functional group-modified inorganic particles in which a modifying group having either a (meth) acrylic group or a vinyl group as a modifying group having a polymerizable functional group is bonded to a hydroxyl group on the surface of the inorganic fine particle, and becomes a thermoplastic polymer by polymerization. A thermoplastic organic-inorganic hybrid material obtained by copolymerizing a polymerizable monomer having either a (meth) acrylic group or a vinyl group as a polymerizable monomer by polymerization using an organic solvent ,
In the polymerizable functional group-modified inorganic fine particles, colloidal silica is used as the inorganic particle, and the modifying group having the polymerizable functional group is covalently bonded only to a part of the surface hydroxyl groups of the colloidal silica,
The modification rate of the modification group with respect to the hydroxyl group of the polymerizable functional group-modified inorganic fine particles is 1% or more and 80% or less, and the modification rate and the polymerizable functional group-modified inorganic in the thermoplastic organic-inorganic hybrid material When the modification rate is 1% or more and 5% or less, the content is 1% by weight or more and 80% by weight or less, and the modification rate is 5% or more and 15% or less. In the case where the content is 1% by weight or more and 60% by weight or less, and when the modification rate is higher than 15% and 30% or less, the content is 1% by weight or more and 25% by weight or less and the modification rate is 30% When the content is 45% or less above, the content is 1% by weight or more and 15% by weight or less, and when the modification rate is above 45% and 80% or less, the content is 1% by weight or more and 5% by weight or less. And
A thermoplastic organic-inorganic hybrid material which is soluble in an organic solvent.
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