JP2010053300A - Organic and inorganic composite material and its preparation - Google Patents
Organic and inorganic composite material and its preparation Download PDFInfo
- Publication number
- JP2010053300A JP2010053300A JP2008222173A JP2008222173A JP2010053300A JP 2010053300 A JP2010053300 A JP 2010053300A JP 2008222173 A JP2008222173 A JP 2008222173A JP 2008222173 A JP2008222173 A JP 2008222173A JP 2010053300 A JP2010053300 A JP 2010053300A
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- JP
- Japan
- Prior art keywords
- organic
- oxide particles
- inorganic oxide
- surface treatment
- fluorine
- 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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- 229910003471 inorganic composite material Inorganic materials 0.000 title abstract 3
- 239000002245 particle Substances 0.000 claims abstract description 123
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 106
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229920000642 polymer Polymers 0.000 claims abstract description 71
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011737 fluorine Substances 0.000 claims abstract description 63
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 63
- -1 organic acid compound Chemical class 0.000 claims abstract description 46
- 239000002033 PVDF binder Substances 0.000 claims abstract description 43
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 43
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002335 surface treatment layer Substances 0.000 claims abstract description 34
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 238000004381 surface treatment Methods 0.000 claims abstract description 22
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 66
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 10
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000000843 powder Substances 0.000 description 34
- 108010025899 gelatin film Proteins 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 27
- 239000012756 surface treatment agent Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- 239000011324 bead Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 230000008878 coupling Effects 0.000 description 12
- 238000010168 coupling process Methods 0.000 description 12
- 238000005859 coupling reaction Methods 0.000 description 12
- 229910000077 silane Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 238000000944 Soxhlet extraction Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920005573 silicon-containing polymer Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
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- 239000000499 gel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229940080350 sodium stearate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、有機無機複合体及びその製造方法に関し、更に詳しくは、無機酸化物粒子の表面に表面処理を施し、この表面処理層を備えた無機酸化物粒子とフッ素含有ポリマーとの間に相溶化剤を介在させることにより、この無機酸化物粒子とフッ素含有ポリマーとの相溶を可能にし、これら無機酸化物粒子及びフッ素含有ポリマーを複合化した有機無機複合体の均一性及び透明性を向上させることが可能な技術に関するものである。 The present invention relates to an organic-inorganic composite and a method for producing the same. More specifically, the surface of the inorganic oxide particles is subjected to a surface treatment, and a phase is provided between the inorganic oxide particles provided with the surface treatment layer and the fluorine-containing polymer. By interposing a solubilizer, compatibility between the inorganic oxide particles and the fluorine-containing polymer is enabled, and the uniformity and transparency of the organic-inorganic composite obtained by combining the inorganic oxide particles and the fluorine-containing polymer are improved. It relates to the technology that can be made to.
従来、酸化ケイ素や酸化チタン等の無機酸化物粒子は、その表面が親水性を有しているために、この無機酸化物粒子をフッ素含有ポリマー中に均一に分散させようとすると、この無機酸化物粒子とフッ素含有ポリマーとが分離したり、あるいは分離こそしないものの無機酸化物粒子が偏在することで濁って失透したりする等の不具合が発生する虞があり、したがって、この無機酸化物粒子をフッ素含有ポリマー中に透明性を維持したまま均一に分散させることは非常に困難であった。
そこで、無機酸化物粒子の表面を表面処理剤等により表面処理してフッ素含有ポリマーへの分散性を高めることで、両者を相溶させる工夫がなされている。
Conventionally, since the surface of inorganic oxide particles such as silicon oxide and titanium oxide has hydrophilicity, when the inorganic oxide particles are uniformly dispersed in a fluorine-containing polymer, the inorganic oxide particles are used. However, the inorganic oxide particles may be separated from the product particles and the fluorine-containing polymer, or the inorganic oxide particles may not be separated, but may become turbid and devitrified. It was very difficult to uniformly disperse in a fluorine-containing polymer while maintaining transparency.
Then, the device which makes both compatible is made by surface-treating the surface of an inorganic oxide particle with a surface treating agent etc., and improving the dispersibility to a fluorine-containing polymer.
この無機酸化物粒子とフッ素含有ポリマーとの相溶を可能にする方法としては、一般的には、無機酸化物粒子の表面に存在する親水基とシランカップリング剤や有機高分子分散剤等の表面処理剤とを反応させて無機酸化物粒子の表面を疎水化し、さらに、この疎水化された表面の有機分子にフッ素を結合させることにより、この無機酸化物粒子とフッ素含有ポリマーとの溶解性パラメーターを近づける方法がとられている。
この無機酸化物粒子の表面を表面処理する方法としては、例えば、二酸化チタンやシリカゲル等の微粒子の表面をＳｉ−Ｈ基を含むシリコーンポリマーで被覆し、このシリコーンポリマーのＳｉ−Ｈ基に、ビニル基またはアリル基を有するパーフルオロ化合物を反応させる方法が提案されている（特許文献１）。
この方法によれば、パーフルオロ基で表面処理された撥水性及び撥油性を有するシリコーンポリマー被覆二酸化チタン微粒子やシリコーンポリマー被覆シリカゲルを得ることができる。
As a method for enabling compatibility between the inorganic oxide particles and the fluorine-containing polymer, generally, hydrophilic groups present on the surface of the inorganic oxide particles and a silane coupling agent, an organic polymer dispersant, or the like are used. Hydrophobic surface of inorganic oxide particles by reacting with a surface treatment agent, and further by binding fluorine to organic molecules on the hydrophobic surface, the solubility of the inorganic oxide particles and fluorine-containing polymer A method is used to bring the parameters closer.
As a method for surface-treating the surface of the inorganic oxide particles, for example, the surface of fine particles such as titanium dioxide and silica gel is coated with a silicone polymer containing Si—H groups, and vinyl is added to the Si—H groups of the silicone polymers. A method of reacting a perfluoro compound having a group or an allyl group has been proposed (Patent Document 1).
According to this method, water- and oil-repellent silicone polymer-coated titanium dioxide fine particles and silicone polymer-coated silica gel surface-treated with perfluoro groups can be obtained.
一方、無機酸化物とフッ素ポリマーとを、透明性を維持したまま均一に複合化させて有機無機複合体を得る方法としては、ゾルゲル法が挙げられる。
例えば、テトラメトキシシランとポリフッ化ビニリデンとを、ジメチルホルムアミド及びγ―ブチロラクトンの共溶媒下でゾルゲル反応させることにより、透明な有機無機複合体を得る方法が提案されている（非特許文献１）。
For example, a method for obtaining a transparent organic-inorganic composite by reacting tetramethoxysilane and polyvinylidene fluoride in a sol-gel reaction in a cosolvent of dimethylformamide and γ-butyrolactone has been proposed (Non-patent Document 1).
ところで、従来の無機酸化物粒子の表面を表面処理する方法では、この無機酸化物粒子を極性の低いフッ素含有ポリマーに分散させる場合には、添加する表面処理剤等の量が多くなり、無機酸化物粒子の特性が十分に得られなくなる可能性があるという問題点があった。また、表面処理に多段の処理工程を要するので、表面処理工程が煩雑になるという問題点もあった。さらに、シングルナノ粒子のような比表面積の大きい無機酸化物粒子を表面処理する場合には、表面処理剤等の量がさらに多くなるという問題点もあった。
また、フッ素含有ポリマーは一般的に結晶性ポリマーであるから、薄膜化した際に白濁した不透明のフィルムとなってしまい、透明フィルムを得ることが困難であった。
By the way, in the conventional method of surface-treating the surface of inorganic oxide particles, when the inorganic oxide particles are dispersed in a fluorine-containing polymer having low polarity, the amount of the surface treatment agent to be added is increased and the inorganic oxidation particles are added. There is a problem in that the properties of physical particles may not be sufficiently obtained. Further, since the surface treatment requires a multi-step treatment process, there is a problem that the surface treatment process becomes complicated. Furthermore, when surface-treating inorganic oxide particles having a large specific surface area such as single nanoparticles, there is a problem that the amount of the surface treatment agent and the like is further increased.
Further, since the fluorine-containing polymer is generally a crystalline polymer, it becomes an opaque film that becomes cloudy when it is thinned, and it is difficult to obtain a transparent film.
一方、ゾルゲル法を用いた有機無機複合体の製造方法では、アルコキシドの加水分解反応が必要となるために、微量の水添加が必要となる等、製造条件を制御することが極めて困難であるという問題点があった。また、アルコキシドの加水分解反応を制御することで透明な有機無機複合体を得たという報告は、唯一酸化ケイ素のみであり、他の酸化物については報告がなされていない。
また、このゾルゲル法では、均質な有機無機複合体を低温で得ることができるものの、無機成分がアモルファス状であるために、無機酸化物が有する特性を十分に得ることができないという問題点もあった。
On the other hand, the method for producing an organic-inorganic composite using the sol-gel method requires a hydrolysis reaction of an alkoxide, so that it is extremely difficult to control the production conditions such as the addition of a small amount of water. There was a problem. Moreover, the report that the transparent organic-inorganic composite was obtained by controlling the hydrolysis reaction of the alkoxide is only silicon oxide, and no other oxide has been reported.
In addition, although this sol-gel method can obtain a homogeneous organic-inorganic composite at a low temperature, the inorganic component is amorphous, so that the characteristics of the inorganic oxide cannot be obtained sufficiently. It was.
本発明は、上記の課題を解決するためになされたものであって、無機酸化物粒子の有する特性を損なうことなく、無機酸化物粒子とフッ素含有ポリマーとの間の相溶性を高めることができ、その結果、これら無機酸化物粒子及びフッ素含有ポリマーを複合化した有機無機複合体の均一性及び透明性を向上させることができる有機無機複合体、及び、この均一性及び透明性に優れた有機無機複合体を容易かつ安価に作製することができる製造方法を提供することを目的とする。 The present invention has been made to solve the above problems, and can improve the compatibility between the inorganic oxide particles and the fluorine-containing polymer without impairing the properties of the inorganic oxide particles. As a result, the organic-inorganic composite capable of improving the uniformity and transparency of the organic-inorganic composite obtained by combining the inorganic oxide particles and the fluorine-containing polymer, and the organic having excellent uniformity and transparency. It aims at providing the manufacturing method which can produce an inorganic composite easily and cheaply.
本発明者等は、無機酸化物粒子とフッ素含有ポリマーとの複合化について鋭意検討を重ねた結果、無機酸化物粒子の表面を表面処理して表面処理層を有する無機酸化物粒子とし、この表面処理層を有する無機酸化物粒子とフッ素含有ポリマーとを、相溶化剤を介して複合化すれば、無機酸化物粒子の有する特性を損なうことなく、無機酸化物粒子とフッ素含有ポリマーとの相溶性を高めることができ、その結果、これら無機酸化物粒子及びフッ素含有ポリマーを複合化した有機無機複合体の均一性及び透明性を向上させることができることを見出し、本発明を完成するに至った。 As a result of intensive studies on the combination of inorganic oxide particles and a fluorine-containing polymer, the present inventors have made inorganic oxide particles having a surface treatment layer by subjecting the surface of the inorganic oxide particles to surface treatment. If the inorganic oxide particles having the treatment layer and the fluorine-containing polymer are combined through a compatibilizing agent, the compatibility between the inorganic oxide particles and the fluorine-containing polymer is maintained without impairing the properties of the inorganic oxide particles. As a result, it was found that the uniformity and transparency of the organic-inorganic composite obtained by combining these inorganic oxide particles and fluorine-containing polymer can be improved, and the present invention has been completed.
すなわち、本発明の有機無機複合体は、表面処理層を有する無機酸化物粒子と、フッ素含有ポリマーとを、相溶化剤を介して複合化してなることを特徴とする。 That is, the organic-inorganic composite of the present invention is characterized in that inorganic oxide particles having a surface treatment layer and a fluorine-containing polymer are combined through a compatibilizing agent.
前記表面処理層は、前記無機酸化物粒子の表面を、有機酸化合物、有機塩基化合物、界面活性剤、有機酸化合物および界面活性剤、有機塩基化合物および界面活性剤の群から選択される１種により表面処理してなることが好ましい。
前記相溶化剤は、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、シクロヘキサノン、γ−ブチロラクトンの群から選択される１種または２種以上であることが好ましい。
前記フッ素含有ポリマーは、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体のいずれか１種であることが好ましい。
前記表面処理層の前記無機酸化物粒子に対する割合は、１５質量％以上かつ５０質量％以下であることが好ましい。
The surface treatment layer is a kind selected from the group consisting of an organic acid compound, an organic base compound, a surfactant, an organic acid compound and a surfactant, an organic base compound and a surfactant. It is preferable that the surface treatment is performed.
The compatibilizer is preferably one or more selected from the group consisting of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, cyclohexanone, and γ-butyrolactone.
The fluorine-containing polymer is preferably any one of polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymer.
The ratio of the surface treatment layer to the inorganic oxide particles is preferably 15% by mass or more and 50% by mass or less.
本発明の有機無機複合体の製造方法は、表面処理層を有する無機酸化物粒子とフッ素含有ポリマーとを相溶化剤を介して複合化してなる有機無機複合体の製造方法であって、表面処理層を有する無機酸化物粒子、相溶化剤及びフッ素含有ポリマーを含む溶液からゲル状の成形体を作製し、次いで、抽出処理により、前記ゲル状の成形体から、この成形体中に残存する相溶化剤を抽出除去することを特徴とする。 The method for producing an organic-inorganic composite of the present invention is a method for producing an organic-inorganic composite comprising a composite of inorganic oxide particles having a surface treatment layer and a fluorine-containing polymer via a compatibilizing agent. A gel-like molded body is prepared from a solution containing inorganic oxide particles having a layer, a compatibilizing agent and a fluorine-containing polymer, and then the phase remaining in the molded body is extracted from the gel-shaped molded body by an extraction process. It is characterized by extracting and removing the solubilizer.
前記無機酸化物粒子の表面を、有機酸化合物、有機塩基化合物、界面活性剤、有機酸化合物および界面活性剤、有機塩基化合物および界面活性剤の群から選択される１種により表面処理し、前記表面処理層を有する無機酸化物粒子とすることが好ましい。
前記表面処理層を有する無機酸化物粒子と前記相溶化剤とを含む溶液に、前記フッ素含有ポリマーを溶解させ、前記表面処理層を有する無機酸化物粒子と前記フッ素含有ポリマーとを相溶化させることが好ましい。
The surface of the inorganic oxide particles is surface-treated with one selected from the group consisting of an organic acid compound, an organic base compound, a surfactant, an organic acid compound and a surfactant, an organic base compound and a surfactant, Inorganic oxide particles having a surface treatment layer are preferable.
Dissolving the fluorine-containing polymer in a solution containing the inorganic oxide particles having the surface treatment layer and the compatibilizer, and compatibilizing the inorganic oxide particles having the surface treatment layer and the fluorine-containing polymer. Is preferred.
本発明の有機無機複合体によれば、表面処理層を有する無機酸化物粒子と、フッ素含有ポリマーとを、相溶化剤を介して複合化したので、この表面処理層を有する無機酸化物粒子をフッ素含有ポリマー中に均一に分散させることができる。
したがって、無機酸化物粒子の特性を十分に発現することができるとともに有機無機複合体の均一性及び透明性を向上させることができる。
According to the organic-inorganic composite of the present invention, since the inorganic oxide particles having the surface treatment layer and the fluorine-containing polymer are combined through the compatibilizing agent, the inorganic oxide particles having the surface treatment layer are combined. It can be uniformly dispersed in the fluorine-containing polymer.
Therefore, the characteristics of the inorganic oxide particles can be fully expressed, and the uniformity and transparency of the organic-inorganic composite can be improved.
本発明の有機無機複合体の製造方法によれば、表面処理層を有する無機酸化物粒子、相溶化剤及びフッ素含有ポリマーを含む溶液からゲル状の成形体を作製し、次いで、抽出処理により、前記ゲル状の成形体から、この成形体中に残存する相溶化剤を抽出除去するので、均一性及び透明性に優れるとともに、無機酸化物粒子の特性を十分に発現することができる無機酸化物粒子とフッ素含有ポリマーとを複合化した有機無機複合体を、容易かつ安価に得ることができる。
また、無機酸化物粒子の表面を表面処理する際に、表面処理剤の種類及び添加量を調整することにより、この表面処理層を有する無機酸化物粒子とフッ素含有ポリマーとの相溶性を最適化することができる。
According to the method for producing an organic-inorganic composite of the present invention, a gel-like molded body is prepared from a solution containing inorganic oxide particles having a surface treatment layer, a compatibilizing agent, and a fluorine-containing polymer, and then, by extraction treatment, Since the compatibilizing agent remaining in the molded body is extracted and removed from the gel-like molded body, the inorganic oxide is excellent in uniformity and transparency and can sufficiently exhibit the characteristics of the inorganic oxide particles. An organic-inorganic composite in which particles and a fluorine-containing polymer are combined can be obtained easily and inexpensively.
In addition, when the surface of the inorganic oxide particles is surface-treated, the compatibility between the inorganic oxide particles having the surface treatment layer and the fluorine-containing polymer is optimized by adjusting the type and addition amount of the surface treatment agent. can do.
本発明の有機無機複合体及びその製造方法を実施するための最良の形態について説明する。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
The best mode for carrying out the organic-inorganic composite of the present invention and the method for producing the same will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
「有機無機複合体」
本発明の有機無機複合体は、表面処理層を有する無機酸化物粒子（以下、表面処理無機酸化物粒子とも称する）と、フッ素含有ポリマーとを、相溶化剤を介して複合化した複合体である。
この無機酸化物粒子は、金属酸化物粒子と非金属酸化物粒子を総称したもので、金属酸化物粒子としては、Ｚｒ、Ｔｉ、Ｓｎ、Ａｌ、Ｆｅ、Ｃｕ、Ｚｎ、Ｙ、Ｎｂ、Ｍｏ、Ｉｎ、Ｇａ、Ｔａ、Ｗ、Ｐｂ、Ｂｉ、Ｃｅ、Ｓｂ、Ｇｅの群から選択される１種または２種以上の金属元素を含有する金属酸化物からなる粒子が好適に用いられる。
"Organic inorganic composite"
The organic-inorganic composite of the present invention is a composite in which inorganic oxide particles having a surface-treated layer (hereinafter also referred to as surface-treated inorganic oxide particles) and a fluorine-containing polymer are combined through a compatibilizing agent. is there.
This inorganic oxide particle is a generic term for metal oxide particles and non-metal oxide particles. As metal oxide particles, Zr, Ti, Sn, Al, Fe, Cu, Zn, Y, Nb, Mo, Particles made of a metal oxide containing one or more metal elements selected from the group of In, Ga, Ta, W, Pb, Bi, Ce, Sb, and Ge are preferably used.
この金属酸化物としては、ＺｒＯ２、ＴｉＯ２、ＳｎＯ２、Ａｌ２Ｏ３、Ｆｅ２Ｏ３、ＣｕＯ、ＺｎＯ、Ｙ２Ｏ３、Ｎｂ２Ｏ５、ＭｏＯ３、Ｉｎ２Ｏ３、Ｔａ２Ｏ５、ＷＯ３、ＰｂＯ、Ｂｉ２Ｏ３、ＣｅＯ２、Ｓｂ２Ｏ５、ＡＴＯ（アンチモン添加酸化スズ）、ＩＴＯ（スズ添加酸化インジウム）、ＩＺＯ（亜鉛添加酸化インジウム）、ＡＺＯ（アルミニウム添加酸化亜鉛）、ＧＺＯ（ガリウム添加酸化亜鉛）等が挙げられる。 As the metal oxide, ZrO 2, TiO 2, SnO 2, Al 2 O 3, Fe 2 O 3, CuO, ZnO, Y 2 O 3, Nb 2 O 5, MoO 3, In 2 O 3, Ta 2 O 5 , WO 3 , PbO, Bi 2 O 3 , CeO 2 , Sb 2 O 5 , ATO (antimony-added tin oxide), ITO (tin-added indium oxide), IZO (zinc-added indium oxide), AZO (aluminum-added oxide) Zinc), GZO (gallium-doped zinc oxide) and the like.
また、非金属酸化物粒子としては、Ｓｉ等の非金属元素を含有する非金属酸化物粒子、例えば、酸化ケイ素（ＳｉＯ２）粒子が挙げられる。 As the non-metal oxide particles, non-metal oxide particles containing a nonmetallic element such as Si, for example, silicon oxide (SiO 2) particles.
この無機酸化物粒子は、それ自体が親水性でありかつ極性を有しているので、フッ素含有ポリマーとの相溶性を高めるためには、その表面を表面処理剤により表面処理し、表面の極性を調整する必要がある。
ここで、表面処理に用いられる表面処理剤としては、有機酸化合物、有機塩基化合物、界面活性剤、有機酸化合物および界面活性剤、有機塩基化合物および界面活性剤の群から選択される１種であることが好ましく、無機酸化物粒子との相性で適宜選択される。
この表面処理剤の種類及び添加量を調整することにより、相溶化剤を用いた場合における、この無機酸化物粒子とフッ素含有ポリマーとの相溶性を最適化することができる。
Since these inorganic oxide particles themselves are hydrophilic and have a polarity, in order to increase the compatibility with the fluorine-containing polymer, the surface is treated with a surface treatment agent, and the polarity of the surface is determined. Need to be adjusted.
Here, the surface treatment agent used for the surface treatment is one selected from the group consisting of organic acid compounds, organic base compounds, surfactants, organic acid compounds and surfactants, organic base compounds and surfactants. It is preferable that it is appropriately selected depending on the compatibility with the inorganic oxide particles.
By adjusting the type and amount of the surface treatment agent, the compatibility between the inorganic oxide particles and the fluorine-containing polymer when a compatibilizer is used can be optimized.
有機酸化合物としては、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、ラウリン酸、ステアリン酸、シュウ酸、マロン酸、コハク酸、安息香酸、フタル酸、イソフタル酸、テレフタル酸、サリチル酸、リンゴ酸、乳酸、クエン酸、フマル酸、マレイン酸、アジピン酸、アミノ酸、トルエンスルホン酸、ベンゼンスルホン酸、メタンスルホン酸等が挙げられる。これらの酸は１種のみを単独で用いてもよく、２種以上を混合して用いてもよい。 Organic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, stearic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid , Salicylic acid, malic acid, lactic acid, citric acid, fumaric acid, maleic acid, adipic acid, amino acids, toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and the like. These acids may be used alone or in combination of two or more.
有機塩基化合物としては、ピリジン、ビピリジン、トリエチルアミン、ジエチルアミン、モノエチルアミン、フォスファゼン塩基等が挙げられる。これらの塩基は１種のみを単独で用いてもよく、２種以上を混合して用いてもよい。 Examples of the organic base compound include pyridine, bipyridine, triethylamine, diethylamine, monoethylamine, and phosphazene base. These bases may be used alone or in combination of two or more.
界面活性剤としては、陰イオン系界面活性剤、陽イオン系界面活性剤、両性イオン界面活性剤、非イオン系界面活性剤のいずれかが用いられる。
陰イオン系界面活性剤としては、オレイン酸ナトリウム、ステアリン酸ナトリウム、ラウリン酸ナトリウム等の脂肪酸ナトリウム系界面活性剤、脂肪酸カリウム、脂肪酸エステルスルフォン酸ナトリウム等の脂肪酸系界面活性剤、アルキルリン酸エステルナトリウム等のリン酸系界面活性剤、アルファオレインスルフォン酸ナトリウム等のオレフィン系界面活性剤、アルキル硫酸ナトリウム等のアルコール系界面活性剤、アルキルベンゼンスルホン酸等のアルキルベンゼン系界面活性剤等が挙げられる。
As the surfactant, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant is used.
Anionic surfactants include fatty acid sodium surfactants such as sodium oleate, sodium stearate, and sodium laurate, fatty acid surfactants such as fatty acid potassium and sodium fatty acid ester sulfonate, and sodium alkyl phosphate ester. And phosphoric acid surfactants such as sodium olein sulfonate, alcoholic surfactants such as sodium alkyl sulfate, and alkylbenzene surfactants such as alkylbenzene sulfonic acid.
陽イオン系界面活性剤としては、塩化アルキルメチルアンモニウム、塩化アルキルジメチルアンモニウム、塩化アルキルトリメチルアンモニウム、塩化アルキルジメチルベンジルアンモニウム等が挙げられる。
両性イオン界面活性剤としては、アルキルアミノカルボン酸塩等のカルボン酸系界面活性剤、フォスフォベタイン等のリン酸エステル系界面活性剤等が挙げられる。
非イオン系界面活性剤としては、ポリオキシエチレンラノリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等の脂肪酸系界面活性剤、ポリオキシエチレンアルキルフェニルエーテル、脂肪酸アルカノールアミド等が挙げられる。
Examples of the cationic surfactant include alkyl methyl ammonium chloride, alkyl dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, and alkyl dimethyl benzyl ammonium chloride.
Examples of zwitterionic surfactants include carboxylic acid surfactants such as alkylaminocarboxylates, and phosphate ester surfactants such as phosphobetaine.
Examples of the nonionic surfactant include fatty acid surfactants such as polyoxyethylene lanolin fatty acid ester and polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, and fatty acid alkanolamide.
この表面処理層の無機酸化物粒子に対する割合、すなわち表面処理量は、１５質量％以上かつ５０質量％以下が好ましく、より好ましくは２０質量％以上かつ４０質量％以下である。
ここで、表面処理層の無機酸化物粒子に対する割合（表面処理量）を１５質量％以上かつ５０質量％以下と限定した理由は、この割合が１５質量％未満では、表面処理剤が少なすぎるために無機酸化物粒子の表面に親水基が残留してしまい、無機酸化物粒子を十分に相溶化することができないからであり、一方、この割合が５０質量％を超えると、表面処理剤の添加量が無機酸化物粒子の表面の疎水化に必要な量を超えてしまい、添加が無駄になるからである。さらに、表面処理剤の量が多くなると、無機酸化物粒子の特性が十分に得られなくなるからである。
The ratio of the surface treatment layer to the inorganic oxide particles, that is, the surface treatment amount is preferably 15% by mass or more and 50% by mass or less, and more preferably 20% by mass or more and 40% by mass or less.
Here, the reason why the ratio of the surface treatment layer to the inorganic oxide particles (surface treatment amount) is limited to 15% by mass or more and 50% by mass or less is that when the ratio is less than 15% by mass, the surface treatment agent is too small. This is because hydrophilic groups remain on the surface of the inorganic oxide particles, and the inorganic oxide particles cannot be sufficiently compatibilized. On the other hand, if this ratio exceeds 50% by mass, the addition of the surface treatment agent This is because the amount exceeds the amount necessary for hydrophobizing the surface of the inorganic oxide particles, and the addition is wasted. Furthermore, when the amount of the surface treatment agent increases, the characteristics of the inorganic oxide particles cannot be obtained sufficiently.
フッ素含有ポリマーとしては、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体のいずれかが用いられる。 As the fluorine-containing polymer, any one of polyvinylidene fluoride and a vinylidene fluoride-hexafluoropropylene copolymer is used.
相溶化剤は、表面処理層を有する無機酸化物粒子とフッ素含有ポリマーとの相溶性を高めるものであればよく、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、シクロヘキサノン、γ−ブチロラクトン等が挙げられる。これらの相溶化剤は、１種のみを単独で用いてもよく、２種以上を混合して用いてもよい。
この相溶化剤を用いることにより、表面処理層が形成された無機酸化物粒子とフッ素含有ポリマーとの間で均一な相溶が達成される。特に、相溶化剤を用いない場合に比べて、表面処理層の量を低減させることができ、さらには表面処理層の表面にフッ素を含有させる必要もなく、相溶化を行うことができる。
Any compatibilizer may be used as long as it enhances the compatibility between the inorganic oxide particles having the surface treatment layer and the fluorine-containing polymer, and examples thereof include dimethylformamide, dimethylacetamide, dimethylsulfoxide, cyclohexanone, and γ-butyrolactone. These compatibilizers may be used alone or in combination of two or more.
By using this compatibilizing agent, uniform compatibility is achieved between the inorganic oxide particles on which the surface treatment layer is formed and the fluorine-containing polymer. In particular, the amount of the surface treatment layer can be reduced as compared with the case where no compatibilizing agent is used, and further compatibilization can be performed without the need to contain fluorine on the surface of the surface treatment layer.
この有機無機複合体では、表面処理無機酸化物粒子とフッ素含有ポリマーとを複合化した場合の無機酸化物粒子の含有量が、フッ素含有ポリマーの結晶化を抑制するのに十分な量であればよく、通常、表面処理無機酸化物粒子の含有量を３０質量％以上かつ９５質量％以下、好ましくは４５質量％以上かつ９０質量％以下、より好ましくは５０質量％以上かつ８０質量％以下の範囲で複合化する。
ここで、表面処理無機酸化物粒子の含有量が３０質量％未満であると、フッ素含有ポリマーの結晶化を抑制し難くなり、透明な複合体を得ることが難しくなる可能性があるからであり、一方、９５質量％を超えると、フッ素含有ポリマーの量が少なすぎてしまい、複合体の形状を維持することが難しくなる可能性があるからである。
In this organic-inorganic composite, if the content of the inorganic oxide particles when the surface-treated inorganic oxide particles and the fluorine-containing polymer are combined is an amount sufficient to suppress crystallization of the fluorine-containing polymer Well, usually the content of the surface-treated inorganic oxide particles is 30% by mass or more and 95% by mass or less, preferably 45% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 80% by mass or less. Combine with.
Here, when the content of the surface-treated inorganic oxide particles is less than 30% by mass, it is difficult to suppress crystallization of the fluorine-containing polymer, and it may be difficult to obtain a transparent composite. On the other hand, if it exceeds 95% by mass, the amount of the fluorine-containing polymer is too small, and it may be difficult to maintain the shape of the composite.
「有機無機複合体の製造方法」
本発明の有機無機複合体の製造方法は、表面処理無機酸化物粒子とフッ素含有ポリマーとを相溶化剤を介して複合化してなる有機無機複合体の製造方法であり、表面処理無機酸化物粒子、相溶化剤及びフッ素含有ポリマーを含む溶液からゲル状の成形体を作製し、次いで、抽出処理により、前記ゲル状の成形体から、この成形体中に残存する相溶化剤を抽出除去する方法である。
"Method for producing organic-inorganic composite"
The method for producing an organic-inorganic composite of the present invention is a method for producing an organic-inorganic composite obtained by combining surface-treated inorganic oxide particles and a fluorine-containing polymer via a compatibilizing agent. A method for producing a gel-like molded body from a solution containing a compatibilizer and a fluorine-containing polymer, and then extracting and removing the compatibilizer remaining in the molded body from the gel-like molded body by an extraction treatment It is.
ここでは、無機酸化物粒子の親水性である表面を相溶化剤と相溶させるために、この無機酸化物粒子の表面に表面処理剤を用いて表面処理を施す。
この表面処理は、無機酸化物粒子を分散媒中に分散させた分散液に、表面処理剤を加えて混合し、その後、分散処理を行うことにより、行うことができる。
Here, in order to make the hydrophilic surface of the inorganic oxide particles compatible with the compatibilizing agent, the surface of the inorganic oxide particles is subjected to a surface treatment using a surface treatment agent.
This surface treatment can be performed by adding and mixing a surface treatment agent to a dispersion obtained by dispersing inorganic oxide particles in a dispersion medium, and then performing a dispersion treatment.
この表面処理剤の添加量は、無機酸化物粒子に対して１５質量％以上かつ５０質量％以下が好ましく、より好ましくは２０質量％以上かつ４０質量％以下である。
ここで、表面処理剤の添加量を上記の範囲に限定した理由は、添加量が１５質量％未満では、表面処理剤が少なすぎるために無機酸化物粒子の表面に親水基が残留してしまい、無機酸化物粒子を十分に相溶化することができないからであり、一方、添加量が５０質量％を超えると、表面処理剤の添加量が無機酸化物粒子の表面の疎水化に必要な量を超えてしまい、添加が無駄になるからである。さらに、表面処理剤の量が多くなると、無機酸化物粒子の特性が十分に得られなくなるからである。
The addition amount of the surface treatment agent is preferably 15% by mass or more and 50% by mass or less, and more preferably 20% by mass or more and 40% by mass or less with respect to the inorganic oxide particles.
Here, the reason for limiting the addition amount of the surface treatment agent to the above range is that if the addition amount is less than 15% by mass, the surface treatment agent is too small, and thus hydrophilic groups remain on the surface of the inorganic oxide particles. This is because the inorganic oxide particles cannot be sufficiently compatibilized. On the other hand, when the addition amount exceeds 50% by mass, the addition amount of the surface treatment agent is an amount necessary for hydrophobizing the surface of the inorganic oxide particles. This is because the addition is wasted. Furthermore, when the amount of the surface treatment agent increases, the characteristics of the inorganic oxide particles cannot be obtained sufficiently.
分散媒としては、無機酸化物粒子を分散させることができ、かつ表面処理剤を溶解することができる溶媒であればよく、例えば、メタノール、エタノール、２−プロパノール、ブタノール、オクタノール等のアルコール類、酢酸エチル、酢酸ブチル、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、γ−ブチロラクトン等のエステル類、ジエチルエーテル、エチレングリコールモノメチルエーテル（メチルセロソルブ）、エチレングリコールモノエチルエーテル（エチルセロソルブ）、エチレングリコールモノブチルエーテル（ブチルセロソルブ）、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のエーテル類、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアセトアミド、Ｎ−メチルピロリドン等のアミド類が好適に用いられ、これらの溶媒のうち１種のみ、または２種以上を混合して用いることができる。 The dispersion medium may be any solvent that can disperse the inorganic oxide particles and dissolve the surface treatment agent. For example, alcohols such as methanol, ethanol, 2-propanol, butanol, octanol, Esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone, diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve) ), Ethers such as ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetone, Ketones such as tilethylketone, methylisobutylketone, acetylacetone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-methylpyrrolidone It is suitably used, and only one of these solvents or a mixture of two or more can be used.
分散処理を施すための手段としては、ジルコニアビーズを用いたビーズミル、ボールミル等が好適に用いられる。分散処理に要する時間としては、無機酸化物粒子が表面処理されるのに十分な時間であればよく、通常は１〜６時間である。これにより、無機酸化物粒子は、その表面が表面処理剤により表面処理が施されて、相溶化剤である有機化合物と相溶可能な表面処理層を有する表面処理無機酸化物粒子となる。 As a means for performing the dispersion treatment, a bead mill using zirconia beads, a ball mill, or the like is preferably used. The time required for the dispersion treatment may be a time sufficient for the surface treatment of the inorganic oxide particles, and is usually 1 to 6 hours. As a result, the surface of the inorganic oxide particles is subjected to a surface treatment with the surface treatment agent, and becomes a surface-treated inorganic oxide particle having a surface treatment layer compatible with the organic compound as the compatibilizer.
この表面処理無機酸化物粒子は分散液中に分散された状態であるから、この表面処理無機酸化物粒子を分散液から分離し、相溶化剤を含む溶液に投入して再分散させる。この際、上記と同様の分散処理を施しても良いが、相溶化剤を溶媒として用いた場合には、室温で攪拌する程度の穏やかな条件下で、表面処理無機酸化物粒子を再分散させることが可能である。 Since the surface-treated inorganic oxide particles are in a state of being dispersed in the dispersion, the surface-treated inorganic oxide particles are separated from the dispersion and charged into a solution containing a compatibilizing agent for redispersion. At this time, a dispersion treatment similar to the above may be performed, but when a compatibilizing agent is used as a solvent, the surface-treated inorganic oxide particles are redispersed under a mild condition of stirring at room temperature. It is possible.
次いで、この表面処理無機酸化物粒子及び相溶化剤を含む再分散液にフッ素含有ポリマーを投入して溶解させ、表面処理無機酸化物粒子とフッ素含有ポリマーとを相溶化する。この際、６０℃程度に加温しながら攪拌すれば、数時間の撹拌でフッ素含有ポリマーを溶解させることができる。
このようにして、表面処理無機酸化物粒子、相溶化剤及びフッ素含有ポリマーを含む溶液である均質なゾルが得られる。
Next, the fluorine-containing polymer is added to and dissolved in the redispersed liquid containing the surface-treated inorganic oxide particles and the compatibilizer, so that the surface-treated inorganic oxide particles and the fluorine-containing polymer are compatibilized. Under the present circumstances, if it stirs, heating at about 60 degreeC, a fluorine-containing polymer can be dissolved by stirring for several hours.
In this way, a homogeneous sol that is a solution containing the surface-treated inorganic oxide particles, the compatibilizer and the fluorine-containing polymer is obtained.
次いで、このゾルを所定量、ガラス、金属、プラスチック等からなる成形用型枠内にキャスト（充填）し、このゾルを加熱することにより乾燥させ、フィルム、シートあるいはバルク等のゲル状の成形体とする。 Next, a predetermined amount of this sol is cast (filled) into a molding mold made of glass, metal, plastic or the like, and the sol is dried by heating to form a gel-like molded body such as a film, sheet or bulk. And
次いで、ソックスレー抽出機等の抽出装置を用いてゲル状の成形体に抽出処理を施し、ゲル状の成形体から、この成形体中に残存する相溶化剤を抽出除去する。
抽出条件としては、相溶化剤を十分に除去することができれば良く、通常、１日〜１か月程度を要する。
また抽出溶媒としては、相溶化剤のみを抽出することができる溶媒が好ましく、メタノール、エタノール、２−プロパノール、ブタノール、オクタノール等のアルコール類が好適に使用できる。
相溶化剤が抽出除去されたゲル状の成形体は、真空下にて加熱乾燥することにより、所望の有機無機複合体となる。
Next, the gel-like molded body is subjected to an extraction process using an extraction device such as a Soxhlet extractor, and the compatibilizing agent remaining in the molded body is extracted and removed from the gel-shaped molded body.
As extraction conditions, it is sufficient that the compatibilizing agent can be sufficiently removed, and usually it takes about 1 day to 1 month.
The extraction solvent is preferably a solvent that can extract only the compatibilizing agent, and alcohols such as methanol, ethanol, 2-propanol, butanol, and octanol can be suitably used.
The gel-like molded body from which the compatibilizing agent has been extracted and removed becomes a desired organic-inorganic composite by heating and drying under vacuum.
本実施形態の有機無機複合体によれば、表面処理無機酸化物粒子と、フッ素含有ポリマーとを、相溶化剤を介して複合化したので、この表面処理無機酸化物粒子における表面処理層の量を低減することができ、さらには表面処理層の表面にフッ素を含有させる必要もない状態で、フッ素含有ポリマー中に均一に分散させることができる。
したがって、無機酸化物粒子の特性を十分に発現することができ、またフッ素含有ポリマーの結晶化を抑制しつつ、有機無機複合体における均一性及び透明性を向上させることができる。
According to the organic-inorganic composite of the present embodiment, since the surface-treated inorganic oxide particles and the fluorine-containing polymer are combined through a compatibilizing agent, the amount of the surface-treated layer in the surface-treated inorganic oxide particles In addition, the surface treatment layer can be uniformly dispersed in the fluorine-containing polymer in a state where it is not necessary to contain fluorine on the surface of the surface treatment layer.
Therefore, the characteristics of the inorganic oxide particles can be fully expressed, and the uniformity and transparency of the organic-inorganic composite can be improved while suppressing the crystallization of the fluorine-containing polymer.
本実施形態の有機無機複合体の製造方法によれば、表面処理無機酸化物粒子、相溶化剤及びフッ素含有ポリマーを含む均質なゾルを作製し、このゾルを加熱することによりゲル状の成形体を作製し、抽出処理により、ゲル状の成形体から、この成形体中に残存する相溶化剤を抽出除去するので、均一性及び透明性に優れるとともに、無機酸化物粒子の特性を十分に発現することができる無機酸化物粒子とフッ素含有ポリマーとを複合化した有機無機複合体を、容易かつ安価に得ることができる。
また、無機酸化物粒子の表面を表面処理する際に、表面処理剤の種類及び添加量を調整することにより、この表面処理無機酸化物粒子とフッ素含有ポリマーとの相溶性を最適化ことができる。
According to the method for producing an organic-inorganic composite of this embodiment, a homogeneous sol containing surface-treated inorganic oxide particles, a compatibilizing agent and a fluorine-containing polymer is prepared, and the sol is heated to form a gel-like molded body Since the compatibilizer remaining in the molded body is extracted and removed from the gel-like molded body by extraction treatment, the uniformity and transparency are excellent, and the characteristics of the inorganic oxide particles are fully expressed. It is possible to easily and inexpensively obtain an organic-inorganic composite obtained by combining inorganic oxide particles and a fluorine-containing polymer.
Moreover, when surface-treating the surface of the inorganic oxide particles, the compatibility between the surface-treated inorganic oxide particles and the fluorine-containing polymer can be optimized by adjusting the type and addition amount of the surface treatment agent. .
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.
[実施例１]
ジルコニア粒子（比表面積１７０ｇ/ｍ２）１０ｇに、分散媒として水を７０ｇ、表面処理剤として酢酸を２０ｇ加えて混合し、次いで、直径が０．１ｍｍのジルコニアビーズを用いたビーズミルにより分散処理を行い、ジルコニア分散液を調製した。
次いで、エバポレーターを用いて、このジルコニア分散液から溶媒を除去し、表面処理ジルコニア粉体を得た。この表面処理ジルコニア粉体の表面処理量は２０質量％であった。
[Example 1]
To 10 g of zirconia particles (specific surface area 170 g / m 2 ), 70 g of water as a dispersion medium and 20 g of acetic acid as a surface treatment agent are added and mixed, and then dispersed by a bead mill using zirconia beads having a diameter of 0.1 mm. And a zirconia dispersion was prepared.
Subsequently, using an evaporator, the solvent was removed from the zirconia dispersion to obtain a surface-treated zirconia powder. The surface treatment amount of this surface-treated zirconia powder was 20% by mass.
この表面処理ジルコニア粉体１ｇを相溶化剤であるジメチルホルムアミド（ＤＭＦ）３．０ｇに投入し、撹拌、混合して透明分散液とした後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、表面処理ジルコニア粒子、ジメチルホルムアミド及びポリフッ化ビニリデンを含む均質な透明ゾルを得た。
次いで、この透明ゾルをポリプロピレン容器にキャストし、大気中、６０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留するジメチルホルムアミドを完全に抽出除去した。その後、８０℃にて真空乾燥を行い、実施例１の有機無機複合体を得た。
1 g of this surface-treated zirconia powder was added to 3.0 g of dimethylformamide (DMF) as a compatibilizer, stirred and mixed to obtain a transparent dispersion, and then 0.2 g of polyvinylidene fluoride (PVdF) was added, By stirring at 60 ° C. for 3 hours, a homogeneous transparent sol containing surface-treated zirconia particles, dimethylformamide and polyvinylidene fluoride was obtained.
Next, this transparent sol was cast into a polypropylene container and dried in the atmosphere at 60 ° C. for 18 hours to obtain a gel film.
Next, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethylformamide remaining in the gel film was completely extracted and removed. Then, it vacuum-dried at 80 degreeC and the organic inorganic composite of Example 1 was obtained.
[実施例２]
ポリフッ化ビニリデン（ＰＶｄＦ）をポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体（ＰＶｄＦ−ｃｏ−ＨＦＰ）に代えた他は、実施例１に準じて、実施例２の有機無機複合体を得た。
[Example 2]
The organic-inorganic composite of Example 2 was obtained according to Example 1 except that polyvinylidene fluoride (PVdF) was replaced with polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP).
[実施例３]
チタニア粒子（比表面積１５０ｇ/ｍ２）１０ｇに、分散媒として水を７０ｇ、表面処理剤として酢酸を２０ｇ加えて混合し、次いで、直径が０．１ｍｍのジルコニアビーズを用いたビーズミルにより分散処理を行い、チタニア分散液を調製した。
次いで、エバポレーターを用いて、このチタニア分散液から溶媒を除去し、表面処理チタニア粉体を得た。この表面処理チタニア粉体の表面処理量は２５．７質量％であった。
[Example 3]
70 g of water as a dispersion medium and 20 g of acetic acid as a surface treatment agent are added to and mixed with 10 g of titania particles (specific surface area 150 g / m 2 ), and then dispersed by a bead mill using zirconia beads having a diameter of 0.1 mm. And titania dispersion was prepared.
Subsequently, the solvent was removed from the titania dispersion using an evaporator to obtain a surface-treated titania powder. The surface treatment amount of this surface-treated titania powder was 25.7% by mass.
この表面処理チタニア粉体０．６５ｇを相溶化剤であるジメチルホルムアミド（ＤＭＦ）３．０ｇに投入し、撹拌、混合して透明分散液とした後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、表面処理チタニア粒子、ジメチルホルムアミド及びポリフッ化ビニリデンを含む均質な透明ゾルを得た。
次いで、この透明ゾルをポリプロピレン容器にキャストし、大気中、６０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルホルムアミドを完全に抽出除去した。
その後、８０℃にて真空乾燥を行い、実施例３の有機無機複合体を得た。
0.65 g of this surface-treated titania powder was added to 3.0 g of dimethylformamide (DMF) as a compatibilizing agent, stirred and mixed to obtain a transparent dispersion, and then 0.2 g of polyvinylidene fluoride (PVdF) was added. By stirring at 60 ° C. for 3 hours, a homogeneous transparent sol containing surface-treated titania particles, dimethylformamide and polyvinylidene fluoride was obtained.
Next, this transparent sol was cast into a polypropylene container and dried in the atmosphere at 60 ° C. for 18 hours to obtain a gel film.
Next, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethylformamide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 80 degreeC and the organic-inorganic composite of Example 3 was obtained.
[実施例４]
ジメチルホルムアミド（ＤＭＦ）を相溶化剤であるジメチルアセトアミド（ＤＭＡｃ）に代えた他は、実施例１に準じて、実施例４の有機無機複合体を得た。
[Example 4]
The organic-inorganic composite of Example 4 was obtained in the same manner as in Example 1 except that dimethylformamide (DMF) was replaced with dimethylacetamide (DMAc) as a compatibilizing agent.
[実施例５]
表面処理ジルコニア粉体を１ｇから１．１３ｇに、ジメチルホルムアミド（ＤＭＦ）を相溶化剤であるジメチルアセトアミド（ＤＭＡｃ）に、ポリフッ化ビニリデン（ＰＶｄＦ）を０．２ｇから０．１ｇに、それぞれ代えた他は、実施例１に準じて、実施例５の有機無機複合体を得た。
[Example 5]
The surface-treated zirconia powder was changed from 1 g to 1.13 g, dimethylformamide (DMF) was changed to dimethylacetamide (DMAc) as a compatibilizer, and polyvinylidene fluoride (PVdF) was changed from 0.2 g to 0.1 g, respectively. Other than that, the organic-inorganic composite of Example 5 was obtained according to Example 1.
[実施例６]
ジメチルホルムアミド（ＤＭＦ）を相溶化剤であるジメチルスルホキシド（ＤＭＳＯ）に代えた他は、実施例１に準じて、表面処理ジルコニア粒子、ジメチルスルホキシド及びポリフッ化ビニリデンを含む均質な透明ゾルを得た。
次いで、この透明ゾルをガラス容器にキャストし、大気中、１２０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルスルホキシドを完全に抽出除去した。
その後、１５０℃にて真空乾燥を行い、実施例６の有機無機複合体を得た。
[Example 6]
A homogeneous transparent sol containing surface-treated zirconia particles, dimethyl sulfoxide and polyvinylidene fluoride was obtained in the same manner as in Example 1 except that dimethylformamide (DMF) was replaced with dimethyl sulfoxide (DMSO) as a compatibilizing agent.
Next, this transparent sol was cast into a glass container and dried in the atmosphere at 120 ° C. for 18 hours to obtain a gel film.
Subsequently, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethyl sulfoxide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 150 degreeC and the organic inorganic composite of Example 6 was obtained.
[実施例７]
ジルコニア粒子（比表面積１７０ｇ/ｍ２）１０ｇに、分散媒として水を４０ｇ、メタノールを４０ｇ、表面処理剤としてカプロン酸を１０ｇ加えて混合し、次いで、直径が０．１ｍｍのジルコニアビーズを用いたビーズミルにより分散処理を行い、ジルコニア分散液を調製した。
次いで、エバポレーターを用いて、このジルコニア分散液から溶媒を除去し、表面処理ジルコニア粉体を得た。この表面処理ジルコニア粉体の表面処理量は３５質量％であった。
[Example 7]
To 10 g of zirconia particles (specific surface area 170 g / m 2 ), 40 g of water as a dispersion medium, 40 g of methanol and 10 g of caproic acid as a surface treatment agent were added and mixed, and then zirconia beads having a diameter of 0.1 mm were used. Dispersion treatment was performed with a bead mill to prepare a zirconia dispersion.
Subsequently, using an evaporator, the solvent was removed from the zirconia dispersion to obtain a surface-treated zirconia powder. The surface treatment amount of this surface-treated zirconia powder was 35% by mass.
この表面処理ジルコニア粉体１．０７ｇを相溶化剤であるジメチルホルムアミド（ＤＭＦ）３．０ｇに投入し、撹拌、混合して透明分散液とした後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、表面処理ジルコニア粒子、ジメチルホルムアミド及びポリフッ化ビニリデンを含む均質な透明ゾルを得た。
次いで、この透明ゾルをポリプロピレン容器にキャストし、大気中、６０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルホルムアミドを完全に抽出除去した。
その後、８０℃にて真空乾燥を行い、実施例７の有機無機複合体を得た。
1.07 g of this surface-treated zirconia powder is added to 3.0 g of dimethylformamide (DMF) as a compatibilizing agent, stirred and mixed to obtain a transparent dispersion, and then 0.2 g of polyvinylidene fluoride (PVdF) is added. By stirring at 60 ° C. for 3 hours, a homogeneous transparent sol containing surface-treated zirconia particles, dimethylformamide and polyvinylidene fluoride was obtained.
Next, this transparent sol was cast into a polypropylene container and dried in the atmosphere at 60 ° C. for 18 hours to obtain a gel film.
Next, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethylformamide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 80 degreeC and the organic inorganic composite of Example 7 was obtained.
[実施例８]
シリカ粒子（比表面積２００ｇ/ｍ２）１０ｇに、分散媒として水を４０ｇ、メタノールを４０ｇ、表面処理剤として２，２’−ビピリジンを１０ｇ加えて混合し、次いで、直径が０．１ｍｍのジルコニアビーズを用いたビーズミルにより分散処理を行い、シリカ分散液を調製した。
このシリカ分散液中の溶媒を、エバポレーターを用いて除去し、表面処理シリカ粉体を得た。この表面処理シリカ粉体の表面処理量は４０質量％であった。
[Example 8]
10 g of silica particles (specific surface area 200 g / m 2 ), 40 g of water as a dispersion medium, 40 g of methanol, 10 g of 2,2′-bipyridine as a surface treatment agent are added and mixed, and then zirconia having a diameter of 0.1 mm Dispersion treatment was performed by a bead mill using beads to prepare a silica dispersion.
The solvent in the silica dispersion was removed using an evaporator to obtain surface-treated silica powder. The surface treatment amount of this surface-treated silica powder was 40% by mass.
この表面処理シリカ粉体０．４８ｇを相溶化剤であるジメチルスルホキシド（ＤＭＳＯ）３．０ｇに投入し、撹拌、混合して透明分散液とした後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、表面処理シリカ粒子、ジメチルスルホキシド及びポリフッ化ビニリデンを含む均質な透明ゾルを得た。
次いで、この透明ゾルをガラス容器にキャストし、大気中、１２０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルスルホキシドを完全に抽出除去した。
その後、１５０℃にて真空乾燥を行い、実施例８の有機無機複合体を得た。
0.48 g of this surface-treated silica powder is added to 3.0 g of dimethyl sulfoxide (DMSO) as a compatibilizing agent, stirred and mixed to obtain a transparent dispersion, and then 0.2 g of polyvinylidene fluoride (PVdF) is added. By stirring at 60 ° C. for 3 hours, a homogeneous transparent sol containing surface-treated silica particles, dimethyl sulfoxide and polyvinylidene fluoride was obtained.
Next, this transparent sol was cast into a glass container and dried in the atmosphere at 120 ° C. for 18 hours to obtain a gel film.
Subsequently, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethyl sulfoxide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 150 degreeC and the organic inorganic composite of Example 8 was obtained.
[実施例９]
表面処理シリカ粉体を０．４８ｇから０．３７ｇに、ポリフッ化ビニリデン（ＰＶｄＦ）を０．２ｇから０．５５ｇに、それぞれ代えた他は、実施例８に準じて、実施例９の有機無機複合体を得た。
[Example 9]
The organic-inorganic of Example 9 according to Example 8 except that the surface-treated silica powder was changed from 0.48 g to 0.37 g and the polyvinylidene fluoride (PVdF) was changed from 0.2 g to 0.55 g. A complex was obtained.
[実施例１０]
シリカ粒子（比表面積２００ｇ/ｍ２）１０ｇに、分散媒として水を８０ｇ、表面処理剤としてジエチルアミンを１０ｇ加えて混合し、次いで、直径が０．１ｍｍのジルコニアビーズを用いたビーズミルにより分散処理を行い、シリカ分散液を調製した。
このシリカ分散液中の溶媒を、エバポレーターを用いて除去し、表面処理シリカ粉体を得た。この表面処理シリカ粉体の表面処理量は３５質量％であった。
[Example 10]
To 10 g of silica particles (specific surface area 200 g / m 2 ), 80 g of water as a dispersion medium and 10 g of diethylamine as a surface treatment agent are added and mixed, and then dispersed by a bead mill using zirconia beads having a diameter of 0.1 mm. And a silica dispersion was prepared.
The solvent in the silica dispersion was removed using an evaporator to obtain surface-treated silica powder. The surface treatment amount of this surface-treated silica powder was 35% by mass.
この表面処理シリカ粉体０．４５ｇを相溶化剤であるジメチルスルホキシド（ＤＭＳＯ）３．０ｇに投入し、撹拌、混合して透明分散液とした後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、表面処理シリカ粒子、ジメチルスルホキシド及びポリフッ化ビニリデンを含む均質な透明ゾルを得た。
次いで、この透明ゾルをガラス容器にキャストし、大気中、１２０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルスルホキシドを完全に抽出除去した。
その後、１５０℃にて真空乾燥を行い、実施例１０の有機無機複合体を得た。
0.45 g of this surface-treated silica powder is added to 3.0 g of dimethyl sulfoxide (DMSO) as a compatibilizing agent, stirred and mixed to obtain a transparent dispersion, and then 0.2 g of polyvinylidene fluoride (PVdF) is added. By stirring at 60 ° C. for 3 hours, a homogeneous transparent sol containing surface-treated silica particles, dimethyl sulfoxide and polyvinylidene fluoride was obtained.
Next, this transparent sol was cast into a glass container and dried in the atmosphere at 120 ° C. for 18 hours to obtain a gel film.
Subsequently, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethyl sulfoxide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 150 degreeC and the organic inorganic composite of Example 10 was obtained.
[比較例１]
ポリフッ化ビニリデン（ＰＶｄＦ）０．５ｇとジメチルホルムアミド（ＤＭＦ）３．０ｇとを、６０℃にて３時間攪拌することにより、均質な透明ゾルを得た。
次いで、この透明ゾルをポリプロピレン容器にキャストし、大気中、６０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルホルムアミドを完全に抽出除去した。
その後、８０℃にて真空乾燥を行い、比較例１のポリマーを得た。
[Comparative Example 1]
A homogeneous transparent sol was obtained by stirring 0.5 g of polyvinylidene fluoride (PVdF) and 3.0 g of dimethylformamide (DMF) at 60 ° C. for 3 hours.
Next, this transparent sol was cast into a polypropylene container and dried in the atmosphere at 60 ° C. for 18 hours to obtain a gel film.
Next, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethylformamide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 80 degreeC and the polymer of the comparative example 1 was obtained.
[比較例２]
ポリフッ化ビニリデン（ＰＶｄＦ）をポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体（ＰＶｄＦ−ｃｏ−ＨＦＰ）に代えた他は、比較例１に準じて、比較例２のポリマーを得た。
[Comparative Example 2]
A polymer of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that polyvinylidene fluoride (PVdF) was replaced with polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP).
[比較例３]
ジルコニア粒子（比表面積１７０ｇ/ｍ２）１０ｇに、分散媒として水を８０ｇ、表面処理剤として硝酸を加えてｐＨを２．０に調整し、次いで、直径が０．１ｍｍのジルコニアビーズを用いたビーズミルにより分散処理を行い、ジルコニア分散液を調製した。
次いで、このジルコニア分散液中の溶媒を、エバポレーターを用いて除去し、表面処理ジルコニア粉体を得た。この表面処理ジルコニア粉体の表面処理量は１２質量％であった。
[Comparative Example 3]
To 10 g of zirconia particles (specific surface area 170 g / m 2 ), 80 g of water as a dispersion medium and nitric acid as a surface treatment agent were added to adjust the pH to 2.0, and then zirconia beads having a diameter of 0.1 mm were used. Dispersion treatment was performed with a bead mill to prepare a zirconia dispersion.
Next, the solvent in the zirconia dispersion was removed using an evaporator to obtain a surface-treated zirconia powder. The surface treatment amount of this surface-treated zirconia powder was 12% by mass.
この表面処理ジルコニア粉体０．９４ｇをジメチルホルムアミド（ＤＭＦ）３．０ｇに投入し、撹拌、混合した後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、表面処理ジルコニア粒子、ジメチルホルムアミド及びポリフッ化ビニリデンを含むゾルを得た。
次いで、このゾルをポリプロピレン容器にキャストし、大気中、６０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルホルムアミドを完全に抽出除去した。
その後、８０℃にて真空乾燥を行い、比較例３の有機無機複合体を得た。
0.94 g of this surface-treated zirconia powder is added to 3.0 g of dimethylformamide (DMF), stirred and mixed, and then 0.2 g of polyvinylidene fluoride (PVdF) is added and stirred at 60 ° C. for 3 hours. Thus, a sol containing surface-treated zirconia particles, dimethylformamide, and polyvinylidene fluoride was obtained.
Next, this sol was cast into a polypropylene container and dried in the atmosphere at 60 ° C. for 18 hours to obtain a gel film.
Next, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethylformamide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 80 degreeC and the organic-inorganic composite of the comparative example 3 was obtained.
[比較例４]
比較例３にて得られたジルコニア分散液１０ｇに、メタノール９．０ｇとシランカップリング剤であるγ−メタクリロキシプロピルトリメトキシシラン（ＭＰＴＳ）１．０ｇとの混合溶液を滴下し、６０℃にて１０時間撹拌することにより、シランカップリング処理を行った。
次いで、濾過を行い、シランカップリング処理された粉体を回収し、この粉体を水−エタノール混合溶液を用いて十分に洗浄し、シランカップリング処理ジルコニア粉体を得た。
このシランカップリング処理ジルコニア粉体の表面処理量は２６．５質量％であった。
[Comparative Example 4]
To 10 g of the zirconia dispersion obtained in Comparative Example 3, a mixed solution of 9.0 g of methanol and 1.0 g of γ-methacryloxypropyltrimethoxysilane (MPTS), which is a silane coupling agent, was added dropwise to 60 ° C. The mixture was stirred for 10 hours to perform silane coupling treatment.
Subsequently, filtration was performed to recover the powder subjected to the silane coupling treatment, and this powder was sufficiently washed with a water-ethanol mixed solution to obtain a silane coupling-treated zirconia powder.
The surface treatment amount of the silane coupling-treated zirconia powder was 26.5% by mass.
このシランカップリング処理ジルコニア粉体１．０９ｇを相溶化剤であるジメチルホルムアミド（ＤＭＦ）３．０ｇに投入し、撹拌、混合して透明分散液とした後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、シランカップリング処理ジルコニア粉体、ジメチルホルムアミド及びポリフッ化ビニリデンを含む均質な透明ゾルを得た。
次いで、この透明ゾルをポリプロピレン容器にキャストし、大気中、６０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルホルムアミドを完全に抽出除去した。
その後、８０℃にて真空乾燥を行い、比較例４の有機無機複合体を得た。
1.09 g of this silane coupling-treated zirconia powder is put into 3.0 g of dimethylformamide (DMF) as a compatibilizing agent, stirred and mixed to obtain a transparent dispersion, and then 0.2 g of polyvinylidene fluoride (PVdF). Was stirred at 60 ° C. for 3 hours to obtain a homogeneous transparent sol containing silane coupling-treated zirconia powder, dimethylformamide and polyvinylidene fluoride.
Next, this transparent sol was cast into a polypropylene container and dried in the atmosphere at 60 ° C. for 18 hours to obtain a gel film.
Next, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethylformamide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 80 degreeC and the organic-inorganic composite of the comparative example 4 was obtained.
[比較例５]
比較例３にて得られたジルコニア分散液１０ｇに、メタノール９．０ｇとシランカップリング剤であるトリフルオロプロピルトリメトキシシラン（ＦＰＴＳ）１．０ｇとの混合溶液を滴下し、６０℃にて１０時間撹拌することにより、シランカップリング処理を行った。
次いで、濾過を行い、シランカップリング処理された粉体を回収し、この粉体を水−エタノール混合溶液を用いて十分に洗浄し、シランカップリング処理ジルコニア粉体を得た。
このシランカップリング処理ジルコニア粉体の表面処理量は２８．０質量％であった。
[Comparative Example 5]
To 10 g of the zirconia dispersion obtained in Comparative Example 3, a mixed solution of 9.0 g of methanol and 1.0 g of trifluoropropyltrimethoxysilane (FPTS), which is a silane coupling agent, was added dropwise, and 10 ° C. at 60 ° C. By stirring for a period of time, a silane coupling treatment was performed.
Subsequently, filtration was performed to recover the powder subjected to the silane coupling treatment, and this powder was sufficiently washed with a water-ethanol mixed solution to obtain a silane coupling-treated zirconia powder.
The surface treatment amount of the silane coupling-treated zirconia powder was 28.0% by mass.
このシランカップリング処理ジルコニア粉体１．１１ｇを相溶化剤であるジメチルスルホキシド（ＤＭＳＯ）３．０ｇに投入し、撹拌、混合した後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、シランカップリング処理ジルコニア粉体、ジメチルスルホキシド及びポリフッ化ビニリデンを含むゾルを得た。
次いで、このゾルをポリプロピレン容器にキャストし、大気中、１２０℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに、メタノールを用いたソックスレー抽出を１０日間施し、このゲルフィルム中に残留したジメチルスルホキシドを完全に抽出除去した。
その後、１５０℃にて真空乾燥を行い、比較例５の有機無機複合体を得た。
1.11 g of this silane coupling-treated zirconia powder was added to 3.0 g of dimethyl sulfoxide (DMSO) as a compatibilizing agent, and after stirring and mixing, 0.2 g of polyvinylidene fluoride (PVdF) was added, and the temperature was 60 ° C. Was stirred for 3 hours to obtain a sol containing silane coupling-treated zirconia powder, dimethyl sulfoxide and polyvinylidene fluoride.
Next, this sol was cast into a polypropylene container and dried in the atmosphere at 120 ° C. for 18 hours to obtain a gel film.
Subsequently, the gel film was subjected to Soxhlet extraction using methanol for 10 days, and dimethyl sulfoxide remaining in the gel film was completely extracted and removed.
Then, it vacuum-dried at 150 degreeC and the organic-inorganic composite of the comparative example 5 was obtained.
[比較例６]
実施例１にて得られた表面処理ジルコニア粉体１ｇを、相溶化剤を用いずに３−オクタノン３．０ｇと混合し、透明分散液とした後、ポリフッ化ビニリデン（ＰＶｄＦ）０．２ｇを投入し、６０℃にて３時間攪拌することにより、表面処理ジルコニア粉体及びポリフッ化ビニリデンを含むゾルを得た。
次いで、このゾルをポリプロピレン容器にキャストし、大気中、１００℃にて１８時間、乾燥させ、ゲルフィルムを得た。
次いで、このゲルフィルムに１２０℃にて真空乾燥を施し、比較例６の有機無機複合体を得た。
[Comparative Example 6]
1 g of the surface-treated zirconia powder obtained in Example 1 was mixed with 3.0 g of 3-octanone without using a compatibilizing agent to form a transparent dispersion, and then 0.2 g of polyvinylidene fluoride (PVdF) was added. The sol containing the surface-treated zirconia powder and polyvinylidene fluoride was obtained by charging and stirring at 60 ° C. for 3 hours.
Next, this sol was cast into a polypropylene container and dried in the air at 100 ° C. for 18 hours to obtain a gel film.
Next, this gel film was vacuum dried at 120 ° C. to obtain an organic-inorganic composite of Comparative Example 6.
［有機無機複合体の評価］
実施例１〜１０及び比較例３〜６各々の有機無機複合体、及び比較例１、２各々のポリマーの可視光線透過率を測定し、評価を行った。
ここでは、分光光度計Ｖ−５７０（日本分光社製）を用い、波長３５０ｎｍ〜８００ｎｍの範囲の可視光線の透過率を測定した。
なお、これら有機無機複合体及びポリマーそれぞれを、約１００μｍの厚みのフィルムとし、大気の透過率を１００％として測定した。
評価は、可視光線透過率が８０％以上の場合を「○」、８０％未満の場合を「×」とした。表１に実施例１〜１０及び比較例１〜６各々の可視光線透過率を示す。
[Evaluation of organic-inorganic composites]
The visible light transmittances of the organic-inorganic composites of Examples 1 to 10 and Comparative Examples 3 to 6 and the polymers of Comparative Examples 1 and 2 were measured and evaluated.
Here, the transmittance of visible light in the wavelength range of 350 nm to 800 nm was measured using a spectrophotometer V-570 (manufactured by JASCO Corporation).
Each of these organic-inorganic composites and polymers was measured with a film having a thickness of about 100 μm and an atmospheric transmittance of 100%.
In the evaluation, the case where the visible light transmittance was 80% or more was “◯”, and the case where it was less than 80% was “x”. Table 1 shows the visible light transmittance of each of Examples 1 to 10 and Comparative Examples 1 to 6.
表１から明らかなように、実施例１〜１０の有機無機複合体は８０％以上の可視光線透過率を有することが分かった。したがって、これらの有機無機複合体を光学部材をはじめ、様々な用途へ適用可能であることが分かった。
一方、比較例１、２のポリマーは、ポリマー自体の結晶化により白濁したフィルムとなり、可視光透過率が大幅に低下した。
また、比較例３、５の有機無機複合体は、ゾル作製時に白濁ゲル化してしまい、フィルムも白濁を呈していた。そのため、可視光線透過率は低いものであった。
比較例４の有機無機複合体は、ゾルの状態では均一な透明ゾルであったが、フィルムに形成した際に白濁してしまい、このフィルムの可視光線透過率は低いものであった。
比較例６の有機無機複合体は、相溶化剤を用いていないために、ゾルを作製した時点でゲル化してしまい、フィルムへの成形が不可能であった。
As is clear from Table 1, it was found that the organic-inorganic composites of Examples 1 to 10 had a visible light transmittance of 80% or more. Therefore, it was found that these organic-inorganic composites can be applied to various uses including optical members.
On the other hand, the polymers of Comparative Examples 1 and 2 became a cloudy film due to crystallization of the polymer itself, and the visible light transmittance was greatly reduced.
Moreover, the organic-inorganic composites of Comparative Examples 3 and 5 were white turbid when forming the sol, and the film was also white turbid. Therefore, the visible light transmittance was low.
The organic-inorganic composite of Comparative Example 4 was a uniform transparent sol in the sol state, but became cloudy when formed into a film, and the visible light transmittance of this film was low.
Since the organic-inorganic composite of Comparative Example 6 did not use a compatibilizing agent, it gelled at the time of producing the sol, and could not be formed into a film.
本発明の有機無機複合体は、表面処理層を有する無機酸化物粒子と、フッ素含有ポリマーとを、相溶化剤を介して複合化したことにより、この表面処理層を有する無機酸化物粒子をフッ素含有ポリマー中に均一に分散させることができ、したがって、無機酸化物粒子の特性を十分に発現することができ、均一性及び透明性を向上させることができるものであるから、フラットパネルディスプレイ（ＦＰＤ）の位相差フィルム、拡散フィルム等の光学フィルム、ＭＯ、ＣＤ、ＤＶＤ等の光情報記録媒体、この光情報記録媒体の読み取り／書き込みを行う光ピックアップ用レンズ等の光学レンズ、ＣＭＯＳ、ＣＣＤ等の光学機器のマイクロレンズアレイ、発光ダイオード（ＬＥＤ）の光取り出しレンズや封止材等、高精度及び信頼性が求められる様々な光学部品に適用可能であり、その工業的効果は大である。 The organic-inorganic composite of the present invention is obtained by combining inorganic oxide particles having a surface treatment layer and a fluorine-containing polymer through a compatibilizing agent so that the inorganic oxide particles having the surface treatment layer are fluorinated. The flat polymer display (FPD) can be uniformly dispersed in the contained polymer, and therefore, the characteristics of the inorganic oxide particles can be sufficiently expressed, and the uniformity and transparency can be improved. ) Retardation film, optical film such as diffusion film, optical information recording medium such as MO, CD, DVD, optical lens such as optical pickup lens for reading / writing of this optical information recording medium, CMOS, CCD, etc. High precision and reliability are required, such as microlens arrays for optical devices, light extraction lenses and sealing materials for light-emitting diodes (LEDs), etc. Is applicable various optical components, its industrial effect is large.
Claims (8)
表面処理層を有する無機酸化物粒子、相溶化剤及びフッ素含有ポリマーを含む溶液からゲル状の成形体を作製し、
次いで、抽出処理により、前記ゲル状の成形体から、この成形体中に残存する相溶化剤を抽出除去することを特徴とする有機無機複合体の製造方法。 A method for producing an organic-inorganic composite comprising a composite of inorganic oxide particles having a surface treatment layer and a fluorine-containing polymer via a compatibilizing agent,
A gel-like molded body is prepared from a solution containing inorganic oxide particles having a surface treatment layer, a compatibilizing agent and a fluorine-containing polymer,
Next, a method for producing an organic-inorganic composite comprising extracting and removing the compatibilizer remaining in the molded body from the gel-shaped molded body by an extraction treatment.
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