US20110135878A1 - Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film - Google Patents
Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film Download PDFInfo
- Publication number
- US20110135878A1 US20110135878A1 US12/929,592 US92959211A US2011135878A1 US 20110135878 A1 US20110135878 A1 US 20110135878A1 US 92959211 A US92959211 A US 92959211A US 2011135878 A1 US2011135878 A1 US 2011135878A1
- Authority
- US
- United States
- Prior art keywords
- metal
- dispersoid
- temperature
- solution
- film
- 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.)
- Abandoned
Links
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 84
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 82
- 239000001301 oxygen Substances 0.000 title claims abstract description 75
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 75
- 239000003960 organic solvent Substances 0.000 claims abstract description 67
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims description 68
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 230000002776 aggregation Effects 0.000 claims description 13
- 238000004220 aggregation Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 182
- 150000002736 metal compounds Chemical class 0.000 abstract description 92
- 238000002156 mixing Methods 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 30
- 230000007062 hydrolysis Effects 0.000 abstract description 27
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 27
- 239000010409 thin film Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 171
- 239000010408 film Substances 0.000 description 150
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 143
- -1 diphenyliodonium hexafluorophosphate Chemical compound 0.000 description 92
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 72
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 65
- 238000007792 addition Methods 0.000 description 63
- 150000001875 compounds Chemical class 0.000 description 60
- 238000000034 method Methods 0.000 description 60
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 59
- 239000007788 liquid Substances 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 239000002904 solvent Substances 0.000 description 55
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 239000002245 particle Substances 0.000 description 49
- 229910052751 metal Inorganic materials 0.000 description 48
- 239000002184 metal Substances 0.000 description 48
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 43
- 239000000203 mixture Substances 0.000 description 43
- 238000003756 stirring Methods 0.000 description 43
- 239000000178 monomer Substances 0.000 description 42
- 150000002430 hydrocarbons Chemical group 0.000 description 31
- 239000010936 titanium Substances 0.000 description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 239000000413 hydrolysate Substances 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 150000004703 alkoxides Chemical class 0.000 description 25
- 238000002834 transmittance Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 23
- 230000003287 optical effect Effects 0.000 description 21
- 125000004429 atom Chemical group 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- 229930195733 hydrocarbon Natural products 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 18
- 238000009826 distribution Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 235000011089 carbon dioxide Nutrition 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 230000036961 partial effect Effects 0.000 description 14
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 13
- 239000004568 cement Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- 150000008282 halocarbons Chemical group 0.000 description 13
- 229920000728 polyester Polymers 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 9
- 230000003301 hydrolyzing effect Effects 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 238000003980 solgel method Methods 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 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 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- FZJCXIDLUFPGPP-UHFFFAOYSA-N propan-2-ol;toluene Chemical compound CC(C)O.CC1=CC=CC=C1 FZJCXIDLUFPGPP-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- YRHRHYSCLREHLE-UHFFFAOYSA-N 2,5-bis(isocyanatomethyl)-1,4-dithiane Chemical compound O=C=NCC1CSC(CN=C=O)CS1 YRHRHYSCLREHLE-UHFFFAOYSA-N 0.000 description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 4
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 108010009736 Protein Hydrolysates Proteins 0.000 description 4
- COYTVZAYDAIHDK-UHFFFAOYSA-N [5-(sulfanylmethyl)-1,4-dithian-2-yl]methanethiol Chemical compound SCC1CSC(CS)CS1 COYTVZAYDAIHDK-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 240000008415 Lactuca sativa Species 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229960001701 chloroform Drugs 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
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- 229920000592 inorganic polymer Polymers 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UWHMFGKZAYHMDJ-UHFFFAOYSA-N propane-1,2,3-trithiol Chemical compound SCC(S)CS UWHMFGKZAYHMDJ-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 235000012045 salad Nutrition 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920005573 silicon-containing polymer Polymers 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- QEMSHZOGUJXBQA-UHFFFAOYSA-N sulfanyl carbamate Chemical compound NC(=O)OS QEMSHZOGUJXBQA-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical class CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VOLGAXAGEUPBDM-UHFFFAOYSA-N $l^{1}-oxidanylethane Chemical compound CC[O] VOLGAXAGEUPBDM-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical class O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- GVEDOIATHPCYGS-UHFFFAOYSA-N 1-methyl-3-(3-methylphenyl)benzene Chemical group CC1=CC=CC(C=2C=C(C)C=CC=2)=C1 GVEDOIATHPCYGS-UHFFFAOYSA-N 0.000 description 2
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 2
- MTZVWTOVHGKLOX-UHFFFAOYSA-N 2,2-bis(sulfanylmethyl)propane-1,3-dithiol Chemical compound SCC(CS)(CS)CS MTZVWTOVHGKLOX-UHFFFAOYSA-N 0.000 description 2
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 2
- XBXGOYDZODCXGV-UHFFFAOYSA-N 2,5-bis(ethenylsulfanylmethyl)-1,4-dithiane Chemical compound C=CSCC1CSC(CSC=C)CS1 XBXGOYDZODCXGV-UHFFFAOYSA-N 0.000 description 2
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 2
- WFUMVIYEGASPLY-UHFFFAOYSA-N 2-[2,3,4-tris(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C(CCS)=C1CCS WFUMVIYEGASPLY-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920001747 Cellulose diacetate Polymers 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- 239000003490 Thiodipropionic acid Substances 0.000 description 2
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- BVEGHZVZLLPALO-UHFFFAOYSA-N [2,4,5-tris(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC(OCS)=C(OCS)C=C1OCS BVEGHZVZLLPALO-UHFFFAOYSA-N 0.000 description 2
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 description 2
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 229940007550 benzyl acetate Drugs 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- VRPKUXAKHIINGG-UHFFFAOYSA-N biphenyl-4,4'-dithiol Chemical group C1=CC(S)=CC=C1C1=CC=C(S)C=C1 VRPKUXAKHIINGG-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 description 2
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- XQKSSABWAPQELS-UHFFFAOYSA-N hexane-2,3,4-trithiol Chemical compound CCC(S)C(S)C(C)S XQKSSABWAPQELS-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 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
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- 229920002578 polythiourethane polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000131 polyvinylidene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 235000019303 thiodipropionic acid Nutrition 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- CAYNCHQZXZMUEX-UHFFFAOYSA-N (hydroxymethyldisulfanyl)methanol 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OCSSCO CAYNCHQZXZMUEX-UHFFFAOYSA-N 0.000 description 1
- BXGKVFOHNHSLHH-UHFFFAOYSA-N (hydroxymethyldisulfanyl)methanol 3-sulfanylpropanoic acid Chemical compound OCSSCO.OC(=O)CCS.OC(=O)CCS BXGKVFOHNHSLHH-UHFFFAOYSA-N 0.000 description 1
- RHMKQRWOFRAOHS-UHFFFAOYSA-N (sulfanylmethyldisulfanyl)methanethiol Chemical compound SCSSCS RHMKQRWOFRAOHS-UHFFFAOYSA-N 0.000 description 1
- GKOTWPKLOWTGAG-NRFIWDAESA-L (z)-4-butoxy-4-oxobut-2-enoate;dioctyltin(2+) Chemical compound CCCCOC(=O)\C=C/C(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)\C=C/C(=O)OCCCC GKOTWPKLOWTGAG-NRFIWDAESA-L 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- IIZCZUMIXHRLAO-UHFFFAOYSA-N 1,2,3,4,5,6,7,7a-octahydroindene-3a,4-diol Chemical compound OC1CCCC2CCCC12O IIZCZUMIXHRLAO-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- FQYVVSNFPLKMNU-UHFFFAOYSA-N 1,2-dipentylbenzene Chemical compound CCCCCC1=CC=CC=C1CCCCC FQYVVSNFPLKMNU-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical group C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 description 1
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- FEWPLEANLZQRRE-UHFFFAOYSA-N 1,3-bis(4-chlorophenyl)propane-2,2-dithiol Chemical compound C=1C=C(Cl)C=CC=1CC(S)(S)CC1=CC=C(Cl)C=C1 FEWPLEANLZQRRE-UHFFFAOYSA-N 0.000 description 1
- CNAIYFIVNYOUFM-UHFFFAOYSA-N 1,3-bis(4-methoxyphenyl)propane-2,2-dithiol Chemical compound C1=CC(OC)=CC=C1CC(S)(S)CC1=CC=C(OC)C=C1 CNAIYFIVNYOUFM-UHFFFAOYSA-N 0.000 description 1
- KADZDOLYFZTSSM-UHFFFAOYSA-N 1,3-diphenylpropane-2,2-dithiol Chemical compound C=1C=CC=CC=1CC(S)(S)CC1=CC=CC=C1 KADZDOLYFZTSSM-UHFFFAOYSA-N 0.000 description 1
- YUIOPHXTILULQC-UHFFFAOYSA-N 1,4-Dithiane-2,5-diol Chemical compound OC1CSC(O)CS1 YUIOPHXTILULQC-UHFFFAOYSA-N 0.000 description 1
- AGJCSCSSMFRMFQ-UHFFFAOYSA-N 1,4-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=C(C(C)(C)N=C=O)C=C1 AGJCSCSSMFRMFQ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- JFLJVRLBIZHFSU-UHFFFAOYSA-N 1,4-dithiane-2,5-dithiol Chemical compound SC1CSC(S)CS1 JFLJVRLBIZHFSU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- FTMOZBNCMQDACZ-UHFFFAOYSA-N 1-(2-sulfanylethylsulfanyl)propane-1,3-dithiol Chemical compound SCCSC(S)CCS FTMOZBNCMQDACZ-UHFFFAOYSA-N 0.000 description 1
- UCPKZMAFNLKQMX-UHFFFAOYSA-N 1-[4-[4-(2-hydroxypropyl)phenyl]sulfanylphenyl]propan-2-ol Chemical compound C1=CC(CC(O)C)=CC=C1SC1=CC=C(CC(C)O)C=C1 UCPKZMAFNLKQMX-UHFFFAOYSA-N 0.000 description 1
- SIYISNUJKMAQBV-UHFFFAOYSA-N 1-benzyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1CC1=CC=CC=C1 SIYISNUJKMAQBV-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- JEARXBADBBQFGS-UHFFFAOYSA-N 1-methoxypropane-1,2-dithiol Chemical compound COC(S)C(C)S JEARXBADBBQFGS-UHFFFAOYSA-N 0.000 description 1
- JWOTWWORMYMZCR-UHFFFAOYSA-N 1-methyl-4-[3-(1-methylpiperidin-4-yl)propyl]piperidine Chemical compound C1CN(C)CCC1CCCC1CCN(C)CC1 JWOTWWORMYMZCR-UHFFFAOYSA-N 0.000 description 1
- DLLOHKQWGFKFLO-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dithiol Chemical compound CC1(S)CCCCC1S DLLOHKQWGFKFLO-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
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- SGLYOTGYKDFSSC-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-dithiol Chemical compound SCC(C)(C)CS SGLYOTGYKDFSSC-UHFFFAOYSA-N 0.000 description 1
- IBLFBCCJUPHGNM-UHFFFAOYSA-N 2,3,5-tris(2-propylsulfanylthiiran-2-yl)-1,4-dithiane Chemical compound C1SC(C2(SC2)SCCC)C(C2(SC2)SCCC)SC1C1(SCCC)CS1 IBLFBCCJUPHGNM-UHFFFAOYSA-N 0.000 description 1
- FQZMBPXSKSSKCP-UHFFFAOYSA-N 2,3-bis(sulfanyl)propyl 2-sulfanylacetate Chemical compound SCC(S)COC(=O)CS FQZMBPXSKSSKCP-UHFFFAOYSA-N 0.000 description 1
- WXDDGAZCUPULGL-UHFFFAOYSA-N 2,3-bis(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSCC(SCS)CSCS WXDDGAZCUPULGL-UHFFFAOYSA-N 0.000 description 1
- PQSMEVPHTJECDZ-UHFFFAOYSA-N 2,3-dimethylheptan-2-ol Chemical compound CCCCC(C)C(C)(C)O PQSMEVPHTJECDZ-UHFFFAOYSA-N 0.000 description 1
- KFBXUKHERGLHLG-UHFFFAOYSA-N 2,4-Nonanedione Chemical compound CCCCCC(=O)CC(C)=O KFBXUKHERGLHLG-UHFFFAOYSA-N 0.000 description 1
- JSGLUMKISYZQHM-UHFFFAOYSA-N 2,4-dimethylbenzene-1,3-dithiol Chemical compound CC1=CC=C(S)C(C)=C1S JSGLUMKISYZQHM-UHFFFAOYSA-N 0.000 description 1
- LOIPCSUANZPEME-UHFFFAOYSA-N 2,5-bis(2-propylsulfanylthiiran-2-yl)-1,4-dithiane Chemical compound C1SC(C2(SC2)SCCC)CSC1C1(SCCC)CS1 LOIPCSUANZPEME-UHFFFAOYSA-N 0.000 description 1
- SDMYZIQYGCCLHR-UHFFFAOYSA-N 2,5-bis(thiiran-2-ylmethylsulfanylmethyl)-1,4-dithiane Chemical compound C1SC1CSCC(SC1)CSC1CSCC1CS1 SDMYZIQYGCCLHR-UHFFFAOYSA-N 0.000 description 1
- XAYMPCGHLKVJSR-UHFFFAOYSA-N 2,5-dichlorobenzene-1,3-dithiol Chemical compound SC1=CC(Cl)=CC(S)=C1Cl XAYMPCGHLKVJSR-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- ASUQXIDYMVXFKU-UHFFFAOYSA-N 2,6-dibromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC=C(Br)C=C3C2=C1 ASUQXIDYMVXFKU-UHFFFAOYSA-N 0.000 description 1
- BSNIAXQXVSMGGM-UHFFFAOYSA-N 2,6-diisocyanato-2-(isocyanatomethyl)hexanoic acid Chemical compound O=C=NCC(N=C=O)(C(=O)O)CCCCN=C=O BSNIAXQXVSMGGM-UHFFFAOYSA-N 0.000 description 1
- SXASCLUSQYBUFW-UHFFFAOYSA-N 2-(2-hydroxyethyldisulfanyl)ethanol 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OCCSSCCO SXASCLUSQYBUFW-UHFFFAOYSA-N 0.000 description 1
- YTAFNCWRRKIZAV-UHFFFAOYSA-N 2-(2-hydroxyethyldisulfanyl)ethanol 3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OCCSSCCO YTAFNCWRRKIZAV-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 1
- CQFQASKMKKPUKN-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.SCCOCCS CQFQASKMKKPUKN-UHFFFAOYSA-N 0.000 description 1
- SPAAESPYCDSRIW-UHFFFAOYSA-N 2-(2-sulfanylethyldisulfanyl)ethanethiol Chemical compound SCCSSCCS SPAAESPYCDSRIW-UHFFFAOYSA-N 0.000 description 1
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 1
- RDNOXVONDLWZCI-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanylmethylsulfanyl)ethanethiol Chemical compound SCCSCSCCS RDNOXVONDLWZCI-UHFFFAOYSA-N 0.000 description 1
- UXUPVPJMGKWUSY-UHFFFAOYSA-N 2-(2-sulfanylphenyl)benzenethiol Chemical group SC1=CC=CC=C1C1=CC=CC=C1S UXUPVPJMGKWUSY-UHFFFAOYSA-N 0.000 description 1
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 1
- UREAOTFLSRRYKQ-UHFFFAOYSA-N 2-(sulfanylmethylsulfanyl)ethylsulfanylmethanethiol Chemical compound SCSCCSCS UREAOTFLSRRYKQ-UHFFFAOYSA-N 0.000 description 1
- MLGITEWCALEOOJ-UHFFFAOYSA-N 2-(thiiran-2-ylmethylsulfanylmethyl)thiirane Chemical compound C1SC1CSCC1CS1 MLGITEWCALEOOJ-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- HQLKZWRSOHTERR-UHFFFAOYSA-N 2-Ethylbutyl acetate Chemical compound CCC(CC)COC(C)=O HQLKZWRSOHTERR-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- JRKRMWWBDZSDMT-UHFFFAOYSA-N 2-[(thiiran-2-ylmethyldisulfanyl)methyl]thiirane Chemical compound C1SC1CSSCC1CS1 JRKRMWWBDZSDMT-UHFFFAOYSA-N 0.000 description 1
- LOSJLAVLYJUGJO-UHFFFAOYSA-N 2-[1,3-bis(sulfanyl)propan-2-ylsulfanyl]propane-1,3-dithiol Chemical compound SCC(CS)SC(CS)CS LOSJLAVLYJUGJO-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- UOTFAJHUGJHBRQ-UHFFFAOYSA-N 2-[2,3,4-tris(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC=C(OCCS)C(OCCS)=C1OCCS UOTFAJHUGJHBRQ-UHFFFAOYSA-N 0.000 description 1
- XEJHIBKTILPFOC-UHFFFAOYSA-N 2-[2,3,4-tris(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC=C(SCCS)C(SCCS)=C1SCCS XEJHIBKTILPFOC-UHFFFAOYSA-N 0.000 description 1
- OWCOEDUEVBPSCD-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC=CC(OCCS)=C1OCCS OWCOEDUEVBPSCD-UHFFFAOYSA-N 0.000 description 1
- YZIGUJRGKPNSGI-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC(CCS)=C1CCS YZIGUJRGKPNSGI-UHFFFAOYSA-N 0.000 description 1
- PDCMFMLWJBVBEU-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC=CC(SCCS)=C1SCCS PDCMFMLWJBVBEU-UHFFFAOYSA-N 0.000 description 1
- QTEWPHJCEXIMRJ-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethylsulfanyl)propylsulfanyl]ethanethiol Chemical compound SCCSCC(SCCS)CSCCS QTEWPHJCEXIMRJ-UHFFFAOYSA-N 0.000 description 1
- XOKSBUBDHKRDFH-UHFFFAOYSA-N 2-[2,4,5-tris(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC(OCCS)=C(OCCS)C=C1OCCS XOKSBUBDHKRDFH-UHFFFAOYSA-N 0.000 description 1
- XZJYDCHXNLYCTQ-UHFFFAOYSA-N 2-[2,4,5-tris(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC(CCS)=C(CCS)C=C1CCS XZJYDCHXNLYCTQ-UHFFFAOYSA-N 0.000 description 1
- MQXLJJBFWICMDS-UHFFFAOYSA-N 2-[2,4,5-tris(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC(SCCS)=C(SCCS)C=C1SCCS MQXLJJBFWICMDS-UHFFFAOYSA-N 0.000 description 1
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSCCSCCO PDHFSBXFZGYBIP-UHFFFAOYSA-N 0.000 description 1
- ISGHUYCZFWLBRU-UHFFFAOYSA-N 2-[2-(2-sulfanylacetyl)oxyethoxy]ethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOCCOC(=O)CS ISGHUYCZFWLBRU-UHFFFAOYSA-N 0.000 description 1
- FMVREPWYVKYHLI-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC=CC=C1OCCS FMVREPWYVKYHLI-UHFFFAOYSA-N 0.000 description 1
- VGBJHKFWZDRMTA-UHFFFAOYSA-N 2-[2-(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC=CC=C1SCCS VGBJHKFWZDRMTA-UHFFFAOYSA-N 0.000 description 1
- ZQLHFUHXRDOCBC-UHFFFAOYSA-N 2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOC(=O)CCS ZQLHFUHXRDOCBC-UHFFFAOYSA-N 0.000 description 1
- OWDBMKZHFCSOOL-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)propoxy]propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(C)COC(C)COC(=O)C(C)=C OWDBMKZHFCSOOL-UHFFFAOYSA-N 0.000 description 1
- DAUUORKACOSESW-UHFFFAOYSA-N 2-[2-[2-(2-sulfanylethylsulfanyl)ethylsulfanyl]ethylsulfanylmethyl]propane-1,2,3-trithiol Chemical compound SCCSCCSCCSCC(S)(CS)CS DAUUORKACOSESW-UHFFFAOYSA-N 0.000 description 1
- DJWGOAOVAKSMIM-UHFFFAOYSA-N 2-[2-[3-[2-(2-hydroxyethylsulfanyl)ethyl]cyclohexyl]ethylsulfanyl]ethanol Chemical compound OCCSCCC1CCCC(CCSCCO)C1 DJWGOAOVAKSMIM-UHFFFAOYSA-N 0.000 description 1
- TYEMOQIIIIFBRK-UHFFFAOYSA-N 2-[3,4,5-tris(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC(OCCS)=C(OCCS)C(OCCS)=C1 TYEMOQIIIIFBRK-UHFFFAOYSA-N 0.000 description 1
- ZVWSJLHJHVTNCA-UHFFFAOYSA-N 2-[3,4,5-tris(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC(CCS)=C(CCS)C(CCS)=C1 ZVWSJLHJHVTNCA-UHFFFAOYSA-N 0.000 description 1
- NPDVUVDYLRPCGZ-UHFFFAOYSA-N 2-[3,4,5-tris(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC(SCCS)=C(SCCS)C(SCCS)=C1 NPDVUVDYLRPCGZ-UHFFFAOYSA-N 0.000 description 1
- IIJYNFRFRXIXDH-UHFFFAOYSA-N 2-[3,4-bis(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC=C(OCCS)C(OCCS)=C1 IIJYNFRFRXIXDH-UHFFFAOYSA-N 0.000 description 1
- YIMJMXYFLBUNMH-UHFFFAOYSA-N 2-[3,4-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C(CCS)=C1 YIMJMXYFLBUNMH-UHFFFAOYSA-N 0.000 description 1
- YTCKYPYEGSOARL-UHFFFAOYSA-N 2-[3,4-bis(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC=C(SCCS)C(SCCS)=C1 YTCKYPYEGSOARL-UHFFFAOYSA-N 0.000 description 1
- IVBVCTKAJMRGCW-UHFFFAOYSA-N 2-[3,5-bis(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC(OCCS)=CC(OCCS)=C1 IVBVCTKAJMRGCW-UHFFFAOYSA-N 0.000 description 1
- GFSULDUIAFNGRB-UHFFFAOYSA-N 2-[3,5-bis(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC(CCS)=CC(CCS)=C1 GFSULDUIAFNGRB-UHFFFAOYSA-N 0.000 description 1
- ADZZATFHQPCLIF-UHFFFAOYSA-N 2-[3,5-bis(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC(SCCS)=CC(SCCS)=C1 ADZZATFHQPCLIF-UHFFFAOYSA-N 0.000 description 1
- UJAZZISPSGMELP-UHFFFAOYSA-N 2-[3-(2-hydroxyethylsulfanyl)-2,2-bis(2-hydroxyethylsulfanylmethyl)propyl]sulfanylethanol Chemical compound OCCSCC(CSCCO)(CSCCO)CSCCO UJAZZISPSGMELP-UHFFFAOYSA-N 0.000 description 1
- UJDBWJBZEDFEIT-UHFFFAOYSA-N 2-[3-(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC=CC(OCCS)=C1 UJDBWJBZEDFEIT-UHFFFAOYSA-N 0.000 description 1
- RKPZXQVJXKNNSB-UHFFFAOYSA-N 2-[3-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=CC(CCS)=C1 RKPZXQVJXKNNSB-UHFFFAOYSA-N 0.000 description 1
- KIVDBXVDNQFFFL-UHFFFAOYSA-N 2-[3-(2-sulfanylethylsulfanyl)-2,2-bis(2-sulfanylethylsulfanylmethyl)propyl]sulfanylethanethiol Chemical compound SCCSCC(CSCCS)(CSCCS)CSCCS KIVDBXVDNQFFFL-UHFFFAOYSA-N 0.000 description 1
- QCWOAMPYKLZILW-UHFFFAOYSA-N 2-[3-(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC=CC(SCCS)=C1 QCWOAMPYKLZILW-UHFFFAOYSA-N 0.000 description 1
- XYHKMRNYSMEEDT-UHFFFAOYSA-N 2-[3-(2-sulfanylethylsulfanyl)propylsulfanyl]ethanethiol Chemical compound SCCSCCCSCCS XYHKMRNYSMEEDT-UHFFFAOYSA-N 0.000 description 1
- BBVKYTNZGMHXIM-UHFFFAOYSA-N 2-[3-butyl-4-[2-butyl-4-(2-hydroxyethoxy)-6-methylphenyl]sulfanyl-5-methylphenoxy]ethanol Chemical compound CCCCC1=CC(OCCO)=CC(C)=C1SC1=C(C)C=C(OCCO)C=C1CCCC BBVKYTNZGMHXIM-UHFFFAOYSA-N 0.000 description 1
- HMAAFPUFWDBSRM-UHFFFAOYSA-N 2-[4-(2-sulfanylethoxy)phenoxy]ethanethiol Chemical compound SCCOC1=CC=C(OCCS)C=C1 HMAAFPUFWDBSRM-UHFFFAOYSA-N 0.000 description 1
- PESHQGQMMIRLMA-UHFFFAOYSA-N 2-[4-(2-sulfanylethyl)phenyl]ethanethiol Chemical compound SCCC1=CC=C(CCS)C=C1 PESHQGQMMIRLMA-UHFFFAOYSA-N 0.000 description 1
- HHCBYYSVNKHLSP-UHFFFAOYSA-N 2-[4-(2-sulfanylethylsulfanyl)phenyl]sulfanylethanethiol Chemical compound SCCSC1=CC=C(SCCS)C=C1 HHCBYYSVNKHLSP-UHFFFAOYSA-N 0.000 description 1
- DOHVUQIYUWSVFX-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]sulfanylphenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1SC1=CC=C(OCCO)C=C1 DOHVUQIYUWSVFX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- WQKFQBSUWRZIAR-UHFFFAOYSA-N 2-[[4-(thiiran-2-ylmethylsulfanylmethyl)cyclohexyl]methylsulfanylmethyl]thiirane Chemical compound C1SC1CSCC(CC1)CCC1CSCC1CS1 WQKFQBSUWRZIAR-UHFFFAOYSA-N 0.000 description 1
- XBWJJGBWRQIKJF-UHFFFAOYSA-N 2-butylcyclohexane-1,1-diol Chemical compound CCCCC1CCCCC1(O)O XBWJJGBWRQIKJF-UHFFFAOYSA-N 0.000 description 1
- IKBFHCBHLOZDKH-UHFFFAOYSA-N 2-chloroethyl(triethoxy)silane Chemical compound CCO[Si](CCCl)(OCC)OCC IKBFHCBHLOZDKH-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 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
- HSSLFJICBPDMPH-UHFFFAOYSA-N 2-isocyanatopropyl 2-methylprop-2-enoate Chemical compound O=C=NC(C)COC(=O)C(C)=C HSSLFJICBPDMPH-UHFFFAOYSA-N 0.000 description 1
- RGDAQLOWLCIMDP-UHFFFAOYSA-N 2-isocyanatopropyl prop-2-enoate Chemical compound O=C=NC(C)COC(=O)C=C RGDAQLOWLCIMDP-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- QNQBPLJBKMDKLK-UHFFFAOYSA-N 2-methylbenzene-1,4-dithiol Chemical compound CC1=CC(S)=CC=C1S QNQBPLJBKMDKLK-UHFFFAOYSA-N 0.000 description 1
- VFHSKESCTSJKNX-UHFFFAOYSA-N 2-methylprop-2-enoic acid prop-1-ene Chemical compound C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C=CC.C=CC.C=CC VFHSKESCTSJKNX-UHFFFAOYSA-N 0.000 description 1
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OEHCVHLWJWZUGM-UHFFFAOYSA-N 2-sulfanylacetic acid;2-(2-sulfanylethoxy)ethanethiol Chemical compound OC(=O)CS.OC(=O)CS.SCCOCCS OEHCVHLWJWZUGM-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- MBTDKTRAPFVPLW-UHFFFAOYSA-N 3,4,5-tribromobenzene-1,2-dithiol Chemical compound SC1=CC(Br)=C(Br)C(Br)=C1S MBTDKTRAPFVPLW-UHFFFAOYSA-N 0.000 description 1
- KOCAIQHVJFBWHC-UHFFFAOYSA-N 3,4-dimethoxybutane-1,2-dithiol Chemical compound COCC(OC)C(S)CS KOCAIQHVJFBWHC-UHFFFAOYSA-N 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 1
- XRFOUBAXHDEFBG-UHFFFAOYSA-N 3-(2,3-dihydroxypropylsulfanyl)propane-1,2-diol Chemical compound OCC(O)CSCC(O)CO XRFOUBAXHDEFBG-UHFFFAOYSA-N 0.000 description 1
- AHHJYDXYFRLFQC-UHFFFAOYSA-N 3-(3-hydroxypropylsulfanyl)propan-1-ol 3-sulfanylpropanoic acid Chemical compound SCCC(=O)O.SCCC(=O)O.OCCCSCCCO AHHJYDXYFRLFQC-UHFFFAOYSA-N 0.000 description 1
- KTJKAUMRBSAQLR-UHFFFAOYSA-N 3-(3-sulfanylpropyldisulfanyl)propane-1-thiol Chemical compound SCCCSSCCCS KTJKAUMRBSAQLR-UHFFFAOYSA-N 0.000 description 1
- GZWIBBZCQMNKPK-UHFFFAOYSA-N 3-(3-sulfanylpropylsulfanyl)propane-1-thiol Chemical compound SCCCSCCCS GZWIBBZCQMNKPK-UHFFFAOYSA-N 0.000 description 1
- XBNYMYZLSBMANG-UHFFFAOYSA-N 3-(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSCCCSCS XBNYMYZLSBMANG-UHFFFAOYSA-N 0.000 description 1
- DUYICINCNBSZMH-UHFFFAOYSA-N 3-[2,3-bis(3-sulfanylpropylsulfanyl)propylsulfanyl]propane-1-thiol Chemical compound SCCCSCC(SCCCS)CSCCCS DUYICINCNBSZMH-UHFFFAOYSA-N 0.000 description 1
- SQTMWMRJFVGAOW-UHFFFAOYSA-N 3-[2,3-bis(sulfanyl)propylsulfanyl]propane-1,2-dithiol Chemical compound SCC(S)CSCC(S)CS SQTMWMRJFVGAOW-UHFFFAOYSA-N 0.000 description 1
- KLGUKVGNYAOWNX-UHFFFAOYSA-N 3-[3-(3-sulfanylpropylsulfanyl)-2,2-bis(3-sulfanylpropylsulfanylmethyl)propyl]sulfanylpropane-1-thiol Chemical compound SCCCSCC(CSCCCS)(CSCCCS)CSCCCS KLGUKVGNYAOWNX-UHFFFAOYSA-N 0.000 description 1
- WNCVPVXTNBBVHH-UHFFFAOYSA-N 3-[3-(3-sulfanylpropylsulfanyl)propylsulfanyl]propane-1-thiol Chemical compound SCCCSCCCSCCCS WNCVPVXTNBBVHH-UHFFFAOYSA-N 0.000 description 1
- BEUBMKJBZXNCAX-UHFFFAOYSA-N 3-[4-[4-(2,3-dihydroxypropoxy)phenyl]sulfanylphenoxy]propane-1,2-diol Chemical compound C1=CC(OCC(O)CO)=CC=C1SC1=CC=C(OCC(O)CO)C=C1 BEUBMKJBZXNCAX-UHFFFAOYSA-N 0.000 description 1
- UUNGBOQAZQUJMZ-UHFFFAOYSA-N 3-bromopropyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CCCBr UUNGBOQAZQUJMZ-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- QDNHFLDYNJTWKV-UHFFFAOYSA-N 3-methoxypropane-1,2-dithiol Chemical compound COCC(S)CS QDNHFLDYNJTWKV-UHFFFAOYSA-N 0.000 description 1
- LEPRPXBFZRAOGU-UHFFFAOYSA-N 3-trichlorosilylpropyl prop-2-enoate Chemical compound Cl[Si](Cl)(Cl)CCCOC(=O)C=C LEPRPXBFZRAOGU-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- YYSCJLLOWOUSHH-UHFFFAOYSA-N 4,4'-disulfanyldibutanoic acid Chemical compound OC(=O)CCCSSCCCC(O)=O YYSCJLLOWOUSHH-UHFFFAOYSA-N 0.000 description 1
- IMBFPOUWDJSNDI-UHFFFAOYSA-N 4,5-dimethylbenzene-1,3-dithiol Chemical compound CC1=CC(S)=CC(S)=C1C IMBFPOUWDJSNDI-UHFFFAOYSA-N 0.000 description 1
- XSZJHTYADIERFI-UHFFFAOYSA-N 4-(3-carboxypropylsulfanyl)butanoic acid Chemical compound OC(=O)CCCSCCCC(O)=O XSZJHTYADIERFI-UHFFFAOYSA-N 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
- FOWDDWLRTIXWET-UHFFFAOYSA-N 4-[4-(4-sulfanylphenyl)pentan-2-yl]benzenethiol Chemical compound C=1C=C(S)C=CC=1C(C)CC(C)C1=CC=C(S)C=C1 FOWDDWLRTIXWET-UHFFFAOYSA-N 0.000 description 1
- LDPJDNSWVHZDPD-UHFFFAOYSA-N 4-[4-[4-(4-hydroxycyclohexyl)oxyphenyl]sulfanylphenoxy]cyclohexan-1-ol Chemical compound C1CC(O)CCC1OC(C=C1)=CC=C1SC(C=C1)=CC=C1OC1CCC(O)CC1 LDPJDNSWVHZDPD-UHFFFAOYSA-N 0.000 description 1
- NIAAGQAEVGMHPM-UHFFFAOYSA-N 4-methylbenzene-1,2-dithiol Chemical compound CC1=CC=C(S)C(S)=C1 NIAAGQAEVGMHPM-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 description 1
- PQCLJXVUAWLNSV-UHFFFAOYSA-N 5-Methyl-2,3-hexanedione Chemical compound CC(C)CC(=O)C(C)=O PQCLJXVUAWLNSV-UHFFFAOYSA-N 0.000 description 1
- HLRRSFOQAFMOTJ-UHFFFAOYSA-L 6-methylheptyl 2-[[2-(6-methylheptoxy)-2-oxoethyl]sulfanyl-dioctylstannyl]sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](CCCCCCCC)(CCCCCCCC)SCC(=O)OCCCCCC(C)C HLRRSFOQAFMOTJ-UHFFFAOYSA-L 0.000 description 1
- VNPRJHMMOKDEDZ-UHFFFAOYSA-L 6-methylheptyl 2-[dibutyl-[2-(6-methylheptoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCCCCCC(C)C VNPRJHMMOKDEDZ-UHFFFAOYSA-L 0.000 description 1
- DMNALYQQZDWQQL-UHFFFAOYSA-N 8-bromooctyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CCCCCCCCBr DMNALYQQZDWQQL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- 229910000897 Babbitt (metal) Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- XWUNIDGEMNBBAQ-UHFFFAOYSA-N Bisphenol A ethoxylate diacrylate Chemical compound C=1C=C(OCCOC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCCOC(=O)C=C)C=C1 XWUNIDGEMNBBAQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- REIYHFWZISXFKU-UHFFFAOYSA-N Butyl acetoacetate Chemical compound CCCCOC(=O)CC(C)=O REIYHFWZISXFKU-UHFFFAOYSA-N 0.000 description 1
- MKEWYGIHZQYQAH-UHFFFAOYSA-N C1=CC(NCC)(NCC)CC=C1C(=O)C1=CC=CC=C1 Chemical compound C1=CC(NCC)(NCC)CC=C1C(=O)C1=CC=CC=C1 MKEWYGIHZQYQAH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000089742 Citrus aurantifolia Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 101000618467 Hypocrea jecorina (strain ATCC 56765 / BCRC 32924 / NRRL 11460 / Rut C-30) Endo-1,4-beta-xylanase 2 Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- PWGOWIIEVDAYTC-UHFFFAOYSA-N ICR-170 Chemical compound Cl.Cl.C1=C(OC)C=C2C(NCCCN(CCCl)CC)=C(C=CC(Cl)=C3)C3=NC2=C1 PWGOWIIEVDAYTC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- SWTBZQOYIMBDQQ-UHFFFAOYSA-N OCSCO.OC(=O)CCS.OC(=O)CCS Chemical compound OCSCO.OC(=O)CCS.OC(=O)CCS SWTBZQOYIMBDQQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000011402 Portland pozzolan cement Substances 0.000 description 1
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 1
- OHPMECDFYMJRGR-UHFFFAOYSA-N SCC(=O)O.SCC(=O)O.OCCCSCCCO Chemical compound SCC(=O)O.SCC(=O)O.OCCCSCCCO OHPMECDFYMJRGR-UHFFFAOYSA-N 0.000 description 1
- MKZWJDSFUIZNMG-UHFFFAOYSA-N SCC(=O)O.SCC(=O)O.OCCCSSCCCO Chemical compound SCC(=O)O.SCC(=O)O.OCCCSSCCCO MKZWJDSFUIZNMG-UHFFFAOYSA-N 0.000 description 1
- OKFFYKLCPLSDRT-UHFFFAOYSA-N SCC(=O)O.SCC(=O)O.OCSCO Chemical compound SCC(=O)O.SCC(=O)O.OCSCO OKFFYKLCPLSDRT-UHFFFAOYSA-N 0.000 description 1
- PGILEVNTXKHSHZ-UHFFFAOYSA-N SCC(=O)O.SCC(=O)O.S(CCO)CCO Chemical compound SCC(=O)O.SCC(=O)O.S(CCO)CCO PGILEVNTXKHSHZ-UHFFFAOYSA-N 0.000 description 1
- GNTSCFPBDDEJHN-UHFFFAOYSA-N SCCC(=O)O.SCCC(=O)O.OCCCSSCCCO Chemical compound SCCC(=O)O.SCCC(=O)O.OCCCSSCCCO GNTSCFPBDDEJHN-UHFFFAOYSA-N 0.000 description 1
- GPQRYTGFZCBZCD-UHFFFAOYSA-N SCCC(=O)O.SCCC(=O)O.OCCSCCO Chemical compound SCCC(=O)O.SCCC(=O)O.OCCSCCO GPQRYTGFZCBZCD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HRSPMOZFFLQNSB-UHFFFAOYSA-N [1-(sulfanylmethyl)cyclohexyl]methanethiol Chemical compound SCC1(CS)CCCCC1 HRSPMOZFFLQNSB-UHFFFAOYSA-N 0.000 description 1
- QULSCWWJJFURRB-UHFFFAOYSA-N [10-(sulfanylmethyl)anthracen-9-yl]methanethiol Chemical compound C1=CC=C2C(CS)=C(C=CC=C3)C3=C(CS)C2=C1 QULSCWWJJFURRB-UHFFFAOYSA-N 0.000 description 1
- AACBJMZVNKWMJC-UHFFFAOYSA-N [2,3,4,6-tetrachloro-5-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=C(Cl)C(Cl)=C(Cl)C(CS)=C1Cl AACBJMZVNKWMJC-UHFFFAOYSA-N 0.000 description 1
- FNTKCWQKAGGZFV-UHFFFAOYSA-N [2,3,4-tris(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C(CS)=C1CS FNTKCWQKAGGZFV-UHFFFAOYSA-N 0.000 description 1
- QSIWGSSZKVQLCZ-UHFFFAOYSA-N [2,3,4-tris(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC=C(SCS)C(SCS)=C1SCS QSIWGSSZKVQLCZ-UHFFFAOYSA-N 0.000 description 1
- BEGORJBMBCDRPF-UHFFFAOYSA-N [2,3-bis(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC=CC(OCS)=C1OCS BEGORJBMBCDRPF-UHFFFAOYSA-N 0.000 description 1
- SDEFSQDZLUZWPW-UHFFFAOYSA-N [2,3-bis(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1CS SDEFSQDZLUZWPW-UHFFFAOYSA-N 0.000 description 1
- IQQCGSKMZYRXLC-UHFFFAOYSA-N [2,3-bis(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC=CC(SCS)=C1SCS IQQCGSKMZYRXLC-UHFFFAOYSA-N 0.000 description 1
- LJODQQVXMSKBHT-UHFFFAOYSA-N [2,4,5-tris(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC(CS)=C(CS)C=C1CS LJODQQVXMSKBHT-UHFFFAOYSA-N 0.000 description 1
- KLYZZKTYGAGJEC-UHFFFAOYSA-N [2,4,5-tris(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC(SCS)=C(SCS)C=C1SCS KLYZZKTYGAGJEC-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- SUZMMPZZULWHPD-UHFFFAOYSA-N [2-(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC=CC=C1OCS SUZMMPZZULWHPD-UHFFFAOYSA-N 0.000 description 1
- NNJWFWSBENPGEY-UHFFFAOYSA-N [2-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC=C1CS NNJWFWSBENPGEY-UHFFFAOYSA-N 0.000 description 1
- YADAPEFZBBZQGC-UHFFFAOYSA-N [2-(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC=CC=C1SCS YADAPEFZBBZQGC-UHFFFAOYSA-N 0.000 description 1
- BDVSVFDFAXCPQO-UHFFFAOYSA-N [3,4,5-tris(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC(OCS)=C(OCS)C(OCS)=C1 BDVSVFDFAXCPQO-UHFFFAOYSA-N 0.000 description 1
- WNXBCBXBGDOZCK-UHFFFAOYSA-N [3,4,5-tris(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC(CS)=C(CS)C(CS)=C1 WNXBCBXBGDOZCK-UHFFFAOYSA-N 0.000 description 1
- VCQMOCQYLBOOQB-UHFFFAOYSA-N [3,4,5-tris(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC(SCS)=C(SCS)C(SCS)=C1 VCQMOCQYLBOOQB-UHFFFAOYSA-N 0.000 description 1
- DSXMIKGNMNOMLL-UHFFFAOYSA-N [3,4-bis(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC=C(OCS)C(OCS)=C1 DSXMIKGNMNOMLL-UHFFFAOYSA-N 0.000 description 1
- OWDDXHQZWJBGMZ-UHFFFAOYSA-N [3,4-bis(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C(CS)=C1 OWDDXHQZWJBGMZ-UHFFFAOYSA-N 0.000 description 1
- OUSRZWDNEXRNIT-UHFFFAOYSA-N [3,4-bis(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC=C(SCS)C(SCS)=C1 OUSRZWDNEXRNIT-UHFFFAOYSA-N 0.000 description 1
- CYVANFZTHHKUSB-UHFFFAOYSA-N [3,5-bis(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC(OCS)=CC(OCS)=C1 CYVANFZTHHKUSB-UHFFFAOYSA-N 0.000 description 1
- STWRQBYJSPXXQE-UHFFFAOYSA-N [3,5-bis(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC(CS)=CC(CS)=C1 STWRQBYJSPXXQE-UHFFFAOYSA-N 0.000 description 1
- IPDLFYXRQIZSAD-UHFFFAOYSA-N [3,5-bis(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC(SCS)=CC(SCS)=C1 IPDLFYXRQIZSAD-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- WWYGZBJGLPHDOT-UHFFFAOYSA-N [3-(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC=CC(OCS)=C1 WWYGZBJGLPHDOT-UHFFFAOYSA-N 0.000 description 1
- JSNABGZJVWSNOB-UHFFFAOYSA-N [3-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC(CS)=C1 JSNABGZJVWSNOB-UHFFFAOYSA-N 0.000 description 1
- VLDJWLWRDVWISM-UHFFFAOYSA-N [3-(sulfanylmethylsulfanyl)-2,2-bis(sulfanylmethylsulfanylmethyl)propyl]sulfanylmethanethiol Chemical compound SCSCC(CSCS)(CSCS)CSCS VLDJWLWRDVWISM-UHFFFAOYSA-N 0.000 description 1
- WSAPARODZGDJER-UHFFFAOYSA-N [3-(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC=CC(SCS)=C1 WSAPARODZGDJER-UHFFFAOYSA-N 0.000 description 1
- LVXYTKROCGJRNI-UHFFFAOYSA-N [4-(sulfanylmethoxy)phenoxy]methanethiol Chemical compound SCOC1=CC=C(OCS)C=C1 LVXYTKROCGJRNI-UHFFFAOYSA-N 0.000 description 1
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 description 1
- VGNFJJWLWFCHMR-UHFFFAOYSA-N [4-(sulfanylmethylsulfanyl)phenyl]sulfanylmethanethiol Chemical compound SCSC1=CC=C(SCS)C=C1 VGNFJJWLWFCHMR-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- HSTSCEGCSUFZCR-UHFFFAOYSA-N [5-(2-sulfanylacetyl)oxy-1,4-dithian-2-yl] 2-sulfanylacetate Chemical compound SCC(=O)OC1CSC(OC(=O)CS)CS1 HSTSCEGCSUFZCR-UHFFFAOYSA-N 0.000 description 1
- OROQMQGETVAGJZ-UHFFFAOYSA-N [5-(3-sulfanylpropanoyloxy)-1,4-dithian-2-yl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OC1CSC(OC(=O)CCS)CS1 OROQMQGETVAGJZ-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- HITZGLBEZMKWBW-UHFFFAOYSA-N ac1n8rtr Chemical group C1CC2OC2CC1CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 HITZGLBEZMKWBW-UHFFFAOYSA-N 0.000 description 1
- SWTCCCJQNPGXLQ-UHFFFAOYSA-N acetaldehyde di-n-butyl acetal Natural products CCCCOC(C)OCCCC SWTCCCJQNPGXLQ-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 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
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZQDJUKZNWBUSNT-UHFFFAOYSA-N benzene-1,2,3,4-tetrathiol Chemical compound SC1=CC=C(S)C(S)=C1S ZQDJUKZNWBUSNT-UHFFFAOYSA-N 0.000 description 1
- KHJIHSHHUDGOPQ-UHFFFAOYSA-N benzene-1,2,3,5-tetrathiol Chemical compound SC1=CC(S)=C(S)C(S)=C1 KHJIHSHHUDGOPQ-UHFFFAOYSA-N 0.000 description 1
- PPQNMKIMOCEJIR-UHFFFAOYSA-N benzene-1,2,3-trithiol Chemical compound SC1=CC=CC(S)=C1S PPQNMKIMOCEJIR-UHFFFAOYSA-N 0.000 description 1
- KVPDTCNNKWOGMZ-UHFFFAOYSA-N benzene-1,2,4,5-tetrathiol Chemical compound SC1=CC(S)=C(S)C=C1S KVPDTCNNKWOGMZ-UHFFFAOYSA-N 0.000 description 1
- UKLXGHUHPLLTKD-UHFFFAOYSA-N benzene-1,2,4-trithiol Chemical compound SC1=CC=C(S)C(S)=C1 UKLXGHUHPLLTKD-UHFFFAOYSA-N 0.000 description 1
- KXCKKUIJCYNZAE-UHFFFAOYSA-N benzene-1,3,5-trithiol Chemical compound SC1=CC(S)=CC(S)=C1 KXCKKUIJCYNZAE-UHFFFAOYSA-N 0.000 description 1
- ZWOASCVFHSYHOB-UHFFFAOYSA-N benzene-1,3-dithiol Chemical compound SC1=CC=CC(S)=C1 ZWOASCVFHSYHOB-UHFFFAOYSA-N 0.000 description 1
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- QSTNBMLCULGCQE-UHFFFAOYSA-N butan-2-yl 3-oxobutanoate Chemical compound CCC(C)OC(=O)CC(C)=O QSTNBMLCULGCQE-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- LPCFGSYLBKGRTH-UHFFFAOYSA-N butane-1,2,3,4-tetrathiol Chemical compound SCC(S)C(S)CS LPCFGSYLBKGRTH-UHFFFAOYSA-N 0.000 description 1
- MGZLGROFYWKSCQ-UHFFFAOYSA-N butane-1,2,3-trithiol Chemical compound CC(S)C(S)CS MGZLGROFYWKSCQ-UHFFFAOYSA-N 0.000 description 1
- QXTVJKYCVXUFLD-UHFFFAOYSA-N butane-1,2,4-trithiol Chemical compound SCCC(S)CS QXTVJKYCVXUFLD-UHFFFAOYSA-N 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
- 238000001818 capillary gel electrophoresis Methods 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- NBBUYPNTAABDEY-UHFFFAOYSA-N cyclobutane-1,1-diol Chemical compound OC1(O)CCC1 NBBUYPNTAABDEY-UHFFFAOYSA-N 0.000 description 1
- CYZQPSLPZSTBHD-UHFFFAOYSA-N cycloheptane-1,1-diol Chemical compound OC1(O)CCCCCC1 CYZQPSLPZSTBHD-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- VSARMWHOISBCGR-UHFFFAOYSA-N cyclohexane-1,1-dithiol Chemical compound SC1(S)CCCCC1 VSARMWHOISBCGR-UHFFFAOYSA-N 0.000 description 1
- YKRCKUBKOIVILO-UHFFFAOYSA-N cyclohexane-1,2-dithiol Chemical compound SC1CCCCC1S YKRCKUBKOIVILO-UHFFFAOYSA-N 0.000 description 1
- SUGGJLOBTAREMB-UHFFFAOYSA-N cyclooctane-1,1-diol Chemical compound OC1(O)CCCCCCC1 SUGGJLOBTAREMB-UHFFFAOYSA-N 0.000 description 1
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- SPEMLMZNIAQIBU-WSYPVFPHSA-L dibutyltin(2+);(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCC[Sn+2]CCCC.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O SPEMLMZNIAQIBU-WSYPVFPHSA-L 0.000 description 1
- FFGHLLOLFQHABK-UHFFFAOYSA-L dibutyltin(2+);dodecane-1-thiolate Chemical compound CCCCCCCCCCCCS[Sn](CCCC)(CCCC)SCCCCCCCCCCCC FFGHLLOLFQHABK-UHFFFAOYSA-L 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- OHABWQNEJUUFAV-UHFFFAOYSA-N dichloro-methyl-(3,3,3-trifluoropropyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)F OHABWQNEJUUFAV-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- VRMCXMQBPZVTQZ-WSYPVFPHSA-L didodecyltin(2+);(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCCCCCCCC[Sn+2]CCCCCCCCCCCC VRMCXMQBPZVTQZ-WSYPVFPHSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- IRFPIPNMASANJY-UHFFFAOYSA-L dimethyltin(2+);2-(6-methylheptoxy)-2-oxoethanethiolate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](C)(C)SCC(=O)OCCCCCC(C)C IRFPIPNMASANJY-UHFFFAOYSA-L 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- SNZAWIWMBQMVSB-BGSQTJHASA-L dioctyltin(2+);(z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCC\C=C/CCCCCCCC SNZAWIWMBQMVSB-BGSQTJHASA-L 0.000 description 1
- BJEVDDTWPUPCPC-WSYPVFPHSA-L dioctyltin(2+);(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC BJEVDDTWPUPCPC-WSYPVFPHSA-L 0.000 description 1
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical compound CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- IBENSVMKFVWLLF-UHFFFAOYSA-N germanium(4+) methanolate Chemical compound [Ge+4].[O-]C.[O-]C.[O-]C.[O-]C IBENSVMKFVWLLF-UHFFFAOYSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- RVVRZLSZZKMJCB-UHFFFAOYSA-N heptane-1,7-dithiol Chemical compound SCCCCCCCS RVVRZLSZZKMJCB-UHFFFAOYSA-N 0.000 description 1
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- OJORSYDWSPGRPT-UHFFFAOYSA-N hexane-1,2,3,4,5-pentathiol Chemical compound CC(S)C(S)C(S)C(S)CS OJORSYDWSPGRPT-UHFFFAOYSA-N 0.000 description 1
- VLPFJMRGIZCCEE-UHFFFAOYSA-N hexane-1,2,3,4-tetrathiol Chemical compound CCC(S)C(S)C(S)CS VLPFJMRGIZCCEE-UHFFFAOYSA-N 0.000 description 1
- SSPIYBJUZFSEMQ-UHFFFAOYSA-N hexane-1,2,3,5-tetrathiol Chemical compound CC(S)CC(S)C(S)CS SSPIYBJUZFSEMQ-UHFFFAOYSA-N 0.000 description 1
- FESFKRHUSGUKKK-UHFFFAOYSA-N hexane-1,2,3-trithiol Chemical compound CCCC(S)C(S)CS FESFKRHUSGUKKK-UHFFFAOYSA-N 0.000 description 1
- CJXWXCHUCIRFKK-UHFFFAOYSA-N hexane-1,2,4,5-tetrathiol Chemical compound CC(S)C(S)CC(S)CS CJXWXCHUCIRFKK-UHFFFAOYSA-N 0.000 description 1
- OHQWPNAORARUOH-UHFFFAOYSA-N hexane-1,2,4-trithiol Chemical compound CCC(S)CC(S)CS OHQWPNAORARUOH-UHFFFAOYSA-N 0.000 description 1
- WGNKHRXGNSVINE-UHFFFAOYSA-N hexane-1,2,5-trithiol Chemical compound CC(S)CCC(S)CS WGNKHRXGNSVINE-UHFFFAOYSA-N 0.000 description 1
- ARJVHELJIBYSAM-UHFFFAOYSA-N hexane-2,3,4,5-tetrathiol Chemical compound CC(S)C(S)C(S)C(C)S ARJVHELJIBYSAM-UHFFFAOYSA-N 0.000 description 1
- QKRLTFZDSQIHHV-UHFFFAOYSA-N hexane-2,3,5-trithiol Chemical compound CC(S)CC(S)C(C)S QKRLTFZDSQIHHV-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([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
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011508 lime plaster Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- GURMJCMOXLWZHZ-UHFFFAOYSA-N n-ethyl-n-[tris(diethylamino)silyl]ethanamine Chemical compound CCN(CC)[Si](N(CC)CC)(N(CC)CC)N(CC)CC GURMJCMOXLWZHZ-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PYNVYLAZKQQFLK-UHFFFAOYSA-N naphthalene-1,2,3,4-tetrol Chemical compound C1=CC=CC2=C(O)C(O)=C(O)C(O)=C21 PYNVYLAZKQQFLK-UHFFFAOYSA-N 0.000 description 1
- NCIAGQNZQHYKGR-UHFFFAOYSA-N naphthalene-1,2,3-triol Chemical compound C1=CC=C2C(O)=C(O)C(O)=CC2=C1 NCIAGQNZQHYKGR-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- HYRAFPWOUAMMQN-UHFFFAOYSA-N naphthalene-1,4-dithiol Chemical compound C1=CC=C2C(S)=CC=C(S)C2=C1 HYRAFPWOUAMMQN-UHFFFAOYSA-N 0.000 description 1
- AAPAGLBSROJFGM-UHFFFAOYSA-N naphthalene-1,5-dithiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1S AAPAGLBSROJFGM-UHFFFAOYSA-N 0.000 description 1
- XMHBJPKFTZSWRJ-UHFFFAOYSA-N naphthalene-2,6-dithiol Chemical compound C1=C(S)C=CC2=CC(S)=CC=C21 XMHBJPKFTZSWRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- PWZUZQNZVZKCBI-UHFFFAOYSA-N o-ethyl carbamothioate Chemical group CCOC(N)=S PWZUZQNZVZKCBI-UHFFFAOYSA-N 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- DCCVNNLAKWGDOJ-UHFFFAOYSA-N pentane-1,2,3,4-tetrathiol Chemical compound CC(S)C(S)C(S)CS DCCVNNLAKWGDOJ-UHFFFAOYSA-N 0.000 description 1
- HXBSJUYBTARPOT-UHFFFAOYSA-N pentane-1,2,3-trithiol Chemical compound CCC(S)C(S)CS HXBSJUYBTARPOT-UHFFFAOYSA-N 0.000 description 1
- KOCQFNLILAGZMO-UHFFFAOYSA-N pentane-1,2,4-trithiol Chemical compound CC(S)CC(S)CS KOCQFNLILAGZMO-UHFFFAOYSA-N 0.000 description 1
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ZTQBLNYKZKMJOU-UHFFFAOYSA-N phenanthrene-1,2,3-triol Chemical compound C1=CC=C2C(C=C(C(=C3O)O)O)=C3C=CC2=C1 ZTQBLNYKZKMJOU-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- UKQMUPLYHOXQQR-UHFFFAOYSA-N phenylmethanedithiol Chemical compound SC(S)C1=CC=CC=C1 UKQMUPLYHOXQQR-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Chemical group 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920001713 poly(ethylene-co-vinyl alcohol) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005735 poly(methyl vinyl ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- JDGOULBXCIOECK-UHFFFAOYSA-N propan-2-ol;tetra(propan-2-yloxy)stannane Chemical compound [Sn+4].CC(C)O.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] JDGOULBXCIOECK-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- LUHFNMZIUWHSET-UHFFFAOYSA-N spiro[3.4]octane-3,3-diol Chemical compound OC1(O)CCC11CCCC1 LUHFNMZIUWHSET-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 1
- WTSBJMAOQNCZBF-UHFFFAOYSA-N sulfanylmethylsulfanylmethanethiol Chemical compound SCSCS WTSBJMAOQNCZBF-UHFFFAOYSA-N 0.000 description 1
- QNITWMBGUWZSSI-UHFFFAOYSA-N sulfanylmethylsulfanylmethylsulfanylmethanethiol Chemical compound SCSCSCS QNITWMBGUWZSSI-UHFFFAOYSA-N 0.000 description 1
- IWOKCMBOJXYDEE-UHFFFAOYSA-N sulfinylmethane Chemical compound C=S=O IWOKCMBOJXYDEE-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 description 1
- OCXPCSGIIJESOA-UHFFFAOYSA-N tert-butyl-dichloro-phenylsilane Chemical compound CC(C)(C)[Si](Cl)(Cl)C1=CC=CC=C1 OCXPCSGIIJESOA-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- BCMKHWMDTMUUSI-UHFFFAOYSA-N tetrahydroxynaphthalene Natural products OC1=CC(O)=CC2=CC(O)=CC(O)=C21 BCMKHWMDTMUUSI-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- TWXMZYPORGXIFB-UHFFFAOYSA-N thiophene-3,4-dithiol Chemical compound SC1=CSC=C1S TWXMZYPORGXIFB-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- OVZUSPADPSOQQN-UHFFFAOYSA-N tri(propan-2-yloxy)indigane Chemical compound [In+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] OVZUSPADPSOQQN-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UUJLHYCIMQOUKC-UHFFFAOYSA-N trimethyl-[oxo(trimethylsilylperoxy)silyl]peroxysilane Chemical compound C[Si](C)(C)OO[Si](=O)OO[Si](C)(C)C UUJLHYCIMQOUKC-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/20—Processes for applying liquids or other fluent materials performed by dipping substances to be applied floating on a fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to dispersoids having metal-oxygen bonds, metal oxide films produced from such dispersoids, and organic-inorganic hybrid materials in which the inorganic component is or includes such a dispersoid.
- Metal oxide sols are useful as metal oxide film-forming materials, as the inorganic component in organic-inorganic hybrid materials, and in other applications. Several methods of preparation are known.
- JP A 10-298769 is a method of preparing a metal oxide precursor sol by hydrolyzing and polymerizing one or more metal compound, which method is characterized by carrying out the addition of water to the metal compound at a temperature of ⁇ 20.degree. C. or below.
- JP A 1-129032 describes a method for preparing an organic solvent-soluble high-molecular-weight ladder-type polytitanoxane by hydrolyzing titanium tetraalkoxide using 1.0 to 1.7 moles of water per mole of the titanium tetraalkoxide at a temperature of 20 to 90.degree. C.
- the object of this method is to provide a high-molecular-weight ladder-type polytitanoxane which, in spite of being a high-molecular-weight compound, dissolves in organic solvents and forms a dense thin-film.
- JP A 2001-342018 describes a method for preparing a metal oxide precursor solution which involves adding an alcohol solution containing 0.1 to 2.0 moles of water to 1 mole of a metallic salt partially hydrolyzed by the addition of water and the application of heat, then heating so as to hydrolyze the metallic salt and form a metal hydroxide, followed by dehydrative condensation then concentration.
- sol particles thus obtained agglomerate, resulting in a large particle size, and thus fail to provide a satisfactory performance when rendered into a metal oxide film or even when prepared as a hybrid with an organic component.
- sols obtained by hydrolyzing a metal alkoxide using an acid or base dehydrative condensation, distilling off the solvent, water and acid or base, and bulk polymerization, complete removal of the water and the acid or base used is difficult and what remains of these has an effect on the polymerization reaction.
- stabilizing the presence of metal alkoxide hydrolysates within the solution requires the use of an acid, base or dispersion stabilizer. Unfortunately, these inhibit polymerization or adversely affect the physical properties of the product.
- inorganic-organic hybrids made with a titanium oxide gel generally tend to have a lower transmittance that inorganic-organic hybrids made with other metal oxide gels, which suggests that the titanium oxide agglomerates in the concentration stage following hydrolysis and dehydrative condensation.
- a homogeneous film-forming sol can easily be prepared.
- much organic matter resistant to high-temperature degradation is also present in the sol or gel film, and so heat treatment at an elevated temperature of about 500° C. is required to remove such organic matter.
- the residual presence of much organic matter in the gel film results in a greater weight loss by the film when it is heat treated.
- the removal of organic matter from the gel film causes numerous pores to form in the film, creating defects in the resulting metal oxide thin-film that prevent the mechanical, optical, electrical and other properties of the metal oxides from being fully achieved.
- These thin-films can be densified to eliminate pores in the film, but doing so requires excessive energy.
- methods which use metallic salts are basically thermal degradation processes, and lead to many problems with film quality following heat treatment.
- the present invention provides the following:
- M is a metal atom
- X is a hydrolyzable group
- R′ is a monovalent hydrocarbon group, a monovalent hydrocarbon group having a substituent, a monovalent halogenated hydrocarbon group, a monovalent hydrocarbon group which includes a linkage or a monovalent halogenated hydrocarbon group which includes a linkage
- M is at least one type of metal atom selected from the group consisting of silicon, germanium, tin, titanium and zirconium atoms
- Y is a hydrolyzable group
- the letter n is any integer from 1 to (m ⁇ 1)
- the letter m is the valence of M; with the proviso that if n is 2 or more, each R 1 may be like or unlike, and if (m ⁇ n) is 2 or more, each Y may be like or unlike)
- R 2 is an alkylene group, a vinylene group, an ethynylene group, an arylene group or a divalent functional group containing a silicon atom and/or an oxygen atom
- Z is a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group or a fluoroalkoxy group
- Y, M and m are as defined above, the letter p is 0 or an integer, the letter q is 0 or 1, and the letter r is 0 or any integer from 1 to (m ⁇ 2)).
- the present invention relates to dispersoids which have metal-oxygen bonds and share some common characteristics.
- Methods for producing these dispersoids are specified above in each of above items (1), (2), (13), (24), (27) and (28).
- dispersoids according to above items (1) and (2) are described as Dispersoid I
- dispersoids according to above item (13) are described as Dispersoid II
- dispersoids according to above item (24) are described as Dispersoid III
- dispersoids according to above items (27) and (28) are described as Dispersoid IV.
- Dispersoids according to above items (1) and (2) are described as Dispersoid I
- dispersoids according to above item (13) are described as Dispersoid II
- dispersoids according to above item (24) are described as Dispersoid III
- dispersoids according to above items (27) and (28) are described as Dispersoid IV.
- Dispersoid I of the present invention is a dispersoid having metal-oxygen bonds which is obtained by mixing a metal compound having at least three hydrolyzable groups with a given amount of water in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, and which is characterized in that the given amount of water is either at least 1.0 mole but less than 2.0 moles, or at least 0.5 mole but less than 1.0 mole, per mole of the metal compound, and the given temperature is a temperature below 0° C.
- dispersoid refers to fine particles dispersed in a dispersion system. Specific examples include colloidal particles and nanometer size particles composed of several polycondensed molecules.
- the acid or base used in this specification is not subject to any particular limitation, provided it functions as either a deflocculant which re-disperses precipitate that arises from coagulation or, as subsequently described, a catalyst for the hydrolysis or dehydrative condensation of the metal compound having at least three hydrolyzable groups to produce a dispersoid of colloidal particles, nanoparticles or the like, and also functions as a dispersant for the dispersoid that has formed.
- the acid include mineral acids such as hydrochloric acid, nitric acid, boric acid, tetrafluoroboric acid and carbonic acid; and organic acids such as acetic acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid and methanesulfonic acid. Additional examples also include photoacid generators which generate acids upon irradiation with light, such as diphenyliodonium hexafluorophosphate and triphenylphosphonium hexafluorophosphate. Specific examples of the base include triethanolamine, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, ammonia and phosphine.
- mineral acids such as hydrochloric acid, nitric acid, boric acid, tetrafluoroboric acid and carbonic acid
- organic acids such as acetic acid, formic acid, oxalic acid, triflu
- disperser refers to a component which is added in order to disperse the dispersoid in the dispersing medium as stably as possible, including coagulation-preventing agents such as deflocculants, protective colloids and surfactants.
- coagulation-preventing agents such as deflocculants, protective colloids and surfactants.
- Specific types of compounds having such an effect include chelating compounds, preferably those which having at least one carboxyl group on the molecular backbone and have a strong metal-chelating ability.
- Illustrative examples of such compounds include polycarboxylic acids such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid and succinic acid, hydroxycarboxylic acids, and also pyrophosphoric acid and tripolyphosphoric acid.
- aliphatic amines such as Surpass 3000, 9000, 17000, 20000 and 24000 (all products available from Zeneca) and Disperbyk-161, Disperbyk-162, Disperbyk-163, and Disperbyk-164 (all products of Byk Chemie GmbH); and also the silicone compounds mentioned in JP A 9-208438 and JP A 2000-53421, such as dimethylpolysiloxane-methyl(polysiloxyalkylene)siloxane copolymers, trimethylsiloxysilicate, carboxy-modified silicone oils and amine-modified silicones.
- silicone compounds mentioned in JP A 9-208438 and JP A 2000-53421 such as dimethylpolysiloxane-methyl(polysiloxyalkylene)siloxane copolymers, trimethylsiloxysilicate, carboxy-modified silicone oils and amine-modified silicones.
- the metal compound having at least three hydrolyzable groups used in the invention is a metal atom-containing compound having on the molecule at least three hydrolyzable groups which are bonded to the metal atom in any manner, be it directly or through linkages such as carbon chains.
- Haldrolyzable group refers to a functional group which hydrolyzes on contact with water or a functional group capable of forming a bond with the metal atom through an oxygen atom, either in the presence or absence of water. Specific examples include halogen atoms, amino groups, alkoxy groups, ester groups, carboxyl groups, phosphoryl groups, isocyanate groups and cyano groups.
- hydrolyzable groups are functional groups whose purpose, after coming into contact with water and hydrolyzing, is to make the metal compound condense with other active groups or self-polycondense, although the hydroxyl group is not a hydrolyzable group in the strictest sense, it is similar in nature and is therefore regarded as a hydrolyzable group in the present specification. (“Hydrolyzable group” is used in the same sense throughout the specification.)
- the metal compound is at least one metal compound having at least three hydrolyzable groups, but may include other metal compounds, such as compounds having two hydrolyzable groups.
- metal compound examples include the compounds of formula (I).
- M is a metal atom, and preferably a metal atom capable of synthesizing a metal alkoxide or a metal carboxylate; i.e., a metal atom with a valence of 3 to 5 from group III, IV or V of the periodic table.
- metal atoms such as silicon, germanium, tin, lead, titanium, zirconium, hafnium, boron, aluminum, gallium, indium, thallium, scandium, yttrium, lanthanum, antimony, bismuth, vanadium, niobium, tantalum, lanthanoid metals and actinoid metals.
- Preferred examples include titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead.
- R represents a hydrogen atom or an organic group which may have a hydrolyzable group capable of forming a bond with the metal atom through an oxygen atom.
- exemplary hydrolyzable groups include functional groups similar to the hydrolyzable groups mentioned above.
- Specific examples of R include alkyl groups with 1 to 12 carbons, such as methyl, ethyl and propyl; halogenated alkyl groups with 1 to 12 carbons, such as chloromethyl, chloroethyl, chloropropyl, bromopropyl, bromooctyl and trifluoropropyl; epoxyalkyl groups with 1 to 12 carbons, such as glycidoxypropyl and epoxycyclohexylethyl; aminoalkyl groups with 1 to 12 carbons, such as aminopropyl and aminobutyl; aromatic groups with 6 to 12 carbons, such as phenyl and benzyl; and photosensitive groups with 2 to 12 carbons, such as vinyl, allyl, acryloxy
- X represents a hydrolyzable group bonded to the metal atom M.
- alkoxy groups such as methoxy, ethoxy, propoxy, butoxy and pentoxy, aminohydroxy groups, aminohydroxy groups, enoxy groups, amino groups, carbamoyl groups, halogen atoms such as chlorine and bromine, and hydroxyl. Alkoxy groups are especially preferred.
- a+b m, where m is the valence of the metal atom.
- the presence of three or more hydrolyzable groups on the molecule is exemplified by cases where the letter b represents 3 or more, and cases where the letter b represents 2 or less and there are one or more R moieties having a hydrolyzable group.
- the metal compound furnished for hydrolysis does not need to be a single molecular compound represented by formula (I).
- the metal compound may be an oligomer obtained by using a similar method to hydrolyze and polycondense a compound of formula (I).
- metal compound of formula (I) examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, germanium tetramethoxide, germanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, tetrachlorosilane, tetrabromosilane, dimethyldichlorosilane, tetrakis(diethylamino)silane, 4-aminobutyltriethoxy
- Especially preferred metal alkoxides include tetramethoxysilane, tetraethoxysilane, titanium tetrapropoxide, zirconium tetrapropoxide and zirconium tetrabutoxide.
- These metal compounds may be used singly or as combinations of two or more thereof.
- suitable metal compounds include double alkoxides obtained by a reaction between metal alkoxides of two or more of the above elements, and double alkoxides obtained by reacting one or more metal alkoxide with one or more metal salt.
- double alkoxides obtained by reacting one or more metal alkoxide with one or more metal salt.
- the use of such double alkoxides in combinations thereof is also possible.
- Exemplary double alkoxides that can be obtained by a reaction between two or more metal alkoxides include double alkoxides obtained by reacting an alkali metal or alkaline earth metal alkoxide with a transition metal alkoxide, and double alkoxides in the form of complex salts obtained by combination with a group 3B element.
- Specific examples include BaTi(OR′) 6 , SrTi(OR′) 6 , BaZr(OR′) 6 , SrZr(OR′) 6 , LiNb(OR′) 6 , LiTa(OR′) 6 and combinations thereof, as well as LiVO(OR′) 4 and MgAl 2 (OR′) 8 .
- Additional examples include the following products of reactions with silicon alkoxides and silicon alkoxide polycondensation products: (R′O) 3 SiOAl(OR′′) 2 , (R′O) 3 SiOTi(OR′′) 3 , (R′O) 3 SiOZr(OR′′) 3 , (R′O) 3 SiOB(OR′′) 2 , (R′O) 3 SiONb(OR′′) 4 and (R′O) 3 SiOTa(OR′′) 4 .
- R′ and R′′ represent alkyl groups.
- Exemplary double alkoxides that can be obtained by reacting one or more metal alkoxide with one or more metal salt include compounds obtained by reacting a metal salt such as a hydrochloride, nitrate, sulfate, acetate, formate or oxalate with an alkoxide.
- water used examples include common tap water, distilled water and ion-exchanged water. Of these, distilled water or ion-exchanged water is preferred. Ion-exchanged water having an electric conductivity of 2 ⁇ s/cm or less is especially preferred.
- the amount of water used is in a range of from at least 0.5 mole to less than 2 moles per mole of the metal compound. At less than 0.5 mole, hydrolysis or polycondensation will not proceed uniformly, as a result of which some metal compound of formula (I), for example, will remain unreacted, making it impossible to form a homogeneous and dense film. On the other hand, at more than 2 moles, gelation or particle aggregation will occur during hydrolysis or polycondensation, also making it impossible to form a homogeneous and dense film.
- the water is preferably used after dilution with an organic solvent.
- the organic solvent is preferably one having a solidification point of 0° C. or below, and also preferably one which has no reactivity with the metal compound when mixed under the conditions of the invention.
- Exemplary organic solvents include alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, ketone ethers, ketone esters and ester ethers.
- benzyl alcohol methyl cyclohexanol, ethanediol, propanediol, butanediol, pentanediol, hexylene glycol, octylene glycol, hexanetriol, 3,5,5-trimethyl-1-hexanol, butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl prop
- organic solvents may be used singly or as combinations of two or more thereof. When the water and the organic solvent are uniformly dissolved and mixed, the resulting mixture may be used directly as is. If the water and the organic solvent do not mix uniformly, they may be used after uniform dispersion by a suitable method such as agitation or ultrasonic processing.
- the amount of organic solvent used for dilution is preferably in a range of 2 to 100 parts by weight per part by weight of water.
- Dispersoid I is obtained by mixing the above-described metal compound with a given amount of water in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer, and at a given temperature.
- the method of mixing the metal compound and the given amount of water is not subject to any particular limitation. Exemplary methods include adding the water to the metal compound under stirring, adding the metal compound to the water under stirring, and adding the metal compound and the water at the same time to a vessel equipped with an agitator. Mixing may be carried out without using a solvent, although mixing with the use of an organic solvent is preferable for efficient production of the target dispersoid I.
- the organic solvent used is an organic substance which is preferably capable of dispersing the target dispersoid I ultimately obtained.
- specific examples include alcohols such as methanol, ethanol and isopropyl alcohol; chlorinated solvents such as methylene chloride and chloroform; hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene and chlorobenzene; ethers such as tetrahydrofuran, diethyl ether and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone; and the silicones such as methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane and methylphenylpolysiloxane
- a solvent which does not solidify at low temperature is preferred.
- Illustrative examples include lower alcohols, ethers, and hydrocarbons such as toluene. These solvents may be used singly or as mixtures of two or more thereof.
- examples of methods that may be used to prepare the dispersoid I of the invention include adding water or water diluted with an organic solvent to an organic solvent solution of the metal compound, adding water diluted with an organic solvent to the metal compound, and adding the metal compound or the metal compound diluted with an organic solvent to the water diluted with an organic solvent.
- the amount of organic solvent used to dilute the metal compound is preferably 10 to 5,000 parts by weight, and more preferably 100 to 3,000 parts by weight, per 100 parts by weight of the metal compound. At less than 10 parts by weight, the fine particles that form grow in a bonded state, which may make the particle size difficult to control. On the other hand, at more than 5,000 parts by weight, the solution is too dilute, which may make formation of the fine particles difficult.
- the amount of organic solvent used to dilute the water is as described above. If only either of the metal compound and the water is to be diluted with an organic solvent prior to use, dilution is not limited within the above range and may be carried out with a larger amount of organic solvent.
- the given temperature during mixture of the metal compound and the water is a temperature below 0° C., although a temperature of ⁇ 20° C. or below is preferred, and a temperature in a range of ⁇ 50 to ⁇ 100° C. is especially preferred. A temperature at or below the temperature at which the metal compound begins to hydrolyze is also preferred.
- the given temperature need not always be fixed, and may fluctuate, provided it does so within the specified temperature range.
- temperature at which the metal compound begins to hydrolyze refers to the lower limit temperature at which hydrolysis proceeds when the metal compound and the water come into contact. Any suitable method may be used to measure the temperature at which the metal compound begins to hydrolyze. Examples include the method described in JP A 1-230407, and a method in which the 1 H-NMR spectrum is measured during a rise in temperature from a low-temperature state so as to determine signal changes for the hydrolyzable groups on the metal compound.
- water is added to the metal compound at the given temperature, it is preferable to add water or a water-containing organic solvent solution of a similar given temperature.
- Dispersoid I of the invention is prepared by carrying out the above-described water addition step at the given temperature, then raising the temperature to or above the given temperature. No particular limitation is imposed on the temperature to which the system is raised. When a solvent is used, the temperature may be raised up to the solvent refluxing temperature.
- Dispersoid II of the present invention is a dispersoid having metal-oxygen bonds obtained by mixing, in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, a partial hydrolysate that is prepared by hydrolyzing a metal compound having at least three hydrolyzable groups in the absence of an acid, base and/or dispersion stabilizer and can be stably dispersed without aggregation in an organic solvent with an amount of water equal to at least 0.5 mole but less than 2 moles per mole of the metal compound minus the amount of water used to prepare the partial hydrolysate, which dispersoid is characterized in that the given temperature is a temperature below 0° C.
- the partial hydrolysate is not subject to any particular limitation, provided it is of a nature that stably disperses in the organic solvent without aggregation.
- a specific example is the polytitanoxane described as Comparative Specimen C-2 in JP A 1-129032. No particular limitation is imposed on the method of preparation, although it is preferable to use a method like that for preparing the inventive dispersoid.
- “Stably dispersed without aggregation” refers herein to a state where the dispersoid having metal-oxygen bonds has not coagulated and heterogeneously separated, and preferably refers to a transparent and homogeneous state.
- “transparent” refers to a state of high transmittance to visible light. Specifically, it refers to a state of preferably 80 to 100% transmittance, expressed as the spectral transmittance measured at a dispersoid concentration of 0.5 wt % (oxide basis), at a quartz cell light path length of 1 cm, using the organic solvent as the control, and at a light wavelength of 550 nm.
- “Stably dispersed without aggregation” is used in the same sense throughout the specification.
- Dispersoid II of the invention is obtained by mixing the partial hydrolysate and water at a temperature of 0° C. or below, preferably a temperature of ⁇ 20° C. or below, and more preferably a temperature in a range of ⁇ 50 to ⁇ 100° C. A temperature at or below the temperature at which the metal compound begins to hydrolyze is also preferred. Other details, including those concerning the metal compound, the water, and the mixing method used, are the same as described above for Dispersoid I.
- Dispersoid III of the present invention is a dispersoid having metal-oxygen bonds which is obtained by mixing a metal compound having at least three hydrolyzable groups with a given amount of water in the absence of an acid, a base and/or a dispersion stabilizer and at a given temperature, which dispersoid is characterized in that the given amount of water is a solution diluted with a hydrocarbon solvent and an alcohol solvent, the diluted solution is added to the metal compound, and the given temperature is room temperature.
- Dispersoid III of the invention can be obtained by the direct addition of an aqueous solution to the metal compound, although the use of an organic solvent is preferable for better control of the reaction.
- the organic solvent used is exemplified by the same solvents and the same amount as those mentioned above for Dispersoid I.
- aromatic hydrocarbon is preferred, and toluene or xylene is especially preferred.
- alcohol solvents examples include methanol, ethanol and isopropyl alcohol. Isopropyl alcohol is preferred.
- the mixing ratio of the hydrocarbon solvent and the alcohol solvent is not subject to any particular limitation, although a mixing ratio in a range of 2:8 to 8:2 is preferred, and a mixing ratio in a range of 4:6 to 6:4 is especially preferred.
- the concentration of water added is preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and even more preferably 1 to 5 wt %. It is desirable for the water to be in a uniformly dissolved state.
- the concentration of water added is preferably from 40% to 1%, more preferably from 30% to 10%, and even more preferably from 25% to 15%, of the saturation solubility of water in a mixed solvent of the hydrocarbon solvent and the alcohol solvent.
- Addition of the mixture of hydrocarbon solvent, alcohol solvent and water to the metal compound is carried out at room temperature. After aging for a fixed period of time, hydrolysis and dehydrative condensation reactions can be carried out at from room temperature to the refluxing temperature of the solvent used.
- Dispersoid IV of the present invention is a dispersoid having metal-oxygen bonds which is obtained by the addition, to a metal compound having least three hydrolyzable groups, of at least 0.5 mole but less than 2 moles of water per mole of the metal compound, which dispersoid is characterized by having steps in which the water is added in a some of divided portions at a given temperature, which steps include at least one step in which the given temperature is a temperature below 0° C.
- the method of preparing this dispersoid of the invention includes the following three essential features:
- “Added in a some of divided portions” refers herein to, for example, addition under varying addition conditions, addition under the same addition conditions but in differing amounts, and addition under the same addition conditions and in the same addition amounts but at fixed intervals; that is, any addition other than one where the required amount of water is added under certain fixed conditions without extended intervals during addition. No particular limitation is imposed, provided the number of portions is two or more. However, taking into account the reaction operations, it is preferable for the water added to be divided into two portions, with at least one portion of water being added at a temperature below 0° C.
- the amount of water added at one time is not subject to any particular limitation, provided the combined amount of water is at least 0.5 mole but less than 2.0 moles per mole of the metal compound, although it is preferable in particular for the amount added at first to be at least 0.5 mole but less than 1 mole per mole of the metal compound.
- the temperature of addition is not subject to any particular limitation, provided the steps in which water is added in a some of divided portions include at least one step in which water is added at a temperature below 0° C. However, it is desirable that, following the first water addition step, the rest of the required amount of water is added at preferably a temperature below 0° C., and more preferably a temperature of ⁇ 20° C. or below; also preferred are a temperature at or below the temperature at which the metal compound beings to hydrolyze, and a temperature in a range of ⁇ 50 to ⁇ 100° C.
- the temperature be raised to the given temperature or above.
- the level to which the temperature is raised when an organic solvent is used, it is preferable to raise the temperature to the refluxing temperature of the organic solvent.
- the water addition step can be carried out in the presence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer, although it is preferably carried out in the absence of these.
- Dispersoids I to IV prepared as described above are characterized by being stably dispersed in an organic solvent even when the weight concentration of the dispersoid (metal oxide basis) in the organic solvent solution is at least 1.2 times, and preferably at least 1.4 times as much as the weight concentration of the metal compound (metal oxide basis) prior to hydrolysis.
- “High-concentration” here includes a solvent-free state. Depending on the metal, the state at this time may be a solid state, liquid state or gelled state, or may be a state that represents a mixture thereof.
- Dispersoids I to IV of the invention are also characterized by being dispersoids which are stably dispersed, without aggregation, in an organic solvent and in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer.
- “Stably dispersed without aggregation” refers herein to a state where the dispersoid having metal-oxygen bonds has not coagulated and heterogeneously separated within the organic solvent, and preferably refers herein to a transparent and homogeneous state.
- “transparent” signifies a state of high transmittance to visible light, and specifically a state of preferably 80 to 100% transmittance, expressed as the spectral transmittance measured at a dispersoid concentration of 0.5 wt % (oxide basis), at a quartz cell light path length of 1 cm, using the organic solvent as the control, and at a light wavelength of 550 nm.
- the organic solvent used for dispersing Dispersoids I to IV of the invention is not subject to any particular limitation provided it is a liquid organic substance and can disperse the dispersoid.
- Specific examples include alcohols such as methanol, ethanol and isopropyl alcohol; chlorinated solvents such as methylene chloride and chloroform; hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene and chlorobenzene; ethers such as tetrahydrofuran, diethyl ether and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone; and the silicones mentioned in JP A 9-208438, such as methylpolysiloxane, octamethylcyclotetrasiloxane
- a solvent which does not solidify at low temperatures is preferred for adding water and carrying out the reaction at a low temperature.
- Illustrative examples of such solvents include lower alcohols, ethers, and hydrocarbons such as toluene. These solvents may be used singly or as mixtures of two or more thereof.
- the Dispersoids I to IV of the invention are additionally characterized by having a particle size in a range of 1 to 100 nm, and also in a range of 1 to 50 nm and a range of 1 to 20 nm.
- the particle size distribution is characterized by being monodisperse with a particle size in a range of 0 to 50 nm.
- a metal oxide film can be produced from a dispersoid having metal-oxygen bonds prepared as described above and/or an inorganic polymer obtained using the dispersoid as the starting material.
- the dispersoid can be used after dilution with a suitable solvent, followed by removal of the solvent by distillation to give a solvent-free state. Alternatively, following removal of the solvent by distillation, the dispersoid can be re-dissolved or re-dispersed in a different solvent and used.
- dispersoid of the invention it is possible to carry out hydrolysis and polycondensation reactions on the hydrolyzable group-bearing metal compound in a high concentration without adding a dispersion stabilizer such as a multidentate compound to stabilize the hydrolysate, thereby enabling a high-concentration dispersion which contains no unnecessary organic matter such as multidentate compounds to be obtained.
- a dispersion stabilizer such as a multidentate compound
- the method of producing metal oxide thin films is characterized by coating a solution containing the dispersoid, then drying at a temperature of 200° C. or below.
- the concentration of the dispersoid in the dispersoid-containing solution varies with the coating method and the desired film thickness, but is not subject to an particular limitation provided it is a concentration capable of being coated onto a substrate. A concentration within a range of 5 to 50 wt %, based on the oxide, is preferred.
- the solvent used in the solution is exemplified by solvents similar to the above-mentioned solvents used for dispersing the dispersoid. It is especially preferable to use the same solvent as was used to disperse the dispersoid, although a different solvent may be used provided it is a solvent which does not affect the dispersibility of the dispersoid.
- ingredients may be added to the dispersoid-containing solution.
- specific examples of other ingredients include inorganic binders such as silicon compounds (e.g., water glass, colloidal silica, polyorganosiloxane), phosphates (e.g., zinc phosphate, aluminum phosphate), biphosphates, cements, limes, gypsums, enamel frits, glazes for glass lining, and plasters; and organic binders such as fluoropolymers, silicone polymers, acrylic resins, epoxy resins, polyester resins, melamine resins, urethane resins and alkyd resins. These binders may be used singly or as combinations of two or more thereof.
- Inorganic binders, fluoropolymers and silicone polymers are especially preferred from the standpoint of bond strength.
- Cements that may be used include Portland cements such as high early-strength cement, normal cement, moderate heat cement, sulfate-resisting cement, white cement, oil well cement and geothermal cement; blended cements such as fly ash cement, highly sulfated slag cement, Portland pozzolan cement and Portland blast-furnace slag cement; and alumina cement.
- Plasters that may be used include gypsum plaster, lime plaster and dolomite plaster.
- Fluoropolymers that may be used include crystalline fluororesins such as polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene-polyhexafluoropropylene copolymers, ethylene-polytetrafluoroethylene copolymers, ethylene-chlorotrifluoroethylene copolymers and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers; noncrystalline fluororesins such as perfluorocyclopolymers, vinyl ether-fluoroolefin copolymers and vinyl ester-fluoroolefin copolymers; and various fluororubbers.
- crystalline fluororesins such as polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene-polyhexa
- Fluororubbers composed primarily of vinyl ether-fluoroolefin copolymers and vinyl ester-fluoroolefin copolymers are especially preferred because they undergo little degradation or deterioration and are easy to handle.
- Silicone polymers that may be used include linear silicone resins, acrylic-modified silicone resins, acrylic-silicone resins, epoxy-silicone resins, and various silicone rubbers.
- the relative amounts of the above-described dispersoid and the foregoing other ingredients, expressed as the weight ratio of the dispersoid to the combined amount of both the dispersoid and the other ingredients is 5 to 98%, preferably 20 to 98%, more preferably 50 to 98%, and even more preferably 70 to 98%.
- other ingredients such as heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, colorants, surfactants, crosslinking agents, dispersants and fillers may also be included in the dispersoid-containing solution.
- Crosslinking agents that may be used include ordinary crosslinking agents such as isocyanate- or melamine-based crosslinking agents.
- Dispersants that may be used include coupling agents.
- any suitable known method may be used to coat the above-described dispersoid-containing solution onto a substrate, including spin coating, dip coating, spray coating, roll coating and screen printing.
- Roll coating is preferred for carrying out mass production inexpensively.
- Especially preferred methods are those which use a bar or a roller-type coating device.
- Screen printing and offset printing are also advantageous in that they enable patterning to be carried out during coating.
- the coating weight varies with the intended use of the resulting thin film, although the coating weight of active ingredients other than the solvent is generally from 0.1 to 10 ml/m 2 , preferably from 0.2 to 7 ml/m 2 , and more preferably from 0.4 to 5 ml/m 2 .
- the substrate may be an object made of an inorganic material such as ceramic or glass, an object made of an organic material such as plastic, rubber, wood or paper, or an object made of a metal material such as a metal (e.g., aluminum) or metal alloy (e.g., steel).
- a metal material such as a metal (e.g., aluminum) or metal alloy (e.g., steel).
- the substrate may be a flat plate, a three-dimensional object or a film. Even a painted object may be used for this purpose. Of these, a plastic film is preferred.
- plastic films that may be used include cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate, syndiotactic polystyrene, polyethylene-coated paper, polyethersulfone, polyarylate, polylvinylidene fluoride and Teflon (registered trademark).
- These substrates may be provided with a polyvinylidene chloride-type polymer-containing waterproofing layer so as to enhance dimensional stability; i.e., the stability to dimensional changes from changes in temperature and humidity.
- an organic and/or inorganic compound thin film may be provided as a gas barrier.
- organic thin films include polyvinyl alcohol and polyethylene-co-vinyl alcohol).
- inorganic compounds include silica, alumina, talc, vermiculite, kaolinite, mica and synthetic mica.
- organic and/or inorganic additives may also included in the substrate to confer other capabilities as well.
- Heating of the applied film is carried out together with drying of the solvent, the purpose being to effect, for example, hydrolysis and dehydrative condensation of the dispersoid. It is desirable for heating after coating to be carried out at a low temperature of 200° C. or below so as not to damage the substrate. Heating is carried out at preferably 20 to 100° C., and more preferably 30 to 80° C.
- the heating time is not subject to any particular limitation, although it is generally suitable to carry out heating for a period of from 1 minute to 120 hours.
- a protective film may be formed thereon.
- a common protective film-forming coating solution such as a silica film-forming coating solution which contains an alkoxysilane hydrolysate, may be used to form this protective coat.
- the addition ratio of the fine metal oxide crystals is preferably 10 to 90 wt %, and more preferably 10 to 80 wt %, of the sol weight when the sol has formed from the dispersoid.
- the seed crystals may be of any size, although a sphere equivalent diameter of 0.1 ⁇ m or less is preferable from the standpoint of light transmittance.
- the seed crystals added are not limited to crystals of the same metal oxide and may instead be ones suitable for heteroepitaxy because they have, for example, the same crystal form and/or a similar lattice constant.
- indium oxide may be used as the seed crystals when forming an ITO film.
- the seed crystals used may be commercially available product or synthesized crystals. If the metal oxide film is to be a ITO film, the seed crystals may be a commercial product made by, for example, Mitsubishi Materials Corporation or Sumitomo Metal Mining Co., Ltd. Examples of methods for synthesizing the seed crystals include sol-gel methods, hydrothermal synthesis, and ordinary sintering.
- sol-gel methods appear in, for example, “Science of the Sol-Gel Process” [Zoru-geru h ⁇ no kagaku] by Sumio Sakka (Agne Shofusha, 1988); “Thin-Film Coating Technology Using the Sol-Gel Process” [Zoru-geru h ⁇ ni yoru hakumaku k ⁇ tingu gijutsu] (Gijutsu Joho Kyokai, 1994); and “The Sol-Gel Process: Today and Tomorrow” [Zoru-geru h ⁇ no genj ⁇ to tenb ⁇ ], edited by Masayuki Yamane (Sol-Gel Process Report Publication Committee of the Association of Technical Information Services (ATIS), 1992).
- ATIS Technical Information Services
- the film-forming method of the invention is preferably one which involves light irradiation during and/or after heating of the applied film.
- the light source used to irradiate the applied film with ultraviolet light or visible light may be any which emits light having a wavelength of 150 to 700 nm.
- Illustrative examples include ultrahigh-pressure mercury vapor lamps, high-pressure mercury vapor lamps, low-pressure mercury vapor lamps, xenon lamps, halogen lamps and sodium lamps.
- Ultrahigh-pressure mercury vapor lamps, high-pressure mercury vapor lamps, low-pressure mercury vapor lamps and xenon lamps are preferred.
- a transparent, electrically conductive pattern can be formed by using a photomask with the light source.
- a laser oscillator may also be used.
- laser oscillators examples include excimer lasers, argon lasers, helium neon lasers, semiconductor lasers, YAG lasers, carbon dioxide lasers and dye lasers.
- laser light When laser light is employed, metal oxide does not form in non-irradiated areas, and so patterning is possible without the use of a process such as screen printing at the time of coating. Use can also be made of synchrotron light.
- These apparatuses can be selected according to the desired wavelength of irradiation.
- the metal oxide that forms is sometimes accompanied by residual metal hydroxide. Given the absorption by metal-OH bonds that occurs in such cases, it is desirable to use an apparatus which emits light that includes ultraviolet radiation having a wavelength of 400 nm or less.
- the metal-oxygen-metal bonds absorb at a shorter wavelength than metal-OH bonds, but crystallization of the metal oxide will proceed with the irradiation of light having a wavelength capable of activating the metal-oxygen-metal bonds.
- the irradiation time is not subject to any particular limitation, although irradiation is generally carried out for a period of from 1 minute to 120 hours.
- the light irradiation process may be carried out in any atmosphere, although irradiation in a somewhat reducing atmosphere is preferred. In a somewhat reducing atmosphere, the greater degree of oxygen deficiency is thought to inhibit increases in carrier density and/or adsorption of the oxygen molecules to the grain boundaries.
- a high-boiling, low-molecular-weight solvent which decomposes under light irradiation may be used.
- solvents include isophorone and benzyl acetate.
- substances such as photodegradable resins may also be added to this dispersion-containing solution.
- Illustrative examples include poly(methyl vinyl ketone), poly(vinyl phenyl ketone), polysulfone, diazonium salts such as the polycondensate of p-diazodiphenylamine and paraformaldehyde, quinonediazides such as the isobutyl ester of 1,2-naphthoquinone-2-diazido-5-sulfonic acid, and poly(methyl methacrylate), poly(phenyl methylsilane) and poly(methyl isopropenyl ketone).
- the metal oxide film obtained as described above is characterized by having a smooth film surface.
- the film surface is characterized by having an average roughness, which is a value indicating smoothness, of 10 nm or less, and preferably 5 nm or less. Because it can be heat treated at a low temperature, even when the metal oxide film has been formed on a plastic substrate, the film is characterized by having a carbon content, expressed as an atomic ratio, of 10% or less.
- the organic-inorganic hybrid material of the invention is characterized by containing at least one selected from the group consisting of a dispersoid having metal-oxygen bonds prepared as described above, an inorganic structural portion derived from the dispersoid, and an inorganic polymer obtained from the dispersoid as the starting material.
- the organic component is not subject to any particular limitation. Any suitable resin, such as an addition polymer, polyadduct or polycondensate may be used. Specific examples are listed below.
- acrylic resins include those obtained by polymerization from the following monomers as the starting materials: monofunctional methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, hexyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, tricyclo[5.2.1.0]decanyl methacrylate and 3,3,3-trifluoroethyl methacrylate; polyfunctional methacrylic acid esters such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, tripropylene dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, penta
- Monofunctional acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, isobornyl acrylate, tricyclo[5.2.1.0]decanyl acrylate and 3,3,3-trifluoroethyl acrylate; and polyfunctional acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
- Monomers that are copolymerizable with the above acrylic or methacrylic compounds include styrene, ring-substituted styrenes such as methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene and divinylbenzene; as well as ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride and N-substituted maleimide. Copolymers of these latter monomers with the above acrylic or methacrylic compounds also are considered herein as acrylic resins.
- Organic monomers which are radical- or cationic-polymerizable are preferred, and organic monomers having at least one type of bond selected from among amide bonds, imide bonds, urethane bonds and urea bonds are especially preferred.
- specific examples of radical-polymerizable organic monomers include (meth)acrylamide, (meth)acrylamide derivatives, (meth)acryloylmorpholine, N-vinylpyrrolidone, urethane (meth)acrylate, and the addition products of aminoalkyl (meth)acrylates and isocyanate.
- (meth)acrylamide stand for both methacrylamide and acrylamide
- (meth)acrylate stands for both methacrylate and acrylate.
- exemplary cation-polymerizable monomers are compounds having an epoxy ring, a vinyl ether bond or an ortho-spiro ring as a polymerization functional group.
- Specific examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and hydrogenated bisphenol A diglycidyl ether.
- Optional organic monomers may be used together with the above essential organic monomer to modify the resulting polymer.
- Such optional organic monomers may or may not have amide bonds, urethane bonds and urea bonds.
- the mode of polymerization for these optional organic monomers must be the same as for the above-described essential monomers (i.e., radical polymerization, cationic polymerization).
- Poly(thio)urethane resins refers herein to polythiourethane or polyurethane resins obtained by reacting a polyisocyanate compound with a polythio compound or a polyhydroxy compound.
- the polyisocyanate compound is not subject to any particular limitation. Specific examples include the following:
- polythiol compounds include the following:
- polyhydroxy compounds include the following:
- Resins composed primarily of diethylene glycol bis(allyl carbonate) are exemplified by homopolymers of diethylene glycol bis(allyl carbonate) and copolymers obtained by reacting diethylene glycol bis(allyl carbonate) with a copolymerizable monomer.
- Examples of monomers that are copolymerizable with diethylene glycol bis(allyl carbonate) include monofunctional methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and adamantyl methacrylate; polyfunctional methacrylic acid esters such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, glycerol dimethacrylate,
- styrene ring-substituted styrenes such as methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene and divinylbenzene; and also ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide, diallyl phthalate, diallyl isophthalate and diallyl terephthalate.
- copolymers of diethylene glycol bis(allyl carbonate) and other monomers are mentioned in, for example, JP A 54-41965, JP A 51-125487 and JP A 01-503809.
- Resins obtained from epithio group-bearing compounds refers herein to resins obtained by polymerizing, as the starting material, an epithio group-bearing monomer or a monomer mixture containing such a monomer.
- Specific examples of epithio group-bearing monomers include the following:
- resins obtainable from epithio group-bearing compounds as lens substrates is already known to the art. Specific examples include those disclosed in the following publications: JP A 09-071580, JP A 09-110979, JP A 09-255781, JP A 03-081320, JP A 11-140070, JP A 11-183702, JP A 11-189592, JP A 11-180977, and JP A 01-810575.
- radical polymers having a (thio)urethane structure on the molecule such as radical polymers prepared from monomers obtained by reacting a linear alkane compound of 3 to 6 carbons having at least two mercapto groups on the molecule with a compound having at least one isocyanate group and at least one (meth)acryloyl group on the molecule.
- (meth)acryloyl group stands for both acryloyl group and methacryloyl group.
- Examples of the linear alkaline compound of 3 to 6 carbons having at least two mercapto groups on the molecule which serves as one of the starting materials in the preparation of radical polymerizable compounds having a thiourethane bond include 1,2,3-trimercaptopropane, 1,2,3-trimercaptobutane, 1,2,4-trimercaptobutane, 1,2,3,4-tetramercaptobutane, 1,2,3-trimercaptopentane, 1,2,4-trimercaptopentane, 1,2,3,4-tetramercaptopentane, 1,2,3-trimercaptohexane, 1,2,4-trimercaptohexane, 1,2,5-trimercaptohexane, 2,3,4-trimercaptohexane, 2,3,5-trimercaptohexane, 3,4,5-trimercaptohexane, 1,2,3,4-tetramercaptohexane, 1,2,3,5-tetramercaptohexane
- Examples of the compound having one isocyanate group and at least one (meth)acryloyl group which serves as the other starting material include acryloyl isocyanate, methacryloyl isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-isocyanatopropyl acrylate and 2-isocyanatopropyl methacrylate. Of these, 2-isocyanatoethyl methacrylate is especially preferred for its ready availability and for the performance of the resulting optical material.
- the above are all examples of compounds having one isocyanate group and one (meth)acryloyl group, but use can also be made of compounds having two or more isocyanate group or two or more (meth)acryloyl groups.
- a compound other than the above polymerizable compounds such as a radical-polymerizable organic monomer
- one or more radical-polymerizable compound which has a radical-polymerizable group and is copolymerizable with the above compounds may be included.
- radical-polymerizable compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene diglycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate,
- (meth)acrylate stands for both acrylate and methacrylate
- (meth)acryloxy group stands for both acryloxy group and methacryloxy group.
- the polymerization reaction is carried out by adding a known radical- or cationic-polymerization initiator.
- the organic monomer is an addition-polymerizable or condensation-polymerizable organic monomer
- the polymerizable reaction is carried out by adding an amine compound such as triethylenediamine, hexamethylenetetraamine, N,N-dimethyloctylamine, N,N,N′,N′-tetramethyl-1,6-diaminohexane, 4,4′-trimethylenebis(1-methylpiperidine) or 1,8-diazabicyclo[5.4.0]-7-undecene; or an organic metal compound such as dimethyltin dichloride, dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate
- a known sensitizer such as benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropane-1-one or acylphosphine oxide may be added to increase the reactivity.
- a known sensitizer such as benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin e
- the above polymerization reaction can be carried out either as solution polymerization or bulk polymerization.
- Polymerization can be carried out by subjecting a mixture of the organic components and the inorganic components to heat or to irradiation with light.
- Exemplary methods for preparing the organic-inorganic hybrid material include:
- a polycondensation product is used as the organic polymer or a water-unstable organic monomer is used, following preparation of the dispersoid having metal-oxygen bonds, it is preferable to add an organic polymer or an organic monomer.
- the organic-inorganic hybrid material of the invention has a high refractive index and a high transmittance to visible light, and so is preferably used as an optical material.
- an optical material may be suitably added, if desired, ultraviolet absorbers, dyes and pigments to improve the light absorbing properties, antioxidants and discoloration inhibitors to improve weather resistance, and parting agents to improve moldability.
- ultraviolet absorbers include benzotriazole, benzophenone and salicylic acid compounds.
- Exemplary dyes and pigments include anthraquinone and azo compounds.
- Exemplary antioxidants and discoloration inhibitors include monophenol, bisphenol, polymeric phenol, sulfur-bearing compounds and phosphorus-bearing compounds.
- Exemplary parting agents include fluorinated surfactants, silicone surfactants, acid phosphoric ester and higher fatty acids.
- the method of producing the optical material of the invention typically involves preparing a uniform mixture composed of, for example, the metal-oxygen bond-bearing dispersoid, the organic monomer, a monomer copolymerizable with the organic monomer, additives and a catalyst.
- the monomer is a radical-polymerizable monomer
- a known cast polymerization process may be used in which the mixture is poured into a mold consisting of the combination of a mold body made of glass or resin, that has transmits ultraviolet light, and a resin gasket, then is irradiated with ultraviolet light to effect curing.
- the monomer is an addition-polymerizable or condensation-polymerizable monomer, the mixture may be heated and cured.
- the mold may be treated beforehand with a parting agent or a parting agent may be included in the uniform mixture.
- a parting agent may be included in the uniform mixture.
- the heating temperature and time will vary according to such factors as the amount of ultraviolet irradiation energy, but are generally 30 to 150° C. and 0.2 to 24 hours.
- Optical materials obtained by production methods such as (1) and (4) above in which preparation of the organic polymer has already been finished can be shaped by, for example, casting the solution in a mold.
- the optical material of the invention can easily be dyed in water or an organic solvent using a conventional disperse dye. To facilitate dyeing at this time, a carrier may be added and heating carried out.
- the present invention also provides optical products made of optical materials obtained as just described.
- optical products include plastic optical lenses such as eyeglass lenses, prisms, optical fibers, substrates for recording media, filters, and drinking glasses and vases.
- plastic optical lenses and particularly eyeglass lenses, are preferred.
- the optical material of the invention can be coated onto the surface of a lens or drinking glass, for example, and cured if necessary by carrying out an operation such as light exposure, enabling it to be used as a starting material for a hard coating that protects the surface or for a multilayer antireflection coating that prevents reflection.
- coating methods include dip coating, spin coating, flow coating, roller coating and brush coating.
- the method of making the monomolecular film of the invention is characterized by contacting a metallic surfactant having at least one hydrolyzable group with a metal oxide film according to the invention.
- the metallic surfactant having at least one hydrolyzable group is not subject to any particular limitation, provided it has a hydrolyzable functional group, can react through the functional group with an active hydrogen on the substrate surface to form a bond, and can have on the same molecule both a hydrophilic site capable of forming the bond and a hydrophobic site.
- Preferred examples include compounds of formula (II).
- R 1 is a monovalent hydrocarbon group, a monovalent hydrocarbon group having a substituent, a monovalent halogenated hydrocarbon group, a monovalent halogenated hydrocarbon group having a substituent, a monovalent hydrocarbon group which includes a linkage or a monovalent halogenated hydrocarbon group which includes a linkage; if the letter n is 2 or more, each R 1 may be like or unlike.
- R 1 is a monovalent hydrocarbon group
- alkyl groups of 1 to 30 carbons, alkenyl groups of 1 to 30 carbons, and aryl groups are preferred.
- group here refers to a group in which one or more hydrogen atom on the hydrocarbon group has been substituted with a halogen atom; groups in which two or more hydrogen atoms on an alkyl group have been substituted with halogen atoms are preferred.
- Suitable halogen atoms include fluorine atoms, chlorine atoms and bromine atoms. Fluorine atoms are preferred.
- R 1 is a fluorinated alkyl group
- a linear or branched structure is preferred. If the structure is branched, the branched portion preferably is a short chain of about 1 to 4 carbons.
- the terminal carbon atom is preferably a group having one or more fluorine atoms bonded thereto; a group having a CF 3 moiety composed of three fluorine atoms bonded to a terminal carbon atom is especially preferred.
- the carbon chain may instead be one which is terminated with a fluorine-unsubstituted hydrocarbon group and is substituted with fluorine at the interior thereof.
- the number of fluorine atoms on the fluorinated alkyl group is preferably at least 60%, and more preferably at least 80%.
- the fluorinated alkyl group is preferably a group terminated with a perfluoroalkyl moiety, which is an alkyl group in which all the hydrogen atoms have been substituted with fluorine atoms, and having, between the perfluoroalkyl moiety and the metal atom, a (CH 2 ) h -(where the letter h is an integer from 1 to 6, and preferably 2 to 4) group.
- a perfluoroalkyl moiety which is an alkyl group in which all the hydrogen atoms have been substituted with fluorine atoms, and having, between the perfluoroalkyl moiety and the metal atom, a (CH 2 ) h -(where the letter h is an integer from 1 to 6, and preferably 2 to 4) group.
- R 1 is a monovalent hydrocarbon group having a substituent
- this refers to a group in which a hydrogen atom on the monovalent hydrocarbon group is substituted with a substituent.
- R 1 is a monovalent halogenated hydrocarbon group having a substituent
- this refers to a group in which a hydrogen atom or halogen atom on the monovalent halogenated hydrocarbon group is substituted with a substituent.
- Illustrative examples of the substituent in these groups include carboxyl, amide, imide, ester and hydroxyl groups. The number of substituents on these groups is preferably from 1 to 3.
- R 1 is a monovalent hydrocarbon group having a linkage or a monovalent halogenated hydrocarbon group having a linkage
- R 1 is exemplified by monovalent hydrocarbon or monovalent halogenated hydrocarbon groups having a linkage between carbon-carbon bonds, and monovalent hydrocarbon or monovalent halogenated hydrocarbon groups having a linkage bonded to the end of the group that bonds to the metal atom.
- Preferred linkages include —O—, —S—, —COO— and —CONR 21 — (wherein R 21 is a hydrogen atom or an alkyl group).
- R 1 is preferably methyl, a fluoroalkyl group, or a fluoroalkyl group having a linkage.
- R 1 is a fluorinated alkyl group or a fluorinated alkyl group having a linkage include the following:
- Y in formula (II) represents a hydrolyzable group, specific examples of which include alkoxy groups of 1 to 6 carbons, acyloxy groups of 1 to 6 carbons, halogen atoms, isocyanate groups, amino groups and amide groups.
- each Y may be like or unlike.
- Alkoxy groups of 1 to 6 carbons that may be substituted, halogen atoms and isocyanate groups are especially preferred.
- hydrolyzable groups are functional groups which are capable of incurring hydrolysis and forming a bond with another functional group having an active hydrogen, for the sake of convenience, in this specification, the hydroxyl group is included among the hydrolyzable groups.
- n in formula (II) is any integer from 1 to (m ⁇ 1). To produce a high-density chemisorption film, it is preferable for the letter n to be 1.
- M represents an atom selected from the group consisting of silicon, germanium, tin, titanium and zirconium atoms. For such reasons as the availability of starting materials and reactivity, a silicon atom is preferred.
- R 2 represents an alkylene group, a vinylene group, an ethynylene group, an arylene group or a divalent functional group containing a silicone atom and/or an oxygen atom.
- Z is a hydrogen atom, an alkyl group or a fluoroalkyl group, and the letter r is 0 or any integer from 1 to (m ⁇ 2). To produce a high-density adsorption film, it is preferable for the letter r to be 0.
- compounds of formula (II) also include:
- the compound of formula (II) include the compounds of the following formulas in which the metal atom is a silicon atom.
- the hydrolyzable groups are not limited to the functional groups shown in the examples; other hydrolyzable groups may likewise be used.
- the above-described metallic surfactant may be used singly or as combinations of two or more thereof. Generally, it is used after dilution with a solvent. If necessary, it may be used together with water in an organic solvent and in the presence of a metal oxide or metal alkoxide partial hydrolysate.
- the method of coating or spraying the metal oxide-containing solution onto the substrate is not subject to any particular limitation, so long as it can smoothly apply the solution to the surface.
- suitable methods include dipping, spin coating, Meyer bar coating and brush coating.
- any method of bringing the metallic surfactant into contact with the substrate may be used without particular limitation, although dipping is preferred for forming a uniform monomolecular film.
- the content of the metallic surfactant within the solution is not subject to any particular limitation, although a silane compound solution in a range of 0.1 to 30 wt % is preferable for producing a dense monomolecular film.
- Plastic substrates that may be used in the invention include sheet, plate-like substrates and films, with films being especially preferred. Specific examples include cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate, syndiotactic polystyrene, polyethylene-coated paper, polyether sulfone, polyarylate, polyvinylidene fluoride and Teflon (registered trademark).
- the substrate may be a flat plate, a three-dimensional object or a film. Even a painted object may be used.
- These substrates may be provided with a polyvinylidene chloride-type polymer-containing waterproofing layer so as to enhance dimensional stability; i.e., the stability to dimensional changes from changes in temperature and humidity.
- an organic and/or inorganic compound thin film may be provided as a gas barrier.
- organic thin films include polyvinyl alcohol, and poly(ethylene-co-vinyl alcohol).
- inorganic compounds include silica, alumina, talc, vermiculite, kaolinite, mica and synthetic mica.
- Various organic and/or inorganic additives may also included in the substrate to confer other capabilities as well.
- FIG. 1 is shows the UV properties of the titanium alkoxide low-temperature hydrolysate prepared in Example 1.
- FIG. 2 is shows the UV properties of the titanium alkoxide low-temperature hydrolysates prepared in Examples 3, 5, 7 and 9.
- FIG. 3 shows the Raman spectra for the solutions prepared in Examples 4 and 8 and Comparative 3.
- FIG. 4 shows the particle size distribution for Sol Solution 1 in Example 35.
- FIG. 5 is a graph showing the results of thermogravimetry on the powder in Example 36.
- FIG. 6 shows the particle size distribution for Sol Solution-2 in Example 38.
- FIG. 7 shows the UV properties of the titanium alkoxide hydrolysate prepared in Example 39.
- FIG. 8 shows the light transmittances of the sol solutions in Examples 41 and 45.
- FIG. 9 shows the particle size distribution for the sol solution in Example 41.
- FIG. 10 shows the results of thermogravimetry on the sol solution in Example 43.
- FIG. 11 shows the surface shape of the metal oxide film formed in Example 44.
- FIG. 12 shows the particle size distribution of the sol solution obtained in Example 45.
- FIG. 13 shows the particle size distribution of the sol solution obtained in Example 47.
- FIG. 14 shows the surface shape of the film obtained from solution C-1 in Example 48.
- FIG. 15 shows the elemental composition in the depth direction of the film formed in Example 48.
- FIG. 16 shows the elemental composition in the depth direction near the surface of the film formed in Example 48.
- FIG. 17 shows the surface shape of the STS-01 film in Comparative Example 10.
- FIG. 1 The UV properties of the solution prepared as described above are shown in FIG. 1 .
- FIG. 1 also shows the UV properties of the titanium tetraisopropoxide.
- the low-temperature hydrolysate had a better ability to block UV radiation than the titanium tetraisopropoxide, indicating the growth of Ti—O—Ti bonds.
- Example 1 Aside from changing the weight of the distilled water added to 1.0 g (55.6 mmol), the same procedure was carried out as in Example 1. The appearance at this time of the resulting tetrahydrofuran solution is indicated in Table 1.
- Example 1 Aside from changing the weight of the distilled water added to 1.2 g (66.7 mmol), the same procedure was carried out as in Example 1. The appearance at this time of the resulting tetrahydrofuran solution is indicated in Table 1.
- Example 1 The tetrahydrofuran solution obtained in Example 1 was vacuum concentrated with a rotary evaporator at a bath temperature of 50° C., giving a clear, light yellow viscous liquid having a titanium oxide equivalent concentration of 40.2 wt %. When tetrahydrofuran solvent was added to this liquid, it re-dissolved.
- Example 3 The solution obtained in Example 3 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 54.3 wt %.
- the Raman spectrum of the solution thus obtained is shown in FIG. 3 .
- toluene solvent was added to this liquid, re-dissolution occurred.
- the appearance at this time of the toluene-isopropanol mixed solution obtained at this time is indicated in Table 2.
- Example 5 The solution obtained in Example 5 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 41.1 wt %. Toluene solvent was added to this liquid, whereupon re-dissolution occurred. The appearance at this time of the toluene-isopropanol mixed solution obtained is indicated in Table 2.
- Example 7 The solution obtained in Example 7 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 45.7 wt %. Toluene solvent was added to this liquid, whereupon re-dissolution occurred. The appearance at this time of the toluene-isopropanol mixed solution obtained is indicated in Table 2.
- Example 9 The solution obtained in Example 9 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 50.8 wt %. Toluene solvent was added to this liquid, whereupon re-dissolution occurred. The appearance at this time of the toluene-isopropanol mixed solution obtained is indicated in Table 2.
- Example 11 The solution obtained in Example 11 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a zirconium oxide equivalent concentration of 43 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- Example 13 The solution obtained in Example 13 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a tantalum oxide equivalent concentration of 64.5 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- Example 15 The solution obtained in Example 15 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a concentrate having a metal oxide equivalent concentration of 70 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- a partial hydrolysate of titanium tetraisopropoxide (the product obtained by adding 0.9 mole of water per mole of titanium isopropoxide and hydrolyzing) was dissolved in 402.74 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to ⁇ 80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 3.38 g of ion-exchanged water was mixed into 30.42 g of isopropanol, following which the mixture was cooled to ⁇ 80 to ⁇ 70° C. and added dropwise in this cooled state to the four-neck flask under stirring.
- Example 17 The solution obtained in Example 17 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 52.3 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- a tetrahydrofuran solution containing the titanium isopropoxide hydrolysate prepared in Example 1 was cooled in a dry ice-containing methanol bath (approx. ⁇ 74° C.), and a tetrahydrofuran solution containing 4.2 g of 2,5-bis(mercaptomethyl)-1,4-dithiane (DMMD) and 4.6 g of 2,5-bis(isocyanatomethyl)-1,4-dithiane (BIMD) was added dropwise and mixed under stirring. Following addition, the temperature was gradually returned to room temperature, then 0.06 g of dibutyltin dilaurate (available from Nakalai Tesque, Inc.) was added and the mixture was stirred.
- DMMD 2,5-bis(mercaptomethyl)-1,4-dithiane
- BIMD 2,5-bis(isocyanatomethyl)-1,4-dithiane
- the solvent was then removed by distillation, and the mixture was degassed.
- the mixture was poured into a glass mold and the mold was tightly closed, following which the temperature was gradually raised from room temperature to 120° C. and polymerization was carried out for 24 hours under heating.
- the contents were then cooled to room temperature and removed from the mold, giving a transparent mass.
- the refractive index of the resulting mass was measured with an Abbe refractometer. The refractive index is shown in Table 3.
- Example 19 Aside from using 1.5 g of the titanium isopropoxide hydrolysate-containing tetrahydrofuran solution prepared in Example 1, the same procedure was carried out as in Example 19. The results are presented in Table 3.
- Example 19 Aside from not using the titanium isopropoxide hydrolysate-containing tetrahydrofuran solution, the same procedure was carried out as in Example 19. The refractive index of the body thus obtained is shown in Table 3.
- a 30 ⁇ 15 mm silicon wafer was dipped in this clear solution and pulled out vertically at a rate of 0.1 mm per second, thereby forming a clear thin-film on the wafer.
- the reflectance spectrum of this thin-film was measured using a Filmetrics F series, model F20 film thickness measurement system (manufactured by Litho Tech Japan). This spectrum was superimposed with a simulation spectrum obtained by changing the optical constant, and the thickness and refractive index at 633 nm of this thin film were measured. The film thickness and refractive index at this time are shown in Table 4.
- Example 21 Aside from preparing a titanium tetraisopropoxide hydrolysate-containing toluene solution by the same method as in Example 21, but in toluene rather than tetrahydrofuran, the same procedure was carried out as in Example 21, giving a clear colorless solution.
- Example 21 This clear solution was used as in Example 21 to form a thin film, and the film thickness and refractive index were measured. The results are given in Table 4.
- Example 21 Aside from preparing a titanium tetraisopropoxide hydrolysate-containing solution by the same method as in Example 21, but using isopropanol instead of tetrahydrofuran to dilute the distilled water, the same procedure was carried out as in Example 21, giving a clear solution.
- Example 21 This clear solution was used as in Example 21 to form a thin film, and the film thickness and refractive index were measured.
- the film thickness was 134 nm and the refractive index was 1.87.
- a tetrahydrofuran solution prepared in the same way as in Example 1 was applied to a glass substrate with a bar coater (No. 5), then dried at 150° C. for 30 minutes, giving a 0.1 ⁇ m thick titanium oxide film.
- This film had a contact angle with water of 42°.
- the contact angle decreased to 12°, indicating good hydrophilicity. This change was probably due to the elimination of residual isopropoxy groups due to UV exposure.
- Example 17 The solution obtained in Example 17 was coated onto a glass substrate with a bar coater (No. 5), then dried at 150° C. for 30 minutes, thereby giving a 0.1 ⁇ l thick titanium oxide film.
- This film had a contact angle with water of 28°.
- the contact angle decreased to 3°, indicating good hydrophilicity. Elemental analysis of the thin film using an XPS spectrometer (Quantum 2000, manufactured by Ulvac Phi, Inc.) showed that the elemental concentration of carbon (formula I) in the film following UV irradiation was less than 5%.
- Elemental concentration of carbon [(elemental concentration of carbon)/(elemental concentration of carbon+elemental concentration of titanium+elemental concentration of oxygen)] ⁇ 100
- a solution was prepared by mixing 270 g of the solution obtained in Example 17 with 30 g of a solution obtained by diluting a photocatalyst titania sol (TKS-251, produced by Tayca Corporation) with toluene to a solids content of 5 wt %.
- the resulting solution was applied to a glass substrate and an aluminum metal substrate by dipping, then dried at 100° C. to give a 0.3 ⁇ m thick film in each case.
- a toluene solution prepared in the same way as in Example 13 was applied with a bar coater (No. 5) onto a gold electrode-coated glass substrate and dried at 150° C. for 30 minutes to give a tantalum oxide film having a thickness of 0.1 ⁇ m.
- a gold electrode was applied by sputtering on top of the film, and the permittivity of the film was measured.
- the film had a permittivity of 18.
- Fine particles of ITO (produced by Sumitomo Metal Mining) were added in an amount of 5 wt % (ITO basis) to the solution obtained in Example 15, following which the mixture was applied with a bar coater (No. 7) to a PET substrate, and dried at 120° C. for 30 minutes, giving a film having a thickness of 0.2 ⁇ m.
- This film was UV irradiated for 10 minutes using a high-pressure mercury vapor lamp.
- the resulting film had a surface resistivity of 350 ⁇ /sq.
- Example 30 Aside from using titanium tetraisopropoxide in place of titanium oxide, a film was formed in the same way as in Example 30. The results are shown in Table 6. The film turned white, and so a clear film was not obtained.
- a dropping funnel capable of being cooled was charged with a solution of 12.4 g (0.69 mol) of distilled water (collected with Advantec GS-200 system) dissolved in 122 g of anhydrous isopropanol (water content, 3.6 ppm), then cooled with dry ice-containing methanol to about ⁇ 40 to ⁇ 35° C.
- this cooled water-isopropanol solution was added in a dropwise manner over a period of 1.5 hours to the toluene solution of titanium tetraisopropoxide, during which time the reaction mixture was held at about ⁇ 40 to ⁇ 35° C.
- a clear titanium tetraisopropoxide hydrolysate solution (a sol having a titanium oxide equivalent concentration of 5 wt %, referred to below as “Sol Solution 1”).
- the wavelength of light having a transmittance through this solution of 50% was 358 nm.
- the sol had an average particle size of 4.5 nm and a sharp, monodispersed particle size distribution.
- FIG. 4 shows the particle size distribution of the sol in the resulting Sol Solution 1.
- the abscissa represents the particle size (nm) and the ordinate represents the peak intensity (%).
- Sol Solution 1 obtained in Example 1 was completely concentrated on a rotary evaporator, giving a powder having a titanium oxide equivalent concentration of 50 wt %. Upon submitting 3.45 mg of this powder to thermogravimetric analysis, an endothermic peak temperature was observed at 255° C. and an exothermic peak temperature was observed at 355° C.
- the thermogravimetric results are shown in FIG. 5 .
- the abscissa represents the measurement temperature (Temperature/° C.)
- the left-hand ordinate represents the percent weight loss (Weight %)
- the right-hand ordinate represents heat flow (Heat Flow/ ⁇ V).
- Plot (1) is the weight change versus temperature
- Plot (2) is the heat flow versus temperature.
- Example 1 The solution obtained in Example 1 was applied with a No. 3 bar coater onto a polyethylene terephthalate (PET) substrate having an ozone treated surface, then dried at 100° C. for 10 minutes to form a titanium oxide film on the substrate, thereby giving a PET substrate bearing a titanium oxide film.
- Measurement of the titanium oxide film surface shape using an SPM system (SPA-400 (SII), manufactured by Seiko Instruments, Inc.) showed that the surface had an average roughness of less than 5 nm, indicating excellent smoothness.
- Sol Solution 2 was a composite of particles having a broad particle size distribution in which the average particle size of primary particles was 5.3 nm, the average particle size of secondary particles was 28.5 nm, and the average particle size of tertiary particles was 187 nm.
- FIG. 6 shows the particle size distribution of the sol within Sol Solution 2.
- the abscissa represents particle size (nm)
- the ordinate represents f(Is) (%).
- the UV properties of the solution thus prepared were measured using a mixture of 95.73 g of anhydrous toluene and 30.42 g of anhydrous IPA as the baseline. Measurement was carried out at an oxide concentration in each solution of about 3.4%. The results are shown in FIG. 7 .
- FIG. 7 also shows the UV properties for titanium tetraisopropoxide. It is apparent from a comparison of the results obtained for the two solutions that the low-temperature hydrolysate had a much better ability to block UV radiation than the titanium tetraisopropoxide, indicating the growth of Ti—O—Ti bonds.
- Example 1 The clear, colorless liquid obtained in Example 1 was vacuum concentrated with a rotary evaporator at a bath temperature of 50° C., thereby giving a viscous liquid that was crusty on top. This liquid easily re-dissolved in anhydrous toluene, anhydrous tetrahydrofuran or anhydrous diethyl ether. It dissolved less readily in anhydrous isopropanol, although dissolution was possible.
- This solution was refluxed for 2 hours at 90 to 100° C., giving a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %.
- the wavelength of light having a transmittance of 50% through this solution was 358 nm ( FIG. 8 ).
- the sol had an average particle size of 6.5 nm and a sharp, monodispersed particle size distribution ( FIG. 9 ).
- Example 41 The solution obtained in Example 41 was vacuum concentrated on a rotary evaporator at a bath temperature of 50° C., yielding a white solid having a titanium oxide equivalent concentration of 56.2 wt %. This re-dissolved when toluene solvent was added. The clear solution obtained after re-dissolution was a monodisperse sol having an average particle size of 7.0 nm.
- Example 41 The solution obtained in Example 41 was concentrated on a rotary evaporator to a solution having a titanium oxide equivalent concentration of 30 wt %. Upon submitting a 3.45 mg sample of this yellow viscous liquid to thermogravimetric analysis, an endothermic peak was observed at 247° C. and an exothermic peak was observed at 357° C. ( FIG. 10 ).
- Example 41 The solution obtained in Example 41 was applied with a No. 3 bar coater onto a polyethylene terephthalate (PET) substrate having an ozone treated surface, then dried at 100° C. for 10 minutes to form a metal oxide film on the substrate.
- the metal oxide film of the invention had an excellent surface smoothness ( FIG. 11 ).
- This solution was refluxed for 2 hours at 90 to 100° C., giving a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %.
- the wavelength of light having a transmittance of 50% through this solution was 358 nm ( FIG. 8 ).
- the sol had an average particle size of 5.6 nm and a sharp, monodispersed particle size distribution ( FIG. 12 ).
- Example 45 The solution obtained in Example 45 was vacuum concentrated on a rotary evaporator at a bath temperature of 50° C., yielding a white solid having a titanium oxide equivalent concentration of 54.8 wt %. This re-dissolved when toluene solvent was added. The clear solution obtained after re-dissolution was a monodisperse sol having an average particle size of 6.1 nm.
- the liquid temperature of the flask during dropwise addition was held at ⁇ 75 to ⁇ 70° C. Following the completion of dropwise addition, the flask contents were held at ⁇ 70° C. for 30 minutes, then the temperature was raised to room temperature over a period of 3 hours, following which stirring was continued for 1 hour, giving a clear, colorless liquid.
- This solution was refluxed at 90 to 100° C. for 2 hours, giving a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %.
- the sol was a composite of particles having a broad particle size distribution in which the average particle size of primary particles was 5.3 nm, the average particle size of secondary particles was 28.5 nm, and the average particle size of tertiary particles was 187 nm ( FIG. 13 ).
- Heptadecatrifluorodecyl trimethoxysilane (FAS-17, produced by Shin-Etsu Chemical Co., Ltd.) was diluted with anhydrous toluene to form a solution (C-6) having a solids concentration of 0.5 wt %.
- the metal oxide film-bearing substrate obtained as described above was cleaned with ozone gas for 2 minutes then immersed in solution (C-6) for 10 minutes and dried at 60° C. for 10 minutes, thereby forming a chemisorption film composed of FAS-17.
- C-6 ozone gas
- C-6 isopropyl alcohol
- 5 ⁇ l amounts of water, toluene (Tol) and isopropyl alcohol (IPA) were placed on the surface of the FAS-17 film and the contact angles, 60 seconds later, were measured using a contact angle goniometer (model 360S, manufactured by Erma, Inc.).
- the values obtained were 106° (water), 62° (toluene) and 40° (IPA), indicating adequate water repellency.
- the surface had an average roughness of 2.3 nm, it was apparent that the FAS-17 film had formed to a high density on the surface of the substrate.
- Example 48 solutions were coated with bar coaters of the indicated No. onto the substrates shown in Table 7 that had been administered surface ozone treatment if necessary, then were dried at a specific drying temperature, giving metal oxide films.
- monomolecular films made of a self-organizing film was formed on the metal oxide films in the same way as in Example 48. The results for these examples are presented in Table 7, along with the results for Example 48.
- Monomolecular films made of self-organizing films having a good adhesion and contact angle were obtained on polyester (PET) substrates and acrylic substrates.
- a solution prepared by diluting a titanium oxide fine particle sol solution (Ishihara Sanyo Kaisha, Ltd.; particle size, 7 nm; referred below as “solution C-9”) with ethanol to 1 wt % was coated, as in Example 48, with a No. 3 bar coater onto an acrylic substrate or a soda lime glass substrate having an ultrasonically cleaned surface with an average roughness of 2 nm, then dried at 150° C. for 30 minutes, thereby forming a thin film on the substrate.
- the results are shown in Table 7. Measurement of the thin-film surface shape using an SPM system (SPA-400 (SII), manufactured by Seiko Instruments, Inc.) indicated that each of these metal oxide films had an average surface roughness of 45 nm. These films had a poor adhesion and poor wear resistance ( FIG. 17 ).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Wood Science & Technology (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Colloid Chemistry (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Dispersoids having metal-oxygen groups that are suitable for the production of metal oxide thin-films at a low temperature of 200° C. or below and for the production of homogeneous organic-inorganic hybrid materials. The dispersoid having metal-oxygen bonds may be obtained by mixing a metal compound having at least three hydrolyzable groups with at least 0.5 mole but less than 2 moles of water per mole of the metal compound in an organic solvent, in the absence of an acid, a base, and/or a dispersion stabilizer, and at a temperature at or below the temperature at which the metal compound begins to hydrolyze, then raising the temperature to at least the temperature at which hydrolysis begins.
Description
- This is a divisional of U.S. application Ser. No. 10/533,580, filed Dec. 30, 2005, which is a National Stage Application of PCT/JP2003/014367, filed Nov. 12, 2003, and claims the benefit of Japanese Patent Application Nos. 2002-329097, filed Nov. 13, 2002, 2002-330837, filed Nov. 14, 2002, 2003-024148, filed Jan. 31, 2003, 2003-057173, filed Mar. 4, 2003, and 2003-179243, filed Jun. 24, 2003. The entire disclosures of the prior applications are hereby incorporated by reference herein in their entirety.
- The present invention relates to dispersoids having metal-oxygen bonds, metal oxide films produced from such dispersoids, and organic-inorganic hybrid materials in which the inorganic component is or includes such a dispersoid.
- Metal oxide sols are useful as metal oxide film-forming materials, as the inorganic component in organic-inorganic hybrid materials, and in other applications. Several methods of preparation are known.
- One specific example, described in JP A 10-298769, is a method of preparing a metal oxide precursor sol by hydrolyzing and polymerizing one or more metal compound, which method is characterized by carrying out the addition of water to the metal compound at a temperature of −20.degree. C. or below.
- JP A 1-129032 describes a method for preparing an organic solvent-soluble high-molecular-weight ladder-type polytitanoxane by hydrolyzing titanium tetraalkoxide using 1.0 to 1.7 moles of water per mole of the titanium tetraalkoxide at a temperature of 20 to 90.degree. C. The object of this method is to provide a high-molecular-weight ladder-type polytitanoxane which, in spite of being a high-molecular-weight compound, dissolves in organic solvents and forms a dense thin-film.
- JP A 2001-342018 describes a method for preparing a metal oxide precursor solution which involves adding an alcohol solution containing 0.1 to 2.0 moles of water to 1 mole of a metallic salt partially hydrolyzed by the addition of water and the application of heat, then heating so as to hydrolyze the metallic salt and form a metal hydroxide, followed by dehydrative condensation then concentration.
- However, the sol particles thus obtained agglomerate, resulting in a large particle size, and thus fail to provide a satisfactory performance when rendered into a metal oxide film or even when prepared as a hybrid with an organic component.
- Moreover, in sols obtained by hydrolyzing a metal alkoxide using an acid or base, dehydrative condensation, distilling off the solvent, water and acid or base, and bulk polymerization, complete removal of the water and the acid or base used is difficult and what remains of these has an effect on the polymerization reaction. Particularly when solution polymerization is carried out in an organic solvent, stabilizing the presence of metal alkoxide hydrolysates within the solution requires the use of an acid, base or dispersion stabilizer. Unfortunately, these inhibit polymerization or adversely affect the physical properties of the product. Furthermore, the above-mentioned inorganic-organic hybrids made with a titanium oxide gel generally tend to have a lower transmittance that inorganic-organic hybrids made with other metal oxide gels, which suggests that the titanium oxide agglomerates in the concentration stage following hydrolysis and dehydrative condensation.
- By using a method which involves adding a multidentate compound to stabilize the metal alkoxide and thus hold down the rate of metal alkoxide hydrolysis, a homogeneous film-forming sol can easily be prepared. However, much organic matter resistant to high-temperature degradation is also present in the sol or gel film, and so heat treatment at an elevated temperature of about 500° C. is required to remove such organic matter. Moreover, the residual presence of much organic matter in the gel film results in a greater weight loss by the film when it is heat treated. In other words, the removal of organic matter from the gel film causes numerous pores to form in the film, creating defects in the resulting metal oxide thin-film that prevent the mechanical, optical, electrical and other properties of the metal oxides from being fully achieved. These thin-films can be densified to eliminate pores in the film, but doing so requires excessive energy. In addition, as noted above, methods which use metallic salts are basically thermal degradation processes, and lead to many problems with film quality following heat treatment.
- It is therefore an object of the invention to provide fine dispersoids which can be stably dispersed in an organic solvent even in the absence of an acid, base or dispersion stabilizer, are capable of producing metal oxide films that are dense and have a smooth surface, and are capable of producing organic-inorganic hybrid materials that are transparent and homogeneous.
- We have conducted extensive investigations, as a result of which we have discovered that the above-described problems can be resolved by adding a given amount of water at a low temperature to a metal compound having hydrolyzable groups, diluting the water to be added in a specific solvent system, even at room temperature, and adding the water in divided amounts at a low temperature.
- Accordingly, the present invention provides the following:
- (1) A dispersoid having metal-oxygen bonds which is obtained by mixing a metal compound having at least three hydrolyzable groups with a given amount of water in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, which dispersoid is characterized in that the given amount of water is at least 1.0 mole but less than 2.0 moles per mole of the metal compound, and the given temperature is a temperature below 0° C.;
- (2) A dispersoid having metal-oxygen bonds which is obtained by mixing a metal compound having at least three hydrolyzable groups with a given amount of water in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, which dispersoid is characterized in that the given amount of water is at least 0.5 mole but less than 1.0 mole per mole of the metal compound, and the given temperature is a temperature below 0° C.;
- (3) The dispersoid having metal-oxygen bonds of (1) or (2) above which is characterized in that the given temperature is a temperature of −20° C. or below;
- (4) The dispersoid having metal-oxygen bonds of (1) or (2) above which is characterized in that the given temperature is at or below the temperature at which the metal compound begins to hydrolyze;
- (5) The dispersoid having metal-oxygen bonds of (1) or (2) above which is characterized in that the given temperature is a temperature in a range of −50 to −100° C.;
- (6) The dispersoid having metal-oxygen bonds of any one of (1) to (5) above which is characterized by using an organic solvent in the step in which the metal compound and the given amount of water are mixed;
- (7) The dispersoid having metal-oxygen bonds of any one of (1) to (6) above which is characterized in that the step in which the metal compound and the given amount of water are mixed is a step in which the given amount of water is added to the metal compound;
- (8) The dispersoid having metal-oxygen bonds of (7) above which is characterized in that the step in which the given amount of water is added to the metal compound is a step in which the given amount of water is added to an organic solvent solution of the metal compound;
- (9) The dispersoid having metal-oxygen bonds of any one of (6) to (8) above which is characterized in that the organic solvent is a hydrocarbon solvent or an ether solvent;
- (10) The dispersoid having metal-oxygen bonds of any one of (1) to (9) above which is characterized in that the given amount of water is a solution diluted with a water-soluble organic solvent;
- (11) The dispersoid having metal-oxygen bonds of (10) above which is characterized in that the water-soluble organic solvent is an alcohol solvent;
- (12) The dispersoid having metal-oxygen bonds of any one of (1) to (11) above which is characterized by being obtained by, following mixture of the metal compound and the water at the given temperature, raising the temperature to the given temperature or above;
- (13) A dispersoid having metal-oxygen bonds obtained by mixing, in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, a partial hydrolysate that is prepared by hydrolyzing a metal compound having at least three hydrolyzable groups in the absence of an acid, a base and/or an dispersion stabilizer and that can be stably dispersed without aggregation in an organic solvent with an amount of water equal to at least 0.5 mole but less than 2 moles per mole of the metal compound minus the amount of water used to prepare the partial hydrolysate, which dispersoid is characterized in that the given temperature is a temperature below 0° C.;
- (14) The dispersoid having metal-oxygen bonds of (13) above which is characterized in that the given temperature is a temperature of −20° C. or below;
- (15) The dispersoid having metal-oxygen bonds of (13) or (14) above which is characterized in that the given temperature is at or below the temperature at which the metal compound begins to hydrolyze;
- (16) The dispersoid having metal-oxygen bonds of (13) or (14) above which is characterized in that the given temperature is a temperature in a range of −50 to −100° C.;
- (17) The dispersoid having metal-oxygen bonds of any one of (13) to (16) above which is characterized by using an organic solvent in the step in which the partial hydrolysate and the given amount of water are mixed;
- (18) The dispersoid having metal-oxygen bonds of any one of (13) to (17) above which is characterized in that the step in which the partial hydrolysate and the given amount of water are mixed is a step in which the given amount of water is added to the partial hydrolysate;
- (19) The dispersoid having metal-oxygen bonds of (18) above which is characterized in that the step in which the given amount of water is added to the partial hydrolysate is a step in which the given amount of water is added to an organic solvent solution of the partial hydrolysate;
- (20) The dispersoid having metal-oxygen bonds of any one of (17) to (19) above which is characterized in that the organic solvent is a hydrocarbon solvent or an ether solvent;
- (21) The dispersoid having metal-oxygen bonds of any one of (13) to (20) above which is characterized in that the given amount of water is a solution diluted with a water-soluble organic solvent;
- (22) The dispersoid having metal-oxygen bonds of (21) above which is characterized in that the water-soluble organic solvent is an alcohol solvent;
- (23) The dispersoid having metal-oxygen bonds of any one of (13) to (22) above which is characterized by being obtained by, following mixture of the partial hydrolysate and the water at the given temperature, raising the temperature to the given temperature or above;
- (24) A dispersoid having metal-oxygen bonds which is obtained by mixing a metal compound having at least three hydrolyzable groups with a given amount of water in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, which dispersoid is characterized in that the given amount of water is a solution diluted with a hydrocarbon solvent and an alcohol solvent, the diluted solution is added to the metal compound, and the given temperature is room temperature;
- (25) The dispersoid having metal-oxygen bonds of (24) above which is characterized in that the given amount of water is at least 0.5 mole but less than 2.0 moles per mole of the metal compound;
- (26) The dispersoid having metal-oxygen bonds of (24) or (25) above which is characterized in that the water in the diluted solution has a concentration that is from 40% to 1% of the saturation solubility of water in a mixed solvent of the hydrocarbon solvent and the alcohol solvent;
- (27) A dispersoid having metal-oxygen bonds which is obtained by the addition, to a metal compound having least three hydrolyzable groups, of at least 0.5 mole but less than 2 moles of water per mole of the metal compound, which dispersoid is characterized by having steps in which the water is added in a some of divided portions at a given temperature, which steps include at least one step in which the given temperature is a temperature below 0° C.;
- (28) A dispersoid having metal-oxygen bonds which is obtained by the addition, to a metal compound having least three hydrolyzable groups, of at least 0.5 mole but less than 2 moles of water per mole of the metal compound, which dispersoid is characterized by having steps in which the water is added in a some of divided portions, at least 0.5 mole but less than 1 mole of the water per mole of the metal compound being added in a first water addition step;
- (29) The dispersoid having metal-oxygen bonds of (28) above which is characterized by having, after the first water addition step, a step in which the rest of the required amount of water is added at a given temperature, the given temperature being a temperature below 0° C.;
- (30) The dispersoid having metal-oxygen bonds of (27) or (29) above which is characterized in that the given temperature is a temperature of −20° C. or below;
- (31) The dispersoid having metal-oxygen bonds of (27) or (29) above which is characterized in that the given temperature is at or below the temperature at which the metal compound begins to hydrolyze;
- (32) The dispersoid having metal-oxygen bonds of (27) or (29) above which is characterized in that the given temperature is in a range of −50 to −100° C.;
- (33) The dispersoid having metal-oxygen bonds of any one of (27) to (32) above which is characterized in that, following the step in which the water is added at the given temperature, the temperature is raised to the given temperature or above;
- (34) A dispersoid having metal-oxygen bonds which is characterized by being obtained by concentrating a solution of the dispersoid having metal-oxygen bonds of any one of (1) to (33) above;
- (35) The dispersoid having metal-oxygen bonds of any one of (1) to (34) above which is characterized in that the metal compound is a compound of formula (I)
-
RaMXb (I) - (wherein M is a metal atom, X is a hydrolyzable group, R is a hydrogen atom or an organic group which may have a hydrolyzable group capable of forming a bond with the metal atom through an oxygen atom, and a+b=m, where m is the valence of the metal atom);
- (36) The dispersoid having metal-oxygen bonds of (35) above which is characterized in that X in formula (I) is an alkoxy group;
- (37) The dispersoid having metal-oxygen bonds of any one of (1) to (36) above which is characterized in that the metal is one or more selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead;
- (38) The dispersoid having metal-oxygen bonds of any one of (1) to (37) above which is characterized by being a dispersoid which stably disperses without aggregation in an organic solvent in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer;
- (39) The dispersoid having metal-oxygen bonds of any one of (1) to (38) above which is characterized in that a solution containing the dispersoid is optically transparent;
- (40) The dispersoid having metal-oxygen bonds of any one of (1) to (39) above which is characterized by having an average particle size, when dispersed in an organic solvent, in a range of 1 to 20 nm;
- (41) The dispersoid having metal-oxygen bonds of (40) above which is characterized by being monodisperse with a particle size distribution in a range of 0 to 50 nm;
- (42) The dispersoid having metal-oxygen bonds of (40) or (41) above which is characterized in that the organic solvent is an ether solvent or a hydrocarbon solvent;
- (43) A dispersoid having metal-oxygen bonds which is characterized by dispersing stably without aggregation in an organic solvent in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer, and by having an average particle size in a range of 1 to 20 nm;
- (44) The dispersoid having metal-oxygen bonds of (43) above which is characterized by being monodisperse with a particle size distribution in a range of 0 to 50 nm;
- (45) The dispersoid having metal-oxygen bonds of (43) or (44) above which is characterized in that the organic solvent is an ether solvent or a hydrocarbon solvent;
- (46) A metal oxide film which is characterized by being produced from the dispersoid of any one of (1) to (45) above;
- (47) A metal oxide film which is characterized by being produced by coating or spraying a solution containing the dispersoid of any one of (1) to (45) above, then heating at a temperature of 200° C. or below;
- (48) A metal oxide film which is characterized by being produced by coating or spraying a solution containing a dispersoid according to any one of (1) to (45) above and fine metal oxide crystals derived from the dispersoid, then heating at a temperature of 200° C. or below;
- (49) The metal oxide film of (47) or (48) above which is characterized by being produced by, additionally, exposure to ultraviolet light having a wavelength of 360 nm or less;
- (50) The metal oxide film of any one of (46) to (49) above which is characterized by having a smooth film surface;
- (51) The metal oxide film of any one of (46) to (49) above which is characterized in that the film surface has an average roughness of 10 nm or less;
- (52) The metal oxide film of any one of (46) to (49) above which is characterized in that the film surface has an average roughness of 5 nm or less;
- (53) The metal oxide film of any one of (46) to (49) above which is characterized by being formed on a plastic substrate and having a carbon content, expressed as an atomic ratio, of 10% or less;
- (54) A metal oxide film which is characterized by being formed by coating or spraying, and by having a smooth film surface;
- (55) The metal oxide film of (54) above which is characterized by being formed by drying at 200° C. or below;
- (56) The metal oxide film of (54) or (55) above which is characterized in that the film surface has an average roughness of 10 nm or less;
- (57) The metal oxide film of (54) or (55) above which is characterized in that the film surface has an average roughness of 5 nm or less;
- (58) A metal oxide film which is characterized by being formed on a plastic substrate and by having a carbon content, expressed as an atomic ratio, of 10% or less;
- (59) An organic-inorganic hybrid material characterized by containing at least one selected from the group consisting of a dispersoid having metal-oxygen bonds according to any one of (1) to (30) above, an inorganic structural portion derived from the dispersoid, and an inorganic polymer obtained from the dispersoid as the starting material;
- (60) The organic-inorganic hybrid material of (59) above which is characterized in that the organic component is at least one selected from the group consisting of acrylic resins, polythiourethane resins and resins obtained from epithio group-bearing compounds;
- (61) The organic-inorganic hybrid material of (59) or (60) above which is characterized by being produced by polymerizing an organic monomer in the presence of a dispersoid having metal-oxygen bonds according to any one of (1) to (45) above;
- (62) An optical material which is characterized by containing an organic-inorganic hybrid material of any one of (59) to (61) above.
- (63) An optical product which is characterized by being made of the optical material of (62) above;
- (64) The optical product of (63) above which is characterized by being a plastic lens;
- (65) A monomolecular film which is characterized by being obtained by forming a metal oxide film having a smooth surface on a substrate, then contacting the metal oxide film with a metallic surfactant having at least one hydrolyzable group;
- (66) The monomolecular film of (65) above which is characterized in that the metal oxide film having a smooth surface is a metal oxide film according to any one of (46) to (59) above;
- (67) A monomolecular film characterized by being obtained by using a dispersoid having metal-oxygen bonds that is stably dispersed without aggregation in an organic solvent in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer, or using a solution containing the dispersoid, to form a metal oxide film on a substrate, then contacting the metal oxide film with a metallic surfactant having at least one hydrolyzable group;
- (68) The monomolecular film of (67) above which is characterized in that the dispersoid having metal-oxygen bonds that is stably dispersed without aggregation in an organic solvent in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer is a dispersoid according to any one of (1) to (45) above;
- (69) The monomolecular film of any one of (65) to 68) above which is characterized in that the metallic surfactant is a compound of formula (II)
-
R1 nMYm-n (II) - (wherein R′ is a monovalent hydrocarbon group, a monovalent hydrocarbon group having a substituent, a monovalent halogenated hydrocarbon group, a monovalent hydrocarbon group which includes a linkage or a monovalent halogenated hydrocarbon group which includes a linkage, M is at least one type of metal atom selected from the group consisting of silicon, germanium, tin, titanium and zirconium atoms, Y is a hydrolyzable group, the letter n is any integer from 1 to (m−1), and the letter m is the valence of M; with the proviso that if n is 2 or more, each R1 may be like or unlike, and if (m−n) is 2 or more, each Y may be like or unlike); and
- (70) The monomolecular film of (69) above which is characterized in that the compound of formula (II) is a compound of formula (III)
-
CF3—(CF3)p—R2 q-MZrYm-r-1 (III) - (wherein R2 is an alkylene group, a vinylene group, an ethynylene group, an arylene group or a divalent functional group containing a silicon atom and/or an oxygen atom, Z is a hydrogen atom, an alkyl group, an alkoxy group, a fluoroalkyl group or a fluoroalkoxy group, Y, M and m are as defined above, the letter p is 0 or an integer, the letter q is 0 or 1, and the letter r is 0 or any integer from 1 to (m−2)).
- The present invention relates to dispersoids which have metal-oxygen bonds and share some common characteristics. Methods for producing these dispersoids are specified above in each of above items (1), (2), (13), (24), (27) and (28). Below, dispersoids according to above items (1) and (2) are described as Dispersoid I, dispersoids according to above item (13) are described as Dispersoid II, dispersoids according to above item (24) are described as Dispersoid III, and dispersoids according to above items (27) and (28) are described as Dispersoid IV. For features that are common to all the dispersoids, the description provided in the explanation of one type of dispersoid applies to the other types as well. Shared characteristics are summarized following the separate explanations given for each type of dispersoid.
- Dispersoid I of the present invention is a dispersoid having metal-oxygen bonds which is obtained by mixing a metal compound having at least three hydrolyzable groups with a given amount of water in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, and which is characterized in that the given amount of water is either at least 1.0 mole but less than 2.0 moles, or at least 0.5 mole but less than 1.0 mole, per mole of the metal compound, and the given temperature is a temperature below 0° C.
- Here, “dispersoid” refers to fine particles dispersed in a dispersion system. Specific examples include colloidal particles and nanometer size particles composed of several polycondensed molecules.
- The acid or base used in this specification is not subject to any particular limitation, provided it functions as either a deflocculant which re-disperses precipitate that arises from coagulation or, as subsequently described, a catalyst for the hydrolysis or dehydrative condensation of the metal compound having at least three hydrolyzable groups to produce a dispersoid of colloidal particles, nanoparticles or the like, and also functions as a dispersant for the dispersoid that has formed. Specific examples of the acid include mineral acids such as hydrochloric acid, nitric acid, boric acid, tetrafluoroboric acid and carbonic acid; and organic acids such as acetic acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid and methanesulfonic acid. Additional examples also include photoacid generators which generate acids upon irradiation with light, such as diphenyliodonium hexafluorophosphate and triphenylphosphonium hexafluorophosphate. Specific examples of the base include triethanolamine, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, ammonia and phosphine.
- In the specification, “dispersion stabilizer” refers to a component which is added in order to disperse the dispersoid in the dispersing medium as stably as possible, including coagulation-preventing agents such as deflocculants, protective colloids and surfactants. Specific types of compounds having such an effect include chelating compounds, preferably those which having at least one carboxyl group on the molecular backbone and have a strong metal-chelating ability. Illustrative examples of such compounds include polycarboxylic acids such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid and succinic acid, hydroxycarboxylic acids, and also pyrophosphoric acid and tripolyphosphoric acid. Illustrative examples of multidentate compounds similarly having a strong metal atom-chelating ability include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione and 5-methylhexanedione. Other examples include aliphatic amines, hydrostearic acid compounds and polyester amines such as Surpass 3000, 9000, 17000, 20000 and 24000 (all products available from Zeneca) and Disperbyk-161, Disperbyk-162, Disperbyk-163, and Disperbyk-164 (all products of Byk Chemie GmbH); and also the silicone compounds mentioned in JP A 9-208438 and JP A 2000-53421, such as dimethylpolysiloxane-methyl(polysiloxyalkylene)siloxane copolymers, trimethylsiloxysilicate, carboxy-modified silicone oils and amine-modified silicones.
- No particular limitation is imposed on the metal compound having at least three hydrolyzable groups used in the invention, provided it is a metal atom-containing compound having on the molecule at least three hydrolyzable groups which are bonded to the metal atom in any manner, be it directly or through linkages such as carbon chains.
- “Hydrolyzable group” refers to a functional group which hydrolyzes on contact with water or a functional group capable of forming a bond with the metal atom through an oxygen atom, either in the presence or absence of water. Specific examples include halogen atoms, amino groups, alkoxy groups, ester groups, carboxyl groups, phosphoryl groups, isocyanate groups and cyano groups. Given that the hydrolyzable groups here are functional groups whose purpose, after coming into contact with water and hydrolyzing, is to make the metal compound condense with other active groups or self-polycondense, although the hydroxyl group is not a hydrolyzable group in the strictest sense, it is similar in nature and is therefore regarded as a hydrolyzable group in the present specification. (“Hydrolyzable group” is used in the same sense throughout the specification.)
- The metal compound is at least one metal compound having at least three hydrolyzable groups, but may include other metal compounds, such as compounds having two hydrolyzable groups.
- Specific examples of the metal compound include the compounds of formula (I).
- In formula (I), M is a metal atom, and preferably a metal atom capable of synthesizing a metal alkoxide or a metal carboxylate; i.e., a metal atom with a valence of 3 to 5 from group III, IV or V of the periodic table. Specific examples include metal atoms such as silicon, germanium, tin, lead, titanium, zirconium, hafnium, boron, aluminum, gallium, indium, thallium, scandium, yttrium, lanthanum, antimony, bismuth, vanadium, niobium, tantalum, lanthanoid metals and actinoid metals. Preferred examples include titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead.
- R represents a hydrogen atom or an organic group which may have a hydrolyzable group capable of forming a bond with the metal atom through an oxygen atom. Exemplary hydrolyzable groups include functional groups similar to the hydrolyzable groups mentioned above. Specific examples of R include alkyl groups with 1 to 12 carbons, such as methyl, ethyl and propyl; halogenated alkyl groups with 1 to 12 carbons, such as chloromethyl, chloroethyl, chloropropyl, bromopropyl, bromooctyl and trifluoropropyl; epoxyalkyl groups with 1 to 12 carbons, such as glycidoxypropyl and epoxycyclohexylethyl; aminoalkyl groups with 1 to 12 carbons, such as aminopropyl and aminobutyl; aromatic groups with 6 to 12 carbons, such as phenyl and benzyl; and photosensitive groups with 2 to 12 carbons, such as vinyl, allyl, acryloxypropyl and methacryloxypropyl.
- In formula (I), X represents a hydrolyzable group bonded to the metal atom M. Specific examples include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy and pentoxy, aminohydroxy groups, aminohydroxy groups, enoxy groups, amino groups, carbamoyl groups, halogen atoms such as chlorine and bromine, and hydroxyl. Alkoxy groups are especially preferred.
- In formula (I), a+b=m, where m is the valence of the metal atom. The presence of three or more hydrolyzable groups on the molecule is exemplified by cases where the letter b represents 3 or more, and cases where the letter b represents 2 or less and there are one or more R moieties having a hydrolyzable group.
- Provided it is a compound which satisfies the condition that it have at least three hydrolyzable groups, the metal compound furnished for hydrolysis does not need to be a single molecular compound represented by formula (I). For example, the metal compound may be an oligomer obtained by using a similar method to hydrolyze and polycondense a compound of formula (I).
- Specific examples of the metal compound of formula (I) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, germanium tetramethoxide, germanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, tetrachlorosilane, tetrabromosilane, dimethyldichlorosilane, tetrakis(diethylamino)silane, 4-aminobutyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, benzyltrichlorosilane, benzyltriethoxysilane, t-butylphenyldichlorosilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrichlorosilane, 8-bromooctyltrichlorosilane, 3-bromopropyltrichlorosilane, (3,3,3-trifluoropropyl)dichlorosilane, (3,3,3-trifluoropropyl)trichlorosilane, chloromethyltrichlorosilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, allyltrichlorosilane, allyltriethoxysilane, vinylmethyldiacetoxysilane, vinylmethylbis(methylethylketoximine)silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrichlorosilane and 3-acryloxypropyltrimethoxysilane. Especially preferred metal alkoxides include tetramethoxysilane, tetraethoxysilane, titanium tetrapropoxide, zirconium tetrapropoxide and zirconium tetrabutoxide.
- These metal compounds may be used singly or as combinations of two or more thereof.
- Additional examples of suitable metal compounds include double alkoxides obtained by a reaction between metal alkoxides of two or more of the above elements, and double alkoxides obtained by reacting one or more metal alkoxide with one or more metal salt. The use of such double alkoxides in combinations thereof is also possible.
- Exemplary double alkoxides that can be obtained by a reaction between two or more metal alkoxides include double alkoxides obtained by reacting an alkali metal or alkaline earth metal alkoxide with a transition metal alkoxide, and double alkoxides in the form of complex salts obtained by combination with a group 3B element. Specific examples include BaTi(OR′)6, SrTi(OR′)6, BaZr(OR′)6, SrZr(OR′)6, LiNb(OR′)6, LiTa(OR′)6 and combinations thereof, as well as LiVO(OR′)4 and MgAl2(OR′)8. Additional examples include the following products of reactions with silicon alkoxides and silicon alkoxide polycondensation products: (R′O)3SiOAl(OR″)2, (R′O)3SiOTi(OR″)3, (R′O)3SiOZr(OR″)3, (R′O)3SiOB(OR″)2, (R′O)3SiONb(OR″)4 and (R′O)3SiOTa(OR″)4. Here, R′ and R″ represent alkyl groups. Exemplary double alkoxides that can be obtained by reacting one or more metal alkoxide with one or more metal salt include compounds obtained by reacting a metal salt such as a hydrochloride, nitrate, sulfate, acetate, formate or oxalate with an alkoxide.
- Examples of the water used include common tap water, distilled water and ion-exchanged water. Of these, distilled water or ion-exchanged water is preferred. Ion-exchanged water having an electric conductivity of 2 μs/cm or less is especially preferred.
- The amount of water used is in a range of from at least 0.5 mole to less than 2 moles per mole of the metal compound. At less than 0.5 mole, hydrolysis or polycondensation will not proceed uniformly, as a result of which some metal compound of formula (I), for example, will remain unreacted, making it impossible to form a homogeneous and dense film. On the other hand, at more than 2 moles, gelation or particle aggregation will occur during hydrolysis or polycondensation, also making it impossible to form a homogeneous and dense film.
- The water is preferably used after dilution with an organic solvent. The organic solvent is preferably one having a solidification point of 0° C. or below, and also preferably one which has no reactivity with the metal compound when mixed under the conditions of the invention. Exemplary organic solvents include alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers, ketone ethers, ketone esters and ester ethers. Specific examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, methyl cyclohexanol, ethanediol, propanediol, butanediol, pentanediol, hexylene glycol, octylene glycol, hexanetriol, 3,5,5-trimethyl-1-hexanol, butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, butyl propionate, pentyl propionate, dimethyl ketone, methyl ethyl ketone, pentanone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonitrile, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, tetrahydropyran, tetrahydropyran, dimethoxyethane, diethoxyethane, dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, methyral, acetal, heptane, hexane, heptane, octane, nonane, decane, dodecane, toluene, xylene, ethylbenzene, cumene, mesitylene, tetralin, butylbenzene, cymene, diethylbenzene, pentylbenzene, dipentylbenzene, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, chloromethane, dichloromethane, trichloromethane, tetrachloromethane, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, chloropropane, dichloropropane, trichloropropane, chlorobutane, chloropentane, chlorobenzene, dichlorobenzene, chlorotoluene, bromomethane, bromoethane, bromopropane, bromobenzene and chlorobromomethane. Of these, alcohols, esters and hydrocarbons are preferred. Butanol, pentanol, hexanol, trimethylhexanol, methyl acetate, propyl acetate, butyl acetate, pentane, hexane, xylene and toluene are especially preferred. The above organic solvents may be used singly or as combinations of two or more thereof. When the water and the organic solvent are uniformly dissolved and mixed, the resulting mixture may be used directly as is. If the water and the organic solvent do not mix uniformly, they may be used after uniform dispersion by a suitable method such as agitation or ultrasonic processing. The amount of organic solvent used for dilution is preferably in a range of 2 to 100 parts by weight per part by weight of water.
- Dispersoid I is obtained by mixing the above-described metal compound with a given amount of water in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer, and at a given temperature. The method of mixing the metal compound and the given amount of water is not subject to any particular limitation. Exemplary methods include adding the water to the metal compound under stirring, adding the metal compound to the water under stirring, and adding the metal compound and the water at the same time to a vessel equipped with an agitator. Mixing may be carried out without using a solvent, although mixing with the use of an organic solvent is preferable for efficient production of the target dispersoid I.
- The organic solvent used is an organic substance which is preferably capable of dispersing the target dispersoid I ultimately obtained. Specific examples include alcohols such as methanol, ethanol and isopropyl alcohol; chlorinated solvents such as methylene chloride and chloroform; hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene and chlorobenzene; ethers such as tetrahydrofuran, diethyl ether and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone; and the silicones such as methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane and methylphenylpolysiloxane which are used as dispersion media for the titanium dioxide dispersions described in JP A 9-208438. As described subsequently, to add water and carry out the reaction at a low temperature, a solvent which does not solidify at low temperature is preferred. Illustrative examples include lower alcohols, ethers, and hydrocarbons such as toluene. These solvents may be used singly or as mixtures of two or more thereof.
- When an organic solvent is used, examples of methods that may be used to prepare the dispersoid I of the invention include adding water or water diluted with an organic solvent to an organic solvent solution of the metal compound, adding water diluted with an organic solvent to the metal compound, and adding the metal compound or the metal compound diluted with an organic solvent to the water diluted with an organic solvent. The amount of organic solvent used to dilute the metal compound is preferably 10 to 5,000 parts by weight, and more preferably 100 to 3,000 parts by weight, per 100 parts by weight of the metal compound. At less than 10 parts by weight, the fine particles that form grow in a bonded state, which may make the particle size difficult to control. On the other hand, at more than 5,000 parts by weight, the solution is too dilute, which may make formation of the fine particles difficult. The amount of organic solvent used to dilute the water is as described above. If only either of the metal compound and the water is to be diluted with an organic solvent prior to use, dilution is not limited within the above range and may be carried out with a larger amount of organic solvent.
- The given temperature during mixture of the metal compound and the water is a temperature below 0° C., although a temperature of −20° C. or below is preferred, and a temperature in a range of −50 to −100° C. is especially preferred. A temperature at or below the temperature at which the metal compound begins to hydrolyze is also preferred. The given temperature need not always be fixed, and may fluctuate, provided it does so within the specified temperature range.
- Here, “temperature at which the metal compound begins to hydrolyze” refers to the lower limit temperature at which hydrolysis proceeds when the metal compound and the water come into contact. Any suitable method may be used to measure the temperature at which the metal compound begins to hydrolyze. Examples include the method described in JP A 1-230407, and a method in which the 1H-NMR spectrum is measured during a rise in temperature from a low-temperature state so as to determine signal changes for the hydrolyzable groups on the metal compound. When water is added to the metal compound at the given temperature, it is preferable to add water or a water-containing organic solvent solution of a similar given temperature.
- No particular limitation is imposed on the method of addition, provided the temperature is maintained at the given temperature. Exemplary methods of addition include continuous dropwise addition, dropwise addition of a fixed amount at fixed intervals, and pouring into the liquid.
- It is advantageous for Dispersoid I of the invention to be prepared by carrying out the above-described water addition step at the given temperature, then raising the temperature to or above the given temperature. No particular limitation is imposed on the temperature to which the system is raised. When a solvent is used, the temperature may be raised up to the solvent refluxing temperature.
- Dispersoid II of the present invention is a dispersoid having metal-oxygen bonds obtained by mixing, in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer and at a given temperature, a partial hydrolysate that is prepared by hydrolyzing a metal compound having at least three hydrolyzable groups in the absence of an acid, base and/or dispersion stabilizer and can be stably dispersed without aggregation in an organic solvent with an amount of water equal to at least 0.5 mole but less than 2 moles per mole of the metal compound minus the amount of water used to prepare the partial hydrolysate, which dispersoid is characterized in that the given temperature is a temperature below 0° C.
- The partial hydrolysate is not subject to any particular limitation, provided it is of a nature that stably disperses in the organic solvent without aggregation. A specific example is the polytitanoxane described as Comparative Specimen C-2 in JP A 1-129032. No particular limitation is imposed on the method of preparation, although it is preferable to use a method like that for preparing the inventive dispersoid.
- “Stably dispersed without aggregation” refers herein to a state where the dispersoid having metal-oxygen bonds has not coagulated and heterogeneously separated, and preferably refers to a transparent and homogeneous state. Here, “transparent” refers to a state of high transmittance to visible light. Specifically, it refers to a state of preferably 80 to 100% transmittance, expressed as the spectral transmittance measured at a dispersoid concentration of 0.5 wt % (oxide basis), at a quartz cell light path length of 1 cm, using the organic solvent as the control, and at a light wavelength of 550 nm. “Stably dispersed without aggregation” is used in the same sense throughout the specification.
- Dispersoid II of the invention is obtained by mixing the partial hydrolysate and water at a temperature of 0° C. or below, preferably a temperature of −20° C. or below, and more preferably a temperature in a range of −50 to −100° C. A temperature at or below the temperature at which the metal compound begins to hydrolyze is also preferred. Other details, including those concerning the metal compound, the water, and the mixing method used, are the same as described above for Dispersoid I.
- Dispersoid III of the present invention is a dispersoid having metal-oxygen bonds which is obtained by mixing a metal compound having at least three hydrolyzable groups with a given amount of water in the absence of an acid, a base and/or a dispersion stabilizer and at a given temperature, which dispersoid is characterized in that the given amount of water is a solution diluted with a hydrocarbon solvent and an alcohol solvent, the diluted solution is added to the metal compound, and the given temperature is room temperature.
- Dispersoid III of the invention can be obtained by the direct addition of an aqueous solution to the metal compound, although the use of an organic solvent is preferable for better control of the reaction. The organic solvent used is exemplified by the same solvents and the same amount as those mentioned above for Dispersoid I.
- Illustrative examples of hydrocarbon solvents that may be used to dilute the water include aliphatic hydrocarbons such as hexane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. An aromatic hydrocarbon is preferred, and toluene or xylene is especially preferred.
- Examples of alcohol solvents include methanol, ethanol and isopropyl alcohol. Isopropyl alcohol is preferred.
- The mixing ratio of the hydrocarbon solvent and the alcohol solvent is not subject to any particular limitation, although a mixing ratio in a range of 2:8 to 8:2 is preferred, and a mixing ratio in a range of 4:6 to 6:4 is especially preferred.
- No particular limitation is imposed on the amount of water added, although it is advantageous to add at least 0.5 mole but less than 5 moles, preferably at least 0.5 mole but less than 2 moles, and most preferably at least 1.0 mole but less than 2% moles, of water per mole of the metal compound. The concentration of water added, based on the combined amount of hydrocarbon solvent, alcohol solvent and water, is preferably 1 to 15 wt %, more preferably 1 to 10 wt %, and even more preferably 1 to 5 wt %. It is desirable for the water to be in a uniformly dissolved state. The concentration of water added, is preferably from 40% to 1%, more preferably from 30% to 10%, and even more preferably from 25% to 15%, of the saturation solubility of water in a mixed solvent of the hydrocarbon solvent and the alcohol solvent.
- Addition of the mixture of hydrocarbon solvent, alcohol solvent and water to the metal compound is carried out at room temperature. After aging for a fixed period of time, hydrolysis and dehydrative condensation reactions can be carried out at from room temperature to the refluxing temperature of the solvent used.
- Other details are the same as described above for Dispersoids I and II.
- Dispersoid IV of the present invention is a dispersoid having metal-oxygen bonds which is obtained by the addition, to a metal compound having least three hydrolyzable groups, of at least 0.5 mole but less than 2 moles of water per mole of the metal compound, which dispersoid is characterized by having steps in which the water is added in a some of divided portions at a given temperature, which steps include at least one step in which the given temperature is a temperature below 0° C.
- That is, the method of preparing this dispersoid of the invention includes the following three essential features:
- (i) adding, to the metal compound having at least three hydrolyzable groups, a total of at least 0.5 mole but less than 2 moles of water per mole of the metal compound;
- (ii) adding the water in two or more divided portions;
- (iii) at least one of the steps in which the water is added in a some of divided portions is a step in which the water is added at a temperature below 0° C.
- “Added in a some of divided portions” refers herein to, for example, addition under varying addition conditions, addition under the same addition conditions but in differing amounts, and addition under the same addition conditions and in the same addition amounts but at fixed intervals; that is, any addition other than one where the required amount of water is added under certain fixed conditions without extended intervals during addition. No particular limitation is imposed, provided the number of portions is two or more. However, taking into account the reaction operations, it is preferable for the water added to be divided into two portions, with at least one portion of water being added at a temperature below 0° C. The amount of water added at one time is not subject to any particular limitation, provided the combined amount of water is at least 0.5 mole but less than 2.0 moles per mole of the metal compound, although it is preferable in particular for the amount added at first to be at least 0.5 mole but less than 1 mole per mole of the metal compound. The temperature of addition is not subject to any particular limitation, provided the steps in which water is added in a some of divided portions include at least one step in which water is added at a temperature below 0° C. However, it is desirable that, following the first water addition step, the rest of the required amount of water is added at preferably a temperature below 0° C., and more preferably a temperature of −20° C. or below; also preferred are a temperature at or below the temperature at which the metal compound beings to hydrolyze, and a temperature in a range of −50 to −100° C.
- In the preparation of the dispersoid, it is preferable that, following each step in which water is added at the given temperature, the temperature be raised to the given temperature or above. Although no particular limitation is imposed on the level to which the temperature is raised, when an organic solvent is used, it is preferable to raise the temperature to the refluxing temperature of the organic solvent.
- The water addition step can be carried out in the presence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer, although it is preferably carried out in the absence of these.
- Other details are the same as described above for Dispersoids I to III.
- Dispersoids I to IV prepared as described above are characterized by being stably dispersed in an organic solvent even when the weight concentration of the dispersoid (metal oxide basis) in the organic solvent solution is at least 1.2 times, and preferably at least 1.4 times as much as the weight concentration of the metal compound (metal oxide basis) prior to hydrolysis. As a result, even when a solution of the dispersoid having metal-oxygen bonds dispersed to a high concentration in the organic solvent is placed in a yet higher concentration state by driving off the organic solvent at a temperature of at least room temperature but preferably not more than 80° C., the dispersoid particles do not coagulate and re-addition of the organic solvent yields a homogeneous and transparent dispersion. “High-concentration” here includes a solvent-free state. Depending on the metal, the state at this time may be a solid state, liquid state or gelled state, or may be a state that represents a mixture thereof.
- Dispersoids I to IV of the invention are also characterized by being dispersoids which are stably dispersed, without aggregation, in an organic solvent and in the absence of at least one selected from the group consisting of an acid, a base and a dispersion stabilizer. “Stably dispersed without aggregation” refers herein to a state where the dispersoid having metal-oxygen bonds has not coagulated and heterogeneously separated within the organic solvent, and preferably refers herein to a transparent and homogeneous state. Here, “transparent” signifies a state of high transmittance to visible light, and specifically a state of preferably 80 to 100% transmittance, expressed as the spectral transmittance measured at a dispersoid concentration of 0.5 wt % (oxide basis), at a quartz cell light path length of 1 cm, using the organic solvent as the control, and at a light wavelength of 550 nm.
- The organic solvent used for dispersing Dispersoids I to IV of the invention is not subject to any particular limitation provided it is a liquid organic substance and can disperse the dispersoid. Specific examples include alcohols such as methanol, ethanol and isopropyl alcohol; chlorinated solvents such as methylene chloride and chloroform; hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene and chlorobenzene; ethers such as tetrahydrofuran, diethyl ether and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone; and the silicones mentioned in JP A 9-208438, such as methylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane and methylphenylpolysiloxane, which are used as dispersion media for titanium dioxide dispersions. As explained later in the specification, a solvent which does not solidify at low temperatures is preferred for adding water and carrying out the reaction at a low temperature. Illustrative examples of such solvents include lower alcohols, ethers, and hydrocarbons such as toluene. These solvents may be used singly or as mixtures of two or more thereof.
- The Dispersoids I to IV of the invention are additionally characterized by having a particle size in a range of 1 to 100 nm, and also in a range of 1 to 50 nm and a range of 1 to 20 nm. The particle size distribution is characterized by being monodisperse with a particle size in a range of 0 to 50 nm.
- A metal oxide film can be produced from a dispersoid having metal-oxygen bonds prepared as described above and/or an inorganic polymer obtained using the dispersoid as the starting material.
- When a metal oxide film is formed, the dispersoid can be used after dilution with a suitable solvent, followed by removal of the solvent by distillation to give a solvent-free state. Alternatively, following removal of the solvent by distillation, the dispersoid can be re-dissolved or re-dispersed in a different solvent and used.
- In the dispersoid of the invention, it is possible to carry out hydrolysis and polycondensation reactions on the hydrolyzable group-bearing metal compound in a high concentration without adding a dispersion stabilizer such as a multidentate compound to stabilize the hydrolysate, thereby enabling a high-concentration dispersion which contains no unnecessary organic matter such as multidentate compounds to be obtained. When this dispersion is used, products such as gel films, gel fibers and bulk gel having a low organic matter content can thus be obtained. When the organic matter from these gel products is removed such as by heat treatment, microstructural breakdown and the number of residual pores in the resulting body can be reduced.
- The method of producing metal oxide thin films is characterized by coating a solution containing the dispersoid, then drying at a temperature of 200° C. or below.
- The concentration of the dispersoid in the dispersoid-containing solution varies with the coating method and the desired film thickness, but is not subject to an particular limitation provided it is a concentration capable of being coated onto a substrate. A concentration within a range of 5 to 50 wt %, based on the oxide, is preferred.
- The solvent used in the solution is exemplified by solvents similar to the above-mentioned solvents used for dispersing the dispersoid. It is especially preferable to use the same solvent as was used to disperse the dispersoid, although a different solvent may be used provided it is a solvent which does not affect the dispersibility of the dispersoid.
- If necessary, other ingredients may be added to the dispersoid-containing solution. Specific examples of other ingredients include inorganic binders such as silicon compounds (e.g., water glass, colloidal silica, polyorganosiloxane), phosphates (e.g., zinc phosphate, aluminum phosphate), biphosphates, cements, limes, gypsums, enamel frits, glazes for glass lining, and plasters; and organic binders such as fluoropolymers, silicone polymers, acrylic resins, epoxy resins, polyester resins, melamine resins, urethane resins and alkyd resins. These binders may be used singly or as combinations of two or more thereof. Inorganic binders, fluoropolymers and silicone polymers are especially preferred from the standpoint of bond strength. Cements that may be used include Portland cements such as high early-strength cement, normal cement, moderate heat cement, sulfate-resisting cement, white cement, oil well cement and geothermal cement; blended cements such as fly ash cement, highly sulfated slag cement, Portland pozzolan cement and Portland blast-furnace slag cement; and alumina cement. Plasters that may be used include gypsum plaster, lime plaster and dolomite plaster. Fluoropolymers that may be used include crystalline fluororesins such as polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene-polyhexafluoropropylene copolymers, ethylene-polytetrafluoroethylene copolymers, ethylene-chlorotrifluoroethylene copolymers and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers; noncrystalline fluororesins such as perfluorocyclopolymers, vinyl ether-fluoroolefin copolymers and vinyl ester-fluoroolefin copolymers; and various fluororubbers. Fluororubbers composed primarily of vinyl ether-fluoroolefin copolymers and vinyl ester-fluoroolefin copolymers are especially preferred because they undergo little degradation or deterioration and are easy to handle. Silicone polymers that may be used include linear silicone resins, acrylic-modified silicone resins, acrylic-silicone resins, epoxy-silicone resins, and various silicone rubbers.
- The relative amounts of the above-described dispersoid and the foregoing other ingredients, expressed as the weight ratio of the dispersoid to the combined amount of both the dispersoid and the other ingredients is 5 to 98%, preferably 20 to 98%, more preferably 50 to 98%, and even more preferably 70 to 98%. If necessary, other ingredients such as heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, colorants, surfactants, crosslinking agents, dispersants and fillers may also be included in the dispersoid-containing solution. Crosslinking agents that may be used include ordinary crosslinking agents such as isocyanate- or melamine-based crosslinking agents. Dispersants that may be used include coupling agents.
- Any suitable known method may be used to coat the above-described dispersoid-containing solution onto a substrate, including spin coating, dip coating, spray coating, roll coating and screen printing. Roll coating is preferred for carrying out mass production inexpensively. Especially preferred methods are those which use a bar or a roller-type coating device. Screen printing and offset printing are also advantageous in that they enable patterning to be carried out during coating. The coating weight varies with the intended use of the resulting thin film, although the coating weight of active ingredients other than the solvent is generally from 0.1 to 10 ml/m2, preferably from 0.2 to 7 ml/m2, and more preferably from 0.4 to 5 ml/m2.
- The substrate may be an object made of an inorganic material such as ceramic or glass, an object made of an organic material such as plastic, rubber, wood or paper, or an object made of a metal material such as a metal (e.g., aluminum) or metal alloy (e.g., steel). No particular limitation is imposed on the size or shape of the substrate. For example, the substrate may be a flat plate, a three-dimensional object or a film. Even a painted object may be used for this purpose. Of these, a plastic film is preferred. Illustrative examples of plastic films that may be used include cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate, syndiotactic polystyrene, polyethylene-coated paper, polyethersulfone, polyarylate, polylvinylidene fluoride and Teflon (registered trademark). These substrates may be provided with a polyvinylidene chloride-type polymer-containing waterproofing layer so as to enhance dimensional stability; i.e., the stability to dimensional changes from changes in temperature and humidity. In addition, an organic and/or inorganic compound thin film may be provided as a gas barrier. Illustrative examples of organic thin films include polyvinyl alcohol and polyethylene-co-vinyl alcohol). Illustrative examples of inorganic compounds include silica, alumina, talc, vermiculite, kaolinite, mica and synthetic mica. Various organic and/or inorganic additives may also included in the substrate to confer other capabilities as well.
- Heating of the applied film is carried out together with drying of the solvent, the purpose being to effect, for example, hydrolysis and dehydrative condensation of the dispersoid. It is desirable for heating after coating to be carried out at a low temperature of 200° C. or below so as not to damage the substrate. Heating is carried out at preferably 20 to 100° C., and more preferably 30 to 80° C. The heating time is not subject to any particular limitation, although it is generally suitable to carry out heating for a period of from 1 minute to 120 hours.
- In the practice of the invention, if the metal oxide film that has formed is required to have mechanical strength, a protective film may be formed thereon. A common protective film-forming coating solution, such as a silica film-forming coating solution which contains an alkoxysilane hydrolysate, may be used to form this protective coat.
- In the practice of the invention, for a metal oxide film that requires crystallization, it is preferable to add fine seed crystals of the target metal oxide to the coating solution containing the dispersoid having metal-oxygen bonds. The addition ratio of the fine metal oxide crystals is preferably 10 to 90 wt %, and more preferably 10 to 80 wt %, of the sol weight when the sol has formed from the dispersoid. As mentioned later in the specification, in the practice of the invention, there are cases where the metal oxide crystallizes upon exposure to light. In such cases, adding seed crystals will further accelerate crystallization of the metal oxide. The seed crystals may be of any size, although a sphere equivalent diameter of 0.1 μm or less is preferable from the standpoint of light transmittance.
- The seed crystals added are not limited to crystals of the same metal oxide and may instead be ones suitable for heteroepitaxy because they have, for example, the same crystal form and/or a similar lattice constant. For example, indium oxide may be used as the seed crystals when forming an ITO film.
- The seed crystals used may be commercially available product or synthesized crystals. If the metal oxide film is to be a ITO film, the seed crystals may be a commercial product made by, for example, Mitsubishi Materials Corporation or Sumitomo Metal Mining Co., Ltd. Examples of methods for synthesizing the seed crystals include sol-gel methods, hydrothermal synthesis, and ordinary sintering. Detailed descriptions of sol-gel methods appear in, for example, “Science of the Sol-Gel Process” [Zoru-geru hō no kagaku] by Sumio Sakka (Agne Shofusha, 1988); “Thin-Film Coating Technology Using the Sol-Gel Process” [Zoru-geru hō ni yoru hakumaku kōtingu gijutsu] (Gijutsu Joho Kyokai, 1994); and “The Sol-Gel Process: Today and Tomorrow” [Zoru-geru hō no genjō to tenbō], edited by Masayuki Yamane (Sol-Gel Process Report Publication Committee of the Association of Technical Information Services (ATIS), 1992).
- The film-forming method of the invention is preferably one which involves light irradiation during and/or after heating of the applied film. The light source used to irradiate the applied film with ultraviolet light or visible light may be any which emits light having a wavelength of 150 to 700 nm. Illustrative examples include ultrahigh-pressure mercury vapor lamps, high-pressure mercury vapor lamps, low-pressure mercury vapor lamps, xenon lamps, halogen lamps and sodium lamps. Ultrahigh-pressure mercury vapor lamps, high-pressure mercury vapor lamps, low-pressure mercury vapor lamps and xenon lamps are preferred. A transparent, electrically conductive pattern can be formed by using a photomask with the light source. A laser oscillator may also be used. Examples of suitable laser oscillators include excimer lasers, argon lasers, helium neon lasers, semiconductor lasers, YAG lasers, carbon dioxide lasers and dye lasers. When laser light is employed, metal oxide does not form in non-irradiated areas, and so patterning is possible without the use of a process such as screen printing at the time of coating. Use can also be made of synchrotron light.
- These apparatuses can be selected according to the desired wavelength of irradiation. When reaction of the dispersoid-containing coating solution is carried out, the metal oxide that forms is sometimes accompanied by residual metal hydroxide. Given the absorption by metal-OH bonds that occurs in such cases, it is desirable to use an apparatus which emits light that includes ultraviolet radiation having a wavelength of 400 nm or less. Also, if the dehydration reaction proceeds to the point where a metalloxane network forms, the metal-oxygen-metal bonds absorb at a shorter wavelength than metal-OH bonds, but crystallization of the metal oxide will proceed with the irradiation of light having a wavelength capable of activating the metal-oxygen-metal bonds. The irradiation time is not subject to any particular limitation, although irradiation is generally carried out for a period of from 1 minute to 120 hours.
- In the practice of the invention, the light irradiation process may be carried out in any atmosphere, although irradiation in a somewhat reducing atmosphere is preferred. In a somewhat reducing atmosphere, the greater degree of oxygen deficiency is thought to inhibit increases in carrier density and/or adsorption of the oxygen molecules to the grain boundaries.
- A high-boiling, low-molecular-weight solvent which decomposes under light irradiation may be used. Examples of such solvents include isophorone and benzyl acetate.
- If light irradiation is carried out, substances such as photodegradable resins may also be added to this dispersion-containing solution. Illustrative examples include poly(methyl vinyl ketone), poly(vinyl phenyl ketone), polysulfone, diazonium salts such as the polycondensate of p-diazodiphenylamine and paraformaldehyde, quinonediazides such as the isobutyl ester of 1,2-naphthoquinone-2-diazido-5-sulfonic acid, and poly(methyl methacrylate), poly(phenyl methylsilane) and poly(methyl isopropenyl ketone). It is desirable to use these resins in an amount of 0 to 1,000 parts by weight per 100 parts by weight of the metal compound. Moreover, when light irradiation is carried out, if the wavelength of the irradiated light differs from the absorption wavelength of the dispersoid differ, it is desirable to add a photosensitizer.
- Even though it has been formed by the simple operation of merely coating or spraying, followed by heat treatment at a low temperature of 200° C. or below, the metal oxide film obtained as described above is characterized by having a smooth film surface. The film surface is characterized by having an average roughness, which is a value indicating smoothness, of 10 nm or less, and preferably 5 nm or less. Because it can be heat treated at a low temperature, even when the metal oxide film has been formed on a plastic substrate, the film is characterized by having a carbon content, expressed as an atomic ratio, of 10% or less.
- The organic-inorganic hybrid material of the invention is characterized by containing at least one selected from the group consisting of a dispersoid having metal-oxygen bonds prepared as described above, an inorganic structural portion derived from the dispersoid, and an inorganic polymer obtained from the dispersoid as the starting material.
- The organic component is not subject to any particular limitation. Any suitable resin, such as an addition polymer, polyadduct or polycondensate may be used. Specific examples are listed below.
- Examples of acrylic resins include those obtained by polymerization from the following monomers as the starting materials: monofunctional methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, hexyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, tricyclo[5.2.1.0]decanyl methacrylate and 3,3,3-trifluoroethyl methacrylate; polyfunctional methacrylic acid esters such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethylacrylate, tripropylene dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, glycerol dimethacrylate, 2,2-bis[4-(methacryloxy)phenyl]propane and 2,2-bis[4-(methacryloxyethoxy)phenyl]propane. Monofunctional acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, isobornyl acrylate, tricyclo[5.2.1.0]decanyl acrylate and 3,3,3-trifluoroethyl acrylate; and polyfunctional acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. Monomers that are copolymerizable with the above acrylic or methacrylic compounds include styrene, ring-substituted styrenes such as methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene and divinylbenzene; as well as α-methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride and N-substituted maleimide. Copolymers of these latter monomers with the above acrylic or methacrylic compounds also are considered herein as acrylic resins.
- Organic monomers which are radical- or cationic-polymerizable are preferred, and organic monomers having at least one type of bond selected from among amide bonds, imide bonds, urethane bonds and urea bonds are especially preferred. Of such organic monomers, specific examples of radical-polymerizable organic monomers include (meth)acrylamide, (meth)acrylamide derivatives, (meth)acryloylmorpholine, N-vinylpyrrolidone, urethane (meth)acrylate, and the addition products of aminoalkyl (meth)acrylates and isocyanate. Here, (meth)acrylamide stand for both methacrylamide and acrylamide, and (meth)acrylate stands for both methacrylate and acrylate.
- Of the above organic monomers, exemplary cation-polymerizable monomers are compounds having an epoxy ring, a vinyl ether bond or an ortho-spiro ring as a polymerization functional group. Specific examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and hydrogenated bisphenol A diglycidyl ether.
- Optional organic monomers may be used together with the above essential organic monomer to modify the resulting polymer. Such optional organic monomers may or may not have amide bonds, urethane bonds and urea bonds. However, the mode of polymerization for these optional organic monomers must be the same as for the above-described essential monomers (i.e., radical polymerization, cationic polymerization).
- “Poly(thio)urethane resins” refers herein to polythiourethane or polyurethane resins obtained by reacting a polyisocyanate compound with a polythio compound or a polyhydroxy compound.
- The polyisocyanate compound is not subject to any particular limitation. Specific examples include the following:
- (i) alicyclic isocyanate compounds such as hydrogenated 2,6-tolylene diisocyanate, hydrogenated m- and p-phenylene diisocyanate, hydrogenated 2,4-tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated m-xylylene diisocyanate, hydrogenated p-xylylene diisocyanate, isophorone diisocyanate, hydrogenated 1,3-bis(isocyanatomethyl)benzene and norbornane diisocyanate;
- (ii) aromatic ring-bearing isocyanate compounds such as m- and p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m- and p-xylylene diisocyanate, m- and p-tetramethylxylylene diisocyanate, 2,6-naphthalene diisocyanate, 1,5-naphthalene diisocyanate and 1,3-bis(isocyanatomethyl)benzene (preferred examples include 2,4- and 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 2,6-naphthalene diisocyanate and 1,3-bis(isocyanatomethyl)benzene);
- (iii) isocyanate compounds without an alicyclic or aromatic ring, such as hexamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, the biuret reaction product of hexarfiethylene diisocyanate, the trimer of hexamethylene diisocyanate, lysine diisocyanate, 2-isocyanatomethyl-2,6-diisocyanatocaproate, 1,6,11-undecane triisocyanate and triphenylmethane triisocyanate; and
- (iv) sulfur-containing isocyanate compounds such as diphenyl disulfide-4,4′-diisocyanate, 2,2′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-6,6′-diisocyanate, 4,4′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethoxyphenyl disulfide-4,4′-diisocyanate, 4,4′-dimethoxydiphenyl disulfide-3,3′-diisocyanate, diphenyl sulfone-4,4′-diisocyanate, diphenyl sulfone-3,3′-diisocyanate, benzylidene sulfone-4,4′-diisocyanate, diphenylmethane sulfone-4,4′-diisocyanate, 4-methyldiphenylmethane sulfone-2,4′-diisocyanate, 4,4′-dimethoxydiphenyl sulfone-3,3′-diisocyanate, 3,3′-dimethoxy-4,4′-diisocyanatodibenzyl sulfone, 4,4′-dimethyldiphenyl sulfone-3,3′-diisocyanate, 4,4′-di-tert-butyldiphenyl sulfone-3,3′-diisocyanate, 4,4′-dimethoxybenzene ethylene disulfone-3,3′-diisocyanate, 4,4′-dichlorodiphenyl sulfone-3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanate phenol ester, 4-methoxy-3-isocyanatobenzenesulfonyl-4′-isocyanate phenol ester, 4-methyl-3-isocyanatobenzenesulfonylanilide-3′-methyl-4′-isocyanate, dibenzenesulfonyl ethylenediamine-4,4′-diisocyanate, 4,4′-dimethoxybenzenesulfonyl ethylenediamine-3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3′-isocyanate, thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanatomethyl, 1,4-dithian-2,5-diisocyanate, 1,4-dithian-2,5-diisocyanatomethyl, 1,4-dithian-2-isocyanatomethyl-5-isocyanatopropyl, 1,3-dithiolan-4,5-diisocyanate, 1,3-dithiolan-4,5-diisocyanatomethyl, 1,3-dithiolan-2-methyl-4,5-diisocyanatomethyl, 1,3-dithiolan-2,2-diisocyanatoethyl, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2,5-diisocyanatomethyl, tetrahydrothiophene-2,5-diisocyanatoethyl and tetrahydrothiophene-3,4-diisocyanatomethyl.
- Specific examples of polythiol compounds include the following:
- (i) aliphatic thiols such as methanedithiol, 1,2-ethanediol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanediol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethyl)methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl)ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane and tetramethylolmethanetetrakis(3-mercaptopropionate);
- (ii) aromatic thiols such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethoxy)benzene, 1,3-bis(mercaptomethoxy)benzene, 1,4-bis(mercaptomethoxy)benzene, 1,2-bis(mercaptoethoxy)benzene, 1,3-bis(mercaptoethoxy)benzene, 1,4-bis(mercaptoethoxy)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 1,2,3-tris(mercaptomethoxy)benzene, 1,2,4-tris(mercaptomethoxy)benzene, 1,3,5-tris(mercaptomethoxy)benzene, 1,2,3-tris(mercaptoethoxy)benzene, 1,2,4-tris(mercaptoethoxy)benzene, 1,3,5-tris(mercaptoethoxy)benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2,4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptomethoxy)benzene, 1,2,4,5-tetrakis(mercaptomethoxy)benzene, 1,2,4,5-tetrakis(mercaptomethoxy)benzene, 1,2,3,4-tetrakis(mercaptoethoxy)benzene, 1,2,3,5-tetrakis(mercaptoethoxy)benzene, 1,2,4,5-tetrakis(mercaptoethoxy)benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-napthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol and 2,4-di(p-mercaptophenyl)pentane;
- (iii) halogen substituted aromatic thiols, including chlorine-substituted and bromine-substituted compounds such as 2,5-dichlorobenzene-1,3-dithiol, 1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene;
- (iv) aromatic thiols containing sulfur atoms as well as mercapto groups, such as 1,2-bis(mercaptomethylthio)benzene, 1,3-bis(mercaptomethylthio)benzene, 1,4-bis(mercaptomethylthio)benzene, 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, 1,2,3,4-tetrakis(mercaptomethylthio)benzene, 1,2,3,5-tetrakis(mercaptomethylthio)benzene, 1,2,4,5-tetrakis(mercaptomethylthio)benzene, 1,2,3,4-tetrakis(mercaptoethylthio)benzene and 1,2,3,5-tetrakis(mercaptoethylthio)benzene and 1,2,4,5-tetrakis(mercaptoethylthio)benzene, as well as ring-alkylated compounds thereof;
- (v) aliphatic thiols containing sulfur atoms as well as mercapto groups, such as bis(mercaptomethyl) sulfide, bis(mercaptoethyl) sulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropyl)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropyl)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) disulfide and bis(mercaptopropyl) disulfide, and the thioglycolic acid and mercaptopropionic acid esters thereof; hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thioglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), 4,4′-thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 4,4′-dithiodibutyric acid bis(2-mercaptoethyl ester), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiglycolic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester), 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol and bis(1,3-dimercapto-2-propyl) sulfide; and
- (vi) heterocyclic compounds containing sulfur atoms as well as mercapto groups, such as 3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 1,4-dithian-2,5-diol bis(2-mercaptoacetate) and 1,4-dithian-2,5-diol bis(3-mercaptopropionate).
- Specific examples of polyhydroxy compounds include the following:
- (i) aliphatic polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, triethylene glycol, polyethylene glycol, tris(2-hydroxyethyl)isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, bicyclo[4.3.0]nonanediol, dicyclohexanediol, tricyclo[5.3.1.1]dodecanediol, spiro[3.4]octanediol and butylcyclohexanediol;
- (ii) aromatic polyols such as dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol and tetrabromobisphenol A;
- (iii) addition reaction products of the polyhydroxy compounds in (i) or (ii) above with an alkylene oxide such as ethylene oxide or propylene oxide; and
- (iv) sulfur-bearing polyols such as bis[4-(hydroxyethoxy)phenyl]sulfide, bis[4-(2-hydroxypropyl)phenyl]sulfide, bis[4-(2,3-dihydroxypropoxy)phenyl]sulfide, bis[4-(4-hydroxycyclohexyloxy)phenyl]sulfide, bis[2-methyl-4-(hydroxyethoxy)-6-butylphenyl]sulfide, and compounds obtained by adding to these compounds an average of three or fewer molecules of ethylene oxide and/or propylene oxide per hydroxyl group; di-(2-hydroxyethyl) sulfide, 1,2-bis-(2-hydroxyethylmercapto)ethane, bis(2-hydroxyethyl) disulfide, 1,4-dithian-2,5-diol, bis(2,3-dihydroxypropyl) sulfide, tetrakis(4-hydroxy-2-thiabutyl)methane, bis(4-hydroxyphenyl) sulfone (trade name: Bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4′-thiobis(6-tert-butyl-3-methylphenol) and 1,3-bis(2-hydroxyethylthioethyl)cyclohexane.
- The use of poly(thio)urethane resins as lens substrates is already known to the art. Specific examples of publications that disclose such use include the following: JP A 58-127914, JP A 57-136601, JP A 01-163012, JP A 03-236386, JP A 03-281312, JP A 04-159275, JP A 05-148340, JP A 06-065193, JP A 06-256459, JP A 06-313801, JP A 06-192250, JP A 07-063902, JP A 07-104101, JP A 07-118263, JP A 07-118390, JP A 07-316250, JP A 60-199016, JP A 60-217229, JP A 62-236818, JP A 62-255901, JP A 62-267316, JP A 63-130615, JP A 63-130614, JP A 63-046213, JP A 63-245421, JP A 63-265201, JP A 01-090167, JP A 01-090168, JP A 01-090169, JP A 01-090170, JP A 01-096208, JP A 01-152019, JP A 01-045611, JP A 01-213601, JP A 01-026622, JP A 01-054021, JP A 01-311118, JP A 01-295201, JP A 01-302202, JP A 02-153302, JP A 01-295202, JP A 02-802, JP A 02-036216, JP A 02-058517, JP A 02-167330, JP A 02-270859, JP A 03-84031, JP A 03-084021, JP A 03-124722, JP A 04-78801, JP A 04-117353, JP A 04-117354, JP A 04-256558, JP A 05-78441, JP A 05-273401, JP A 05-093801 JP A 05-080201, JP A 05-297201, JP A 05-320301, JP A 05-208950, JP A 06-072989, JP A 06-256342, JP A 06-122748, JP A 07-165859, JP A 07-118357, JP A 07-242722, JP A 07-247335, JP A 07-252341, JP A 08-73732, JP A 08-092345, JP A 07-228659, JP A 08-3267, JP A 07-252207, JP A 07-324118 and JP A 09-208651. The polyisocyanate compounds, polythiol compounds and polyhydroxy compounds disclosed in these publications can be used as the starting monomers for preparing what are referred to herein as poly(thio)urethane resins.
- Resins composed primarily of diethylene glycol bis(allyl carbonate) are exemplified by homopolymers of diethylene glycol bis(allyl carbonate) and copolymers obtained by reacting diethylene glycol bis(allyl carbonate) with a copolymerizable monomer.
- Examples of monomers that are copolymerizable with diethylene glycol bis(allyl carbonate) include monofunctional methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and adamantyl methacrylate; polyfunctional methacrylic acid esters such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, glycerol dimethacrylate, 2,2-bis[4-(methacryloxy)phenyl]propane and 2,2-bis[4-(methacryloxyethoxy)phenyl]propane; and acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, isobornyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 2,2-bis[4-(acryloxy)phenyl]propane and 2,2-bis[4-(acryloxyethoxy)phenyl]propane. Additional examples include styrene, ring-substituted styrenes such as methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene and divinylbenzene; and also α-methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide, diallyl phthalate, diallyl isophthalate and diallyl terephthalate.
- Examples of copolymers of diethylene glycol bis(allyl carbonate) and other monomers are mentioned in, for example, JP A 54-41965, JP A 51-125487 and JP A 01-503809.
- “Resins obtained from epithio group-bearing compounds” refers herein to resins obtained by polymerizing, as the starting material, an epithio group-bearing monomer or a monomer mixture containing such a monomer. Specific examples of epithio group-bearing monomers include the following:
- (i) episulfide compounds having an alicyclic skeleton, such as 1,3- and 1,4-bis(1′-epithiopropylthio)cyclohexane, 1,3- and 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane and bis[4-(β-epithiopropylthio)cyclohexyl]sulfide;
- (ii) episulfide compounds having an aromatic skeleton, such as 1,3- and 1,4-bis(β-epithiopropylthio)benzene, 1,3- and 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfine and 4,4-bis(β-epithiopropylthio)biphenyl;
- (iii) episulfide compounds having a dithiane ring skeleton, such as 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethyl)-1,4-dithiane and 2,3,5-tri(β-epithiopropylthioethyl)-1,4-dithiane; and
- (iv) epithio compounds having an aliphatic skeleton, such as 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropylthio)propane, 1,2-bis[(2-β-epithiopropylthioethypthio]-3-(β-epithiopropylthio)propane, tetrakis(β-epithiopropylthiomethyl)methane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, bis-(β-epithiopropyl) sulfide, and bis-(β-epithiopropyl) disulfide.
- The use of resins obtainable from epithio group-bearing compounds as lens substrates is already known to the art. Specific examples include those disclosed in the following publications: JP A 09-071580, JP A 09-110979, JP A 09-255781, JP A 03-081320, JP A 11-140070, JP A 11-183702, JP A 11-189592, JP A 11-180977, and JP A 01-810575.
- Other examples include radical polymers having a (thio)urethane structure on the molecule, such as radical polymers prepared from monomers obtained by reacting a linear alkane compound of 3 to 6 carbons having at least two mercapto groups on the molecule with a compound having at least one isocyanate group and at least one (meth)acryloyl group on the molecule. Here, (meth)acryloyl group stands for both acryloyl group and methacryloyl group.
- Examples of the linear alkaline compound of 3 to 6 carbons having at least two mercapto groups on the molecule which serves as one of the starting materials in the preparation of radical polymerizable compounds having a thiourethane bond include 1,2,3-trimercaptopropane, 1,2,3-trimercaptobutane, 1,2,4-trimercaptobutane, 1,2,3,4-tetramercaptobutane, 1,2,3-trimercaptopentane, 1,2,4-trimercaptopentane, 1,2,3,4-tetramercaptopentane, 1,2,3-trimercaptohexane, 1,2,4-trimercaptohexane, 1,2,5-trimercaptohexane, 2,3,4-trimercaptohexane, 2,3,5-trimercaptohexane, 3,4,5-trimercaptohexane, 1,2,3,4-tetramercaptohexane, 1,2,3,5-tetramercaptohexane, 1,2,4,5-tetramercaptohexane, 2,3,4,5-tetramercaptohexane and 1,2,3,4,5-pentamercaptohexane. Of these, 1,2,3-trimercaptopropane is especially preferred for its ready availability and for the performance of the resulting optical material.
- Examples of the compound having one isocyanate group and at least one (meth)acryloyl group which serves as the other starting material include acryloyl isocyanate, methacryloyl isocyanate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-isocyanatopropyl acrylate and 2-isocyanatopropyl methacrylate. Of these, 2-isocyanatoethyl methacrylate is especially preferred for its ready availability and for the performance of the resulting optical material. The above are all examples of compounds having one isocyanate group and one (meth)acryloyl group, but use can also be made of compounds having two or more isocyanate group or two or more (meth)acryloyl groups.
- If a compound other than the above polymerizable compounds, such as a radical-polymerizable organic monomer, is employed to suitably enhance the physical properties of the above-described organic-inorganic hybrid material for use as an optical material, one or more radical-polymerizable compound which has a radical-polymerizable group and is copolymerizable with the above compounds may be included. Illustrative examples of such radical-polymerizable compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene diglycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bis(allyl carbonate), styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, 2,5-bis(2-thia-3-butenyl)-1,4-dithiane and 2,5-bis((meth)acryloylthiomethyl)-1,4-dithiane. 2,5-bis(2-thia-3-butenyl)-1,4-dithiane are especially preferred. Here, (meth)acrylate stands for both acrylate and methacrylate, and (meth)acryloxy group stands for both acryloxy group and methacryloxy group.
- When the organic monomer is a radical- or cationic-polymerizable organic monomer, the polymerization reaction is carried out by adding a known radical- or cationic-polymerization initiator. When the organic monomer is an addition-polymerizable or condensation-polymerizable organic monomer, the polymerizable reaction is carried out by adding an amine compound such as triethylenediamine, hexamethylenetetraamine, N,N-dimethyloctylamine, N,N,N′,N′-tetramethyl-1,6-diaminohexane, 4,4′-trimethylenebis(1-methylpiperidine) or 1,8-diazabicyclo[5.4.0]-7-undecene; or an organic metal compound such as dimethyltin dichloride, dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymers, dibutyltin diricinolate, dibutyltin bis(dodecylmercaptide), dibutyltin bis(isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymers, dioctyltin bis(butylmaleate), dioctyltin dilaurate, dioctyltin diricinolate, dioctyltin dioleate, dioctyltin di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate), didodecyltin diricinolate, copper oleate, copper acetylacetonate, iron acetylacetonate, iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octanoate and 2-ethylhexyl titanate. Of the above polyaddition or polycondensation reaction catalysts, dibutyltin dichloride and dibutyltin dilaurate are preferred. These catalysts may be used singly or as combinations of two or more thereof.
- When radical photopolymerization is carried out, to enhance reactivity, a known sensitizer such as benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropane-1-one or acylphosphine oxide may be added to increase the reactivity.
- The above polymerization reaction can be carried out either as solution polymerization or bulk polymerization. Polymerization can be carried out by subjecting a mixture of the organic components and the inorganic components to heat or to irradiation with light.
- Exemplary methods for preparing the organic-inorganic hybrid material include:
- (1) mixing a organic polymer with the inventive dispersoid having metal-oxygen bonds prepared from a metal compound such as a metal alkoxide, in an organic solvent or in bulk, then shaping;
- (2) preparing the inventive dispersoid having metal-oxygen bonds from a metal compound such as a metal alkoxide in an organic solvent, then adding an organic monomer, carrying out solution polymerization or bulk polymerization, and shaping;
- (3) mixing a metal compound such as a metal alkoxide and an organic monomer in an organic solvent, adding water and hydrolyzing to form a mixture of the organic monomer and the inventive dispersoid having metal-oxygen bonds, then carrying out solution polymerization or bulk polymerization, and shaping;
- (4) mixing an organic polymer and a metal compound such as a metal alkoxide in an organic solvent, adding water and hydrolyzing, then shaping;
- (5) adding an organic solvent containing an organic polymer in a dropwise manner to, and mixing with, an organic solvent containing the inventive dispersoid having metal-oxygen bonds prepared from a metal compound such as a metal alkoxide, then shaping;
- (6) preparing an oligomer from an organic monomer, mixing the oligomer with the inventive dispersoid having metal-oxygen bonds prepared beforehand from a metal compound such as a metal alkoxide, then solution polymerizing or bulk polymerizing, and shaping.
Methods (2), (3) and (6) are especially preferred. - If a polycondensation product is used as the organic polymer or a water-unstable organic monomer is used, following preparation of the dispersoid having metal-oxygen bonds, it is preferable to add an organic polymer or an organic monomer.
- The organic-inorganic hybrid material of the invention has a high refractive index and a high transmittance to visible light, and so is preferably used as an optical material. To this optical material may be suitably added, if desired, ultraviolet absorbers, dyes and pigments to improve the light absorbing properties, antioxidants and discoloration inhibitors to improve weather resistance, and parting agents to improve moldability. Exemplary ultraviolet absorbers include benzotriazole, benzophenone and salicylic acid compounds. Exemplary dyes and pigments include anthraquinone and azo compounds. Exemplary antioxidants and discoloration inhibitors include monophenol, bisphenol, polymeric phenol, sulfur-bearing compounds and phosphorus-bearing compounds. Exemplary parting agents include fluorinated surfactants, silicone surfactants, acid phosphoric ester and higher fatty acids.
- The method of producing the optical material of the invention typically involves preparing a uniform mixture composed of, for example, the metal-oxygen bond-bearing dispersoid, the organic monomer, a monomer copolymerizable with the organic monomer, additives and a catalyst. If the monomer is a radical-polymerizable monomer, a known cast polymerization process may be used in which the mixture is poured into a mold consisting of the combination of a mold body made of glass or resin, that has transmits ultraviolet light, and a resin gasket, then is irradiated with ultraviolet light to effect curing. If the monomer is an addition-polymerizable or condensation-polymerizable monomer, the mixture may be heated and cured. To facilitate removal of the molded resin, the mold may be treated beforehand with a parting agent or a parting agent may be included in the uniform mixture. Following exposure to ultraviolet light, it is advantageous to also carry out heating so as to bring polymerization to completion or to ease stresses that arise at the interior of the material. The heating temperature and time will vary according to such factors as the amount of ultraviolet irradiation energy, but are generally 30 to 150° C. and 0.2 to 24 hours. When cast polymerization with heating is carried out, it is preferable to set the initial temperature in a relatively low temperature range of 5 to 40° C. and gradually raise the temperature over 10 to 70 hours to a high temperature of 100 to 130° C. Optical materials obtained by production methods such as (1) and (4) above in which preparation of the organic polymer has already been finished can be shaped by, for example, casting the solution in a mold. The optical material of the invention can easily be dyed in water or an organic solvent using a conventional disperse dye. To facilitate dyeing at this time, a carrier may be added and heating carried out.
- The present invention also provides optical products made of optical materials obtained as just described. Illustrative, non-limiting examples of these optical products include plastic optical lenses such as eyeglass lenses, prisms, optical fibers, substrates for recording media, filters, and drinking glasses and vases. Of these, plastic optical lenses, and particularly eyeglass lenses, are preferred.
- Instead of being cast polymerized, the optical material of the invention can be coated onto the surface of a lens or drinking glass, for example, and cured if necessary by carrying out an operation such as light exposure, enabling it to be used as a starting material for a hard coating that protects the surface or for a multilayer antireflection coating that prevents reflection. Illustrative, non-limiting examples of coating methods that may be used include dip coating, spin coating, flow coating, roller coating and brush coating.
- The method of making the monomolecular film of the invention is characterized by contacting a metallic surfactant having at least one hydrolyzable group with a metal oxide film according to the invention.
- The metallic surfactant having at least one hydrolyzable group is not subject to any particular limitation, provided it has a hydrolyzable functional group, can react through the functional group with an active hydrogen on the substrate surface to form a bond, and can have on the same molecule both a hydrophilic site capable of forming the bond and a hydrophobic site. Preferred examples include compounds of formula (II).
- In formula (II), R1 is a monovalent hydrocarbon group, a monovalent hydrocarbon group having a substituent, a monovalent halogenated hydrocarbon group, a monovalent halogenated hydrocarbon group having a substituent, a monovalent hydrocarbon group which includes a linkage or a monovalent halogenated hydrocarbon group which includes a linkage; if the letter n is 2 or more, each R1 may be like or unlike.
- When R1 is a monovalent hydrocarbon group, alkyl groups of 1 to 30 carbons, alkenyl groups of 1 to 30 carbons, and aryl groups are preferred. When R1 is a monovalent halogenated hydrocarbon group, “group” here refers to a group in which one or more hydrogen atom on the hydrocarbon group has been substituted with a halogen atom; groups in which two or more hydrogen atoms on an alkyl group have been substituted with halogen atoms are preferred. Suitable halogen atoms include fluorine atoms, chlorine atoms and bromine atoms. Fluorine atoms are preferred.
- When R1 is a fluorinated alkyl group, a linear or branched structure is preferred. If the structure is branched, the branched portion preferably is a short chain of about 1 to 4 carbons. When R1 is a fluorinated alkyl group, the terminal carbon atom is preferably a group having one or more fluorine atoms bonded thereto; a group having a CF3 moiety composed of three fluorine atoms bonded to a terminal carbon atom is especially preferred. However, the carbon chain may instead be one which is terminated with a fluorine-unsubstituted hydrocarbon group and is substituted with fluorine at the interior thereof.
- The number of fluorine atoms on the fluorinated alkyl group, expressed as [(number of fluorine atoms on fluorinated alkyl group)/(number of hydrogen atoms on alkyl group of same number of carbons as fluorinated alkyl group)×100]%, is preferably at least 60%, and more preferably at least 80%. Moreover, the fluorinated alkyl group is preferably a group terminated with a perfluoroalkyl moiety, which is an alkyl group in which all the hydrogen atoms have been substituted with fluorine atoms, and having, between the perfluoroalkyl moiety and the metal atom, a (CH2)h-(where the letter h is an integer from 1 to 6, and preferably 2 to 4) group. These preferences similarly apply when R1 is a monovalent halogenated hydrocarbon group having a substituent or a linkage.
- When R1 is a monovalent hydrocarbon group having a substituent, this refers to a group in which a hydrogen atom on the monovalent hydrocarbon group is substituted with a substituent. When R1 is a monovalent halogenated hydrocarbon group having a substituent, this refers to a group in which a hydrogen atom or halogen atom on the monovalent halogenated hydrocarbon group is substituted with a substituent. Illustrative examples of the substituent in these groups include carboxyl, amide, imide, ester and hydroxyl groups. The number of substituents on these groups is preferably from 1 to 3.
- When R1 is a monovalent hydrocarbon group having a linkage or a monovalent halogenated hydrocarbon group having a linkage, R1 is exemplified by monovalent hydrocarbon or monovalent halogenated hydrocarbon groups having a linkage between carbon-carbon bonds, and monovalent hydrocarbon or monovalent halogenated hydrocarbon groups having a linkage bonded to the end of the group that bonds to the metal atom. Preferred linkages include —O—, —S—, —COO— and —CONR21— (wherein R21 is a hydrogen atom or an alkyl group).
- Of these, for good water repellent and durability, R1 is preferably methyl, a fluoroalkyl group, or a fluoroalkyl group having a linkage. Specific examples in which R1 is a fluorinated alkyl group or a fluorinated alkyl group having a linkage include the following:
- CF3—,
- CF3CF2—,
- (CF3)2CF—,
- (CF3)3C—,
- CF3(CH2)2—,
- CF3(CF2)3(CH2)2—,
- CF3(CF2)5(CH2)2—,
- CF3(CF2)7(CH2)2—,
- CF3(CF2)3(CH2)3—,
- CF3(CF2)5(CH2)3',
- CF3(CF2)7(CH2)3—,
- CF3(CF2)4O(CF2)2(CH2)2—,
- CF3(CF2)4O(CF2)2(CH2)3—,
- CF3(CF2)7O(CF2)2(CH2)2—,
- CF3(CF2)7CONH(CH2)2—,
- CF3(CF2)7CONH(CH2)3—,
- CF3(CF2)3O[CF(CF3)CF(CF3)O]2CF(CF3)CO—,
- NH(CH2)3—,
- CH3(CF2)7(CH2)2—,
- CH3(CF2)8(CH2)2—,
- CH3(CF2)9(CH2)2—,
- CH3(CF2)10(CH2)2—,
- CH3(CF2)11(CH2)2—,
- CH3(CF2)12(CH2)2—,
- CH3(CF2)7(CH2)3—,
- CH3(CF2)9(CH2)3—,
- CH3(CF2)11(CH2)3—)
- CH3CH2(CF2)6(CH2)2—,
- CH3CH2(CF2)8(CH2)2—,
- CH3CH2(CF2)10(CH2)2—,
- CH3(CF2)4O(CF2)2(CH2)2—,
- CH3(CF2)7(CF2)2O(CH2)3—,
- CH3 (CF2)8(CF2)2—O—(CH2)3—,
- CH3(CF2)9(CF2)2—O—(CH2)3—,
- CH3CH2(CF2)6(CH2)2—O—(CH2)3—,
- CH3(CF2)6CONH(CH2)3—,
- CH3(CF2)8CONH(CH2)3—,
- CH3(CF2)3O[CF(CF3)CF(CF)3O]2CF(CF3)CO—,
- NH(CH2)m—,
- Y in formula (II) represents a hydrolyzable group, specific examples of which include alkoxy groups of 1 to 6 carbons, acyloxy groups of 1 to 6 carbons, halogen atoms, isocyanate groups, amino groups and amide groups. When (m−n) is 2 or more, each Y may be like or unlike. Alkoxy groups of 1 to 6 carbons that may be substituted, halogen atoms and isocyanate groups are especially preferred. Also, as noted earlier, given that hydrolyzable groups are functional groups which are capable of incurring hydrolysis and forming a bond with another functional group having an active hydrogen, for the sake of convenience, in this specification, the hydroxyl group is included among the hydrolyzable groups.
- The letter n in formula (II) is any integer from 1 to (m−1). To produce a high-density chemisorption film, it is preferable for the letter n to be 1. M represents an atom selected from the group consisting of silicon, germanium, tin, titanium and zirconium atoms. For such reasons as the availability of starting materials and reactivity, a silicon atom is preferred.
- Of the compounds of formula (II), compounds of formula (III) are preferred. In compound (II), R2 represents an alkylene group, a vinylene group, an ethynylene group, an arylene group or a divalent functional group containing a silicone atom and/or an oxygen atom.
- In the above formula, the letters a and b each represent any integer greater than or equal to 1.
- In formula (III), Z is a hydrogen atom, an alkyl group or a fluoroalkyl group, and the letter r is 0 or any integer from 1 to (m−2). To produce a high-density adsorption film, it is preferable for the letter r to be 0.
- Aside from compounds of formula (III), compounds of formula (II) also include:
- (1) CH3—(CH2)g-MZrYm-r-1
- (2) CH3—(CH2)s—O—(CH2)t-MZrYm-r-1
- (3) CH3—(CH2)u—Si(CH3)2—(CH2)v-MZrYm-r-1
- (4) CF3COO—(CH2)w-MZrYm-r-1
In the formulas, the letters g, s, u, v and w each represent any integer. Preferred ranges are 1 to 25 for g, 0 to 12 for s, 1 to 20 for t, 0 to 12 for u, 1 to 20 for v, and 1 to 25 for w. In addition, Z, Y, r and m have the same meanings as in formula (III). - Specific examples of the compound of formula (II) include the compounds of the following formulas in which the metal atom is a silicon atom. The hydrolyzable groups are not limited to the functional groups shown in the examples; other hydrolyzable groups may likewise be used.
- CH3CH2O(CH2)15Si(OCH3)3,
- CF3CH2O(CH2)15Si(OCH3)3,
- CH3(CH2)2Si(CH3)2(CH2)15Si(OCH3)3,
- CH3(CH2)6Si(CH3)2(CH2)9Si(OCH3)3,
- CH3COO(OCH2)15Si(OCH3)3,
- CF3(CF2)5(CH2)2Si(OCH3)3,
- CF3(CF2)7—(CH═CH)3—Si(OCH3)3,
- CH3CH2O(CH2)15Si(OC2H5)3,
- CH3(CH2)2Si(CH3)2(CH2)15Si(OC2H5)3,
- CH3(CH2)6Si(CH3)2(CH2)9Si(OC2H5)3,
- CF3(CH2)6Si(CH3)2(CH2)9Si(OC2H5)3,
- CH3COO(CH2)15Si(OC2H5)3,
- CF3COO(CH2)15Si(OC2H5)3,
- CF3COO(CH2)15Si(OCH3)3,
- CF3(CF2)9(CH2)2Si(OC2H5)3,
- CF3(CF2)7(CH2)2Si(OC2H5)3,
- CF3(CF2)5(CH2)2Si(OC2H5)3,
- CF3(CF2)7(CH═CH)3Si(OC2H5)3,
- CF3(CF2)9(CH2)2Si(OCH3)3,
- CF3(CF2)5(CH2)2Si(OCH3)3,
- CF3(CF2)7(CH2)2Si(CH3)(OC2H5)2,
- CF3(CF2)7(CH2)2Si(CH3)(OCH3)2,
- CF3(CF2)7(CH2)2Si(CH3)2(OC2H5),
- CF3(CF2)7(CH2)2Si(CH3)2(OCH3),
- CF3(CH2)2SiCl3,
- CF3(CF2)3(CH2)2SiCl3,
- CF3(CF2)5(CH2)2SiCl3,
- CF3(CF2)7(CH2)2SiCl3,
- CF3(CF2)3(CH2)3SiCl3,
- CF3(CF2)5(CH2)3SiCl3,
- CF3(CF2)7(CH2)3SiCl3,
- CF3(CF2)4O(CF2)2(CH2)2SiCl3
- CF3(CF2)4O(CF2)2(CH2)3SiCl3
- CF3(CF2)7(CH2)2O(CH2)3SiCl3
- CF3(CF2)7CONH(CH2)2SiCl3
- CF3(CF2)7CONH(CH2)3SiCl3
- CF3(CF2)3O[CF(CF3)CF(CF3)O]2CF(CF3)CONH(CH2)3SiCl3
- CF3(CF2)3(CH2)2Si(CH3)Cl2
- CF3(CF2)5(CH2)2Si(CH3)Cl2
- CF3(CH2)2Si(CH3)Cl2
- CF3(CF2)3(CH2)3Si(CH3)Cl2
- CF3(CF2)5(CH2)3Si(CH3)Cl2
- CF3(CF2)7(CH2)3Si(CH3)Cl2
- CF3(CF2)4(CF2)2(CH2)2Si(CH3)Cl2
- CF3(CF2)4(CF2)2(CH2)3Si(CH3)Cl2
- CF3(CF2)4(CH2)2O(CH2)3Si(CH3)Cl2
- CF3(CF2)7CONH(CH2)2Si(CH3)Cl2
- CF3(CF2)7CONH(CH2)3Si(CH3)Cl2
- CF3(CF2)3O[CF(CF3)CF(CF3)O]2CF(CF3)CONH(CH2)3Si(CH3)Cl2
- CH3(CH2)7SiCl3
- CH3(CF2)7(CH2)2SiCl3
- CH3(CF2)7(CH2)2Si(CH3)Cl2
- CH3(CF2)7(CH2)2Si(OCH3)3
- CH3(CF2)7(CH2)2Si(NCO)3
- CH3(CF2)8(CH2)2SiCl3
- CH3(CF2)8(CH2)2Si(OCH3)3
- CH3(CF2)8(CH2)2Si(NCO)3
- CH3(CF2)9(CH2)2SiCl3
- CH3(CF2)9(CH2)2Si(OCH3)3
- CH3(CF2)9(CH2)2Si(NCO)3
- CH3CH2(CF2)6(CH2)2SiCl3
- CH3CH2(CF2)6(CH2)2Si(OCH3)3
- CH3CH2(CF2)6(CH2)2Si(NCO)3
- CH3CH2(CF2)8(CH2)2SiCl3
- CH3CH2(CF2)8(CH2)2Si(OCH3)3
- CH3CH2(CF2)8(CH2)2Si(NCO)3
- CH3CH2(CF2)10(CH2)2SiCl3
- CH3(CF2)40(CF2)2(CH2)2SiCl3
- CH3(CF2)7(CH2)2O(CH2)3SiCl3
- CH3(CF2)8(CH2)2O(CH2)3SiCl3
- CH3(CF2)9(CH2)2O(CH2)3SiCl3
- CH3CH2(CF2)6(CH2)2O(CH2)3SiCl3
- CH3(CF2)6CONH(CH2)3SiCl3
- CH3(CF2)8CONH(CH2)3SiCl3
- CH3(CF2)3O[CF(CF3)CF(CF3)O]2CF(CF3)CONH(CH2)3SiCl3
- The above-described metallic surfactant may be used singly or as combinations of two or more thereof. Generally, it is used after dilution with a solvent. If necessary, it may be used together with water in an organic solvent and in the presence of a metal oxide or metal alkoxide partial hydrolysate.
- In the method of producing the monomolecular film of the invention, the following steps are preferably carried out in order:
- (i) coating or spraying a solution containing the dispersoid onto a substrate, and drying to form a metal oxide film; and
- (ii) bringing a solution of the metallic surfactant into contact with the substrate on which the metal oxide film has been formed, and drying.
- In above step (i), the method of coating or spraying the metal oxide-containing solution onto the substrate is not subject to any particular limitation, so long as it can smoothly apply the solution to the surface. Examples of suitable methods include dipping, spin coating, Meyer bar coating and brush coating.
- In above step (ii), any method of bringing the metallic surfactant into contact with the substrate may be used without particular limitation, although dipping is preferred for forming a uniform monomolecular film.
- In the practice of the invention, the content of the metallic surfactant within the solution is not subject to any particular limitation, although a silane compound solution in a range of 0.1 to 30 wt % is preferable for producing a dense monomolecular film.
- Plastic substrates that may be used in the invention include sheet, plate-like substrates and films, with films being especially preferred. Specific examples include cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate, syndiotactic polystyrene, polyethylene-coated paper, polyether sulfone, polyarylate, polyvinylidene fluoride and Teflon (registered trademark).
- No particular limitation is imposed on the size or shape of the substrate; for example, the substrate may be a flat plate, a three-dimensional object or a film. Even a painted object may be used. These substrates may be provided with a polyvinylidene chloride-type polymer-containing waterproofing layer so as to enhance dimensional stability; i.e., the stability to dimensional changes from changes in temperature and humidity. In addition, an organic and/or inorganic compound thin film may be provided as a gas barrier. Illustrative examples of organic thin films include polyvinyl alcohol, and poly(ethylene-co-vinyl alcohol). Illustrative examples of inorganic compounds include silica, alumina, talc, vermiculite, kaolinite, mica and synthetic mica. Various organic and/or inorganic additives may also included in the substrate to confer other capabilities as well.
-
FIG. 1 is shows the UV properties of the titanium alkoxide low-temperature hydrolysate prepared in Example 1. -
FIG. 2 is shows the UV properties of the titanium alkoxide low-temperature hydrolysates prepared in Examples 3, 5, 7 and 9. -
FIG. 3 shows the Raman spectra for the solutions prepared in Examples 4 and 8 andComparative 3. -
FIG. 4 shows the particle size distribution forSol Solution 1 in Example 35. -
FIG. 5 is a graph showing the results of thermogravimetry on the powder in Example 36. -
FIG. 6 shows the particle size distribution for Sol Solution-2 in Example 38. -
FIG. 7 shows the UV properties of the titanium alkoxide hydrolysate prepared in Example 39. -
FIG. 8 shows the light transmittances of the sol solutions in Examples 41 and 45. -
FIG. 9 shows the particle size distribution for the sol solution in Example 41. -
FIG. 10 shows the results of thermogravimetry on the sol solution in Example 43. -
FIG. 11 shows the surface shape of the metal oxide film formed in Example 44. -
FIG. 12 shows the particle size distribution of the sol solution obtained in Example 45. -
FIG. 13 shows the particle size distribution of the sol solution obtained in Example 47. -
FIG. 14 shows the surface shape of the film obtained from solution C-1 in Example 48. -
FIG. 15 shows the elemental composition in the depth direction of the film formed in Example 48. -
FIG. 16 shows the elemental composition in the depth direction near the surface of the film formed in Example 48. -
FIG. 17 shows the surface shape of the STS-01 film in Comparative Example 10. - The invention is described more fully below by way of examples, although the examples are not intended to limit the invention.
- Measurements of particle size distribution and light transmittance were carried out using the following equipment.
- Particle size distribution: dynamic light scattering photometer (DLS-7000: dynamic light scattering measurement; argon laser, 75 mW; manufactured by Otsuka Electric Co., Ltd.)
- Light transmittance: self-recording spectrophotometer (U-4000; manufactured by Hitachi, Ltd.)
- First, 7.87 g (27.7 mmol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) was dissolved in tetrahydrofuran within a four-neck flask. The flask was flushed with nitrogen, then cooled in a dry ice-containing methanol bath (approx. −74° C.). After about 20 minutes of cooling, 0.8 g (44.4 mmol) of distilled water diluted with tetrahydrofuran was added under stirring. The total weight of the tetrahydrofuran solution at this time was 32.12 g. The amount of water added at this time, expressed as a molar ratio with the titanium, was H2O/Ti=1.6. The system was then gradually returned to room temperature, yielding a clear, light yellow tetrahydrofuran solution of titanium isopropoxide hydrolysate. The appearance at this time of the tetrahydrofuran solution obtained is indicated in Table 1. This solution had a visible light transmittance (550 nm) of 87%.
- The UV properties of the solution prepared as described above are shown in
FIG. 1 .FIG. 1 also shows the UV properties of the titanium tetraisopropoxide. On comparing both results, the low-temperature hydrolysate had a better ability to block UV radiation than the titanium tetraisopropoxide, indicating the growth of Ti—O—Ti bonds. - Aside from changing the weight of the distilled water added to 1.0 g (55.6 mmol), the same procedure was carried out as in Example 1. The appearance at this time of the resulting tetrahydrofuran solution is indicated in Table 1.
- Aside from changing the weight of the distilled water added to 1.2 g (66.7 mmol), the same procedure was carried out as in Example 1. The appearance at this time of the resulting tetrahydrofuran solution is indicated in Table 1.
- The tetrahydrofuran solution obtained in Example 1 was vacuum concentrated with a rotary evaporator at a bath temperature of 50° C., giving a clear, light yellow viscous liquid having a titanium oxide equivalent concentration of 40.2 wt %. When tetrahydrofuran solvent was added to this liquid, it re-dissolved.
-
TABLE 1 (Distilled water)/ TiO2 equivalent (Titanium tetraisopropoxide) concentration Appearance at time Appearance (molar ratio) (wt %) of water mixture of sol obtained EX 11.6 5.4 clear, light yellow clear, light yellow EX 2 1.6 40.2 — clear, light yellow CE 1 2.0 5.4 clear, light yellow cloudy gel CE 2 2.4 5.4 clear, light yellow cloudy gel - First, 12.4 g of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99% purity; titanium oxide equivalent concentration, 28.2 wt %) was dissolved in 45.0 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 1.26 g of ion-exchanged water (molar ratio H2O/Ti=1.6) was mixed into 11.3 g of isopropanol, following which the mixture was cooled to −80 to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring, thereby carrying out hydrolysis. During dropwise addition, the liquid temperature within the flask was maintained at −80 to −70° C. After the end of dropwise addition, mixing was continued for 30 minutes under cooling, then the temperature was raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. The appearance at this time of the toluene/isopropanol mixed solution obtained is indicated in Table 2. This solution had a visible light transmittance (550 nm) of 85%.
- The UV properties of the solution prepared as described above are shown in
FIG. 2 . - The solution obtained in Example 3 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 54.3 wt %. The Raman spectrum of the solution thus obtained is shown in
FIG. 3 . When toluene solvent was added to this liquid, re-dissolution occurred. The appearance at this time of the toluene-isopropanol mixed solution obtained at this time is indicated in Table 2. - First, 35.4 g of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99% purity; titanium oxide equivalent concentration, 28.2 wt %) was dissolved in 152.2 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −25° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 1.24 g of ion-exchanged water (molar ratio H2O/Ti=0.55) was mixed into 11.2 g of isopropanol, following which the mixture was cooled to −25° C. and added dropwise in this cooled state to the four-neck flask under stirring. After the end of dropwise addition, the temperature was held at the same level for 30 minutes, then raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 95%. The UV properties of the solution prepared as described above are shown in
FIG. 2 . - The solution obtained in Example 5 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 41.1 wt %. Toluene solvent was added to this liquid, whereupon re-dissolution occurred. The appearance at this time of the toluene-isopropanol mixed solution obtained is indicated in Table 2.
- First, 35.4 g of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99% purity; titanium oxide equivalent concentration, 28.2 wt %) was dissolved in 144 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −25° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 2.04 g of ion-exchanged water (molar ratio H2O/Ti=0.9) was mixed into 18.3 g of isopropanol, following which the mixture was cooled to −25° C. and added dropwise in this cooled state to the four-neck flask under stirring. After the end of dropwise addition, the temperature was held at the same level for 30 minutes, then raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 92%. The UV properties of the solution prepared as described above are shown in
FIG. 2 . - The solution obtained in Example 7 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 45.7 wt %. Toluene solvent was added to this liquid, whereupon re-dissolution occurred. The appearance at this time of the toluene-isopropanol mixed solution obtained is indicated in Table 2.
- First, 17.7 g of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99% purity; titanium oxide equivalent concentration, 28.2 wt %) was dissolved in 68.7 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −70° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 1.36 g of ion-exchanged water (molar ratio H2O/Ti=1.2) was mixed into 12.2 g of isopropanol, following which the mixture was cooled to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring. After the end of dropwise addition, the temperature was held at the same level for 30 minutes, then raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 93%. The Raman spectrum of the liquid thus obtained is shown in
FIG. 3 . The UV properties of the solution prepared as described above are shown inFIG. 2 . - The solution obtained in Example 9 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 50.8 wt %. Toluene solvent was added to this liquid, whereupon re-dissolution occurred. The appearance at this time of the toluene-isopropanol mixed solution obtained is indicated in Table 2.
- First, 35.4 g of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99% purity; titanium oxide equivalent concentration, 28.2 wt %) was dissolved in 144 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then warmed to and held at 80 to 90° C. in an oil bath. In a separate procedure, 2.04 g of ion-exchanged water (molar ratio H2O/Ti=0.9) was mixed into 18.3 g of isopropanol, following which the mixture was added dropwise to the four-neck flask under stirring, thereby carrying out hydrolysis. Following the completion of dropwise addition, heating and refluxing was carried out at 90 to 100° C. for 30 minutes. Next, the flask contents were cooled to room temperature under stirring, yielding a clear, light yellow sol having a titanium oxide equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 75%.
-
TABLE 2 (Distilled water)/ TiO2 equivalent (Titanium tetraisopropoxide) concentration Appearance at time Appearance (molar ratio) (wt %) of water mixture of sol obtained EX 31.6 5.01 clear, light yellow clear, light yellow EX 4 1.6 54.3 — clear, light yellow EX 5 0.55 5.00 clear, colorless clear, colorless EX 6 0.55 41.1 — clear, colorless EX 7 0.9 4.98 clear, colorless clear, colorless EX 8 0.9 45.7 — clear, colorless EX 9 1.2 5.01 clear, colorless clear, colorless EX 10 1.2 50.8 — clear, colorless CE 3 0.9 4.95 clear, light yellow clear, light yellow - First, 10.8 g of zirconium tetra-n-butoxide (TBZR, produced by Nippon Soda Co., Ltd.; 87% purity; zirconium oxide equivalent concentration, 32.2 wt %) was dissolved in 46.9 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 0.812 g of ion-exchanged water (molar ratio H2O/Zr=1.6) was mixed into 7.30 g of 2-butanol, following which the mixture was cooled to −80 to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring. During dropwise addition, the liquid temperature within the flask was maintained at −80 to −70° C. Following the end of dropwise addition, mixing was continued for 30 minutes under cooling, then the temperature was raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, colorless sol having a zirconium oxide equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 88%.
- The solution obtained in Example 11 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a zirconium oxide equivalent concentration of 43 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- First, 9.12 g of tantalum pentaethoxide (produced by Kojundo Chemical Laboratory Co., Ltd.; 99% purity; tantalum oxide equivalent concentration, 54.4 wt %) was dissolved in a mixed solution of 42.1 g toluene and 42.1 g ethanol within a four-neck flask. The flask was flushed with nitrogen, then cooled to −80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 0.652 g of ion-exchanged water (molar ratio H2O/Ta=1.6) was mixed into a mixed solution of 2.96 g toluene and 2.96 g ethanol, following which the mixture was cooled to −80 to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring. During dropwise addition, the liquid temperature within the flask was maintained at −80 to −70° C. Following the end of dropwise addition, mixing was continued for 30 minutes under cooling, then the temperature was raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, colorless sol having a tantalum oxide equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 88%.
- The solution obtained in Example 13 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a tantalum oxide equivalent concentration of 64.5 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- First, 5.00 g of indium triisopropoxide (produced by Kojundo Chemical Laboratory Co., Ltd.; 99% purity; indium oxide equivalent concentration, 47.4 wt %) and 0.79 g of tin tetraisopropoxide-isopropanol adduct (produced by AZmax Co., Ltd.; 99% purity; tin dioxide equivalent concentration, 42.6 wt %) were dissolved in 44.5 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 0.370 g of ion-exchanged water (molar ratio H2O/(In+Sn)=1.08) was mixed into 3.33 g of isopropanol, following which the mixture was cooled to −80 to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring. During dropwise addition, the liquid temperature within the flask was maintained at −80 to −70° C. Following the end of dropwise addition, mixing was continued for 30 minutes under cooling, then the temperature was raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, light yellow mixed sol of indium oxide and tin oxide having a metal oxide (In2O3, SnO2) equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 75%.
- The solution obtained in Example 15 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a concentrate having a metal oxide equivalent concentration of 70 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- First, 66.84 g of a partial hydrolysate of titanium tetraisopropoxide (the product obtained by adding 0.9 mole of water per mole of titanium isopropoxide and hydrolyzing) was dissolved in 402.74 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 3.38 g of ion-exchanged water was mixed into 30.42 g of isopropanol, following which the mixture was cooled to −80 to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring. During dropwise addition, the liquid temperature within the flask was maintained at −80 to −70° C. After the completion of dropwise addition, mixing was continued for 30 minutes under cooling, then the temperature was raised to room temperature under stirring and hydrolysis was carried out, yielding a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. This solution had a visible light transmittance (550 nm) of 92%.
- The solution obtained in Example 17 was concentrated with a rotary evaporator at a bath temperature of 50° C., giving a viscous liquid having a titanium oxide equivalent concentration of 52.3 wt %. When toluene solvent was added to this liquid, re-dissolution occurred.
- First, 3.0 g of a tetrahydrofuran solution containing the titanium isopropoxide hydrolysate prepared in Example 1 was cooled in a dry ice-containing methanol bath (approx. −74° C.), and a tetrahydrofuran solution containing 4.2 g of 2,5-bis(mercaptomethyl)-1,4-dithiane (DMMD) and 4.6 g of 2,5-bis(isocyanatomethyl)-1,4-dithiane (BIMD) was added dropwise and mixed under stirring. Following addition, the temperature was gradually returned to room temperature, then 0.06 g of dibutyltin dilaurate (available from Nakalai Tesque, Inc.) was added and the mixture was stirred. The solvent was then removed by distillation, and the mixture was degassed. Next, the mixture was poured into a glass mold and the mold was tightly closed, following which the temperature was gradually raised from room temperature to 120° C. and polymerization was carried out for 24 hours under heating. The contents were then cooled to room temperature and removed from the mold, giving a transparent mass. The refractive index of the resulting mass was measured with an Abbe refractometer. The refractive index is shown in Table 3.
- Aside from using 1.5 g of the titanium isopropoxide hydrolysate-containing tetrahydrofuran solution prepared in Example 1, the same procedure was carried out as in Example 19. The results are presented in Table 3.
- Aside from not using the titanium isopropoxide hydrolysate-containing tetrahydrofuran solution, the same procedure was carried out as in Example 19. The refractive index of the body thus obtained is shown in Table 3.
-
TABLE 3 Hydrolysate DMMD BIMD Refractive solution (g) (g) (g) index Example 19 3.0 4.2 4.6 1.656 Example 20 1.5 4.2 4.6 1.640 Comparative Example 4 0.0 4.2 4.6 1.633 - First, 3.56 g (12.5 mmol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) was dissolved in 12 g of tetrahydrofuran within a four-neck flask. The flask was flushed with nitrogen, then cooled in a dry ice-containing methanol bath (approx. −74° C.). After about 20 minutes of cooling, 0.36 g (20 mmol) of distilled water diluted with 4 g of tetrahydrofuran was added under stirring. The amount of water added at this time, expressed as a molar ratio with the titanium, was H2O/Ti=1.6. The system was then gradually returned to room temperature, yielding a clear, light yellow tetrahydrofuran solution containing titanium isopropoxide hydrolysate. While still in the nitrogen-flushed state, this solution was again cooled with dry ice-containing methanol. In a separate procedure, 5.0 g of tetrahydrofuran to which had been added 1.0 g of 2,5-bis(mercaptomethyl)-1,4-dithiane (DMMD), 1.0 g of 2,5-bis(isocyanatomethyl)-1,4-dithiane (BIMD) and 0.025 g of dibutyltin dilaurate was shake-stirred in a 60° C. bath for 1 hour, giving a viscous tetrahydrofuran solution containing a polymer of DMMD and BIMD. This polymer-containing viscous tetrahydrofuran solution was added dropwise over 10 minutes to the titanium tetraisopropoxide hydrolysate-containing tetrahydrofuran solution. The resulting mixture was stirred for 30 minutes under cooling, following which the dry ice-containing methanol bath was removed and the temperature was gradually returned to room temperature, giving a clear, light yellow tetrahydrofuran solution. The solids concentration in the solution was 11.1 wt %, and the titanium oxide equivalent concentration based on the total solids was 58.2 mol %.
- A 30×15 mm silicon wafer was dipped in this clear solution and pulled out vertically at a rate of 0.1 mm per second, thereby forming a clear thin-film on the wafer. The reflectance spectrum of this thin-film was measured using a Filmetrics F series, model F20 film thickness measurement system (manufactured by Litho Tech Japan). This spectrum was superimposed with a simulation spectrum obtained by changing the optical constant, and the thickness and refractive index at 633 nm of this thin film were measured. The film thickness and refractive index at this time are shown in Table 4.
- Aside from preparing a titanium tetraisopropoxide hydrolysate-containing toluene solution by the same method as in Example 21, but in toluene rather than tetrahydrofuran, the same procedure was carried out as in Example 21, giving a clear colorless solution.
- This clear solution was used as in Example 21 to form a thin film, and the film thickness and refractive index were measured. The results are given in Table 4.
-
TABLE 4 Film thickness (nm) Refractive index Example 21 130 1.87 Example 22 250 1.88 - Aside from preparing a titanium tetraisopropoxide hydrolysate-containing solution by the same method as in Example 21, but using isopropanol instead of tetrahydrofuran to dilute the distilled water, the same procedure was carried out as in Example 21, giving a clear solution.
- This clear solution was used as in Example 21 to form a thin film, and the film thickness and refractive index were measured. The film thickness was 134 nm and the refractive index was 1.87.
- A tetrahydrofuran solution prepared in the same way as in Example 1 was applied to a glass substrate with a bar coater (No. 5), then dried at 150° C. for 30 minutes, giving a 0.1 μm thick titanium oxide film. This film had a contact angle with water of 42°. When this film was irradiated with near-ultraviolet light from a 15 W black light for 1 hour, the contact angle decreased to 12°, indicating good hydrophilicity. This change was probably due to the elimination of residual isopropoxy groups due to UV exposure.
- The solution obtained in Example 17 was coated onto a glass substrate with a bar coater (No. 5), then dried at 150° C. for 30 minutes, thereby giving a 0.1 μl thick titanium oxide film. This film had a contact angle with water of 28°. When the film was irradiated with 2 mW/cm2 of near-ultraviolet light from a 15 W black light for 1 hour, the contact angle decreased to 3°, indicating good hydrophilicity. Elemental analysis of the thin film using an XPS spectrometer (Quantum 2000, manufactured by Ulvac Phi, Inc.) showed that the elemental concentration of carbon (formula I) in the film following UV irradiation was less than 5%.
-
Elemental concentration of carbon=[(elemental concentration of carbon)/(elemental concentration of carbon+elemental concentration of titanium+elemental concentration of oxygen)]×100 Formula (I) - A solution was prepared by mixing 270 g of the solution obtained in Example 17 with 30 g of a solution obtained by diluting a photocatalyst titania sol (TKS-251, produced by Tayca Corporation) with toluene to a solids content of 5 wt %. The resulting solution was applied to a glass substrate and an aluminum metal substrate by dipping, then dried at 100° C. to give a 0.3 μm thick film in each case.
- To determine the photocatalytic activity of the film, about 0.1 mg/cm2 of salad oil was applied to the film, following which ultraviolet light was applied at an intensity of 2 mW/cm2 with a black light. The results are shown in Table 5. The salad oil decomposed in a short time, indicating a high photocatalytic activity.
-
TABLE 5 Salad oil Specimen Substrate Appearance Adhesion decomposition* 26-1 glass clear good 70% 26-2 aluminum metal clear good 80% *BLB irradiation time, 72 hours - A toluene solution prepared in the same way as in Example 13 was applied with a bar coater (No. 5) onto a gold electrode-coated glass substrate and dried at 150° C. for 30 minutes to give a tantalum oxide film having a thickness of 0.1 μm. A gold electrode was applied by sputtering on top of the film, and the permittivity of the film was measured. The film had a permittivity of 18.
- Fine particles of ITO (produced by Sumitomo Metal Mining) were added in an amount of 5 wt % (ITO basis) to the solution obtained in Example 15, following which the mixture was applied with a bar coater (No. 7) to a PET substrate, and dried at 120° C. for 30 minutes, giving a film having a thickness of 0.2 μm. This film was UV irradiated for 10 minutes using a high-pressure mercury vapor lamp. The resulting film had a surface resistivity of 350 Ω/sq.
- An acrylic-silicon resin (Gemlac YC3918, produced by Kaneka Corporation) and a titania sol prepared in the same way as in Example 3 were mixed in the proportions shown in Table 6 so as to prepare a toluene solution having a solids content of 10 wt % (sum of resin solids weight and titanium oxide equivalent weight). This solution was coated with a bar coater (No. 12) onto various substrates, giving hybrid films. The properties of the resulting films are shown in Table 6. Clear hybrid films were obtained in each case.
- Aside from using titanium tetraisopropoxide in place of titanium oxide, a film was formed in the same way as in Example 30. The results are shown in Table 6. The film turned white, and so a clear film was not obtained.
-
TABLE 6 Resin solids weight/ titanium oxide Appear- Adhe- Substrate equivalent weight ance sion Example 29 glass substrate 80/20 clear good Example 30 glass substrate 50/50 clear good Example 31 glass substrate 30/70 clear good Example 32 PET substrate 80/20 clear good Example 33 PET substrate 50/50 clear good Example 34 PET substrate 30/70 clear good Comparative glass substrate 50/50 cloudy separated Example 5 - First, 130 g (0.46 mol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) was dissolved in 481 g of toluene (Nakalai Tesque, Inc.) in a 1-liter, 4-neck flask. The interior of the flask was flushed with nitrogen, following which the entire contents were cooled in a dry ice-containing methanol bath (approx. −40° C.). In a separate procedure, a dropping funnel capable of being cooled was charged with a solution of 12.4 g (0.69 mol) of distilled water (collected with Advantec GS-200 system) dissolved in 122 g of anhydrous isopropanol (water content, 3.6 ppm), then cooled with dry ice-containing methanol to about −40 to −35° C. Next, this cooled water-isopropanol solution was added in a dropwise manner over a period of 1.5 hours to the toluene solution of titanium tetraisopropoxide, during which time the reaction mixture was held at about −40 to −35° C. Following the end of dropwise addition, the flask contents were stirred at the same temperature for 1 hour, then stirred for another 2 hours at room temperature and subsequently refluxed for 2 hours at 80 to 82° C., yielding a clear titanium tetraisopropoxide hydrolysate solution (a sol having a titanium oxide equivalent concentration of 5 wt %, referred to below as “
Sol Solution 1”). The wavelength of light having a transmittance through this solution of 50% was 358 nm. The sol had an average particle size of 4.5 nm and a sharp, monodispersed particle size distribution. -
FIG. 4 shows the particle size distribution of the sol in the resultingSol Solution 1. InFIG. 4 , the abscissa represents the particle size (nm) and the ordinate represents the peak intensity (%). -
Sol Solution 1 obtained in Example 1 was completely concentrated on a rotary evaporator, giving a powder having a titanium oxide equivalent concentration of 50 wt %. Upon submitting 3.45 mg of this powder to thermogravimetric analysis, an endothermic peak temperature was observed at 255° C. and an exothermic peak temperature was observed at 355° C. The thermogravimetric results are shown inFIG. 5 . InFIG. 5 , the abscissa represents the measurement temperature (Temperature/° C.), the left-hand ordinate represents the percent weight loss (Weight %), and the right-hand ordinate represents heat flow (Heat Flow/μV). Plot (1) is the weight change versus temperature, and Plot (2) is the heat flow versus temperature. - The solution obtained in Example 1 was applied with a No. 3 bar coater onto a polyethylene terephthalate (PET) substrate having an ozone treated surface, then dried at 100° C. for 10 minutes to form a titanium oxide film on the substrate, thereby giving a PET substrate bearing a titanium oxide film. Measurement of the titanium oxide film surface shape using an SPM system (SPA-400 (SII), manufactured by Seiko Instruments, Inc.) showed that the surface had an average roughness of less than 5 nm, indicating excellent smoothness.
- First, 88.3 g (0.31 mol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) was dissolved in 327 g of toluene (Nakalai Tesque, Inc.) in a 2-liter, 4-neck flask. The interior of the flask was flushed with nitrogen, following which the entire contents were cooled in a dry ice-containing methanol bath (approx. −75° C.). To this was added in a dropwise manner over a period of 90 minutes, and under stirring, a separately prepared mixed solution of 8.5 g (H2O/Ti=1.5 mol/mol) of ion-exchanged water diluted with 76 g of isopropanol. The liquid temperature of the flask during dropwise addition was held at −75 to −70° C. Following the completion of dropwise addition, the flask contents were stirred for 30 minutes at −70° C., following which the temperature was raised to room temperature over a period of 3 hours and the mixture was stirred for another 1 hour, giving a clear, colorless liquid. This liquid (reaction mixture) was refluxed at 90 to 100° C. for 2 hours, giving a color, colorless sol having a titanium oxide equivalent concentration of 5 wt % (referred to hereinafter as “
Sol Solution 2”).Sol Solution 2 was a composite of particles having a broad particle size distribution in which the average particle size of primary particles was 5.3 nm, the average particle size of secondary particles was 28.5 nm, and the average particle size of tertiary particles was 187 nm.FIG. 6 shows the particle size distribution of the sol withinSol Solution 2. InFIG. 6 , the abscissa represents particle size (nm), and the ordinate represents f(Is) (%). - First, 17.79 g (62.6 mmol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) and 65.31 g of anhydrous toluene were dissolved by mixing and stirring in a flask under a nitrogen atmosphere (liquid temperature, 18° C.). To this was added, over a period of 2 hours and under stirring, a mixture of 1.69 g (93.9 mmol) of water, 30.42 g of anhydrous isopropanol and 30.42 g of anhydrous toluene (the water concentration of the mixture was 22% the saturation concentration of water in a mixed solvent of isopropanol and toluene) at a liquid temperature of 18 to 20° C., thereby giving a clear, light yellow titanium isopropoxide hydrolysate-containing isopropanol-toluene solution. The amount of water added at this time, expressed as a molar ratio, was H2O/Ti=1.5. An additional 1.5 hours of stirring at a liquid temperature of 18° C. resulted in a somewhat stronger yellow color, and 2.5 hours of refluxing thereafter produced a clear, colorless solution.
- The UV properties of the solution thus prepared were measured using a mixture of 95.73 g of anhydrous toluene and 30.42 g of anhydrous IPA as the baseline. Measurement was carried out at an oxide concentration in each solution of about 3.4%. The results are shown in
FIG. 7 .FIG. 7 also shows the UV properties for titanium tetraisopropoxide. It is apparent from a comparison of the results obtained for the two solutions that the low-temperature hydrolysate had a much better ability to block UV radiation than the titanium tetraisopropoxide, indicating the growth of Ti—O—Ti bonds. - The clear, colorless liquid obtained in Example 1 was vacuum concentrated with a rotary evaporator at a bath temperature of 50° C., thereby giving a viscous liquid that was crusty on top. This liquid easily re-dissolved in anhydrous toluene, anhydrous tetrahydrofuran or anhydrous diethyl ether. It dissolved less readily in anhydrous isopropanol, although dissolution was possible.
- First, 178 g (0.63 mol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) was dissolved in 654 g of tetrahydrofuran in a 4-neck flask. The flask was flushed with nitrogen, then cooled in a dry ice-containing methanol bath (approx. −15° C.). A separately prepared mixed solution of 10.1 g of ion-exchanged water (H2O/Ti=0.9 mol/mol) diluted in 91 g of tetrahydrofuran was added dropwise over a period of 90 minutes under stirring. The liquid temperature of the flask during dropwise addition was held at −15 to −10° C. Following the completion of dropwise addition, the flask contents were held at −10° C. for 30 minutes, then the temperature was raised to room temperature and stirring was continued for 1 hour, giving a clear, colorless liquid. The liquid was then cooled to about −80° C. in a dry-ice-containing methanol bath, and a mixed solution of 6.8 g of ion-exchanged water (H2O/Ti=0.6 mol/mol) diluted with 61 g of tetrahydrofuran was added dropwise over 90 minutes under stirring. Following the completion of dropwise addition, the temperature was raised to room temperature over a period of 3 hours. This solution was refluxed for 2 hours at 90 to 100° C., giving a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. The wavelength of light having a transmittance of 50% through this solution was 358 nm (
FIG. 8 ). Moreover, the sol had an average particle size of 6.5 nm and a sharp, monodispersed particle size distribution (FIG. 9 ). - The solution obtained in Example 41 was vacuum concentrated on a rotary evaporator at a bath temperature of 50° C., yielding a white solid having a titanium oxide equivalent concentration of 56.2 wt %. This re-dissolved when toluene solvent was added. The clear solution obtained after re-dissolution was a monodisperse sol having an average particle size of 7.0 nm.
- The solution obtained in Example 41 was concentrated on a rotary evaporator to a solution having a titanium oxide equivalent concentration of 30 wt %. Upon submitting a 3.45 mg sample of this yellow viscous liquid to thermogravimetric analysis, an endothermic peak was observed at 247° C. and an exothermic peak was observed at 357° C. (
FIG. 10 ). - The solution obtained in Example 41 was applied with a No. 3 bar coater onto a polyethylene terephthalate (PET) substrate having an ozone treated surface, then dried at 100° C. for 10 minutes to form a metal oxide film on the substrate. Measurement of the metal oxide film surface shape using an SPM system (SPA-400 (SII), manufactured by Seiko Instruments, Inc.) indicated that the surface had an average roughness of less than 5 nm. Hence, the metal oxide film of the invention had an excellent surface smoothness (
FIG. 11 ). - First, 530 g (1.86 mol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) was dissolved in 1,960 g of toluene in a 4-neck flask. The flask was flushed with nitrogen, then cooled in a dry ice-containing methanol bath (approx. −15° C.). A separately prepared mixed solution of 30.4 g of ion-exchanged water (H2O/Ti=0.9 mol/mol) diluted in 274 g of isopropanol was added dropwise over a period of 90 minutes under stirring. The liquid temperature of the flask during dropwise addition was held at −15 to −10° C. Following the completion of dropwise addition, the flask contents were held at −10° C. for 30 minutes, then the temperature was raised to room temperature and stirring was continued for 1 hour, giving a clear, colorless liquid. The liquid was then cooled to about −80° C. in a dry-ice-containing methanol bath, and a mixed solution of 20.3 g of ion-exchanged water (H2O/Ti=0.6 mol/mol) diluted in 183 g of isopropanol was added dropwise over 90 minutes under stirring. Following the completion of dropwise addition, the temperature was raised to room temperature over a period of 3 hours. This solution was refluxed for 2 hours at 90 to 100° C., giving a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. The wavelength of light having a transmittance of 50% through this solution was 358 nm (
FIG. 8 ). Moreover, the sol had an average particle size of 5.6 nm and a sharp, monodispersed particle size distribution (FIG. 12 ). - The solution obtained in Example 45 was vacuum concentrated on a rotary evaporator at a bath temperature of 50° C., yielding a white solid having a titanium oxide equivalent concentration of 54.8 wt %. This re-dissolved when toluene solvent was added. The clear solution obtained after re-dissolution was a monodisperse sol having an average particle size of 6.1 nm.
- First, 88.3 g (0.31 mol) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99.9% purity; titanium oxide equivalent concentration, 28 wt %) was dissolved in 327 g of toluene in a 4-neck flask. The flask was flushed with nitrogen, then cooled in a dry ice-containing methanol bath (approx. −75° C.). A separately prepared mixed solution of 8.5 g of ion-exchanged water (H2O/Ti=1.5 mol/mol) diluted in 76 g of isopropanol was added dropwise over a period of 90 minutes under stirring. The liquid temperature of the flask during dropwise addition was held at −75 to −70° C. Following the completion of dropwise addition, the flask contents were held at −70° C. for 30 minutes, then the temperature was raised to room temperature over a period of 3 hours, following which stirring was continued for 1 hour, giving a clear, colorless liquid. This solution was refluxed at 90 to 100° C. for 2 hours, giving a clear, colorless sol having a titanium oxide equivalent concentration of 5 wt %. The sol was a composite of particles having a broad particle size distribution in which the average particle size of primary particles was 5.3 nm, the average particle size of secondary particles was 28.5 nm, and the average particle size of tertiary particles was 187 nm (
FIG. 13 ). -
- (i) First, 530 g of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.) was dissolved in 1,960 g of toluene within a nitrogen-flushed 4-neck flask, then cooled to −15° C. in an ethanol/dry ice bath. In a separate procedure, 30.4 g of ion-exchanged water (molar ratio, H2O/Ti=0.9) was mixed in 274 g of isopropanol and added dropwise to the four-neck flask over a period of 90 minutes under stirring, thereby carrying out hydrolysis. During stirring, the liquid temperature within the flask was held at −15 to −10° C. Following the completion Of dropwise addition, the temperature was held at −10° C. for 30 minutes, then raised to room temperature, after which stirring was continued for 1 hour, giving a clear, colorless liquid. Next, this solution was cooled to −80° C. in an ethanol/dry ice bath, and a mixed solution of 20.3 g of ion-exchanged water (molar ratio H2O/Ti=0.6) and 183 g of isopropanol was added dropwise over 90 minutes under stirring. Following the completion of dropwise addition, the temperature was returned to room temperature over 3 hours. This solution was refluxed at 90 to 100° C. for 2 hours, giving a clear, colorless solution (C-1). The solution had a solids concentration (titanium oxide basis) of 5 wt %. The sol had an average particle size of 5.6 nm and exhibited monodisperse properties with a sharp particle size distribution.
- (ii) First, 12.4 g of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99% purity; titanium oxide equivalent concentration, 28.2 wt %) was dissolved in 45.0 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 1.26 g of ion-exchanged water (molar ratio H2O/Ti=1.6) was mixed into 11.3 g of isopropanol, following which the mixture was cooled to −80 to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring. During dropwise addition, the liquid temperature within the flask was maintained at −80 to −70° C. After the end of dropwise addition, mixing was continued for 30 minutes under cooling, then the temperature was raised to room temperature under stirring, yielding a clear, colorless solution (C-2). The solution had a solids concentration (titanium oxide basis) of 5 wt %. The solution was diluted with anhydrous toluene, giving a clear, colorless solution (C-3). The solution had a solids concentration (titanium oxide basis) of 1 wt %.
- (iii) First, 10.8 g of zirconium tetra-n-butoxide (TBZR, produced by Nippon Soda Co., Ltd.; 87% purity; zirconium oxide equivalent concentration, 32.2 wt %) was dissolved in 46.9 g of toluene within a four-neck flask. The flask was flushed with nitrogen, then cooled to −80° C. in an ethanol/liquid nitrogen bath. In a separate procedure, 0.812 g of ion-exchanged water (molar ratio, H2O/Zr=1.6) was mixed into 7.30 g of 2-butanol, following which the mixture was cooled to −80 to −70° C. and added dropwise in this cooled state to the four-neck flask under stirring, thereby carrying out hydrolysis. During dropwise addition, the liquid temperature within the flask was maintained at −80 to −70° C. Following the completion of dropwise addition, mixing was continued for 30 minutes under cooling, then the temperature was raised to room temperature under stirring, yielding a clear, colorless solution (C-4) having a solids concentration (zirconium oxide basis) of 5 wt %. The solution was diluted with anhydrous toluene, giving a clear, colorless solution (C-5). The resulting solution had a solids concentration (zirconium oxide basis) of 1 wt %.
- (i) Heptadecatrifluorodecyl trimethoxysilane (FAS-17, produced by Shin-Etsu Chemical Co., Ltd.) was diluted with anhydrous toluene to form a solution (C-6) having a solids concentration of 0.5 wt %.
- (ii) First, 3.36 g of solution (C-1) was mixed into 100 g of a 5 wt % heptadecatrifluorodecyl trimethoxysilane (FAS-17, Shin-Etsu Chemical) solution obtained by diluting FAS-17 with anhydrous toluene, then the mixture was stirred for 30 minutes. To this solution was added in a dropwise manner 900 g of a toluene solution saturated with ion-exchanged water. Following the completion of dropwise addition, the mixture was stirred for 2 hours, thereby carrying out hydrolysis. This solution was filtered, giving a solution (C-7).
- Solution (C-1) was coated with a No. 3 bar coater onto an ultrasonically cleaned soda lime glass substrate having an average surface roughness of 2 nm, then dried at 150° C. for 30 minutes, thereby forming a thin film on the glass substrate. Measurement of the thin-film surface shape using an SPM system (SPA-400 (SII), manufactured by Seiko Instruments, Inc.) indicated that the surface had an average roughness of 2.5 nm. Hence, the metal oxide film of the invention had a smooth surface and was clearly well-suited for the efficient formation of a monomolecular film (
FIG. 14 ). - The metal oxide film-bearing substrate obtained as described above was cleaned with ozone gas for 2 minutes then immersed in solution (C-6) for 10 minutes and dried at 60° C. for 10 minutes, thereby forming a chemisorption film composed of FAS-17. Using a microsyringe, 5 μl amounts of water, toluene (Tol) and isopropyl alcohol (IPA) were placed on the surface of the FAS-17 film and the contact angles, 60 seconds later, were measured using a contact angle goniometer (model 360S, manufactured by Erma, Inc.). The values obtained were 106° (water), 62° (toluene) and 40° (IPA), indicating adequate water repellency. In addition, because the surface had an average roughness of 2.3 nm, it was apparent that the FAS-17 film had formed to a high density on the surface of the substrate.
- Analysis of the elements in the chemisorption film made of FAS-17 using an XPS system (Quantum 2000, manufactured by Ulvac Phi, Inc.) gave a molar ratio of fluorine atoms to carbon atoms (F/C) of 1.72, which agreed well with the theoretical value of 1.70 when hydrolysis proceeds to completion. Also, the results of an elemental composition analysis in the depth direction of this self-organizing film indicate that the chemisorption film made of FAS-17 formed a thin monomolecular film having a thickness of 2 nm (
FIGS. 15 and 16 ). Moreover, because substantially no carbon remains in the metal oxide film, it was possible to obtain a film free of organic matter even with low-temperature treatment at 200° C. or below. - The changes in the contact angles on the above chemisorption film made of FAS-17 following 3 hours of exposure to 245 nm UV light at an intensity of 2 mW/cm2 were measured. After three hours, these contact angles were respectively 3.5° (water), 0° (toluene) and 0° (IPA). This means that UV exposure removed the FAS-17 on the substrate, exposing the titanium oxide film. This suggests that a specific pattern can easily be formed by exposing specific positions to energy such as ultraviolet light.
- As in Example 48, solutions were coated with bar coaters of the indicated No. onto the substrates shown in Table 7 that had been administered surface ozone treatment if necessary, then were dried at a specific drying temperature, giving metal oxide films. In addition, aside from using the solutions prepared by the specific methods indicated in Table 7 and immersing the above metal oxide film-bearing substrates for given lengths of time in the specific metallic surfactant solutions indicated in Table 7, monomolecular films made of a self-organizing film was formed on the metal oxide films in the same way as in Example 48. The results for these examples are presented in Table 7, along with the results for Example 48. Monomolecular films made of self-organizing films having a good adhesion and contact angle were obtained on polyester (PET) substrates and acrylic substrates.
- Aside from forming a metal oxide film on the specific substrates indicated in Table 7 using a solution (C-8) of titanium tetraisopropoxide (A-1, produced by Nippon Soda Co., Ltd.; 99% purity; titanium oxide equivalent concentration, 28.2 wt %) diluted with ethanol (titanium oxide concentration of solution, 0.5 wt %), monomolecular films were produced in the same way as in Example 48. The results are presented in Table 7. The metal oxide films had a poor adhesion to the polyester (PET) substrate and the acrylic substrate, resulting in film separation. On a glass substrate, formation of a monomolecular film made of a self-organizing film was inadequate, making it impossible to achieve a sufficient water repellency.
- A solution prepared by diluting a titanium oxide fine particle sol solution (Ishihara Sanyo Kaisha, Ltd.; particle size, 7 nm; referred below as “solution C-9”) with ethanol to 1 wt % was coated, as in Example 48, with a No. 3 bar coater onto an acrylic substrate or a soda lime glass substrate having an ultrasonically cleaned surface with an average roughness of 2 nm, then dried at 150° C. for 30 minutes, thereby forming a thin film on the substrate. The results are shown in Table 7. Measurement of the thin-film surface shape using an SPM system (SPA-400 (SII), manufactured by Seiko Instruments, Inc.) indicated that each of these metal oxide films had an average surface roughness of 45 nm. These films had a poor adhesion and poor wear resistance (
FIG. 17 ). -
TABLE 7 Substrate Metal oxide film Monomolecular film Ozone Bar coater Drying temp. Immersion Contact angle (°) Type a) treatment b) Solution (No.) (° C.) Solution time (min) Water Toluene IPA EX 48 G yes C-1 3 150 C-6 10 106 62 40 EX 49 P yes C-1 3 100 C-7 10 103 62 38 EX 50 A yes C-1 3 60 C-7 10 105 62 40 EX 51 G yes C-2 3 150 C-7 10 107 63 41 EX 52 A yes C-3 5 60 C-7 10 102 61 38 EX 53 G yes C-4 3 150 C-6 10 105 62 42 EX 54 G no C-5 3 150 C-7 10 102 59 39 EX 55 P yes C-5 5 100 C-7 20 100 58 38 EX 56 A yes C-5 3 60 C-7 20 100 58 38 CE 6 A no C-8 3 60 *1 CE 7 P no C-8 3 100 *1 CE 8 G yes C-8 3 150 C-7 60 75 31 25 CE 9 A no C-9 5 60 *1 CE 10 G yes C-9 3 150 *2 a) G: glass; P: PET; A: acrylic b) Yes: ozone-treated; No: not ozone-treated *1 The metal oxide films all peeled off, making it impossible to form a monomolecular film. *2 Monomolecular film formation was not carried out because it was apparent from visual examination that the surface of the metal oxide film was uneven. - As explained above, by using the dispersoid having metal-oxygen bonds of the invention, uniform and transparent organic-inorganic hybrid materials and metal oxide films can be produced. Because such substances have a broad range of possible uses, including as optical materials, this invention has a high industrial applicability.
Claims (6)
1. A metal oxide film formed by coating or spraying, and having a smooth film surface.
2. The metal oxide film of claim 1 , wherein the metal oxide film is formed by drying at a temperature of 200° C. or below.
3. The metal oxide film of claim 1 , wherein the film surface has an average roughness of 10 nm or less.
4. A metal oxide film formed on a plastic substrate, the metal oxide film having a carbon content, expressed as an atomic ratio, of 10% or less.
5. A monomolecular film obtained by forming a metal oxide film having a smooth surface on a substrate, then contacting the metal oxide film with a metallic surfactant having at least one hydrolyzable group.
6. A monomolecular film obtained by:
using a dispersoid having metal-oxygen bonds that are stably dispersed without aggregation in an organic solvent in the absence of at least one selected from the group consisting of an acid, a base, and a dispersion stabilizer, or
using a solution containing the dispersoid, to form a metal oxide film on a substrate, then contacting the metal oxide film with a metallic surfactant having at least one hydrolyzable group.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/929,592 US20110135878A1 (en) | 2002-11-13 | 2011-02-02 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
US13/325,723 US20120082793A1 (en) | 2002-11-13 | 2011-12-14 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
Applications Claiming Priority (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-329097 | 2002-11-13 | ||
JP2002329097 | 2002-11-13 | ||
JP2002-330837 | 2002-11-14 | ||
JP2002330837 | 2002-11-14 | ||
JP2003-024148 | 2003-01-31 | ||
JP2003024148 | 2003-01-31 | ||
JP2003-057173 | 2003-03-04 | ||
JP2003057173 | 2003-03-04 | ||
JP2003179243 | 2003-06-24 | ||
JP2003-179243 | 2003-06-24 | ||
US10/533,580 US7909929B2 (en) | 2002-11-13 | 2003-11-12 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
PCT/JP2003/014367 WO2004043853A1 (en) | 2002-11-13 | 2003-11-12 | Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film |
US12/929,592 US20110135878A1 (en) | 2002-11-13 | 2011-02-02 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/014367 Division WO2004043853A1 (en) | 2002-11-13 | 2003-11-12 | Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film |
US10/533,580 Division US7909929B2 (en) | 2002-11-13 | 2003-11-12 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/325,723 Continuation US20120082793A1 (en) | 2002-11-13 | 2011-12-14 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
Publications (1)
Publication Number | Publication Date |
---|---|
US20110135878A1 true US20110135878A1 (en) | 2011-06-09 |
Family
ID=32314986
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/533,580 Expired - Fee Related US7909929B2 (en) | 2002-11-13 | 2003-11-12 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
US12/929,592 Abandoned US20110135878A1 (en) | 2002-11-13 | 2011-02-02 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
US13/325,723 Abandoned US20120082793A1 (en) | 2002-11-13 | 2011-12-14 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/533,580 Expired - Fee Related US7909929B2 (en) | 2002-11-13 | 2003-11-12 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/325,723 Abandoned US20120082793A1 (en) | 2002-11-13 | 2011-12-14 | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film |
Country Status (5)
Country | Link |
---|---|
US (3) | US7909929B2 (en) |
EP (1) | EP1580164A4 (en) |
JP (3) | JP5008869B2 (en) |
KR (1) | KR100746067B1 (en) |
WO (1) | WO2004043853A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11015117B2 (en) | 2016-09-29 | 2021-05-25 | Fujifilm Corporation | Semiconductor nanoparticle-containing dispersion liquid and film |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040226620A1 (en) | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
JPWO2004081130A1 (en) * | 2003-03-11 | 2006-06-15 | 株式会社豊田中央研究所 | Composition for photocatalyst coating and coating film |
US7141617B2 (en) | 2003-06-17 | 2006-11-28 | The Board Of Trustees Of The University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
US20060009536A1 (en) * | 2004-07-12 | 2006-01-12 | Guang-Way Jang | Functionalized sol-gel material, sol-gel film derived therefrom, and method for preparing the same |
US9158197B2 (en) | 2004-07-12 | 2015-10-13 | Industrial Technology Research Institute | Organic-inorganic hybrid material, hybrid film derived therefrom, and method for preparing the same |
US8178615B2 (en) * | 2004-09-01 | 2012-05-15 | Ppg Industries Ohio, Inc | Process for making polymers having nanostructures incorporated into the matrix of the polymer |
JP2006299049A (en) * | 2005-04-19 | 2006-11-02 | Nippon Soda Co Ltd | Organic-inorganic compounded material and silylated derivative |
US8010032B2 (en) * | 2005-05-23 | 2011-08-30 | Xerox Corporation | Fuser member comprising deflocculated material |
JP5150890B2 (en) * | 2005-07-20 | 2013-02-27 | 国立大学法人 東京大学 | Polymer coated particles |
JP5019151B2 (en) * | 2005-09-22 | 2012-09-05 | 大日本印刷株式会社 | Anti-reflection laminate |
JP4725510B2 (en) * | 2006-01-23 | 2011-07-13 | 三菱化学株式会社 | Titanium oxide fine particle composition, titanium oxide fine particle dispersion and production method thereof |
JP2008231400A (en) * | 2007-02-20 | 2008-10-02 | Suzuka Fuji Xerox Co Ltd | Resin composition for optical element and curable resin composition |
JP4933941B2 (en) * | 2007-04-05 | 2012-05-16 | 花王株式会社 | Method for producing titanic acid nanosheet |
US7956102B2 (en) * | 2007-04-09 | 2011-06-07 | The Board Of Trustees Of The University Of Illinois | Sol-gel inks |
WO2008152744A1 (en) * | 2007-06-15 | 2008-12-18 | Kazufumi Ogawa | Bonding method, and biochemical chip and optical part produced using the method |
WO2008152743A1 (en) * | 2007-06-15 | 2008-12-18 | Kazufumi Ogawa | Bonding method, and biochemical chip and optical part produced using the method |
JP2009037829A (en) * | 2007-08-01 | 2009-02-19 | Akita Univ | Positive electrode for lead-acid storage battery, lead-acid storage battery, and method of manufacturing positive electrode for lead-acid storage battery |
US20090148600A1 (en) * | 2007-12-05 | 2009-06-11 | Xerox Corporation | Metal Nanoparticles Stabilized With a Carboxylic Acid-Organoamine Complex |
US7943116B1 (en) * | 2008-01-24 | 2011-05-17 | Sandia Corporation | High-yield synthesis of brookite TiO2 nanoparticles |
JP5319929B2 (en) * | 2008-02-08 | 2013-10-16 | マツモトファインケミカル株式会社 | Aqueous surface treatment composition |
JP5276024B2 (en) * | 2008-02-22 | 2013-08-28 | 日本曹達株式会社 | Organic thin film forming solution and method for producing the same |
US7922939B2 (en) | 2008-10-03 | 2011-04-12 | The Board Of Trustees Of The University Of Illinois | Metal nanoparticle inks |
US8187500B2 (en) | 2008-10-17 | 2012-05-29 | The Board Of Trustees Of The University Of Illinois | Biphasic inks |
JP2011038012A (en) * | 2009-08-12 | 2011-02-24 | Kri Inc | Production process of optical resin composition |
JP5700259B2 (en) * | 2010-02-17 | 2015-04-15 | 住友金属鉱山株式会社 | Method for producing transparent conductive film, transparent conductive film, element using the same, transparent conductive substrate and device using the same |
JP2014506943A (en) * | 2011-02-22 | 2014-03-20 | ビーエーエスエフ ソシエタス・ヨーロピア | Polymers based on glycerol carbonate and amines |
JP5441975B2 (en) * | 2011-10-11 | 2014-03-12 | 日本曹達株式会社 | Organic-inorganic composite |
KR101634895B1 (en) * | 2012-07-10 | 2016-06-29 | 닛뽕소다 가부시키가이샤 | Thin-film laminate having self-assembled monolayer |
WO2015146127A1 (en) * | 2014-03-27 | 2015-10-01 | 日本曹達株式会社 | Method for producing substrate having hydrophobized surface |
US10172882B2 (en) | 2014-06-22 | 2019-01-08 | Dexcel Pharma Technologies Ltd. | Pharmaceutical compositions comprising ferric citrate and methods for the production thereof |
JPWO2016006212A1 (en) * | 2014-07-11 | 2017-05-25 | 日本曹達株式会社 | Laminate |
WO2017090512A1 (en) | 2015-11-26 | 2017-06-01 | 東レ株式会社 | Polymetalloxane, method for producing same, composition thereof, cured film and method for producing same, and members and electronic components provided with same |
US9995950B2 (en) * | 2016-01-29 | 2018-06-12 | Carl Zeiss Vision International Gmbh | Spectacle lens for car drivers |
US10118195B2 (en) * | 2016-03-16 | 2018-11-06 | The Boeing Company | Methods for depositing a transparent thin film onto substrates using an atmospheric plasma generating device |
JP2020050566A (en) * | 2018-09-28 | 2020-04-02 | リンテック株式会社 | Method for producing crystalline titanium oxide gel |
WO2022018980A1 (en) * | 2020-07-22 | 2022-01-27 | 三井金属鉱業株式会社 | Tantalate dispersion and tantalate compound |
JPWO2023171020A1 (en) * | 2022-03-11 | 2023-09-14 | ||
CN114573878B (en) * | 2022-03-18 | 2023-03-17 | 潍坊潍森纤维新材料有限公司 | Preparation method and application of food-pharmaceutical grade biological cellulose transparent material |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4801399A (en) * | 1986-02-25 | 1989-01-31 | University Of Florida | Inorganic salts as peptizing agents in the preparation of metal oxide sol-gel compositions |
US5482768A (en) * | 1993-05-14 | 1996-01-09 | Asahi Glass Company Ltd. | Surface-treated substrate and process for its production |
US5871843A (en) * | 1996-03-27 | 1999-02-16 | Asahi Glass Company Ltd. | Laminate and process for its production |
US5904989A (en) * | 1996-04-18 | 1999-05-18 | Alusuisse Technology & Management Ltd. | Aluminum surface with interference colors |
US6121647A (en) * | 1996-06-26 | 2000-09-19 | Tdk Corporation | Film structure, electronic device, recording medium, and process of preparing ferroelectric thin films |
US6143063A (en) * | 1996-03-04 | 2000-11-07 | Symetrix Corporation | Misted precursor deposition apparatus and method with improved mist and mist flow |
US6235260B1 (en) * | 1997-05-26 | 2001-05-22 | Kri International, Inc. | Method for producing In2O3—SnO2 precursor sol |
US20010007006A1 (en) * | 1999-12-17 | 2001-07-05 | Noritaka Tanimura | Polyacetal resin composition |
US6284197B1 (en) * | 1998-06-05 | 2001-09-04 | The Regents Of The University Of California | Optical amplification of molecular interactions using liquid crystals |
US20020015852A1 (en) * | 2000-04-27 | 2002-02-07 | Tdk Corporation | Multilayer thin film and its fabrication process as well as electron device |
US6413883B1 (en) * | 1996-03-04 | 2002-07-02 | Symetrix Corporation | Method of liquid deposition by selection of liquid viscosity and other precursor properties |
US20040106697A1 (en) * | 2002-08-22 | 2004-06-03 | Degussa Ag | Stabilized, aqueous silicon dioxide dispersion |
US20040197254A1 (en) * | 2001-08-03 | 2004-10-07 | Motoyuki Toki | Dispersed ingredient having metal-oxygen |
Family Cites Families (107)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51125487A (en) | 1975-03-26 | 1976-11-01 | Japan Atom Energy Res Inst | Aprocess for producing transparent plastic shaped articles |
JPS5441965A (en) | 1977-09-09 | 1979-04-03 | Asahi Glass Co Ltd | Manufacture of optical element |
JPS57136601A (en) | 1981-02-19 | 1982-08-23 | Toray Ind Inc | Urethan resin plastic lens |
US4440918A (en) | 1982-01-18 | 1984-04-03 | Minnesota Mining And Manufacturing Company | Contact lens containing a fluorinated telechelic polyether |
JPS60199016A (en) | 1984-03-23 | 1985-10-08 | Mitsui Toatsu Chem Inc | Thiocarbomic acid s-alkyl ester resin for lens |
JPS60217229A (en) | 1984-04-11 | 1985-10-30 | Mitsui Toatsu Chem Inc | Sulfur atom-containing polyurethane resin for lens |
JPH079481B2 (en) | 1984-04-11 | 1995-02-01 | 三井東圧化学株式会社 | Polyurethane-based plastic lens containing sulfur atoms |
JPS6346213A (en) | 1986-03-01 | 1988-02-27 | Mitsui Toatsu Chem Inc | Resin for high-refractive index plastic lens |
EP0237081B1 (en) * | 1986-03-14 | 1992-01-22 | Matsushita Electric Industrial Co., Ltd. | Process for the preparation of complex perovskite type compounds |
JPH0660016B2 (en) * | 1986-03-14 | 1994-08-10 | 松下電器産業株式会社 | Method for producing compound perovskite type compound |
JPS62236818A (en) | 1986-04-07 | 1987-10-16 | Mitsui Toatsu Chem Inc | Casting of sulfur-containing urethane resin |
JPS62255901A (en) | 1986-04-30 | 1987-11-07 | Mitsui Toatsu Chem Inc | Method for coloring lens made of sulfur-containing urethane |
JPS62267316A (en) | 1986-05-16 | 1987-11-20 | Mitsui Toatsu Chem Inc | Resin for plastic lens having high refractive index |
JPH0678415B2 (en) | 1986-11-21 | 1994-10-05 | 三井東圧化学株式会社 | Resin for high refractive index plastic lenses |
JPH0689097B2 (en) | 1986-11-21 | 1994-11-09 | 三井東圧化学株式会社 | Method for producing resin for high refractive index plastic lens |
JPH0777733B2 (en) | 1986-12-15 | 1995-08-23 | 三井東圧化学株式会社 | Cast polymerization method for lenses made of sulfur-containing urethane resin |
JPS63245421A (en) | 1987-04-01 | 1988-10-12 | Mitsui Toatsu Chem Inc | Lowly hygroscopic, sulfur-containing urethane resin |
JP2612295B2 (en) | 1987-04-01 | 1997-05-21 | 三井東圧化学株式会社 | Resins for high refractive index plastic lenses and lenses made of these resins |
JPS63265201A (en) | 1987-04-23 | 1988-11-01 | Mitsui Toatsu Chem Inc | Production of colored plastic lens |
JPH0816144B2 (en) | 1987-05-26 | 1996-02-21 | 三井東圧化学株式会社 | Method for producing resin for high refractive index plastic lens and lens made of resin obtained by the method |
JP2668364B2 (en) | 1987-09-19 | 1997-10-27 | 三井東圧化学株式会社 | High refractive index plastic lens |
JPH07118989B2 (en) | 1987-09-22 | 1995-12-20 | ホーヤ株式会社 | Polyurethane lens manufacturing method |
JPH07116128B2 (en) | 1987-09-29 | 1995-12-13 | 三井東圧化学株式会社 | Polythiol |
JPH07116127B2 (en) | 1987-09-29 | 1995-12-13 | 三井東圧化学株式会社 | Polythiol |
JPH07116129B2 (en) | 1987-09-29 | 1995-12-13 | 三井東圧化学株式会社 | Polythiol |
JP2541582B2 (en) | 1987-09-29 | 1996-10-09 | 三井東圧化学株式会社 | Polythiol |
JPH0196208A (en) | 1987-10-09 | 1989-04-14 | Mitsui Toatsu Chem Inc | Thermosetting composition |
JPH01129032A (en) | 1987-11-12 | 1989-05-22 | Nippon Soda Co Ltd | Ladderlike polytitanoxane and its production |
JPH01152019A (en) | 1987-11-16 | 1989-06-14 | Mitsui Toatsu Chem Inc | Molding method for sulfuric polyurethane |
JP2600341B2 (en) * | 1987-11-17 | 1997-04-16 | 日本合成ゴム株式会社 | Method for producing particulate metal compound |
US4929707A (en) | 1988-02-16 | 1990-05-29 | Mitsui Toatsu Chemicals, Inc. | Polyurethane base lens resin, plastic lens comprising the resin and preparation method of the lens |
CA1320806C (en) | 1988-02-17 | 1993-08-03 | Teruyuki Nagata | Plastic lenses having a high-refracting index and process for the preparation thereof |
JP2615182B2 (en) | 1988-02-17 | 1997-05-28 | 三井東圧化学株式会社 | Method for producing high refractive index optical element and plastic lens, optical element obtained by the method, and plastic lens |
JP2615183B2 (en) | 1988-02-18 | 1997-05-28 | 三井東圧化学株式会社 | Method for producing optical element and lens made of thiocarbamic acid S-alkyl ester resin, optical element and lens obtained by the method |
JP2680593B2 (en) | 1988-02-22 | 1997-11-19 | 三井東圧化学株式会社 | Urethane resin lens and manufacturing method thereof |
CA1316315C (en) | 1988-02-22 | 1993-04-20 | Nobuyuki Kajimoto | Highly-refractive plastic lens and process for making the lens |
JP2575811B2 (en) | 1988-06-09 | 1997-01-29 | 三井東圧化学株式会社 | Thiocarbamic acid S-alkyl ester resin for lenses and lens made of the resin |
EP0351073B1 (en) | 1988-07-14 | 1994-09-21 | MITSUI TOATSU CHEMICALS, Inc. | Lens comprising a resin having a large refractive index and process for preparing the lens |
JP2621991B2 (en) | 1988-12-22 | 1997-06-18 | 三井東圧化学株式会社 | Mercapto compound and method for producing the same |
CA2010689A1 (en) * | 1989-02-27 | 1990-08-27 | Nobuhiro Mukai | Process for producing powders |
JPH0618849B2 (en) | 1989-05-24 | 1994-03-16 | 三井東圧化学株式会社 | Method for producing resin for high refractive index plastic lens |
JPH0369506A (en) * | 1989-08-07 | 1991-03-25 | Ricoh Co Ltd | Multiple metal oxide superfine grains |
JPH0832304B2 (en) * | 1989-08-18 | 1996-03-29 | 株式会社日立製作所 | Method for forming inorganic polymer thin film |
JP2955298B2 (en) | 1989-08-24 | 1999-10-04 | 三井化学株式会社 | Epoxy resin lens and manufacturing method thereof |
JP2950862B2 (en) | 1989-08-29 | 1999-09-20 | 三井化学株式会社 | Thiocarbamic acid S-alkyl ester-based lens and method for producing the same |
JP3084028B2 (en) | 1989-08-29 | 2000-09-04 | 三井化学株式会社 | Polysulfide resin and lens made of the resin |
JPH0768326B2 (en) | 1989-10-09 | 1995-07-26 | 三井東圧化学株式会社 | Method for manufacturing urethane lens resin |
US5318857A (en) * | 1989-11-06 | 1994-06-07 | Dow Corning Corporation | Low temperature ozonolysis of silicon and ceramic oxide precursor polymers to ceramic coatings |
JPH065323B2 (en) | 1989-12-28 | 1994-01-19 | ホーヤ株式会社 | Optical material and optical product obtained by using polythiol compound |
JPH0620752B2 (en) | 1990-03-30 | 1994-03-23 | ホーヤ株式会社 | Polyurethane lens manufacturing method |
JP3171589B2 (en) | 1990-07-23 | 2001-05-28 | 三井化学株式会社 | Manufacturing method of lens |
JP2871039B2 (en) | 1990-09-06 | 1999-03-17 | 三井化学株式会社 | Isocyanate compound and sulfur-containing urethane resin and lens using the same |
JP2854944B2 (en) | 1990-09-06 | 1999-02-10 | 三井化学株式会社 | Isocyanate compound and sulfur-containing urethane resin and lens using the same |
JP2998982B2 (en) | 1990-10-19 | 2000-01-17 | ホーヤ株式会社 | Polyisocyanate compound, optical material and optical product obtained using the same |
JPH05805A (en) * | 1991-06-20 | 1993-01-08 | Sumitomo Electric Ind Ltd | Thin film formation by a sol-gel method |
JPH04256558A (en) | 1991-02-06 | 1992-09-11 | Mitsui Toatsu Chem Inc | Processing method for sulphur containing lens |
JP3222182B2 (en) | 1991-03-25 | 2001-10-22 | 三井化学株式会社 | Plastic lens made of resin with improved hue, total light transmittance and optical distortion of urethane resin for optical use |
JP2740714B2 (en) | 1991-08-08 | 1998-04-15 | 三井東圧化学株式会社 | Mercapto compound and method for producing the same |
JP3115371B2 (en) | 1991-09-03 | 2000-12-04 | ホーヤ株式会社 | Polymer for optical material and method for producing the same |
EP0545135B1 (en) * | 1991-11-30 | 1998-06-17 | MERCK PATENT GmbH | Production of sols of metal oxides by electrolysis |
JP3083196B2 (en) | 1992-03-25 | 2000-09-04 | 三井化学株式会社 | Sulfur-containing plastic lens and manufacturing method thereof |
JP3118304B2 (en) | 1992-04-17 | 2000-12-18 | 三井化学株式会社 | Sulfur-containing plastic lens and manufacturing method thereof |
JP3103670B2 (en) | 1992-05-22 | 2000-10-30 | 三井化学株式会社 | Method for producing sulfur-containing urethane resin and lens |
JP2931161B2 (en) | 1992-08-11 | 1999-08-09 | ホーヤ株式会社 | Polyisocyanate compound |
JP3222940B2 (en) | 1992-08-26 | 2001-10-29 | 三井化学株式会社 | Method for producing pentaerythrithiol |
JP3270581B2 (en) | 1992-08-26 | 2002-04-02 | 三井化学株式会社 | Composition and lens for high refractive index plastic lens |
JPH06256459A (en) | 1993-03-02 | 1994-09-13 | Hoya Corp | Polymer for optical material and its production |
JP3205115B2 (en) | 1993-03-05 | 2001-09-04 | 三井化学株式会社 | Polythiol compound, resin and lens using the same |
JP3571358B2 (en) | 1993-04-27 | 2004-09-29 | Hoya株式会社 | Dyeing method for plastic lens and dyed lens |
JP3583161B2 (en) * | 1993-05-12 | 2004-10-27 | 朝日化学工業株式会社 | Method for producing titanium oxide compound having photochromic properties |
JP2644671B2 (en) | 1993-08-31 | 1997-08-25 | ホーヤ株式会社 | Composition for plastic lens and method for producing plastic lens |
JP3279784B2 (en) | 1993-09-03 | 2002-04-30 | 三井化学株式会社 | Composition for plastic lens, lens, and method for producing them |
JP2695599B2 (en) | 1993-09-29 | 1997-12-24 | ホーヤ株式会社 | Manufacturing method of polyurethane lens |
JP2813535B2 (en) | 1993-10-19 | 1998-10-22 | ホーヤ株式会社 | Optical material and method for manufacturing the same |
JP2766611B2 (en) | 1993-10-19 | 1998-06-18 | ホーヤ株式会社 | Reactive oligomer |
JP3256358B2 (en) | 1993-12-17 | 2002-02-12 | 三井化学株式会社 | Composition and lens for high refractive index plastic lens |
JP3279848B2 (en) | 1993-12-20 | 2002-04-30 | 三井化学株式会社 | High-speed polymerizable resin composition and lens |
US5608115A (en) | 1994-01-26 | 1997-03-04 | Mitsui Toatsu Chemicals, Inc. | Polythiol useful for preparing sulfur-containing urethane-based resin and process for producing the same |
JP3238269B2 (en) | 1994-03-04 | 2001-12-10 | 三井化学株式会社 | Composition and lens for high refractive index plastic lens |
JP3205163B2 (en) | 1994-03-11 | 2001-09-04 | 三井化学株式会社 | Composition for plastic lens, lens, and method for producing them |
JP3205164B2 (en) | 1994-03-16 | 2001-09-04 | 三井化学株式会社 | Composition for plastic lens, lens, and method for producing them |
JPH07324118A (en) | 1994-04-06 | 1995-12-12 | Mitsui Toatsu Chem Inc | Urethane plastic lens composition of low specific gravity, lens obtained therefrom, resin for lens, and production thereof |
JPH07316250A (en) | 1994-05-30 | 1995-12-05 | Hoya Corp | Plastic lens for spectacles |
JP3328440B2 (en) | 1994-09-08 | 2002-09-24 | 三井化学株式会社 | Method for producing near-infrared absorbing urethane resin |
JPH0892345A (en) | 1994-09-26 | 1996-04-09 | Mitsui Toatsu Chem Inc | Production of thermosetting polyurethane resin-based molded article |
JP2614427B2 (en) | 1994-12-28 | 1997-05-28 | 三井東圧化学株式会社 | Urethane lens |
JP3491660B2 (en) | 1995-08-16 | 2004-01-26 | 三菱瓦斯化学株式会社 | Novel linear alkyl sulfide type episulfide compound |
JP3864998B2 (en) | 1995-09-08 | 2007-01-10 | 三菱瓦斯化学株式会社 | Novel branched alkyl sulfide type episulfide compounds |
WO1997011975A1 (en) * | 1995-09-29 | 1997-04-03 | Nippon Kayaku Kabushiki Kaisha | Actinic radiation-curable and heat ray-shielding resin composition and film coated with the same |
JP3224750B2 (en) | 1995-11-28 | 2001-11-05 | 石原産業株式会社 | Fine particle titanium dioxide silicone dispersion |
JPH09255781A (en) | 1996-01-17 | 1997-09-30 | Mitsubishi Gas Chem Co Inc | New episulfide compound |
JPH09208651A (en) | 1996-01-30 | 1997-08-12 | Mitsui Toatsu Chem Inc | Production of urethane plastic lens and urethane plastic lens obtained thereby |
WO1998002378A1 (en) * | 1996-07-17 | 1998-01-22 | Citizen Watch Co., Ltd. | Ferroelectric element and process for producing the same |
JP3955122B2 (en) * | 1996-08-30 | 2007-08-08 | 花王株式会社 | Zinc oxide ultrafine particles and method for producing the same |
JP4095694B2 (en) | 1997-04-18 | 2008-06-04 | 株式会社Kri | Method for producing metal oxide precursor sol and method for producing metal oxide molded body |
JP3883272B2 (en) | 1997-09-03 | 2007-02-21 | 三井化学株式会社 | Novel (thio) epoxy compounds |
DE69822480T2 (en) * | 1997-09-05 | 2004-08-12 | Cambridge Display Technology Ltd. | TRANSPORT LAYERS IN SELF-ASSEMBLY TECHNOLOGY FOR OLED'S |
JPH11180977A (en) | 1997-10-16 | 1999-07-06 | Mitsubishi Gas Chem Co Inc | New episulfide compound |
JP3963546B2 (en) | 1997-12-18 | 2007-08-22 | 三井化学株式会社 | New (thio) epoxy resin |
JP3987179B2 (en) | 1997-12-25 | 2007-10-03 | 三井化学株式会社 | Sulfur-containing epoxy compounds and uses thereof |
FR2775914B1 (en) * | 1998-03-13 | 2000-04-21 | Saint Gobain Vitrage | METHOD FOR DEPOSITING LAYERS BASED ON METAL OXIDE (S) |
JP3609262B2 (en) | 1998-08-07 | 2005-01-12 | 石原産業株式会社 | Titanium oxide sol and method for producing the same |
JP2000351610A (en) * | 1999-06-10 | 2000-12-19 | Suzuka Fuji Xerox Co Ltd | Synthesis of sol-gel liquid |
DE60118052T2 (en) * | 2000-04-13 | 2006-10-26 | Jsr Corp. | Coating agent, method of preparation, cured product and coating film |
JP2001342018A (en) | 2000-05-31 | 2001-12-11 | Japan Carlit Co Ltd:The | Metal oxide precursor solution and metal oxide thin film |
US20040058380A1 (en) * | 2002-09-12 | 2004-03-25 | Kalle Levon | Surface imprinting: integration of molecular recognition and transduction |
JP4311134B2 (en) * | 2002-09-20 | 2009-08-12 | 株式会社村田製作所 | Metal oxide ultrafine particle dispersion solution and metal oxide ultrafine particle thin film |
-
2003
- 2003-11-12 EP EP03772702A patent/EP1580164A4/en not_active Withdrawn
- 2003-11-12 JP JP2005505670A patent/JP5008869B2/en not_active Expired - Fee Related
- 2003-11-12 US US10/533,580 patent/US7909929B2/en not_active Expired - Fee Related
- 2003-11-12 KR KR1020057008272A patent/KR100746067B1/en not_active IP Right Cessation
- 2003-11-12 WO PCT/JP2003/014367 patent/WO2004043853A1/en active Application Filing
-
2011
- 2011-02-02 US US12/929,592 patent/US20110135878A1/en not_active Abandoned
- 2011-03-04 JP JP2011048116A patent/JP5430594B2/en not_active Expired - Fee Related
- 2011-12-14 US US13/325,723 patent/US20120082793A1/en not_active Abandoned
-
2012
- 2012-03-19 JP JP2012062286A patent/JP5639103B2/en not_active Expired - Fee Related
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4801399A (en) * | 1986-02-25 | 1989-01-31 | University Of Florida | Inorganic salts as peptizing agents in the preparation of metal oxide sol-gel compositions |
US5482768A (en) * | 1993-05-14 | 1996-01-09 | Asahi Glass Company Ltd. | Surface-treated substrate and process for its production |
US6143063A (en) * | 1996-03-04 | 2000-11-07 | Symetrix Corporation | Misted precursor deposition apparatus and method with improved mist and mist flow |
US6413883B1 (en) * | 1996-03-04 | 2002-07-02 | Symetrix Corporation | Method of liquid deposition by selection of liquid viscosity and other precursor properties |
US5871843A (en) * | 1996-03-27 | 1999-02-16 | Asahi Glass Company Ltd. | Laminate and process for its production |
US5904989A (en) * | 1996-04-18 | 1999-05-18 | Alusuisse Technology & Management Ltd. | Aluminum surface with interference colors |
US6387712B1 (en) * | 1996-06-26 | 2002-05-14 | Tdk Corporation | Process for preparing ferroelectric thin films |
US6121647A (en) * | 1996-06-26 | 2000-09-19 | Tdk Corporation | Film structure, electronic device, recording medium, and process of preparing ferroelectric thin films |
US6235260B1 (en) * | 1997-05-26 | 2001-05-22 | Kri International, Inc. | Method for producing In2O3—SnO2 precursor sol |
US6284197B1 (en) * | 1998-06-05 | 2001-09-04 | The Regents Of The University Of California | Optical amplification of molecular interactions using liquid crystals |
US20020142453A1 (en) * | 1998-06-05 | 2002-10-03 | The Regents Of The University Of California | Optical amplification of molecular interactions using liquid crystals |
US20010007006A1 (en) * | 1999-12-17 | 2001-07-05 | Noritaka Tanimura | Polyacetal resin composition |
US20020015852A1 (en) * | 2000-04-27 | 2002-02-07 | Tdk Corporation | Multilayer thin film and its fabrication process as well as electron device |
US20040197254A1 (en) * | 2001-08-03 | 2004-10-07 | Motoyuki Toki | Dispersed ingredient having metal-oxygen |
US20040106697A1 (en) * | 2002-08-22 | 2004-06-03 | Degussa Ag | Stabilized, aqueous silicon dioxide dispersion |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11015117B2 (en) | 2016-09-29 | 2021-05-25 | Fujifilm Corporation | Semiconductor nanoparticle-containing dispersion liquid and film |
Also Published As
Publication number | Publication date |
---|---|
US20060239902A1 (en) | 2006-10-26 |
WO2004043853A1 (en) | 2004-05-27 |
US7909929B2 (en) | 2011-03-22 |
JP5430594B2 (en) | 2014-03-05 |
JP5008869B2 (en) | 2012-08-22 |
KR20050086468A (en) | 2005-08-30 |
EP1580164A4 (en) | 2010-12-29 |
EP1580164A1 (en) | 2005-09-28 |
US20120082793A1 (en) | 2012-04-05 |
JPWO2004043853A1 (en) | 2006-03-09 |
KR100746067B1 (en) | 2007-08-03 |
JP5639103B2 (en) | 2014-12-10 |
JP2011157553A (en) | 2011-08-18 |
JP2012136428A (en) | 2012-07-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7909929B2 (en) | Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film | |
JP5133815B2 (en) | Dispersoid with metal-oxygen | |
US8648130B2 (en) | Resin composition, transparent member obtained from the resin composition, and use of the same | |
KR101718584B1 (en) | Composite nickel nanoparticles and method for producing same | |
JPWO2012176439A1 (en) | Polymerizable composition | |
JP4139701B2 (en) | Organic-inorganic composite | |
WO2010050580A1 (en) | Curable compositions | |
JP5441975B2 (en) | Organic-inorganic composite | |
JPWO2004067447A1 (en) | Method for producing dispersoid having metal-oxygen bond and dispersoid | |
JP2006299049A (en) | Organic-inorganic compounded material and silylated derivative | |
JP2008015465A (en) | Method for manufacturing optical product | |
JP6389497B2 (en) | Flexible transparent heat-resistant film | |
Gu et al. | Polythiourethane composite film with high transparency, high refractive index and low dispersion containing ZnS nanoparticle via thiol-ene click chemistry | |
JPH08252829A (en) | Manufacture of plastic lens, and laminated body |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |