JP4731137B2 - Method for producing silica-based fine particles - Google Patents
Method for producing silica-based fine particles Download PDFInfo
- Publication number
- JP4731137B2 JP4731137B2 JP2004199756A JP2004199756A JP4731137B2 JP 4731137 B2 JP4731137 B2 JP 4731137B2 JP 2004199756 A JP2004199756 A JP 2004199756A JP 2004199756 A JP2004199756 A JP 2004199756A JP 4731137 B2 JP4731137 B2 JP 4731137B2
- Authority
- JP
- Japan
- Prior art keywords
- silica
- fine particles
- based fine
- sio
- range
- 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.)
- Expired - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 550
- 239000010419 fine particle Substances 0.000 title claims description 283
- 239000000377 silicon dioxide Substances 0.000 title claims description 272
- 238000004519 manufacturing process Methods 0.000 title claims description 54
- 239000006185 dispersion Substances 0.000 claims description 148
- 238000000576 coating method Methods 0.000 claims description 102
- 239000011248 coating agent Substances 0.000 claims description 99
- 239000000758 substrate Substances 0.000 claims description 78
- 239000002245 particle Substances 0.000 claims description 60
- 239000002131 composite material Substances 0.000 claims description 56
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 53
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 150000003839 salts Chemical class 0.000 claims description 40
- 239000003792 electrolyte Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 21
- -1 ammonium ions Chemical class 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 150000002484 inorganic compounds Chemical class 0.000 claims description 11
- 229910010272 inorganic material Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000005641 methacryl group Chemical group 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims description 3
- 125000005372 silanol group Chemical group 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 4
- 230000005070 ripening Effects 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 81
- 235000002639 sodium chloride Nutrition 0.000 description 27
- 239000011347 resin Substances 0.000 description 26
- 229920005989 resin Polymers 0.000 description 26
- 239000007787 solid Substances 0.000 description 26
- 239000011734 sodium Substances 0.000 description 25
- 239000011159 matrix material Substances 0.000 description 20
- 238000000108 ultra-filtration Methods 0.000 description 17
- 239000012528 membrane Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 10
- 239000011164 primary particle Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 101710201629 Ribulose bisphosphate carboxylase/oxygenase activase 2, chloroplastic Proteins 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 description 1
- HNJCRKROKIPREU-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F HNJCRKROKIPREU-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-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
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、内部に空洞を有するシリカ系微粒子およびその製造方法と、該シリカ系微粒子を含む被膜形成用塗料と、該シリカ系微粒子を含む被膜が基材表面上に形成された被膜付基材に関するものである。 The present invention relates to silica-based fine particles having cavities therein, a method for producing the same, a coating-forming coating material containing the silica-based fine particles, and a coated substrate in which a film containing the silica-based fine particles is formed on the surface of the substrate It is about.
従来、粒径が０．１〜３００μｍ程度の中空シリカ粒子は公知である（特許文献１、特許文献２など参照）。また、珪酸アルカリ金属水溶液から活性シリカをシリカ以外の材料からなるコア上に沈殿させ、該材料をシリカシェルを破壊させることなく除去することによって、稠密なシリカシェルからなる中空粒子を製造する方法が公知である（特許文献３など参照）。
さらに、外周部が殻、中心部が中空で、殻は外側が緻密で内側ほど粗な濃度傾斜構造をもったコア・シェル構造であるミクロンサイズの球状シリカ粒子が公知である（特許文献４など参照）。
Conventionally, hollow silica particles having a particle size of about 0.1 to 300 μm are known (see Patent Document 1, Patent Document 2, etc.). Also, there is a method for producing hollow particles made of a dense silica shell by precipitating active silica from an alkali metal silicate aqueous solution on a core made of a material other than silica and removing the material without destroying the silica shell. It is publicly known (see, for example, Patent Document 3).
Furthermore, micron-sized spherical silica particles having a core-shell structure in which the outer peripheral portion is a shell, the central portion is hollow, the outer shell is denser on the outer side, and has a coarser concentration gradient structure on the inner side are known (Patent Document 4, etc.) reference).
また、本願出願人は先に、多孔性の無機酸化物微粒子の表面をシリカ等で完全に被覆することにより、低屈折率のナノメーターサイズの複合酸化物微粒子が得られることを提案すると共に（特許文献５参照）、さらに、シリカとシリカ以外の無機酸化物からなる複合酸化物の核粒子にシリカ被覆層を形成し、ついでシリカ以外の無機酸化物を除去し、必要に応じてシリカを被覆することによって、内部に空洞を有する低屈折率のナノメーターサイズのシリカ系微粒子が得られることを提案している（特許文献６参照）。
しかしながら、上記本願出願人の提案に係る粒子では、粒子の使用目的および用途によっては充分な低屈折率効果が得られない場合があった。また、特許文献６記載の製造方法では、前記シリカ以外の無機酸化物の除去に先立ってシリカ被覆層を形成するなど、製造工程が複雑となり、再現性や生産性の点が隘路となっていた。
さらに、前記した従来の微粒子では被膜付基材の製造に用いる被膜形成用塗料の安定性が不充分で、該被膜形成用塗料を用いて得られる被膜は厚さが不均一であったり膜強度が不充分となることがあった。
In addition, the applicant of the present application previously proposed that nanometer-sized composite oxide particles having a low refractive index can be obtained by completely covering the surface of porous inorganic oxide particles with silica or the like ( Furthermore, a silica coating layer is formed on the core particles of a composite oxide composed of silica and an inorganic oxide other than silica, and then the inorganic oxide other than silica is removed, and silica is coated as necessary. By doing so, it has been proposed that nanometer-sized silica-based fine particles with a low refractive index having cavities inside can be obtained (see Patent Document 6).
However, in the particles according to the proposal of the applicant of the present application, a sufficient low refractive index effect may not be obtained depending on the purpose and application of the particles. Moreover, in the manufacturing method described in Patent Document 6, the manufacturing process is complicated, such as forming a silica coating layer prior to the removal of inorganic oxides other than silica, and the points of reproducibility and productivity have become bottlenecks. .
Further, the conventional fine particles described above are insufficient in the stability of the film-forming paint used for the production of the coated substrate, and the film obtained using the film-forming paint has a nonuniform thickness or film strength. May be insufficient.
本発明は、前記特許文献６記載の発明に基づきこれを発展させたものであり、低屈折率のシリカ系微粒子を得ることを目的とするものであって、多孔質の複合酸化物粒子（一次粒子）を、電解質塩の存在下で粒子成長させ、ついで電解質塩の存在下でシリカ以外の無機酸化物を除去することにより、外殻内部に空洞を有する中空で球状のシリカ系微粒子の製造方法を提供することを目的としている。
また、本発明は前記中空で球状のシリカ系微粒子と被膜形成用マトリックスとを含有し、安定性、膜形成性等に優れた被膜形成用塗料を提供することを目的とするものである。
また、本発明は前記中空で球状のシリカ系微粒子を含有する被膜を基材の表面に形成して、低屈折率で、樹脂等との密着性、強度、反射防止能等に優れた被膜付きの基材を提供することを目的とするものである。
The present invention has been developed on the basis of the invention described in Patent Document 6 and aims to obtain silica-based fine particles having a low refractive index. Particles) are grown in the presence of an electrolyte salt, and then inorganic oxides other than silica are removed in the presence of the electrolyte salt, thereby producing hollow spherical silica-based fine particles having a cavity inside the outer shell. The purpose is to provide.
Another object of the present invention is to provide a coating material for forming a film which contains the hollow spherical silica-based fine particles and a film forming matrix and is excellent in stability, film forming property and the like.
In addition, the present invention forms a coating containing the above-mentioned hollow, spherical silica-based fine particles on the surface of the substrate, and has a coating having a low refractive index, excellent adhesion to a resin, strength, antireflection ability, etc. It aims at providing the base material of this.
本発明に係るシリカ系微粒子の製造方法は下記工程（ａ）、（ｂ）、（ｄ）および（ｅ）からなるものである。
（ａ）珪酸塩の水溶液および／または酸性珪酸液と、アルカリ可溶の無機化合物水溶液とをアルカリ水溶液中に、または、必要に応じて種粒子が分散したアルカリ水溶液中に同時に添加して、シリカをＳｉＯ2で表し、シリカ以外の無機酸化物をＭＯXで表したときのモル比ＭＯX／ＳｉＯ2が０.３〜１.０の範囲にある複合酸化物微粒子分散液を調製する際に、複合酸化物微粒子の平均粒子径が５〜３００ｎｍになった時点で電解質塩を電解質塩のモル数（ＭE）とＳｉＯ2のモル数（ＭS）との比（ＭE／ＭS）が０.１〜１０の範囲で添加する工程
（ｂ）前記複合酸化物微粒子分散液に、必要に応じてさらに電解質塩を加えた後、酸を加えて前記複合酸化物微粒子を構成する珪素以外の元素の少なくとも一部を除去してシリカ系微粒子分散液とする工程
（ｄ）必要に応じて洗浄した後、シリカ系微粒子分散液を常温〜３００℃の範囲で熟成する工程
（ｅ）必要に応じて洗浄した後、５０〜３００℃の範囲で水熱処理する工程
The method for producing silica-based fine particles according to the present invention comprises the following steps (a), (b), (d) and (e).
(A) An aqueous solution of silicate and / or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound are simultaneously added to an alkaline aqueous solution or an alkaline aqueous solution in which seed particles are dispersed, if necessary. When preparing a composite oxide fine particle dispersion having a molar ratio MO X / SiO 2 in the range of 0.3 to 1.0 when SiO 2 is represented by SiO 2 and an inorganic oxide other than silica is represented by MO X When the average particle diameter of the composite oxide fine particles becomes 5 to 300 nm, the ratio of the electrolyte salt to the number of moles of electrolyte salt (M E ) and the number of moles of SiO 2 (M S ) (M E / M S ) Is added in the range of 0.1 to 10 (b) Other than silicon constituting the composite oxide fine particles by adding an electrolyte salt to the composite oxide fine particle dispersion as necessary and then adding an acid. Silica-based fine particle dispersion by removing at least part of the element Step (d) After washing as necessary, the silica-based fine particle dispersion is aged in the range of room temperature to 300 ° C. (e) After washing as necessary, hydrothermal treatment in the range of 50 to 300 ° C. Process
工程（ｅ）は複数回繰り返すことが好ましい。
工程（ｂ）と工程（ｄ）の間で下記工程（ｃ）を実施することが好ましい。
（ｃ）前記工程（ｂ）で得られたシリカ系微粒子分散液に、アルカリ水溶液と、下記化学式（１）で表される有機珪素化合物および／またはその部分加水分解物とを添加し、該微粒子にシリカ被覆層を形成する工程
ＲnＳｉＸ(4-n) ・・・（１）
〔但し、Ｒ：炭素数１〜１０の非置換または置換炭化水素基、アクリル基、エポキシ基、メタクリル基、アミノ基、ＣＦ 3 基、Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲンまたは水素、ｎ：０〜３の整数〕
The step (e) is preferably repeated a plurality of times.
It is preferable to carry out the following step (c) between step (b) and step (d).
(C) An aqueous alkali solution and an organosilicon compound represented by the following chemical formula (1) and / or a partial hydrolyzate thereof are added to the silica-based fine particle dispersion obtained in the step (b), and the fine particles Forming a silica coating on the substrate
R n SiX (4-n) (1)
[However, R: unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, acrylic group, epoxy group, methacryl group, amino group, CF 3 group , X: alkoxy group having 1 to 4 carbon atoms, silanol group, halogen Or hydrogen, n: an integer of 0 to 3]
前記アルカリ水溶液または、必要に応じて種粒子が分散したアルカリ水溶液のｐＨは、１０以上であることが好ましい。
前記シリカ以外の無機酸化物はアルミナであることが好ましい。
前記で得られたシリカ系微粒子分散液を洗浄し、乾燥し、必要に応じて焼成することが好ましい。
前記シリカ系微粒子の平均粒子径は５ｎｍ〜５００ｎｍの範囲にあることが好ましく、前記シリカ系微粒子におけるアルカリ金属酸化物の含有量がＭ2Ｏ（Ｍ：アルカリ金属元素）として５ｐｐｍ以下であり、アンモニア及び／又はアンモニウムイオンの含有量がＮＨ3として１５００ｐｐｍ以下であることが好ましい。
The pH of the alkaline aqueous solution or the alkaline aqueous solution in which seed particles are dispersed as required is preferably 10 or more.
The inorganic oxide other than silica is preferably alumina.
It is preferable that the silica-based fine particle dispersion obtained above is washed, dried, and fired as necessary.
The average particle diameter of the silica-based fine particles is preferably in the range of 5 nm to 500 nm, the content of alkali metal oxide in the silica-based fine particles is 5 ppm or less as M 2 O (M: alkali metal element), and ammonia In addition, the content of ammonium ions is preferably 1500 ppm or less as NH 3 .
本発明に係る外殻内部に空洞を有するシリカ系微粒子は、平均粒子径が５〜５００ｎｍの範囲にあり、屈折率が１．１５〜１．３８の範囲にあり、シリカをＳｉＯ2で表し、シリカ以外の無機酸化物をＭＯXで表したときのモル比ＭＯX／ＳｉＯ2が０.０００１〜０.２の範囲にあり、アルカリ金属酸化物の含有量がＭ2Ｏ（Ｍ：アルカリ金属元素）として５ｐｐｍ以下であることを特徴とするものである。該シリカ系微粒子におけるアンモニアおよび／またはアンモニウムイオンの含有量はＮＨ3として１５００ｐｐｍ以下であることが好ましい。
本発明に係る被膜形成用塗料は、前記シリカ系微粒子または前記製造方法によって得られたシリカ系微粒子と、被膜形成用マトリックスとを含んでなるものである。
本発明に係る被膜付基材は、前記シリカ系微粒子または前記製造方法によって得られたシリカ系微粒子と被膜形成用マトリックスとを含んでなる被膜が、単独でまたは他の被膜とともに基材表面上に形成されたものである。
The silica-based fine particles having cavities inside the outer shell according to the present invention have an average particle diameter in the range of 5 to 500 nm, a refractive index in the range of 1.15 to 1.38, and silica is represented by SiO 2 . molar ratio MO X / SiO 2 when the inorganic oxide other than silica, expressed in MO X is in the range of 0.0001 to 0.2, the content of alkali metal oxide M 2 O (M: an alkali metal Element) is 5 ppm or less. The content of ammonia and / or ammonium ions in the silica-based fine particles is preferably 1500 ppm or less as NH 3 .
The coating film-forming paint according to the present invention comprises the silica-based fine particles or the silica-based fine particles obtained by the production method and a film-forming matrix.
The coated substrate according to the present invention is a coating comprising the silica-based fine particles or the silica-based fine particles obtained by the production method and a film-forming matrix, either alone or together with other coatings on the surface of the substrate. It is formed.
本発明方法によれば、電解質塩の存在下で複合酸化物粒子（一次粒子）を粒子成長させるので、後続する脱元素工程においても当該複合酸化物微粒子が球状を維持して、破壊されることがなく、極めて簡易な製造工程により非常に低屈折率のシリカ系微粒子を得ることができる。また、シリカ系微粒子の製造再現性や生産性の点でも優れている。
さらに、脱元素工程あるいはシリカ被覆層を形成して熟成した後、高温で水熱処理するのでアルカリ金属酸化物とアンモニア等が低減され、得られるシリカ系微粒子を配合した被膜形成用塗料は安定性が高く、得られる被膜は強度に優れている。
本発明の被膜形成用塗料は、配合するシリカ系微粒子あるいはシリカ系微粒子分散液中のアルカリ金属酸化物とアンモニアの含有量が少ないので、安定性に優れ、これを用いて得られる被膜は強度に優れている。
また、本発明の被膜付基材は、低屈折率で、樹脂等との密着性、強度、透明性、反射防止能等に優れている。
According to the method of the present invention, since the composite oxide particles (primary particles) are grown in the presence of the electrolyte salt, the composite oxide fine particles are maintained in a spherical shape and destroyed in the subsequent de-elementary process. The silica-based fine particles having a very low refractive index can be obtained by an extremely simple manufacturing process. In addition, the production reproducibility and productivity of silica-based fine particles are also excellent.
In addition, since the film is aged after forming a silica coating layer or aging, hydrothermal treatment is performed at a high temperature, so that alkali metal oxides and ammonia are reduced. High and the resulting coating is excellent in strength.
The coating material for forming a film of the present invention is excellent in stability because the content of alkali metal oxide and ammonia in the silica-based fine particles or silica-based fine particle dispersion is low, and the film obtained by using this has high strength. Are better.
Moreover, the base material with a film of the present invention has a low refractive index and is excellent in adhesion to a resin and the like, strength, transparency, antireflection ability and the like.
以下、本発明の好適な実施形態を説明する。
〔シリカ系微粒子の製造方法〕
本発明に係るシリカ系微粒子の製造方法は、下記工程（ａ）、（ｂ）、（ｄ）および（ｅ）からなる。また、工程（ｂ）と工程（ｄ）の間に工程（ｃ）を実施することもある。以下、工程順に説明する。
（ａ）珪酸塩の水溶液および／または酸性珪酸液と、アルカリ可溶の無機化合物水溶液とをアルカリ水溶液中に、または、必要に応じて種粒子が分散したアルカリ水溶液中に同時に添加して、シリカをＳｉＯ2で表し、シリカ以外の無機酸化物をＭＯXで表したときのモル比ＭＯX／ＳｉＯ2が０.３〜１.０の範囲にある複合酸化物微粒子分散液を調製する際に、複合酸化物微粒子の平均粒子径が５〜３００ｎｍになった時点で電解質塩を電解質塩のモル数（ＭE）とＳｉＯ2のモル数（ＭS）との比（ＭE）／（ＭS）が０.１〜１０の範囲で添加する工程
（ｂ）前記複合酸化物微粒子分散液に、必要に応じてさらに電解質塩を加えた後、酸を加えて前記複合酸化物微粒子を構成する珪素以外の元素の少なくとも一部を除去してシリカ系微粒子分散液とする工程
（ｃ）前記工程（ｂ）で得られたシリカ系微粒子分散液に、アルカリ水溶液と、下記化学式（１）で表される有機珪素化合物および／またはその部分加水分解物とを添加し、該微粒子にシリカ被覆層を形成する工程
ＲnＳｉＸ(4-n) ・・・（１）
〔但し、Ｒ：炭素数１〜１０の非置換または置換炭化水素基、アクリル基、エポキシ基、メタクリル基、アミノ基、ＣＦ 3 基、Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲンまたは水素、ｎ：０〜３の整数〕
（ｄ）必要に応じて洗浄した後、シリカ系微粒子分散液を常温〜３００℃の範囲で熟成する工程
（ｅ）必要に応じて洗浄した後、５０〜３００℃の範囲で水熱処理する工程
Hereinafter, preferred embodiments of the present invention will be described.
[Method for producing silica-based fine particles]
The method for producing silica-based fine particles according to the present invention comprises the following steps (a), (b), (d) and (e). Moreover, a process (c) may be implemented between a process (b) and a process (d). Hereinafter, it demonstrates in order of a process.
(A) An aqueous solution of silicate and / or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound are simultaneously added to an alkaline aqueous solution or an alkaline aqueous solution in which seed particles are dispersed, if necessary. When preparing a composite oxide fine particle dispersion having a molar ratio MO X / SiO 2 in the range of 0.3 to 1.0 when SiO 2 is represented by SiO 2 and an inorganic oxide other than silica is represented by MO X When the average particle diameter of the composite oxide fine particles becomes 5 to 300 nm, the electrolyte salt is converted into the ratio of the number of moles of electrolyte salt (M E ) to the number of moles of SiO 2 (M S ) (M E ) / (M S ) is added in the range of 0.1 to 10 (b) An electrolyte salt is further added to the composite oxide fine particle dispersion as necessary, and then an acid is added to form the composite oxide fine particles. Silica-based fine particles by removing at least part of elements other than silicon Step (c) to make a liquid dispersion To the silica-based fine particle dispersion obtained in the step (b), an alkaline aqueous solution and an organosilicon compound represented by the following chemical formula (1) and / or a partial hydrolyzate thereof are added. Adding and forming a silica coating layer on the fine particles
R n SiX (4-n) (1)
[However, R: unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, acrylic group, epoxy group, methacryl group, amino group, CF 3 group , X: alkoxy group having 1 to 4 carbon atoms, silanol group, halogen Or hydrogen, n: an integer of 0 to 3]
(D) A step of aging the silica-based fine particle dispersion in the range of room temperature to 300 ° C. after washing as necessary (e) A step of hydrothermal treatment in the range of 50 to 300 ° C. after washing as necessary.
工程（ａ）
珪酸塩としては、アルカリ金属珪酸塩、アンモニウム珪酸塩および有機塩基の珪酸塩から選ばれる１種または２種以上の珪酸塩が好ましく用いられる。アルカリ金属珪酸塩としては、珪酸ナトリウム（水ガラス）や珪酸カリウムが、有機塩基としては、テトラエチルアンモニウム塩などの第４級アンモニウム塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアミン類を挙げることができ、アンモニウムの珪酸塩または有機塩基の珪酸塩には、珪酸液にアンモニア、第４級アンモニウム水酸化物、アミン化合物などを添加したアルカリ性溶液も含まれる。
酸性珪酸液としては、珪酸アルカリ水溶液を陽イオン交換樹脂で処理すること等によって、アルカリを除去して得られる珪酸液を用いることができ、特に、ｐＨ２〜ｐＨ４、ＳｉＯ2濃度が約７重量％以下の酸性珪酸液が好ましい。
Step (a)
As the silicate, one or more silicates selected from alkali metal silicates, ammonium silicates and organic base silicates are preferably used. Examples of the alkali metal silicate include sodium silicate (water glass) and potassium silicate, and examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or organic base silicate includes an alkaline solution in which ammonia, quaternary ammonium hydroxide, an amine compound, or the like is added to the silicic acid solution.
As the acidic silicic acid solution, a silicic acid solution obtained by removing an alkali by treating an alkali silicate aqueous solution with a cation exchange resin or the like can be used. In particular, pH 2 to pH 4 and SiO 2 concentration is about 7% by weight. The following acidic silicic acid solutions are preferred.
無機酸化物としては、Ａｌ2Ｏ3、Ｂ2Ｏ3、ＴｉＯ2、ＺｒＯ2、ＳｎＯ2、Ｃｅ2Ｏ3、Ｐ2Ｏ5、Ｓｂ2Ｏ3、ＭｏＯ3、ＺｎＯ2、ＷＯ3等の１種または２種以上を挙げることができる。２種以上の無機酸化物として、ＴｉＯ2−Ａｌ2Ｏ3、ＴｉＯ2−ＺｒＯ2等を例示することができる。
このような無機酸化物の原料として、アルカリ可溶の無機化合物を用いることが好ましく、前記した無機酸化物を構成する金属または非金属のオキソ酸のアルカリ金属塩またはアルカリ土類金属塩、アンモニウム塩、第４級アンモニウム塩を挙げることができ、より具体的には、アルミン酸ナトリウム、四硼酸ナトリウム、炭酸ジルコニルアンモニウム、アンチモン酸カリウム、錫酸カリウム、アルミノ珪酸ナトリウム、モリブデン酸ナトリウム、硝酸セリウムアンモニウム、燐酸ナトリウム等が好適である。
Examples of the inorganic oxide include Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , Ce 2 O 3 , P 2 O 5 , Sb 2 O 3 , MoO 3 , ZnO 2 and WO 3 . 1 type or 2 or more types can be mentioned. Examples of the two or more inorganic oxides include TiO 2 —Al 2 O 3 and TiO 2 —ZrO 2 .
As a raw material for such an inorganic oxide, an alkali-soluble inorganic compound is preferably used, and an alkali metal salt, an alkaline earth metal salt, or an ammonium salt of a metal or a non-metal oxo acid constituting the inorganic oxide described above. Quaternary ammonium salts, and more specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, Sodium phosphate and the like are preferred.
複合酸化物微粒子分散液を調製するためには、予め、前記無機化合物のアルカリ水溶液を個別に調製するか、または、混合水溶液を調製しておき、この水溶液を目的とするシリカとシリカ以外の無機酸化物の複合割合に応じて、アルカリ水溶液中に、好ましくはｐＨ１０以上のアルカリ水溶液中に攪拌しながら徐々に添加する。
アルカリ水溶液中に添加するシリカ原料と無機化合物の添加割合は、シリカ成分をＳｉＯ2 で表し、シリカ以外の無機化合物をＭＯXで表したときのモル比ＭＯX／ＳｉＯ2が０. ３〜１. ０、特に、０. ３５〜０. ８５の範囲となるようにすることが好ましい。ＭＯX／ＳｉＯ2が０. ３未満では、最終的に得られるシリカ系微粒子の空洞容積が十分大きくならず、他方、ＭＯX／ＳｉＯ2が１. ０を越えると、球状の複合酸化物微粒子を得ることが困難となり、この結果、得られる中空微粒子中の空洞容積の割合が低下する。
モル比ＭＯX／ＳｉＯ2が０. ３〜１. ０の範囲にあれば、複合酸化物微粒子の構造は主として、珪素と珪素以外の元素が酸素を介在して交互に結合した構造となる。即ち、珪素原子の４つの結合手に酸素原子が結合し、この酸素原子にはシリカ以外の元素Ｍが結合した構造が多く生成し、後述の工程（ｂ）でシリカ以外の元素Ｍを除去する際、元素Ｍに随伴させて珪素原子も珪酸モノマーやオリゴマーとして除去することができるようになる。
In order to prepare the composite oxide fine particle dispersion, either an alkali aqueous solution of the inorganic compound is separately prepared in advance, or a mixed aqueous solution is prepared, and the target silica and inorganic other than silica are prepared. Depending on the composite ratio of the oxide, it is gradually added with stirring to an aqueous alkali solution, preferably an aqueous alkali solution having a pH of 10 or higher.
The addition ratio of the silica raw material and the inorganic compound added to the alkaline aqueous solution is such that the molar ratio MO X / SiO 2 is 0.3 to 1 when the silica component is expressed by SiO 2 and the inorganic compound other than silica is expressed by MO X. It is preferable that the range be in the range of 0, in particular 0.35 to 0.85. When MO X / SiO 2 is less than 0.3, the finally obtained silica-based fine particles do not have a sufficiently large cavity volume. On the other hand, when MO X / SiO 2 exceeds 1.0, spherical composite oxide fine particles As a result, the ratio of the cavity volume in the obtained hollow microparticles decreases.
When the molar ratio MO X / SiO 2 is in the range of 0.3 to 1.0, the composite oxide fine particles have a structure in which silicon and an element other than silicon are alternately bonded through oxygen. That is, oxygen atoms are bonded to the four bonds of silicon atoms, and many structures in which elements M other than silica are bonded to the oxygen atoms are generated, and the elements M other than silica are removed in the step (b) described later. At this time, the silicon atom can be removed as a silicic acid monomer or oligomer in association with the element M.
本発明の製造方法では、複合酸化物微粒子分散液を調製する際に種粒子の分散液を出発原料とすることも可能である。この場合には、種粒子として、ＳｉＯ2、Ａｌ2Ｏ3、ＴｉＯ2、ＺｒＯ2、ＳｎＯ2およびＣｅＯ2等の無機酸化物またはこれらの複合酸化物、例えば、ＳｉＯ2−Ａｌ2Ｏ3、ＴｉＯ2−Ａｌ2Ｏ3、ＴｉＯ2−ＺｒＯ2、ＳｉＯ2−ＴｉＯ2、ＳｉＯ2−ＴｉＯ2−Ａｌ2Ｏ3等の微粒子が用いられ、通常、これらのゾルを用いることができる。このような種粒子の分散液は、従来公知の方法によって調製することができる。例えば、上記無機酸化物に対応する金属塩、金属塩の混合物あるいは金属アルコキシド等に酸またはアルカリを添加して加水分解し、必要に応じて熟成することによって得ることができる。
この種粒子分散アルカリ水溶液中に、好ましくはｐＨ１０以上に調整した種粒子分散アルカリ水溶液中に前記化合物の水溶液を、上記したアルカリ水溶液中に添加する方法と同様にして、攪拌しながら添加する。このように、種粒子を種として複合酸化物微粒子を成長させると、成長粒子の粒径コントロールが容易であり、粒度の揃ったものを得ることができる。種粒子分散液中に添加するシリカ原料および無機酸化物の添加割合は、前記したアルカリ水溶液に添加する場合と同じ範囲とする。
上記したシリカ原料および無機酸化物原料はアルカリ側で高い溶解度をもっている。しかしながら、この溶解度の高いｐＨ領域で両者を混合すると、珪酸イオンおよびアルミン酸イオンなどのオキソ酸イオンの溶解度が低下し、これらの複合物が析出してコロイド粒子に成長し、あるいは、種粒子上に析出して粒子成長が起こる。
In the production method of the present invention, it is also possible to use a seed particle dispersion as a starting material when preparing a composite oxide fine particle dispersion. In this case, inorganic particles such as SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , SnO 2 and CeO 2 or composite oxides thereof such as SiO 2 —Al 2 O 3 , Fine particles such as TiO 2 —Al 2 O 3 , TiO 2 —ZrO 2 , SiO 2 —TiO 2 , SiO 2 —TiO 2 —Al 2 O 3 are used, and these sols can be usually used. Such a dispersion of seed particles can be prepared by a conventionally known method. For example, it can be obtained by adding an acid or alkali to a metal salt, a mixture of metal salts, a metal alkoxide, or the like corresponding to the inorganic oxide, hydrolyzing, and aging as necessary.
In the seed particle-dispersed alkaline aqueous solution, the aqueous solution of the compound is preferably added to the seed particle-dispersed alkaline aqueous solution adjusted to a pH of 10 or more with stirring in the same manner as in the method of adding the above-mentioned alkaline aqueous solution. As described above, when the composite oxide fine particles are grown using the seed particles as seeds, it is easy to control the particle size of the grown particles, and particles having uniform particle sizes can be obtained. The addition ratio of the silica raw material and the inorganic oxide to be added to the seed particle dispersion is set to the same range as the case of adding to the aqueous alkali solution.
The silica raw material and inorganic oxide raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into colloidal particles, or on the seed particles. Precipitates into particles and causes particle growth.
上記複合酸化物微粒子分散液の調製に際し、シリカ原料として後述する化学式（１）に示す有機珪素化合物および／またはその加水分解物をアルカリ水溶液中に添加しても良い。
該有機珪素化合物としては、具体的に、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、３，３，３−トリフルオロプロピルトリメトキシシラン、メチル−３，３，３−トリフルオロプロピルジメトキシシラン、β−（３，４エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシトリプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、トリメチルシラノール、メチルトリクロロシラン、メチルジクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、フェニルトリクロロシラン、ジフェニルジクロロシラン、ビニルトリクロルシラン、トリメチルブロモシラン、ジエチルシラン等が挙げられる。
When preparing the composite oxide fine particle dispersion, an organosilicon compound represented by the following chemical formula (1) and / or a hydrolyzate thereof may be added as a silica raw material to an alkaline aqueous solution.
Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, and dimethyldiethoxy. Silane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl- 3,3,3-trifluoropropyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxytripropyltrimethoxysilane, -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- Methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane Examples include orchid, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, and diethylsilane.
上記有機珪素化合物でｎが１〜３の化合物は親水性に乏しいので、予め加水分解しておくことにより、反応系に均一に混合できるようにすることが好ましい。加水分解には、これら有機珪素化合物の加水分解法として周知の方法を採用することができる。加水分解触媒として、アルカリ金属の水酸化物や、アンモニア水、アミン等の塩基性のものを用いた場合、加水分解後これらの塩基性触媒を除去して、酸性溶液にして用いることもできる。また、有機酸や無機酸などの酸性触媒を用いて加水分解物を調製した場合、加水分解後、イオン交換等によって酸性触媒を除去することが好ましい。なお、得られた有機珪素化合物の加水分解物は、水溶液の形態で使用することが望ましい。ここで水溶液とは加水分解物がゲルとして白濁した状態になく透明性を有している状態を意味する。 Since the above-mentioned organosilicon compound having n of 1 to 3 is poor in hydrophilicity, it is preferable that the compound be uniformly mixed in the reaction system by hydrolysis in advance. For the hydrolysis, a well-known method can be adopted as a hydrolysis method of these organosilicon compounds. When a basic catalyst such as an alkali metal hydroxide, aqueous ammonia, or an amine is used as the hydrolysis catalyst, these basic catalysts can be removed after hydrolysis and used as an acidic solution. Moreover, when preparing a hydrolyzate using acidic catalysts, such as an organic acid and an inorganic acid, it is preferable to remove an acidic catalyst by ion exchange etc. after a hydrolysis. The obtained hydrolyzate of the organosilicon compound is desirably used in the form of an aqueous solution. Here, the aqueous solution means a state in which the hydrolyzate has transparency without being clouded as a gel.
本発明では、上記工程（ａ）において、複合酸化物微粒子の平均粒子径が概ね５〜３００ｎｍになった時点（このときの複合酸化物微粒子を一次粒子ということがある）で電解質塩を電解質塩のモル数（ＭE）とＳｉＯ2 のモル数（ＭS）との比（ＭE／ＭS）が０.１〜１０、好ましくは０.２〜８の範囲で添加する。
電解質塩としては、塩化ナトリウム、塩化カリウム、硝酸ナトリウム、硝酸カリウム、硫酸ナトリウム、硫酸カリウム、硝酸アンモニウム、硫酸アンモニウム、塩化マグネシウム、硝酸マグネシウムなどの水溶性の電解質塩が挙げられる。
なお、電解質塩はこの時点で全量を添加してもよく、アルカリ金属珪酸塩やシリカ以外の無機化合物を添加して複合酸化物微粒子の粒子成長を行いながら連続的にあるいは断続的に添加してもよい。
In the present invention, in the step (a), when the average particle diameter of the composite oxide fine particles becomes approximately 5 to 300 nm (the composite oxide fine particles at this time may be referred to as primary particles), the electrolyte salt is converted into the electrolyte salt. the ratio (M E / M S) is 0.1 to 10, preferably added in the range of 0.2 to 8 of the number of moles and (M E) SiO 2 moles and (M S).
Examples of the electrolyte salt include water-soluble electrolyte salts such as sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, ammonium nitrate, ammonium sulfate, magnesium chloride, and magnesium nitrate.
The electrolyte salt may be added in its entirety at this point, or continuously or intermittently while adding inorganic compounds other than alkali metal silicate and silica and growing the composite oxide fine particles. Also good.
電解質塩の添加量は、複合酸化物微粒子分散液の濃度にもよるが、前記モル比（ＭE／ＭS）が０.１未満の場合は、電解質塩を加えた効果が不充分となり、工程（ｂ）で酸を加えて複合酸化物微粒子を構成する珪素以外の元素の少なくとも一部を除去する際に複合酸化物微粒子が球状を維持できず破壊され、内部に空洞を有するシリカ系微粒子を得ることが困難となることがある。このような電解質塩を加える効果についてその理由は明らかではないが、粒子成長した複合酸化物微粒子の表面にシリカが多くなり、酸に不溶性のシリカが複合酸化物微粒子の保護膜的な作用をしているものと考えられる。 The amount of the electrolyte salt added depends on the concentration of the composite oxide fine particle dispersion, but when the molar ratio (M E / M S ) is less than 0.1, the effect of adding the electrolyte salt becomes insufficient, When removing at least a part of the elements other than silicon constituting the composite oxide fine particles by adding an acid in the step (b), the composite oxide fine particles cannot be maintained in a spherical shape and are destroyed, and silica-based fine particles having cavities therein May be difficult to obtain. The reason for the effect of adding such an electrolyte salt is not clear, but the amount of silica on the surface of the grown complex oxide fine particles increases, and the acid-insoluble silica acts as a protective film for the composite oxide fine particles. It is thought that.
前記モル比（ＭE／ＭS）が１０を越えても、前記電解質を添加する効果が向上することもなく、新たな微粒子が生成するなど、経済性が低下する。
また、電解質塩を添加する際の一次粒子の平均粒子径が５ｎｍ未満の場合は、新たな微粒子が生成して一次粒子の選択的な粒子成長が起きず、複合酸化物微粒子の粒子径分布が不均一となることがある。電解質塩を添加する際の一次粒子の平均粒子径が３００ｎｍを越えると、工程（ｂ）での珪素以外の元素の除去に時間を要したり、困難となることがある。このようにして得られる複合酸化物微粒子は、最終的に得られるシリカ系微粒子と同程度の、平均粒子径が５〜５００ｎｍの範囲にある。
Even if the molar ratio (M E / M S ) exceeds 10, the effect of adding the electrolyte is not improved, and the economic efficiency is lowered, for example, new fine particles are formed.
In addition, when the average particle size of the primary particles when the electrolyte salt is added is less than 5 nm, new fine particles are generated and selective particle growth of the primary particles does not occur, and the particle size distribution of the composite oxide fine particles is May be non-uniform. If the average particle diameter of the primary particles when adding the electrolyte salt exceeds 300 nm, it may take time or difficulty to remove elements other than silicon in the step (b). The composite oxide fine particles thus obtained have an average particle diameter in the range of 5 to 500 nm, which is about the same as the finally obtained silica-based fine particles.
工程（ｂ）
工程（ｂ）では前記複合酸化物微粒子から、該複合酸化物微粒子を構成する珪素以外の元素の一部または全部を除去することにより内部に空洞を有する中空球状のシリカ系微粒子を製造する。
元素の除去に際しては、複合酸化物微粒子分散液に、電解質塩のモル数（ＭE）とＳｉＯ2のモル数（ＭS）との比（ＭE／ＭS）が０.１〜１０、好ましくは０.２〜８の範囲となるように、必要に応じて再び電解質塩を添加した後、例えば、鉱酸や有機酸を添加することによって溶解除去したり、陽イオン交換樹脂と接触させてイオン交換除去したり、あるいは、これらの方法を組み合わせることによって除去する。
Step (b)
In step (b), hollow spherical silica-based fine particles having cavities therein are produced by removing a part or all of elements other than silicon constituting the composite oxide fine particles from the composite oxide fine particles.
Upon removal of the element, the composite oxide fine particle dispersion, the number of moles of the electrolyte salt (M E) and SiO 2 of moles (M S) and the ratio of (M E / M S) is 0.1 to 10, Preferably, the electrolyte salt is added again as necessary so as to be in the range of 0.2 to 8, and then dissolved and removed, for example, by adding a mineral acid or an organic acid, or contacted with a cation exchange resin. To remove by ion exchange or a combination of these methods.
このとき、複合酸化物微粒子分散液中の複合酸化物微粒子の濃度は処理温度によっても異なるが、酸化物に換算して０．１〜５０重量％、特に０．５〜２５重量％の範囲にあることが好ましい。複合酸化物微粒子の濃度が０．１重量％未満では、シリカの溶解量が多くなり、複合酸化物微粒子の形状を維持できないことがあり、できたとしても低濃度のために処理効率が低下する。また、複合酸化物微粒子の濃度が５０重量％を越えると、粒子の分散性が不充分となり、珪素以外の元素の含有量が多い複合酸化物微粒子では均一に、あるいは効率的に少ない回数で除去できないことがある。
上記元素の除去は、得られるシリカ系微粒子のＭＯX／ＳｉＯ2が、０. ０００１〜０. ２、特に、０. ０００１〜０. １となるまで行うことが好ましい。
At this time, the concentration of the composite oxide fine particles in the composite oxide fine particle dispersion varies depending on the treatment temperature, but in the range of 0.1 to 50% by weight, particularly 0.5 to 25% by weight in terms of oxide. Preferably there is. When the concentration of the composite oxide fine particles is less than 0.1% by weight, the amount of silica dissolved increases, and the shape of the composite oxide fine particles may not be maintained. Even if it is possible, the processing efficiency decreases due to the low concentration. . If the concentration of the composite oxide fine particles exceeds 50% by weight, the dispersibility of the particles becomes insufficient, and the composite oxide fine particles having a high content of elements other than silicon are uniformly or efficiently removed in a small number of times. There are things that cannot be done.
The removal of the above elements is preferably performed until the MO x / SiO 2 of the silica-based fine particles obtained is from 0.0001 to 0.2, particularly from 0.0001 to 0.1.
工程（ｃ）
本工程（ｃ）は任意工程である。
前記化学式（１）に示す有機珪素化合物としては、前記工程（ａ）と同様の有機珪素化合物を用いることができ、化学式（１）において、ｎ＝０の有機珪素化合物を用いる場合はそのまま用いることができるが、ｎ＝１〜３の有機珪素化合物を用いる場合は前記工程（ａ）と同様の有機珪素化合物の部分加水分解物を用いることが好ましい。
Step (c)
This step (c) is an optional step.
As the organosilicon compound represented by the chemical formula (1), the same organosilicon compound as in the step (a) can be used. In the chemical formula (1), when an organosilicon compound with n = 0 is used, it should be used as it is. However, when an organosilicon compound with n = 1 to 3 is used, it is preferable to use a partial hydrolyzate of an organosilicon compound similar to the step (a).
このようなシリカ被覆層は緻密であるために、内部が屈折率の低い気相あるいは液層に保たれ、被膜の形成等に用いる場合、屈折率の高い物質、例えば塗料用樹脂等が内部に進入することがなく、低屈折率効果の高い被膜を形成することができる。
また、上記において、シリカ被覆層の形成にｎ＝１〜３の有機珪素化合物を用いる場合は有機溶媒への分散性が良く、樹脂との親和性の高いシリカ系微粒子分散液を得ることができる。さらに、シランカップリング剤等で表面処理して用いることもできるが、有機溶媒への分散性、樹脂との親和性等に優れているため、このような処理を特別に必要とすることもない。
Since such a silica coating layer is dense, the inside is kept in a gas phase or liquid layer having a low refractive index, and when used for forming a film, a substance having a high refractive index, such as a coating resin, is contained inside. It is possible to form a film having a low refractive index effect without entering.
In the above, when an organosilicon compound of n = 1 to 3 is used for forming the silica coating layer, a silica-based fine particle dispersion having good dispersibility in an organic solvent and high affinity with the resin can be obtained. . Furthermore, it can be used after being surface-treated with a silane coupling agent or the like, but since it is excellent in dispersibility in an organic solvent, affinity with a resin, etc., such treatment is not particularly required. .
また、シリカ被覆層の形成に含フッ素有機珪素化合物を用いる場合は、Ｆ原子を含む被覆層が形成されるために、得られる粒子はより低屈折率となると共に有機溶媒への分散性が良く、樹脂との親和性の高いシリカ系微粒子分散液を得ることができる。このような含フッ素有機珪素化合物としては、３，３，３−トリフルオロプロピルトリメトキシシラン、メチル−３，３，３−トリフルオロプロピルジメトキシシラン、ヘプタデカフルオロデシルメチルジメトキシシラン、ヘプタデカフルオロデシルトリクロロシシラン、ヘプタデカフルオロデシルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、トリデカフルオロオクチルトリメトキシシラン等が挙げられる。また、下記〔化２〕として化学式（２）で表される化合物、下記〔化３〕として化学式（３）で表される化合物も同様の効果を有することから好適に用いることができる。 In addition, when a fluorine-containing organosilicon compound is used for forming the silica coating layer, since the coating layer containing F atoms is formed, the resulting particles have a lower refractive index and good dispersibility in organic solvents. A silica-based fine particle dispersion having high affinity with the resin can be obtained. Such fluorine-containing organic silicon compounds include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecyl. Examples include trichlorosisilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane. Further, the compound represented by the chemical formula (2) as the following [Chemical Formula 2] and the compound represented by the chemical formula (3) as the following [Chemical Formula 3] can also be preferably used because they have the same effect.
［化２］
Ｒ3 Ｒ5
｜ ｜
Ｒ1Ｏ−Ｓｉ−（Ｘ）−Ｓｉ−ＯＲ2 ・・・（２）
｜ ｜
Ｒ4 Ｒ6
[Chemical 2]
R 3 R 5
｜ ｜
R 1 O—Si— (X) —Si—OR 2 (2)
｜ ｜
R 4 R 6
［化３］
Ｒ3
｜
Ｒ1Ｏ−Ｓｉ−(Ｘ)−Ｒ7 ・・・（３）
｜
Ｒ4
[Chemical formula 3]
R 3
｜
R 1 O—Si— (X) —R 7 (3)
｜
R 4
上記化学式（２）と（３）中、Ｒ1とＲ2およびＲ1とＲ7とは互いに同一であっても異なっていてもよく、アルキル基、ハロゲン化アルキル基、アリール基、アルキルアリール基、アリールアルキル基、アルケニル基、水素原子またはハロゲン原子を示す。
Ｒ3〜Ｒ6は互いに同一であっても異なっていてもよく、アルコキシ基、アルキル基、ハロゲン化アルキル基、アリール基、アルキルアリール基、アリールアルキル基、アルケニル基、水素原子またはハロゲン原子を示す。
Ｘは、−（ＣaＨbＦc）−を示し、ａは２以上の偶数である整数、ｂとｃは０以上の偶数である整数とする。
例えば、（ＣＨ3Ｏ）3ＳｉＣ2Ｈ4Ｃ6Ｆ12Ｃ2Ｈ4Ｓｉ（ＣＨ3Ｏ）3で表されるメトキシシランは上記化学式（２）で表される化合物の１つである。
In the chemical formulas (2) and (3), R 1 and R 2 and R 1 and R 7 may be the same or different from each other, and may be an alkyl group, a halogenated alkyl group, an aryl group, or an alkylaryl group. Represents an arylalkyl group, an alkenyl group, a hydrogen atom or a halogen atom.
R 3 to R 6 may be the same or different from each other, and each represents an alkoxy group, an alkyl group, a halogenated alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkenyl group, a hydrogen atom or a halogen atom. .
X represents-(C a H b F c )-, where a is an integer that is an even number of 2 or more, and b and c are integers that are an even number of 0 or more.
For example, methoxysilane represented by (CH 3 O) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (CH 3 O) 3 is one of the compounds represented by the chemical formula (2).
工程（ｄ）
工程（ｄ）では必要に応じて洗浄した後、シリカ系微粒子分散液を常温〜３００℃の範囲で熟成する。
元素を除去した分散液は、必要に応じて限外濾過等の公知の洗浄方法により洗浄することができ、洗浄によって溶解したケイ素以外の元素の一部を除去する。この場合、予め分散液中のアルカリ金属イオン、アルカリ土類金属イオンおよびアンモニウムイオン等の一部を除去した後に限外濾過すれば、分散安定性の高いシリカ系微粒子が分散したゾルが得られる。
また、元素を除去した分散液は、陽イオン交換樹脂および／または陰イオン交換樹脂と接触させることによっても溶解したケイ素以外の元素の一部あるいはアルカリ金属イオン、アルカリ土類金属イオンおよびアンモニウムイオン等を除去することができる。また、洗浄する際、加温して行うと効果的に洗浄することができる。
Step (d)
In the step (d), after washing as necessary, the silica-based fine particle dispersion is aged in the range of room temperature to 300 ° C.
The dispersion from which the elements have been removed can be washed by a known washing method such as ultrafiltration, if necessary, and a part of the elements other than silicon dissolved by the washing is removed. In this case, a sol in which silica-based fine particles with high dispersion stability are dispersed can be obtained by previously removing a part of alkali metal ions, alkaline earth metal ions, ammonium ions and the like in the dispersion liquid and then performing ultrafiltration.
In addition, the dispersion from which the element has been removed is a part of the element other than silicon dissolved by contact with the cation exchange resin and / or anion exchange resin, or alkali metal ions, alkaline earth metal ions, ammonium ions, etc. Can be removed. In addition, when washing, heating can be effectively performed.
このように洗浄することによって、後述する水熱処理して得られるシリカ系微粒子中のアルカリ金属酸化物、アンモニアの含有量を効果的に低減することができ、このため、後述するシリカ系微粒子を用いて得られる被膜形成用塗料の安定性、膜形成等が向上し、得られる被膜は強度に優れている。
ついで、常温〜３００℃、好ましくは５０〜２５０℃で通常１〜２４時間程度熟成する。熟成を行うとシリカ被覆層が均一でより緻密になり、前述したように屈折率の高い物質が粒子内部に進入することができなくなるため、低屈折率効果の高い被膜を形成することができる。
By washing in this way, the content of alkali metal oxides and ammonia in silica-based fine particles obtained by hydrothermal treatment described later can be effectively reduced. For this reason, silica-based fine particles described later are used. The stability and film formation of the coating film-forming coating obtained are improved, and the resulting coating film is excellent in strength.
Next, the mixture is aged at room temperature to 300 ° C., preferably 50 to 250 ° C., usually for about 1 to 24 hours. When aging is performed, the silica coating layer becomes uniform and denser, and a substance having a high refractive index cannot enter the inside of the particle as described above, so that a film having a high low refractive index effect can be formed.
工程（ｅ）
工程（ｅ）では、必要に応じて洗浄した後、５０〜３００℃の範囲で水熱処理する。
洗浄方法は工程（ｄ）と同様、従来公知の方法を採用することができる。
水熱処理温度が５０℃未満の場合は最終的に得られるシリカ系微粒子またはシリカ系微粒子分散液中のアルカリ金属酸化物および／またはアンモニアの含有量を効果的に低減することができず、被膜形成用塗料の安定性、膜形成等の向上効果が不充分となり、得られる被膜の強度の向上も不充分となる。
水熱処理温度が３００℃を超えても被膜形成用塗料の安定性、膜形成性、膜強度等がさらに向上することもなく、場合によってはシリカ系微粒子が凝集することがある。
なお、前記水熱処理温度が１５０℃〜３００℃の範囲にあれば、シリカ系微粒子を用いて得られる被膜は耐水性に優れ、被膜上に水滴が落ちた場合に拭き取りやすく、水滴が乾燥した場合にも水滴の跡形が残り難い等の効果が得られる。
Step (e)
In the step (e), hydrothermal treatment is performed in the range of 50 to 300 ° C. after washing as necessary.
As in the step (d), a conventionally known method can be adopted as the cleaning method.
When the hydrothermal treatment temperature is less than 50 ° C., the content of alkali metal oxide and / or ammonia in the finally obtained silica-based fine particles or silica-based fine particle dispersion cannot be effectively reduced, and a film is formed. The effect of improving the stability of the paint for coating and film formation is insufficient, and the strength of the resulting coating is also insufficiently improved.
Even when the hydrothermal treatment temperature exceeds 300 ° C., the stability, film formability, film strength and the like of the coating film-forming coating material are not further improved, and in some cases, silica-based fine particles may aggregate.
If the hydrothermal treatment temperature is in the range of 150 ° C. to 300 ° C., the coating obtained using silica-based fine particles is excellent in water resistance, and is easy to wipe off when water drops fall on the coating. In addition, it is possible to obtain an effect such that traces of water droplets hardly remain.
工程（ｅ）は複数回繰り返しても良い。工程（ｅ）を繰り返すことによって、得られるシリカ系微粒子中のアルカリ金属酸化物および／またはアンモニア（アンモニウムイオンを含む）の含有量を低減することができる。
このようにして得られたシリカ系微粒子は、平均粒子径が５〜５００ｎｍ、さらには１０〜４００ｎｍの範囲にあることが好ましい。平均粒子径が５ｎｍ未満では、充分な空洞が得られず、低屈折率の効果が充分得られないことがある。平均粒子径が５００ｎｍを越えると、安定した分散液が得にくくなり、また、該微粒子を含有する塗膜の表面に凹凸が生じたりヘーズが高くなることがある。なお、本発明のシリカ系微粒子の平均粒子径は動的光散乱法によって求めることができる。
Step (e) may be repeated a plurality of times. By repeating the step (e), the content of alkali metal oxide and / or ammonia (including ammonium ions) in the obtained silica-based fine particles can be reduced.
The silica-based fine particles thus obtained preferably have an average particle size in the range of 5 to 500 nm, more preferably 10 to 400 nm. If the average particle diameter is less than 5 nm, sufficient cavities cannot be obtained, and the low refractive index effect may not be sufficiently obtained. When the average particle diameter exceeds 500 nm, it is difficult to obtain a stable dispersion, and irregularities may be formed on the surface of the coating film containing the fine particles or haze may be increased. The average particle size of the silica-based fine particles of the present invention can be determined by a dynamic light scattering method.
前記シリカ系微粒子中のアルカリ金属酸化物の含有量は、Ｍ2Ｏ（Ｍ：アルカリ金属元素）として５ｐｐｍ以下、さらには２ｐｐｍ以下であることが好ましい。前記アルカリ金属酸化物の含有量が５ｐｐｍを超えると、シリカ系微粒子を配合した被膜形成用塗料の安定性が不充分で、粘度が高くなり、膜形成性が低下し、得られる被膜の強度が不充分であったり、膜厚が不均一となることがある。
また、前記シリカ系微粒子中のアンモニア（アンモニウムイオンを含む）の含有量は、ＮＨ3として１５００ｐｐｍ以下、さらには１０００ｐｐｍ以下であることが好ましい。前記アンモニアの含有量が１５００ｐｐｍを超えると、前記アルカリ金属酸化物の場合と同様にシリカ系微粒子を配合した被膜形成用塗料の安定性が不充分で、粘度が高くなり、膜形成性が低下し、得られる被膜の強度が不充分であったり、膜厚が不均一となることがある。
The content of the alkali metal oxide in the silica-based fine particles is preferably 5 ppm or less, more preferably 2 ppm or less as M 2 O (M: alkali metal element). When the content of the alkali metal oxide exceeds 5 ppm, the stability of the coating material for forming a film containing silica-based fine particles is insufficient, the viscosity is increased, the film forming property is lowered, and the strength of the resulting coating is increased. It may be insufficient or the film thickness may be uneven.
Further, the content of ammonia (including ammonium ions) in the silica-based fine particles is preferably 1500 ppm or less, more preferably 1000 ppm or less as NH 3 . When the ammonia content exceeds 1500 ppm, the stability of the film-forming coating material containing silica-based fine particles is insufficient as in the case of the alkali metal oxide, the viscosity increases, and the film-forming property decreases. In some cases, the strength of the resulting film is insufficient or the film thickness is not uniform.
なお、本発明のシリカ系微粒子の製造方法では、得られたシリカ系微粒子分散液を限外濾過膜、ロータリーエバポレーター等を用いて有機溶媒で置換することによって有機溶媒分散ゾルを得ることができる。
また、本発明のシリカ系微粒子の製造方法では、洗浄後、乾燥し、必要に応じて焼成することができる。
このようにして得られたシリカ系微粒子は、内部に空洞を有し、低屈折率となる。従って、該シリカ系微粒子を用いて形成される被膜は低屈折率となり、反射防止性能に優れた被膜が得られる。
In the method for producing silica-based fine particles of the present invention, an organic solvent-dispersed sol can be obtained by substituting the obtained silica-based fine particle dispersion with an organic solvent using an ultrafiltration membrane, a rotary evaporator or the like.
Moreover, in the manufacturing method of the silica type microparticles | fine-particles of this invention, after washing | cleaning, it can dry and it can bake as needed.
The silica-based fine particles obtained in this way have cavities inside and have a low refractive index. Therefore, the film formed using the silica-based fine particles has a low refractive index, and a film excellent in antireflection performance can be obtained.
本発明に係るシリカ系微粒子は、内部に空洞を有している。このため、通常シリカの屈折率が１.４５であるのに対し、シリカ系微粒子の屈折率は、１．１５〜１．３８であった。なお、空洞については、粒子断面の透過型電子顕微鏡写真（ＴＥＭ）を観察することによって確認することができる。 The silica-based fine particles according to the present invention have cavities inside. For this reason, the refractive index of silica-based fine particles was 1.15 to 1.38, whereas the refractive index of silica was usually 1.45. In addition, about a cavity, it can confirm by observing the transmission electron micrograph (TEM) of a particle | grain cross section.
〔被膜形成用塗料〕
続いて、本発明に係る被膜形成用塗料について説明する。
本発明に係る被膜形成用塗料は、前記シリカ系微粒子と、被膜形成用マトリックスと、必要に応じて配合される有機溶媒とからなっている。
被膜形成用マトリックスとは、基材の表面に被膜を形成し得る成分をいい、基材との密着性や硬度、塗工性等の条件に適合する樹脂等から選択して用いることができ、例えば、従来から用いられているポリエステル樹脂、アクリル樹脂、ウレタン樹脂、塩化ビニル樹脂、エポキシ樹脂、メラミン樹脂、フッ素樹脂、シリコン樹脂、ブチラール樹脂、フェノール樹脂、酢酸ビニル樹脂、紫外線硬化樹脂、電子線硬化樹脂、エマルジョン樹脂、水溶性樹脂、親水性樹脂、これら樹脂の混合物、さらにはこれら樹脂の共重合体や変性体などの塗料用樹脂、または、前記アルコキシシラン等の加水分解性有機珪素化合物およびこれらの部分加水分解物等が挙げられる。
[Coating paint]
Next, the coating film forming paint according to the present invention will be described.
The coating film-forming paint according to the present invention comprises the silica-based fine particles, the film-forming matrix, and an organic solvent blended as necessary.
The matrix for forming a film refers to a component that can form a film on the surface of a substrate, and can be selected and used from a resin that meets conditions such as adhesion to the substrate, hardness, and coating properties, For example, conventionally used polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluorine resin, silicon resin, butyral resin, phenol resin, vinyl acetate resin, UV curable resin, electron beam curing Resins, emulsion resins, water-soluble resins, hydrophilic resins, mixtures of these resins, coating resins such as copolymers and modified products of these resins, hydrolyzable organosilicon compounds such as alkoxysilanes, and the like And a partial hydrolyzate thereof.
マトリックスとして塗料用樹脂を用いる場合には、例えば、シリカ系微粒子分散液の分散媒をアルコール等の有機溶媒で置換した有機溶媒分散ゾル、好ましくは前記有機基を含む有機ケイ素化合物によりシリカ被覆層を形成したシリカ系微粒子を用いることができ、必要に応じて前記微粒子を公知のカップリング剤で処理した後、有機溶媒に分散させた有機溶媒分散ゾルと塗料用樹脂とを適当な有機溶剤で希釈して、塗布液とすることができる。 When a coating resin is used as the matrix, for example, an organic solvent dispersion sol obtained by replacing the dispersion medium of the silica-based fine particle dispersion with an organic solvent such as alcohol, preferably the silica coating layer with an organic silicon compound containing the organic group. The formed silica-based fine particles can be used. If necessary, the fine particles are treated with a known coupling agent, and then the organic solvent-dispersed sol dispersed in an organic solvent and the coating resin are diluted with a suitable organic solvent. Thus, a coating solution can be obtained.
一方、マトリックスとして加水分解性有機珪素化合物を用いる場合には、例えば、アルコキシシランとアルコールの混合液に、水および触媒としての酸またはアルカリを加えることにより、アルコキシシランの部分加水分解物を得、これに前記ゾルを混合し、必要に応じて有機溶剤で希釈して、塗布液とすることができる。 On the other hand, when using a hydrolyzable organosilicon compound as a matrix, for example, by adding water or an acid or alkali as a catalyst to a mixture of alkoxysilane and alcohol, a partially hydrolyzed product of alkoxysilane is obtained, The sol can be mixed with this and diluted with an organic solvent as necessary to obtain a coating solution.
被膜形成用塗布液中のシリカ系微粒子とマトリックスの重量割合は、シリカ系微粒子／マトリックス＝１／９９〜９／１の範囲が好ましい。重量比が９／１を越えると被膜の強度や基材との密着性が低下して実用性に欠ける一方、１／９９未満では当該シリカ系微粒子の添加による被膜の低屈折率化、基材との密着性向上、被膜強度向上等の効果が不充分となる。 The weight ratio between the silica-based fine particles and the matrix in the coating-forming coating solution is preferably in the range of silica-based fine particles / matrix = 1/99 to 9/1. If the weight ratio exceeds 9/1, the strength of the coating and the adhesion to the substrate will be reduced, resulting in lack of practicality. The effects of improving adhesion with the film and improving the film strength are insufficient.
〔被膜付基材〕
本発明に係る被膜付基材は、前記シリカ系微粒子と被膜形成用マトリックスとを含む被膜が単独でまたは他の被膜とともに基材表面上に形成されている。
当該基材は、ガラス、ポリカーボネート、アクリル樹脂、ＰＥＴ、ＴＡＣ等のプラスチックシート、プラスチックフィルム、プラスチックレンズ、プラスチックパネル等の基材、陰極線管、蛍光表示管、液晶表示板等の基材の表面に被膜を形成したものであり、用途によって異なるが被膜が単独であるいは基材上に保護膜、ハードコート膜、平坦化膜、高屈折率膜、絶縁膜、導電性樹脂膜、導電性金属微粒子膜、導電性金属酸化物微粒子膜、その他必要に応じて用いるプライマー膜等と組み合わせて形成されている。なお、組み合わせて用いる場合、本発明の被膜が必ずしも最外表面に形成されている必要はない。
このような被膜は、前記被膜形成用塗料をディップ法、スプレー法、スピナー法、ロールコート法などの周知の方法で基材に塗布し、乾燥し、更に必要に応じて、加熱あるいは紫外線照射等により硬化して得ることができる。
[Base material with coating]
In the substrate with a coating according to the present invention, the coating containing the silica-based fine particles and the coating-forming matrix is formed on the substrate surface alone or together with other coatings.
The base material is formed on the surface of a base material such as glass, polycarbonate, acrylic resin, plastic sheet such as PET, TAC, plastic film, plastic lens, plastic panel, cathode ray tube, fluorescent display tube, liquid crystal display plate, etc. A film is formed. Depending on the application, the film may be used alone or on a substrate, protective film, hard coat film, planarizing film, high refractive index film, insulating film, conductive resin film, conductive metal fine particle film In addition, the conductive metal oxide fine particle film and other primer films used as necessary are formed in combination. When used in combination, the coating of the present invention is not necessarily formed on the outermost surface.
Such a coating is applied to the substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, dried, and further heated or irradiated with ultraviolet rays as necessary. Can be obtained by curing.
上記基材の表面に形成される被膜の屈折率は、シリカ系微粒子とマトリックス成分等の混合比率および使用するマトリックスの屈折率によっても異なるが、１. １５〜１. ４２と低屈折率となる。なお、本発明のシリカ系微粒子自体の屈折率は、１．１５〜１．３８であった。これは、本発明のシリカ系微粒子が内部に空洞を有し、樹脂等のマトリックス形成成分は粒子外部に止まり、シリカ系微粒子内部の空洞が保持されるからである。 The refractive index of the coating film formed on the surface of the base material is 1.15 to 1.42, although it varies depending on the mixing ratio of silica-based fine particles and matrix components and the refractive index of the matrix used. . The refractive index of the silica-based fine particle itself of the present invention was 1.15 to 1.38. This is because the silica-based fine particles of the present invention have cavities inside, matrix forming components such as resin remain outside the particles, and the cavities inside the silica-based fine particles are retained.
さらに、上記した被膜付基材において、基材の屈折率が１. ６０以下の場合には、基材表面に屈折率が１. ６０以上の被膜（以下、中間被膜という。）を形成した上で、前記本発明のシリカ系微粒子を含む被膜を形成することが推奨される。中間被膜の屈折率が１. ６０以上であれば前記本発明のシリカ系微粒子を含む被膜の屈折率との差が大きく反射防止性能に優れた被膜付基材が得られる。中間被膜の屈折率は、中間被膜の屈折率を高めるために用いる金属酸化物微粒子の屈折率、金属酸化物微粒子と樹脂等の混合比率および使用する樹脂の屈折率によって調整することができる。
中間被膜の被膜形成用塗布液は、金属酸化物粒子と被膜形成用マトリックスとの混合液であり、必要により有機溶媒が混合される。被膜形成用マトリックスとしては前記本発明のシリカ系微粒子を含む被膜と同様のものを用いることができ、同一の被膜形成用マトリックスを用いることにより、両被膜間の密着性に優れた被膜付基材が得られる。
続いて、以下実施例を示して、本発明を更に具体的に説明する。
Furthermore, in the above-mentioned coated substrate, when the refractive index of the substrate is 1.60 or less, a coating having a refractive index of 1.60 or more (hereinafter referred to as an intermediate coating) is formed on the surface of the substrate. Therefore, it is recommended to form a film containing the silica-based fine particles of the present invention. When the refractive index of the intermediate coating is 1.60 or more, a coated substrate having a large difference from the refractive index of the coating containing the silica-based fine particles of the present invention and excellent antireflection performance can be obtained. The refractive index of the intermediate coating can be adjusted by the refractive index of the metal oxide fine particles used for increasing the refractive index of the intermediate coating, the mixing ratio of the metal oxide fine particles and the resin, and the refractive index of the resin used.
The coating solution for forming an intermediate coating is a mixed solution of metal oxide particles and a matrix for forming a coating, and an organic solvent is mixed as necessary. As the film forming matrix, the same film as that containing the silica-based fine particles of the present invention can be used. By using the same film forming matrix, the coated substrate having excellent adhesion between the two films Is obtained.
Next, the present invention will be described more specifically with reference to the following examples.
シリカ系微粒子(P-1)の調製
平均粒径５ｎｍ、ＳｉＯ2濃度２０重量％のシリカゾル１００ｇと純水１９００ｇの混合物を８０℃に加温した。この反応母液のｐＨは１０．５であり、同母液にＳｉＯ2として１．１７重量％の珪酸ナトリウム水溶液９０００ｇとＡｌ2Ｏ3として０．８３重量％のアルミン酸ナトリウム水溶液９０００ｇとを同時に添加した。その間、反応液の温度を８０℃に保持した。反応液のｐＨは添加直後、１２．５に上昇し、その後、殆ど変化しなかった。添加終了後、反応液を室温まで冷却し、限外濾過膜で洗浄して固形分濃度２０重量％のＳｉＯ2・Ａｌ2Ｏ3一次粒子分散液を調製した。
この一次粒子分散液５００ｇに純水１，７００ｇを加えて９８℃に加温し、この温度を保持しながら、濃度０.５重量％の硫酸ナトリウム５０,４００ｇを添加し、ついでＳｉＯ2として濃度１.１７重量％の珪酸ナトリウム水溶液３，０００ｇとＡｌ2Ｏ3としての濃度０.５重量％のアルミン酸ナトリウム水溶液９,０００ｇを添加して複合酸化物微粒子(1)の分散液を得た。
ついで、限外濾過膜で洗浄して固形分濃度１３重量％になった複合酸化物微粒子(1)の分散液５００ｇに純水１,１２５ｇを加え、さらに濃塩酸（濃度３５.５重量％）を滴下してｐＨ１.０とし、脱アルミニウム処理を行った。次いで、ｐＨ３の塩酸水溶液１０Ｌと純水５Ｌを加えながら限外濾過膜で溶解したアルミニウム塩を分離・洗浄して固形分濃度２０重量％のシリカ系微粒子(P-1-1)の水分散液を得た。
Preparation of silica-based fine particles (P-1) A mixture of 100 g of silica sol having an average particle diameter of 5 nm and SiO 2 concentration of 20% by weight and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of a 1.17 wt% sodium silicate aqueous solution as SiO 2 and 9000 g of a 0.83 wt% sodium aluminate aqueous solution as Al 2 O 3 were simultaneously added to the mother liquor. . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO 2 .Al 2 O 3 primary particle dispersion having a solid content concentration of 20% by weight.
1,700 g of pure water was added to 500 g of this primary particle dispersion and heated to 98 ° C., and while maintaining this temperature, 50,400 g of sodium sulfate having a concentration of 0.5% by weight was added, and then the concentration was set as SiO 2. A dispersion of composite oxide fine particles (1) was obtained by adding 3,000 g of a 1.17 wt% sodium silicate aqueous solution and 9,000 g of a 0.5 wt% sodium aluminate aqueous solution as Al 2 O 3 . .
Next, 1,125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles (1) having a solid concentration of 13 wt% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5 wt%). Was dropped to pH 1.0, and dealumination was performed. Next, an aqueous dispersion of silica-based fine particles (P-1-1) having a solid concentration of 20% by weight by separating and washing the aluminum salt dissolved in the ultrafiltration membrane while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water. Got.
つぎに、シリカ系微粒子(P-1-1)分散液にアンモニア水を加えて分散液のｐＨを１０．５に調整し、ついで１５０℃にて１１時間熟成した後、常温に冷却し、陽イオン交換樹脂（三菱化学（株）製：ダイヤイオンＳＫ１Ｂ）４００ｇを用いて３時間イオン交換し、ついで、陰イオン交換樹脂（三菱化学（株）製：ダイヤイオンＳＡ２０Ａ）２００ｇを用いて３時間イオン交換し、さらに陽イオン交換樹脂（三菱化学（株）製：ダイヤイオンＳＫ１Ｂ）２００ｇを用い、８０℃で３時間イオン交換して洗浄を行い、固形分濃度２０重量％のシリカ系微粒子(P-1-2)の水分散液を得た。このとき、シリカ系微粒子(P-1-2)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々６ｐｐｍ、１２００ｐｐｍであった。
ついで、再び、シリカ系微粒子(P-1-2)分散液を１５０℃にて１１時間水熱処理した後、純水５Ｌを加えながら限外濾過膜で洗浄して固形分濃度２０重量％のシリカ系微粒子(P-1-3)の水分散液を得た。このとき、シリカ系微粒子(P-1-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々０．５ｐｐｍ、６００ｐｐｍであった。
ついで限外濾過膜を用いて溶媒をエタノールに置換した固形分濃度２０重量％のシリカ系微粒子（P-1）のアルコール分散液を調製した。
このシリカ系微粒子（P-1）の平均粒子径、ＭＯx／ＳｉＯ2（モル比）、および屈折率を、調製条件と共に表１に示す。ここで、平均粒子径は動的光散乱法により測定し、屈折率は標準屈折液としてCARGILL製のSeriesＡ、ＡＡを用い、以下の方法で測定した。
Next, aqueous ammonia is added to the dispersion of silica-based fine particles (P-1-1) to adjust the pH of the dispersion to 10.5, then aging at 150 ° C. for 11 hours, and then cooled to room temperature. Ion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B) is used for 3 hours, and then anion exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SA20A) is used for 3 hours. Then, using 200 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B), it was ion-exchanged at 80 ° C. for 3 hours for washing to obtain silica-based fine particles (P- An aqueous dispersion of 1-2) was obtained. At this time, the Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-1-2) were 6 ppm and 1200 ppm, respectively, per silica-based fine particle.
Next, the silica-based fine particle (P-1-2) dispersion was again hydrothermally treated at 150 ° C. for 11 hours, washed with an ultrafiltration membrane while adding 5 L of pure water, and a silica having a solid content concentration of 20% by weight. An aqueous dispersion of the system fine particles (P-1-3) was obtained. At this time, the Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-1-3) were 0.5 ppm and 600 ppm, respectively, per silica-based fine particle.
Next, an alcohol dispersion of silica-based fine particles (P-1) having a solid content concentration of 20% by weight was prepared by replacing the solvent with ethanol using an ultrafiltration membrane.
Table 1 shows the average particle size, MO x / SiO 2 (molar ratio), and refractive index of the silica-based fine particles (P-1) together with the preparation conditions. Here, the average particle diameter was measured by a dynamic light scattering method, and the refractive index was measured by the following method using Series A and AA manufactured by CARGILL as a standard refractive liquid.
粒子の屈折率の測定方法
（１）シリカ系微粒子分散液をエバポレーターに採り、分散媒を蒸発させる。
（２）これを１２０℃で乾燥し、粉末とする。
（３）屈折率が既知の標準屈折液を２、３滴ガラス板上に滴下し、これに上記粉末を混合する。
（４）上記（３）の操作を種々の標準屈折液で行い、混合液が透明になったときの標準屈折液の屈折率を微粒子の屈折率とする。
Method for Measuring Refractive Index of Particle (1) The silica-based fine particle dispersion is taken in an evaporator and the dispersion medium is evaporated.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the fine particles.
透明被膜付基材（A-1)の製造
シリカ系微粒子（P-1)のアルコール分散液をエタノールで固形分濃度５重量％に希釈した分散液５０ｇと、アクリル樹脂（ヒタロイド１００７、日立化成（株）製）３ｇおよびイソプロパノールとｎ−ブタノールの１／１（重量比）混合溶媒４７ｇとを充分に混合して塗布液を調製した。
この塗布液をＰＥＴフィルムにバーコーター法で塗布し、８０℃で、１分間乾燥させて、透明被膜の膜厚が１００ｎｍの透明被膜付基材（A-1）を得た。この透明被膜付基材（A-1）の全光線透過率、ヘイズ、波長５５０ｎｍの光線の反射率、被膜の屈折率、および鉛筆硬度を表２に示す。全光線透過率およびヘイズは、ヘーズメーター（スガ試験機（株）製）により、反射率は分光光度計（日本分光社、Ubest-55）により夫々測定した。また、被膜の屈折率は、エリプソメーター（ＵＬＶＡＣ社製、ＥＭＳ−１）により測定した。なお、未塗布のＰＥＴフィルムは全光線透過率が９０. ７％、ヘイズが２. ０％、波長５５０ｎｍの光線の反射率が７. ０％であった。鉛筆硬度は、JIS K 5400に準じて、鉛筆硬度試験器で測定した。即ち、被膜表面に対して４５度の角度に鉛筆をセットし、所定の加重を負荷して一定速度で引っ張り、傷の有無を観察した。
Production of substrate with transparent coating (A-1) 50 g of an alcohol dispersion of silica-based fine particles (P-1) diluted with ethanol to a solid concentration of 5% by weight, acrylic resin (Hitaroid 1007, Hitachi Chemical ( 3 g) and isopropanol and n-butanol 1/1 (weight ratio) mixed solvent 47 g were sufficiently mixed to prepare a coating solution.
This coating solution was applied to a PET film by a bar coater method and dried at 80 ° C. for 1 minute to obtain a substrate with transparent coating (A-1) having a transparent coating thickness of 100 nm. Table 2 shows the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, refractive index of the film, and pencil hardness of the substrate with a transparent film (A-1). The total light transmittance and haze were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the reflectance was measured with a spectrophotometer (JASCO Corporation, Ubest-55). Moreover, the refractive index of the film was measured with an ellipsometer (manufactured by ULVAC, EMS-1). The uncoated PET film had a total light transmittance of 90.7%, a haze of 2.0%, and a reflectance of light having a wavelength of 550 nm of 7.0%. The pencil hardness was measured with a pencil hardness tester according to JIS K 5400. That is, a pencil was set at an angle of 45 degrees with respect to the coating surface, a predetermined load was applied, and the film was pulled at a constant speed, and the presence or absence of scratches was observed.
また、透明被膜付基材（A-1)の表面にナイフで縦横１ｍｍの間隔で１１本の平行な傷を付け１００個の升目を作り、これにセロファンテープを接着し、次いで、セロファンテープを剥離したときに被膜が剥離せず残存している升目の数を、以下の３段階に分類することによって密着性を評価した。結果を表２に示す。
残存升目の数９０個以上 ：◎
残存升目の数８５〜８９個：○
残存升目の数８４個以下 ：△
In addition, 11 parallel scratches were made on the surface of the substrate (A-1) with a transparent coating at intervals of 1 mm in length and width with a knife to make 100 squares, cellophane tape was adhered to this, and then cellophane tape was attached. Adhesion was evaluated by classifying the number of cells remaining without peeling off when the film was peeled into the following three stages. The results are shown in Table 2.
Number of remaining squares more than 90: ◎
Number of remaining squares: 85 to 89: ○
Number of remaining squares: 84 or less: △
透明被膜付基材（B-1)の製造
エチルシリケート（ＳｉＯ2濃度２８重量％）２０ｇ、エタノール４５ｇおよび純水５．３３ｇの混合溶液に少量の塩酸を添加して、エチルシリケートの部分加水分解物を含有したマトリックス分散液を得た。このマトリックス分散液に、シリカ系微粒子（P-1）のアルコール分散液（固形分濃度１８重量％）１６．７ｇを混合して塗布液を調製した。
この塗布液を透明ガラス板の表面に５００ｒｐｍ、１０秒の条件でスピナー法により塗布した後、１６０℃で３０分間、加熱処理して透明被膜の膜厚が２００ｎｍの透明被膜付基材（B-1）を得た。この透明被膜付基材（B-1）の全光線透過率、ヘイズ、波長５５０ｎｍの光線の反射率、被膜の屈折率および鉛筆硬度を表３に示す。なお、未塗布のガラス基板は、全光線透過率が９２．０％、ヘイズが０. １％、波長５５０ｎｍの光線の反射率が４. ５％であった。
Production of substrate with transparent coating (B-1) Partial hydrolysis of ethyl silicate by adding a small amount of hydrochloric acid to a mixed solution of 20 g of ethyl silicate (SiO 2 concentration 28 wt%), 45 g of ethanol and 5.33 g of pure water A matrix dispersion containing the product was obtained. The matrix dispersion was mixed with 16.7 g of an alcohol dispersion (solid content concentration: 18% by weight) of silica-based fine particles (P-1) to prepare a coating solution.
This coating solution was applied on the surface of a transparent glass plate by a spinner method at 500 rpm for 10 seconds, and then heat-treated at 160 ° C. for 30 minutes to form a transparent film-coated substrate (B- 1) got. Table 3 shows the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, refractive index of the film, and pencil hardness of the substrate with transparent film (B-1). The uncoated glass substrate had a total light transmittance of 92.0%, a haze of 0.1%, and a reflectance of light having a wavelength of 550 nm was 4.5%.
シリカ系微粒子(P-2)の調製
実施例１と同様にして調製した固形分濃度２０重量％のシリカ系微粒子(P-１-1)の水分散液１５００ｇと、純水５００ｇ、エタノール１，７５０ｇおよび２８％アンモニア水６２６ｇとの混合液を３５℃に加温した後、エチルシリケート（ＳｉＯ2濃度２８重量％）１０４ｇを添加してシリカ被膜を形成し、純水５Ｌを加えながら限外濾過膜で洗浄して固形分濃度２０重量％のシリカ系微粒子(P-2-1)の水分散液を得た。
つぎに、シリカ系微粒子(P-2-1)分散液を２００℃にて１時間熟成した後、純水５Ｌを加えながら限外濾過膜で洗浄して固形分濃度２０重量％のシリカ系微粒子(P-2-2)の水分散液を得た。このとき、シリカ系微粒子(P-2-2)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々１ｐｐｍ、２５００ｐｐｍであった。
ついで、再び、シリカ系微粒子(P-2-2)分散液を１５０℃にて１１時間水熱処理した後、純水５Ｌを加えながら限外濾過膜で洗浄して固形分濃度２０重量％のシリカ系微粒子(P-2-3)の水分散液を得た。このとき、シリカ系微粒子(P-2-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々０．５ｐｐｍ、９００ｐｐｍであった。
ついで限外濾過膜を用いて分散媒をエタノールに置換した固形分濃度２０重量％のシリカ系微粒子（P-2）のアルコール分散液を調製した。
透明被膜付基材（A-2）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-2)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-2）を得た。
透明被膜付基材（B-2）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-2)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-2）を得た。
Preparation of silica-based fine particles (P-2) 1500 g of an aqueous dispersion of silica-based fine particles (P-1-1) having a solid content concentration of 20% by weight prepared in the same manner as in Example 1, 500 g of pure water, ethanol 1, A mixture of 750 g and 28% aqueous ammonia 626 g was heated to 35 ° C., then 104 g of ethyl silicate (SiO 2 concentration 28 wt%) was added to form a silica film, and ultrafiltration was performed while adding 5 L of pure water. The membrane was washed to obtain an aqueous dispersion of silica-based fine particles (P-2-1) having a solid content concentration of 20% by weight.
Next, the silica-based fine particle (P-2-1) dispersion was aged at 200 ° C. for 1 hour, and then washed with an ultrafiltration membrane while adding 5 L of pure water to obtain a silica-based fine particle having a solid content concentration of 20% by weight. An aqueous dispersion of (P-2-2) was obtained. At this time, the Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-2-2) were 1 ppm and 2500 ppm, respectively, per silica-based fine particle.
Next, the silica-based fine particle (P-2-2) dispersion was again hydrothermally treated at 150 ° C. for 11 hours, washed with an ultrafiltration membrane while adding 5 L of pure water, and a silica having a solid content concentration of 20% by weight. An aqueous dispersion of the system fine particles (P-2-3) was obtained. At this time, the Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-2-3) were 0.5 ppm and 900 ppm, respectively, per silica-based fine particle.
Next, an alcohol dispersion of silica-based fine particles (P-2) having a solid content concentration of 20% by weight was prepared by replacing the dispersion medium with ethanol using an ultrafiltration membrane.
Production of substrate with transparent coating (A-2) In Example 1, except that an alcohol dispersion of silica-based fine particles (P-2) was used instead of an alcohol dispersion of silica-based fine particles (P-1) Thus, a substrate with a transparent coating (A-2) was obtained.
Production of substrate with transparent coating (B-2) In Example 1 except that an alcohol dispersion of silica particles (P-2) was used instead of an alcohol dispersion of silica particles (P-1) Thus, a substrate with a transparent coating (B-2) was obtained.
シリカ系微粒子(P-3)の調製
実施例２において、濃度０.５重量％の硫酸ナトリウム５０,４００ｇの代わりに濃度０.５重量％の硝酸カリウム３０，０００ｇを用いた以外は同様にして固形分濃度２０重量％のシリカ系微粒子(P-3)のアルコール分散液を調製した。
なお、シリカ系微粒子(P-3-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々０．４ｐｐｍ、８００ｐｐｍであった。
透明被膜付基材（A-3）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-3)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-3）を得た。
透明被膜付基材（B-3）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-3)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-3）を得た。
Preparation of silica-based fine particles (P-3) In Example 2, the same procedure was followed except that 30,000 g of 0.5 wt% potassium nitrate was used instead of 50,400 g of 0.5 wt% sodium sulfate. An alcohol dispersion of silica-based fine particles (P-3) having a partial concentration of 20% by weight was prepared.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-3-3) were 0.4 ppm and 800 ppm, respectively, per silica-based fine particle.
Production of substrate with transparent coating (A-3) In Example 1 except that an alcohol dispersion of silica fine particles (P-3) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (A-3) was obtained.
Production of substrate with transparent coating (B-3) In Example 1 except that an alcohol dispersion of silica fine particles (P-3) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (B-3) was obtained.
シリカ系微粒子(P-4)の調製
実施例２において、濃度０.５重量％の硫酸ナトリウム５０,４００ｇの代わりに濃度０.５重量％の硫酸アンモニウム５３，２００ｇを用いた以外は同様にして固形分濃度２０重量％のシリカ系微粒子(P-4)のアルコール分散液を調製した。
なお、シリカ系微粒子(P-4-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々０．５ｐｐｍ、８００ｐｐｍであった。
透明被膜付基材（A-4）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-4)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-4）を得た。
透明被膜付基材（B-4）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-4)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-4）を得た。
Preparation of silica-based fine particles (P-4) In Example 2, a solid was obtained in the same manner except that 53,200 g of 0.5 wt% ammonium sulfate was used instead of 50,400 g of 0.5 wt% sodium sulfate. An alcohol dispersion of silica-based fine particles (P-4) having a partial concentration of 20% by weight was prepared.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-4-3) were 0.5 ppm and 800 ppm, respectively, per silica-based fine particle.
Production of substrate with transparent coating (A-4) In Example 1, except that an alcohol dispersion of silica-based fine particles (P-4) was used instead of an alcohol dispersion of silica-based fine particles (P-1) Thus, a substrate with a transparent coating (A-4) was obtained.
Production of substrate with transparent coating (B-4) In Example 1 except that the silica fine particle (P-4) alcohol dispersion was used instead of the silica fine particle (P-1) alcohol dispersion. Thus, a substrate with a transparent coating (B-4) was obtained.
シリカ系微粒子(P-5)の調製
実施例２において、濃度０.５重量％の硫酸ナトリウム５０,４００ｇの代わりに濃度０.５重量％の硝酸アンモニウム４１，１００ｇを用いた以外は同様にして固形分濃度２０重量％のシリカ系微粒子(P-5)のアルコール分散液を調製した。
なお、シリカ系微粒子(P-5-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々０．８ｐｐｍ、７００ｐｐｍであった。
透明被膜付基材（A-5）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-5)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-5）を得た。
透明被膜付基材（B-5）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-5)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-5）を得た。
Preparation of silica-based fine particles (P-5) In Example 2, solids were similarly prepared except that 41,100 g of ammonium nitrate having a concentration of 0.5 wt% was used instead of 50,400 g of sodium sulfate having a concentration of 0.5 wt%. An alcohol dispersion of silica-based fine particles (P-5) having a partial concentration of 20% by weight was prepared.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-5-3) were 0.8 ppm and 700 ppm, respectively, per silica-based fine particle.
Production of substrate with transparent coating (A-5) In Example 1 except that an alcohol dispersion of silica-based fine particles (P-5) was used instead of an alcohol dispersion of silica-based fine particles (P-1) Thus, a substrate with a transparent coating (A-5) was obtained.
Production of substrate with transparent coating (B-5) In Example 1 except that an alcohol dispersion of silica-based fine particles (P-5) was used instead of an alcohol dispersion of silica-based fine particles (P-1) Thus, a substrate with a transparent coating (B-5) was obtained.
シリカ系微粒子(P-6)の調製
実施例２において、エチルシリケート（ＳｉＯ2濃度２８重量％）１０４ｇの代わりにビニルシラン（信越化学（株）製：ＫＢＥ−１００３、濃度６２.７重量％）４６.４ｇを用いた以外は同様にして固形分濃度２０重量％のシリカ系微粒子(P-6)のアルコール分散液を調製した。
なお、シリカ系微粒子(P-6-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々１ｐｐｍ、９００ｐｐｍであった。
透明被膜付基材（A-6）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-6)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-6）を得た。
透明被膜付基材（B-6）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-6)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-6）を得た。
Preparation of silica-based fine particles (P-6) In Example 2, vinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-1003, concentration 62.7% by weight) 46 instead of 104 g of ethyl silicate (SiO 2 concentration 28% by weight) 46 An alcohol dispersion of silica-based fine particles (P-6) having a solid concentration of 20% by weight was prepared in the same manner except that 0.4 g was used.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-6-3) were 1 ppm and 900 ppm, respectively, per silica-based fine particle.
Production of substrate with transparent coating (A-6) In Example 1 except that an alcohol dispersion of silica fine particles (P-6) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent film (A-6) was obtained.
Production of substrate with transparent coating (B-6) In Example 1 except that an alcohol dispersion of silica fine particles (P-6) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (B-6) was obtained.
シリカ系微粒子(P-7)の調製
実施例２において、濃度０．５重量％の硫酸ナトリウム５０，４００ｇの代わりに濃度０．２重量％の硫酸ナトリウム５０，４００ｇを用い、エチルシリケート（ＳｉＯ2濃度２８重量％）１０４ｇの代わりにエポキシシラン（信越化学（株）製：ＫＭＢ−４０３、濃度８４.９重量％）３４.３ｇを用いた以外は同様にして固形分濃度２０重量％のシリカ系微粒子(P-7)のアルコール分散液を調製した。
なお、シリカ系微粒子(P-7-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々０．８ｐｐｍ、８００ｐｐｍであった。
透明被膜付基材（A-7）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-7)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-7）を得た。
透明被膜付基材（B-7）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-7)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-7）を得た。
Preparation of silica-based fine particles (P-7) In Example 2, 50,400 g of sodium sulfate having a concentration of 0.2% by weight was used instead of 50,400 g of sodium sulfate having a concentration of 0.5% by weight, and ethyl silicate (SiO 2 Silica system having a solid content concentration of 20% by weight, except that 34.3 g of epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd .: KMB-403, concentration of 84.9% by weight) was used instead of 104 g. An alcohol dispersion of fine particles (P-7) was prepared.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-7-3) were 0.8 ppm and 800 ppm, respectively, per silica-based fine particle.
Production of substrate with transparent coating (A-7) In Example 1 except that an alcohol dispersion of silica-based fine particles (P-7) was used instead of an alcohol dispersion of silica-based fine particles (P-1) Thus, a substrate with a transparent coating (A-7) was obtained.
Production of substrate with transparent coating (B-7) In Example 1 except that an alcohol dispersion of silica-based fine particles (P-7) was used instead of an alcohol dispersion of silica-based fine particles (P-1) Thus, a substrate with a transparent coating (B-7) was obtained.
シリカ系微粒子(P-8)の調製
実施例２において、エチルシリケート（ＳｉＯ2濃度２８重量％）１０４ｇの代わりにフッ素系アルキルシラン（信越化学（株）製：ＫＭＢ−７０８３、濃度８３.８重量％）３４.７５ｇを用いた以外は同様にして固形分濃度２０重量％のシリカ系微粒子(P-8)のアルコール分散液を調製した。
なお、シリカ系微粒子(P-8-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々０．９ｐｐｍ、８００ｐｐｍであった。
透明被膜付基材（A-8）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-8)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-8）を得た。
透明被膜付基材（B-8）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-8)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-8）を得た。
Preparation of silica-based fine particles (P-8) In Example 2, instead of 104 g of ethyl silicate (SiO 2 concentration 28 wt%), fluorine-based alkylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KMB-7083, concentration 83.8 wt. %) An alcohol dispersion of silica-based fine particles (P-8) having a solid concentration of 20% by weight was prepared in the same manner except that 34.75 g was used.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-8-3) were 0.9 ppm and 800 ppm, respectively, per silica-based fine particle.
Production of substrate with transparent film (A-8) In Example 1 except that an alcohol dispersion of silica fine particles (P-8) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (A-8) was obtained.
Production of substrate with transparent coating (B-8) In Example 1 except that an alcohol dispersion of silica fine particles (P-8) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (B-8) was obtained.
シリカ系微粒子(P-9)の調製
実施例２の工程(a)において、ＳｉＯ2として０．７６重量％の珪酸ナトリウム水溶液９０００ｇとＡｌ2Ｏ3として１．２５重量％のアルミン酸ナトリウム水溶液９０００ｇとを同時に添加し、濃度０．５重量％の硫酸ナトリウム５０，４００ｇの代わりに濃度２．０重量％の硫酸ナトリウム５０，４００ｇを用いた以外は同様にして固形分濃度２０重量％のシリカ系微粒子(P-9)のアルコール分散液を調製した。
なお、シリカ系微粒子(P-9-3)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々１ｐｐｍ、８００ｐｐｍであった。
透明被膜付基材（A-9）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-9)のアルコール分散液を用いた以外は同様にして透明被膜付基材（A-9）を得た。
透明被膜付基材（B-9）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(P-9)のアルコール分散液を用いた以外は同様にして透明被膜付基材（B-9）を得た。
Preparation of silica-based fine particles (P-9) In step (a) of Example 2, 9000 g of 0.76 wt% sodium silicate aqueous solution as SiO 2 and 9000 g of 1.25 wt% sodium aluminate aqueous solution as Al 2 O 3 were used. In the same manner except that 50,400 g of sodium sulfate having a concentration of 2.0% by weight was used instead of 50,400 g of sodium sulfate having a concentration of 0.5% by weight. An alcohol dispersion of fine particles (P-9) was prepared.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-9-3) were 1 ppm and 800 ppm, respectively, per silica-based fine particle.
Production of substrate with transparent coating (A-9) In Example 1 except that an alcohol dispersion of silica fine particles (P-9) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (A-9) was obtained.
Production of substrate with transparent coating (B-9) In Example 1 except that an alcohol dispersion of silica fine particles (P-9) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (B-9) was obtained.
シリカ系微粒子(RP-1)の調製
実施例１と同様にして固形分濃度２０重量％のシリカ系微粒子(P-1-1)の水分散液を調製した。なお、シリカ系微粒子(P-1-1)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々１０００ｐｐｍ、１０ｐｐｍ未満であった。
ついで限外濾過膜を用いて溶媒をエタノールに置換した固形分濃度２０重量％のシリカ系微粒子（RP-1）のアルコール分散液を調製した。
透明被膜付基材（RA-1）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-1)のアルコール分散液を用いた以外は同様にして透明被膜付基材(RA-1)を得た。
透明被膜付基材（RB-1）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-1) のアルコール分散液を用いた以外は同様にして透明被膜付基材（RB-1）を得た。
Preparation of silica-based fine particles (RP-1) In the same manner as in Example 1, an aqueous dispersion of silica-based fine particles (P-1-1) having a solid concentration of 20% by weight was prepared. The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-1-1) were 1000 ppm and less than 10 ppm, respectively, per silica-based fine particle.
Next, an alcohol dispersion of silica-based fine particles (RP-1) having a solid content concentration of 20% by weight was prepared by replacing the solvent with ethanol using an ultrafiltration membrane.
Production of substrate with transparent coating (RA-1) In Example 1 except that an alcohol dispersion of silica-based fine particles (RP-1) was used instead of an alcohol dispersion of silica-based fine particles (P-1) As a result, a substrate with transparent coating (RA-1) was obtained.
Production of transparent coated substrate (RB-1) In Example 1, except that silica-based fine particle (RP-1) alcohol dispersion was used instead of silica-based fine particle (P-1) alcohol dispersion Thus, a substrate with a transparent coating (RB-1) was obtained.
シリカ系微粒子(RP-2)の調製
実施例１と同様にして固形分濃度２０重量％のシリカ系微粒子(P-1-2)の水分散液を調製し、ついで限外濾過膜を用いて溶媒をエタノールに置換した固形分濃度２０重量％のシリカ系微粒子（RP-2）のアルコール分散液を調製した。なお、シリカ系微粒子(P-1-2)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々６ｐｐｍ、１２００ｐｐｍであった。
透明被膜付基材（RA-2）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-2)のアルコール分散液を用いた以外は同様にして透明被膜付基材(RA-2)を得た。
透明被膜付基材（RB-2）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-2) のアルコール分散液を用いた以外は同様にして透明被膜付基材（RB-2）を得た。
Preparation of silica-based fine particles (RP-2) An aqueous dispersion of silica-based fine particles (P-1-2) having a solid content of 20% by weight was prepared in the same manner as in Example 1, and then using an ultrafiltration membrane. An alcohol dispersion of silica-based fine particles (RP-2) having a solid content concentration of 20% by weight in which the solvent was replaced with ethanol was prepared. The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (P-1-2) were 6 ppm and 1200 ppm, respectively, per silica-based fine particle.
Production of transparent-coated substrate (RA-2) In Example 1, except that silica-based fine particle (RP-2) alcohol dispersion was used instead of silica-based fine particle (P-1) alcohol dispersion In this way, a transparent coated substrate (RA-2) was obtained.
Production of transparent coated substrate (RB-2) In Example 1, except that silica-based fine particle (RP-2) alcohol dispersion was used instead of silica-based fine particle (P-1) alcohol dispersion Thus, a substrate with a transparent coating (RB-2) was obtained.
シリカ系微粒子(RP-3)の調製
比較例１の工程(a) において、ＳｉＯ2として１．５重量％の珪酸ナトリウム水溶液と、Ａl2Ｏ3として０．５重量％のアルミン酸ナトリウム水溶液とを使用した以外は同様にして固形分濃度２０重量％のシリカ系微粒子(RP-3) のアルコール分散液を調製した。
なお、シリカ系微粒子(RP-1-1)の水分散液のＮa2Ｏ含有量およびＮＨ3含有量はシリカ系微粒子当たり各々１２００ｐｐｍ、１０ｐｐｍ未満であった。
明被膜付基材（RA-3）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-3)のアルコール分散液を用いた以外は同様にして透明被膜付基材（RA-3）を得た。
透明被膜付基材（RB-3）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-3)のアルコール分散液を用いた以外は同様にして透明被膜付基材（RB-3）を得た。
Preparation of silica-based fine particles (RP-3) In the step (a) of Comparative Example 1, 1.5 wt% sodium silicate aqueous solution as SiO 2 and 0.5 wt% sodium aluminate aqueous solution as Al 2 O 3 An alcohol dispersion of silica-based fine particles (RP-3) having a solid concentration of 20% by weight was prepared in the same manner except that was used.
The Na 2 O content and NH 3 content of the aqueous dispersion of silica-based fine particles (RP-1-1) were 1200 ppm and less than 10 ppm, respectively, per silica-based fine particle.
Production of substrate with bright film (RA-3) In Example 1 except that an alcohol dispersion of silica-based fine particles (RP-3) was used instead of an alcohol dispersion of silica-based fine particles (P-1) Thus, a substrate with a transparent coating (RA-3) was obtained.
Production of substrate with transparent coating (RB-3) In Example 1, except that an alcohol dispersion of silica fine particles (RP-3) was used instead of an alcohol dispersion of silica fine particles (P-1) Thus, a substrate with a transparent coating (RB-3) was obtained.
シリカ系微粒子（RP-4）
シリカ系微粒子としてシリカゾル（触媒化成工業（株）製：SI-45P、平均粒子径４５ｎｍ、ＳｉＯ2濃度：２０重量％）を用い、これを限外濾過膜にてエタノールに分散媒を置換し、固形分濃度２０重量％のシリカ系微粒子（RP-4）のアルコール分散液として用いた。
なお、シリカゾルのＮa2Ｏ含有量およびＮＨ3含有量はシリカ粒子当たり各々２０５００ｐｐｍ、１００ｐｐｍであった。
透明被膜付基材（RA-4）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-4)のアルコール分散液を用いた以外は同様にして透明被膜付基材（RA-4）を得た。
透明被膜付基材（RB-2）の製造
実施例１において、シリカ系微粒子(P-1)のアルコール分散液の代わりにシリカ系微粒子(RP-2)のアルコール分散液を用いた以外は同様にして透明被膜付基材（RB-2）を得た。
Silica-based fine particles (RP-4)
Silica sol (Catalyst Kasei Kogyo Co., Ltd. product: SI-45P, average particle diameter 45 nm, SiO 2 concentration: 20% by weight) was used as silica-based fine particles, and this was replaced with ethanol by an ultrafiltration membrane, It was used as an alcohol dispersion of silica-based fine particles (RP-4) having a solid content concentration of 20% by weight.
The Na 2 O content and NH 3 content of the silica sol were 20500 ppm and 100 ppm, respectively, per silica particle.
Production of transparent-coated substrate (RA-4) In Example 1, except that silica-based fine particle (RP-4) alcohol dispersion was used instead of silica-based fine particle (P-1) alcohol dispersion In this way, a transparent coated substrate (RA-4) was obtained.
Production of transparent coated substrate (RB-2) In Example 1, except that silica-based fine particle (RP-2) alcohol dispersion was used instead of silica-based fine particle (P-1) alcohol dispersion Thus, a substrate with a transparent coating (RB-2) was obtained.
シリカ系微粒子(RP-5)の調製
実施例１と同様にして固形分濃度２０重量％のＳｉＯ2・Ａｌ2Ｏ3一次粒子分散液を調製した。
この一次粒子分散液５００ｇに純水１，７００ｇを加えて９８℃に加温し、この温度を保持しながら、ＳｉＯ2として濃度１.１７重量％の珪酸ナトリウム水溶液３，０００ｇとＡｌ2Ｏ3としての濃度０.５重量％のアルミン酸ナトリウム水溶液９,０００ｇを添加して複合酸化物微粒子(RP-5)の分散液を得た。
ついで、限外濾過膜で洗浄して固形分濃度１３重量％になった複合酸化物微粒子(RP-5)の分散液５００ｇに純水１,１２５ｇを加え、さらに濃塩酸（濃度３５.５重量％）を滴下してｐＨ１.０とし、脱アルミニウム処理を行った。次いで、ｐＨ３の塩酸水溶液１０Ｌと純水５Ｌを加えながら限外濾過膜で溶解したアルミニウム塩を分離・洗浄して固形分濃度２０重量％のシリカ系微粒子(RP-5)の水分散液を得た。
シリカ系微粒子(RP-5)について平均粒子径を測定したところ、約５ｎｍであり、屈折率は１．４３であった。また、透過型電子顕微鏡写真（ＴＥＭ）を撮影して観察したところ、殆どが微小粒子であり、中空粒子は殆ど存在しなかった。
Preparation of silica-based fine particles (RP-5) In the same manner as in Example 1, a SiO 2 .Al 2 O 3 primary particle dispersion having a solid content concentration of 20% by weight was prepared.
1,700 g of pure water was added to 500 g of this primary particle dispersion and heated to 98 ° C., and while maintaining this temperature, 3,000 g of an aqueous sodium silicate solution having a concentration of 1.17 wt% as SiO 2 and Al 2 O 3 As a result, 9,000 g of a sodium aluminate aqueous solution having a concentration of 0.5 wt% was added to obtain a dispersion of composite oxide fine particles (RP-5).
Next, 1,125 g of pure water was added to 500 g of the dispersion of composite oxide fine particles (RP-5) which had been washed with an ultrafiltration membrane to a solid content concentration of 13 wt%, and concentrated hydrochloric acid (concentration 35.5 wt. %) Was added dropwise to adjust the pH to 1.0, and dealumination was performed. Next, an aqueous dispersion of silica-based fine particles (RP-5) having a solid content concentration of 20% by weight is obtained by separating and washing the aluminum salt dissolved in the ultrafiltration membrane while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water. It was.
The average particle diameter of the silica-based fine particles (RP-5) was measured and found to be about 5 nm and the refractive index was 1.43. Further, when a transmission electron micrograph (TEM) was taken and observed, most were fine particles, and there were almost no hollow particles.
［表１］
一次粒子 電解質塩 シリカ被覆 シリカ系微粒子 微量成分
符号 のモル比 種類 M E /M S 種類 層厚 モル比 平均粒径 屈折率 Na 2 O NH 3
(MOX/SiO2) (nm) (MOX/SiO2) (nm) (ppm)(ppm)
P-1 0.35 Na2SO4 1.09 - - 0.0097 40 1.30 0.5 600
P-2 0.35 Na2SO4 1.09 ET 8 0.0019 46 1.28 0.5 900
P-3 0.35 KNO3 0.91 ET 8 0.0019 46 1.27 0.4 800
P-4 0.35 (NH4)2SO4 1.24 ET 8 0.0019 46 1.28 0.5 800
P-5 0.35 NH4NO3 1.58 ET 8 0.0017 47 1.30 0.8 700
P-6 0.35 Na2SO4 1.09 V 8 0.0017 47 1.27 1.0 900
P-7 0.35 Na2SO4 0.44 EP 8 0.0017 47 1.27 0.8 800
P-8 0.35 Na2SO4 1.09 F 8 0.0012 53 1.25 0.9 800
P-9 0.75 Na2SO4 5.39 ET 8 0.0023 60 1.30 1.0 800
・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・
RP-1 0.35 Na2SO4 1.09 - - 0.0097 40 1.30 1000 10>
RP-2 0.35 Na2SO4 1.09 - - 0.0097 40 1.30 6 1200
RP-3 0.171 Na2SO4 0.94 - - 0.0005 30 1.42 1200 10>
RP-4 0.000 - - - - 0.000 45 1.46 20500 100
RP-5 0.35 - - - - 0.0097 5 1.43 - -
[Table 1]
Primary particle electrolyte salt silica-coated silica fine particle minor component
The molar ratio of the code type M E / M S type thickness molar ratio average particle size refractive index Na 2 O NH 3
(MO X / SiO 2 ) (nm) (MO X / SiO 2 ) (nm) (ppm) (ppm)
P-1 0.35 Na 2 SO 4 1.09--0.0097 40 1.30 0.5 600
P-2 0.35 Na 2 SO 4 1.09 ET 8 0.0019 46 1.28 0.5 900
P-3 0.35 KNO 3 0.91 ET 8 0.0019 46 1.27 0.4 800
P-4 0.35 (NH 4 ) 2 SO 4 1.24 ET 8 0.0019 46 1.28 0.5 800
P-5 0.35 NH 4 NO 3 1.58 ET 8 0.0017 47 1.30 0.8 700
P-6 0.35 Na 2 SO 4 1.09 V 8 0.0017 47 1.27 1.0 900
P-7 0.35 Na 2 SO 4 0.44 EP 8 0.0017 47 1.27 0.8 800
P-8 0.35 Na 2 SO 4 1.09 F 8 0.0012 53 1.25 0.9 800
P-9 0.75 Na 2 SO 4 5.39 ET 8 0.0023 60 1.30 1.0 800
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・
RP-1 0.35 Na 2 SO 4 1.09--0.0097 40 1.30 1000 10>
RP-2 0.35 Na 2 SO 4 1.09--0.0097 40 1.30 6 1200
RP-3 0.171 Na 2 SO 4 0.94--0.0005 30 1.42 1200 10>
RP-4 0.000----0.000 45 1.46 20 500 100
RP-5 0.35----0.0097 5 1.43--
［表２］
透明被膜付基材（有機樹脂マトリックス）
符号 全光線 ヘイズ 反射率 被膜 密着性 鉛筆硬度
透過率 屈折率
（％） （％） （％）
A-1 96.5 0.3 0.5 1.35 ◎ 4H
A-2 95.5 0.3 0.4 1.33 ◎ 3H
A-3 96.1 0.2 0.3 1.32 ◎ 3H
A-4 96.2 0.2 0.4 1.33 ◎ 3H
A-5 95.9 0.3 0.5 1.34 ◎ 3H
A-6 96.8 0.1 0.3 1.32 ◎ 3H
A-7 96.5 0.1 0.4 1.31 ◎ 3H
A-8 96.7 0.1 0.2 1.31 ◎ 3H
A-9 96.7 0.1 0.3 1.34 ◎ 3H
・・・・・・・・・・・・・・・・・・・・・・・・・・・
RA-1 96.5 0.3 0.5 1.35 △ H
RA-2 95.4 0.3 0.5 1.33 △ H
RA-3 94.3 1.8 1.0 1.45 ○ H
RA-4 94.3 0.3 1.5 1.46 ○ H
[Table 2]
Transparent coated substrate ( organic resin matrix )
Code total light haze reflectivity film adhesion pencil hardness
Transmittance refractive index (%) (%) (%)
A-1 96.5 0.3 0.5 1.35 ◎ 4H
A-2 95.5 0.3 0.4 1.33 ◎ 3H
A-3 96.1 0.2 0.3 1.32 ◎ 3H
A-4 96.2 0.2 0.4 1.33 ◎ 3H
A-5 95.9 0.3 0.5 1.34 ◎ 3H
A-6 96.8 0.1 0.3 1.32 ◎ 3H
A-7 96.5 0.1 0.4 1.31 ◎ 3H
A-8 96.7 0.1 0.2 1.31 ◎ 3H
A-9 96.7 0.1 0.3 1.34 ◎ 3H
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・
RA-1 96.5 0.3 0.5 1.35 △ H
RA-2 95.4 0.3 0.5 1.33 △ H
RA-3 94.3 1.8 1.0 1.45 ○ H
RA-4 94.3 0.3 1.5 1.46 ○ H
［表３］
透明被膜付基材（シリコン樹脂マトリックス）
符号 全光線 ヘイズ 反射率 被膜 鉛筆硬度
透過率 屈折率
（％） （％） （％）
B-1 96.1 0.3 0.5 1.35 8H
B-2 96.4 0.3 0.2 1.31 7H
B-3 96.2 0.2 0.3 1.33 7H
B-4 96.2 0.2 0.3 1.33 7H
B-5 96.5 0.1 0.4 1.34 7H
B-6 96.7 0.1 0.2 1.31 7H
B-7 96.0 0.1 0.3 1.31 7H
B-8 97.0 0.1 0.3 1.32 7H
B-9 96.5 0.1 0.1 1.34 7H
・・・・・・・・・・・・・・・・・・・・・・・
RB-1 96.2 0.3 0.5 1.35 5H
RB-2 96.1 0.3 0.5 1.35 5H
RB-3 94.8 0.8 1.2 1.41 5H
RB-4 94.0 0.2 1.3 1.43 5H
[Table 3]
Transparent coated substrate ( silicone resin matrix )
Code total light haze reflectance coating pencil hardness
Transmittance refractive index (%) (%) (%)
B-1 96.1 0.3 0.5 1.35 8H
B-2 96.4 0.3 0.2 1.31 7H
B-3 96.2 0.2 0.3 1.33 7H
B-4 96.2 0.2 0.3 1.33 7H
B-5 96.5 0.1 0.4 1.34 7H
B-6 96.7 0.1 0.2 1.31 7H
B-7 96.0 0.1 0.3 1.31 7H
B-8 97.0 0.1 0.3 1.32 7H
B-9 96.5 0.1 0.1 1.34 7H
...
RB-1 96.2 0.3 0.5 1.35 5H
RB-2 96.1 0.3 0.5 1.35 5H
RB-3 94.8 0.8 1.2 1.41 5H
RB-4 94.0 0.2 1.3 1.43 5H
Claims (12)
（ａ）珪酸塩の水溶液および／または酸性珪酸液と、アルカリ可溶の無機化合物水溶液とをアルカリ水溶液中に同時に添加して、シリカをＳｉＯ2で表し、シリカ以外の無機酸化物をＭＯXで表したときのモル比ＭＯX／ＳｉＯ2が０.３〜１.０の範囲にある複合酸化物微粒子分散液を調製する際に、複合酸化物微粒子の平均粒子径が５〜３００ｎｍになった時点で電解質塩を電解質塩のモル数（ＭE）とＳｉＯ2のモル数（ＭS）との比（ＭE／ＭS）が０.１〜１０の範囲で添加する工程
（ｂ）前記複合酸化物微粒子分散液に、電解質塩のモル数（Ｍ E ）とＳｉＯ 2 のモル数（Ｍ S ）との比（Ｍ E ／Ｍ S ）が０.１〜１０の範囲で必要に応じてさらに電解質塩を加えた後、酸を加えて前記複合酸化物微粒子を構成する珪素以外の元素の少なくとも一部を除去してシリカ系微粒子分散液とする工程
（ｄ）洗浄した後、シリカ系微粒子分散液を常温〜３００℃の範囲で熟成する工程
（ｅ）５０〜３００℃の範囲で水熱処理する工程 A method for producing silica-based fine particles comprising the following steps (a), (b), (d) and (e).
(A) an aqueous solution of silicate and / or an acidic silicic acid solution and an inorganic compound aqueous solution of an alkali-soluble by adding simultaneously in the alkaline aqueous solution, the silica expressed as SiO 2, the inorganic oxide other than silica MO X When the composite oxide fine particle dispersion having a molar ratio MO X / SiO 2 in the range of 0.3 to 1.0 is prepared, the average particle size of the composite oxide fine particles becomes 5 to 300 nm. Step (b) of adding an electrolyte salt in a ratio (M E / M S ) of the number of moles of electrolyte salt (M E ) to the number of moles of SiO 2 (M S ) in the range of 0.1 to 10 If necessary, the composite oxide fine particle dispersion may have a ratio (M E / M S ) of the number of moles of electrolyte salt (M E ) to the number of moles of SiO 2 (M S ) in the range of 0.1 to 10. After further adding an electrolyte salt, an acid is added to at least contain elements other than silicon constituting the composite oxide fine particles. After partially removed by step (d) washing the silica-based fine particle dispersion, water in the range of step (e) 5 0~300 ℃ ripening the silica-based fine particle dispersion in the range of room temperature to 300 ° C. Heat treatment process
（ａ）珪酸塩の水溶液および／または酸性珪酸液と、アルカリ可溶の無機化合物水溶液とをアルカリ水溶液中に同時に添加して、シリカをＳｉＯ(A) An aqueous solution of a silicate and / or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound are simultaneously added to an aqueous alkaline solution, and silica is dissolved in SiO. 22 で表し、シリカ以外の無機酸化物をＭＯInorganic oxides other than silica XX で表したときのモル比ＭＯMolar ratio MO expressed as XX ／ＳｉＯ/ SiO 22 が０.３〜１.０の範囲にある複合酸化物微粒子分散液を調製する際に、複合酸化物微粒子の平均粒子径が５〜３００ｎｍになった時点で電解質塩を電解質塩のモル数（ＭWhen preparing a composite oxide fine particle dispersion in which the average particle size of the composite oxide fine particles becomes 5 to 300 nm, the electrolyte salt is converted into the number of moles of electrolyte salt ( M EE ）とＳｉＯ) And SiO 22 のモル数（ＭMoles (M SS ）との比（Ｍ) And ratio (M EE ／Ｍ/ M SS ）が０.１〜１０の範囲で添加する工程) Is added in the range of 0.1 to 10
（ｂ）前記複合酸化物微粒子分散液に、電解質塩のモル数（Ｍ(B) The number of moles of electrolyte salt (M EE ）とＳｉＯ) And SiO 22 のモル数（ＭMoles (M SS ）との比（Ｍ) And ratio (M EE ／Ｍ/ M SS ）が０.１〜１０の範囲で必要に応じてさらに電解質塩を加えた後、酸を加えて前記複合酸化物微粒子を構成する珪素以外の元素の少なくとも一部を除去してシリカ系微粒子分散液とする工程) Is in the range of 0.1 to 10, further adding an electrolyte salt as necessary, and then adding an acid to remove at least a part of elements other than silicon constituting the composite oxide fine particles, thereby dispersing silica-based fine particles. Liquid process
（ｄ）シリカ系微粒子分散液を常温〜３００℃の範囲で熟成する工程(D) A step of aging the silica-based fine particle dispersion in the range of room temperature to 300 ° C.
（ｅ）洗浄した後、５０〜３００℃の範囲で水熱処理する工程(E) The process of hydrothermally treating in the range of 50 to 300 ° C. after washing.
（ａ）珪酸塩の水溶液および／または酸性珪酸液と、アルカリ可溶の無機化合物水溶液とを種粒子が分散したアルカリ水溶液中に同時に添加して、シリカをＳｉＯ(A) An aqueous solution of silicate and / or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound are simultaneously added to an alkaline aqueous solution in which seed particles are dispersed, and silica is added to SiO. 22 で表し、シリカ以外の無機酸化物をＭＯInorganic oxides other than silica XX で表したときのモル比ＭＯMolar ratio MO expressed as XX ／ＳｉＯ/ SiO 22 が０.３〜１.０の範囲にある複合酸化物微粒子分散液を調製する際に、複合酸化物微粒子の平均粒子径が５〜３００ｎｍになった時点で電解質塩を電解質塩のモル数（ＭWhen preparing a composite oxide fine particle dispersion in which the average particle size of the composite oxide fine particles becomes 5 to 300 nm, the electrolyte salt is converted into the number of moles of electrolyte salt ( M EE ）とＳｉＯ) And SiO 22 のモル数（ＭMoles (M SS ）との比（Ｍ) And ratio (M EE ／Ｍ/ M SS ）が０.１〜１０の範囲で添加する工程) Is added in the range of 0.1 to 10
（ｂ）前記複合酸化物微粒子分散液に、電解質塩のモル数（Ｍ(B) The number of moles of electrolyte salt (M EE ）とＳｉＯ) And SiO 22 のモル数（ＭMoles (M SS ）との比（Ｍ) And ratio (M EE ／Ｍ/ M SS ）が０.１〜１０の範囲で必要に応じてさらに電解質塩を加えた後、酸を加えて前記複合酸化物微粒子を構成する珪素以外の元素の少なくとも一部を除去してシリカ系微粒子分散液とする工程) Is in the range of 0.1 to 10, further adding an electrolyte salt as necessary, and then adding an acid to remove at least a part of elements other than silicon constituting the composite oxide fine particles, thereby dispersing silica-based fine particles. Liquid process
（ｄ）洗浄した後、シリカ系微粒子分散液を常温〜３００℃の範囲で熟成する工程(D) A step of aging the silica-based fine particle dispersion in the range of room temperature to 300 ° C. after washing.
（ｅ）５０〜３００℃の範囲で水熱処理する工程(E) Hydrothermal treatment in the range of 50 to 300 ° C
（ａ）珪酸塩の水溶液および／または酸性珪酸液と、アルカリ可溶の無機化合物水溶液とを種粒子が分散したアルカリ水溶液中に同時に添加して、シリカをＳｉＯ(A) An aqueous solution of silicate and / or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound are simultaneously added to an alkaline aqueous solution in which seed particles are dispersed, and silica is added to SiO. 22 で表し、シリカ以外の無機酸化物をＭＯInorganic oxides other than silica XX で表したときのモル比ＭＯMolar ratio MO expressed as XX ／ＳｉＯ/ SiO 22 が０.３〜１.０の範囲にある複合酸化物微粒子分散液を調製する際に、複合酸化物微粒子の平均粒子径が５〜３００ｎｍになった時点で電解質塩を電解質塩のモル数（ＭWhen preparing a composite oxide fine particle dispersion in which the average particle size of the composite oxide fine particles becomes 5 to 300 nm, the electrolyte salt is converted into the number of moles of electrolyte salt ( M EE ）とＳｉＯ) And SiO 22 のモル数（ＭMoles (M SS ）との比（Ｍ) And ratio (M EE ／Ｍ/ M SS ）が０.１〜１０の範囲で添加する工程) Is added in the range of 0.1 to 10
（ｂ）前記複合酸化物微粒子分散液に、電解質塩のモル数（Ｍ(B) The number of moles of electrolyte salt (M EE ）とＳｉＯ) And SiO 22 のモル数（ＭMoles (M SS ）との比（Ｍ) And ratio (M EE ／Ｍ/ M SS ）が０.１〜１０の範囲で必要に応じてさらに電解質塩を加えた後、酸を加えて前記複合酸化物微粒子を構成する珪素以外の元素の少なくとも一部を除去してシリカ系微粒子分散液とする工程) Is in the range of 0.1 to 10, further adding an electrolyte salt as necessary, and then adding an acid to remove at least a part of elements other than silicon constituting the composite oxide fine particles, thereby dispersing silica-based fine particles. Liquid process
（ｄ）シリカ系微粒子分散液を常温〜３００℃の範囲で熟成する工程(D) A step of aging the silica-based fine particle dispersion in the range of room temperature to 300 ° C.
（ｅ）洗浄した後、５０〜３００℃の範囲で水熱処理する工程(E) The process of hydrothermally treating in the range of 50-300 degreeC after wash | cleaning.
（ｃ）前記工程（ｂ）で得られたシリカ系微粒子分散液に、アルカリ水溶液と、下記化学式（１）で表される有機珪素化合物および／またはその部分加水分解物とを添加し、該微粒子にシリカ被覆層を形成する工程
ＲnＳｉＸ(4-n) ・・・（１）
〔但し、Ｒ：炭素数１〜１０の非置換または置換炭化水素基、アクリル基、エポキシ基、メタクリル基、アミノ基、ＣＦ 3 基、Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲンまたは水素、ｎ：０〜３の整数〕 The method for producing silica-based fine particles according to any one of claims 1 to 4, wherein the following step (c) is carried out between the step (b) and the step (d).
(C) An aqueous alkali solution and an organosilicon compound represented by the following chemical formula (1) and / or a partial hydrolyzate thereof are added to the silica-based fine particle dispersion obtained in the step (b), and the fine particles Forming a silica coating on the substrate
R n SiX (4-n) (1)
[However, R: unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, acrylic group, epoxy group, methacryl group, amino group, CF 3 group , X: alkoxy group having 1 to 4 carbon atoms, silanol group, halogen Or hydrogen, n: an integer of 0 to 3]
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| CN102196996B (en) * | 2008-10-31 | 2013-08-07 | 旭硝子株式会社 | Hollow particle, method for producing the same, coating composition and article |
| JP5688649B2 (en) * | 2009-04-10 | 2015-03-25 | 国立大学法人 香川大学 | Water / oil repellent member, method for producing the same, and article using them |
| JP2014001294A (en) * | 2012-06-18 | 2014-01-09 | Hitachi Chemical Co Ltd | Low refractive index resin film, and composite film using the same |
| JP5766251B2 (en) * | 2013-10-30 | 2015-08-19 | 日揮触媒化成株式会社 | Method for producing a coating for forming a transparent film |
| JP6440551B2 (en) * | 2015-03-31 | 2018-12-19 | 日揮触媒化成株式会社 | Method for producing silica particles |
| JP6462459B2 (en) * | 2015-03-31 | 2019-01-30 | 日揮触媒化成株式会社 | Method for producing silica particles |
| CN110323439A (en) * | 2019-07-31 | 2019-10-11 | 深圳大学 | A kind of lithium ion battery negative material and preparation method thereof |
| CN115627159B (en) * | 2022-09-09 | 2024-02-27 | 吉林大学 | Nanoemulsion for deep drilling pore blocking and wetting regulation and control and preparation thereof |
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| JP2003026417A (en) * | 2001-07-13 | 2003-01-29 | Catalysts & Chem Ind Co Ltd | Method for producing silica sol and silica-based composite oxide sol |
| JP2004203683A (en) * | 2002-12-25 | 2004-07-22 | Catalysts & Chem Ind Co Ltd | Method for producing silica-based fine particles and coated substrate containing the silica-based fine particles |
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| JP2003026417A (en) * | 2001-07-13 | 2003-01-29 | Catalysts & Chem Ind Co Ltd | Method for producing silica sol and silica-based composite oxide sol |
| JP2004203683A (en) * | 2002-12-25 | 2004-07-22 | Catalysts & Chem Ind Co Ltd | Method for producing silica-based fine particles and coated substrate containing the silica-based fine particles |
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