JP2020032719A - Component and manufacturing method of component - Google Patents
Component and manufacturing method of component Download PDFInfo
- Publication number
- JP2020032719A JP2020032719A JP2019143857A JP2019143857A JP2020032719A JP 2020032719 A JP2020032719 A JP 2020032719A JP 2019143857 A JP2019143857 A JP 2019143857A JP 2019143857 A JP2019143857 A JP 2019143857A JP 2020032719 A JP2020032719 A JP 2020032719A
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- JP
- Japan
- Prior art keywords
- less
- porous layer
- silica
- silica particles
- particle dispersion
- 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.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 165
- 239000002245 particle Substances 0.000 claims description 76
- 239000006185 dispersion Substances 0.000 claims description 63
- 239000000377 silicon dioxide Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 40
- -1 silane compound Chemical class 0.000 claims description 24
- 230000002209 hydrophobic effect Effects 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 230000001681 protective effect Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 17
- 238000003384 imaging method Methods 0.000 claims description 16
- 229940054273 1-propoxy-2-propanol Drugs 0.000 claims description 15
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 80
- 238000010521 absorption reaction Methods 0.000 description 27
- 239000010954 inorganic particle Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 230000008859 change Effects 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 229910052814 silicon oxide Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- BAYAKMPRFGNNFW-UHFFFAOYSA-N 2,4-dimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)C BAYAKMPRFGNNFW-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- IWTBVKIGCDZRPL-LURJTMIESA-N 3-Methylbutanol Natural products CC[C@H](C)CCO IWTBVKIGCDZRPL-LURJTMIESA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- IWTBVKIGCDZRPL-UHFFFAOYSA-N 3-methylpentanol Chemical compound CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- ZIXLDMFVRPABBX-UHFFFAOYSA-N alpha-methylcyclopentanone Natural products CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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Images
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Abstract
Description
本発明は、吸湿性能に優れた部材に関し、特に防曇性能および光学性能に優れた部材および部材の製造方法に関する。 The present invention relates to a member excellent in moisture absorption performance, and more particularly to a member excellent in antifogging performance and optical performance and a method for manufacturing the member.
ガラスやプラスチック等の透明な基板は、基板表面が露点温度以下になると微細な水滴が基材表面に付着することで透過光が散乱し透明性が損なわれ、いわゆる「曇り」の状態となる。 When the substrate surface becomes lower than the dew point temperature, a transparent substrate such as glass or plastic is scattered by transmitted light due to fine water droplets adhering to the substrate surface, resulting in a loss of transparency and a so-called "cloudy" state.
曇りを防ぐ手段としては、基板表面に吸湿性のある層を設けることで、層に水分を吸収させ水滴発生を防ぐ方法が提案されている。特許文献１は、無機微粒子と水溶性樹脂からなる吸湿性の層で基板表面を被覆する方法を示している。 As means for preventing fogging, a method has been proposed in which a layer having a hygroscopic property is provided on the surface of the substrate to absorb moisture in the layer and to prevent generation of water droplets. Patent Literature 1 discloses a method of coating a substrate surface with a hygroscopic layer composed of inorganic fine particles and a water-soluble resin.
基板表面を濡れ易くし、水滴の発生を抑える方法も考えられている。特許文献２は、無機粒子を含有する凹凸膜で基板表面を被覆し、水の濡れ性を上げることで曇りを防ぐ方法を示している。 A method of making the substrate surface easy to wet and suppressing the generation of water droplets has also been considered. Patent Literature 2 discloses a method of covering a substrate surface with an uneven film containing inorganic particles and increasing wettability of water to prevent fogging.
しかしながら、吸湿性や濡れ性を上げて水滴発生を防ぐ方法は、高湿度下（６０％ＲＨ以上９０％ＲＨ未満）において吸湿や濡れにより屈折率が変化してしまうという課題が存在した。 However, the method of preventing the generation of water droplets by increasing the hygroscopicity or wettability has a problem that the refractive index changes due to moisture absorption or wetting under high humidity (60% RH or more and less than 90% RH).
本発明は、この様な背景技術に鑑みてなされたものであり、高湿度下（６０％ＲＨ以上９０％ＲＨ未満）での屈折率変化を低減する多孔質層およびその製造方法を提供するものである。 The present invention has been made in view of such background art, and provides a porous layer that reduces a change in refractive index under high humidity (60% RH or more and less than 90% RH), and a method for producing the same. It is.
本発明は、基材と、前記基材の少なくとも一つの表面に多孔質層と、を有する部材であって、前記多孔質層は、窒素吸着における微分細孔分布において微分細孔容積が最大となるときの空孔径ｄＮ２が５ｎｍ以上２０ｎｍ以下であり、水蒸気吸着における微分細孔分布において微分細孔容積が最大となるときの空孔径ｄＨ２Ｏが２５ｎｍ以上７５ｎｍ以下であり、水に対する接触角が６０°未満であることを特徴とする部材に関する。 The present invention is a member having a substrate and a porous layer on at least one surface of the substrate, wherein the porous layer has a maximum differential pore volume in a differential pore distribution in nitrogen adsorption. When the pore diameter dN 2 is 5 nm or more and 20 nm or less, the pore diameter dH 2 O when the differential pore volume is maximum in the differential pore distribution in water vapor adsorption is 25 nm or more and 75 nm or less, and the contact angle with water Is less than 60 °.
また、本発明は、筐体と、保護カバーと、前記筐体と前記保護カバーとに囲まれた内部空間に配置された撮像センサと、備える撮像装置であって、前記保護カバーは、基材と、前記内部空間側の前記基材の表面に多孔質層と、を有し、前記多孔質層は、窒素吸着における微分細孔分布において微分細孔容積が最大となるときの空孔径ｄＮ２が５ｎｍ以上２０ｎｍ以下であり、水蒸気吸着における微分細孔分布において微分細孔容積が最大となるときの空孔径ｄＨ２Ｏが２５ｎｍ以上７５ｎｍ以下であり、水に対する接触角が６０°未満であることを特徴とする撮像装置に関する。 Further, the present invention is an imaging apparatus including a housing, a protection cover, and an imaging sensor arranged in an internal space surrounded by the housing and the protection cover, wherein the protection cover includes a base material. And a porous layer on the surface of the substrate on the side of the internal space, wherein the porous layer has a pore diameter dN 2 when the differential pore volume is maximized in the differential pore distribution in nitrogen adsorption. Is 5 nm or more and 20 nm or less, the pore diameter dH 2 O when the differential pore volume is maximized in the differential pore distribution in water vapor adsorption is 25 nm or more and 75 nm or less, and the contact angle with water is less than 60 °. The present invention relates to an imaging device characterized by the above.
さらに、本発明は、疎水性官能基を有する有機シラン化合物と、シリカ粒子と、を溶媒中に含有するシリカ粒子分散液を準備する工程と、基材上または前記基材上に形成した他の層上に、前記シリカ粒子分散液を塗工し、前記シリカ粒子分散液の塗膜を形成する工程と、前記塗膜を乾燥させる工程と、を含み、前記シリカ粒子の平均粒子径が８ｎｍ以上２５ｎｍ以下であり、前記シリカ粒子分散液は、前記シリカ粒子に対して、ＳｉＯ２換算で前記疎水性官能基を有するシラン化合物を１ｗｔ％以上３０ｗｔ％以下で含むことを特徴とする上記部材の製造方法に関する。 Furthermore, the present invention provides an organic silane compound having a hydrophobic functional group, and silica particles, a step of preparing a silica particle dispersion containing the solvent in a solvent, and other steps formed on the substrate or on the substrate. Coating the silica particle dispersion on a layer, forming a coating film of the silica particle dispersion, and drying the coating film, wherein the average particle diameter of the silica particles is 8 nm or more. 25 nm or less, wherein the silica particle dispersion liquid contains the silane compound having a hydrophobic functional group in an amount of 1 wt% or more and 30 wt% or less in terms of SiO 2 with respect to the silica particles. About the method.
本発明によれば、基材の表面に高湿度下（６０％ＲＨ以上９０％ＲＨ未満）の屈折率変化の低減および防曇性に優れる多孔質層を有する部材を提供することができる。 According to the present invention, it is possible to provide a member having a porous layer on the surface of a base material, which has a reduced refractive index change under high humidity (60% RH or more and less than 90% RH) and is excellent in antifogging property.
以下、本発明を詳細に説明する。
［部材］
図１は、本発明の部材の一実施形態を示す模式図である。
本発明の部材１は、基材２と多孔質層３から構成されている。
Hereinafter, the present invention will be described in detail.
[Element]
FIG. 1 is a schematic view showing an embodiment of the member of the present invention.
The member 1 of the present invention includes a substrate 2 and a porous layer 3.
図１に示すように、多孔質層３は多孔質であり無機物４と空孔５を含んでいる。空孔５同士は互いに繋がっていることが好ましく、多孔質層３の表面に連通している。 As shown in FIG. 1, the porous layer 3 is porous and includes an inorganic substance 4 and pores 5. The holes 5 are preferably connected to each other, and are connected to the surface of the porous layer 3.
多孔質層３は、湿度９０％ＲＨ未満での吸湿量が少ないため、高湿度下（６０％ＲＨ以上９０％ＲＨ未満）の屈折率変化を低減でき、湿度９０％ＲＨ以上の超高湿度下で吸湿量が増加するため、結露が発生するような環境に暴露しても曇りが発生しない。そのため本発明の部材１は、透明基材を用いる、窓ガラス、鏡、レンズ、透明フィルムなど広い用途に用いることができる。また、部材１を透過する像に歪みが発生しないため、撮像系や投影系の光学レンズ、光学ミラー、光学フィルター、アイピース、屋外カメラや監視カメラ用の平面カバーやドームカバーなど光学用途に特に適している。 Since the porous layer 3 has a small amount of moisture absorption at a humidity of less than 90% RH, a change in the refractive index under a high humidity (60% RH or more and less than 90% RH) can be reduced, and under a super high humidity of 90% RH or more. , The amount of moisture absorption increases, so that fogging does not occur even when exposed to an environment where dew condensation occurs. Therefore, the member 1 of the present invention can be used for a wide range of uses such as a window glass, a mirror, a lens, and a transparent film using a transparent substrate. Also, since no distortion occurs in the image transmitted through the member 1, it is particularly suitable for optical applications such as an optical lens, an optical mirror, an optical filter, an eyepiece of an imaging system and a projection system, a flat cover and a dome cover for outdoor cameras and surveillance cameras. ing.
（多孔質層）
多孔質層３の水に対する接触角は６０°未満である。ここで、接触角は基板２上に形成された多孔質層３に純水を滴下したときに得られる接触角である。接触角が６０°未満であると水分子が多孔質層３の内部に十分に侵入することができるため、多孔質層３の吸湿量を確保できる。
(Porous layer)
The contact angle of the porous layer 3 with water is less than 60 °. Here, the contact angle is a contact angle obtained when pure water is dropped on the porous layer 3 formed on the substrate 2. When the contact angle is less than 60 °, water molecules can sufficiently enter the inside of the porous layer 3, so that the moisture absorption of the porous layer 3 can be secured.
図２に本発明に係る多孔質層３の窒素吸着等温線からＢＪＨ法により求めた微分細孔分布を示す。窒素吸着における微分細孔分布において、微分細孔容積が最大となるときの空孔径をｄＮ２と定義する。ｄＮ２はＳＥＭの画像観察などによって得られる空孔径と近い値を取る。 FIG. 2 shows the differential pore distribution obtained by the BJH method from the nitrogen adsorption isotherm of the porous layer 3 according to the present invention. In the differential pore distribution in nitrogen adsorption, the pore diameter at which the differential pore volume becomes maximum is defined as dN 2 . dN 2 takes a value close to the pore diameter obtained by SEM image observation or the like.
空孔径ｄＮ２は吸湿量を確保するために５ｎｍ以上２０ｎｍ以下であることが望ましい。ｄＮ２が５ｎｍ以上であると、多孔質層３は低湿度（湿度６０％ＲＨ未満）で吸湿することがなく、高湿度（６０％ＲＨ以上９０％ＲＨ未満）での吸湿量を確保することができる。またｄＮ２が２０ｎｍ以下であると水蒸気が凝集し易くなり吸湿量を確保することができる。なお、空孔の容積（細孔容積）は０．３７ｃｍ３／ｇ以上であることがより好ましい。 The pore diameter dN 2 is desirably 5 nm or more and 20 nm or less in order to secure a moisture absorption amount. When dN 2 is 5 nm or more, the porous layer 3 does not absorb moisture at low humidity (humidity less than 60% RH), and secures an amount of moisture absorption at high humidity (60% RH or more and less than 90% RH). Can be. When dN 2 is 20 nm or less, water vapor easily aggregates, and the amount of moisture absorption can be secured. The volume of the pores (pore volume) is more preferably 0.37 cm 3 / g or more.
図３に本発明に係る多孔質層３の水蒸気吸着等温線からＢＪＨ法により求めた微分細孔分布を示す。水蒸気吸着における微分細孔分布において、微分細孔容積が最大となるときの空孔径をｄＨ２Ｏと定義する。 FIG. 3 shows the differential pore distribution obtained by the BJH method from the water vapor adsorption isotherm of the porous layer 3 according to the present invention. In the differential pore distribution in water vapor adsorption, the pore diameter when the differential pore volume becomes maximum is defined as dH 2 O.
多孔質層３のｄＨ２Ｏは２５ｎｍ以上７５ｎｍ以下であることが望ましい。ｄＨ２Ｏが２５ｎｍ以上であると空孔表面が過度な親水性とならず、高湿度（６０％ＲＨ以上９０％ＲＨ未満）で毛管凝集が発生しないため、高湿度（６０％ＲＨ以上９０％ＲＨ未満）で屈折率が変化しない。ｄＨ２Ｏが７５ｎｍ以下であると、空孔表面が過度な疎水性とならず、水蒸気が凝集しやすい範囲となることから吸湿量を確保することができる。ｄＨ２Ｏが２５ｎｍ以上７５ｎｍ以下であると、湿度９０％ＲＨ未満の吸湿を抑制して屈折率変化を低減でき、超高湿度（９０％ＲＨ以上）で吸湿し吸湿量を確保することができる。 The dH 2 O of the porous layer 3 is desirably 25 nm or more and 75 nm or less. When dH 2 O is 25 nm or more, the pore surface does not become excessively hydrophilic, and capillary aggregation does not occur at high humidity (60% RH to less than 90% RH). (Less than RH), the refractive index does not change. When dH 2 O is 75 nm or less, the surface of the pores does not become excessively hydrophobic, and the water vapor is easily aggregated, so that the moisture absorption can be secured. When dH 2 O is 25 nm or more and 75 nm or less, moisture absorption below 90% RH can be suppressed to reduce the change in refractive index, and moisture can be absorbed at ultra-high humidity (90% RH or more) to secure the amount of moisture absorption. .
空孔径ｄＨ２Ｏは空孔表面の親・疎水性を間接的に距離で表しておりｄＨ２Ｏの値がｄＮ２の値より大きいほどその表面は疎水性である。そのため、本発明に係る多孔質層３では、ｄＮ２でｄＨ２Ｏを除した値が１．２５以上１５以下であることが好ましく、２．５以上６．２以下であることがさらに好ましい。 The pore diameter dH 2 O indirectly represents the hydrophilicity / hydrophobicity of the pore surface as a distance, and the surface is more hydrophobic as the value of dH 2 O is larger than the value of dN 2 . Therefore, in the porous layer 3 according to the present invention, the value obtained by dividing dH 2 O by dN 2 is preferably 1.25 or more and 15 or less, more preferably 2.5 or more and 6.2 or less.
このように屈折率変化の低減と吸湿量の維持ができる理由としては、以下のように考えられる。ｄＨ２Ｏが前記範囲であると湿度９０％ＲＨ未満では、多孔質層３の空孔表面が疎水性であるため、水蒸気が凝集しにくい。このため、湿度９０％ＲＨ未満では、多孔質層３は吸湿しにくく、屈折率も変化しない。しかしながら、湿度が９０％ＲＨに近づくと徐々に多孔質層３の空孔表面に水分子が吸着し、空孔表面の水分子が吸着した部分が親水化する。湿度９０％ＲＨ以上になると空孔表面全体が親水化し、多孔質層３の内部に水蒸気が凝集しやすくなり、吸湿量を確保することができる。 The reason why the change in the refractive index can be reduced and the amount of moisture absorption can be maintained as described above is considered as follows. When dH 2 O is within the above range, if the humidity is lower than 90% RH, the pore surface of the porous layer 3 is hydrophobic, so that water vapor hardly aggregates. Therefore, when the humidity is lower than 90% RH, the porous layer 3 hardly absorbs moisture and the refractive index does not change. However, when the humidity approaches 90% RH, water molecules are gradually adsorbed on the pore surface of the porous layer 3, and the portion of the pore surface where the water molecules are adsorbed becomes hydrophilic. When the humidity becomes 90% RH or more, the entire surface of the pores becomes hydrophilic, and the water vapor easily aggregates inside the porous layer 3, and the amount of moisture absorption can be secured.
多孔質層３は真空で堆積した層でも、ゾル−ゲル法などで無機物４の前駆体をウェット成膜した層でも良い。 The porous layer 3 may be a layer deposited in a vacuum or a layer formed by wet deposition of a precursor of the inorganic substance 4 by a sol-gel method or the like.
多孔質層３に含まれる無機物４は、上記水に対する接触角、ｄＮ２、およびｄＨ２Ｏを満足するものであれば、いかなる無機物であってもよい。具体的な無機物４としては、シリカ、ジルコニアなどがあげられる。中でも、多孔質層３の屈折率を低くし、化学的安定性をよくするために無機物４はシリカを主成分とすることが好ましい。 The inorganic substance 4 contained in the porous layer 3 may be any inorganic substance as long as it satisfies the contact angle with water, dN 2 , and dH 2 O. Specific examples of the inorganic substance 4 include silica and zirconia. In particular, it is preferable that the inorganic substance 4 contains silica as a main component in order to lower the refractive index of the porous layer 3 and improve the chemical stability.
図４は、本発明の部材の一実施形態を示す模式図である。
図４に記載の部材１は、多孔質層３において無機物４が無機粒子６を含んでおり、好ましくは無機物４が無機粒子６である。無機物４が無機粒子６であることで、空孔５同士が連結し易く、平均空孔径や空孔率が一定にできる点で好ましい。無機物４が無機粒子６である多孔質層３は、無機粒子６の分散液からウェット成膜することで形成できる。
多孔質層３に含まれる無機粒子６の量は８０ｗｔ％以上であることが好ましい。
FIG. 4 is a schematic view showing an embodiment of the member of the present invention.
In the member 1 illustrated in FIG. 4, the inorganic substance 4 includes the inorganic particles 6 in the porous layer 3, and preferably, the inorganic substance 4 is the inorganic particles 6. It is preferable that the inorganic substance 4 is the inorganic particles 6 because the pores 5 are easily connected to each other and the average pore diameter and the porosity can be made constant. The porous layer 3 in which the inorganic substance 4 is the inorganic particles 6 can be formed by wet film formation from a dispersion of the inorganic particles 6.
The amount of the inorganic particles 6 contained in the porous layer 3 is preferably at least 80 wt%.
無機粒子６の形状は球状、鎖状、円盤状、楕円状、棒状、針状、角型など様々な形状から適宜選択して使用できる。成膜性に優れ、十分な膜硬度を得ながら空孔率を上げられる点で、球状または鎖状が好ましく、鎖状がより好ましい。 The shape of the inorganic particles 6 can be appropriately selected from various shapes such as a sphere, a chain, a disk, an ellipse, a bar, a needle, and a square. Spherical or chain-like is preferable, and chain-like is more preferable, since it is excellent in film-forming property and can increase porosity while obtaining sufficient film hardness.
本発明において無機粒子６として用いることができる鎖状の粒子とは、複数個の粒子が鎖状もしくは数珠状に直線状にまたは屈曲しながら連なった粒子の集合体である。鎖状の無機粒子を形作る一個一個の粒子の形状は、明確に観察できる形状でも、融着などして形が崩れているために明確に観察できない形状でも構わず、層を形成した際に、その鎖状の粒子の構造が維持されていればよい。この場合、球状粒子などを用いた時に比較して粒子間の空隙を広げることができるため空孔率の高い多孔質層３を形成できる。 The chain-like particles that can be used as the inorganic particles 6 in the present invention are an aggregate of particles in which a plurality of particles are connected in a chain or bead shape while being linear or bent. The shape of each particle that forms the chain-like inorganic particles may be a shape that can be clearly observed, or a shape that cannot be clearly observed because the shape has collapsed due to fusion or the like, and when forming a layer, It is only necessary that the structure of the chain-like particles is maintained. In this case, the voids between the particles can be expanded as compared with the case where spherical particles or the like are used, so that the porous layer 3 having a high porosity can be formed.
無機粒子６の平均粒子径は８ｎｍ以上２５ｎｍ以下が好ましい。平均粒子径はｄＮ２と近い値を取るため、平均粒子径が８ｎｍ以上２５ｎｍ以下であればｄＮ２の値が５ｎｍ以上２０ｎｍ以下になり吸湿量を確保できる。 The average particle diameter of the inorganic particles 6 is preferably from 8 nm to 25 nm. Since the average particle size has a value close to the dN 2, the value of the average long diameter is at 8nm than 25nm or less dN 2 can be secured to the moisture absorption becomes 5nm or 20nm or less.
無機粒子６が鎖状、棒状、または針状の場合、無機粒子６は短径と長径を持った形状の粒子であり、長径／短径の比が３以上１２以下であることが好ましい。長径／短径の比が３以上であると、空孔率を上げる効果を得易くなり、１２以下であると平均空孔径が一定の範囲となり、光の散乱を抑制し透明性を保つことができる。より好ましい長径／短径の比は４以上１０以下である。長径、短径の比は透過電子顕微鏡像によって観察することによって算出できる。 When the inorganic particles 6 are chain-shaped, rod-shaped, or needle-shaped, the inorganic particles 6 are particles having a minor axis and a major axis, and the ratio of major axis / minor axis is preferably 3 or more and 12 or less. When the ratio of the major axis / minor axis is 3 or more, it is easy to obtain the effect of increasing the porosity, and when it is 12 or less, the average pore diameter becomes a certain range, and it is possible to suppress light scattering and maintain transparency. it can. A more preferred ratio of major axis / minor axis is 4 or more and 10 or less. The ratio of the major axis to the minor axis can be calculated by observing with a transmission electron microscope image.
ここで無機粒子の平均粒子径とは、ＢＥＴ法を用いて算出した粒子径（ＢＥＴ粒子径）である。ＢＥＴ粒子径は窒素ガス吸着法によって測定した窒素吸着等温線をＢＥＴ解析して算出される比表面積から計算できる。計算方法はＢＥＴ粒子径、比表面積、無機粒子を構成する元素の密度をそれぞれｄ（ｎｍ）、Ａ（ｍ２／ｇ）、ρ（ｇ／ｃｍ３）とすると、式（１）で表される。
ｄ＝６０００／（Ａ×ρ） （１）
Here, the average particle diameter of the inorganic particles is a particle diameter (BET particle diameter) calculated using the BET method. The BET particle diameter can be calculated from the specific surface area calculated by BET analysis of a nitrogen adsorption isotherm measured by a nitrogen gas adsorption method. The calculation method is represented by Expression (1), where the BET particle diameter, the specific surface area, and the density of the elements constituting the inorganic particles are d (nm), A (m 2 / g), and ρ (g / cm 3 ), respectively. You.
d = 6000 / (A × ρ) (1)
無機粒子６には、鎖状の粒子以外に真円状、楕円状、円盤状、棒状、針状、角型などの鎖状以外の形状の粒子を適宜混合して使用しても良い。多孔質層３全体に対して鎖状以外の形状の粒子を混合できる割合は、４０ｗｔ％以下であることが好ましく、２０ｗｔ％以下であることがより好ましい。 As the inorganic particles 6, particles other than chain-like particles, such as perfectly circular, elliptical, disk-like, rod-like, needle-like, and square-like particles other than chain-like shapes, may be appropriately mixed and used. The ratio at which particles having a shape other than the chain shape can be mixed with the entire porous layer 3 is preferably 40 wt% or less, and more preferably 20 wt% or less.
無機粒子６の主成分はたとえばシリカ、ジルコニアがあげられる。多孔質層３の屈折率を低くし、化学的安定性をよくするために無機粒子６はシリカを主成分とすることが好ましい。 The main components of the inorganic particles 6 include, for example, silica and zirconia. In order to lower the refractive index of the porous layer 3 and improve the chemical stability, the inorganic particles 6 preferably contain silica as a main component.
多孔質層３の耐擦傷性を高めるためにシリカ粒子同士を結合させることができる。シリカ粒子同士を結合させる方法としてはバインダーを用いてシリカ粒子を物理的に結合する方法や、活性を高めたシラノール基を介してシリカ粒子同士を化学的に結着させる方法が挙げられる。シリカ粒子同士を化学的に結着させる方法としては、シリカ粒子の表面を強酸などで処理する方法やシリカ粒子の表面にシラノール基を付着させる方法が挙げられる。 In order to enhance the scratch resistance of the porous layer 3, the silica particles can be bonded to each other. Examples of the method for bonding the silica particles include a method for physically bonding the silica particles using a binder and a method for chemically bonding the silica particles through a silanol group having enhanced activity. Examples of a method of chemically binding the silica particles include a method of treating the surface of the silica particles with a strong acid or the like, and a method of attaching a silanol group to the surface of the silica particles.
シリカ粒子同士を結合させるために加えるバインダーは、シラン化合物であることが好ましい。シラン化合物の好適な例はケイ酸エステルを加水分解・縮合することにより得られる酸化ケイ素オリゴマーである。 The binder added for bonding the silica particles is preferably a silane compound. A preferred example of the silane compound is a silicon oxide oligomer obtained by hydrolyzing and condensing a silicate ester.
多孔質層３中のシラン化合物の量は、無機粒子６としてのシリカ粒子に対してＳｉＯ２換算で１ｗｔ％以上３０ｗｔ％以下が好ましい。シラン化合物の量が１ｗｔ％以上だと、多孔質層３の耐擦傷性が十分となり、３０ｗｔ％以下であると空孔５の一部がシラン化合物で埋まることなく、多孔質層３の防曇性能を保つことができる。より好ましいシラン化合物の量はＳｉＯ２換算で４ｗｔ％以上２０ｗｔ％以下である。 The amount of the silane compound in the porous layer 3 is preferably from 1 wt% to 30 wt% in terms of SiO 2 with respect to the silica particles as the inorganic particles 6. When the amount of the silane compound is 1 wt% or more, the abrasion resistance of the porous layer 3 becomes sufficient. When the amount is 30 wt% or less, part of the pores 5 is not filled with the silane compound, and the antifogging of the porous layer 3 is prevented. Performance can be maintained. A more preferred amount of the silane compound is 4 wt% or more and 20 wt% or less in terms of SiO 2 .
多孔質層３の層厚は１００ｎｍ〜５μｍが好ましく、５００ｎｍ〜３μｍがより好ましい。層厚が１００ｎｍ以上であれば吸湿量を確保しやすくなる。また、層厚が５μｍ以下であれば、光の散乱の発生を抑制でき好ましい。 The layer thickness of the porous layer 3 is preferably from 100 nm to 5 μm, more preferably from 500 nm to 3 μm. When the layer thickness is 100 nm or more, it becomes easy to secure a moisture absorption amount. When the layer thickness is 5 μm or less, the occurrence of light scattering can be suppressed, which is preferable.
（基材）
基材２は、ガラス、樹脂などを用いることが可能である。部材１を光学部材として用いる場合は、可視光域の光透過率が７０％以上の透明な基材（透明基材）が用いられる。また、その形状は限定されることはなく、平面、曲面、凹面、凸面、フィルム状であっても良い。
(Base material)
As the base material 2, glass, resin, or the like can be used. When the member 1 is used as an optical member, a transparent substrate (transparent substrate) having a light transmittance of 70% or more in a visible light region is used. The shape is not limited, and may be a flat surface, a curved surface, a concave surface, a convex surface, or a film shape.
ガラスとしては、酸化ジルコニウム、酸化チタン、酸化タンタル、酸化ニオブ、酸化ハフニウム、酸化ランタン、酸化ガドリニウム、酸化ケイ素、酸化カルシウム、酸化バリウム、酸化ナトリウム、酸化カリウム、酸化ホウ素、酸化アルミニウムなどを含有する無機ガラスを用いることができる。ガラス基材としては研削研磨、モールド成形、フロート成形などで成形されたガラス基材を用いることができる。 As glass, inorganic materials containing zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, lanthanum oxide, gadolinium oxide, silicon oxide, calcium oxide, barium oxide, sodium oxide, potassium oxide, boron oxide, aluminum oxide, etc. Glass can be used. As the glass substrate, a glass substrate formed by grinding and polishing, molding, float molding, or the like can be used.
樹脂としては、ポリエチレンテレフタレート、ポリエチレンナフタレート、トリアセチルセルロース、アクリル樹脂、ポリカーボネート、シクロオレフィンポリマー、ポリビニルアルコールなどが挙げられる。 Examples of the resin include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, acrylic resin, polycarbonate, cycloolefin polymer, and polyvinyl alcohol.
基材２の密着性、強度、平坦性などを向上したり、反射防止や防眩性などの機能を持たせたりするために、基材表面を洗浄したり、研磨したり、多孔質層３と基材２の間に接着層、ハードコート層、屈折率調節層などを設けたりすることができる。 In order to improve the adhesion, strength, flatness and the like of the base material 2 and to provide functions such as anti-reflection and anti-glare properties, the base material surface is washed, polished, An adhesive layer, a hard coat layer, a refractive index adjusting layer, and the like can be provided between the substrate and the base material 2.
（製造方法）
本発明に係る部材の製造方法について、一例として、無機物４をシリカとしたシリカ多孔質膜を多孔質層３として有する部材１について説明する。
(Production method)
As a method for manufacturing a member according to the present invention, as an example, a member 1 having a porous silica layer as a porous layer 3 using silica as an inorganic substance 4 will be described.
基材２上の少なくともいずれか一面に多孔質層３が形成された部材１の製造方法は、疎水性官能基を有する有機シラン化合物と、シリカ粒子と、を溶媒中に含有するシリカ粒子分散液を準備する工程と、前記シリカ粒子分散液を基材２上または基材２上に形成した他の層上に塗工し、シリカ粒子分散液の塗膜を形成する工程と、シリカ粒子分散液の塗膜を乾燥させて多孔質層３を形成する工程を含む。 The method for manufacturing the member 1 in which the porous layer 3 is formed on at least one surface of the base material 2 includes a silica particle dispersion containing an organic silane compound having a hydrophobic functional group and silica particles in a solvent. Preparing a silica particle dispersion, coating the silica particle dispersion on the substrate 2 or another layer formed on the substrate 2 to form a coating film of the silica particle dispersion, And drying the coating film to form the porous layer 3.
多孔質層３を形成する工程が、シリカを主成分とする無機粒子６を分散した分散液を用いる工程であることが好ましい。 The step of forming the porous layer 3 is preferably a step of using a dispersion in which inorganic particles 6 containing silica as a main component are dispersed.
多孔質層３の形成に用いるシリカ粒子の分散液は、ゾル−ゲル法、水熱合成法などの湿式法で作製したシリカ粒子の分散液を水や溶媒で希釈する方法、同様の分散液の溶媒を蒸留や限外濾過で所望の溶媒に置換する方法、フュームドシリカのような乾式法で合成したシリカ粒子を超音波やビーズミルなどで水や溶媒に分散する方法、などにより調製される。 A dispersion of silica particles used for forming the porous layer 3 is prepared by diluting a dispersion of silica particles prepared by a wet method such as a sol-gel method or a hydrothermal method with water or a solvent, or a similar dispersion. It is prepared by a method in which the solvent is replaced with a desired solvent by distillation or ultrafiltration, or a method in which silica particles synthesized by a dry method such as fumed silica are dispersed in water or a solvent by ultrasonic waves or a bead mill.
シリカ粒子同士を結合させるために加えるバインダーは、有機シラン化合物であることが好ましい。有機シラン化合物の好適な例はケイ酸エステルを加水分解・縮合することにより得られる酸化ケイ素オリゴマーである。 The binder added to bond the silica particles is preferably an organic silane compound. A preferred example of the organic silane compound is a silicon oxide oligomer obtained by hydrolyzing and condensing a silicate ester.
酸化ケイ素オリゴマーは、予め水や溶媒中で調製した酸化ケイ素オリゴマー溶液をシリカ粒子の分散液に混ぜる方法や酸化ケイ素オリゴマーの原料をシリカ粒子の分散液に混ぜてから酸化ケイ素オリゴマーに転換する方法などが挙げられる。酸化ケイ素オリゴマーは、溶媒中または分散液中でケイ酸メチル、ケイ酸エチルなどのケイ酸エステルに水や酸または塩基を加えて加水分解縮合することによって調製される。ケイ酸エステルの加水分解縮合に用いることができる酸は塩酸、硝酸、メタンスルホン酸、トリフルオロ酢酸、トリフルオロメタンスルホン酸、リン酸、ｐ−トルエンスルホン酸などであり、塩基はアンモニアや各種アミン類であり、溶媒への溶解性やケイ酸エステルの反応性を考慮して選択される。バインダー溶液を調製する際には８０℃以下の温度で加熱することも可能である。 The silicon oxide oligomer is prepared by mixing a silicon oxide oligomer solution prepared in advance in water or a solvent with a dispersion of silica particles, or a method of mixing the raw material of the silicon oxide oligomer with the dispersion of silica particles and then converting the mixture into the silicon oxide oligomer. Is mentioned. The silicon oxide oligomer is prepared by adding water, an acid, or a base to a silicate ester such as methyl silicate or ethyl silicate in a solvent or a dispersion, followed by hydrolysis and condensation. Acids that can be used for hydrolytic condensation of silicate esters include hydrochloric acid, nitric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, p-toluenesulfonic acid, and the like. Is selected in consideration of solubility in a solvent and reactivity of a silicate ester. When preparing the binder solution, heating at a temperature of 80 ° C. or less is also possible.
バインダー溶液に含まれる酸化ケイ素縮合物の重量平均分子量としては、ポリスチレン換算で５００以上３０００以下が好ましい。重量平均分子量が５００以上であると硬化後のクラックの発生を抑制でき、また塗料としてのバインダー溶液の安定性が保てる。また重量平均分子量が３０００以下であるとバインダー溶液の粘度の上昇を抑制できるため、バインダー内部のボイドが均一になりやすくなる。 The weight average molecular weight of the silicon oxide condensate contained in the binder solution is preferably 500 or more and 3000 or less in terms of polystyrene. When the weight average molecular weight is 500 or more, generation of cracks after curing can be suppressed, and the stability of a binder solution as a coating material can be maintained. When the weight average molecular weight is 3,000 or less, an increase in the viscosity of the binder solution can be suppressed, so that the voids inside the binder tend to be uniform.
ｄＨ２Ｏを２５ｎｍ以上７５ｎｍ以下とするために空孔表面に疎水性官能基を導入する必要がある。そのような方法としてはシリカ粒子合成時に導入する、合成後のシリカ粒子に導入する、成膜後の空孔表面に導入する方法があげられる。 In order to make dH 2 O 25 nm or more and 75 nm or less, it is necessary to introduce a hydrophobic functional group on the surface of the pore. Examples of such a method include a method of introducing silica particles during synthesis, a method of introducing silica particles after synthesis, and a method of introducing silica particles into the surface of pores after film formation.
疎水性官能基を導入する際に用いる処理剤としては有機シラン化合物があげられ、たとえば、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、トリメチルエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、フェニルトリメトキシシラン、ベンジルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ジエトキシメチルフェニルシラン、アリルトリエトキシシラン、ビニルトリエトキシシラン、アミノプロピルトリエトキシシラン、アミノプロピルトリメトキシシラン、ヘキサメチルジシラザン等の分子中に一種または二種以上の置換アルキル基、フェニル基、ビニル基等を有するアルコキシシラン類；トリメチルクロロシラン、ジエチルジクロロシラン等のクロロシラン類などが挙げられ、好ましくはメチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ヘキサメチルジシラザン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシランなど疎水性官能基の炭素数が１〜３である有機シラン化合物を使用する。疎水性官能基の炭素数が１〜３であると、湿度変化によって空孔表面が疎水性から親水性に変わりやすくなる。 Examples of the treating agent used when introducing the hydrophobic functional group include organic silane compounds, for example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, phenyltrimethoxysilane, benzyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, diethoxymethylphenylsilane, allyltriethoxysilane , Vinyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, hexamethyldisilazane, etc. Alkoxysilanes having a substituted alkyl group, a phenyl group, a vinyl group and the like; chlorosilanes such as trimethylchlorosilane and diethyldichlorosilane, and the like, preferably methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane An organic silane compound having a hydrophobic functional group having 1 to 3 carbon atoms such as silane, hexamethyldisilazane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, and propyltriethoxysilane is used. When the number of carbon atoms in the hydrophobic functional group is 1 to 3, the pore surface is likely to change from hydrophobic to hydrophilic due to a change in humidity.
シリカ粒子の分散液に用いることができる溶媒は、原料が均一に溶解し、かつ反応物が析出しない溶媒であれば良い。例えばメタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、２−メチルプロパノール、１−ペンタノール、２−ペンタノール、シクロペンタノール、２−メチルブタノール、３−メチルブタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、４−メチル−２−ペンタノール、２−メチル−１−ペンタノール、２−エチルブタノール、２，４−ジメチル−３−ペンタノール、３−エチルブタノール、１−ヘプタノール、２−ヘプタノール、１−オクタノール、２−オクタノールなどの１価のアルコール類。エチレングリコール、トリエチレングリコールなどの２価以上のアルコール類。メトキシエタノール、エトキシエタノール、プロポキシエタノール、イソプロポキシエタノール、ブトキシエタノール、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、１−プロポキシ−２−プロパノールなどのエーテルアルコール類、ジメトキシエタン、ジグライム、テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル、ジブチルエーテル、シクロペンチルメチルエーテルのようなエーテル類。ギ酸エチル、酢酸エチル、酢酸ｎ−ブチル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどのエステル類。ｎ−ヘキサン、ｎ−オクタン、シクロヘキサン、シクロペンタン、シクロオクタンのような各種の脂肪族系ないしは脂環族系の炭化水素類。トルエン、キシレン、エチルベンゼンなどの各種の芳香族炭化水素類。アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノンなどの各種のケトン類。クロロホルム、メチレンクロライド、四塩化炭素、テトラクロロエタンのような、各種の塩素化炭化水素類。Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルフォルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、エチレンカーボネートのような、非プロトン性極性溶媒等が挙げられるが、好ましくは１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、１−プロポキシ−２−プロパノール、１−ブトキシ−２−プロパノール、２−イソプロポキシエタノール、３−メトキシ−１−ブタノール、乳酸メチル、乳酸エチルなど炭素数が５から７の分岐構造を持つアルコールを使用する。炭素数が５から７の分岐構造を持つアルコールの立体障害によって、シリカ粒子表面の水酸基の一部が有機シラン化合物と反応せずに残るため、疎水性官能基の表面密度を制御しやすくなると考えられる。炭素数が５から７の分岐構造を持つアルコールの鎖長（炭素数）が長くなると溶媒の沸点が高くなる。そのため、アルコールを気化させるために高い乾燥温度および／または焼成温度が必要となり、多孔質層３を作製する基材によっては高温によってダメージを受け、変形や変色などを起こしてしまう。そのため、炭素数が５から７の分岐構造を持つアルコールとしては、より低沸点の溶媒が好ましい。しかしながら、あまりに低沸点であると溶媒の急激な気化によって空隙が広がり、ｄＮ２が２０ｎｍを超えてしまい、多孔質層が吸湿量を確保しがたくなるという問題を生ずる。疎水性官能基の表面密度によってはシリカ粒子の分散性が落ちる場合があるが、炭素数が５から７の分岐構造を持つアルコールを使用することで分散性を維持することができると考えられる。溶媒は２種類を混ぜて使用することもできる。 The solvent that can be used for the dispersion of silica particles may be any solvent in which the raw materials are uniformly dissolved and the reactants do not precipitate. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1-pentanol, 2-pentanol, cyclopentanol, 2-methylbutanol, 3-methylbutanol, 1-hexanol, 2-hexanol, 3-hexanol, 4-methyl-2-pentanol, 2-methyl-1-pentanol, 2-ethylbutanol, 2,4-dimethyl-3-pentanol, 3-ethylbutanol And monohydric alcohols such as 1-heptanol, 2-heptanol, 1-octanol and 2-octanol. Dihydric or higher alcohols such as ethylene glycol and triethylene glycol. Methoxyethanol, ethoxyethanol, propoxyethanol, isopropoxyethanol, butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ether alcohols such as 1-propoxy-2-propanol, dimethoxyethane, diglyme, Ethers such as tetrahydrofuran, dioxane, diisopropyl ether, dibutyl ether and cyclopentyl methyl ether. Esters such as ethyl formate, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate. Various aliphatic or alicyclic hydrocarbons such as n-hexane, n-octane, cyclohexane, cyclopentane and cyclooctane. Various aromatic hydrocarbons such as toluene, xylene and ethylbenzene. Various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone. Various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, and tetrachloroethane. Non-protonic polar solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene carbonate and the like are preferable, and 1-methoxy-2-propanol, 1-ethoxy is preferable. Branched structure having 5 to 7 carbon atoms such as -2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-isopropoxyethanol, 3-methoxy-1-butanol, methyl lactate and ethyl lactate Use alcohol with. Due to the steric hindrance of the alcohol having a branched structure having 5 to 7 carbon atoms, a part of the hydroxyl groups on the surface of the silica particles remains without reacting with the organosilane compound, so that the surface density of the hydrophobic functional group can be easily controlled. Can be As the chain length (carbon number) of an alcohol having a branched structure having 5 to 7 carbon atoms increases, the boiling point of the solvent increases. Therefore, a high drying temperature and / or a sintering temperature is required to vaporize the alcohol, and depending on the base material on which the porous layer 3 is formed, the porous layer 3 may be damaged by the high temperature, causing deformation or discoloration. Therefore, as the alcohol having a branched structure having 5 to 7 carbon atoms, a solvent having a lower boiling point is preferable. However, if the boiling point is too low, voids are widened due to rapid vaporization of the solvent, and dN 2 exceeds 20 nm, which causes a problem that it is difficult for the porous layer to secure a sufficient amount of moisture absorption. Although the dispersibility of the silica particles may decrease depending on the surface density of the hydrophobic functional group, it is considered that the dispersibility can be maintained by using an alcohol having a branched structure having 5 to 7 carbon atoms. The solvent may be used as a mixture of two types.
多孔質層３を形成するための分散液を基材上に塗布する方法としては、スピンコート法、スプレー法、ブレードコート法、ロールコート法、スリットコート法、印刷法やディップコート法などが挙げられる。凹面などの立体的に複雑な形状を有する部材を製造する場合、層厚の均一性の観点からスピンコート法やスプレー法が好ましい。 Examples of a method for applying the dispersion for forming the porous layer 3 on a substrate include a spin coating method, a spraying method, a blade coating method, a roll coating method, a slit coating method, a printing method and a dip coating method. Can be When manufacturing a member having a three-dimensionally complicated shape such as a concave surface, a spin coating method or a spraying method is preferred from the viewpoint of uniformity of the layer thickness.
多孔質層３を形成するために分散液を塗布した後に、乾燥および硬化が行われる。乾燥および硬化は、溶媒を除去したり、酸化ケイ素バインダー同士あるいは酸化ケイ素バインダーとシリカ粒子との反応を進めたりするための工程である。乾燥および硬化の温度は、２０℃以上２００℃以下が好ましく、６０℃以上１５０℃以下がより好ましい。乾燥および硬化の温度が２０℃未満だと溶媒が残留して耐摩耗性が低下する。また、乾燥および硬化の温度が２００℃を超えると、バインダーの硬化が進み過ぎて、バインダーに割れが発生しやすくなる。乾燥および硬化の時間は５分以上２４時間以下が好ましく、１５分以上５時間以下がより好ましい。乾燥および硬化の時間が５分未満だと部分的に溶媒が残留して部分的に曇りやすくなったり、２４時間を超えると層にクラックが入りやすくなったりする。 After applying the dispersion to form the porous layer 3, drying and curing are performed. Drying and curing are steps for removing the solvent and for promoting the reaction between the silicon oxide binders or between the silicon oxide binder and the silica particles. The drying and curing temperature is preferably from 20 ° C to 200 ° C, more preferably from 60 ° C to 150 ° C. If the drying and curing temperature is lower than 20 ° C., the solvent remains and the abrasion resistance decreases. On the other hand, when the drying and curing temperature exceeds 200 ° C., the curing of the binder proceeds excessively, and the binder is liable to crack. The drying and curing time is preferably from 5 minutes to 24 hours, more preferably from 15 minutes to 5 hours. If the drying and curing time is less than 5 minutes, the solvent partially remains and the film becomes partially cloudy. If the drying and curing time is more than 24 hours, the layer easily cracks.
（適用例）
本発明に係る部材が好適に用いられる例として、撮像装置の保護カバーとして用いる例を説明する。図５に撮像装置の構成例の概略を示す。
(Application example)
As an example in which the member according to the present invention is suitably used, an example in which the member is used as a protective cover of an imaging device will be described. FIG. 5 shows an outline of a configuration example of the imaging apparatus.
撮像装置３０は、本発明に係る部材である保護カバー３１と筐体３７で囲まれた内部空間を有しており、該内部空間内に、レンズ３２、撮像センサ３３、映像エンジン３４、圧縮出力回路３５が配置されており、さらに該空間内または外に出力部３６を備えている。 The imaging device 30 has an internal space surrounded by a protective cover 31 which is a member according to the present invention and a housing 37, and a lens 32, an image sensor 33, a video engine 34, a compression output A circuit 35 is arranged, and an output unit 36 is provided inside or outside the space.
外部から入射する像が、保護カバー３１およびレンズ３２によって撮像センサ３３へと導かれ、撮像センサ３３によって映像アナログ信号（電気信号）に変換されて出力される。撮像センサ３３から出力される映像アナログ信号は、映像エンジン３４によって映像デジタル信号に変換され、映像エンジン３４から出力される映像デジタル信号は、圧縮出力回路３５においてデジタルファイルに圧縮される。映像エンジン３４は、映像アナログ信号を映像デジタル信号に変換する過程で、輝度、コントラスト、色補正、ノイズ除去などの画質を調整する処理を行ってもよい。圧縮出力回路３５から出力された信号は、出力部３６から配線および／またはネットワークを介して外部機器へと出力される。 An image incident from the outside is guided to the image sensor 33 by the protective cover 31 and the lens 32, and is converted into a video analog signal (electric signal) by the image sensor 33 and output. The video analog signal output from the image sensor 33 is converted into a video digital signal by a video engine 34, and the video digital signal output from the video engine 34 is compressed by a compression output circuit 35 into a digital file. In the process of converting the video analog signal into the video digital signal, the video engine 34 may perform processing for adjusting the image quality such as luminance, contrast, color correction, and noise removal. The signal output from the compression output circuit 35 is output from the output unit 36 to an external device via wiring and / or a network.
保護カバー３１は、基材３１１の少なくとも一方の面に多孔質層３１２を備える構成をしており、図５に示した撮像装置の構成例では、多孔質層３１２が設けられた面が筐体３７の内部空間側となるように設置されている。基材３１１は、撮像センサ３３に入射する像を透過させる透明な部材である。ここで、「透明」とは、可視光域の光透過率が７０％以上のものをいう。 The protective cover 31 has a configuration in which a porous layer 312 is provided on at least one surface of the base material 311. In the configuration example of the imaging device illustrated in FIG. 5, the surface on which the porous layer 312 is provided is a housing. It is installed so as to be on the inner space side of 37. The base material 311 is a transparent member that transmits an image incident on the image sensor 33. Here, "transparent" means that the light transmittance in the visible light region is 70% or more.
このような構成によれば、保護カバー３１と筐体３７とで囲まれた内部空間は、外部との間で空気の出入りが制限されている上に、外部環境の温度変化への追随が遅れる。例えば外部の温度が急に低下すると、筐体３７の外側と内側との境界に位置する保護カバー３１の温度が、筐体内部の露点温度よりも低くなってしまう場合がある。このような場合、保護カバー３１が防曇機能を有していないと、保護カバー３１の筐体３７内側の面に水滴が付着して曇りが生じる。しかし、本発明に係る保護カバー３１の場合、保護カバー３１の温度が筐体３７内部の露点温度より低くなってしまっても、筐体内部の水分は多孔質層３１２の孔内部に吸着される。そのため、保護カバー３１の表面には曇りの原因となる水滴が形成されず、曇りを抑制することができる。 According to such a configuration, in the internal space surrounded by the protective cover 31 and the housing 37, the ingress and egress of air between the outside and the outside are restricted, and following the temperature change of the outside environment is delayed. . For example, if the temperature of the outside suddenly drops, the temperature of the protective cover 31 located at the boundary between the outside and the inside of the housing 37 may be lower than the dew point temperature inside the housing. In such a case, if the protective cover 31 does not have the anti-fogging function, water drops adhere to the surface of the protective cover 31 inside the housing 37, and fogging occurs. However, in the case of the protective cover 31 according to the present invention, even if the temperature of the protective cover 31 becomes lower than the dew point temperature inside the housing 37, moisture inside the housing is adsorbed inside the holes of the porous layer 312. . Therefore, water droplets that cause fogging are not formed on the surface of the protective cover 31, and fogging can be suppressed.
図５の変形例として、保護カバー３１の表面に多孔質層３１２を設けず筐体３７の内壁を基材として、内壁の上に多孔質層３１２を設けてもよい。保護カバーの設ける場合と同様、レンズの曇りを抑制することができる。また、保護カバー３１の表面に加えて筐体３７の内壁に多孔質層３１２を設けてもよい。このような構成によれば、保護カバー３１の表面および筐体３７の内壁に設けた多孔質層３１２によって、筐体内部の水分を吸湿することができるため、レンズの曇りをさらに抑制することができる。 As a modification of FIG. 5, the porous layer 312 may not be provided on the surface of the protective cover 31, and the porous layer 312 may be provided on the inner wall using the inner wall of the housing 37 as a base material. As in the case where the protective cover is provided, the fogging of the lens can be suppressed. Further, a porous layer 312 may be provided on the inner wall of the housing 37 in addition to the surface of the protective cover 31. According to such a configuration, the moisture inside the housing can be absorbed by the porous layer 312 provided on the surface of the protective cover 31 and the inner wall of the housing 37, so that clouding of the lens can be further suppressed. it can.
保護カバー３１を介して入射した光が筐体３７の内壁で反射して画像を劣化させるのを抑制するために、筐体３７の内壁には反射防止層や反射防止構造が設けられている場合が多い。従って、筐体３７の内壁に本発明の構成を用いれば、湿度９０％ＲＨ未満の吸湿を抑制して多孔質層３１２の屈折率変化を低減できるため反射防止効果を維持し、超高湿度（９０％ＲＨ以上）で吸湿して吸湿量を確保することができるため好ましい。 A case in which an anti-reflection layer or an anti-reflection structure is provided on the inner wall of the housing 37 in order to suppress the light incident through the protective cover 31 from being reflected on the inner wall of the housing 37 and deteriorating the image. There are many. Therefore, when the configuration of the present invention is used for the inner wall of the housing 37, the absorption of moisture below 90% RH can be suppressed and the change in the refractive index of the porous layer 312 can be reduced. (90% RH or more), which is preferable because the amount of moisture absorption can be secured.
撮像装置３０に、画角調整するパンチルト、撮像条件等を制御するコントローラ、取得した映像データを保存しておく記憶装置、出力部３６から出力されたデータを外部に転送する転送手段などを加え、撮像システムを構成することができる。 The imaging device 30 includes a pan / tilt for adjusting the angle of view, a controller for controlling imaging conditions and the like, a storage device for storing the acquired video data, a transfer unit for transferring data output from the output unit 36 to the outside, and the like. An imaging system can be configured.
以下、実施例により本発明を具体的に説明する。ただし本発明はその要旨を超えない限り、以下の実施例により限定されるものではない。 Hereinafter, the present invention will be described specifically with reference to examples. However, the present invention is not limited by the following examples unless it exceeds the gist.
（１）粒子分散液の調製
（シリカ粒子分散液１の調製）
純水７５０ｇ、２５％アンモニア水１３８ｇ、１−プロポキシ−２−プロパノール４１１２ｇのアンモニア濃度０．６９ｗｔ％からなる混合液Ａに、テトラメトキシシラン３７５ｇ、１−プロポキシ−２−プロパノール１２５ｇ、疎水性官能基処理剤としてメチルトリエトキシシラン３７ｇからなる混合液Ｂを、１０℃に保ちつつ３０分かけて撹拌しながら滴下し、滴下が終わったあとに５０℃で５時間撹拌し、ゾル溶液を作製した。この粒子溶液を減圧下にて加熱濃縮を行い、濃縮液をイオン交換樹脂（オルガノ株式会社製 Ａｍｂｅｒｌｉｔｅ ＩＲ１２０Ｂ Ｈ ＡＧ）に通してアンモニアを除去し、ゾル溶液のｐＨを８以下にした。その後、水分が１％以下になるまで１−プロポキシ−２−プロパノールを滴下しつつ蒸留を続け、３μｍメンブレンフィルターを用いてろ過を行い、固形分濃度１５ｗｔ％のシリカ粒子分散液１を調製した。
(1) Preparation of Particle Dispersion (Preparation of Silica Particle Dispersion 1)
In a mixed solution A consisting of 750 g of pure water, 138 g of 25% aqueous ammonia, and 4112 g of 1-propoxy-2-propanol, an ammonia concentration of 0.69 wt%, 375 g of tetramethoxysilane, 125 g of 1-propoxy-2-propanol, and a hydrophobic functional group A mixed solution B consisting of 37 g of methyltriethoxysilane as a treating agent was added dropwise with stirring over 30 minutes while maintaining the temperature at 10 ° C. After the dropwise addition, the mixture was stirred at 50 ° C. for 5 hours to prepare a sol solution. The particle solution was heated and concentrated under reduced pressure, and the concentrated solution was passed through an ion exchange resin (Amberlite IR120B HAG manufactured by Organo Co., Ltd.) to remove ammonia, and the pH of the sol solution was adjusted to 8 or less. Thereafter, distillation was continued while 1-propoxy-2-propanol was added dropwise until the water content became 1% or less, and filtration was performed using a 3 μm membrane filter to prepare a silica particle dispersion 1 having a solid content concentration of 15 wt%.
（シリカ粒子分散液２の調製）
混合液Ｂの疎水性官能基処理剤をプロピルトリエトキシシランにして２２ｇを加えること以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液２を調製した。
(Preparation of silica particle dispersion liquid 2)
A silica particle dispersion 2 was prepared in the same manner as the silica particle dispersion 1, except that the hydrophobic functional group treating agent of the mixture B was propyltriethoxysilane and 22 g was added.
（シリカ粒子分散液３の調製）
混合液Ｂの疎水性官能基処理剤をジメチルジメトキシシランにして２５ｇを加えること以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液３を調製した。
(Preparation of silica particle dispersion 3)
Silica particle dispersion 3 was prepared in the same manner as silica particle dispersion 1, except that 25 g of dimethyldimethoxysilane was used as the hydrophobic functional group treating agent of mixture B.
（シリカ粒子分散液４の調製）
混合液Ａのアンモニア濃度が０．９２ｗｔ％になるように２５％アンモニア水を１８５ｇ、１−プロポキシ−２−プロパノールを４０６５ｇとすること以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液４を調製した。
(Preparation of silica particle dispersion liquid 4)
Silica particle dispersion liquid 4 was prepared in the same manner as silica particle dispersion liquid 1 except that 185 g of 25% aqueous ammonia and 4065 g of 1-propoxy-2-propanol were used so that the ammonia concentration of mixed liquid A was 0.92 wt%. Was prepared.
（シリカ粒子分散液５の調製）
混合液Ａのアンモニア濃度が０．５６ｗｔ％になるように２５％アンモニア水を１１１ｇ、１−プロポキシ−２−プロパノールを４１３９ｇとすること以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液５を調製した。
(Preparation of silica particle dispersion 5)
Silica particle dispersion liquid 5 was prepared in the same manner as silica particle dispersion liquid 1 except that 111 g of 25% aqueous ammonia and 4139 g of 1-propoxy-2-propanol were used so that the ammonia concentration of mixed liquid A was 0.56 wt%. Was prepared.
（シリカ粒子分散液６の調製）
鎖状のシリカ粒子の２−プロパノール（ＩＰＡ）分散液（日産化学工業株式会社製 ＩＰＡ−ＳＴ−ＵＰ（登録商標）、粒子径１２ｎｍ；ＢＥＴ法・固形分濃度１５ｗｔ％）をエバポレーターを用いて２−プロパノールを留去し、１−プロポキシ−２−プロパノールに置換することで、鎖状シリカ粒子の１−プロポキシ−２−プロパノール分散液（固形分濃度３３ｗｔ％）を１２１２ｇ作製した。
(Preparation of silica particle dispersion 6)
Using a 2-propanol (IPA) dispersion liquid of chain silica particles (IPA-ST-UP (registered trademark) manufactured by Nissan Chemical Industries, Ltd., particle diameter 12 nm; BET method, solid content concentration 15 wt%) using an evaporator. -Propanol was distilled off and replaced with 1-propoxy-2-propanol to prepare 1212 g of a 1-propoxy-2-propanol dispersion of solid silica particles (solid content concentration: 33 wt%).
前記鎖状シリカ粒子の１−プロポキシ−２−プロパノール分散液に１−プロポキシ−２−プロパノール５４８ｇ、乳酸エチル９０７ｇを添加して１０分間撹拌後、ジメチルジメトキシシランを２４ｇと触媒としてｐＨ＝４の酢酸水溶液２７ｇを添加し５０℃のオイルバス中で５時間撹拌して固形分濃度１５ｗｔ％のシリカ粒子分散液６を調製した。 548 g of 1-propoxy-2-propanol and 907 g of ethyl lactate were added to a dispersion of 1-propoxy-2-propanol of the chain silica particles, and the mixture was stirred for 10 minutes. 27 g of an aqueous solution was added, and the mixture was stirred in an oil bath at 50 ° C. for 5 hours to prepare a silica particle dispersion 6 having a solid content of 15 wt%.
（シリカ粒子分散液７の調製）
混合液Ａのアンモニア濃度が０．９６ｗｔ％になるように２５％アンモニア水を１９２ｇ、１−プロポキシ−２−プロパノールを４０５８ｇとし、混合液Ｂを混合液Ａに滴下する際、５０℃に保つこと以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液７を調製した。
(Preparation of silica particle dispersion liquid 7)
192 g of 25% ammonia water and 4058 g of 1-propoxy-2-propanol so that the ammonia concentration of the mixed solution A becomes 0.96 wt%, and when the mixed solution B is dropped into the mixed solution A, the temperature is maintained at 50 ° C. Except for the above, a silica particle dispersion 7 was prepared in the same manner as the silica particle dispersion 1.
（シリカ粒子分散液８の調製）
疎水性官能基処理剤を加えないこと以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液８を調製した。
(Preparation of silica particle dispersion liquid 8)
A silica particle dispersion 8 was prepared in the same manner as the silica particle dispersion 1, except that the hydrophobic functional group treating agent was not added.
（シリカ粒子分散液９の調製）
混合液Ｂの疎水性官能基処理剤をプロピルトリエトキシシランにして４３ｇを加えること以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液９を調製した。
(Preparation of silica particle dispersion liquid 9)
A silica particle dispersion 9 was prepared in the same manner as the silica particle dispersion 1, except that the hydrophobic functional group treating agent of the mixture B was changed to propyltriethoxysilane and 43 g was added.
（シリカ粒子分散液１０の調製）
混合液Ａのアンモニア濃度が０．９６ｗｔ％になるように２５％アンモニア水を１９２ｇ、１−プロポキシ−２−プロパノールを４０５８ｇとすること以外はシリカ粒子分散液３と同様にしてシリカ粒子分散液１０を調製した。
(Preparation of silica particle dispersion liquid 10)
Silica particle dispersion 10 was prepared in the same manner as silica particle dispersion 3 except that 192 g of 25% ammonia water and 4058 g of 1-propoxy-2-propanol were used so that the ammonia concentration of mixture A was 0.96 wt%. Was prepared.
（シリカ粒子分散液１１の調製）
混合液Ａのアンモニア濃度が０．５２ｗｔ％になるように２５％アンモニア水を１０５ｇ、１−プロポキシ−２−プロパノールを４１４５ｇとすること以外はシリカ粒子分散液１と同様にしてシリカ粒子分散液１１を調製した。
(Preparation of silica particle dispersion liquid 11)
Silica particle dispersion liquid 11 was prepared in the same manner as silica particle dispersion liquid 1, except that 105 g of 25% aqueous ammonia and 4145 g of 1-propoxy-2-propanol were used so that the ammonia concentration of mixed liquid A became 0.52 wt%. Was prepared.
（２）部材の作成
（実施例１）
実施例１は、シリカ粒子分散液１をφ３０ｍｍの平板ガラス基板（Ｓ−ＢＳＬ７、ｎｄ＝１．５２、オハラ製）に適量滴下し、１０００ｒｐｍで３０秒スピンコートした後、１４０℃の熱風循環オーブンで３０分焼成することで実施例１の部材を作製した。実施例１の部材の有する多孔質層の層厚は２．６μｍであった。
(2) Creation of member (Example 1)
In Example 1, an appropriate amount of the silica particle dispersion liquid 1 was dropped on a flat glass substrate (S-BSL7, nd = 1.52, manufactured by OHARA) having a diameter of 30 mm, spin-coated at 1000 rpm for 30 seconds, and then heated in a hot air circulating oven at 140 ° C. By baking for 30 minutes at, the member of Example 1 was produced. The thickness of the porous layer of the member of Example 1 was 2.6 μm.
（実施例２〜６および比較例１〜５）
シリカ粒子分散液１を表１に記載のシリカ粒子分散液とすること以外は実施例１と同様に実施例２〜６および比較例１〜５の部材を作製した。表１に実施例２〜６および比較例１〜５の部材の有する多孔質層の層厚を示す。
(Examples 2 to 6 and Comparative Examples 1 to 5)
Members of Examples 2 to 6 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 except that the silica particle dispersion 1 was changed to the silica particle dispersion shown in Table 1. Table 1 shows the thickness of the porous layers of the members of Examples 2 to 6 and Comparative Examples 1 to 5.
（３）評価
各実施例、比較例で得られた部材について、下記の方法で評価を行った。結果は表１に示した。
(3) Evaluation The members obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Table 1.
（３−１）ｄＮ２の測定
自動蒸気吸着量測定装置（日本ベル株式会社製 ＢＥＬＳＯＲＰ−ＭＡＸ）を用いて、−１９６℃における窒素吸着等温線を測定しＢＪＨ法によって微分細孔分布を得た。得られた微分細孔分布において、微分細孔容積が最大となるときの空孔径をｄＮ２とした。
(3-1) Measurement of dN 2 Nitrogen adsorption isotherm at −196 ° C. was measured using an automatic vapor adsorption measuring device (BELSORP-MAX manufactured by Bell Japan Co., Ltd.), and the differential pore distribution was obtained by the BJH method. . In the obtained differential pore distribution, the pore diameter at the time when the differential pore volume was the maximum was defined as dN 2 .
（３−２）ｄＨ２Ｏの測定
自動蒸気吸着量測定装置（日本ベル株式会社製 ＢＥＬＳＯＲＰ１８）を用いて、２５℃における吸着等温線を測定しＢＪＨ法によって微分細孔分布を得た。得られた微分細孔分布において、微分細孔容積が最大となるときの空孔径をｄＨ２Ｏとした。
(3-2) Measurement of dH 2 O The adsorption isotherm at 25 ° C. was measured using an automatic vapor adsorption amount measuring device (BELSORP18 manufactured by Nippon Bell Co., Ltd.), and the differential pore distribution was obtained by the BJH method. In the obtained differential pore distribution, the pore diameter at the time when the differential pore volume became maximum was defined as dH 2 O.
（３−３）細孔容積の測定
自動蒸気吸着量測定装置（日本ベル株式会社製 ＢＥＬＳＯＲＰ−ＭＡＸ）を用いて、−１９６℃における窒素吸着等温線を測定しＢＪＨ法によって細孔容積を求めた。
(3-3) Measurement of pore volume Nitrogen adsorption isotherm at -196 ° C was measured using an automatic vapor adsorption measuring device (BELSORP-MAX manufactured by Japan Bell Co., Ltd.), and the pore volume was determined by the BJH method. .
（３−４）平均粒子径の測定
自動蒸気吸着量測定装置（日本ベル株式会社製 ＢＥＬＳＯＲＰ−ＭＡＸ）を用いて、−１９６℃における窒素吸着等温線を測定しＢＥＴ法によって比表面積Ａ（ｍ２／ｇ）を求めた。その後平均粒子径、無機粒子を構成する酸化ケイ素の密度をそれぞれｄ（ｎｍ）、２０２（ｇ／ｃｍ３）として、下記の式（２）よりＢＥＴ法による平均粒子径（ＢＥＴ粒子径）を求めた。
ｄ＝６０００／（Ａ×２．２） （２）
(3-4) Measurement of average particle diameter Using an automatic vapor adsorption amount measuring apparatus (BELSORP-MAX manufactured by Bell Japan Co., Ltd.), the nitrogen adsorption isotherm at -196 ° C was measured, and the specific surface area A (m 2 / G). Thereafter, the average particle diameter and the density of silicon oxide constituting the inorganic particles are set to d (nm) and 202 (g / cm 3 ), respectively, and the average particle diameter (BET particle diameter) by the BET method is calculated from the following equation (2). Was.
d = 6000 / (A × 2.2) (2)
（３−５）接触角の評価
全自動接触角計（共和界面科学株式会社製 ＤＭ−７０１）を用い、純水２μｌの液滴を接触した時の接触角を２３℃４０％ＲＨの環境で測定した。
(3-5) Evaluation of Contact Angle Using a fully automatic contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle at the time of contacting a 2 μl droplet of pure water in an environment of 23 ° C. and 40% RH. It was measured.
（３−６）屈折率の測定
温度を２５℃、湿度６０、８０、９０、９５％ＲＨの環境に部材を１時間静置したあとに、各湿度下において反射率計（ウシオ電機株式会社製 ＵＲＥ−５０）を用いて反射率を測定した。解析ソフト（Ｊ．Ａ Ｗｏｏｌｌａｍ製 ＷＶＡＳＥ）によって反射率データから波長５５０ｎｍの屈折率を求めた。得られた屈折率から屈折率変化を以下の基準で評価した。
Ａ：湿度６０％ＲＨおよび９５％ＲＨでの部材の屈折率の差が０．０１５未満
Ｂ：湿度６０％ＲＨおよび９０％ＲＨでの屈折率の差が０．０１５未満であり、湿度６０％ＲＨおよび９５％ＲＨでの屈折率の差が０．０１５以上
Ｃ：湿度６０％ＲＨおよび９０％ＲＨの各屈折率の差が０．０１５以上
(3-6) Measurement of Refractive Index After the members were allowed to stand for 1 hour in an environment at a temperature of 25 ° C. and a humidity of 60, 80, 90, and 95% RH, a reflectometer (manufactured by Ushio Inc.) under each humidity was used. The reflectance was measured using URE-50). The refractive index at a wavelength of 550 nm was determined from the reflectance data using analysis software (WVASE manufactured by JA Woollam). From the obtained refractive index, the change in the refractive index was evaluated according to the following criteria.
A: The difference in refractive index between the members at a humidity of 60% RH and 95% RH is less than 0.015. B: The difference in the refractive index at a humidity of 60% RH and 90% RH is less than 0.015, and the humidity is 60%. Difference in refractive index between RH and 95% RH is 0.015 or more C: Difference in refractive index between 60% RH and 90% RH is 0.015 or more
（３−７）防曇性評価
自動蒸気吸着量測定装置（日本ベル株式会社製 ＢＥＬＳＯＲＰ１８）を用いて、相対湿度を６０％ＲＨから９８％ＲＨに変化させたときの吸湿量を測定した。得られた吸湿量を以下の基準で評価した。
Ａ：３５０（ｃｍ３／ｇ）以上
Ｂ：２５０（ｃｍ３／ｇ）以上３５０（ｃｍ３／ｇ）未満
Ｃ：２５０（ｃｍ３／ｇ）未満
(3-7) Evaluation of antifogging property The amount of moisture absorption when the relative humidity was changed from 60% RH to 98% RH was measured using an automatic vapor adsorption amount measuring device (BELSORP18 manufactured by Bell Japan Co., Ltd.). The obtained moisture absorption was evaluated based on the following criteria.
A: 350 (cm 3 / g) or more B: 250 (cm 3 / g) or more and less than 350 (cm 3 / g) C: less than 250 (cm 3 / g)
（実施例および比較例の評価）
実施例１から６の部材の評価結果の比較より、ｄＨ２Ｏが２５ｎｍ以上７５ｎｍ以下であると、湿度９０％ＲＨ未満の吸湿を抑制して屈折率変化を低減でき、湿度９０％ＲＨ以上で吸湿し吸湿量を確保することができることが分かる。また、ｄＨ２Ｏが大きいほど屈折率変化を低減できることも分かった。一方、比較例１の部材は、ｄＨ２Ｏが７５ｎｍよりも大きいため吸湿量を確保できないことが分かる。また、比較例２の部材は、ｄＨ２Ｏが２５ｎｍより小さいため、高湿度（６０％ＲＨ以上９０％ＲＨ未満）における屈折率変化が大きいことが分かる。
(Evaluation of Examples and Comparative Examples)
From the comparison of the evaluation results of the members of Examples 1 to 6, when dH 2 O is 25 nm or more and 75 nm or less, the change in the refractive index can be reduced by suppressing the moisture absorption below the humidity of 90% RH. It can be seen that moisture can be absorbed and a sufficient amount of moisture can be secured. It was also found that the larger the dH 2 O, the more the change in the refractive index can be reduced. On the other hand, it can be seen that the member of Comparative Example 1 cannot secure a moisture absorption amount because dH 2 O is larger than 75 nm. In addition, since the member of Comparative Example 2 has dH 2 O of less than 25 nm, it can be seen that the change in the refractive index at high humidity (60% RH or more and less than 90% RH) is large.
実施例３および比較例３の部材の評価結果の比較より、接触角が６０°以上になると層内部に侵入する水分子が大きく減少してしまうため、比較例３の部材は吸湿量を確保できず防曇性が悪いことが分かる。 From the comparison of the evaluation results of the members of Example 3 and Comparative Example 3, when the contact angle is 60 ° or more, water molecules penetrating into the inside of the layer are greatly reduced, so that the member of Comparative Example 3 can secure the moisture absorption. It can be seen that the antifogging property was poor.
実施例４および比較例４の部材の評価結果の比較より、ｄＮ２が２０ｎｍ以上になると多孔質層中の空孔に水蒸気が凝集しにくくなり吸湿量が低下することが分かる。実施例５および比較例５の部材の評価結果の比較より、ｄＮ２が５ｎｍ以下になると低湿度（湿度６０％ＲＨ未満）で吸湿してしまうため、多孔質層中の空孔が埋まってしまい、高湿度（６０％ＲＨ以上９０％ＲＨ未満）で吸湿量を確保できないことが分かる。 From a comparison of the evaluation results of the members of Example 4 and Comparative Example 4, it can be seen that when dN 2 is 20 nm or more, water vapor hardly aggregates in the pores in the porous layer, and the moisture absorption decreases. From the comparison of the evaluation results of the members of Example 5 and Comparative Example 5, when dN 2 is 5 nm or less, moisture is absorbed at low humidity (less than 60% RH), so that the pores in the porous layer are buried. It can be seen that the amount of moisture absorption cannot be secured at high humidity (60% RH or more and less than 90% RH).
実施例６の部材の評価結果より、鎖状粒子に疎水性官能基を導入することによっても、ｄＮ２が５ｎｍ以上２０ｎｍ以下とし、接触角が６０°未満であり、ｄＨ２Ｏが２５ｎｍ以上７５ｎｍ以下とすることができることが分かる。また、実施例６の部材は、ｄＮ２、ｄＨ２Ｏ、および接触角が前記範囲であるため、高湿度（６０％ＲＨ以上９０％ＲＨ未満）における屈折率変化の低減と吸湿量の維持ができることが分かる。 From the evaluation results of the member of Example 6, it was found that dN 2 was 5 nm or more and 20 nm or less, the contact angle was less than 60 °, and dH 2 O was 25 nm or more and 75 nm by introducing a hydrophobic functional group into the chain particles. It can be seen that the following can be performed. In the member of Example 6, since dN 2 , dH 2 O, and the contact angle are in the above ranges, the change in the refractive index and the maintenance of the moisture absorption at high humidity (60% RH or more and less than 90% RH) can be achieved. You can see what you can do.
以上のことより、本発明の要件を満たす多孔質層を有する実施例の部材は、比較例の部材に対して、屈折率変化の低減と吸湿量の維持の両立に優れることが示された。 From the above, it was shown that the member of the example having the porous layer satisfying the requirements of the present invention was superior to the member of the comparative example in reducing the change in the refractive index and maintaining the moisture absorption.
本発明の部材は、窓ガラス、鏡、レンズ、透明フィルムなど一般的な用途から、撮像系や投影系の光学レンズ、光学ミラー、光学フィルター、アイピース、屋外カメラや監視カメラ用の平面カバーやドームカバーなど光学部品に好ましく利用することが可能である。 The members of the present invention can be used for general purposes such as window glass, mirrors, lenses, and transparent films, and for optical lenses, optical mirrors, optical filters, eye filters, eyepieces, outdoor cameras and surveillance cameras for imaging and projection systems. It can be preferably used for optical parts such as covers.
１ 部材
２ 基材
３ 多孔質層
４ 無機物
５ 空孔
６ 無機粒子
Reference Signs List 1 member 2 base material 3 porous layer 4 inorganic substance 5 pore 6 inorganic particle
Claims (13)
保護カバーと、
前記筐体と前記保護カバーとに囲まれた内部空間に配置された撮像センサと、
を備える撮像装置であって、
前記保護カバーは、基材と、前記内部空間側の前記基材の表面に多孔質層と、を有し、
前記多孔質層は、窒素吸着における微分細孔分布において微分細孔容積が最大となるときの空孔径ｄＮ２が５ｎｍ以上２０ｎｍ以下であり、水蒸気吸着における微分細孔分布において微分細孔容積が最大となるときの空孔径ｄＨ２Ｏが２５ｎｍ以上７５ｎｍ以下であり、水に対する接触角が６０°未満であることを特徴とする撮像装置。 A housing,
A protective cover,
An image sensor arranged in an internal space surrounded by the housing and the protective cover,
An imaging device comprising:
The protective cover has a base material and a porous layer on the surface of the base material on the inner space side,
The porous layer, differential pore volume in the differential pore distribution in nitrogen adsorption is less than 20nm pore diameter dN 2 is 5nm or more when the maximum, maximum differential pore volume in the differential pore distribution in water vapor adsorption Wherein the pore diameter dH 2 O is 25 nm or more and 75 nm or less, and the contact angle with water is less than 60 °.
基材上または前記基材上に形成した他の層上に、前記シリカ粒子分散液を塗工し、
前記シリカ粒子分散液の塗膜を形成する工程と、
前記塗膜を乾燥させる工程と、
を含み、
前記シリカ粒子の平均粒子径が８ｎｍ以上２５ｎｍ以下であり、
前記シリカ粒子分散液は、前記シリカ粒子に対して、ＳｉＯ２換算で前記疎水性官能基を有するシラン化合物を１ｗｔ％以上３０ｗｔ％以下で含むことを特徴とする請求項１に記載の部材の製造方法。 An organic silane compound having a hydrophobic functional group, and silica particles, and a step of preparing a silica particle dispersion containing the solvent in a solvent,
On the substrate or on another layer formed on the substrate, coated with the silica particle dispersion,
A step of forming a coating film of the silica particle dispersion,
Drying the coating film,
Including
The average particle diameter of the silica particles is 8 nm or more and 25 nm or less,
2. The member according to claim 1, wherein the silica particle dispersion contains the silane compound having the hydrophobic functional group in an amount of 1 wt% or more and 30 wt% or less in terms of SiO 2 with respect to the silica particles. 3. Method.
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| JP2005126461A (en) * | 2003-10-21 | 2005-05-19 | Sumitomo Chemical Co Ltd | Resin molded article subjected to hydrophilizing treatment |
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