CN100519681C - Anti-fogging treatment liquid, production method therefor, anti-fogging article and production method therefor - Google Patents
Anti-fogging treatment liquid, production method therefor, anti-fogging article and production method therefor Download PDFInfo
- Publication number
- CN100519681C CN100519681C CNB2004800347454A CN200480034745A CN100519681C CN 100519681 C CN100519681 C CN 100519681C CN B2004800347454 A CNB2004800347454 A CN B2004800347454A CN 200480034745 A CN200480034745 A CN 200480034745A CN 100519681 C CN100519681 C CN 100519681C
- Authority
- CN
- China
- Prior art keywords
- treatment solution
- condenses
- antifog
- organosilane
- sulphur
- 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 - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 title description 10
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 107
- 230000008878 coupling Effects 0.000 claims abstract description 86
- 238000010168 coupling process Methods 0.000 claims abstract description 86
- 238000005859 coupling reaction Methods 0.000 claims abstract description 86
- 239000000539 dimer Substances 0.000 claims abstract description 84
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000003960 organic solvent Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 87
- 239000005864 Sulphur Substances 0.000 claims description 86
- 229920000642 polymer Polymers 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 41
- 239000000758 substrate Substances 0.000 claims description 34
- 238000007711 solidification Methods 0.000 claims description 30
- 230000008023 solidification Effects 0.000 claims description 30
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 21
- 125000002228 disulfide group Chemical group 0.000 claims description 20
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 20
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 17
- 239000013543 active substance Substances 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 11
- 238000003618 dip coating Methods 0.000 claims description 11
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 abstract description 20
- 230000005494 condensation Effects 0.000 abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 5
- 238000005242 forging Methods 0.000 abstract 2
- 125000004434 sulfur atom Chemical group 0.000 abstract 2
- 238000007865 diluting Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 196
- 239000010408 film Substances 0.000 description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 65
- -1 glycol ethers Chemical class 0.000 description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000011521 glass Substances 0.000 description 34
- 238000012545 processing Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 19
- 230000003287 optical effect Effects 0.000 description 17
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 13
- 230000002950 deficient Effects 0.000 description 13
- 238000009832 plasma treatment Methods 0.000 description 13
- 206010018612 Gonorrhoea Diseases 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002310 reflectometry Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000012795 verification Methods 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 239000003595 mist Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000002688 persistence Effects 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000006978 adaptation Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920001214 Polysorbate 60 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920013701 VORANOL™ Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 210000001951 dura mater Anatomy 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- YACCECLVHQLZQK-UHFFFAOYSA-N methoxyperoxyethane Chemical compound CCOOOC YACCECLVHQLZQK-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IEDKVDCIEARIIU-UHFFFAOYSA-N 2-Nonadecanone Chemical compound CCCCCCCCCCCCCCCCCC(C)=O IEDKVDCIEARIIU-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 1
- SXMKVGVZHSQBRP-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-sulfonic acid Chemical compound CO[Si](OC)(OC)CCCS(O)(=O)=O SXMKVGVZHSQBRP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DSSHAUHXYBCMFX-UHFFFAOYSA-N 4-[methoxy(dimethyl)silyl]butane-1-thiol Chemical compound CO[Si](C)(C)CCCCS DSSHAUHXYBCMFX-UHFFFAOYSA-N 0.000 description 1
- DIXJKOKICQAOGC-UHFFFAOYSA-N 4-[methoxy(dimethyl)silyl]butane-2-thiol Chemical compound CO[Si](C)(C)CCC(C)S DIXJKOKICQAOGC-UHFFFAOYSA-N 0.000 description 1
- LIFHMKCDDVTICL-UHFFFAOYSA-N 6-(chloromethyl)phenanthridine Chemical compound C1=CC=C2C(CCl)=NC3=CC=CC=C3C2=C1 LIFHMKCDDVTICL-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- SFTWBNDYAJWGQX-UHFFFAOYSA-N CC(CCS)OOOC Chemical compound CC(CCS)OOOC SFTWBNDYAJWGQX-UHFFFAOYSA-N 0.000 description 1
- QVHJGNRVLAWVIV-UHFFFAOYSA-N CC(N(C)C)C(=O)O.N1=CC=CC2=CC=CC=C12.C(CCCCCCCCCCC)C1=C(N=C(N1)CCO)CC(=O)O Chemical compound CC(N(C)C)C(=O)O.N1=CC=CC2=CC=CC=C12.C(CCCCCCCCCCC)C1=C(N=C(N1)CCO)CC(=O)O QVHJGNRVLAWVIV-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- NLGOTHQMVKZTBP-KVVVOXFISA-N acetic acid;(z)-octadec-9-en-1-amine Chemical compound CC(O)=O.CCCCCCCC\C=C/CCCCCCCCN NLGOTHQMVKZTBP-KVVVOXFISA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical class CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 1
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RQSYOFXVTSYQAD-UHFFFAOYSA-N propan-2-yl propane-1-sulfonate Chemical compound CCCS(=O)(=O)OC(C)C RQSYOFXVTSYQAD-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Images
Abstract
An anti-fogging treating fluid which is produced by providing an organosilane containing at least one sulfur atom at least one non-coupling position or a hydrolyzate thereof being controlled in its condensation degree and being a monomer or a condensate having a condensation degree of two or more and diluting the organosilane or a hydrolyzate thereof with a hydrophilic organic solvent; the anti-fogging treating fluid, wherein a dimer or a higher degree condensate of an organosilane containing at least one sulfur atom at least one non-coupling position or a hydrolyzate thereof accounts for 1 wt % or more and less than 70 wt % of the total organosilane; a method for producing the anti-fogging treating fluid which comprises controlling the circumstance for holding the treating fluid or/and using a catalyst. The anti-fogging treating fluid and the method allows the production of an anti-fogging article which is excellent in anti-forging performance capability and anti-forging durability, and also exhibits high film strength.
Description
Technical field
The present invention relates to form on the surface of various base materials the antifog property treatment solution and the manufacture method thereof of the overlay film of antifog property excellence, the antifog property article and the manufacture method thereof of the overlay film that useful this antifog property treatment solution forms on the surface of various base materials.
Background technology
The surface of article if adhere to tiny water droplet or since scar etc. to cause the surface to have concavo-convex, then owing to scattering of light produces blushing.The present invention relates to prevent owing on the optical article surface, adhering to the technology that tiny water droplet produces the blushing phenomenon, promptly so-called technology of giving antifog property.
In the past, as the method for giving the antifog property of article surface, the surface is given method that water-absorbent absorbs water droplet, uses method that porous film absorbs water droplet, improved the surface static contact angle of water is made method that water droplet is difficult to adhere to, optical article heated the method etc. that water droplet is evapotranspired or improves surperficial dew point thereby can list.
In such method, as giving surface hydrophilicity, the surface is descended the method for water droplet diffusion to the static contact angle of water, proposed article surface coating surface promoting agent or form the method (for example TOHKEMY 2001-190471 communique) of the film that contains tensio-active agent on the surface.
And, disclosed following method, article surface is especially made thin film have under the situation of antifog property, in order to present and to keep antifog property, use the high method with sulfonic group or sulfonic organosilane or its hydrolyzate (for example No. 4325638 specification sheets of United States Patent (USP) and TOHKEMY 2002-60692 communique) of wetting ability at article surface.
But, shown in TOHKEMY 2001-190471 communique, forming in the structure of the film that contains tensio-active agent,, also having problems aspect the persistence of anti-fog effect owing to attached water causes coming off of tensio-active agent to article surface coating surface promoting agent or on the surface.And when article were used to optical applications, there are the following problems, and the reflection characteristic on surface is according to the Thickness Variation of the film that is formed at the surface, thus changes in optical properties such as light reflectance and transmissivity.
And, the disclosed wetting ability article that obtain by the processing of sulfonic acid modified organosilane in No. 4325638 specification sheets of United States Patent (USP), because the effect of simultaneously employed a large amount of tensio-active agent, after just handling, can access sufficient antifog property, but owing to cause tensio-active agent to come off, thereby almost there is not persistence through cleaning to wait.
And, TOHKEMY 2002-60692 communique is disclosed a kind of wetting ability article that obtain by following antifog coating liquid, described antifog coating liquid dilutes in hydrophilic organic solvent organosilane or its hydrolyzate that contains sulfonic acid or sulfonic acid precursor, the density deficiency of the hydrophilic radical of this wetting ability article is even also exist the problem that can not obtain high antifog property after just handling.
Summary of the invention
The objective of the invention is to solve so existing problem, the antifog property article and the manufacture method thereof that a kind of antifog treatment solution and manufacture method thereof are provided and are provided at the overlay film that useful this antifog property treatment solution forms on the surface of various base materials, this antifog treatment solution can be given antifog property and not damage optical property, and under any environment for use, all can prevent the blushing that tiny water droplet causes, and can access the antifog property article that antifog property aspect has persistence.
What the present inventor concentrated on studies found that, by using the different hydroaropic substance of condensation degree, can make following antifog property article, described antifog property article do not descend in the hydrophilic radical density of article surface, and has sufficient film toughness, promptly have excellent anti-mist characteristic, under any environment for use, all can prevent the blushing that tiny water droplet causes, and antifog property aspect has persistence.
The mist phenomenon that water droplet on the article causes is owing to following reason produces: under the water vapour that contains in the atmosphere was in situation smaller or equal to dew point, water vapour condensed at article surface.Any a plurality of places of condensing with article surface of water vapour are nuclear, and water droplet is grown up from this, in the process of growing up adjacent water droplet repeatedly in conjunction with and produce condensing of water vapour.
For the surface of article being given antifog property, in the process that this water droplet is grown up, make adjacent water droplet combination as early as possible, be effective thereby make the water droplet expansion make the absent variable method of blushing phenomenon.That is it is effective, making the method for surperficial possess hydrophilic property.But, form in the structure of the film that contains tensio-active agent at well-known coating surface promoting agent or on the surface, though the anti-fog effect excellence at initial stage, because attached water causes coming off of tensio-active agent, existing problems aspect the persistence of anti-fog effect.Therefore, continue for making anti-fog effect, hydrophilic component is particularly important with respect to the immobilization of article surface.
But, utilize existing method, be used for hydrophilic component is fixed on the position on the article surface or carries out crosslinked position in film when having, then the density of the hydrophilic radical in the film reduces, and can not obtain sufficient antifog property.And when being used for that hydrophilic component is fixed on the position on the article surface or carrying out crosslinked position when insufficient in film, then film itself does not have weather resistance.
In order to solve the above problems, antifog treatment solution of the present invention, it is characterized in that, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate (at least one side of organosilane and hydrolyzate thereof) of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer.
According to above-mentioned, can provide the antifog treatment solution that to make film with sufficient antifog property and the weather resistance of film own.Promptly, the organosilane and/or its hydrolyzate that contain at least 1 sulphur at non-coupling position that exist with monomeric form, except the immobilized effect of playing base material and film, also between dimer or the polymer condenses or between dimer or polymer condenses and the monomer molecule and react between the monomer molecule, and to the effect with the paste of gap landfill.Thus, exist hydrophilic component is fixed on the position on the article surface and carries out crosslinked position in film, can make film with sufficient antifog property and the weather resistance of film own.
In addition, antifog treatment solution of the present invention is characterised in that, is to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than 70wt% (weight %) as the dimer of the organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses.
According to above-mentioned, can provide the antifog treatment solution that to make film with sufficient antifog property and the weather resistance of film own.Promptly, the organosilane and/or its hydrolyzate that contain at least 1 sulphur at non-coupling position that exist with monomeric form, except the immobilized effect of playing base material and film, also between dimer or the polymer condenses or between dimer or polymer condenses and the monomer molecule and react between the monomer molecule, and to the effect with the paste of gap landfill.Contain the dimer of organosilane of at least 1 sulphur or polymer condenses at non-coupling position and be more than the 1wt% of total amount of the monomer of the organosilane that contains at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than 70wt%, the organosilane that contains at least 1 sulphur at non-coupling position in addition is under the monomeric situation, be used for hydrophilic component is fixed on position on the article surface, and carries out crosslinked position evenly exist in film, can make film with sufficient antifog property and the weather resistance of film own.
In addition, antifog treatment solution of the present invention is characterised in that, contains the organosilane of at least 1 sulphur and/or its hydrolyzate at non-coupling position and contains and be selected from sulfonate group, thiol group, sulfenyl, disulfide group, sulfonic at least a kind of functional group.
According to above-mentioned,, can make film with good antifog property by contain at least a kind at least 1 sulfonate group that demonstrates good hydrophilicity, thiol group, sulfenyl, disulfide group, the sulfonic group at non-coupling position.
In addition, antifog treatment solution of the present invention is characterised in that, in the described antifog treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, and contains tensio-active agent in the described antifog treatment solution.
According to above-mentioned, there are following monomer and condenses to be diluted in the hydrophilic organic solvent in the antifog treatment solution, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, by in so antifog treatment solution, containing tensio-active agent, when article being handled, can make the good and uniform film of outward appearance with it, and anti-mist characteristic is not caused obstruction, can further improve anti-mist characteristic.
In addition, antifog property article of the present invention are characterised in that the antifog property film that utilizes described antifog treatment solution to form is arranged at substrate surface.
According to above-mentioned, can obtain to have the antifog property article of the film of sufficient antifog property and the weather resistance of film own.
In addition, antifog property article of the present invention are characterised in that described base material is lens.
According to above-mentioned, there are following monomer and condenses to be diluted in the hydrophilic organic solvent in the described treatment solution, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer.Utilize the formed antifog property film of such treatment solution, can make the lens that do not damage optical characteristics and have antifog property.When article are used for optical applications, the reflection characteristic on surface is according to the Thickness Variation of the film that is formed at the surface, optical characteristics such as light reflectance and transmissivity also might change, but extremely thin by the formed antifog property film of treatment solution that is diluted in the described hydrophilic organic solvent, so can not have influence on optical characteristics.Therefore, can obtain to have the lens of good antifog property.
In addition, the manufacture method of antifog treatment solution of the present invention is characterised in that, to contain the organosilane of at least 1 sulphur and/or its hydrolyzate at non-coupling position and keep 0.1 hour～200 hours down, thereby obtain monomer and as dimer or polymeric condenses at 0 ℃～70 ℃.
According to above-mentioned, contain the coupling position of organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, be hydrolyzed lentamente at low temperatures and condensation, temperature is high more carries out soon more.By controlling its temperature and time, can make as the dimer of organosilane that contains at least 1 sulphur at non-coupling position or polymer condenses is to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than the antifog treatment solution of 70wt%.
In addition, the manufacture method of antifog treatment solution of the present invention is characterised in that, in the presence of at least a kind of catalyzer that is selected from acid catalyst, alkaline catalysts, amines catalyst, metal compound as catalyst, described organosilane and/or its hydrolyzate that contains at least 1 sulphur at non-coupling position handled, thereby obtained monomer and as dimer or polymeric condenses.
According to above-mentioned, by being selected from least a kind of catalyzer of acid catalyst, alkaline catalysts, amines catalyst, metal compound as catalyst, condensation and hydrolysis to the coupling position of the organosilane that contains at least 1 sulphur at non-coupling position and/or its hydrolyzate are controlled, and can make as the dimer of the organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses is to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than the antifog treatment solution of 70wt%.
In addition, the manufacture method of antifog treatment solution of the present invention is characterised in that, described organosilane and/or its hydrolyzate that contains at least 1 sulphur at non-coupling position contains at least a kind of functional group that is selected from sulfonate group, thiol group, sulfenyl, disulfide group, in the described manufacture method this functional group is converted into sulfonic group.
According to above-mentioned, the described organosilane of at least 1 sulphur and/or sulfonate group, thiol group, sulfenyl, the disulfide group of its hydrolyzate of containing at non-coupling position, demonstrate the more sulfonic group of good hydrophilicity by being converted to, thereby can make film with better antifog property.
In addition, the manufacture method of antifog property article of the present invention is characterised in that, comprise following operation: the operation that treatment solution is applied to substrate surface, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer; And the base material that is coated with behind the described treatment solution carried out the operation that heat treated is come dry solidification.
According to above-mentioned, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, by this treatment solution is applied to substrate surface, it is carried out heat treated come dry solidification, thereby finish the reaction at the coupling position of the organosilane that contains at least 1 sulphur at non-coupling position and/or its hydrolyzate, the antifog property article that can obtain to have sufficient antifog property and the weather resistance of film own.
In addition, the manufacture method of antifog property article of the present invention is characterised in that, comprise following operation: at least a kind of functional group of being contained in the treatment solution that is selected from sulfonate group, thiol group, sulfenyl, disulfide group is converted into sulfonic operation, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer; The described treatment solution that is diluted in the hydrophilic organic solvent is applied to the operation of substrate surface; And the base material that is coated with behind the described treatment solution carried out the operation that heat treated is come dry solidification.
According to above-mentioned, contain the organosilane of at least 1 sulphur and/or sulfonate group, thiol group, sulfenyl, the disulfide group of its hydrolyzate at non-coupling position, demonstrate the more sulfonic group of good hydrophilicity by being converted into, can have better antifog property.And, after this treatment solution is applied to substrate surface, it is carried out heat treated come dry solidification, finish the reaction at the coupling position of the organosilane that contains at least 1 sulphur at non-coupling position and/or its hydrolyzate, can obtain to have the antifog property article of the film of sufficient antifog property and the weather resistance of film own.
In addition, the manufacture method of antifog property article of the present invention is characterised in that, comprise following operation: the operation that treatment solution is applied to substrate surface, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer; The base material that is coated with behind the described treatment solution is carried out the operation that heat treated is come dry solidification; And at least a kind of functional group that is selected from sulfonate group, thiol group, sulfenyl, disulfide group that non-coupling position is contained is converted into sulfonic operation.
According to above-mentioned, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, after such treatment solution is applied to substrate surface, it is carried out heat treated come dry solidification, finish the reaction at the coupling position of the organosilane that contains at least 1 sulphur at non-coupling position and/or its hydrolyzate, making has the film of antifog property and the weather resistance of film own, the further sulfonate group that is selected from by non-coupling position is contained, thiol group, sulfenyl, at least a kind of functional group of disulfide group is converted into sulfonic group, can obtain to have the antifog property article of better antifog property.
In addition, the manufacture method of antifog property article of the present invention is characterised in that, carries out heat treated and comes the operation of dry solidification to carry out 1 minute～24 hours 50 ℃～300 ℃ temperature range being coated with base material behind the described treatment solution.
According to above-mentioned, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, and such treatment solution is applied to after the substrate surface, removes the solvent in the treatment solution that is coated with, finish the reaction of organosilane, can obtain to have the antifog property article of sufficient antifog property and the weather resistance of film own.
In addition, the manufacture method of antifog property article of the present invention is characterised in that the method that described treatment solution is applied to substrate surface is a dip coating.
According to above-mentioned,, can obtain to have the antifog property article of the good and uniform film of outward appearance by using dip coating.
In addition, the manufacture method of antifog property article of the present invention is characterised in that the method that described treatment solution is applied to substrate surface is a spin-coating method.
According to above-mentioned,, can obtain to have the antifog property article of the good and uniform film of outward appearance by using spin-coating method.
The organosilane that contains at least 1 sulphur at non-coupling position in the antifog treatment solution of the present invention comprises monomer and dimer or polymer condenses.Dimer or polymer condenses improve the density of the hydrophilic radical in the film.And, the organosilane that exists with monomeric form, the immobilized effect between performance base material and film, also reacting between dimer or the polymer condenses or between dimer or polymer condenses and the monomer molecule and between the monomer molecule, the described organosilane that exists with monomeric form is also brought into play the effect with the paste of gap landfill.Thus, have the film toughness of demonstrating and with the effect of the high adaptation of article surface.And, owing to contain hydrophilic radical, therefore, the density of the hydrophilic radical of film is reduced as sticking with paste in the monomer that plays a role, can demonstrate excellent anti-mist characteristic.
For the dimer or the polymer condenses that contain the organosilane of at least 1 sulphur at non-coupling position in the antifog treatment solution of the present invention,, just can obtain the density of sufficient hydrophilic radical as long as this condenses is dimer or polymer.In order to obtain the density of higher hydrophilic radical, preferably include the condenses of various condensation degrees such as dimer or polymer, more preferably among dimer or the various condensess of polymer, the content than big that condensation degree is little is many, thereby prevents that filling ratio reduces in the film.
Employed suitable hydrophilic organic solvent is meant ethers such as ketones such as glycol ethers such as di-alcoholss such as alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, glycerol, propylene glycol monomethyl ether, acetone, methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF), dioxane, water etc. in the antifog treatment solution of the present invention.Hydrophilic organic solvent can be a kind, also can be at least 2 kinds mixed solvent.
Preferred 0.1wt%～the 25wt% of content that contains the organosilane of at least 1 sulphur at non-coupling position.During less than 0.1wt%, the attenuation of antifog property film, there is problem the weather resistance aspect.And, even use high density, on the thickness of antifog property film, performance, do not see variation greater than 25wt%, unfavorable economically.When article were used for optical applications, this film must be the film that following situation can not take place, promptly, the reflection characteristic on surface is according to the Thickness Variation of the film that is formed at the surface, and light reflectance and transmissivity change, thus changes in optical properties, under this situation, the preferred 0.1wt%～2wt% of content.
Conduct in the antifog treatment solution of the present invention contains the dimer of the organosilane of at least 1 sulphur and/or its hydrolyzate or polymer condenses at non-coupling position be to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than 70wt%.During less than 1wt%, the hydrophilic radical density in the film reduces, and can not obtain anti-fully mist characteristic.In addition, during more than or equal to 70wt%, the monomer organosilane can not play one's part to the full as paste, can not obtain sufficient film toughness.In order to obtain higher antifog property and film toughness, what contain the organosilane of at least 1 sulphur and/or its hydrolyzate monomer and dimer or polymer condenses at non-coupling position exists ratio particularly important.But optimum ratio depends on the kind of employed organosilane, can't limit, but preferred dimer or polymer condenses is 5wt% or greater than 5wt% and less than 50wt%.
The organosilane that contains at least 1 sulphur at non-coupling position that uses among the present invention and/or its hydrolyzate contain and are selected from sulfonate group, thiol group, sulfenyl, disulfide group, sulfonic at least a kind of functional group.Preferred sulfonate group, thiol group, sulfenyl, disulfide group are oxidized into sulfonic group or sulfate.
Sulfonate group, thiol group, sulfenyl, disulfide group be positioned at organosilane and/or its hydrolyzate any position can, but in order to present wetting ability easily, preferably when changing into sulfonic acid or sulfate, be positioned at end.The reactive site of organosilane is a following radicals, is converted into silanol as chlorosilane, organoalkoxysilane, silazane, and can carry out condensation and with the group of the active group of article surface reaction.
As containing the organosilane of at least 1 sulphur and/or the example of its hydrolyzate, can list 3-sulfydryl propyl triethoxy silicomethane at non-coupling position, 3-sulfydryl propyl trimethoxy silicomethane, 3-sulfydryl propyl group methyl dimethoxy oxygen base silicomethane, 3-sulfydryl propyl-dimethyl methoxy methyl silane, 2-sulfydryl propyl triethoxy silicomethane, 2-sulfydryl propyl trimethoxy silicomethane, 2-sulfydryl propyl group methyl dimethoxy oxygen base silicomethane, 2-sulfydryl propyl-dimethyl methoxy methyl silane, 2-mercaptoethyl triethoxy-silicane, 2-mercaptoethyl trimethoxy silicomethane, 2-mercaptoethyl methyl dimethoxy oxygen base silicomethane, 2-mercaptoethyl dimethyl methoxy base silicomethane, 2-(2-chloroethyl sulphur ethyl) triethoxy-silicane, mercapto methyl trimethoxy silicomethane, dimethoxy-3-sulfydryl propyl group methyl-silicane, 2-(2-aminoethyl sulphur ethyl) diethoxymethyl silicomethane, dimethoxy-methyl-3-(3-phenoxy propyl thiopropyl) silicomethane, 3-(2-acetoxyl group ethyl thiopropyl) dimethoxy-methyl silicomethane, 2-(2-aminoethyl sulphur ethyl) triethoxy-silicane, 3-Trimethoxy silane base propanesulfonic acid isopropyl ester, two [3-(triethoxysilicane) propyl group] tetrasulfide, two [3-(triethoxysilicane) propyl group] disulphide, two [3-(triethoxysilicane) propyl group] thioether, 3-trimethoxysilyl propanesulfonic acid etc.
For homogeneity and the outward appearance that improves antifog processing film, but mixed surfactant in the antifog treatment solution of the present invention.Can list aniorfic surfactant, nonionic surface active agent, cationic surfactant, amphoterics etc. surfactant-based, with and reactive derivatives etc., according to the interaction of the sulfur-containing group of organosilane side, preferred anionic type tensio-active agent, more preferably the anionic property group is the aniorfic surfactant of sulfuric acid or vitriol, sulfonic acid or sulfonate.Employed tensio-active agent can be that specific a kind of or general mixes use at least two kinds.Can be in the scope of not damaging antifog property film toughness mixed surfactant.Therefore, with respect to the organosilane and/or its hydrolyzate that contain at least 1 sulphur at non-coupling position, can be at the scope mixed surfactant of 1wt%～50wt%.
Specifically, comprise as aniorfic surfactant: alkyl sulfuric ester salt such as Sodium Lauryl Sulphate BP/USP, higher alcohol sulfate, triethanolamine lauryl sulfate; Alkylbenzene sulfonates such as Sodium dodecylbenzene sulfonate; Sulfonated alkyl naphathalenes such as sodium alkyl naphthalene sulfonate; Alkyl sulfo succinates such as dialkyl sodium sulfosuccinate; Alkyl diphenyl ether disulfonates such as alkyl diphenyl ether disulphonic acid sodium; Alkylphosphonics such as alkylphosphonic acid carboxylic acid potassium; Polyxyethylated (or alkylaryl) sulfuric acids such as polyoxyethylene lauryl ether sodium sulfate, Voranol EP 2001 sodium sulfate, Voranol EP 2001 sulfuric acid trolamine, polyxyethylated phenylate sodium sulfate; Special reaction type anion surfactant; Special carboxylic acid type tensio-active agent; The naphthalene sulfonic acidformaldehyde condensation products such as sodium salt of the sodium salt of beta-naphthalenesulfonic-acid formaldehyde condensation compound, special aromatic sulphonic acid formaldehyde condensation products; Special polyocarboxy acid type polymeric surface active agent; Polyxyethylated phosphoric acid ester etc.
Comprise as nonionic surface active agent: polyoxyethylene alkylaryl ethers such as Voranol EP 2001, polyoxyethylene nonylplenyl ether such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether, the senior alcohol ether of polyoxyethylene; Polyoxyethylene deriv; Sorbitan-fatty acid esters such as Span-20, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, Span-83, sorbitan SUNSOFT Q-182S; Polyoxyethylene sorbitan fatty acid esters such as Tween-20, TWEEN40, Tween-60, polyox-yethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate; Polyoxyethylene sorbitol fatty acid esters such as four oleic acid polyoxyethylene sorbitan esters; Glycerol fatty acid esters such as glycerol monostearate, glycerol monoleate, self-emulsifying type glycerol monostearate; Polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol mono stearate, polyglycol distearate, polyethylene glycol monooleate; Polyoxyethylene alkyl amine; Polyoxyethylene hydrogenated castor oil; Alkyl alkylolamide etc.
Comprise as cationic surfactant and amphoterics: alkylamine salts such as coconut oleyl amine acetate, octadecylamine acetate; Quaternary ammonium salts such as Trimethyllaurylammonium chloride, octadecyl trimethyl ammonium chloride, cetyltrimethylammonium chloride, the two octadecyl Dimethyl Ammonium of chlorination, chlorination alkyl benzyl dimethyl ammonium; Alkyl betaines such as lauryl betaine, octadecyl betaine, lauryl carboxymethyl hydroxyethyl imidazole quinoline trimethyl-glycine; Amine oxides such as oxidation lauryl dimethyl amine.
The coupling position of containing the organosilane of at least 1 sulphur at non-coupling position in the antifog treatment solution of the present invention is hydrolyzed and condensation under low temperature in hydrophilic organic solvent lentamente, and temperature is high more carries out soon more.Less than 0 ℃ the time, condensation is very slow, and making dimer or polymer condenses needs the very long time, and operation is poor.During greater than 70 ℃, condensation is very fast, so be difficult to control.Therefore, will contain after the organosilane of at least 1 sulphur and/or its hydrolyzate be diluted in the hydrophilic organic solvent, preferably keep 0.1 hour～200 hours down at 0 ℃～70 ℃ at non-coupling position.And, in order more stably to carry out the control of condensation degree, preferably kept 2 hours～200 hours down at 0 ℃～40 ℃.
Be produced on non-coupling position when containing the dimer of organosilane of at least 1 sulphur or polymer condenses, preferably the method that will control according to environment and the method combination of using at least a kind of catalyzer that is selected from acid catalyst, alkaline catalysts, amines catalyst, metal compound as catalyst.
By being selected from acid catalyst, alkaline catalysts, amines catalyst, at least a kind of catalyzer of metal compound as catalyst, controlling the condensation and the hydrolysis at the coupling position of the organosilane that contains at least 1 sulphur at non-coupling position in the antifog treatment solution of the present invention and/or its hydrolyzate, is to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than the antifog treatment solution of 70wt% thereby can easily make as the dimer of the organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses.
Acid catalyst can list hydrochloric acid, sulfuric acid, nitric acid, acetate, formic acid, tartrate, citric acid, carbonic acid.Do not have the acid of carboxyl for hydrochloric acid, sulfuric acid, nitric acid, charcoal acid etc., have the effect of the hydrolysis that promotes organosilane, and have the acid of carboxyl since with the organosilane coordination, therefore have the effect that suppresses condensation.Therefore, mix use with the acid that contains carboxyl, then can more easily carry out the control of condensation degree if will not have the acid of carboxyl.
Alkaline catalysts can list sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium compound etc.For amines catalyst, specifically, can be quadrol, N, amino acid, glyoxal ethylines, 2 such as amine, glycine such as N-dimethyl benzylamine, tripropylamine, tributylamine, three amylamines, n-butylamine, triethylamine, guanidine, in the imidazoles such as 4-diethyl imidazoles, 2-phenylimidazole any one, owing to contain the amine of hydroxyl hydrolysis and condenses are formed hydrogen bond, have the effect of control condensation reaction, so preferably contain the amine of hydroxyl.
As metal compound as catalyst, can list metal salts of organic acids, SnCl such as cetylacetone metallics such as aluminium acetylacetonate, titanium acetylacetone, chromium acetylacetonate, sodium acetate, zinc naphthenate, stannous octoate
4, TiCl
4, ZnCl
2Deng Lewis acid, magnesium perchlorate etc.
For tertiary amine, organo-tin compound catalyzer, well-known also can the mixing for its effect of raising used these materials.Because the effect difference of each catalyzer, so the amount of catalyzer cannot treat different things as the same, and preferably uses under the prerequisite of the anti-mist characteristic that does not damage film, and specifically, with respect to the solid formation branch in the treatment solution, preferred combined amount is smaller or equal to 75%.
Contain the organosilane of at least 1 sulphur and/or sulfonate group, thiol group, sulfenyl, the disulfide group of its hydrolyzate at non-coupling position in the antifog treatment solution of the present invention, present the more sulfonic group of good hydrophilicity by being converted to, can have better antifog property.
The oxidation of sulfonate group, thiol group, sulfenyl, disulfide group can also can in order to carry out oxidation more efficiently, preferably be carried out before organosilane and/or its hydrolyzate condensation after condensation before organosilane and/or its hydrolyzate condensation.Oxidation is undertaken by common employed oxidizing reaction (by means of sodium permanganate, hydrogen peroxide, hydrochloric acid, hydrogen bromide, contain the oxidation of ozone gas etc.).
For improving the reactivity that contains organosilane and/or its hydrolyzate and the article surface of at least 1 sulphur at non-coupling position, if implement plasma treatment, alkaline purification, to improve the activity of article surface, then, also can improve anti-fog effect to effective with the reactivity of article surface.
The article of handling with antifog treatment solution of the present invention are materials of the material selected from the group that glass, plastics, oxide compound, metal, timber, pottery, cement, concrete, fiber, paper, stone and leather are formed.When considering the reaction with organosilane, preferably contain the oxide surface of glass.
The implication of the statement that uses in the present specification and detailed description of the present invention as above in order to be convenient to understand the present invention more, are described below feature of the present invention.
At first, the of the present invention the 1st is characterised in that, by containing the density that following monomer and condenses obtain sufficient hydrophilic radical, present excellent antifog property, described monomer is organosilane and/or its hydrolyzate that contains at least 1 sulphur at non-coupling position, and described condenses is described monomeric dimer or polymer.And, as the dimer of the organosilane that contains at least 1 sulphur at non-coupling position and/or its hydrolyzate or polymeric condenses is to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than 70wt%, thereby in film, dispose hydrophilic radical effectively, with improve film toughness and with the article surface adaptation.
The 2nd is characterised in that, contains organosilane and/or the dimer of its hydrolyzate or the method for polymer condenses of at least 1 sulphur as being produced on non-coupling position, by treatment solution is remained under the certain environment, it is controlled.And,, can carry out the making of condenses under the state that contains at least a kind of catalyzer that is selected from acid catalyst, alkaline catalysts, amines catalyst, metal compound as catalyst or do not contain under the state of catalyzer.
The 3rd is characterised in that, by substrate surface being handled with treatment solution, can access the density of sufficient hydrophilic radical, can make the antifog property article that formed excellent antifog property film, in the described treatment solution, have following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, and described condenses is described monomeric dimer or polymer.
And, as the dimer of the organosilane that contains at least 1 sulphur at non-coupling position and/or its hydrolyzate or polymeric condenses is to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than 70wt%, thereby can in film, dispose hydrophilic radical effectively, can make improved film toughness and with the antifog property article of the adaptation of substrate surface.And, contain tensio-active agent in the treatment solution, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer.
The 4th is characterised in that, is that lens are the antifog system article of feature with described base material.In the treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, extremely thin by the formed antifog property film of such treatment solution, so can make the lens that do not damage optical characteristics and have antifog property.
The 5th is characterised in that, shown in manufacturing process's schema of the antifog property article of Fig. 1 (a), the manufacture method of antifog property article comprises following operation: the operation that treatment solution is applied to substrate surface, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer; And the base material that is coated with behind the described treatment solution carried out the operation that heat treated is come dry solidification.
And, shown in manufacturing process's schema of the antifog property article of Fig. 1 (b), the manufacture method of antifog property article comprises following operation: at least a kind of functional group of being contained in the treatment solution that is selected from sulfonate group, thiol group, sulfenyl, disulfide group is converted into sulfonic operation, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer; Described treatment solution is applied to the operation of substrate surface; And the base material that is coated with behind the described treatment solution carried out the operation that heat treated is come dry solidification.
And, shown in manufacturing process's schema of the antifog property article of Fig. 1 (c), the manufacture method of antifog property article comprises following operation: the operation that treatment solution is applied to substrate surface, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer; The base material that is coated with behind the described treatment solution is carried out the operation that heat treated is come dry solidification; And at least a kind of functional group that is selected from sulfonate group, thiol group, sulfenyl, disulfide group that non-coupling position is contained is converted into sulfonic operation.
Description of drawings
The 1st figure is the schema of the manufacturing process of antifog property article of the present invention, manufacturing process's schema of 3 examples is shown in (a)～(c) of this figure.
Embodiment
Below, antifog treatment solution of the present invention and manufacture method thereof are described.In addition, about antifog treatment solution, the treatment solution A～I of 9 kinds is described.
(treatment solution A)
The 3-sulfydryl propyl trimethoxy silicomethane of 0.01mol is dissolved in the ethanol of 1.19ml, adds the 0.2N sulfuric acid of 0.238g, stirred 2 hours down, carry out the hydrolysis of methoxyl group at 30 ℃., add 7.6% hydrogen peroxide of 77.54g herein, under 60 ℃ environment, stirred 24 hours, carry out the oxidizing reaction of thiol group and the condensation reaction of silanol group.
With FT-NMR this solution is analyzed, be found that sulfydryl generation oxidation, methoxyl group is hydrolyzed, and has three siloxy-propanesulfonic acid to be synthesized.With this solution dilution to 200 times, utilize LC/MS to analyze with pure water, results verification is to the existence of dimer or polymer condenses, and its ratio is for all forming the 42wt% in the component admittedly.And, measuring the solid formation branch concentration of three siloxy-propanesulfonic acid solutions, the result is 2.4wt%.
With ethanol this three siloxyies propanesulfonic acid solutions being diluted to solid formation branch concentration is 0.15wt%, obtains the diluent of 150g.In this diluent, with respect to the dilauryl sodium sulfosuccinate (the system NIKKOLOTP-100 of Nippon Light Chemical Co., Ltd.) of treatment solution total amount adding 100ppm, as treatment solution A.
(treatment solution B)
Two [3-(triethoxysilicane) propyl group] disulphide of 0.01mol (4.75g) are dissolved in the trimethyl carbinol of 47.5g, add the 0.1N nitric acid of 1.7g, stirred 2 hours down at 25 ℃.With FT-NMR it is analyzed, results verification is hydrolyzed to oxyethyl group, has two [3-(three siloxy-silicon) propyl group] disulphide to form.
With this solution dilution to 100 of 1.5g times, total amount is 150g with ethanol.Then, mix the 1N sodium hydroxide solution of 0.1g therein, at room temperature stir 30 minutes (B-1 solution).With pure water the part of this B-1 solution is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is 30% in whole compound amounts.Then, in B-1 solution, with respect to the Sodium Lauryl Sulphate BP/USP of treatment solution total amount adding 50ppm, as treatment solution B.
(treatment solution C)
Two [3-(triethoxysilicane) propyl group] disulphide of 0.02mol (4.75g) are dissolved in the trimethyl carbinol of 40.5g, add the 0.1N nitric acid of 1.2g, stirred 5 hours down at 30 ℃.With FT-NMR it is analyzed, results verification is hydrolyzed to oxyethyl group, has two [3-(three siloxy-silicon) propyl group] disulphide to form.
With this solution dilution to 100 of 2.25g times, the solution that with total amount is 150g is as treatment solution C with ethanol.With pure water the part of this treatment solution C is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is the 29wt% in whole compound amounts.
(treatment solution D)
To be diluted to 10 times with two [3-(three siloxy-silicon) propyl group] disulfide solution that the mode identical with treatment solution C made with ethanol/water (50/50vol%) solvent, (ozone content is 200g/m to the ozone gas that contains that ozone is diluted with oxygen with the speed feeding of 2.5l/min in this solution
3) 30 minutes carry out oxidation.With FT-NMR this solution is analyzed, results verification is oxidized to disulfide group, has three siloxy-propanesulfonic acid to be synthesized.Solid formation branch concentration to the three siloxy-propanesulfonic acid solutions that obtain is like this measured, and the result is 2.0%.
With ethanol this three siloxyies propanesulfonic acid solutions is diluted to solid formation branch concentration and reaches 0.15wt%, obtain the diluent of 150g, as treatment solution D.With pure water the part of this treatment solution D is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is for all forming the 30wt% in the component admittedly.
(treatment solution E)
The 3-sulfydryl propyl trimethoxy silicomethane of dissolving 0.02mol in the acetone of 60ml is keeping dripping 1 hour this solution under the ice-cooled state with the 0.4mol/l potassium permanganate solution of ice-cooled 200ml.After dripping end, stirred 2 hours down, make unreacted potassium permanganate become Manganse Dioxide at 25 ℃.This reaction solution is taken care of one day one night down at 0 ℃, made the Manganse Dioxide particulate deposits, its filtration.With FT-NMR this filtrate is analyzed, the result proves sulfydryl generation oxidation, and methoxyl group is hydrolyzed, and has three siloxy-propanesulfonic acid potassium to be synthesized.And, the solid formation branch concentration of three siloxy-propanesulfonic acid potassium solutions is measured, the result is 3wt%.
Make the three siloxy-propanesulfonic acid potassium solutions that obtain with in the regenerated storng-acid cation exchange resin (the Japanese ORGANO system AmberliteIR-120Na of Co., Ltd.) of velocity of flow SV4 by 100ml.The pH that confirms three siloxy-propanesulfonic acid potassium solutions is 10.5, and with respect to this, the pH of the solution after the ion-exchange is 1.3, and potassium sulfonate is become sulfonic acid by ion-exchange, becomes three siloxy-propanesulfonic acid solutions.The result that the solid formation branch concentration of three siloxy-propanesulfonic acid solutions is measured is 1.5wt%.
With ethanol this three siloxyies propanesulfonic acid solutions is diluted to solid formation branch concentration and reaches 0.15wt%, obtain the diluent of 150g.This diluent was taken care of 72 hours down at 0 ℃, generated after the condenses,, add the dilauryl sodium sulfosuccinate (the system NIKKOL OTP-100 of Nippon Light Chemical Co., Ltd.) of 100ppm, as treatment solution E with respect to the treatment solution total amount.
With pure water the part of this treatment solution E is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is for all forming the 15wt% in the component admittedly.
(treatment solution F)
With with the same mode of modulation treatment liquid E, make three siloxy-propanesulfonic acid solutions, with ethanol this solution dilution to the solid branch concentration that forms is reached 0.15wt%, obtain the diluent of 150g.The N-N-aminoethyl ethanolamine that in diluent, mixes 0.3g, kept 2 hours down at 40 ℃, generate after the condenses, with respect to the treatment solution total amount, add the dilauryl sodium sulfosuccinate (the system NIKKOL OTP-100 of Nippon Light Chemical Co., Ltd.) of 100ppm, as treatment solution F.
With pure water the part of this treatment solution F is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is for all forming the 62wt% in the component admittedly.
(treatment solution G)
With with the same mode of modulation treatment liquid E, make three siloxy-propanesulfonic acid solutions, with ethanol this solution dilution to the solid branch concentration that forms is reached 0.15wt%, obtain the diluent of 150g.With the solution that just diluted as treatment solution G.
With pure water the part of this treatment solution G is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is for all forming the 0.6wt% in the component admittedly.
(treatment solution H)
With with the same mode of modulation treatment liquid F, make three siloxy-propanesulfonic acid solutions, with ethanol this solution dilution to the solid branch concentration that forms is reached 0.15wt%, obtain the diluent of 150g.The N-N-aminoethyl ethanolamine that mixes 0.3g in this solution kept 200 hours down at 75 ℃, generated condenses, as treatment solution H.
With pure water the part of this treatment solution H is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is for all forming the 79wt% in the component admittedly.
(treatment solution I)
In treatment solution C, use the basic just triethoxy-silicane of 4.96g to substitute two [3-(triethoxysilicane) propyl group] disulphide, in addition, be hydrolyzed in the same way, condensation, reach 0.15wt% with alcohol dilution to the solid branch concentration that forms, obtain the treatment solution of 150g.
With pure water the part of this treatment solution I is diluted to 20 times, utilizes LC/MS to analyze, results verification is to the existence of dimer or polymer condenses, and its ratio is the 52wt% in whole compound amounts.
Then, antifog treatment solution (the treatment solution A～I), formed the antifog property article of antifog property film and the embodiment of manufacture method thereof at substrate surface that uses above explanation is described.In addition, as base material, use glasses plastic lens, projector optics, photographic camera eyepiece, blank glass.
(embodiment 1)
The operation that substrate surface is coated with by dip-coating: as lens material, prepare to have dura mater, (outermost layer is SiO to antireflection film
2The glasses plastic lens (" SEIKO SUPERSOVEREIGN " Seiko Epson Corp's system) of layer film).For these glasses are cleaned with the surface of plastic lens, carry out plasma treatment.The condition enactment of plasma treatment is processing pressure: 0.1Torr imports gas: dry air, interelectrode distance: 24cm, power: direct current 1KV, treatment time: 15 seconds.
Glasses after plasma treatment be impregnated in treatment solution A with plastic lens, utilize the average rate lifting device to apply with the speed of mentioning that 20cm/ divides.
Carry out heat treated and come the operation of dry solidification: the glasses that will be coated with treatment solution B kept 4 hours down at 60 ℃ in the heated air circulation type thermostatic bath with plastic lens, finished the reaction with base material, obtained Anti-fog glasses lens (sample 1).
The Anti-fog glasses lens that obtain are smaller or equal to 5 ° to the contact angle of pure water, do not find apparent defectives such as gonorrhoea.And, reflectivity before processing and after do not see variation.
(embodiment 2)
The operation that substrate surface is coated with by spin coating: use spin coater adopt following method to projector with optics coating processing liquid B, this projector floods in 40 ℃ 1.6N potassium hydroxide solution with optics and fully cleaned with pure water after 3 minutes.With carrying out the vacuum suck clamping near the central part of optics, under the state with revolution 500rpm rotation, the treatment solution of ejection 5ml rotated for 10 seconds with revolution 2500rpm, and remaining treatment solution is got rid of to projector.
Carry out heat treated and come the operation of dry solidification: the projector that will be coated with treatment solution B kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath with optics, finished the reaction with base material.
Functional group is converted into sulfonic operation: by 90 ℃ down with oxygen with ozone gas dilute get contain ozone gas (ozone content 200g/m
3) contact 10 minutes, carry out oxide treatment, thereby sulfenyl is converted into sulfonic group, obtain antifog projector optics (sample 2).
By dyeing, confirm sulfonic existence by means of methylene blue.As everyone knows, methylene blue and sulfonic acid form very strong ionic linkage, and therefore, when having sulfonic group, dyeing is blueness.After the antifog projector that obtains flooded 1 minute in 1mM aqueous solution of methylene blue (pH4) under 25 ℃ with the part of optics, with the Ultrasonic Cleaners of having filled pure water (2.6 liters of tankages, oscillation frequency: 45kHz, power: 120W) cleaned 3 minutes, confirm to be coloured to blueness, thereby proved sulfonic existence.The antifog projector that obtains with optics to the contact angle of pure water for smaller or equal to 5 °, do not find apparent defectives such as gonorrhoea.Reflectivity before processing and after do not see variation.
(embodiment 3)
The operation that substrate surface is coated with by spin coating: prepare in 40 ℃ 1.6N potassium hydroxide solution dipping 3 minutes and fully clean with pure water after the projector optics.Use spin coater to this projector optics coating processing liquid B.Having used the treatment solution coating of spin coater is to carry out as follows, to projector with carrying out vacuum suck clamping (chuck) near the central part of optics, under state with revolution 500rpm rotation, the treatment solution of ejection 3ml, keep rotation in 3 seconds, rotated for 10 seconds with revolution 2500rpm again, remaining treatment solution is got rid of.
Carry out heat treated and come the operation of dry solidification: the projector that will be coated with treatment solution C kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath with optics, finished the reaction with base material.
Functional group is converted into sulfonic operation: by at normal temperatures with the ozone water of having dissolved ozone gas (ozone content 70ppm～80ppm) contact 20 minutes, carry out oxide treatment, sulfenyl is converted into sulfonic group, obtains antifog projector optics (sample 3).
By dyeing, confirm sulfonic existence by means of methylene blue.After the antifog projector that obtains flooded 1 minute in 1mM methylene blue solution (pH4) under 25 ℃ with the part of optics, with the Ultrasonic Cleaners of having filled pure water (2.6 liters of tankages, oscillation frequency: 45kHz, power: 120W) cleaned 3 minutes, confirm and be coloured to blueness, thereby proved sulfonic existence.The antifog projector that obtains with optics to the contact angle of pure water for smaller or equal to 5 °, do not find apparent defectives such as gonorrhoea.Reflectivity before processing and after do not see variation.
(embodiment 4)
The operation that substrate surface is coated with by dip-coating: as lens material (base material), prepare to have dura mater, (outermost layer is SiO to antireflection film
2The glasses plastic lens (" SEIKOSUPER SOVEREIGN " Seiko Epson Corp's system) of layer film).For these glasses are cleaned with the surface of plastic lens, carry out plasma treatment.The condition enactment of plasma treatment is processing pressure: 0.1Torr imports gas: dry air, interelectrode distance: 24cm, power: direct current 1KV, treatment time: 15 seconds.
Glasses after plasma treatment be impregnated in treatment solution C with plastic lens, utilize the average rate lifting device to apply with the speed of mentioning that 20cm/ divides.
Carry out heat treated and come the operation of dry solidification: the glasses that will be coated with treatment solution C kept 4 hours down at 60 ℃ in the heated air circulation type thermostatic bath with plastic lens, finished the reaction with base material, obtained Anti-fog glasses lens (sample 4).
The Anti-fog glasses lens that obtain are smaller or equal to 5 ° to the contact angle of pure water, do not find apparent defectives such as gonorrhoea.And, reflectivity before processing and after do not see variation.
(embodiment 5)
The operation that substrate surface is coated with by dip-coating: prepare in 40 ℃ 1.6N potassium hydroxide solution dipping 3 minutes and fully clean with pure water after the projector optics.This projector be impregnated in treatment solution D with optics, utilize the average rate lifting device to apply with the speed of mentioning that 20cm/ divides.
Carry out heat treated and come the operation of dry solidification: the projector that will be coated with treatment solution D kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath with optics, finished the reaction with base material, obtained antifog projector with optics (sample 5).
The antifog projector that obtains with optics to the contact angle of pure water for smaller or equal to 5 °, do not find apparent defectives such as gonorrhoea.Reflectivity before processing and after do not see variation.
(embodiment 6)
The operation that substrate surface is coated with by dip-coating: prepare in 40 ℃ 1.6N potassium hydroxide solution dipping 3 minutes and fully clean with pure water after blank glass.In treatment solution E, utilize the average rate lifting device to apply the blank glass-impregnated with the speed of mentioning that 20cm/ divides.
Carry out heat treated and come the operation of dry solidification: the blank glass that will be coated with treatment solution E kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath, finished the reaction with base material, obtained antifog blank glass (sample 6).
The blank glass that obtains is smaller or equal to 5 ° to the contact angle of pure water, does not find apparent defectives such as gonorrhoea.And, reflectivity before processing and after do not see variation.
(embodiment 7)
The operation that substrate surface is coated with by dip-coating:, prepare to have carried out the photographic camera eyepiece of 60 seconds kind plasma treatment as base material.The condition enactment of plasma treatment is processing pressure: 0.1Torr imports gas: dry air, interelectrode distance: 24cm, power: direct current 1KV, treatment time: 60 seconds.The photographic camera that will carry out this plasma treatment impregnated in treatment solution F with eyepiece, utilizes the average rate lifting device to apply with the speed of mentioning that 20cm/ divides.
Carry out heat treated and come the operation of dry solidification: the photographic camera that will be coated with treatment solution F kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath with eyepiece, finished the reaction with base material, obtained antifog photographic camera with eyepiece (sample 7).
The antifog photographic camera that obtains with eyepiece to the contact angle of pure water for smaller or equal to 5 °, do not find apparent defectives such as gonorrhoea.Reflectivity before processing and after do not see variation.
(comparative example 1)
The operation that substrate surface is coated with by dip-coating and carry out the operation that heat treated is come dry solidification: will in 40 ℃ 1.6N potassium hydroxide solution, flood 3 minutes and fully clean with pure water after the blank glass-impregnated in treatment solution G, utilize the average rate lifting device to apply with the speed of mentioning that 20cm/ divides.By this blank glass was kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath, carry out dry solidification, obtain antifog blank glass (sample 8).
The antifog blank glass that obtains is 10 ° to the contact angle of pure water, does not find apparent defectives such as gonorrhoea.Reflectivity before processing and after do not see variation.
(comparative example 2)
The operation that substrate surface is coated with by dip-coating: will in 40 ℃ 1.6N potassium hydroxide solution, flood 3 minutes and fully clean with pure water after projector impregnated in treatment solution H with optics, utilize the average rate lifting device to apply with the speed of mentioning that 20cm/ divides.
Carry out heat treated and come the operation of dry solidification: the projector that will be coated with treatment solution H kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath with optics, carry out dry solidification, finish the reaction with base material, obtain antifog projector with optics (sample 9).
The antifog projector that obtains is 12 ° with optics to the contact angle of pure water, finds some gonorrhoea in appearance.The single face reflectivity is 5% before processing, and is increased to 8% after handling.
(comparative example 3)
The operation that substrate surface is coated with by spin coating: use spin coater to adopt following method dialogue sheet glass coating processing liquid I, this blank glass flooded 3 minutes in 40 ℃ 1.6N potassium hydroxide solution and fully cleans with pure water.The central part of dialogue sheet glass is paid and is closely carried out the vacuum suck clamping, and under the state with revolution 500rpm rotation, the treatment solution of ejection 3ml kept for 3 seconds, and rotated for 10 seconds with revolution 2500rpm again, and remaining treatment solution is got rid of.
Carry out heat treated and come the operation of dry solidification: the blank glass that will be coated with treatment solution I kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath, finished the reaction (sample 10) with base material.
Obtain handle with treatment solution I after antifog blank glass be 43 ° to the contact angle of pure water, do not find apparent defectives such as gonorrhoea.Reflectivity before processing and after do not see variation.By the methylene blue staining method, this antifog blank glass is dyeed, but be not colored.
(comparative example 4)
The operation that substrate surface is coated with by spin coating: use spin coater to adopt following method dialogue sheet glass coating processing liquid I, this blank glass flooded 3 minutes in 40 ℃ 1.6N potassium hydroxide solution and fully cleans with pure water.The central part of dialogue sheet glass is paid and is closely carried out the vacuum suck clamping, under state with revolution 500rpm rotation, and the treatment solution of ejection 3ml, rotation kept for 3 seconds, and rotated for 10 seconds with revolution 2500rpm again, and remaining treatment solution is got rid of.
Carry out heat treated and come the operation of dry solidification: the blank glass that will be coated with treatment solution I kept 1 hour down at 120 ℃ in the heated air circulation type thermostatic bath, finished the reaction with base material.
Functional group is converted into sulfonic operation: by 90 ℃ down with oxygen with ozone gas dilute get contain ozone gas (ozone content 200g/m
3) contact 10 minutes, carry out oxide treatment, thereby obtain antifog blank glass (sample 11).
By dyeing, confirm sulfonic existence by means of methylene blue.With the part of the antifog blank glass that obtains under 25 ℃ in 1mM aqueous solution of methylene blue (pH4) after the dipping 1 minute, with the Ultrasonic Cleaners of having filled pure water (2.6 liters of tankages, oscillation frequency: 45kHz, power: 120W) cleaned 3 minutes, confirm and be coloured to blueness, thereby proved sulfonic existence.The antifog blank glass that obtains is smaller or equal to 7 ° to the contact angle of pure water, does not find apparent defectives such as gonorrhoea.Reflectivity before processing and after do not see variation.
(comparative example 5)
The operation that substrate surface is coated with by dip-coating:, prepare to have carried out the photographic camera eyepiece of 60 seconds plasma treatment as base material.The condition enactment of plasma treatment is processing pressure: 0.1Torr imports gas: dry air, interelectrode distance: 24cm, power: direct current 1KV, treatment time: 60 seconds.The photographic camera that will carry out this plasma treatment impregnated in treatment solution E with eyepiece, utilizes the average rate lifting device to apply with the speed of mentioning that 20cm/ divides.
Carry out heat treated and come the operation of dry solidification: the photographic camera that will be coated with treatment solution E kept 1 hour down at 40 ℃ in the heated air circulation type thermostatic bath with eyepiece, finished the reaction with base material, obtained antifog photographic camera with eyepiece (sample 12).
The antifog photographic camera that obtains with eyepiece to the contact angle of pure water for smaller or equal to 5 °, do not find apparent defectives such as gonorrhoea.And, reflectivity before processing and after do not see variation.
The manufacturing conditions of the antifog property article (sample 1～12) in each above embodiment and the comparative example is shown in table 1.
Table 1
And, utilize evaluation method shown below that the optical article that obtains in each above embodiment and the comparative example is estimated.It is the results are shown in table 2.Assessment item is set at antifog property of initial stage, antifog weather resistance, scuff resistance, water spotting, stain test.Below, the evaluation method to each assessment item is described.
(evaluation method)
Antifog property of initial stage: will through 20 ℃ down the sample transfer of keeping in the environment that remains on 40 ℃ of temperature, humidity 90%, the mist production on visual observation surface.Be divided into following 3 grades and estimate this blushing situation.That is, zero expression does not have mist fully.△ represents that burn-off is lost (problem is arranged in the practical application) after 2 minutes.* expression does not disappear through 2 minutes mists yet.
Antifog weather resistance: the loading that applies 500g with cloth (cotton) is carried out article surface after 1000 times the friction, cleans up and dry with pure water.To transfer in the environment that remains on 40 ℃ of temperature, humidity 90% the mist production on visual observation surface through carrying out sample certainly at 20 ℃.Be divided into 3 following grades and estimate this blushing situation.That is, zero expression does not have mist fully.△ represents that burn-off is lost (problem is arranged in the practical application) after 2 minutes.* expression does not disappear through 2 minutes mists yet.
Scuff resistance: 50 times friction is carried out in the loading that applies 1kg with the steel wool of #0000 to the optical article surface.Be divided into 3 following grades and estimate the scuffing degree.Zero expression does not scratch fully.△ represents to have 1～10 tiny scuffing (problem is arranged in the practical application).* expression has countless scuffings.
Water spotting: with tap water flushing optical article surface, make its drying after, with cloth residue is wiped away.Zero expression is wiped away fully.△ represents to leave part residue (problem is arranged in the practical application).* expression residue is nearly all residual.
Stain test:, confirm sulfonic existence by dyeing by means of methylene blue.As everyone knows, methylene blue and sulfonic acid form very strong ionic linkage, and therefore, when having sulfonic group, dyeing is blueness.With the part of the antifog blank glass that obtains under 25 ℃ in 1mM aqueous solution of methylene blue (pH4) after the dipping 1 minute, with the Ultrasonic Cleaners of having filled pure water (2.6 liters of tankages, oscillation frequency: 45kHz, power: 120W) cleaned 3 minutes, confirm whether to be coloured to blueness.Zero expression is colored.* expression is not colored.
Table 2
| Treatment solution | Antifog property of initial stage | Antifog weather resistance | Scuff resistance | Water spotting | Stain test | |
| Sample 1 | A | ○ | ○ | ○ | ○ | ○ |
| Sample 2 | B | ○ | ○ | △ | ○ | － |
| Sample 3 | C | ○ | ○ | △ | ○ | ○ |
| Sample 4 | C | ○ | ○ | △ | ○ | ○ |
| Sample 5 | D | ○ | ○ | ○ | ○ | ○ |
| Sample 6 | E | ○ | ○ | ○ | ○ | ○ |
| Sample 7 | F | ○ | ○ | ○ | ○ | ○ |
| Sample 8 | G | △ | × | △ | △ | ○ |
| Sample 9 | H | △ | △ | × | △ | ○ |
| Sample 10 | I | × | × | ○ | ○ | × |
| Sample 11 | I | × | × | ○ | ○ | × |
| Sample 12 | E | ○ | × | × | × | ○ |
Result according to table 2, antifog property of initial stage and the antifog weather resistance of embodiment 1～7 (having used the sample 1～7 of treatment solution A～F), scuff resistance is good, antifog property of initial stage and the antifog poor durability of comparative example 3 (having used the sample 10 of treatment solution I) and embodiment 11 (having used the sample 11 of treatment solution I), hence one can see that, by article surface being handled with following treatment solution, can access the density of sufficient hydrophilic radical, can access the antifog treatment solution that forms excellent antifog property film, in this treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer.
And, antifog property of initial stage and the antifog weather resistance of embodiment 1～7 (having used the sample 1～7 of treatment solution A～F), scuff resistance is good, the antifog property of initial stage and the antifog weather resistance of comparative example 1 (having used the sample 8 of treatment solution G) and comparative example 2 (having used the sample 9 of treatment solution H), scuff resistance is poor, hence one can see that, because as the dimer that contains the organosilane of at least 1 sulphur and/or its hydrolyzate at non-coupling position or polymeric condenses is to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than 70wt%, so can in film, effectively dispose hydrophilic radical, can obtain to form improved film toughness and with the antifog treatment solution of the antifog property film of the adaptation of article surface.
And, antifog property of initial stage and the antifog weather resistance of embodiment 1～7 (having used the sample 1～7 of treatment solution A～F) are good, it can be said that, in antifog treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, this monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, this condenses is described monomeric dimer or polymer, and can contain tensio-active agent in the antifog treatment solution.
And, in embodiment 1～7 (having used the sample 1～7 of treatment solution A～F), do not find apparent defective, hence one can see that, extremely thin with the formed antifog property film of following treatment solution, so can make the antifog blank glass (optical article) that can not damage optical characteristics and have antifog property, in this treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, condenses is described monomeric dimer or polymer.Comparative example 2 (having used the sample 9 of treatment solution H) has produced defective in appearance, and this is because the content of condenses is many, and the film constitute is failed in film due to the evenly configuration.
And, antifog weather resistance among the embodiment 1～7 (having used the sample 1～7 of treatment solution A～F), anti-water stain property, scuff resistance are good, antifog weather resistance, anti-water stain property, the scuff resistance of comparative example 5 (use treatment solution E, carry out heat treated and come the operation of dry solidification to keep 1 hour sample 12 down at 40 ℃) are poor.Therefore, carry out 1 minute～200 hours heat treated by the base material that will be coated with following treatment solution 50 ℃～300 ℃ temperature range and come the operation of dry solidification, can make the antifog property article that formed excellent antifog property film, in this treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, condenses is described monomeric dimer or polymer.
Claims (14)
1. antifog treatment solution, in described antifog treatment solution, have following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, and described condenses is described monomeric dimer or polymer; Described antifog treatment solution is characterised in that, the dimer of the described organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses are to contain more than the 1wt% of total amount of the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses and less than 70wt%.
2. antifog treatment solution as claimed in claim 1 is characterized in that, the described organosilane that contains at least 1 sulphur at non-coupling position and/or its hydrolyzate contain and be selected from sulfonate group, thiol group, sulfenyl, disulfide group, sulfonic at least a kind of functional group.
3. antifog treatment solution as claimed in claim 1, it is characterized in that, in the described antifog treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, and contains tensio-active agent in the described antifog treatment solution.
4. antifog property article wherein, have any antifog property film that described antifog treatment solution forms that utilizes claim 1 to 3 at substrate surface.
5. antifog property article as claimed in claim 4 is characterized in that described base material is lens.
6. the manufacture method of an antifog treatment solution, wherein, will be after non-coupling position be contained the organosilane of at least 1 sulphur and/or its hydrolyzate and is diluted in the hydrophilic organic solvent, kept 0.1 hour～200 hours down at 0 ℃～70 ℃, thus obtain the dimer of the described organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses be contain the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses the 1wt% of total amount more than and less than the condenses of 70wt%.
7. the manufacture method of antifog treatment solution as claimed in claim 6, it is characterized in that, in the presence of at least a kind of catalyzer that is selected from acid catalyst, alkaline catalysts, amines catalyst, metal compound as catalyst, described organosilane and/or its hydrolyzate that contains at least 1 sulphur at non-coupling position handled, thereby obtained monomer and as described monomeric dimer or polymeric condenses.
8. as the manufacture method of claim 6 or 7 described antifog treatment solutions, it is characterized in that, described organosilane and/or its hydrolyzate that contains at least 1 sulphur at non-coupling position contains at least a kind of functional group that is selected from sulfonate group, thiol group, sulfenyl, disulfide group, in the described manufacture method this functional group is converted into sulfonic group.
9. the manufacture method of antifog property article, it comprises following operation: the operation that treatment solution is applied to substrate surface, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, the dimer of the wherein said organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses be contain the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses the 1wt% of total amount more than and less than 70wt%; And the base material that is coated with behind the described treatment solution carried out the operation that heat treated is come dry solidification.
10. the manufacture method of antifog property article, it comprises following operation: with the sulfonate group that is selected from that is contained in the treatment solution, thiol group, sulfenyl, at least a kind of functional group of disulfide group is converted into sulfonic operation, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, the dimer of the wherein said organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses be contain the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses the 1wt% of total amount more than and less than 70wt%; Described treatment solution is applied to the operation of substrate surface; And the base material that is coated with behind the described treatment solution carried out the operation that heat treated is come dry solidification.
11. the manufacture method of antifog property article, wherein, comprise following operation: the operation that treatment solution is applied to substrate surface, in the described treatment solution, there are following monomer and condenses to be diluted in the hydrophilic organic solvent, described monomer is for containing organosilane and/or its hydrolyzate of at least 1 sulphur at non-coupling position, described condenses is described monomeric dimer or polymer, the dimer of the wherein said organosilane that contains at least 1 sulphur at non-coupling position or polymeric condenses be contain the monomer of the organosilane of at least 1 sulphur and/or its hydrolyzate and dimer or polymeric condenses the 1wt% of total amount more than and less than 70wt%; The base material that is coated with behind the described treatment solution is carried out the operation that heat treated is come dry solidification; And at least a kind of functional group that is selected from sulfonate group, thiol group, sulfenyl, disulfide group that non-coupling position is contained is converted into sulfonic operation.
12. manufacture method as any described antifog property article of claim 9 to 11, it is characterized in that, carry out heat treated and come the operation of dry solidification to carry out 1 minute～24 hours 50 ℃～300 ℃ temperature range to being coated with base material behind the described treatment solution.
13. the manufacture method as any described antifog property article of claim 9 to 11 is characterized in that the method that described treatment solution is applied to substrate surface is a dip coating.
14. the manufacture method as any described antifog property article of claim 9 to 11 is characterized in that the method that described treatment solution is applied to substrate surface is a spin-coating method.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003399352 | 2003-11-28 | ||
| JP399352/2003 | 2003-11-28 | ||
| JP009174/2004 | 2004-01-16 | ||
| JP169026/2004 | 2004-06-07 | ||
| JP169025/2004 | 2004-06-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1886477A CN1886477A (en) | 2006-12-27 |
| CN100519681C true CN100519681C (en) | 2009-07-29 |
Family
ID=37584042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800347454A Expired - Fee Related CN100519681C (en) | 2003-11-28 | 2004-11-26 | Anti-fogging treatment liquid, production method therefor, anti-fogging article and production method therefor |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4939492B2 (en) |
| CN (1) | CN100519681C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519971A (en) * | 2016-11-22 | 2017-03-22 | 徐煜 | Hydrophilic siliceous coating solution and coating method |
| CN109096491B (en) * | 2018-07-06 | 2021-06-08 | 福建拓烯新材料科技有限公司 | Preparation method of hydrophilic polyether silicone oil and hydrophilic treatment method of glass |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098429A (en) * | 1993-04-16 | 1995-02-08 | 株式会社乐喜 | Antifogging abrasion resistant coating composition and with the synthetic resin article of its coating |
| JP2000239607A (en) * | 1999-02-17 | 2000-09-05 | Mitsubishi Materials Corp | Coating fluid for forming hydrophilic coating film |
| CN1265408A (en) * | 2000-03-30 | 2000-09-06 | 吉林大学 | Hydrophilic antifogging and antifrosting anti-friction coating and its application |
-
2004
- 2004-11-26 CN CNB2004800347454A patent/CN100519681C/en not_active Expired - Fee Related
-
2008
- 2008-07-16 JP JP2008184654A patent/JP4939492B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098429A (en) * | 1993-04-16 | 1995-02-08 | 株式会社乐喜 | Antifogging abrasion resistant coating composition and with the synthetic resin article of its coating |
| JP2000239607A (en) * | 1999-02-17 | 2000-09-05 | Mitsubishi Materials Corp | Coating fluid for forming hydrophilic coating film |
| CN1265408A (en) * | 2000-03-30 | 2000-09-06 | 吉林大学 | Hydrophilic antifogging and antifrosting anti-friction coating and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008248260A (en) | 2008-10-16 |
| CN1886477A (en) | 2006-12-27 |
| JP4939492B2 (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW517082B (en) | A process for pre-treating the surface of a substrate before the formation of a photocatalytically hydrophilifiable coating, the cleaning agent used therein and the undercoating composition. | |
| EP2188226B1 (en) | Method and fluid compositions for producing optically clear photocatalytic coatings | |
| US8304083B2 (en) | Hydrophilic member and process for producing the same | |
| US20070116968A1 (en) | Hydrophilic coating based on polysilazane | |
| KR20080106510A (en) | Coating system | |
| MXPA06013794A (en) | Hydrophilic compositions, methods for their production, and substrates coated with such compositions. | |
| EP0866101A1 (en) | Photocatalytic coating composition and photocatalyst-bearing structure | |
| JP4840899B2 (en) | Hydrophilic antifouling coating composition, film forming method using the same and use thereof | |
| US20100221513A1 (en) | Self sintering transparent nanoporous thin-films for use in self-cleaning, anti-fogging, anti-corrosion, anti-erosion electronic and optical applications | |
| US4235638A (en) | Sulfonato-organosilanol compounds and aqueous solutions | |
| CN100519681C (en) | Anti-fogging treatment liquid, production method therefor, anti-fogging article and production method therefor | |
| AU8888898A (en) | Surface treatment composition, method of surface treatment, substrate, and article | |
| JP4687009B2 (en) | Anti-fogging article and manufacturing method thereof | |
| JP4778206B2 (en) | Antifogging treatment liquid and method for producing the same | |
| JP2001145982A (en) | Hygroscopic anti-fogging film and method of manufacturing the same | |
| JP2001040294A (en) | Hygroscopic coating composition | |
| US20050137302A1 (en) | Anti-fogging treatment liquid, production method therefor, anti-fogging article and production method therefor | |
| JP4524936B2 (en) | Method for imparting antifogging performance and optical article | |
| KR102250103B1 (en) | Easy-clean coating | |
| WO2005052079A1 (en) | Anti-fogging treating fluid and method for production thereof, anti-fogging article and method for production thereof | |
| JP2000001340A (en) | Production of hydrophilic coating | |
| JP4301061B2 (en) | Anti-fogging article | |
| JP2003057403A (en) | Antifog optical article and method for manufacturing the article | |
| JP2010228958A (en) | Glass member | |
| JPH09301742A (en) | Hydrophilic glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1096703 Country of ref document: HK |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1096703 Country of ref document: HK |
|
| ASS | Succession or assignment of patent right |
Owner name: HOYA OPTICAL MANUFACTURING PHILIPPINES CORP. Free format text: FORMER OWNER: SEIKO EPSON CORP. Effective date: 20130903 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130903 Address after: Philippines province of Cavite Patentee after: SEIKO EPSON CORP. Address before: Tokyo, Japan Patentee before: Seiko Epson Corp. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090729 Termination date: 20181126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |