JPH03256003A - Formation of antireflection layer - Google Patents
Formation of antireflection layerInfo
- Publication number
- JPH03256003A JPH03256003A JP2055766A JP5576690A JPH03256003A JP H03256003 A JPH03256003 A JP H03256003A JP 2055766 A JP2055766 A JP 2055766A JP 5576690 A JP5576690 A JP 5576690A JP H03256003 A JPH03256003 A JP H03256003A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- antireflection
- group
- silicon alkoxide
- antireflection layer
- 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.)
- Pending
Links
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000010410 layer Substances 0.000 claims abstract description 129
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- 239000002356 single layer Substances 0.000 claims abstract description 5
- 230000003068 static effect Effects 0.000 claims abstract description 4
- 125000003277 amino group Chemical group 0.000 claims abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920000620 organic polymer Polymers 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 31
- 239000011248 coating agent Substances 0.000 abstract description 29
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- 229920000307 polymer substrate Polymers 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000003667 anti-reflective effect Effects 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
- 239000010408 film Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 150000004703 alkoxides Chemical class 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 241000272517 Anseriformes Species 0.000 description 1
- 241000501754 Astronotus ocellatus Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 1
- YDVQLGHYJSJBKA-UHFFFAOYSA-N [diacetyloxy(3-chloropropyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)CCCCl YDVQLGHYJSJBKA-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- VLFKGWCMFMCFRM-UHFFFAOYSA-N [diacetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 VLFKGWCMFMCFRM-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 description 1
- FPOSCXQHGOVVPD-UHFFFAOYSA-N chloromethyl(trimethoxy)silane Chemical compound CO[Si](CCl)(OC)OC FPOSCXQHGOVVPD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- OSDDERYBYVDGCN-UHFFFAOYSA-N dimethoxy-(oxiran-2-ylmethoxymethyl)-phenylsilane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)COCC1CO1 OSDDERYBYVDGCN-UHFFFAOYSA-N 0.000 description 1
- OLGFJVSABRBVFE-UHFFFAOYSA-N dimethoxy-bis(oxiran-2-ylmethoxymethyl)silane Chemical compound C1OC1COC[Si](OC)(OC)COCC1CO1 OLGFJVSABRBVFE-UHFFFAOYSA-N 0.000 description 1
- KYZBSTMQNIESBN-UHFFFAOYSA-N dimethoxy-bis[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound C1OC1COCC[Si](OC)(OC)CCOCC1CO1 KYZBSTMQNIESBN-UHFFFAOYSA-N 0.000 description 1
- CAEPKDWOZATEMI-UHFFFAOYSA-N dimethoxy-methyl-(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](C)(OC)COCC1CO1 CAEPKDWOZATEMI-UHFFFAOYSA-N 0.000 description 1
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- YSRDUADNUDFRQJ-UHFFFAOYSA-N dimethoxy-methyl-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](C)(OC)CCCCOCC1CO1 YSRDUADNUDFRQJ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
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- CCXVULQMXGVDGY-UHFFFAOYSA-N ethoxy-tris[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound C1OC1COCC[Si](CCOCC1OC1)(OCC)CCOCC1CO1 CCXVULQMXGVDGY-UHFFFAOYSA-N 0.000 description 1
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- BFMUNUUIHLWYSN-UHFFFAOYSA-N ethyl-dimethoxy-(oxiran-2-ylmethoxymethyl)silane Chemical compound CC[Si](OC)(OC)COCC1CO1 BFMUNUUIHLWYSN-UHFFFAOYSA-N 0.000 description 1
- CSJWBNAOYWNTBI-UHFFFAOYSA-N ethyl-dimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CC[Si](OC)(OC)CCOCC1CO1 CSJWBNAOYWNTBI-UHFFFAOYSA-N 0.000 description 1
- MIGKJZBVYIRTKU-UHFFFAOYSA-N ethyl-dimethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CC[Si](OC)(OC)CCCCOCC1CO1 MIGKJZBVYIRTKU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LQKLWNAGFLCROC-UHFFFAOYSA-N methoxy-dimethyl-(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](C)(C)COCC1CO1 LQKLWNAGFLCROC-UHFFFAOYSA-N 0.000 description 1
- UZVGEBIWBCCMAY-UHFFFAOYSA-N methoxy-dimethyl-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](C)(C)CCOCC1CO1 UZVGEBIWBCCMAY-UHFFFAOYSA-N 0.000 description 1
- PXHGLKUGRYOERP-UHFFFAOYSA-N methoxy-dimethyl-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](C)(C)CCCCOCC1CO1 PXHGLKUGRYOERP-UHFFFAOYSA-N 0.000 description 1
- ZNEANRFOVQWASK-UHFFFAOYSA-N methoxy-tris(oxiran-2-ylmethoxymethyl)silane Chemical compound C1OC1COC[Si](COCC1OC1)(OC)COCC1CO1 ZNEANRFOVQWASK-UHFFFAOYSA-N 0.000 description 1
- KNDSIIWXDUZDJI-UHFFFAOYSA-N methoxy-tris[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound C1OC1COCC[Si](CCOCC1OC1)(OC)CCOCC1CO1 KNDSIIWXDUZDJI-UHFFFAOYSA-N 0.000 description 1
- DRXHEPWCWBIQFJ-UHFFFAOYSA-N methyl(triphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C)OC1=CC=CC=C1 DRXHEPWCWBIQFJ-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- KCTGOQZIKPDZNK-UHFFFAOYSA-N tetrapentyl silicate Chemical compound CCCCCO[Si](OCCCCC)(OCCCCC)OCCCCC KCTGOQZIKPDZNK-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- UCSBCWBHZLSFGC-UHFFFAOYSA-N tributoxysilane Chemical compound CCCCO[SiH](OCCCC)OCCCC UCSBCWBHZLSFGC-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- QMBSEKLOGVDBLD-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-yl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCC1CO1 QMBSEKLOGVDBLD-UHFFFAOYSA-N 0.000 description 1
- RWJUTPORTOUFDY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCOCC1CO1 RWJUTPORTOUFDY-UHFFFAOYSA-N 0.000 description 1
- LCQILSDRWQKXDO-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-yl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCC1CO1 LCQILSDRWQKXDO-UHFFFAOYSA-N 0.000 description 1
- GSUGNQKJVLXBHC-UHFFFAOYSA-N triethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCOCC1CO1 GSUGNQKJVLXBHC-UHFFFAOYSA-N 0.000 description 1
- XQVLEZMEMDWETM-UHFFFAOYSA-N trihydroxy-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](O)(O)O XQVLEZMEMDWETM-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- LFBULLRGNLZJAF-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](OC)(OC)COCC1CO1 LFBULLRGNLZJAF-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- NVHGPBWXDPPIDQ-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-yl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCC1CO1 NVHGPBWXDPPIDQ-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- INFBTIHDWYFQPG-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-yl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCC1CO1 INFBTIHDWYFQPG-UHFFFAOYSA-N 0.000 description 1
- GUKYSRVOOIKHHB-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCOCC1CO1 GUKYSRVOOIKHHB-UHFFFAOYSA-N 0.000 description 1
- PLMGQXSAZYOCBT-UHFFFAOYSA-N tris(1,1,2,2,2-pentafluoroethoxy)-(trifluoromethyl)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)F PLMGQXSAZYOCBT-UHFFFAOYSA-N 0.000 description 1
- CESKYMDZTHKIPO-UHFFFAOYSA-N tris(2-methoxyethoxy)-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound COCCO[Si](OCCOC)(OCCOC)CCCOCC1CO1 CESKYMDZTHKIPO-UHFFFAOYSA-N 0.000 description 1
- OLTVTFUBQOLTND-UHFFFAOYSA-N tris(2-methoxyethoxy)-methylsilane Chemical compound COCCO[Si](C)(OCCOC)OCCOC OLTVTFUBQOLTND-UHFFFAOYSA-N 0.000 description 1
- BZKDNBCUFVUMJG-UHFFFAOYSA-N tris(trifluoromethoxy)-(trifluoromethyl)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)F BZKDNBCUFVUMJG-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は有機高分子基板上に耐汚染性に優れた反射防止
層を形成する方法に関する。有機高分子基板上に反射防
止層を有するものは眼鏡用レンズ、カメラ用レンズ等の
光学用レンズ、デイスプレーの前面板、計器類の前面板
、自動車用窓ガラス等への使用を目的としている。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for forming an antireflection layer with excellent stain resistance on an organic polymer substrate. Products with an antireflection layer on an organic polymer substrate are intended for use in optical lenses such as eyeglass lenses and camera lenses, display front panels, instrument front panels, and automobile window glass. .
（従来の技術）
透明な材料を通して物を見る場合、その材料表面で反射
した光が強いと反射像が明確になってみたい物を良く見
ようとするのに障害となる。このような現象を避けるた
めに屈折率が基材とは異なる物質を基材表面に被覆して
反射防止層とすることが知られている。この反射防止層
としては、単層のものも、２層以上の層から形成される
多層の反射防止層も知られている。(Prior Art) When viewing an object through a transparent material, if the light reflected from the surface of the material is strong, the reflected image becomes clear and becomes an obstacle to seeing the object clearly. In order to avoid such a phenomenon, it is known to coat the surface of a substrate with a substance having a different refractive index from that of the substrate to form an antireflection layer. As this anti-reflection layer, a single-layer anti-reflection layer and a multi-layer anti-reflection layer formed from two or more layers are known.
この反射防止層は金属酸化物や金属弗化物等を真空蒸着
することにより形成されている。This antireflection layer is formed by vacuum-depositing metal oxide, metal fluoride, or the like.
これらには、反射防止層を有する積層体の基板として、
ガラスの他にプラスチック材料も用い得ることが記載さ
れており、このプラスチック材料は軽量、安全性、取扱
い性等の長所を有するものである。These include, as a substrate of a laminate having an antireflection layer,
It is described that a plastic material can be used in addition to glass, and this plastic material has advantages such as light weight, safety, and ease of handling.
特開昭６１−２３６５０１号公報や特開昭５８−４６３
０１号公報には最表層にシリカ微粒子を含ませて表面高
度を付与することが知られている。JP-A-61-236501 and JP-A-58-463
It is known from Japanese Patent No. 01 that fine silica particles are included in the outermost layer to impart a surface height.
耐汚染性を考慮したものとしては特開昭６２−１４８９
０２号公報に無機物からなる単層又は多層の反射防止膜
の表面に末端シラノール有機ポリシロキサンからなる物
質による水に対する接触角が６０”以上である層を形成
させたものが提案されている。Japanese Patent Application Laid-Open No. 1489-1989 takes stain resistance into consideration.
No. 02 proposes a single-layer or multi-layer antireflection film made of an inorganic substance, in which a layer is formed on the surface of a substance made of a terminal silanol organic polysiloxane and has a contact angle with water of 60'' or more.
（発明が解決しようとする課題）
しかし、真空蒸着法によって形成された反射防止膜は主
として金属酸化物や金属弗化物からなり、特開昭６１−
２３６５０１号公報や特開昭５８−４６３０１号公報に
よるものではシリカ微粒子が添加されているのでこれら
は高い表面硬度を有するが、いずれも指紋、手垢、汗等
によって汚染され易く、又、−旦付着した汚れの除去が
困難であるという問題があった。(Problems to be Solved by the Invention) However, antireflection films formed by vacuum evaporation are mainly composed of metal oxides and metal fluorides.
236501 and Japanese Unexamined Patent Publication No. 58-46301 have high surface hardness because they contain fine silica particles, but they are easily contaminated by fingerprints, hand dirt, sweat, etc. There was a problem in that it was difficult to remove the dirt.
又、特開昭６２−１４８９０２号公報に開示された方法
によれば優れた耐汚染性のものが得られるが、汚染防止
層の耐摩耗性が充分とは言えないという問題があり、し
かもこれらの反射防止層は塩水に浸漬するとクラックが
生じるという問題があった。Furthermore, although the method disclosed in JP-A-62-148902 provides excellent stain resistance, there is a problem that the abrasion resistance of the stain prevention layer is not sufficient; The anti-reflection layer had a problem of cracking when immersed in salt water.
（課題を解決するための手段）
本発明者らは、このような状況に鑑み鋭意検討した結果
、反射防止層の最外層の少なくとも表面あるいは反射防
止層の外側に珪素アルコキシドと特定のシラン化合物と
からなる組成物を加水分解、共縮合させてなる層を形成
させると反射防止性能を維持しつつ、汚染防止性を有し
、しかも耐摩耗性、耐塩水性を有するものとすることが
できることを見出し、本発明に到達した。(Means for Solving the Problems) As a result of intensive studies in view of the above situation, the present inventors have discovered that silicon alkoxide and a specific silane compound are added to at least the surface of the outermost layer of the antireflection layer or the outside of the antireflection layer. It has been discovered that by forming a layer by hydrolyzing and co-condensing a composition consisting of the following, it is possible to maintain anti-reflection performance, have anti-staining properties, and also have abrasion resistance and salt water resistance. , arrived at the present invention.
即ち、本発明の要旨は有機高分子基板上に単層又は多層
の反射防止層を形成し、該反射防止層の最表層が珪素ア
ルコキシドと下記一般式（１）で表わされるシラン化合
物とを含む珪素アルコキシド混合物を部分加水分解、共
縮合せしめたものを塗布、加熱硬化してなり、水に対す
る静止接触角が６０°以上であり、屈折率が１．５以下
であるものとすることを特徴とする反射防止層の形成法
にある。That is, the gist of the present invention is to form a single layer or multilayer antireflection layer on an organic polymer substrate, and the outermost layer of the antireflection layer contains silicon alkoxide and a silane compound represented by the following general formula (1). It is characterized by being made by partially hydrolyzing and co-condensing a silicon alkoxide mixture, applying it and curing it by heating, and having a static contact angle with water of 60° or more and a refractive index of 1.5 or less. A method for forming an antireflection layer is provided.
Ｓ Ｉ Ｒ’ａＲ”ｎ （ｏ Ｒ１）４−ｍ−ｎ
（１）（式中、Ｒ１，Ｒ２は各々独立にビニル基、アミ
ノ基、（メタ）アクリロイルオキシ基、メルカプト基、
エポキシ基、塩素及び弗素から選ばれる置換基を有して
いてもよい炭素数１〜６のアルキル基、炭素数１〜６の
アルケニル基又は炭素数６〜１２のアリール基であり、
Ｒ１は炭素数１〜４の炭化水素基を示し、ｍ及びｎは０
１１又は２であって、但し、ｍ ＋ ｎは１又は２を満
足するものである。）本発明において用いられる有機高
分子基板としては、その主要用途が光学用途であること
を勘案すると透明性、屈折率、分散等の光学特性の適切
なものであることが好ましく、このような有機高分子と
してはポリメチルメタクリレート及びその共重合体、ポ
リカーボネート、ジエチレングリコールビスアリルカー
ボネート、ポリスチレン、ＡＳ樹脂、塩化ビニル樹脂、
ポリエチレンテレフタレート等のポリエステル樹脂等を
例示できる。S I R'aR”n (o R1)4-m-n
(1) (wherein R1 and R2 are each independently a vinyl group, an amino group, a (meth)acryloyloxy group, a mercapto group,
an epoxy group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may have a substituent selected from chlorine and fluorine;
R1 represents a hydrocarbon group having 1 to 4 carbon atoms, m and n are 0
11 or 2, provided that m + n satisfies 1 or 2. ) The organic polymer substrate used in the present invention preferably has appropriate optical properties such as transparency, refractive index, and dispersion, considering that its main use is optical use. Examples of polymers include polymethyl methacrylate and its copolymers, polycarbonate, diethylene glycol bisallyl carbonate, polystyrene, AS resin, vinyl chloride resin,
Examples include polyester resins such as polyethylene terephthalate.
本発明における多層の反射防止層が機能を果たすために
は各層の膜厚と屈折率とが一定の条件の範囲内に制御さ
れていることが好ましい。反射防止層の層の数は、多い
ほど広い波長範囲で反射率を下げることが可能になるが
、暦数が多ければ多いほど製造工程が煩雑となり、あま
りに多い工程は実際的でなくなる。好ましい層の数とし
ては２〜８層であり、２〜６層であることがより好まし
い。層の数が３層以上である場合は基板側から最外層に
隣接する層まで順に屈折率が高くなっていることが好ま
しい。In order for the multilayer antireflection layer of the present invention to function properly, it is preferable that the thickness and refractive index of each layer be controlled within a certain range. The greater the number of layers in the antireflection layer, the more it becomes possible to lower the reflectance over a wider wavelength range, but the greater the number of layers, the more complicated the manufacturing process becomes, and too many processes become impractical. The preferred number of layers is 2 to 8 layers, more preferably 2 to 6 layers. When the number of layers is three or more, it is preferable that the refractive index increases in order from the substrate side to the layer adjacent to the outermost layer.
以下、ｎ＋を基板側から１層目の層の屈折率、ｄＩを基
板側から１層目の層の厚さ、ａを正の整数、ｂ、ｃ、ｅ
を正の奇数、えを可視周辺領域内で選ばれる任意の基準
波長（単位ｎｍ）、好ましくは５００〜６００ｎｍの範
囲内の任意の波長として、２〜４層の場合を例に取り各
層の膜厚と屈折率の好ましい条件を示すと、
反射防止層が２層の場合：
１．５５＜ｎｉ ＜２．２５．ｎｒ ｘｄ、４ｂＸ
λ／４．１．３８＜ｎｘ ＜１．５０．ｎ２ ｘｄ２＝
ｆｉｘλ／４の条件を満足することが好ましく、
３層の場合：
１．５５＜ｒｚ ＜１．８５．ｎｉ ｘｄ、ａｖｂ
Ｘλ／４．１．６５＜ｎｉ ＜２．２５． ｎｉ Ｘ
ｄｉ ’＝ａＸλ／４．１．３８＜ｎｓ ＜１．５０．
ｎｍ Ｘ ｄａ ＆、 ＣＸλ／４、ｎｌ ＜ｎｚ
の条件を満足することが好ましく、
４層の場合：
１．３８＜ｎｉ ＜１．６５．ｎｌ ｘｄ、−＝−
ｂＸｌ／４．１．５５＜ ｎ２＜１．８５． ｎｘ
Ｘ ｄ２ ”、 ＣＸλ／４．１．６５＜ｎｓ ＜
２．４０．ｎｓ ｘｄ、４ａＸλ／４．１．３８＜
ｎ４＜１．５０． ｎ−ａ Ｘ ｄ４＆、 ｅ Ｘ
λ／４、ｎｌ ＜ｎｉ ＜ｎｓ
の条件を満足することが好ましい。Hereinafter, n+ is the refractive index of the first layer from the substrate side, dI is the thickness of the first layer from the substrate side, a is a positive integer, b, c, e
is a positive odd number, and e is any reference wavelength (unit: nm) selected within the visible peripheral region, preferably any wavelength within the range of 500 to 600 nm, and the film of each layer, taking the case of 2 to 4 layers as an example. Preferred conditions for thickness and refractive index are as follows: When the antireflection layer has two layers: 1.55<ni<2.25. nr xd, 4bX
λ/4.1.38<nx<1.50. n2 xd2=
It is preferable to satisfy the condition of fixλ/4, and in the case of three layers: 1.55<rz<1.85. ni xd, avb
Xλ/4.1.65<ni<2.25. ni X
di'=aXλ/4.1.38<ns<1.50.
It is preferable to satisfy the following conditions: nm nl xd, -=-
bXl/4.1.55<n2<1.85. nx
X d2 ”, CXλ/4.1.65<ns<
2.40. ns xd, 4aXλ/4.1.38<
n4<1.50. n-a X d4&, e X
It is preferable to satisfy the following conditions: λ/4, nl < ni < ns.
なお、ここで「尋」は±１５％の範囲内、好ましくは±
１０％の範囲内にあることを示す。In addition, "hiro" here is within the range of ±15%, preferably ±
It shows that it is within the range of 10%.
このような構成の反射防止層において最表層の組成が珪
素アルコキシドと上記一般式（１）で表わされるシラン
化合物とを含む珪素アルコキシド混合物を部分加水分解
、共縮合せしめたものを塗布、加熱硬化してなり、水に
対する静止接触角が６０°以上、好ましくは７５°以上
であり、屈折率が１．５以下であるものである必要があ
る。接触角が６０°未満であると耐汚染性が不充分とな
り、屈折率が１．５より高いと反射防止硬化が不充分と
なる。In the anti-reflection layer having such a structure, the outermost layer is partially hydrolyzed and co-condensed with a silicon alkoxide mixture containing a silicon alkoxide and a silane compound represented by the above general formula (1), and then cured by heating. Therefore, the static contact angle with water must be 60° or more, preferably 75° or more, and the refractive index must be 1.5 or less. If the contact angle is less than 60°, stain resistance will be insufficient, and if the refractive index is higher than 1.5, antireflection curing will be insufficient.
珪素アルコキシドのアルコキシドとしては炭素数１〜５
のアルコキシドであることが好ましく、この範囲内であ
れば単一のアルコキシドであっても複数種のアルコキシ
ドの混合物であってもよい。The alkoxide of silicon alkoxide has 1 to 5 carbon atoms.
The alkoxide is preferably an alkoxide, and within this range, it may be a single alkoxide or a mixture of a plurality of alkoxides.
炭素数６以上のアルコキシドを用いた珪素アルコキシド
を用いると水との相溶性が不充分でかつ粘度も高くなる
傾向にあり、外観の優れた薄膜が得られ難くなる傾向に
ある。このような珪素アルコキシドの具体例としてテト
ラメチルオルソシリケート、テトラエチルオルソシリケ
ート、テトラミープロピルオルソシリケート、テトラｎ
−ブチルオルソシリケート、テトラＳ−ブチルオルソシ
リケート、テトラｔ−ブチルオルソシリケート、テトラ
アミルオルソシリケート等を例示できる。If a silicon alkoxide containing an alkoxide having 6 or more carbon atoms is used, the compatibility with water tends to be insufficient and the viscosity tends to increase, making it difficult to obtain a thin film with an excellent appearance. Specific examples of such silicon alkoxides include tetramethyl orthosilicate, tetraethyl orthosilicate, tetramypropyl orthosilicate, and tetra-n.
Examples include -butyl orthosilicate, tetra S-butyl orthosilicate, tetra t-butyl orthosilicate, and tetraamyl orthosilicate.
式（１）で示されるシラン化合物としてはメチルトリメ
トキシシラン、エチルトリメトキシシラン等のアルキル
トリメトキシシラン、メチルトリエトキシシラン、エチ
ルトリエトキシシラン等のアルキルトリエトキシシラン
、メチルトリブトキシシラン等のアルキルトリブトキシ
シラン、メチルトリアセトキシシラン等のアルキルトリ
アセトキシシラン、メチルトリ（メトキシエトキシ）シ
ラン、ビニルトリメトキシシラン、ビニルトリエトキシ
シラン、ビニルトリアセトキシシラン、ビニルトＩ）、
（メトキシエトキシ）シラン、フェニルトリメトキシシ
ラン、フェニルトリエトキシシラン、フェニルトリアセ
トキシシラン、γ−クロロプロピルトリメトキシシラン
、γ−クロロプロピルトリエトキシシラン、γ−クロロ
プロピルトリアセトキシシラン、３．３．３−トリフル
オロプロピルトリメトキシシラン、２．２．２−トリフ
ルオロエチルトリメトキシシラン、パーフルオロメチル
トリメトキシシラン、パーフルオロメチルトリエトキシ
シラン等のパーフルオロアルキル基を有するトリアルコ
キシシラン、γ−メタクリロイルオキシプロピルトリメ
トキシシラン、γ−アミノプロピルトリメトキシシラン
、γ−アミノプロピルトリエトキシシラン、γ−メルカ
プトプロピルトリメトキシシラン、γ−メルカプトプロ
ピルトリエトキシシラン、Ｎ−β−（アミノエチル）−
丁−アミノプロピルトリメトキシシラン、β−シアノエ
チルトリエトキシシラン、メチルトリフエノキシシラン
、クロロメチルトリメトキシシラン、クロロメチルトリ
エトキシシラン、ジメチルジメトキシシラン、ジメチル
ジェトキシシラン、フェニルメチルジメトキシシラン、
−フェニルメチルジェトキシシラン、γ−クロロプロピ
ルメチルジメトキシシラン、γ−クロロプロピルメチル
ジェトキシシラン、ジメチルジアセトキシシラン、γ−
メタクリロイルオキシプロピルメチルジメトキシシラン
、γ−メタクリロイルオキシプロピルメチルジェトキシ
シラン、γ−メルカプトプロピルメチルジメトキシシラ
ン、５−メルカプトプロピルメチルジェトキシシラン、
γ−アミノプロピルメチルジメトキシシラン、γ−アミ
ノプロピルメチルジェトキシシラン、メチルビニルジメ
トキシシラン、メチルビニルジェトキシシラン、グリシ
ジルオキシメチルトリメトキシシラン、グリシジルオキ
シメチルトリエトキシシラン、β−グリシジルオキシエ
チルトリメトキシシラン、β−グリシジルオキシエチル
トリエトキシシラン、γ−グリシジルオキシプロビルト
リメトキシシラン、γ−グリシジルオキシブロビルトリ
エトキシシラン、γ−グリシジルオキシブロピルトリ（
メトキシエトキシ）シラン、γ−グリシジルオキシブロ
ビルトリアセトキシシラン、δ−グリシジルオキシブチ
ルトリメトキシシラン、δ−グリシジルオキシブチルト
リエトキシシラン、グリシジルオキシメチル（メチル）
ジメトキシシラン、グリシジルオキシメチル（メチル）
ジェトキシシラン、グリシジルオキシメチル（エチル）
ジメトキシシラン、グリシジルオキシメチル（フェニル
）ジメトキシシラン、グリシジルオキシメチル（ビニル
）ジメトキシシラン、グリシジルオキシメチル（ジメチ
ル）メトキシシラン、β−グリシジルオキシエチル（メ
チル）ジメトキシシラン、β−グリシジルオキシエチル
（エチル）ジメトキシシラン、β−グリシジルオキシエ
チル（ジメチル）メトキシシラン、γ−グリシジルオキ
シブロビル（メチル）ジメトキシシラン、γ−グリシジ
ルオキシブロビル（エチル）ジメトキシシラン、γ−グ
リシジルオキシブロビル（ジメチル）メトキシシラン、
δ−グリシジルオキシブチル（メチル）ジメトキシシラ
ン、δ−グリシジルオキシブチル（エチル）ジメトキシ
シラン、δ−グリシジルオキシブチル（ジメチル）メト
キシシラン、ビス（グリシジルオキシメチル）ジメトキ
シシラン、ビス（グリシジルオキシメチル）ジェトキシ
シラン、ビス（β−グリシジルオキシエチル）ジメトキ
シシラン、ビス（γ−グリシジルオキシプロビル）ジェ
トキシシラン、トリス（グリシジルオキシメチル）メト
キシシラン、トリス（グリシジルオキシメチル）エトキ
シシラン、トリス（β−グリシジルオキシエチル）メト
キシシラン、トリス（β−グリシジルオキシエチル）エ
トキシシラン、トリス（γ−グリシジルオキシブロビル
）メトキシシラン、トリス（γ−グリシジルオキシプロ
ビル）エトキシシラン、グリシジルメチルトリメトキシ
シラン、グリシジルメチルトリエトキシシラン、β−グ
リシジルエチルトリメトキシシラン、β−グリシジルエ
チルトリエトキシシラン、γ−グリシジルプロビルトリ
メトキシシラン、γ−グリシジルプロビルトリエトキシ
シラン、γグリシジルプロビルトリ（メトキシエトキシ
）シラン、γ−グリシジルプロビルトリアセトキシシラ
ン、３．４−エポキシシクロヘキシルメチルトリメトキ
シシラン、３．４−エポキシシクロヘキシルメチルトリ
エトキシシラン、３．４−エポキシシクロヘキシルエチ
ルトリメトキシシラン、３．４−エポキシシクロヘキシ
ルプロピルトリメトキシシラン、３．４−エポキシシク
ロへキシルブチルトリメトキシシラン等を例示できる。Examples of the silane compound represented by formula (1) include alkyltrimethoxysilanes such as methyltrimethoxysilane and ethyltrimethoxysilane, alkyltriethoxysilanes such as methyltriethoxysilane and ethyltriethoxysilane, and alkyltriethoxysilanes such as methyltributoxysilane. Alkyltriacetoxysilanes such as tributoxysilane and methyltriacetoxysilane, methyltri(methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinylt I),
(methoxyethoxy)silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3.3.3 - Trialkoxysilane having a perfluoroalkyl group such as trifluoropropyltrimethoxysilane, 2.2.2-trifluoroethyltrimethoxysilane, perfluoromethyltrimethoxysilane, perfluoromethyltriethoxysilane, γ-methacryloyloxy Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β-(aminoethyl)-
D-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, phenylmethyldimethoxysilane,
-Phenylmethyljethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-
Methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 5-mercaptopropylmethyljethoxysilane,
γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, glycidyloxymethyltrimethoxysilane, glycidyloxymethyltriethoxysilane, β-glycidyloxyethyltrimethoxysilane , β-glycidyloxyethyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxybrobyltriethoxysilane, γ-glycidyloxypropyltri(
methoxyethoxy)silane, γ-glycidyloxybrobyltriacetoxysilane, δ-glycidyloxybutyltrimethoxysilane, δ-glycidyloxybutyltriethoxysilane, glycidyloxymethyl (methyl)
Dimethoxysilane, glycidyloxymethyl (methyl)
Jetoxysilane, glycidyloxymethyl (ethyl)
Dimethoxysilane, glycidyloxymethyl (phenyl) dimethoxysilane, glycidyloxymethyl (vinyl) dimethoxysilane, glycidyloxymethyl (dimethyl) methoxysilane, β-glycidyloxyethyl (methyl) dimethoxysilane, β-glycidyloxyethyl (ethyl) dimethoxy Silane, β-glycidyloxyethyl(dimethyl)methoxysilane, γ-glycidyloxybrobyl(methyl)dimethoxysilane, γ-glycidyloxybrobyl(ethyl)dimethoxysilane, γ-glycidyloxybrobyl(dimethyl)methoxysilane,
δ-glycidyloxybutyl(methyl)dimethoxysilane, δ-glycidyloxybutyl(ethyl)dimethoxysilane, δ-glycidyloxybutyl(dimethyl)methoxysilane, bis(glycidyloxymethyl)dimethoxysilane, bis(glycidyloxymethyl)jethoxy Silane, bis(β-glycidyloxyethyl)dimethoxysilane, bis(γ-glycidyloxypropyl)jethoxysilane, tris(glycidyloxymethyl)methoxysilane, tris(glycidyloxymethyl)ethoxysilane, tris(β-glycidyloxy ethyl)methoxysilane, tris(β-glycidyloxyethyl)ethoxysilane, tris(γ-glycidyloxybrobyl)methoxysilane, tris(γ-glycidyloxyprobyl)ethoxysilane, glycidylmethyltrimethoxysilane, glycidylmethyltriethoxy Silane, β-glycidylethyltrimethoxysilane, β-glycidylethyltriethoxysilane, γ-glycidylprobyltrimethoxysilane, γ-glycidylprobyltriethoxysilane, γ-glycidylprobyltri(methoxyethoxy)silane, γ-glycidyl Probyltriacetoxysilane, 3.4-epoxycyclohexylmethyltrimethoxysilane, 3.4-epoxycyclohexylmethyltriethoxysilane, 3.4-epoxycyclohexylethyltrimethoxysilane, 3.4-epoxycyclohexylpropyltrimethoxysilane, Examples include 3.4-epoxycyclohexylbutyltrimethoxysilane.
最表層の組成物中の珪素アルコキシドと式（１）で示さ
れるシラン化合物のモル比は珪素アルコキシド１モルあ
たり０．００５〜０．５モルであることが好ましい。式
（１）で示されるシラン化合物のモル比が上記上限を越
えると耐擦傷性、耐候性及び透明性が不良となる傾向に
あり、上記下限以下であると汚染防止効果が不充分とな
る傾向にある。The molar ratio of the silicon alkoxide and the silane compound represented by formula (1) in the composition of the outermost layer is preferably 0.005 to 0.5 mol per 1 mol of silicon alkoxide. When the molar ratio of the silane compound represented by formula (1) exceeds the above upper limit, scratch resistance, weather resistance and transparency tend to be poor, and when it is below the above lower limit, the stain prevention effect tends to be insufficient. It is in.
反射防止層の最表層の膜厚はその光学的膜厚が対象とす
る光波長の１／４あるいはその奇数倍の前後１５％程度
であることが好ましく、同前後ｌＯ％程度であることが
より好ましい。The optical thickness of the outermost layer of the antireflection layer is preferably about 15% around 1/4 of the target light wavelength or an odd multiple thereof, and more preferably about 10% around the same wavelength. preferable.
本発明における反射防止層の最表層の形成にあたっては
、上述の珪素アルコキシドと一般式（１）で示されるシ
ラン化合物とを溶媒に溶解し、水と酸とを添加して部分
加水分解・縮合させたものを塗布し、加熱硬化させるこ
とにより形成させる。In forming the outermost layer of the antireflection layer in the present invention, the above-mentioned silicon alkoxide and the silane compound represented by the general formula (1) are dissolved in a solvent, and water and an acid are added to cause partial hydrolysis and condensation. It is formed by applying a coating material and curing it by heating.
この組成物に添加する水と酸とは上記組成物を加水分解
重縮合させるために添加するもので、水の添加量は水と
酸とを添加してなる混合物中３〜ｌＯ重量％であること
が好ましく、酸の添加量は０．３〜１重量％であること
が好ましい。この酸としては有機酸であっても無機酸で
あってもよく、無機酸としては塩酸、硫酸、硝酸、炭酸
等を例示でき、有機酸としては酢酸、乳酸等を例示でき
る。酸や水の添加量が上記の下限より少ない場合は形成
される層が不透明になり易く、水の量が上記上限より多
いとこの溶液を基板に塗布したときにはじきが生じて均
質な厚みの塗膜が得難くなる傾向にあり、酸の量が上記
上限より多いとこの層がもろくなる傾向にある。The water and acid added to this composition are added to cause hydrolytic polycondensation of the above composition, and the amount of water added is 3 to 10% by weight of the mixture formed by adding water and acid. The amount of acid added is preferably 0.3 to 1% by weight. This acid may be an organic acid or an inorganic acid; examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, etc., and examples of the organic acid include acetic acid, lactic acid, etc. If the amount of acid or water added is less than the above lower limit, the layer formed tends to become opaque, while if the amount of water is more than the above upper limit, flutters occur when the solution is applied to the substrate, making it difficult to form a uniformly thick coating. It tends to be difficult to obtain a film, and if the amount of acid is more than the above upper limit, this layer tends to become brittle.
ここで用いられる溶媒としてはメタノール、エタノール
、プロパツール、ブタノール等のアルコール；ｎ−ペン
タン、ｎ−ヘキサン、ｎ−へブタン、ｎ−オクタン等の
炭水化物；アセトン、メチルアセトン、メチルエチルケ
トン等のケトン類；エチルエーテル、イソプロピルエー
テル、ｎ−ブチルエーテル等のエーテル類；酢酸エチル
、酢酸ブチル等のエステル類；メチルセロソルブ、エチ
ルセロソルブ、ブチルセロソルブ等のセロソルブ類；塩
化メチル、塩化メチレン、クロロホルム、１，１．１−
トリクロロエタン等のハロゲン化炭化水素；蟻酸、酢酸
、プロピオン酸等のカルボン酸類；トルエン、キシレン
等の芳香族化合物を用いることができる。Solvents used here include alcohols such as methanol, ethanol, propatool, and butanol; carbohydrates such as n-pentane, n-hexane, n-hebutane, and n-octane; ketones such as acetone, methylacetone, and methyl ethyl ketone; Ethers such as ethyl ether, isopropyl ether and n-butyl ether; Esters such as ethyl acetate and butyl acetate; Cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Methyl chloride, methylene chloride, chloroform, 1,1.1-
Halogenated hydrocarbons such as trichloroethane; carboxylic acids such as formic acid, acetic acid, and propionic acid; and aromatic compounds such as toluene and xylene can be used.
これらの中ではメタノール、エタノール、プロパツール
、ブタノール等の低級アルコール、メチルセロソルブ、
エチルセロソルブ、ブチルセロソルブ、蟻酸、酢酸、プ
ロピオン酸、トルエン、キシレン、酢酸エチル、酢酸ブ
チル類はこれらの混合物を好ましいものとして挙げるこ
とができる。Among these, lower alcohols such as methanol, ethanol, propatool, butanol, methyl cellosolve,
Preferred examples include ethyl cellosolve, butyl cellosolve, formic acid, acetic acid, propionic acid, toluene, xylene, ethyl acetate, and butyl acetate.
この溶液の粘度は塗布のし易さ、塗布された塗膜の均質
性の観点から２０センチポアズ以下であることが好まし
く、１０センチポアズ以下であることがより好ましい。The viscosity of this solution is preferably 20 centipoise or less, more preferably 10 centipoise or less, from the viewpoint of ease of application and homogeneity of the applied coating film.
この溶液には必要に応じてキレート剤、界面活性剤、染
料等を添加してもよい。A chelating agent, surfactant, dye, etc. may be added to this solution as necessary.
上述の基板上への塗布後の加水分解・共縮合は、塗布後
に溶剤を蒸発させ、次いで焼成あるいは活性エネルギー
照射による加熱硬化により行われる。The above-mentioned hydrolysis/cocondensation after coating on the substrate is performed by evaporating the solvent after coating, and then heating and curing by baking or irradiation with active energy.
焼成の温度条件は６０℃以上、かつ基板の熱変形温度よ
り低い温度であることが好ましい。The firing temperature condition is preferably 60° C. or higher and lower than the thermal deformation temperature of the substrate.
反射防止層の最表層以外の層としては前述の屈折率の範
囲になるように適宜層形成物質を選択すればよく、中・
高屈折率の層を形成するのに適した物質としては、Ｔｉ
０ｇ、 ＺｒＯ＊、 Ｃｅ０ｚ、 ＩｎｇＯｓ、 Ｈｆ
Ｏ＊。For layers other than the outermost layer of the antireflection layer, layer forming substances may be appropriately selected so that the refractive index falls within the above-mentioned range.
A suitable material for forming a layer with a high refractive index is Ti.
0g, ZrO*, Ce0z, IngOs, Hf
O*.
Ｙ＊Ｏｓ、 Ｐｒ Ｓｏ ｌ ｌ 、 Ｔａｘｅｓ、
ＮｄＯｓ、 Ｓｂ＊Ｏｘ、 Ｓｎｏｗ、 ＺｎＯ，Ａｌ
□ｏｓ。Y*Os, Pr Sol l, Taxes,
NdOs, Sb*Ox, Snow, ZnO, Al
□os.
Ｂ１１０ｉ 、 Ｅｕ１Ｏｓ 、 Ｌａｇ’ｓ 、 Ｃ
ｅＦｓ、 Ｍｏ５ｓ、 ＭｇＯ，Ｓｗａｎｓ 、 ５ｃ
２ｎｓ ＊ＷＯ，Ｙｂ１Ｏｓ、 ＬａＦｓ、 ＬｉＦ、
ＮｄＦｓ、 ＰｂＦ＊、 ＳｍＦｍ等を挙げることが
でき、低屈折率の層を形成するのに適した物質としては
ＡＩＦｓ、 ＢａＦａ、 ＣａＦｓ、 ＣａＦ、 Ｌａ
Ｆｓ、 ＬｉＦ。B110i, Eu1Os, Lag's, C
eFs, Mo5s, MgO, Swans, 5c
2ns *WO, Yb1Os, LaFs, LiF,
NdFs, PbF*, SmFm, etc. can be mentioned, and materials suitable for forming a low refractive index layer include AIFs, BaFa, CaFs, CaF, La.
Fs, LiF.
ＭｇＦｉ、 Ｎａ５Ａ１ｓＦｓ、 ＮａＪｌｓＦ ｌ
１１． ＮａＦ、 ＳｒＦ＊、 ５ｔｏ２等を挙げるこ
とができる。MgFi, Na5A1sFs, NaJlsFl
11. Examples include NaF, SrF*, 5to2, etc.
又、これらの物質は混合して用いることもできる。Moreover, these substances can also be used in combination.
本発明の方法においては、最表層以外の層も適切な金属
アルコキシド又は金属アルコキシド混合物を部分加水分
解：縮合したものを塗布、加熱硬化したものであっても
よい。In the method of the present invention, layers other than the outermost layer may also be formed by partially hydrolyzing and condensing an appropriate metal alkoxide or metal alkoxide mixture, and then applying and curing the layer by heating.
金属アルコキシドのアルコキシドとしては前述の珪素ア
ルコキシドのアルコキシドについて述べたと同様のもの
が好ましく、溶剤の種類、酸、水の量、溶液に添加でき
るその他の成分についても上述の最表層について述べた
ものがそのまま準用できる。金属アルコキシド溶液中の
金属アルコキシド濃度は５〜４０重量％であることが好
ましい。The alkoxide of the metal alkoxide is preferably the same as that described above for the alkoxide of silicon alkoxide, and the type of solvent, acid, amount of water, and other components that can be added to the solution are also the same as those described for the outermost layer above. Can be applied mutatis mutandis. The metal alkoxide concentration in the metal alkoxide solution is preferably 5 to 40% by weight.
この溶液の粘度も２０センチポアズ以下であることが好
ましく、１０センチポアズ以下とすることがより好まし
い。The viscosity of this solution is also preferably 20 centipoise or less, more preferably 10 centipoise or less.
又、高分子基板と反射防止層の熱膨張係数の差に由来す
るクラックの発生を防止するために基板と反射防止層の
間にアンダーコート層を設けてもよい。アンダーコート
層としては反射防止層の中量も基板に近い層の熱膨張係
数と基板の熱膨張係数の間の熱膨張係数を持つものが用
いられるが、このようなものとして反射防止層最表層の
形成に用いた珪素アルコキシドとコロイダルシリカを含
む溶液を部分加水分解・縮合させたものを塗布、加熱硬
化させたもの、上述の珪素アルコキシドと金属アルコキ
シドを部分加水分解・共縮合したものを塗布、加熱硬化
させたもの等を例示できる。Furthermore, an undercoat layer may be provided between the substrate and the antireflection layer in order to prevent cracks from occurring due to the difference in thermal expansion coefficient between the polymer substrate and the antireflection layer. As an undercoat layer, a layer with a thermal expansion coefficient between the thermal expansion coefficient of the layer close to the substrate and that of the substrate is used. A solution containing silicon alkoxide and colloidal silica used for the formation of the silicon alkoxide and colloidal silica was applied by partial hydrolysis and condensation, and then cured by heating. Examples include those cured by heating.
コロイダルシリカの粒径としては１００〜１０ｏＯ人で
あることが好ましく、アンダーコート用溶液に用いる溶
剤は最表層形成に用いた溶剤と同様のものを用いること
ができる。The particle size of the colloidal silica is preferably 100 to 100 μm, and the solvent used in the undercoat solution can be the same as the solvent used to form the outermost layer.
これらの加水分解物からなる層の厚みのコントロールは
塗布法が浸漬法であれば引き上げ速度で、スピンコード
法であれば回転数等を調節することにより行うことがで
きる。The thickness of the layer made of these hydrolyzates can be controlled by adjusting the pulling speed if the coating method is a dipping method, or by adjusting the rotation speed, etc. if the coating method is a spin cord method.
（実施例） 以下に実施例を用いて本発明を説明する。(Example) The present invention will be explained below using Examples.
なお、実施例において下記の各評価項目は下記に従って
評価した。In addition, in the examples, the following evaluation items were evaluated according to the following.
接触角：接触角計（協和科学社製）を用い、液滴法で測
定した。（測定温度２４℃）
耐汚染性：反射防止層の最表層の上に水道水２ｍｌを滴
下し、室温で２４時間放置した後、乾燥した布でこれを
拭き取り、水垢が実質的に除去可能であった場合を良好
、困難であった場合を不良とした。Contact angle: Measured by droplet method using a contact angle meter (manufactured by Kyowa Kagakusha). (Measurement temperature: 24°C) Stain resistance: Drop 2 ml of tap water onto the outermost layer of the anti-reflection layer, leave it at room temperature for 24 hours, then wipe it with a dry cloth to ensure that water scale can be virtually removed. If it was difficult, it was judged as good, and if it was difficult, it was judged as poor.
密着性二反射防止層をカミソリでクロスカットして１
ｍｍＸ １ ｍｍの升目を１００個作り、その上に市販
のセロハン粘着テープにチバン４０５）を充分密着させ
た後、これを剥離することを３回繰り返し、剥離しない
で残った反射防止層の升目の数を密着性の尺度（％）と
した。Cross-cut the adhesion anti-reflection layer with a razor.
After making 100 squares of mm x 1 mm, adhering Chiban 405) to commercially available cellophane adhesive tape and peeling it off three times, the remaining squares of the anti-reflection layer were removed. The number was taken as a measure (%) of adhesion.
膜厚：エリプソメーター（溝尻光学工業所製）を用いて
測定した。Film thickness: Measured using an ellipsometer (manufactured by Mizojiri Optical Co., Ltd.).
粘度二回転粘度計（東京計器社製）を用いて測定した。Viscosity was measured using a two-rotation viscometer (manufactured by Tokyo Keiki Co., Ltd.).
クラック二反射防止層におけるクラックの存在の有無を
光学顕微鏡（倍率４００倍）で観察した。Cracks The presence or absence of cracks in the antireflection layer was observed using an optical microscope (400x magnification).
全光線透過率： ＪＩＳ Ｋ ７１０５に従って測定し
た。Total light transmittance: Measured according to JIS K 7105.
耐塩水性二反射防止層を形成した基板を２４℃で５％の
塩水に２４時間浸漬した後の外観を観察し、クラックの
有無を調べた。The substrate on which the salt water-resistant anti-reflection layer was formed was immersed in 5% salt water at 24° C. for 24 hours, and then its appearance was observed and the presence or absence of cracks was examined.
耐摩耗性：反射防止層を有する板をビロード布（４０６
枚重ね、加重０．２８ｋｇ／ｃｍ”、３０往復／分、５
０００回）で摩擦し、傷の発生の有無を調べた。Abrasion resistance: The plate with anti-reflection layer is coated with velvet cloth (406
Layered, load 0.28kg/cm”, 30 round trips/min, 5
000 times), and the presence or absence of scratches was examined.
参考例１
１０℃でγ−グリシドキシプロビルトリメトキシシラン
８．５ｇに０．０５規定塩酸水溶液１．３ｇを滴下混合
し、滴下終了後、室温で更に１時間撹拌を行って、シラ
ン部分加水分解物を得た。Reference Example 1 1.3 g of 0.05N hydrochloric acid aqueous solution was added dropwise to 8.5 g of γ-glycidoxypropyl trimethoxysilane at 10°C, and after the dropwise addition was completed, stirring was further performed at room temperature for 1 hour to separate the silane portion. A hydrolyzate was obtained.
このシラン部分加水分解物にイソプロピルアルコールに
分散した平均粒径１００〜２００人のコロイダルシリカ
（触媒化成製オスカル１４３２、固形分３２％）３０ｇ
とイソプロピルアルコール４０ｇを添加し、１時間撹拌
混合してアンダーコート履用コーティング溶液を得た。30 g of colloidal silica (Oscar 1432 manufactured by Catalyst Kasei Co., Ltd., solid content 32%) with an average particle size of 100 to 200 particles dispersed in isopropyl alcohol in this silane partial hydrolyzate.
and 40 g of isopropyl alcohol were added and mixed with stirring for 1 hour to obtain an undercoat shoe coating solution.
溶液の粘度は４．７センチボアズであった。The viscosity of the solution was 4.7 centiboads.
参考例２
参考例１と同様にしてγ−グリシドキシプロビルトリメ
トキシシランからのシラン部分加水分解物を得、別途、
テトライソブロビルオルソチタネー）−７，０ｇとアセ
チルアセトン５．０ｇとを混合してチタンキレート化合
物を調製し、この１０．４ｇに上記のシラン部分加水分
解物２．６ｇとイソプロピルアルコール６０．０ｇとを
滴下混合し、室温で１０分間撹拌した後、更に水０．６
ｇ、塩酸０．１ｇ及びイソプロピルアルコール１０．０
ｇを加えて室温で３０分間撹拌してアンダーコート履用
コーティング溶液を得た。Reference Example 2 A silane partial hydrolyzate from γ-glycidoxypropyltrimethoxysilane was obtained in the same manner as in Reference Example 1, and separately,
A titanium chelate compound was prepared by mixing 7.0 g of tetraisobrovir orthotitane) and 5.0 g of acetylacetone, and 2.6 g of the above silane partial hydrolyzate and 60.0 g of isopropyl alcohol were added to this 10.4 g. was mixed dropwise, stirred at room temperature for 10 minutes, and then added with 0.6 ml of water.
g, hydrochloric acid 0.1 g and isopropyl alcohol 10.0
g and stirred at room temperature for 30 minutes to obtain an undercoat shoe coating solution.
溶液の粘度は２．７センチボアズであった。The viscosity of the solution was 2.7 centiboads.
参考例３
テトラエチルオルソシリケート２０．８ｇ、テトライソ
プロピルオルソチタネート１８．０ｇとエチルアルコー
ル１５０ｍ１の混合溶液に水４．８ｇ、塩酸１ｇ及びエ
チルアルコール１２５ｍ１を添加し、室温で１時間撹拌
混合してＳｉＯ□／ＴｉＯ□層用コーティング溶用コー
ティング溶液の粘度は１．９センチポアズであった。Reference Example 3 4.8 g of water, 1 g of hydrochloric acid, and 125 ml of ethyl alcohol were added to a mixed solution of 20.8 g of tetraethyl orthosilicate, 18.0 g of tetraisopropyl orthotitanate, and 150 ml of ethyl alcohol, and the mixture was stirred and mixed at room temperature for 1 hour to form SiO□ The viscosity of the coating solution for the /TiO□ layer was 1.9 centipoise.
参考例４
テトライソプロピルオルソチタネート１４．２ｇ、イソ
プロピルアルコール２５＋ｎｌ及びｎ−ブチルアルコー
ル２５ｍ１の混合溶液に２規定の塩酸水溶液１．３５ｇ
、イソプロピルアルコール２５ｍ１及びｎ−ブチルアル
コール２５ｍ１の混合物を添加し、室温で１時間撹拌混
合してＴｉ０ｇ層用コーティング溶液を得た。この溶液
の粘度は３．５センチポアズであった。Reference Example 4 1.35 g of 2N hydrochloric acid aqueous solution was added to a mixed solution of 14.2 g of tetraisopropylorthotitanate, 25+nl of isopropyl alcohol, and 25ml of n-butyl alcohol.
A mixture of 25 ml of isopropyl alcohol and 25 ml of n-butyl alcohol was added thereto, and the mixture was stirred and mixed at room temperature for 1 hour to obtain a coating solution for a Ti0g layer. The viscosity of this solution was 3.5 centipoise.
参考例５
テトラエチルオルソシリケート１９．８ｇ 、オクチル
トリメトキシシラン（ＮＵＣシリコーン（Ｙ−９１８７
））１．０ｇ及びイソプロピルアルコール６２．５ｍｌ
の混合溶液に水９ｇ、塩酸１ｇ及びイソプロピルアルコ
ール６２、５０１１の混合物を添加し、室温で１時間撹
拌混合して最表層用コーティング溶液を得た。この溶液
の粘度は２．８センチポアズであった。Reference example 5 19.8 g of tetraethyl orthosilicate, octyltrimethoxysilane (NUC silicone (Y-9187)
)) 1.0g and 62.5ml of isopropyl alcohol
A mixture of 9 g of water, 1 g of hydrochloric acid, and isopropyl alcohol 62,5011 was added to the mixed solution, and the mixture was stirred and mixed at room temperature for 1 hour to obtain a coating solution for the outermost layer. The viscosity of this solution was 2.8 centipoise.
参考例６
テトラエチルオルソシリケートＩＬ７ｇ 、オクチルト
リメトキシシラン（ＮＵＣシリコーン（Ｙ−９１８７）
）２．１ｇ及びイソプロピルアルコール６２．５ｍｌの
混合溶液に水９ｇ、塩酸１ｇ及びイソプロピルアルコー
ル６２、５ｍｌの混合物を添加し、室温で１時間撹拌混
合して最表層用コーティング溶液を得た。この溶液の粘
度は２．８センチポアズであった。Reference example 6 Tetraethyl orthosilicate IL 7g, octyltrimethoxysilane (NUC silicone (Y-9187)
) and 62.5 ml of isopropyl alcohol was added with a mixture of 9 g of water, 1 g of hydrochloric acid, and 62.5 ml of isopropyl alcohol, and the mixture was stirred and mixed at room temperature for 1 hour to obtain a coating solution for the outermost layer. The viscosity of this solution was 2.8 centipoise.
参考例７
テトラエチルオルソシリケートの量を２０．７ｇ １オ
クチルトリメトキシシランの量をｏ、 Ｉｇとした以外
は参考例５と同様にして最表層用コーティング溶液を得
た。この溶液の粘度は２．８センチポアズであった。Reference Example 7 A coating solution for the outermost layer was obtained in the same manner as in Reference Example 5, except that the amount of tetraethyl orthosilicate was 20.7 g and the amount of 1-octyltrimethoxysilane was o and Ig. The viscosity of this solution was 2.8 centipoise.
参考例８
テトラエチルオルソシリケート２０．８ｇとイソプロピ
ルアルコール６２．５ｍｌの混合溶液に水９ｇ、塩酸Ｉ
ｇ及びイソプロピルアルコール６２．５ｍｌの混合物を
添加し、室温で１時間撹拌混合して比較例用最表層用コ
ーティング溶液を得た。この溶液の粘度は２．８センチ
ポアズであった。Reference Example 8 A mixed solution of 20.8 g of tetraethyl orthosilicate and 62.5 ml of isopropyl alcohol, 9 g of water, and hydrochloric acid I
A mixture of g and 62.5 ml of isopropyl alcohol was added thereto, and the mixture was stirred and mixed at room temperature for 1 hour to obtain a comparative example outermost layer coating solution. The viscosity of this solution was 2.8 centipoise.
実施例１
ポリメチルメタクリレートＡＲ板（三菱レイヨン株製、
屈折率１．４９）に参考例１で合成したアンダーコート
用溶液を浸漬法で引き上げ速度３０ｃｍ／ｍｉｎで塗布
した後、室温で５分間、更に８０℃で１時間加熱して硬
化させた。この上に参考例３で合成したＳｉＯ□／Ｔｉ
０ａ層用コーティング溶用コーティング溶液げ速度１３
ｃｍ／ｗｉｎで塗布した後、室温で５分間、更に８０℃
で１時間加熱して硬化させた。更に、その上に参考例４
で合成したＴｉＯ□層用コーティング溶液を浸漬法で引
き上げ速度Ｉｓ、 ６ｃｍ／ｍｉｎで塗布した後、室温
で５分間、更に８０℃で１時間加熱しして硬化させた。Example 1 Polymethyl methacrylate AR plate (manufactured by Mitsubishi Rayon Co., Ltd.,
The undercoat solution synthesized in Reference Example 1 (with a refractive index of 1.49) was applied by dipping at a pulling rate of 30 cm/min, and then cured by heating at room temperature for 5 minutes and then at 80° C. for 1 hour. On top of this, SiO□/Ti synthesized in Reference Example 3
0a layer coating melting coating melting speed 13
cm/win, then at room temperature for 5 minutes and then at 80°C
It was heated for 1 hour to harden it. Furthermore, reference example 4 is added on top of that.
The coating solution for the TiO□ layer synthesized above was applied by a dipping method at a pulling rate Is of 6 cm/min, and then heated at room temperature for 5 minutes and then at 80° C. for 1 hour to cure.
次に、その上に参考例５で合成した最表層用コーティン
グ溶液を浸漬法で引き上げ速度６．５ｃｍ／ｗｉｎで塗
布した後、室温で５分間、更に８０℃で１時間加熱して
硬化させた。Next, the coating solution for the outermost layer synthesized in Reference Example 5 was applied thereon by a dipping method at a pulling rate of 6.5 cm/win, and then heated at room temperature for 5 minutes and further heated at 80° C. for 1 hour to cure. .
得られた板のアンダーコート層の屈折率は１．４９、膜
厚は１ μｍ 、 ５ｉｎ２／Ｔｉ１ｔ層の屈折率は１
．５８、膜厚は８７０人、ＴｉＯ□層の屈折率は１．８
１．膜厚は１５２０入であり、最表層の屈折率は１．４
４、膜厚は９５５人であった。The refractive index of the undercoat layer of the obtained plate was 1.49, the film thickness was 1 μm, and the refractive index of the 5in2/Ti1t layer was 1.
．． 58, film thickness is 870 people, refractive index of TiO□ layer is 1.8
1. The film thickness is 1520mm, and the refractive index of the outermost layer is 1.4.
4. The film thickness was 955 people.
こうして得られた板の全光線透過率は９８％であり、接
触角は９９°、反射防止層にクラックは認められず、反
射防止層の密着性は１００％であり、耐汚染性試験の結
果は良好であった。又、耐塩水性テストでクラックの発
生はなく、耐摩耗性も良好であった。The total light transmittance of the thus obtained plate was 98%, the contact angle was 99°, no cracks were observed in the antireflection layer, the adhesion of the antireflection layer was 100%, and the results of the stain resistance test was in good condition. In addition, no cracks occurred in the salt water resistance test, and the abrasion resistance was also good.
実施例２
実施例で用いたと同様のポリメチルメタクリレートＡＲ
板に参考例２で合成したアンダーコート要用コーティン
グ溶液を浸漬法で引き上げ速度５、７ｃｎ＋／ｍｉｎで
塗布した後、室温で５分間、更に８０℃で１時間加熱し
て硬化させた。その上に参考例４で合成したＴｉ０−履
用コーティング溶液を浸漬法で引き上げ速度１５．６ｃ
ｍ／ｗｉｎで塗布した後、室温で５分間、更に８０℃で
１時間加熱して硬化させた。Example 2 Polymethyl methacrylate AR similar to that used in Example
The coating solution for undercoat synthesized in Reference Example 2 was applied to the plate by a dipping method at a pulling rate of 5.7 cn+/min, and then heated at room temperature for 5 minutes and then heated at 80° C. for 1 hour to cure. On top of that, the Ti0-wear coating solution synthesized in Reference Example 4 was pulled up by dipping at a rate of 15.6c.
After coating with m/win, it was cured by heating at room temperature for 5 minutes and then at 80° C. for 1 hour.
更に、その上に参考例５で合成した最表層用コーティン
グ溶液を浸漬法で引き上げ速度６．５ｃｍ／ｆｉＩｉｎ
で塗布した後、室温で５分間、更に８０℃で１時間加熱
して硬化させた。Furthermore, the coating solution for the outermost layer synthesized in Reference Example 5 was applied thereon by a dipping method at a pulling rate of 6.5 cm/fiIin.
After coating, it was cured by heating at room temperature for 5 minutes and then at 80° C. for 1 hour.
得られた板のアンダーコート層の屈折率は１．５８、膜
厚は８７０人、Ｔｉ０□層の屈折率は１．８１．膜厚は
１５２０人であり、最表層の屈折率は１．４４、膜厚は
９５５入であった。The refractive index of the undercoat layer of the obtained plate was 1.58, the film thickness was 870 mm, and the refractive index of the Ti0□ layer was 1.81. The film thickness was 1520, the refractive index of the outermost layer was 1.44, and the film thickness was 955.
こうして得られた板の全光線透過率は９８％であり、接
触角は９９°、反射防止層にクラックは認められず、反
射防止層の密着性は１００％であり、耐汚染性試験の結
果は良好であった。又、耐塩水性テストでクラックの発
生はなく、耐摩耗性も良好であった。The total light transmittance of the thus obtained plate was 98%, the contact angle was 99°, no cracks were observed in the antireflection layer, the adhesion of the antireflection layer was 100%, and the results of the stain resistance test was in good condition. In addition, no cracks occurred in the salt water resistance test, and the abrasion resistance was also good.
実施例３
オクチルトリメトキシシランの代わりに回置のフルオロ
アルキルトリメトキシシラン（ＸＣ９５−４１８、東芝
シリコーン製）を用いた以外は実施例１と同様にした。Example 3 The same procedure as Example 1 was carried out except that fluoroalkyltrimethoxysilane (XC95-418, manufactured by Toshiba Silicone) was used instead of octyltrimethoxysilane.
最表層用コーティング溶液の粘度は２．８センチポアズ
であり、得られた板の全光線透過率は９８％であり、最
表層の屈折率は１．４４であり、膜厚は９５５人であり
、接触角は８２°、反射防止層にクラックは認められず
、反射防止層の密着性は１００％であり、耐汚染性試験
の結果は良好であった。又、耐塩水性テストでクラック
の発生はなく、耐摩耗性も良好であった。The viscosity of the coating solution for the outermost layer was 2.8 centipoise, the total light transmittance of the obtained plate was 98%, the refractive index of the outermost layer was 1.44, and the film thickness was 955 centipoise. The contact angle was 82°, no cracks were observed in the antireflection layer, the adhesion of the antireflection layer was 100%, and the results of the stain resistance test were good. In addition, no cracks occurred in the salt water resistance test, and the abrasion resistance was also good.
実施例４
オクチルトリメトキシシランの代わりに同量のメチルト
リエトキシシランを用いた以外は実施例１と同様にした
。Example 4 The same procedure as Example 1 was carried out except that the same amount of methyltriethoxysilane was used instead of octyltrimethoxysilane.
最表層用コーティング溶液の粘度は２．８センチポアズ
であり、得られた板の全光線透過率は９８％であり、最
表層の屈折率は１．４４であり、膜厚は９５５人であり
、接触角は７８°、反射防止層にクラックは認められず
、反射防止層の密着性は１００％であり、耐汚染性試験
の結果は良好であった。反射防止層の密着性は１００％
であり、耐汚染性試験の結果は良好であった。又、耐塩
水性テストでクラックの発生はなく、耐摩耗性も良好で
あった。The viscosity of the coating solution for the outermost layer was 2.8 centipoise, the total light transmittance of the obtained plate was 98%, the refractive index of the outermost layer was 1.44, and the film thickness was 955 centipoise. The contact angle was 78°, no cracks were observed in the antireflection layer, the adhesion of the antireflection layer was 100%, and the results of the stain resistance test were good. Adhesion of anti-reflection layer is 100%
The results of the stain resistance test were good. In addition, no cracks occurred in the salt water resistance test, and the abrasion resistance was also good.
実施例５
最表層用コーティング溶液として参考例６で合成したも
のを用いた以外は実施例１と同様にした。Example 5 The same procedure as Example 1 was carried out except that the solution synthesized in Reference Example 6 was used as the coating solution for the outermost layer.
得られた板の全光線透過率は９８％であり、最表層の屈
折率は１．４４であり、膜厚は９５５人であり、接触角
は９８°、反射防止層にクラックは認められず、反射防
止層の密着性は１００％であり、耐汚染性試験の結果は
良好であった。又、耐塩水性テストでクラックの発生は
なく、耐摩耗性も良好であった。The total light transmittance of the obtained plate was 98%, the refractive index of the outermost layer was 1.44, the film thickness was 955 mm, the contact angle was 98°, and no cracks were observed in the antireflection layer. The adhesion of the antireflection layer was 100%, and the results of the stain resistance test were good. In addition, no cracks occurred in the salt water resistance test, and the abrasion resistance was also good.
実施例６
最表層用コーティング溶液として参考例７で合成したも
のを用いた以外は実施例１と同様にした。Example 6 The same procedure as Example 1 was carried out except that the solution synthesized in Reference Example 7 was used as the coating solution for the outermost layer.
得られた板の全光線透過率は９８％であり、最表層の屈
折率は１．４４であり、膜厚は９５５人であり、接触角
は８５°、反射防止層にクラックは認められず、反射防
止層の密着性は１００％であり、耐汚染性試験の結果は
良好であった。又、耐塩水性テストでクラックの発生は
なく、耐摩耗性も良好であった。The total light transmittance of the obtained plate was 98%, the refractive index of the outermost layer was 1.44, the film thickness was 955 mm, the contact angle was 85°, and no cracks were observed in the antireflection layer. The adhesion of the antireflection layer was 100%, and the results of the stain resistance test were good. In addition, no cracks occurred in the salt water resistance test, and the abrasion resistance was also good.
比較例１
最表層用コーティング溶液として参考例８で合成したも
のを用いた以外は実施例１と同様にした。Comparative Example 1 The same procedure as Example 1 was carried out except that the solution synthesized in Reference Example 8 was used as the coating solution for the outermost layer.
得られた板の全光線透過率は９８％であり、最表層の屈
折率は１．４４であり、膜厚は９５５人であり、接触角
は５５＠であった。反射防止層にクラックは認められず
、反射防止層の密着性は１００％であったが、耐汚染性
試験の結果は不良であった。The total light transmittance of the obtained plate was 98%, the refractive index of the outermost layer was 1.44, the film thickness was 955 mm, and the contact angle was 55@. Although no cracks were observed in the antireflection layer and the adhesion of the antireflection layer was 100%, the results of the stain resistance test were poor.
比較例２
実施例１で用いたと同様のポリメチルメタクリレート板
に蒸着法で膜厚９５５人のＳｉ０ｇ膜を形成させた。得
られた板の接触角は１６°であり、Ｓｉ０ｇ膜の密着性
は１００％であり、Ｓｉ０ｇ膜にクラックの発生は見ら
れなかったが、耐汚染性試験の結果は不良であった。Comparative Example 2 A SiOg film having a thickness of 955 mm was formed on a polymethyl methacrylate plate similar to that used in Example 1 by vapor deposition. The contact angle of the obtained plate was 16°, the adhesion of the Si0g film was 100%, and no cracks were observed in the Si0g film, but the results of the stain resistance test were poor.
比較例３
ポリメチルメタクリレート板Ｒ板（三菱レイヨン■製、
屈折率１．４９）に参考例１で合成したアンダーコート
用溶液を浸漬法で引き上げ速度３０（：ｍ／ｒｎｉｎで
塗布した後、室温で５分間、更に８０℃で１時間加熱し
て硬化させた。この板の接触角は５１”であり、耐汚染
性試験の結果は不良であった。Comparative example 3 Polymethyl methacrylate plate R plate (manufactured by Mitsubishi Rayon ■,
The undercoat solution synthesized in Reference Example 1 was applied to the undercoat solution synthesized in Reference Example 1 (with a refractive index of 1.49) by a dipping method at a pulling rate of 30 (m/rnin), and then heated at room temperature for 5 minutes and then heated at 80°C for 1 hour to cure. The contact angle of this plate was 51'', and the results of the stain resistance test were poor.
の発生も少なく、反射防止膜の基板への密着性に優れ、
しかも、耐汚染性に優れた反射防止膜を形成することが
できるという優れた特徴を有する。The anti-reflection coating has excellent adhesion to the substrate, with less occurrence of
Furthermore, it has an excellent feature of being able to form an antireflection film with excellent stain resistance.
Claims (1)
成し、該反射防止層の最表層が珪素アルコキシドと下記
一般式（１）で表わされるシラン化合物とを含む珪素ア
ルコキシド混合物を部分加水分解、共縮合せしめたもの
を塗布、加熱硬化してなり、水に対する静止接触角が６
０°以上であり、屈折率が１．５以下であるものとする
ことを特徴とする反射防止層の形成法。 ＳｉＲ＾１＿ｍＲ＾２＿ｎ（ＯＲ＾２）＿４＿−＿ｍ＿
−＿ｎ（１）（式中、Ｒ＾１、Ｒ＾２は各々独立にビニ
ル基、アミノ基、（メタ）アクリロイルオキシ基、メル
カプト基、エポキシ基、塩素及び弗素から選ばれる置換
基を有していてもよい炭素数１〜６のアルキル基、炭素
数１〜６のアルケニル基又は炭素数６〜１２のアリール
基であり、Ｒ＾２は炭素数１〜４の炭化水素基を示し、
ｍ及びｎは０、１又は２であって、但し、ｍ＋ｎは１又
は２を満足するものである。）[Scope of Claims] 1) A single-layer or multi-layer antireflection layer is formed on an organic polymer substrate, and the outermost layer of the antireflection layer contains silicon alkoxide and a silane compound represented by the following general formula (1). A silicon alkoxide mixture containing a silicon alkoxide mixture is partially hydrolyzed and co-condensed, then applied and heated to harden, and the static contact angle with water is 6.
A method for forming an antireflection layer, characterized in that the angle is 0° or more and the refractive index is 1.5 or less. SiR^1_mR^2_n (OR^2)_4_-_m_
-_n(1) (wherein R^1 and R^2 each independently have a substituent selected from a vinyl group, an amino group, a (meth)acryloyloxy group, a mercapto group, an epoxy group, chlorine, and fluorine. is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R^2 represents a hydrocarbon group having 1 to 4 carbon atoms,
m and n are 0, 1 or 2, provided that m+n satisfies 1 or 2. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2055766A JPH03256003A (en) | 1990-03-07 | 1990-03-07 | Formation of antireflection layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2055766A JPH03256003A (en) | 1990-03-07 | 1990-03-07 | Formation of antireflection layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03256003A true JPH03256003A (en) | 1991-11-14 |
Family
ID=13007985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2055766A Pending JPH03256003A (en) | 1990-03-07 | 1990-03-07 | Formation of antireflection layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03256003A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021210371A1 (en) * | 2020-04-14 | 2021-10-21 | フクビ化学工業株式会社 | Anti-reflection laminate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51126505A (en) * | 1975-04-26 | 1976-11-04 | Shinpo Kogyo Kk | Rotor case for type eluid machines |
| JPS578388A (en) * | 1980-06-16 | 1982-01-16 | Sanyo Electric Co Ltd | Rotary compressor |
| JPS5853690A (en) * | 1981-09-25 | 1983-03-30 | Jidosha Kiki Co Ltd | Vane pump |
| JPH01139091U (en) * | 1988-03-17 | 1989-09-22 | ||
| JPH0212088U (en) * | 1988-07-08 | 1990-01-25 |
-
1990
- 1990-03-07 JP JP2055766A patent/JPH03256003A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51126505A (en) * | 1975-04-26 | 1976-11-04 | Shinpo Kogyo Kk | Rotor case for type eluid machines |
| JPS578388A (en) * | 1980-06-16 | 1982-01-16 | Sanyo Electric Co Ltd | Rotary compressor |
| JPS5853690A (en) * | 1981-09-25 | 1983-03-30 | Jidosha Kiki Co Ltd | Vane pump |
| JPH01139091U (en) * | 1988-03-17 | 1989-09-22 | ||
| JPH0212088U (en) * | 1988-07-08 | 1990-01-25 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021210371A1 (en) * | 2020-04-14 | 2021-10-21 | フクビ化学工業株式会社 | Anti-reflection laminate |
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