JPH0222147A - Article having anti-fogging property - Google Patents
Article having anti-fogging propertyInfo
- Publication number
- JPH0222147A JPH0222147A JP16977488A JP16977488A JPH0222147A JP H0222147 A JPH0222147 A JP H0222147A JP 16977488 A JP16977488 A JP 16977488A JP 16977488 A JP16977488 A JP 16977488A JP H0222147 A JPH0222147 A JP H0222147A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- coating
- thickness
- particle diameter
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000008119 colloidal silica Substances 0.000 claims abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract 2
- 238000012986 modification Methods 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- -1 β -Glycidoxyethyl Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 208000035874 Excoriation Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HTVULPNMIHOVRU-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CC(C)OCC1CO1 HTVULPNMIHOVRU-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- PLXLQGPXPXIVKM-UHFFFAOYSA-N 3-chloropropyl(tripropoxy)silane Chemical compound CCCO[Si](CCCCl)(OCCC)OCCC PLXLQGPXPXIVKM-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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- KEBBHXFLBGHGMA-UHFFFAOYSA-K aluminum;4-ethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O KEBBHXFLBGHGMA-UHFFFAOYSA-K 0.000 description 1
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- LQJYZOSQIDYKOM-UHFFFAOYSA-N dimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]-propylsilane Chemical compound CCC[Si](OC)(OC)CCOCC1CO1 LQJYZOSQIDYKOM-UHFFFAOYSA-N 0.000 description 1
- PWPGWRIGYKWLEV-UHFFFAOYSA-N dimethoxy-methyl-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](C)(OC)CCOCC1CO1 PWPGWRIGYKWLEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- HWYVEGFZRODYQT-UHFFFAOYSA-N ethenyl(triethoxy)silane 2-methoxyethoxysilane Chemical compound C(=C)[Si](OCC)(OCC)OCC.COCCO[SiH3] HWYVEGFZRODYQT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OOPKJVYUAXPGHS-UHFFFAOYSA-N tributoxy(3-chloropropyl)silane Chemical compound CCCCO[Si](CCCCl)(OCCCC)OCCCC OOPKJVYUAXPGHS-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、耐久性を有する防曇性被膜に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a durable anti-fog coating.
窓ガラス、航空機の風防ガラス、自動車用窓ガラス、フ
ロント、リヤーなどの各ウィンドーなど広い分野で好適
に使用される。Suitable for use in a wide range of fields including window glass, aircraft windshields, automobile window glasses, front and rear windows, etc.
［従来の技術］
プラスチック材料、無機ガラス等は従来から透明基材と
しての性質を生かして例えば窓ガラス、鏡面、眼鏡レン
ズあるいはゴーグルなどの物品に広く利用されているが
、これらの素材においては、高温多湿の場所または温度
や湿度差の大きい境界面などに、おいて使用すると表面
が曇る、あるいは傷がつくなどの問題を有していた。そ
のため、これらの物品に対して防曇性、耐久性を付与し
ようとする試みが提案されている。[Prior Art] Plastic materials, inorganic glasses, etc. have traditionally been widely used in products such as window glasses, mirror surfaces, eyeglass lenses, and goggles, taking advantage of their properties as transparent base materials. When used in hot and humid places or at interfaces with large temperature or humidity differences, there have been problems such as the surface becoming cloudy or being scratched. Therefore, attempts have been made to impart antifogging properties and durability to these articles.
防曇性に耐久性を付与するために、ポリビニルアルコー
ルを使用することが、例えば米国特許筒４、１２７．６
８２号で提案されている。In order to impart durability to antifogging properties, polyvinyl alcohol may be used, for example, as described in U.S. Patent No. 4, 127.6.
Proposed in No. 82.
一方、ポリビニルアルコールが微粒子状シリカによって
架橋し、耐水性のある被膜を与えることは公知である（
米国特許筒３．７７３．７７６号）。On the other hand, it is known that polyvinyl alcohol can be crosslinked with particulate silica to provide a water-resistant coating (
No. 3,773,776).
さらにポリビニルアルコール
レックスを主成分とする硬化性］ーティング組成物も提
案されている（米国特許筒４，０１６， １２９号）。Furthermore, a curable coating composition containing polyvinyl alcohol Rex as a main component has also been proposed (US Pat. No. 4,016,129).
また、特開昭５８−３２６６４号公報においては、ポリ
ビニルアルコール、微粒子状シリカおよび有機ケイ素化
合物および／またはその加水分解物からなる耐久性を向
上させた防曇性被膜が提案されている。Further, JP-A-58-32664 proposes an antifogging coating with improved durability, which is made of polyvinyl alcohol, particulate silica, and an organosilicon compound and/or a hydrolyzate thereof.
［発明が解決しようとする課題］
しかしながら、米国特許筒４， １２７， ６８２号に
よる方法は、−時的に物品に防会性を付与するのみであ
り、さらに硬度の向上という点で不充分であるといった
問題点があった。[Problems to be Solved by the Invention] However, the method disclosed in U.S. Pat. There were some problems.
これらの欠点を改良する目的から提案された米国特許筒
３， ７７３， ７７６号および米国特許筒４，０１６
，１２９号による技術も、ポリビニルアルコールの親水
性を著しく低下せしめるもので防曇性被膜材料とは言い
難い。U.S. Pat. No. 3,773,776 and U.S. Pat. No. 4,016 were proposed for the purpose of improving these drawbacks.
, No. 129 also significantly reduces the hydrophilicity of polyvinyl alcohol and cannot be called an anti-fog coating material.
さらに特開昭５８−３２６６／１号公報による技術は、
以上の従来技術の欠点を大幅に向上させた防β性被膜で
あるが、硬度が不足するものであり、窓ガラス用、航空
機の風防、さらには自動車用途などには、さらに−段と
表面硬度の高い防曇性被膜が要求される。Furthermore, the technology disclosed in Japanese Patent Application Laid-Open No. 58-3266/1 is
Although this anti-β coating has greatly improved the drawbacks of the above-mentioned conventional technologies, it lacks hardness, and needs an even higher level of surface hardness for applications such as window glass, aircraft windshields, and even automobiles. A highly antifogging coating is required.
本発明はかかる従来技術の欠点を解消しようとするもの
であり、耐久性のある防曇性と高い表面硬度を有する被
膜を提供することを目的とする。The present invention attempts to eliminate the drawbacks of the prior art, and aims to provide a coating having durable antifogging properties and high surface hardness.
［発明が解決しようとする課題］
本発明は、上記目的を達成するために下記の構成を有す
る。[Problems to be Solved by the Invention] The present invention has the following configuration to achieve the above object.
「無機ガラス基板の表面に接着性を有し、かつ下記式［
Ｉ］によって示される変形率Ｄ（％）ｈり１０％以上の
ポリマーからなる厚さ２．０μｍ以上の被膜を設け、さ
らに該被膜上に下記Ａ成分およびＢ成分を主成分として
なる防曇性被膜を設けてなることを特徴とする防曇性を
有する物品。"Has adhesive properties on the surface of the inorganic glass substrate, and has the following formula [
A coating with a thickness of 2.0 μm or more made of a polymer with a deformation rate D (%) h of 10% or more, which is represented by I], is provided, and furthermore, an antifogging property consisting of the following components A and B as main components is provided on the coating. An article having antifogging properties characterized by being provided with a film.
Ｌ。L.
（式中、Ｌｏは無荷重における厚み、Ｌは２０ｋａ／ｄ
の荷重下における厚みを示す。）
Ａ．ポリビニルアルコール
Ｂ．平均粒子径か５〜２００ｍμのコロイド状シリカ」
本発明は無機ガラス基板の表面に、接着性を有し、かつ
下記式［Ｉ］によって示される変形率Ｄ（％）が１０％
以上のポリマからなる厚さ２． ０μｍ以上の被膜を設
けたものであるが、ここで変形率Ｄ（％）を定義する方
法としては、ＪＩＳ Ｋ７２０８の試験方法にもとづい
て被膜形成材料を２０ｋｇ／−の荷重下で変形させた時
に、下記式［Ｉ］によって求められる変形ｆｆｌ（Ｄ（
％））で表すことができる。(In the formula, Lo is the thickness under no load, L is 20ka/d
Indicates the thickness under load. )A. Polyvinyl alcohol B. "Colloidal silica with an average particle diameter of 5 to 200 mμ" The present invention has adhesive properties on the surface of an inorganic glass substrate, and has a deformation rate D (%) of 10% as represented by the following formula [I].
The thickness of the polymer is 2. A film with a thickness of 0 μm or more is provided, but the method for defining the deformation rate D (%) here is that when the film forming material is deformed under a load of 20 kg/- based on the test method of JIS K7208. , the deformation ffl(D(
It can be expressed as %)).
（Ｌｏ−Ｌ）
Ｄ（％）− ｘｌｏｏ ［Ｉ］Ｏ
ここでり。は無荷重時の被膜を形成する材料の厚み、Ｌ
は２０ｋＯ１０ｒｆの荷重下での被膜を形成する材料の
厚みである。(Lo-L) D (%) - xloo [I]O here. is the thickness of the material forming the film under no load, L
is the thickness of the material forming the coating under a load of 20kO10rf.
本発明に使用される被膜を形成する材料としては、変形
率（Ｄ（％））が１０％以上のもので、とくに苛酷な条
件下で使用される場合には、１５％以上の変形量を有す
るものが好ましい。The material forming the coating used in the present invention should have a deformation rate (D (%)) of 10% or more, and especially when used under harsh conditions, a deformation amount of 15% or more. It is preferable to have one.
かかる変形することが可能な弾性を有する被膜の好まし
い成分としては、熱可塑性樹脂および／または熱硬化性
樹脂からなるものが挙げられ、ポリアミド樹脂、ポリエ
ステル樹脂、セルロース類、エチレン−酢酸ビニルコポ
リマー、酢酸ビニル樹脂またはその誘導体、ポリスチレ
ンまたはそのコポリマー、ブチルメタクリル樹脂または
そのコポリマーなどの熱可塑性樹脂、またはジエチレン
グリコールビスアリルカーボネートポリマー、多官能（
メタ）アクリレートポリマーおよびその共重合体などの
熱硬化性樹脂が具体例として挙げられる。とくに防曇性
の要求される用途が主として光の透過、反射など、光学
的分野が多いことがら、これらの被膜についても透明な
ものが好ましい。Preferred components of such a deformable and elastic coating include thermoplastic resins and/or thermosetting resins, such as polyamide resins, polyester resins, celluloses, ethylene-vinyl acetate copolymers, acetic acid, etc. Thermoplastic resins such as vinyl resins or their derivatives, polystyrene or its copolymers, butyl methacrylic resins or its copolymers, or diethylene glycol bisallyl carbonate polymers, polyfunctional (
Specific examples include thermosetting resins such as meth)acrylate polymers and copolymers thereof. In particular, since many applications requiring antifogging properties are mainly optical fields such as light transmission and reflection, transparent films are also preferred for these coatings.
また、かかる被膜が設けられる目的は、表面硬度、とく
にテーパー摩耗硬度の向上に有効であることであるが、
同時に防曇性能を向上させるために、前記式［Ｉ］で示
されるＤ（％）が１０％以上で、かつ吸水性をも有する
ポリマーの使用も好適である。具体的には防曇性被膜よ
り吸水性の大きい、例えば、Ａ成分であるポリビニルア
ルコールの含有但の多い組成物、加水分解されたセルロ
ースアセテート系組成物、ポリヒドロキシアルキル（メ
タ）アクリレートおよびその共重合体、ポリ（メタ）ア
クリル酸およびその共重合体などを例示することができ
る。これらの樹脂は、適当な架橋剤、たとえばメラミン
樹脂、エポキシ樹脂、イソシアネートなどで三次元架橋
されることが耐水性向上の点から好ましい。In addition, the purpose of providing such a coating is to be effective in improving surface hardness, especially taper wear hardness.
At the same time, in order to improve the antifogging performance, it is also suitable to use a polymer represented by the above formula [I] that has a D (%) of 10% or more and also has water absorbency. Specifically, compositions that have higher water absorption than the antifogging film, such as compositions containing a large amount of polyvinyl alcohol (component A), hydrolyzed cellulose acetate compositions, polyhydroxyalkyl (meth)acrylates, and their co-acrylates, etc. Examples include polymers, poly(meth)acrylic acid, and copolymers thereof. These resins are preferably three-dimensionally crosslinked with a suitable crosslinking agent such as melamine resin, epoxy resin, isocyanate, etc. from the viewpoint of improving water resistance.
また、これらの被膜の膜厚は、２．０μｍ以上であるこ
とが必要であるが、とくに効果を顕著に発現させるため
には３．００ｍ以上であることが好ましい。一方、膜厚
の上限は、とくに限定されないが、作業性、表面外観の
点から５００μｍ以下が実用的である。膜厚が２．０μ
ｍ未満の場合には本発明の目的における十分な表面硬度
が得られない。Further, the thickness of these coatings needs to be 2.0 μm or more, but is preferably 3.00 m or more in order to particularly exhibit remarkable effects. On the other hand, the upper limit of the film thickness is not particularly limited, but from the viewpoint of workability and surface appearance, 500 μm or less is practical. Film thickness is 2.0μ
If it is less than m, sufficient surface hardness for the purpose of the present invention cannot be obtained.
本発明においてＡ成分として用いられるポリビニルアル
コールとは、ポリ酢酸ビニルのようなポリビニルエステ
ルの部分加水分解あるいは完全加水分解によって得られ
るものをいい、中でも平均重合度が２５０〜３０００．
ケン化度が７０モル％以上のポリビニルアルコールが本
発明には好ましく用いられる。平均重合度が２５０未満
である場合は、耐久性、特に耐水性に乏しく、また３０
００より大きい場合は塗料とした時に粘度が大きくなる
ため平滑な塗膜が１９にくくなる。さらにケン化度が７
０モル％より低い場合には防曇性の点で充分な性能が期
待できない。The polyvinyl alcohol used as component A in the present invention refers to one obtained by partial or complete hydrolysis of polyvinyl ester such as polyvinyl acetate, and has an average degree of polymerization of 250 to 3000.
Polyvinyl alcohol having a saponification degree of 70 mol% or more is preferably used in the present invention. When the average degree of polymerization is less than 250, durability, especially water resistance, is poor, and
If it is larger than 00, the viscosity increases when used as a paint, making it difficult to form a smooth coating film. In addition, the degree of saponification is 7
If it is less than 0 mol%, sufficient antifogging performance cannot be expected.
Ｂ成分である平均粒子径が５〜２００ｍμのコロイド状
シリカの効果的な例としては、シリカゾルが挙げられる
。シリカゾルとは高分子量無水ケイ酸の水および／また
はアルコールなどの有機溶媒中の］ロイド状分散体であ
る。本発明の目的のためには平均粒子径５〜２００ｍμ
のものが使用されるが、約７〜５０ｍμの径のものが特
に好ましい。平均粒子径が５ｍμに満たないものは分散
状態の安定性が悪く、品質の一定したものを得ることが
困難であり、また２００ｍμを越えるものは生成塗膜の
透明性が悪く、濁りの大きなものしか得られない。An effective example of colloidal silica having an average particle diameter of 5 to 200 mμ, which is component B, is silica sol. A silica sol is a loid-like dispersion of high molecular weight silicic anhydride in water and/or an organic solvent such as an alcohol. For the purpose of the present invention, the average particle size is 5 to 200 mμ.
Although diameters of about 7 to 50 mμ are particularly preferred. If the average particle size is less than 5 mμ, the stability of the dispersion state is poor and it is difficult to obtain products of consistent quality.If the average particle size is over 200 mμ, the resulting coating film will have poor transparency and large turbidity. I can only get it.
本発明の防曇性被膜中のΔおよびＢ成分の組成比は、要
求される防曇性、表面硬度、さらには耐水性などの特性
によって決定されるべきであるが、窓ガラス用、航空機
用風防おるいは自動車用などの苛酷な条件下で使用され
る用途においてはＡ成分１００重量部に対して、Ｂ成分
が５〜２００重吊部の範囲で好ましく使用される。さら
に、特に苛酷な条件にさらされる用途においては、表面
硬度向上の点からＡ成分１００重量部に対して、Ｂ成分
が５０〜２００重は部の範囲が好ましい。The composition ratio of the Δ and B components in the antifogging film of the present invention should be determined depending on the required properties such as antifogging properties, surface hardness, and water resistance. In applications that are used under severe conditions, such as windshields and automobiles, component B is preferably used in an amount of 5 to 200 parts by weight per 100 parts by weight of component A. Furthermore, in applications where the composition is exposed to particularly severe conditions, from the viewpoint of improving surface hardness, it is preferable that the amount of component B be in the range of 50 to 200 parts by weight per 100 parts by weight of component A.
本発明の防曇性被膜には前述した必須成分の他にさらに
溶媒、添加剤、各種改質剤などを含有させることも可能
である。特に一般式が
Ｒ１Ｒ２ａ ＳｉＸ ３−ａで表される有機ケイ素化合
物は、耐水性向上、基材との接着性、表面硬度向上に有
用な成分であり、具体的な例としては、β−グリシドキ
シエチルトリメトキシシラン、γ−グリシドキシプロビ
ルトリメトキシシラン、γ−グリシドキシプロピルトリ
エトキシシラン、β−グリシドキシプロピルトリメトキ
シシラン、β−グリシドキシエチルメチルジメトキシシ
ラン、β−グリシドキシエチルメチルジェトキシシラン
、γ−グリシドキシプロピルメヂルジメトキシシラン、
γ−グリシドキシプロピルメチルジェトキシシラン、β
−グリシドキシエチルエヂルジメトキシシラン、γ−グ
リシドキシプ【コピルエ、デルジメトキシシラン、γ−
グリシドキシプロピルエチルジェトキシシラン、β−グ
リリドキシプロピルエチルジェトキシシラン、β−グリ
シドキシエチルプロビルジメトキシシラン、β−（３，
４エポキシシクロヘキシル）エチルトリメトキシシラン
、β−（３，４エポキシシクロヘキシル）エチルトリエ
トキシシラン、メチルトリメトキシシラン、メチルトリ
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
ルトリメトキシエトキシシフン、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−クロロピロピルトリプロポキシシラン、γ−
クロロプロピルトリブトキシシラン、フェニルトリメ１
〜キシシラン、フェニルトリエトキシシラン、３．３．
３−トリフロロプロピルトリメトキシシラン、γ−メタ
クリロキシプロピルトリメトキシシラン、ジメチルジメ
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−メタクリロキシプロビルメチルジメ１〜キシ
シランなどが挙げられる。またこれらの化合物は単独の
みならず、２種以上混合して用いることも可能である。In addition to the above-mentioned essential components, the antifogging film of the present invention can also contain solvents, additives, various modifiers, and the like. In particular, organosilicon compounds represented by the general formula R1R2a SiX 3-a are useful components for improving water resistance, adhesion to substrates, and surface hardness. xyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxypropyltrimethoxysilane Sidoxyethylmethyljethoxysilane, γ-glycidoxypropylmedyldimethoxysilane,
γ-glycidoxypropylmethyljethoxysilane, β
-Glycidoxyethyl edyldimethoxysilane, γ-glycidoxyp [copyrue, deldimethoxysilane, γ-
Glycidoxypropylethyljethoxysilane, β-glyridoxypropylethyljethoxysilane, β-glycidoxyethylpropyldimethoxysilane, β-(3,
4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4epoxycyclohexyl)ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane Methoxyethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, γ-
Chloropropyltributoxysilane, phenyltrime 1
~xysilane, phenyltriethoxysilane, 3.3.
Examples include 3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, dimethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane. Moreover, these compounds can be used not only alone but also in a mixture of two or more.
これらの有機ケイ素化合物の使用に際しては、そのまま
成分として添加することもできるし、あらかじめ加水分
解を行った後、該シラン加水分解物を添加して用いるこ
とも可能である。また加水分解に際しては通常の方法、
例えば塩酸などの無機酸、酢酸などの有機酸またはカセ
イソーダのようなアルカリによって、あるいは水のみを
用いて加水分解する方法を利用することができる。When using these organosilicon compounds, they can be added as they are as components, or they can be hydrolyzed in advance and then the silane hydrolyzate is added thereto. In addition, for hydrolysis, the usual method,
For example, a method of hydrolysis using an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid, an alkali such as caustic soda, or using only water can be used.
溶媒としては、例えば水、各種アルコール、ケトン、エ
ステル、エーテル、環状エーテル、ジメチルホルムアミ
ド、ジメチルスルホキシド、ジメチルイミダゾリジノン
などを適宜用いることができる。As the solvent, for example, water, various alcohols, ketones, esters, ethers, cyclic ethers, dimethylformamide, dimethyl sulfoxide, dimethylimidazolidinone, etc. can be used as appropriate.
また、添加剤としては、表面平滑性を改良する目的で各
種の界面活性剤が使用可能であり、例としては、シリコ
ーン系化合物、フッ素系界面活性剤、有機界面活性剤な
どが使用できる。Further, as additives, various surfactants can be used for the purpose of improving surface smoothness, and examples include silicone compounds, fluorine surfactants, and organic surfactants.
さらに改質剤としては、本発明防曇性被膜組成物と相溶
性のよい有機ポリマー、例えばヒドロキシエチルセルロ
ース、ポリヒドロキシエチル（メタ）アクリレートまた
はその共重合体、アルコール可溶性ナイロン、ポリアク
リルアミド、ポリビニルピロリドンまたはその共重合体
などが挙げられる。さらにはエチルシリケート、ｎ−プ
ロピルシリケート、ｉ−プロピルシリケート、ｎ−ブチ
ルシリケート、ｉ−ブチルシリケート、ｔ−ブチルシリ
ケートなどの４官能シラン化合物も添加することか可能
である。また、各種エポキシ樹脂、メラミン樹脂、アミ
ド樹脂なども添加することができる。Furthermore, as a modifier, organic polymers having good compatibility with the antifogging coating composition of the present invention, such as hydroxyethyl cellulose, polyhydroxyethyl (meth)acrylate or a copolymer thereof, alcohol-soluble nylon, polyacrylamide, polyvinylpyrrolidone, or Examples include copolymers thereof. Furthermore, it is possible to add tetrafunctional silane compounds such as ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, i-butyl silicate, and t-butyl silicate. Furthermore, various epoxy resins, melamine resins, amide resins, etc. can also be added.
また必要に応じて、硬化を促進する目的で、シラノール
の縮合および／またはシラノールと水酸基の反応触媒と
して知られる各種の触媒が用いられるが、一般式がＡ１
・Ｘ、・Ｙ３−ｎで表されるアルミニウムキレート化合
物を好ましく用いることができる。（ここでＸは、低級
アルコキシ基、ＹはＭ１ＣＯＣＨ２、Ｃ０Ｍ２およびＭ
３ＣＯＣＨ２ＣＯＯＭ４からなる群から選ばれた化合物
から生ずる配位子（Ｍｌ 、Ｍ２、Ｍ３およびＭ４は低
級アルキルｇ＞、ｎは０．１または２である。）アルミ
ニウムキレ−１−化合物は、各種の化合物が使用できる
が、触媒活性、組成物中への溶解性および安定性の観点
から好ましい化合物の例としては、アルミニウムアセチ
ルアセトナート、アルミニウムエチルアセトアセテート
ビスアセチルアセトナート、アルミニウムビスエチルア
セトアセテートアセチルアセトナート、アルミニウムジ
ｎブトキシドモノエチルアセトアセテート、アルミニウ
ムジー１−プロポキシドモノメチルアセ１〜アセテート
などであり、これらの化合物の混合物を用いることもで
きる。In addition, various catalysts known as catalysts for condensation of silanol and/or reaction between silanol and hydroxyl groups are used as necessary for the purpose of promoting curing.
An aluminum chelate compound represented by .X, .Y3-n can be preferably used. (Here, X is a lower alkoxy group, Y is M1COCH2, C0M2 and M
A ligand derived from a compound selected from the group consisting of 3COCH2COOM4 (Ml, M2, M3 and M4 are lower alkyl g>, n is 0.1 or 2). Examples of preferable compounds from the viewpoint of catalytic activity, solubility in the composition, and stability include aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, and aluminum bisethylacetoacetate acetylacetonate. , aluminum di-n-butoxide monoethylacetoacetate, aluminum di-1-propoxide monomethylacetoacetate, and mixtures of these compounds can also be used.
このような必須成分以外の添加成分は、本発明の防曇性
被膜に対して耐熱性、耐候性、耐水性、接着性あるいは
耐薬品性など本発明が適用される用途に応じて種々の実
用特性を改良しうるちのである。These additive components other than the essential components may have various practical effects on the antifogging coating of the present invention, depending on the application of the present invention, such as heat resistance, weather resistance, water resistance, adhesion, or chemical resistance. It is made of urethane with improved characteristics.
また本発明の防曇性被膜には、透明性を損わない範囲で
染顔料を添加して硬化被膜を着色せしめることも可能で
ある。It is also possible to add dyes and pigments to the antifogging film of the present invention to color the cured film within a range that does not impair transparency.
本発明の防曇性被膜の組成物を得るには、例えば各成分
を単に混合する方法、あるいは成分によってはあらかじ
め加水分解などの処理を施したものを用いて、さらに他
の成分を混合する方法などが挙げられ、これらはいずれ
も本発明の防曇性被膜組成物製造には有用な方法である
。In order to obtain the composition of the antifogging film of the present invention, for example, each component may be simply mixed together, or some components may be subjected to a treatment such as hydrolysis in advance, and then other components may be further mixed. All of these methods are useful for producing the antifogging coating composition of the present invention.
防曇性被膜の形成は５０〜２５０℃で通常行われる。あ
まり低温では硬化が不充分であるし、高温では被膜の着
色や劣化を生ずる。Formation of the antifogging film is usually carried out at 50 to 250°C. If the temperature is too low, curing will be insufficient, and if the temperature is too high, the coating will become discolored or deteriorate.
本発明によって得られる物品は、防曇性を有するもので
あるが、さらに防曇性を高める目的から、防曇性被膜形
成組成物を塗布後、硬化前または硬化後に湿潤処理する
ことによって、より防曇性を高めることが可能である。The article obtained by the present invention has anti-fogging properties, but in order to further improve the anti-fogging properties, the anti-fogging film-forming composition can be wet-treated after application, before or after curing, to further improve the anti-fogging properties. It is possible to improve anti-fogging properties.
ここで湿潤処理とは、該被膜の水または有機溶媒中への
浸漬もしくは高い湿度雰囲気下での放置をいう。この際
、必要に応じ加温される。Here, the wet treatment refers to immersing the film in water or an organic solvent, or leaving it in a high humidity atmosphere. At this time, it is heated if necessary.
さらに上記の湿潤処理の代わりに、塗膜表面をガーゼ、
不織布などで代表されろ布おるいは紙類などの柔軟性の
ある物品、もしくは水などをしめらすことによって、よ
り柔軟性を持たせた物品などで拭く摩隙処理によっても
同様の効果が発現される。Furthermore, instead of the above-mentioned wet treatment, the coating surface can be covered with gauze,
A similar effect can be achieved by abrasion treatment, which involves wiping with a flexible article such as a filter cloth or paper, such as non-woven fabric, or an article made more flexible by soaking it with water. be done.
本発明の防曇性を有する被膜は種々の形状を有するガラ
ス基材に対して適用が可能であり、実用的価値の大きい
例としては、浴室などの窓、自動車もしくは電車などの
窓などに好ましく用いられる。The anti-fogging film of the present invention can be applied to glass substrates having various shapes, and examples of great practical value include windows of bathrooms, windows of automobiles, trains, etc. used.
また、本発明にａ３いては、無機ガラス基板に代えて、
他の無機物品を用いた場合においても、効果的であり、
例えば金属、セラミックなどが挙げられる。Moreover, in the present invention, in place of the inorganic glass substrate,
It is also effective when using other inorganic products,
Examples include metals and ceramics.
基板へ塗布する方法としては、例えばへヶ塗り、浸漬塗
り、スピンコーティング、流し塗り、スプレー塗装、ロ
ール塗装、カーテンフロー塗装など通常当業界で知られ
ている各種の方法を用いることが可能である。As a method for coating the substrate, various methods commonly known in the art can be used, such as dip coating, dip coating, spin coating, flow coating, spray coating, roll coating, curtain flow coating, etc. .
以下、実施例により本発明をさらに詳しく説明覆る。Hereinafter, the present invention will be explained in more detail with reference to Examples.
［実施例］
実施例１
（１）ポリマー層の形成
無機ガラス基板上にビスフェノールＡ型エポキシ樹脂か
らなる熱硬化被膜（２０ｋ（］／ｃ＋ｒｆ押圧時におけ
る変形量は２５％）を１００μｍの厚みににコーティン
グしてポリマー層を有する無機ガラス基板を得た。[Example] Example 1 (1) Formation of polymer layer A thermosetting film (deformation amount when pressed with 20k(]/c+rf: 25%) made of bisphenol A type epoxy resin was formed to a thickness of 100 μm on an inorganic glass substrate. An inorganic glass substrate having a polymer layer was obtained by coating.
（２）防曇性コーティング組成物の調整（ａ）γ−グリ
シドキシプロピルトリメトキシシラン加水分解物の調製
ビーカーにγ−グリシドキシプロピルトリメトキシシラ
ン４０．０ｇを仕込み、液温を１０°Ｃに保ち、攪拌し
ながら０．０１規定塩酸水溶液９゜１５ｇを徐々に滴下
した。滴下終了後冷却をやめて、Ｔ−グリシドキシプロ
ピル］ヘリメトキシシランの加水分解物を得た。(2) Preparation of antifogging coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate 40.0 g of γ-glycidoxypropyltrimethoxysilane was placed in a beaker, and the liquid temperature was adjusted to 10°. 9.15 g of a 0.01N hydrochloric acid aqueous solution was gradually added dropwise while stirring. After the dropwise addition was completed, cooling was stopped to obtain a hydrolyzate of T-glycidoxypropyl]helimethoxysilane.
（ｂ）防曇塗液の調製
蒸溜水４４７ｇにポリビニルアルコール（ケン化度９１
〜９４、重合度１０００以下：カタログ値）５４．．１
Ｃ］を入れ、９０’Ｃで１時間攪拌溶解した。溶解終了
後室温までもとした。次に前記シラン加水分解物２０．
４Ｑ、メタノールシリカゾル（固形分３０％、平均粒子
径１３ｍμ）２７０ｑを加え、攪拌混合した。さらに、
１，４−ジオキサン２０６ｇ、フッ素系界面活性剤０．
５ｇ、アセチルアセトンアルミニウム２．９ｇを混合溶
解して防曇塗液とした。(b) Preparation of anti-fog coating liquid Add polyvinyl alcohol (saponification degree 91) to 447 g of distilled water.
~94, degree of polymerization 1000 or less: catalog value) 54. ．． 1
C] and stirred and dissolved at 90'C for 1 hour. After completion of dissolution, the temperature was increased to room temperature. Next, the silane hydrolyzate 20.
270q of 4Q methanol silica sol (solid content 30%, average particle size 13 mμ) were added and mixed with stirring. moreover,
1,4-dioxane 206g, fluorine surfactant 0.
5 g of acetylacetone aluminum and 2.9 g of aluminum acetylacetonate were mixed and dissolved to prepare an anti-fog coating liquid.
（２） 防曇性物品の作製
（１）で作製したポリマー層を有する無）幾ガラス基板
に、（１）の（ｂ）で調製した防曇塗液をディッピング
法（引き上げ速度５ｃｍ／ｍ１ｎ）にてコーティングし
た。その後、８０℃の熱風乾燥機で１０分間、１３０℃
で２時間の加熱硬化させた。さらに防曇性向上のため９
０’Ｃの熱水に６０分間浸漬し湿潤処理を行った。湿潤
処理後乾燥させて防曇性をイ１する物品を得た。(2) Preparation of anti-fog article The anti-fog coating liquid prepared in (b) of (1) was applied to the glass substrate having the polymer layer prepared in (1) by dipping method (pulling speed 5 cm/m1n). Coated with. Then, dry in a hot air dryer at 80°C for 10 minutes at 130°C.
It was heated and cured for 2 hours. 9 to further improve anti-fog properties.
A wet treatment was performed by immersing it in hot water at 0'C for 60 minutes. After the wet treatment, the product was dried to obtain an article with excellent antifogging properties.
（３）評価
前記（２）で得られた防曇性被膜は透明性も良く、均一
な被膜が１ｑられた。また、塗膜面に１ｍｍ角のポリマ
ー層に達するゴバン目を塗膜の上から鋼ナイフで１００
個いれて、セロハン粘着テープ（商品名“セロテープ″
ニチバン（株）製品）を強く貼りつけ、９０度方向に急
速に剥がし、塗膜剥離の有無を調べたところ、塗膜剥離
は認められず良好な接着性を有していた。硬磨試験とし
てテーパー摩耗試験（Ｊ Ｉｓ Ｒ３２１２＞を行い
１００回転後のヘーズゲイン値は３．８％でおった。ま
た、呼気を防曇性被膜に吹きつりだが、曇らず、防曇性
を有していた。(3) Evaluation The antifogging film obtained in the above (2) had good transparency and a uniform film of 1q. In addition, a steel knife was used to make a 100 mm square mark on the coating surface that reached the polymer layer.
Insert the cellophane adhesive tape (product name "Cellotape")
Nichiban Co., Ltd. product) was firmly attached and rapidly peeled off in a 90-degree direction, and the presence or absence of paint film peeling was examined. No peeling of the paint film was observed, indicating that it had good adhesion. A taper abrasion test (J Is R3212> was conducted as a hard polishing test, and the haze gain value after 100 revolutions was 3.8%.Also, when exhaled breath was blown onto the anti-fog coating, it did not fog and had anti-fog properties. Was.
比較例１
ポリマー層を設（プない以外は、実施例１と同様にして
防曇性物品を作製し、評価した。その結果、防曇性につ
いては、実施例１との有意差は全く認められなかったが
、テーパー摩耗試験におけるヘーズゲイン値が９．６％
と不良であった。Comparative Example 1 An anti-fog article was produced and evaluated in the same manner as in Example 1, except that a polymer layer was not provided. As a result, no significant difference from Example 1 was observed in terms of anti-fog properties. However, the haze gain value in the taper wear test was 9.6%.
It was defective.
［発明の効果］
本発明によって１ｑられた物品には次のような効果があ
る。[Effects of the Invention] The article produced by the present invention has the following effects.
〈１）防曇性を低下させることなく、表面硬度、とくに
テーパー摩耗性を大幅に向上させることができる。(1) Surface hardness, especially taper abrasion resistance, can be significantly improved without reducing antifogging properties.
（２）耐久性、とくに耐水性などに優れた防曇性を有す
る物品が１ｑられる。(2) 1q of articles with excellent durability, especially water resistance, and antifogging properties.
Claims (1)
式［ I ］によつて示される変形率Ｄ（％）が１０％以
上のポリマーからなる厚さ２．０μｍ以上の被膜を設け
、さらに該被膜上に下記Ａ成分およびＢ成分を主成分と
してなる防曇性被膜を設けてなることを特徴とする防曇
性を有する物品。 Ｄ（％）＝｛（Ｌ＿０−Ｌ）／Ｌ＿０｝×１００［ I
］ （式中、Ｌ＿０は無荷重における厚み、Ｌは２０ｋｇ／
ｃｍ＾２の荷重下における厚みを示す。） Ａ、ポリビニルアルコール Ｂ、平均粒子径が５〜２００ｍμのコロイド状シリカ(1) A coating with a thickness of 2.0 μm or more is provided on the surface of an inorganic glass substrate, which is made of a polymer that has adhesive properties and has a deformation rate D (%) of 10% or more as expressed by the following formula [I]. An article having antifogging properties, further comprising an antifogging coating containing the following components A and B as main components on the coating. D (%) = {(L_0-L)/L_0}×100[I
] (In the formula, L_0 is the thickness without load, L is 20kg/
Indicates the thickness under a load of cm^2. ) A, polyvinyl alcohol B, colloidal silica with an average particle size of 5 to 200 mμ
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16977488A JPH0222147A (en) | 1988-07-07 | 1988-07-07 | Article having anti-fogging property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16977488A JPH0222147A (en) | 1988-07-07 | 1988-07-07 | Article having anti-fogging property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0222147A true JPH0222147A (en) | 1990-01-25 |
Family
ID=15892615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16977488A Pending JPH0222147A (en) | 1988-07-07 | 1988-07-07 | Article having anti-fogging property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0222147A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1101748A1 (en) * | 1999-11-19 | 2001-05-23 | Central Glass Company, Limited | Article with antifogging film and process for producing same |
-
1988
- 1988-07-07 JP JP16977488A patent/JPH0222147A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1101748A1 (en) * | 1999-11-19 | 2001-05-23 | Central Glass Company, Limited | Article with antifogging film and process for producing same |
| US6420020B1 (en) | 1999-11-19 | 2002-07-16 | Central Glass Company Limited | Article with antifogging film and process for producing same |
| US6800365B2 (en) | 1999-11-19 | 2004-10-05 | Central Glass Company, Limited | Article with antifogging film and process for producing the same |
| EP1477466A1 (en) * | 1999-11-19 | 2004-11-17 | Central Glass Company, Limited | Article with antifogging film and process for producing same |
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