JPH02311332A - Preparation of water-repellent glass - Google Patents
Preparation of water-repellent glassInfo
- Publication number
- JPH02311332A JPH02311332A JP13378289A JP13378289A JPH02311332A JP H02311332 A JPH02311332 A JP H02311332A JP 13378289 A JP13378289 A JP 13378289A JP 13378289 A JP13378289 A JP 13378289A JP H02311332 A JPH02311332 A JP H02311332A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- water
- metal oxide
- repellent
- glass substrate
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 72
- 239000005871 repellent Substances 0.000 title claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 17
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000005357 flat glass Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 6
- 239000005304 optical glass Substances 0.000 abstract description 5
- 239000005046 Chlorosilane Substances 0.000 abstract description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract description 3
- 239000002356 single layer Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 239000005308 flint glass Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052814 silicon oxide Inorganic materials 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 206010036790 Productive cough Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910004481 Ta2O3 Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、建築物の窓ガラス、自動車、車両、航空機あ
るいは船舶等の風防ガラス、眼鏡やカメラなどに使われ
る光学用ガラス、家庭用ガラス器具（例えば、ガラス製
のコツプ、食器、水槽、花瓶、哺乳瓶など）、及びその
他撥水性を必要とするガラス製品に有用な撥水性ガラス
の製造方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is applicable to window glass for buildings, windshield glass for automobiles, vehicles, aircraft, ships, etc., optical glass used in eyeglasses and cameras, household glass, etc. The present invention relates to a method for producing water-repellent glass useful for utensils (e.g., glass cups, tableware, water tanks, vases, baby bottles, etc.) and other glass products that require water repellency.
（従来の技術）
従来より、ガラスの撥水処理剤としてシロキサン結合を
有するシリル化合物が多く使用されており、そしてガラ
スの表面にシロキサン重合物膜を形成して撥水化させる
方法としては、例えば、■アルキルハロシラン類の単量
体ガスをガラス表面に作用させ、しかる後加水分解する
方法、■ポリジメチルシロキサン類の溶液をガラス表面
に塗布し、しかる後加熱乾燥してシリコーン膜をガラス
表面に形成させる方法、■テトラメトキシシラン及びテ
トラエトキシシランをプラズマ重合により重合させると
共に、この重合物をガラス表面に形成させる方法がある
。(Prior Art) Silyl compounds having siloxane bonds have been widely used as water-repellent treatment agents for glass, and methods for forming a siloxane polymer film on the surface of glass to make it water-repellent include, for example. , ■ A method in which monomer gas of alkylhalosilanes is applied to the glass surface and then hydrolyzed; ■ A solution of polydimethylsiloxane is applied to the glass surface, and then heated and dried to form a silicone film on the glass surface. (2) A method in which tetramethoxysilane and tetraethoxysilane are polymerized by plasma polymerization and this polymerized product is formed on the glass surface.
（発明が解決しようとする課題）
しかしながら、上記したいずれの方法においても、ガラ
ス表面に形成された撥水性処理膜とガラスとの接着力が
弱いため、あるいはその撥水性処理膜の表面硬度が低い
ために耐久性に劣る問題があり、時間の経過とともに撥
水性が低下していた。(Problem to be Solved by the Invention) However, in any of the above methods, the adhesion between the water-repellent film formed on the glass surface and the glass is weak, or the surface hardness of the water-repellent film is low. Therefore, there was a problem with poor durability, and water repellency decreased over time.
本発明は、かかる問題を解決するためになされたもので
あって、長期間撥水性を維持することが可能な撥水性ガ
ラスの製造方法を提供することを目的とする。The present invention was made to solve this problem, and an object of the present invention is to provide a method for manufacturing water-repellent glass that can maintain water-repellency for a long period of time.
（課題を解決するための手段）
本発明の撥水性ガラスの製造方法は、表面に金属酸化物
層が形成されたガラス基材の表面を、クロルシラン化合
物、アルコキシシラン化合物及びフルオロアルキルシラ
ン化合物からなる群から選ばれた少なくとも一種のシリ
ル化合物でシリル化することを特徴としており、そのこ
とにより上記目的が達成される。(Means for Solving the Problems) The method for producing water-repellent glass of the present invention provides that the surface of a glass substrate on which a metal oxide layer is formed is made of a chlorosilane compound, an alkoxysilane compound, and a fluoroalkylsilane compound. It is characterized in that it is silylated with at least one silyl compound selected from the group, thereby achieving the above object.
本発明で使用されるガラス基材としては、例えば、はう
硅クラウン、クラウン、フリント、重フリント、バリウ
ムクラウン、重バリウムクラウン、バリウムフリント、
重バリウムフリント、ランタンフリント、ランタンクラ
ウン、重ランタンフリント等の光学ガラス及び板ガラス
等の無機ガラスがあげられる。これらの光学ガラスや板
ガラスは、レンズ、プリズム等の光学材料として、また
窓ガラスとして広く使用されているものである。Examples of the glass substrate used in the present invention include silicon crown, crown, flint, heavy flint, barium crown, heavy barium crown, barium flint,
Examples include optical glasses such as heavy barium flint, lanthanum flint, lanthanum crown, and heavy lanthanum flint, and inorganic glasses such as plate glass. These optical glasses and sheet glasses are widely used as optical materials for lenses, prisms, etc., and as window glasses.
ガラス基材上に、金属酸化物層を形成する手段としては
、ゾル−ゲル法、真空蒸着法、スパッタリング法、ＣＶ
Ｄ法、メッキ法などがあげられ、特に、親水性基である
水酸基を表面に多量に生成可能なゾル−ゲル法が好まし
い。金属酸化物の厚さは、用途によって適宜法めればよ
い。Methods for forming a metal oxide layer on a glass substrate include a sol-gel method, a vacuum evaporation method, a sputtering method, and a CV method.
Examples include the D method and the plating method, and the sol-gel method is particularly preferred since it can produce a large amount of hydroxyl groups, which are hydrophilic groups, on the surface. The thickness of the metal oxide may be determined as appropriate depending on the application.
金属酸化物層を構成する材料は、例えば、５ｉ０２、Ａ
ｌ２Ｏ３、Ｍｇｏ、 ＺｒＯ２、ＣａＯ１Ｔｉ０２．５
ｎ０２．１ｎ２０３、ＷＯ２、Ｍ２Ｏ３、Ｔａ２Ｏ３、
■ｆＯ２、Ｂａｄ、 ＺｎＯ、ムライト等があげられる
。ガラス基材表面に形成された金属酸化物は、上記材料
にて形成される単層膜や、２種以上の材料の複合膜であ
ってもよく、あるいは単層膜及び／又は複合膜を積層し
た積層膜であってもよい。特に、金属酸化物層の最上層
がシリコン酸化物かシリコン酸化物を含む組成であるこ
とが好ましい。The material constituting the metal oxide layer is, for example, 5i02, A
l2O3, Mgo, ZrO2, CaO1Ti02.5
n02.1n203, WO2, M2O3, Ta2O3,
■ Examples include fO2, Bad, ZnO, and mullite. The metal oxide formed on the surface of the glass substrate may be a single layer film formed of the above materials, a composite film of two or more materials, or a stack of single layer films and/or composite films. It may also be a laminated film. In particular, it is preferable that the uppermost layer of the metal oxide layer is silicon oxide or has a composition containing silicon oxide.
このようにして表面が金属酸化物層で被覆されたガラス
基材をシリル化合物でシリル化する。The glass substrate whose surface is thus coated with a metal oxide layer is silylated with a silyl compound.
シリル化合物としては、クロルシラン化合物、アルコキ
シシラン化合物、フルオロアルキルシラン化合物の１種
または２種以上を併用してもよい。As the silyl compound, one or more of chlorosilane compounds, alkoxysilane compounds, and fluoroalkylsilane compounds may be used in combination.
上記クロルシラン化合物としては、例えば、Ｃ１ｇＨ３
７（ＣＨ３）２ＳｉＣ１、Ｃ＋５Ｈ３ｙ（ＣＨ３）Ｓｉ
Ｃ１２、Ｃ４ＢＨ３７Ｓ ｉ Ｃ１３、ＣｇＨ＋７（Ｃ
Ｈ３）２ＳｉＣ１，Ｃ８■Ｉ□（ＣＨ３）５ｉＣ１２、
ＣｇＪ７ＳｉＣ１３、Ｃ４）１ｇ（ＣＨ３）２ＳｉＣＩ
ＳＣ４Ｈｇ（ＣＨ３）ＳｉＣ１２、Ｃ４Ｈｇ５ｉＣ１３
、（ＣＨｓ）３ＳｉＣ１１（ＣＨ３）２ｓｉｃ１２、Ｃ
Ｈ３ＳｉＣｌ３、（ＣｅＨｓ）３ＳｉｃｌＳＣ６Ｈ６（
ＣＨ３）２ＳｉＣ１，Ｃ６Ｈｓ（ＣＨ３）ＳｉＣ１２、
Ｃ６Ｈ５５ｉＣ１３、（Ｃ６）１５）２ＣＨ３ＳｉＣ１
などがあげられ、アルコキシシラン化合物としては、例
えば、ＣＨ３５ｉ （ＯＣＨｓ）ｓ、（ＣＨｓ） ２ｓ
ｉ （ＯＣＨ３） ２、（ＣＨ３）５ｓｉＯｃＨ３、Ｃ
Ｈ３５ｉ （ＯＣ２Ｈ５）３、（ＣＨ３） ２Ｓｉ （
ＯＣ２Ｈ５）２、（ＣＨ３）３ＳｉＯＣ２Ｈ５、Ｃ６Ｈ
５５ｉ （ＯＣＨ３）３、Ｃ（ＩＨ５Ｓｉ（ＯＣ２Ｈ５
）３、（Ｃ６Ｈｓ）２ｓｉ（ＯＣＨ３）２、（Ｃ，Ｈ５
）２Ｓｉ（ＯＣ２Ｈｓｈなどがあげられ、 フルオロア
ルキルシランとしては、例えば、ＣＦ３ＣＨ２ＣＨ２Ｓ
ｉ （ＯＣＨ３） ａ、ＣＦ３ＣＨ２ＣＨ２５ｉＣ１３
、ＣＦ３（ＣＦ２）５ＣＨ２ＣＨ２ＳｉＣ１３、ＣＦ３
（ＣＦ２）５ＣＨ２ＣＨ２Ｓｔ （ＯＣＨ３）３、ＣＦ
３（ＣＦ２）７ＣＨ２ＣＨ２ＳｉＣ１３、ＣＦ３（ＣＦ
２）７ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）ａ、ＣＦ３ （Ｃ
Ｆ２）７ＣＨ２ＣＨ２ＳｉＣＨ３Ｃ１２、ＣＦ３（ＣＦ
２）７ＣＨ２ＣＨ２ＳｉＣＨ３（ＯＣＨ３）２などがあ
げられる。Examples of the chlorosilane compound include C1gH3
7(CH3)2SiC1, C+5H3y(CH3)Si
C12, C4BH37S i C13, CgH+7 (C
H3)2SiC1,C8■I□(CH3)5iC12,
CgJ7SiC13,C4)1g(CH3)2SiCI
SC4Hg(CH3)SiC12, C4Hg5iC13
, (CHs)3SiC11(CH3)2sic12,C
H3SiCl3, (CeHs)3SiclSC6H6(
CH3)2SiC1, C6Hs(CH3)SiC12,
C6H55iC13, (C6)15)2CH3SiC1
Examples of alkoxysilane compounds include CH35i (OCHs)s, (CHs)2s
i (OCH3) 2, (CH3)5siOcH3,C
H35i (OC2H5)3, (CH3) 2Si (
OC2H5)2, (CH3)3SiOC2H5, C6H
55i (OCH3)3, C(IH5Si(OC2H5
)3, (C6Hs)2si(OCH3)2, (C,H5
)2Si(OC2Hsh, etc.), and examples of fluoroalkylsilane include CF3CH2CH2S
i (OCH3) a, CF3CH2CH25iC13
, CF3(CF2)5CH2CH2SiC13, CF3
(CF2)5CH2CH2St (OCH3)3, CF
3(CF2)7CH2CH2SiC13, CF3(CF
2) 7CH2CH2Si(OCH3)a, CF3 (C
F2)7CH2CH2SiCH3C12, CF3(CF
2) 7CH2CH2SiCH3(OCH3)2 and the like.
金属酸化物で被覆されたガラス基材をシリル化するには
、シリル化合物を含む処理剤でその表面−５＝
を処理すればよく、シリル化合物が粘度の低い液体であ
る場合にはそのまま処理剤として用いることができ、粘
度が高い液体あるいは固体である場合にはベンゼン、ト
ルエン、ヘキサン等の有機溶媒で希釈した溶液を処理剤
として金属酸化物で被覆されたガラス基材表面に接触さ
せることにより、表面処理を行えばよい。このとき、ピ
リジンやヘキサメチレンジシアミン等を加えてお（と、
処理剤とガラス基材表面との反応はよりスムーズに行わ
れる。To silylate a glass substrate coated with a metal oxide, it is sufficient to treat its surface -5= with a treatment agent containing a silyl compound.If the silyl compound is a liquid with low viscosity, the treatment agent can be used as is. If it is a highly viscous liquid or solid, it can be used as a treatment agent by contacting a solution diluted with an organic solvent such as benzene, toluene, or hexane to the surface of a glass substrate coated with a metal oxide. , surface treatment may be performed. At this time, add pyridine, hexamethylene dicyamine, etc. (and
The reaction between the treatment agent and the surface of the glass substrate is carried out more smoothly.
処理方法は、いずれの方法が採用されてもよく、例えば
、■金属酸化物で被覆されたガラス基材を処理剤に浸漬
した後、そのガラス基材を処理剤から引き上げ乾燥後加
熱する方法、■ガラス基材の表面に処理剤をスプレーし
、乾燥後加熱する方法、■金属酸化物で被覆されたガラ
ス基材を減圧下で処理剤に加えて処理剤の沸点付近で加
熱還流を１〜２０時間行い、メタシロキサン結合させる
方法等がある。上記■及び■の方法において、加熱する
ことにより金属酸化物層表面に存在する水酸基とメタロ
シロキサン結合させることができる。その加熱は通常１
００°Ｃ〜４００°Ｃで行えばよい。Any method may be adopted as the treatment method, for example, (1) a method in which a glass substrate coated with a metal oxide is immersed in a treatment agent, and then the glass substrate is pulled up from the treatment agent, dried, and then heated; ■Method of spraying a treatment agent onto the surface of a glass substrate and heating it after drying; ■Adding a glass substrate coated with a metal oxide to the treatment agent under reduced pressure and heating under reflux near the boiling point of the treatment agent for 1 to 30 minutes. There is a method in which the process is carried out for 20 hours to form a metasiloxane bond. In the above methods (1) and (2), metallosiloxane bonds can be formed with the hydroxyl groups present on the surface of the metal oxide layer by heating. The heating is usually 1
It may be carried out at 00°C to 400°C.
このようにして得られた撥水性ガラスの表面は優れた撥
水性を有し、しかも耐久性にも優れているものである。The surface of the water-repellent glass thus obtained has excellent water repellency and is also excellent in durability.
（実施例） 以下に本発明を実施例に基づいて具体的に説明する。(Example) The present invention will be specifically described below based on Examples.
実ｍ
テトラエチルシリケート（コルコート社製）エタ７−ル
溶液と、水と、触媒として塩酸とを混合して加水分解溶
液を調製した。この溶液をホウケイ酸ガラスのスライド
ガラス（マツナミ社製）の表面にコーティングした後乾
燥し、さらに５００°Ｃで熱処理することによってシリ
コン酸化物層を形成した。シリコン酸化物層の厚さは約
０．２μｍであった。次に、シリコン酸化物層で被覆さ
れたガラスを、減圧下（約１．５Ｔｏｒｒ） 、１５０
°Ｃ，３時間加熱処理を行い脱湿した後、減圧下にＣＨ
Ｈ３７（ＣＨ３）２ＳｉＣ１１ｇ１ピリジン１ｇの入っ
たトルエン溶液１００ｃｃの中＝７−
に浸漬し、１４０℃、６時間加熱還流した。その後、ト
ルエン、メタノールで順次充分洗浄し、乾燥して撥水性
ガラスを得た。A hydrolyzed solution was prepared by mixing an ethanol solution of tetraethyl silicate (manufactured by Colcourt), water, and hydrochloric acid as a catalyst. This solution was coated on the surface of a borosilicate glass slide glass (manufactured by Matsunami Co., Ltd.), dried, and further heat-treated at 500°C to form a silicon oxide layer. The thickness of the silicon oxide layer was approximately 0.2 μm. Next, the glass coated with the silicon oxide layer was heated at 150° C. under reduced pressure (approximately 1.5 Torr).
After heat treatment at °C for 3 hours and dehumidification, CH
It was immersed in 100 cc of a toluene solution containing 11 g of H37(CH3)2SiC1 and 1 g of pyridine, and heated under reflux at 140°C for 6 hours. Thereafter, the glass was thoroughly washed with toluene and methanol in order, and dried to obtain water-repellent glass.
次に、この撥水性ガラスの撥水性及び鉛筆硬度の評価を
行った。撥水性の評価は撥水性ガラスの水に対する接触
角にて評価した。また、耐久性は６０°Ｃ１９０％Ｒ１
（中に撥水性ガラスを１ケ月放置した後、上記と同様の
方法で接触角を測定した（耐湿性）。鉛筆硬度の評価は
ＪＩＳ Ｋ ５４００に準じて行った。結果を表１に示
した。Next, the water repellency and pencil hardness of this water repellent glass were evaluated. Water repellency was evaluated based on the contact angle of water repellent glass with water. In addition, the durability is 60°C 190% R1
(After leaving the water-repellent glass inside for one month, the contact angle was measured using the same method as above (moisture resistance). Evaluation of pencil hardness was performed according to JIS K 5400. The results are shown in Table 1. .
及痰且主
Ｃ＋ ８Ｈ３７（ＣＨ３）２５４Ｃ１の代わりにＣＨＨ
３７ＳｉＣ１３を用いた以外は、実施例１と同様にして
撥水性ガラスを得た。and sputum and main C+ 8H37 (CH3) CHH instead of 254C1
A water-repellent glass was obtained in the same manner as in Example 1 except that 37SiC13 was used.
この撥水性ガラスの撥水性、耐久性及び鉛筆硬度を実施
例１と同様にして評価した。その結果を表１に示した。The water repellency, durability, and pencil hardness of this water-repellent glass were evaluated in the same manner as in Example 1. The results are shown in Table 1.
Ｋ籠外主
実施例１と同様にしてシリコン酸化物層で被覆されたガ
ラスを得た。次に、このガラスをＣＰ３Ｃ１！２ＣＨ２
Ｓｉ （ＯＣＨ３）３１ ｇの入ったトルエン溶液１０
０ｃｃの中に浸漬し、引き上げることによりガラス表面
に溶液を均一に塗布した。塗布後、４００℃の電気炉中
に５分間入れ、シリコン酸化物層表面の水酸基とフルオ
ロアルキルシランとを化学結合させ、撥水性ガラスを得
た。A glass coated with a silicon oxide layer was obtained in the same manner as in Example 1. Next, this glass is CP3C1!2CH2
10 toluene solution containing 31 g of Si (OCH3)
The solution was applied uniformly to the glass surface by immersing it in 0 cc of water and pulling it up. After coating, the glass was placed in an electric furnace at 400° C. for 5 minutes to chemically bond the hydroxyl groups on the surface of the silicon oxide layer and the fluoroalkylsilane to obtain water-repellent glass.
この撥水性ガラスの撥水性、耐久性及び鉛筆硬度を実施
例１と同様にして評価した。その結果を表１に示した。The water repellency, durability, and pencil hardness of this water-repellent glass were evaluated in the same manner as in Example 1. The results are shown in Table 1.
友監匠土
スライドガラス表面に、５ｔＯ２／Ｍｇ０＝ ９／ １
（重量比）となる組成の金属酸化物層を厚さ０．２μ
ｍにゾル−ゲル法により形成した。この金属酸化物層被
覆スライドガラスを実施例１と同様に処理して撥水性ガ
ラスを得た。5tO2/Mg0=9/1 on the slide glass surface
A metal oxide layer with a composition of (weight ratio) of 0.2μ thick
It was formed by the sol-gel method. This slide glass coated with a metal oxide layer was treated in the same manner as in Example 1 to obtain water-repellent glass.
この撥水性ガラスの撥水性、耐久性及び鉛筆硬度を実施
例１と同様にして評価した。その結果を表１に示した。The water repellency, durability, and pencil hardness of this water-repellent glass were evaluated in the same manner as in Example 1. The results are shown in Table 1.
ン酸化物層（Ｓ１０２）をゾル−ゲル法により形成し、
さらにその上に厚さ０．１μｍの酸化ジルコニウム層（
Ｚｒ０２）をゾル−ゲル法により形成した。この金属酸
化物層被覆スライドガラスを実施例１と同様に処理して
撥水性ガラスを得た。Form an oxide layer (S102) by a sol-gel method,
Further on top of that is a 0.1 μm thick zirconium oxide layer (
Zr02) was formed by a sol-gel method. This slide glass coated with a metal oxide layer was treated in the same manner as in Example 1 to obtain water-repellent glass.
この撥水性ガラスの撥水性、耐久性及び鉛筆硬度を実施
例１と同様にして評価した。その結果を表１に示した。The water repellency, durability, and pencil hardness of this water-repellent glass were evaluated in the same manner as in Example 1. The results are shown in Table 1.
嵐狡匠エ
シリコン酸化物層被覆スライドガラスの代わりに、シリ
コン酸化物層が形成されてないスライドガラスを用いた
以外は、実施例１と同様に処理し−て撥−水性ガラスを
得た。A water-repellent glass was obtained by processing in the same manner as in Example 1, except that a slide glass on which no silicon oxide layer was formed was used instead of the silicon oxide layer-coated slide glass.
この撥水性ガラスの撥水性、耐久性及び鉛筆硬度を実施
例１と同様にして評価した。その結果を表１に示した。The water repellency, durability, and pencil hardness of this water-repellent glass were evaluated in the same manner as in Example 1. The results are shown in Table 1.
坂蝮匠主
シリコン酸化物層被覆スライドガラスの代わりに、シリ
コン酸化物層が形成されてないスライドガラスを用いた
以外は、実施例３と同様に処理して撥水性ガラスを得た
。A water-repellent glass was obtained in the same manner as in Example 3, except that a slide glass on which no silicon oxide layer was formed was used instead of the silicon oxide layer-coated slide glass.
この撥水性ガラスの撥水性、耐久性及び鉛筆硬度を実施
例１と同様にして評価した。その結果を表１に示した。The water repellency, durability, and pencil hardness of this water-repellent glass were evaluated in the same manner as in Example 1. The results are shown in Table 1.
表１
（発明の効果）
本発明の撥水性ガラスの製造方法によれば、撥水性と耐
久性が共に優れた撥水性ガラスを得ることができ、建築
物の窓ガラス、自動車などの風防ガラス、眼鏡やカメラ
などに使われる光学用ガラス、家庭用ガラス器具、及び
その他撥水性を必要とするガラス製品などに長期に亘っ
て撥水性を付与することができる。Table 1 (Effects of the invention) According to the method for producing water-repellent glass of the present invention, water-repellent glass that is excellent in both water repellency and durability can be obtained, and can be used as a window glass for buildings, a windshield glass for automobiles, etc. It is possible to impart long-term water repellency to optical glass used in eyeglasses, cameras, etc., household glassware, and other glass products that require water repellency.
以上 出願人 積水化学工業株式会社 代表者 廣１） 馨that's all Applicant: Sekisui Chemical Co., Ltd. Representative: Hiro 1) Kaoru
Claims (1)
を、クロルシラン化合物、アルコキシシラン化合物及び
フルオロアルキルシラン化合物からなる群から選ばれた
少なくとも一種のシリル化合物でシリル化することを特
徴とする撥水性ガラスの製造方法。1. The surface of a glass substrate on which a metal oxide layer is formed is silylated with at least one silyl compound selected from the group consisting of chlorosilane compounds, alkoxysilane compounds, and fluoroalkylsilane compounds. A method for producing water-repellent glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13378289A JPH02311332A (en) | 1989-05-26 | 1989-05-26 | Preparation of water-repellent glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13378289A JPH02311332A (en) | 1989-05-26 | 1989-05-26 | Preparation of water-repellent glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02311332A true JPH02311332A (en) | 1990-12-26 |
Family
ID=15112870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13378289A Pending JPH02311332A (en) | 1989-05-26 | 1989-05-26 | Preparation of water-repellent glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02311332A (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132637A (en) * | 1990-09-26 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Glass and production thereof |
| JPH04285037A (en) * | 1991-03-14 | 1992-10-09 | Tokai Rika Co Ltd | Electrochromic mirror with water-repellent film |
| EP0513727A2 (en) * | 1991-05-13 | 1992-11-19 | Toyota Jidosha Kabushiki Kaisha | Water repellent glass and process for producing the same |
| JPH04359031A (en) * | 1991-06-04 | 1992-12-11 | Matsushita Electric Ind Co Ltd | Water-and-oil repellent film |
| JPH0531441A (en) * | 1990-10-25 | 1993-02-09 | Matsushita Electric Ind Co Ltd | Fluorocarbon coating film and its production |
| EP0545201A2 (en) * | 1991-11-29 | 1993-06-09 | Ppg Industries, Inc. | Durable water repellent glass surface |
| JPH061636A (en) * | 1992-05-19 | 1994-01-11 | Toyota Motor Corp | Water-repellent glass |
| FR2694551A1 (en) * | 1992-08-06 | 1994-02-11 | Mitsubishi Motors Corp | Hydrophobic glass pane, method of manufacture and corresponding glass article. |
| US5424130A (en) * | 1991-05-13 | 1995-06-13 | Toyota Jidosha Kabushiki Kaisha | Water repellent glass and process for producing the same |
| EP0692463A1 (en) * | 1994-07-13 | 1996-01-17 | Saint-Gobain Vitrage | Hydrophobic multilayer glazing |
| US5523161A (en) * | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
| US5523162A (en) * | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment for plastic and coated plastic substrates |
| US5674967A (en) * | 1990-04-03 | 1997-10-07 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
| US5683804A (en) * | 1994-04-28 | 1997-11-04 | Central Glass Company, Limited | Glass plate with ultraviolet and infrared absorbing film |
| US5707740A (en) * | 1990-04-03 | 1998-01-13 | Ppg Industries, Inc. | Water repellent surface treatment with acid activation |
| EP0864622A2 (en) * | 1991-01-23 | 1998-09-16 | Matsushita Electric Industrial Co., Ltd | Water- and oil- repellant article |
| WO1998040323A1 (en) * | 1997-03-11 | 1998-09-17 | Nippon Sheet Glass Co., Ltd. | A substrate having a treatment surface |
| JPH10310455A (en) * | 1991-01-23 | 1998-11-24 | Matsushita Electric Ind Co Ltd | Production comprising glass base body having oil-and water-repellent coating film and its production |
| FR2769318A1 (en) * | 1997-10-06 | 1999-04-09 | Saint Gobain Vitrage | Hydrophobic coating for e.g. glass |
| WO1999028534A1 (en) | 1997-12-04 | 1999-06-10 | Nippon Sheet Glass Co., Ltd. | Process for the production of articles covered with silica-base coats |
| US6025025A (en) * | 1990-04-03 | 2000-02-15 | Ppg Industries Ohio, Inc. | Water-repellent surface treatment |
| USRE37698E1 (en) | 1990-10-25 | 2002-05-14 | Matsushita Electric Industrial Co. | Method of manufacturing a fluorocarbon-based coating film |
| JP2004002187A (en) * | 1991-01-23 | 2004-01-08 | Matsushita Electric Ind Co Ltd | Water repellent and oil repellent coating film |
| WO2004058418A1 (en) * | 2002-12-24 | 2004-07-15 | Ppg Industries Ohio, Inc. | Water repellent surface treatment and treated articles |
| JP2009512551A (en) * | 2005-10-24 | 2009-03-26 | アキュロン， インコーポレイテッド | Polymeric organometallic film |
| WO2023136000A1 (en) * | 2022-01-13 | 2023-07-20 | 日本板硝子株式会社 | Glass article with easy-to-clean coating |
| WO2023135999A1 (en) * | 2022-01-13 | 2023-07-20 | 日本板硝子株式会社 | Glass article with easy-to-clean coating |
-
1989
- 1989-05-26 JP JP13378289A patent/JPH02311332A/en active Pending
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5707740A (en) * | 1990-04-03 | 1998-01-13 | Ppg Industries, Inc. | Water repellent surface treatment with acid activation |
| US5674967A (en) * | 1990-04-03 | 1997-10-07 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
| US5523162A (en) * | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment for plastic and coated plastic substrates |
| US5523161A (en) * | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
| US5980990A (en) * | 1990-04-03 | 1999-11-09 | Ppg Industries Ohio, Inc. | Water repellent surface treatment with acid activation |
| US6025025A (en) * | 1990-04-03 | 2000-02-15 | Ppg Industries Ohio, Inc. | Water-repellent surface treatment |
| JPH04132637A (en) * | 1990-09-26 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Glass and production thereof |
| JPH0531441A (en) * | 1990-10-25 | 1993-02-09 | Matsushita Electric Ind Co Ltd | Fluorocarbon coating film and its production |
| USRE37698E1 (en) | 1990-10-25 | 2002-05-14 | Matsushita Electric Industrial Co. | Method of manufacturing a fluorocarbon-based coating film |
| USRE38752E1 (en) | 1990-10-25 | 2005-07-05 | Matsushita Electric Industrial Co., Ltd | Method of manufacturing a fluorocarbon-based coating film |
| EP0864622A3 (en) * | 1991-01-23 | 2000-04-26 | Matsushita Electric Industrial Co., Ltd | Water- and oil- repellant article |
| EP1224983A2 (en) * | 1991-01-23 | 2002-07-24 | Matsushita Electric Industrial Co., Ltd. | Transparent substrate and method for preparing same |
| EP1224983A3 (en) * | 1991-01-23 | 2002-12-18 | Matsushita Electric Industrial Co., Ltd. | Transparent substrate and method for preparing same |
| EP0867490A2 (en) * | 1991-01-23 | 1998-09-30 | Matsushita Electric Industrial Co., Ltd. | Water- and oil- repellant article |
| JP2004002187A (en) * | 1991-01-23 | 2004-01-08 | Matsushita Electric Ind Co Ltd | Water repellent and oil repellent coating film |
| EP0867490A3 (en) * | 1991-01-23 | 1999-02-03 | Matsushita Electric Industrial Co., Ltd. | Water- and oil- repellant article |
| EP0864622A2 (en) * | 1991-01-23 | 1998-09-16 | Matsushita Electric Industrial Co., Ltd | Water- and oil- repellant article |
| JPH10310455A (en) * | 1991-01-23 | 1998-11-24 | Matsushita Electric Ind Co Ltd | Production comprising glass base body having oil-and water-repellent coating film and its production |
| JPH04285037A (en) * | 1991-03-14 | 1992-10-09 | Tokai Rika Co Ltd | Electrochromic mirror with water-repellent film |
| US5424130A (en) * | 1991-05-13 | 1995-06-13 | Toyota Jidosha Kabushiki Kaisha | Water repellent glass and process for producing the same |
| EP0513727A2 (en) * | 1991-05-13 | 1992-11-19 | Toyota Jidosha Kabushiki Kaisha | Water repellent glass and process for producing the same |
| JPH04359031A (en) * | 1991-06-04 | 1992-12-11 | Matsushita Electric Ind Co Ltd | Water-and-oil repellent film |
| EP0545201A3 (en) * | 1991-11-29 | 1995-01-25 | Ppg Industries Inc | |
| EP0545201A2 (en) * | 1991-11-29 | 1993-06-09 | Ppg Industries, Inc. | Durable water repellent glass surface |
| JPH061636A (en) * | 1992-05-19 | 1994-01-11 | Toyota Motor Corp | Water-repellent glass |
| FR2694551A1 (en) * | 1992-08-06 | 1994-02-11 | Mitsubishi Motors Corp | Hydrophobic glass pane, method of manufacture and corresponding glass article. |
| US5683804A (en) * | 1994-04-28 | 1997-11-04 | Central Glass Company, Limited | Glass plate with ultraviolet and infrared absorbing film |
| FR2722493A1 (en) * | 1994-07-13 | 1996-01-19 | Saint Gobain Vitrage | MULTILAYER HYDROPHOBIC GLAZING |
| EP0692463A1 (en) * | 1994-07-13 | 1996-01-17 | Saint-Gobain Vitrage | Hydrophobic multilayer glazing |
| US6482524B1 (en) | 1997-03-11 | 2002-11-19 | Nippon Sheet Glass Co., Ltd. | Substrate having a treatment surface |
| WO1998040323A1 (en) * | 1997-03-11 | 1998-09-17 | Nippon Sheet Glass Co., Ltd. | A substrate having a treatment surface |
| WO1999018168A1 (en) * | 1997-10-06 | 1999-04-15 | Saint-Gobain Vitrage | Hydrophobic coating in particular for glazing sheet |
| FR2769318A1 (en) * | 1997-10-06 | 1999-04-09 | Saint Gobain Vitrage | Hydrophobic coating for e.g. glass |
| US6465108B1 (en) | 1997-12-04 | 2002-10-15 | Nippon Sheet Glass Co., Ltd. | Process for the production of articles covered with silica-base coats |
| WO1999028534A1 (en) | 1997-12-04 | 1999-06-10 | Nippon Sheet Glass Co., Ltd. | Process for the production of articles covered with silica-base coats |
| WO2004058418A1 (en) * | 2002-12-24 | 2004-07-15 | Ppg Industries Ohio, Inc. | Water repellent surface treatment and treated articles |
| JP2009512551A (en) * | 2005-10-24 | 2009-03-26 | アキュロン， インコーポレイテッド | Polymeric organometallic film |
| WO2023136000A1 (en) * | 2022-01-13 | 2023-07-20 | 日本板硝子株式会社 | Glass article with easy-to-clean coating |
| WO2023135999A1 (en) * | 2022-01-13 | 2023-07-20 | 日本板硝子株式会社 | Glass article with easy-to-clean coating |
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