JPS6125663B2 - - Google Patents
Info
- Publication number
- JPS6125663B2 JPS6125663B2 JP1562978A JP1562978A JPS6125663B2 JP S6125663 B2 JPS6125663 B2 JP S6125663B2 JP 1562978 A JP1562978 A JP 1562978A JP 1562978 A JP1562978 A JP 1562978A JP S6125663 B2 JPS6125663 B2 JP S6125663B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- metal oxide
- water
- coating
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000011521 glass Substances 0.000 claims description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000005329 float glass Substances 0.000 description 4
- 239000006060 molten glass Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical class CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- -1 isodium Chemical compound 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001415 sodium ion 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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
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)
Description
【発明の詳細な説明】
本発明は光学特性の優れた透明な金属酸化物被
膜を付着したガラス、特に光学特性の優れた透明
な電気伝導性金属酸化物被膜を付着したガラスの
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glass coated with a transparent metal oxide coating having excellent optical properties, particularly glass coated with a transparent electrically conductive metal oxide coating having excellent optical properties.
従来から加熱されたガラスに、高温で分解して
錫、アンチモン、インジウム、鉄、クロム、コバ
ルト、チタン、ニツケル又は珪素等の金属酸化物
となり得る金属化合物の溶液をスプレーして、ガ
ラス上に透明なこれらの金属酸化物被膜を付着せ
しめる方法が知られている。 Conventionally, heated glass is sprayed with a solution of a metal compound that can decompose at high temperatures to form metal oxides such as tin, antimony, indium, iron, chromium, cobalt, titanium, nickel, or silicon, creating a transparent coating on the glass. Methods for depositing these metal oxide films are known.
この方法により製造される透明な金属酸化物被
膜を付着したガラスは電気伝導ガラス、熱線反射
ガラス、あるいは耐擦傷ガラスとして実用に供さ
れているが、該金属酸化物被膜の光学特性の更に
優れたもの、特に該金属酸化物被膜の白濁状曇り
（ヘイズ）のない光学特性の優れたものが要求さ
れている。 Glass with a transparent metal oxide coating produced by this method is used in practical applications as electrically conductive glass, heat-reflecting glass, or scratch-resistant glass. In particular, there is a demand for metal oxide coatings with excellent optical properties without cloudy cloudiness (haze).
本発明者はこの金属酸化物被膜の白濁状曇り現
象について鋭意研究した結果、金属酸化物被膜を
形成されるガラスが溶融ガラスから成形されてか
ら長い日時を経ていない場合により強い白濁状曇
りを生じることに着眼し、本発明者は溶融ガラス
から成形された後、長い日時を経ていない吸着水
をほとんど有しないガラス表面では金属酸化物被
膜に分解する金属化合物の分解が十分に行なわれ
ないので白濁状曇りを生じるためであろうと推定
した。 As a result of intensive research into this cloudy clouding phenomenon of metal oxide coatings, the inventors of the present invention have found that stronger cloudy clouding occurs when the glass on which the metal oxide coating is formed has not passed a long time since it was formed from molten glass. Focusing on this, the present inventor discovered that on glass surfaces that have not been molded from molten glass for a long time and have almost no adsorbed water, metal compounds that decompose into metal oxide films are not sufficiently decomposed, resulting in cloudiness. It is assumed that this is due to the formation of cloudy weather.
ここにいうガラス表面の吸着水とはガラス表面
の珪酸原子に直接結合した水酸基（珪素原子とと
もにシラノール基とよばれる）を示す化学的吸着
水と、この化学吸着水にフアンデルワールスカに
より吸着した物理吸着水とを意味する。 The adsorbed water on the glass surface refers to chemically adsorbed water that represents hydroxyl groups (together with silicon atoms, called silanol groups) directly bonded to silicic acid atoms on the glass surface, and chemically adsorbed water that is adsorbed to this chemically adsorbed water by van der Waalska. Physically adsorbed water.
本発明は溶融ガラスから成形された直後の新し
いガラスに適用しても白濁状曇りのほとんどでな
い優れた光学特性を有する透明な金属酸化物被膜
を付着したガラスの製造方法を提供するものであ
つて、本発明は珪酸網目構造を有するガラスを加
熱し、この加熱されたガラスに熱分解により金属
酸化物に転化する金属化合物の溶液を付着せしめ
てガラス上に金属酸化物被膜を付着せしめる方法
において、該ガラスをあらかじめ水中で煮沸して
おくことを特徴とする透明な金属酸化物被膜を付
着したガラスの製造方法である。 The present invention provides a method for producing glass to which a transparent metal oxide coating is attached, which has excellent optical properties with almost no cloudy clouding even when applied to new glass immediately after being molded from molten glass. The present invention provides a method of heating glass having a silicate network structure and depositing a metal oxide film on the glass by depositing a solution of a metal compound that is converted into a metal oxide by thermal decomposition on the heated glass. This is a method for producing glass coated with a transparent metal oxide film, which is characterized in that the glass is boiled in water in advance.
本発明において、珪酸網目構造を有するガラス
とはソーダ石灰ガラス、硼珪酸ガラス、シリカガ
ラス等の珪酸網目構造を有するガラスを意味す
る。 In the present invention, glass having a silicate network structure means glass having a silicate network structure such as soda lime glass, borosilicate glass, and silica glass.
本発明において、金属化合物は熱によつて分解
して金属酸化物となり得るものであつて、例えば
錫、アンチモン、イソジウム、鉄、コバルト、チ
タン、ニツケル、アルミニウム等の金属のハロゲ
ン化物、アルコキシド、アセチルアセトネート、
キレート化合物、特に塩化第二錫、塩化アンチモ
ン等の化合物が用いられる。 In the present invention, the metal compound is one that can be decomposed by heat to become a metal oxide, such as metal halides, alkoxides, acetyl, etc., such as tin, antimony, isodium, iron, cobalt, titanium, nickel, and aluminum. acetonate,
Chelate compounds are used, especially compounds such as stannic chloride, antimony chloride, and the like.
本発明において金属酸化物被膜を付着しようと
するガラスの煮沸は該ガラスを高温の水中に入れ
て行い、好ましくは水中の気泡が出る沸騰水中で
30分間以上煮沸する。 In the present invention, the glass to which the metal oxide film is to be attached is boiled by placing the glass in high-temperature water, preferably in boiling water where air bubbles are generated in the water.
Boil for at least 30 minutes.
本発明は金属酸化物被膜を付着させるガラスを
あらかじめ煮沸しておくことにより、白濁状曇り
のほとんどない優れた光学特性をもつ透明な金属
酸化物被膜を付着したガラスを製造することがで
きる。この理由は定かではないが、ソーダ石灰ガ
ラス等の珪酸網目構造を有するガラスを煮沸する
と、ガラス表面のナトリウムイオンが減少し、ガ
ラス表面部分の珪酸網目構造端部にシラノール基
を有するようになるとともに水分がガラス内部に
侵入した形で吸着し、このような表面状態の加熱
されたガラスに金属化合物の溶液を付着せしめる
と、吸着水が金属化合物の分解を助長し、形成さ
れる金属酸化物被膜中に未分解の金属化合物を残
さないため、該被膜に白濁状曇りをほとんど生じ
させず、またガラス表面のシラノール基の活性度
の高い酸素原子と被膜を形成する金属酸化物の金
属とが直接結合して該被膜の耐候性と耐摩耗性を
も向上させるものと考えられる。 In the present invention, by boiling the glass to which the metal oxide coating is to be applied in advance, it is possible to produce glass with a transparent metal oxide coating that has excellent optical properties with almost no cloudy cloudiness. The reason for this is not clear, but when a glass with a silicate network structure such as soda-lime glass is boiled, sodium ions on the glass surface decrease, and the ends of the silicate network structure on the glass surface begin to have silanol groups. When water is adsorbed inside the glass and a solution of a metal compound is applied to heated glass with such a surface condition, the adsorbed water promotes the decomposition of the metal compound and a metal oxide film is formed. Since no undecomposed metal compounds are left in the coating, there is almost no cloudiness in the coating, and the highly active oxygen atoms of the silanol groups on the glass surface are directly connected to the metal of the metal oxide forming the coating. It is believed that the combination also improves the weather resistance and abrasion resistance of the coating.
以下、本発明の一実施例について述べる。 An embodiment of the present invention will be described below.
溶融ガラスから成形した後、約１カ月を経過し
た通常の板ガラス組成のフロートガラス板１をガ
ラス板煮沸容器２の水中の立掛け台４，４′に互
に間隙をおいて立掛けて水面３下に位置させ、立
掛け台４の下に設けたスチーム供給パイプ５から
スチームを供給し、水を60分間沸騰させ煮沸処理
をした。 A float glass plate 1 of a normal plate glass composition, which has been molded from molten glass for about one month, is placed on the submerged stands 4 and 4' of the glass plate boiling vessel 2 with a gap between them, and then the float glass plate 1 is placed on the water surface 3. Steam was supplied from a steam supply pipe 5 located below the stand 4, and the water was boiled for 60 minutes for boiling treatment.
次に前記の煮沸処理をしたガラス板を645℃に
加熱し、そのガラス板に、塩化第２錫：80重量
％、塩化アンチモン：２重量％、アルコール８重
量％、水：10重量％に調合した溶液をスプレーで
吹き付けて、塩化第二錫、及び塩化アンチモンを
熱によつて分解させてガラス板上に錫及びアンチ
モンの電導性酸化物被膜を形成した。 Next, the glass plate that has been subjected to the boiling process is heated to 645°C, and a mixture of 80% by weight of tin chloride, 2% by weight of antimony chloride, 8% by weight of alcohol, and 10% by weight of water is added to the glass plate. The resulting solution was sprayed to decompose the stannic chloride and antimony chloride with heat to form a conductive oxide film of tin and antimony on the glass plate.
得られた錫及びアンチモン酸化物被膜をもつ電
気伝導ガラス板は白濁状曇りがほとんど認められ
なかつた。 The electrically conductive glass plate having the tin and antimony oxide coating had almost no cloudy cloudiness.
一方、比較試料として前記フロートガラス板と
同一ロツトのガラス板を用いて煮沸処理のみをせ
ず、他は前記と同様の条件で錫及びアンチモンの
酸化物被膜をもつ電気伝導ガラス板を製造したと
ころ、やや強い白濁状曇りが認められ、前記した
煮沸処理したものに比べてきわめて劣つたもので
あつた。 On the other hand, as a comparison sample, an electrically conductive glass plate with a tin and antimony oxide film was produced using a glass plate from the same lot as the float glass plate, without the boiling treatment, and under the same conditions as above. A somewhat strong white cloudiness was observed, and the product was extremely inferior to the one subjected to the boiling treatment described above.
図面は本発明の一実施例を示すものであつて、
第１図はガラス板の煮沸容器の縦断面図である。
１…フロートガラス板、２…ガラス板煮沸容
器、４，４′…立掛け台、５…スチーム供給パイ
プ。
The drawings show one embodiment of the invention,
FIG. 1 is a longitudinal sectional view of a boiling vessel made of glass plate. 1... Float glass plate, 2... Glass plate boiling container, 4, 4'... Stand, 5... Steam supply pipe.
Claims (1)
加熱されたガラスに熱分解により金属酸化物に転
化する金属化合物の溶液を付着せしめてガラス上
に金属酸化物被膜を付着せしめる方法において、
該ガラスをあらかじめ水中で煮沸しておくことを
特徴とする透明な金属酸化物被膜を付着したガラ
スの製造方法。1. A method of heating glass having a silicate network structure and depositing a metal oxide film on the glass by depositing a solution of a metal compound that is converted into a metal oxide by thermal decomposition on the heated glass,
A method for producing glass with a transparent metal oxide coating, which comprises boiling the glass in water in advance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1562978A JPS54107919A (en) | 1978-02-13 | 1978-02-13 | Production of transparent metal oxide coated glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1562978A JPS54107919A (en) | 1978-02-13 | 1978-02-13 | Production of transparent metal oxide coated glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54107919A JPS54107919A (en) | 1979-08-24 |
| JPS6125663B2 true JPS6125663B2 (en) | 1986-06-17 |
Family
ID=11893999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1562978A Granted JPS54107919A (en) | 1978-02-13 | 1978-02-13 | Production of transparent metal oxide coated glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54107919A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11021467B2 (en) | 2014-06-13 | 2021-06-01 | Gilead Sciences, Inc. | Phosphatidylinositol 3-kinase inhibitors |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340408A (en) * | 1980-04-28 | 1982-07-20 | National Research Development Corporation | High silica glass |
-
1978
- 1978-02-13 JP JP1562978A patent/JPS54107919A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11021467B2 (en) | 2014-06-13 | 2021-06-01 | Gilead Sciences, Inc. | Phosphatidylinositol 3-kinase inhibitors |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54107919A (en) | 1979-08-24 |
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