JPH06316439A - Heat ray shielding glass plate and production thereof - Google Patents
Heat ray shielding glass plate and production thereofInfo
- Publication number
- JPH06316439A JPH06316439A JP5104526A JP10452693A JPH06316439A JP H06316439 A JPH06316439 A JP H06316439A JP 5104526 A JP5104526 A JP 5104526A JP 10452693 A JP10452693 A JP 10452693A JP H06316439 A JPH06316439 A JP H06316439A
- Authority
- JP
- Japan
- Prior art keywords
- heat ray
- film
- glass plate
- tin oxide
- ray shielding
- 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.)
- Granted
Links
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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (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)
- Special Wing (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、乗り物用窓ガラスまた
は建物用窓ガラスに好適な熱線遮蔽ガラス板、およびそ
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray-shielding glass plate suitable for a vehicle window glass or a building window glass, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、熱線遮蔽ガラス板を製造する方法
として次の方法が知られている。 （１）ガラス板上に誘電体の多層膜をスパッタリング、
真空蒸着、又はゾル−ゲル法等により形成する方法 （２）ガラス板上に金属蒸着膜、または金属窒化物、金
属炭化物のスパッタリング薄膜を形成する方法 （３）ガラスの組成により、熱線遮蔽性を付与する方法 （４）ガラス板上に、有機チタン化合物の熱分解による
ＴｉＯ2 薄膜を形成する方法2. Description of the Related Art Conventionally, the following method is known as a method for producing a heat ray shielding glass plate. (1) Sputtering a dielectric multilayer film on a glass plate,
Method of forming by vacuum deposition, sol-gel method, etc. (2) Method of forming a metal vapor deposition film, or a sputtering thin film of metal nitride or metal carbide on a glass plate (3) Heat-shielding property by glass composition Method of applying (4) Method of forming TiO 2 thin film on glass plate by thermal decomposition of organic titanium compound
【０００３】上記（１）の誘電体の多層膜をスパッタリ
ング、又は真空蒸着法により形成する方法は、高屈折率
物質と低屈折率物質を交互に５〜１５層積層していくも
のであるが、成膜速度が遅く量産性に乏しいため高コス
トであるという問題点がある。In the method (1) of forming a multilayered dielectric film by sputtering or vacuum deposition, 5 to 15 layers of a high refractive index substance and a low refractive index substance are alternately laminated. However, there is a problem that the film formation speed is slow and mass productivity is poor, resulting in high cost.
【０００４】また、ゾル−ゲル法による熱線遮蔽皮膜形
成方法は、金属アルコキシド加水分解液をガラス板上に
塗布し、これに５００〜７００℃の焼成を施す工程を５
〜１５回繰り返して、高屈折率物質と低屈折率物質の膜
を交互に積層していくものであるが、塗布回数が多いた
め、大型のガラスに用いる場合、塗布に要する時間が長
くなり生産性に乏しく、このため、実際上、ＴｉＯ2 ／
ＳｉＯ2 膜がハロゲンランプ等の小物の熱線遮蔽膜に利
用されているのみである。Further, the method of forming a heat ray shielding film by the sol-gel method comprises the steps of applying a metal alkoxide hydrolyzed liquid on a glass plate and firing it at 500 to 700 ° C.
It repeats up to 15 times to alternately stack films of high refractive index material and low refractive index material, but since the number of times of coating is large, the time required for coating becomes long when used for large glass It is poor in nature and, for this reason, in practice TiO 2 /
The SiO 2 film is only used as a heat ray shielding film for small items such as halogen lamps.
【０００５】また上記（２）の金属蒸着膜による方法に
は、Ａｌ，Ｚｎ，Ｃｕ，Ａｇ，Ａｕなどの金属が使われ
ているが、可視光の透過性と、熱線遮蔽性との両方を満
足させる膜を得ることは困難で、どちらかを犠牲にする
か、どちらも不十分な膜としか得られず、さらに、生産
性やコスト面で難がある。Further, in the method (2) using the metal vapor deposition film, metals such as Al, Zn, Cu, Ag, and Au are used, but both the visible light transmittance and the heat ray shielding property are obtained. It is difficult to obtain a satisfying film, and either one is sacrificed, or neither is obtained as an insufficient film, and further there is a difficulty in productivity and cost.
【０００６】また、金属窒化物、金属炭化物の薄膜をス
パッタリング法により形成する方法には、ＴｉＮ，Ｃｒ
Ｎ，ＴａＮ，ＺｒＮ，ＳｉＣ，ＴｉＣなどが用いられて
いるが、金属蒸着膜と同様、可視光の透過性と熱線遮蔽
性との両方を同時に満足させる膜を得ることは困難であ
る。Further, a method of forming a thin film of metal nitride or metal carbide by a sputtering method includes TiN and Cr.
Although N, TaN, ZrN, SiC, TiC and the like are used, it is difficult to obtain a film that satisfies both visible light transmittance and heat ray shielding property at the same time, like a metal vapor deposition film.
【０００７】上記（３）のガラス組成による方法は、ソ
ーダ石灰ガラスの組成中に微量の鉄、ニッケル、コバル
ト、セレンなどを添加し着色透明ガラスとするものであ
るが、添加量に制限があるため、遮蔽力が弱く、また遮
蔽のすべてが吸収によるためガラス本体からの熱の再放
射があり効果が弱い。In the method using the glass composition of the above (3), a small amount of iron, nickel, cobalt, selenium, etc. is added to the composition of soda-lime glass to make a colored transparent glass, but the addition amount is limited. Therefore, the shielding power is weak, and since all of the shielding is due to absorption, heat is re-radiated from the glass body and the effect is weak.
【０００８】上記（４）の有機Ｔｉ化合物の熱分解によ
りＴｉＯ2 薄膜を形成する方法は、ガラス製造ライン上
で、有機Ｔｉ化合物をガラス板上にスプレーし、ガラス
片面に成膜する方法と、オフラインで浸漬塗布法により
ガラス板両面に成膜する方法があるが、可視光の透過性
と熱線遮蔽性との両方を同時に満足させる膜を得ること
が困難であり、乗り物用途には、透過率が低すぎるため
利用出来ず、また建物用途には、遮断性能に不満があ
る。The method (4) of forming a TiO 2 thin film by thermal decomposition of an organic Ti compound is a method of spraying an organic Ti compound on a glass plate on a glass manufacturing line to form a film on one side of the glass. Although there is a method of forming a film on both sides of a glass plate by an off-line dip coating method, it is difficult to obtain a film that satisfies both the visible light transmittance and the heat ray shielding property at the same time. Is too low to be used, and for building applications, it is unsatisfactory in the blocking performance.
【０００９】本発明者らは、先に透明導電膜を得る方法
として、酸化スズ微粒子をバインダーに均一分散して成
膜する方法を開示している（特開平２−１０５８７５号
公報）が、そこでは表面導電性のみに着目しており、熱
線遮蔽性については全く言及しておらず、そこで開示し
ている透明導電膜は、膜厚が薄く熱線遮蔽性の低いもの
であった。またそこで開示している熱線遮蔽膜は、膜強
度については考慮されておらず、これを乗り物用窓ガラ
スまたは建物用窓ガラスに用いた場合、膜強度が低く実
用性に乏しいものであった。The present inventors have previously disclosed a method for uniformly forming tin oxide fine particles in a binder to form a film as a method for obtaining a transparent conductive film (JP-A-2-105875). Pays attention only to the surface conductivity and does not refer to the heat ray shielding property at all, and the transparent conductive film disclosed therein has a thin film thickness and a low heat ray shielding property. Further, the heat ray shielding film disclosed therein does not consider the film strength, and when it is used for a vehicle window glass or a building window glass, the film strength is low and the utility is poor.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、従来技術の
上記問題点を解消し、可視光透過率が高く、熱線遮蔽性
に優れ、且つ低価格の熱線遮蔽ガラス板、およびその製
造方法を提供しようとするものである。本発明は、特に
乗り物用、または建物用に適した熱線遮蔽ガラス板、お
よびその製造方法を提供することを目的とするものであ
る。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has a high visible light transmittance, an excellent heat ray-shielding property, and a low-cost heat ray-shielding glass plate, and a manufacturing method thereof. It is the one we are trying to provide. It is an object of the present invention to provide a heat ray-shielding glass plate particularly suitable for vehicles or buildings, and a manufacturing method thereof.
【００１１】[0011]
【課題を解決するための手段】本発明の熱線遮蔽ガラス
板は、透明なガラス板と、このガラス板上に形成された
熱線遮蔽性皮膜とを有し、前記熱線遮蔽性皮膜が、５０
０Å以下の粒径を有する酸化スズ微粒子により形成さ
れ、かつ１０００Å以上の厚さを有する皮膜と、有機シ
リコン化合物の焼成物から形成され、かつ、前記酸化ス
ズ微粒子の間隙を充填しているマトリックスと、により
形成されている、ことを特徴とするものである。The heat ray shielding glass plate of the present invention comprises a transparent glass plate and a heat ray shielding film formed on the glass plate, and the heat ray shielding film is 50
A film formed of tin oxide fine particles having a particle size of 0 Å or less and having a thickness of 1000 Å or more; and a matrix formed of a fired product of an organic silicon compound and filling the gaps of the tin oxide fine particles. It is formed by.
【００１２】本発明の熱線遮蔽ガラス板において、前記
酸化スズ微粒子がアンチモンによりドープされており、
かつ５００Å以下の粒径を有することが好ましい。In the heat ray-shielding glass plate of the present invention, the tin oxide fine particles are doped with antimony,
And, it is preferable that the particle size is 500 Å or less.
【００１３】また、本発明の熱線遮蔽ガラス板は、前記
熱線遮蔽性皮膜上に形成され、かつ有機シリコン化合物
の焼成物からなる保護膜をさらに有していてもよい。The heat ray shielding glass plate of the present invention may further have a protective film formed on the heat ray shielding film and made of a fired product of an organic silicon compound.
【００１４】本発明の熱線遮蔽ガラス板の製造方法は、
透明なガラス板上に、５００Å以下の粒径を有する酸化
スズ微粒子からなり、１０００Å以上の厚さを有する皮
膜を形成し、前記酸化スズ微粒子皮膜に、前記酸化スズ
微粒子の間隙を充填するように、有機シリコン化合物を
含有する処理液を含浸させ、これに３５０℃以上の温度
における焼成を施し、それによって、前記有機シリコン
化合物の焼成物からなるマトリックスと、このマトリッ
クス中に分散している前記酸化スズ微粒子とからなる熱
線遮蔽性皮膜を形成することを特徴とするものである。The method for producing the heat ray shielding glass plate of the present invention is as follows:
On a transparent glass plate, a film made of tin oxide fine particles having a particle size of 500 Å or less and having a thickness of 1000 Å or more is formed, and the tin oxide fine particle film is filled in the gaps of the tin oxide fine particles. , A treatment liquid containing an organic silicon compound is impregnated, and this is baked at a temperature of 350 ° C. or higher, whereby a matrix made of the baked product of the organic silicon compound and the oxidation dispersed in the matrix. It is characterized in that a heat ray-shielding film composed of tin fine particles is formed.
【００１５】本発明の熱線遮蔽ガラス板製造方法におい
て、前記酸化スズ微粒子皮膜を、５００Å以下の粒径を
有し、かつアンチモンによりドープされた酸化スズ微粒
子を含むゾル状水性分散液を、前記ガラス板上に塗布し
乾燥して形成してもよい。In the method for producing a heat ray-shielding glass plate of the present invention, the tin oxide fine particle coating has a particle size of 500 Å or less and a sol-like aqueous dispersion containing tin oxide fine particles doped with antimony is added to the glass. It may be formed by coating on a plate and drying.
【００１６】本発明の熱線遮蔽ガラス板の製造方法にお
いて、前記アンチモンドープ酸化スズ微粒子含有ゾル状
水性分散液が、熱分散性水溶性高分子材料を含んでいて
もよい。In the method for producing a heat ray-shielding glass plate of the present invention, the sol-like aqueous dispersion containing antimony-doped tin oxide fine particles may contain a heat-dispersible water-soluble polymer material.
【００１７】本発明の熱線遮蔽ガラス板の製造方法は、
前記熱線遮蔽性皮膜上に、有機シリコン化合物を含有す
る処理液を塗布し、これを焼成して保護膜を形成するこ
とをさらに含んでいてもよい。The manufacturing method of the heat ray shielding glass plate of the present invention is as follows.
The method may further include applying a treatment liquid containing an organic silicon compound onto the heat ray-shielding film, and baking the treatment liquid to form a protective film.
【００１８】[0018]
【作用】以下に本発明を詳しく説明する。本発明におけ
る熱線遮蔽性皮膜は、ガラス板上に酸化スズのゾル状分
散液を塗布し乾燥することにより、酸化スズ微粒子を高
密度に堆積させて形成することができる。本発明で使用
される酸化スズ微粒子は、出来るだけ粒径が小さく、単
分散状態のゾル状分散液であることが望ましく、その粒
径は５００Å以下、好ましくは１０〜３００Åである。
粒径が５００Åを越える場合は、粒子により可視光が散
乱されて透明性が低下し、また皮膜の厚さに対して粒径
が大きすぎるため緻密な膜を形成することができない。The present invention will be described in detail below. The heat ray shielding film in the present invention can be formed by depositing tin oxide fine particles at a high density by applying a sol-like dispersion liquid of tin oxide on a glass plate and drying. It is desirable that the tin oxide fine particles used in the present invention be a sol dispersion liquid in a monodispersed state having a particle size as small as possible.
When the particle size exceeds 500 Å, visible light is scattered by the particles to reduce transparency, and since the particle size is too large with respect to the thickness of the film, a dense film cannot be formed.
【００１９】本発明における熱線遮蔽膜の熱線遮蔽効果
は、導電性金属酸化物のプラズマ周波数に対応した光の
反射によるものと考えられるので、酸化スズ微粒子の導
電性をさらに高くすることにより、より低波長側から熱
線を反射することが出来るようになる。そのためにアン
チモンをドーピングした酸化スズ微粒子を使用すること
が好ましい。The heat ray shielding effect of the heat ray shielding film in the present invention is considered to be due to the reflection of light corresponding to the plasma frequency of the conductive metal oxide. Therefore, by further increasing the conductivity of the tin oxide fine particles, It becomes possible to reflect heat rays from the low wavelength side. Therefore, it is preferable to use tin oxide fine particles doped with antimony.
【００２０】酸化スズのゾル状分散液の製造方法には特
に制限はないが、例えば、先に特開平２−１０５８７５
号公報中に記載の方法により製造することが出来る。こ
の方法によれば、アンチモンをドープした酸化スズの１
０〜１００Åの粒径を有する微粒子のゾル状分散液を得
ることが出来る。このゾル状分散液の濃度を適宜に調整
し、これをスプレー、スピンコート、ディップコート等
の方法によりガラス板上に塗布、乾燥することにより酸
化スズ微粒子の皮膜を得ることが出来る。The method for producing the sol-like dispersion of tin oxide is not particularly limited, but, for example, the above-mentioned Japanese Patent Laid-Open No. 2-105875.
It can be manufactured by the method described in the publication. According to this method, 1% of tin oxide doped with antimony
It is possible to obtain a sol-like dispersion liquid of fine particles having a particle size of 0 to 100Å. A tin oxide fine particle film can be obtained by appropriately adjusting the concentration of the sol dispersion liquid, applying this on a glass plate by a method such as spraying, spin coating, dip coating, and drying.
【００２１】このゾル状分散液はそのままでも成膜性は
あるが、より成膜性を改善するために、界面活性剤、水
溶性高分子、又は水溶性有機溶剤を微量添加してもよ
い。特に熱分解性の水溶性高分子材料は、成膜性に優れ
ており、このような高分子材料としてメチルセルロー
ス、エチルセルロース、ヒドロキシエチルセルロース、
ヒドロキシプロピルセルロース、カルボキシメチルセル
ロース、ヒドロキシエチルメチルセルロース、ポリビニ
ルアルコール、ポリビニルピロリドン、ポリビニルメチ
ルエーテル、カルボキシビニルポリマー、ポリアクリル
酸ソーダ、ポリエチレンオキサイド、エチレンオキサイ
ド・プロピレンオキサイドブロック共重合体、ゼラチ
ン、カゼイン、アルブミン、コラーゲン等を例示するこ
とが出来る。Although the sol dispersion liquid has a film-forming property as it is, a trace amount of a surfactant, a water-soluble polymer or a water-soluble organic solvent may be added in order to further improve the film-forming property. Particularly, the heat-decomposable water-soluble polymer material is excellent in film-forming property, and as such polymer material, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl methyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxy vinyl polymer, sodium polyacrylate, polyethylene oxide, ethylene oxide / propylene oxide block copolymer, gelatin, casein, albumin, collagen Etc. can be illustrated.
【００２２】上記のような熱分解性の水溶性高分子を酸
化スズ微粒子分散液に添加した場合は、これをガラス板
上に塗布、乾燥後、熱分解温度以上で焼成することによ
り酸化スズ微粒子の皮膜を得ることが出来る。このよう
にして形成した皮膜は、ガラス板上に酸化スズの微粒子
が最密充填に近い状態で堆積されているが、しかし粒子
間には間隙が有り、ガラス板と粒子との間の接着力は、
凝集力のみによるものである。従ってこのままでは膜強
度が弱く実用的ではない。When the thermally decomposable water-soluble polymer as described above is added to the tin oxide fine particle dispersion, the tin oxide fine particles are obtained by coating the dried solution on a glass plate, drying and firing at a temperature not lower than the thermal decomposition temperature. Can be obtained. In the film thus formed, fine particles of tin oxide are deposited on the glass plate in a state close to the closest packing, but there is a gap between the particles, and the adhesive force between the glass plate and the particles is large. Is
This is due to the cohesive force only. Therefore, as it is, the film strength is weak and not practical.
【００２３】そこで本発明では、粒子間隙に有機シリコ
ン化合物を含んだ溶液を含浸し、さらにこの有機Ｓｉ化
合物をその熱分解温度以上で焼成し、その焼成物（Ｓｉ
−Ｏ構造を有する）からなるマトリックスを形成するこ
とにより、ガラス板と粒子との間の密着力を改善し、膜
強度を強化する。Therefore, in the present invention, a solution containing an organic silicon compound is impregnated in the interstices of the particles, and the organic Si compound is further baked at a temperature above its thermal decomposition temperature to obtain a baked product (Si
By forming a matrix composed of (having an —O structure), the adhesion between the glass plate and the particles is improved and the film strength is enhanced.
【００２４】使用される有機Ｓｉ化合物として、ポリシ
ルメチレン、ポリシルフェニレン、ポリシロキサン、ポ
リシラザン、ポリシルチアン、ポリシルフェニレンシロ
キサン、ポリフェニレンオキシシロキサン、およびポリ
メタロシロキサン等をあげることが出来る。Examples of the organic Si compound used include polysilmethylene, polysilphenylene, polysiloxane, polysilazane, polysilthiane, polysilphenylenesiloxane, polyphenyleneoxysiloxane, and polymetallosiloxane.
【００２５】上記有機シリコン化合物含有処理液を前記
酸化スズ微粒子よりなる皮膜上に塗布してこれを含浸
し、大気中で焼成することにより、Ｓｉ−Ｏ結合を有す
る焼成物からなるマトリックスを形成することが出来
る。The treatment liquid containing the organosilicon compound is applied onto the film made of the tin oxide fine particles, impregnated with the film, and baked in the atmosphere to form a matrix made of a fired product having a Si--O bond. You can
【００２６】上記有機シリコン化合物のうち、特にポリ
シルメチレン、ポリシロキサン、ポリシラザン、ポリメ
タロシロキサン化合物が好適で、これらを塗布し、大気
中で焼成した時、それぞれ−Ｓｉ−Ｏ−Ｓｉ−Ｃ−，−
Ｓｉ−Ｏ−，−Ｓｉ−Ｎ−Ｓｉ−Ｏ−，−Ｓｉ−Ｏ−Ｍ
−Ｏ−（Ｍ＝Ａｌ，Ｔｉ，Ｚｒ，Ｂ，Ｐ等）結合を主鎖
とする無機高分子マトリックスが形成される。Of the above-mentioned organosilicon compounds, polysilmethylene, polysiloxane, polysilazane, and polymetallosiloxane compounds are particularly preferable, and when these are coated and baked in the atmosphere, they are each -Si-O-Si-C-. ,-
Si-O-, -Si-N-Si-O-, -Si-OM
An inorganic polymer matrix having a main chain of —O— (M = Al, Ti, Zr, B, P, etc.) bonds is formed.
【００２７】これらの有機シリコン化合物を酸化スズ粒
子間隙に含浸する方法は、スプレー、スピンコート、デ
ィップコート等の通常の塗布含浸方法を利用することが
出来る。このとき有機シリコン化合物の濃度を適当に調
整し、酸化スズ微粒子間隙を充填してこれらを結着し、
さらに酸化スズ皮膜の厚さよりも１００〜２０００Åだ
け厚くなるようにして、これを被覆することが好まし
く、これにより熱線遮蔽性皮膜の強度をあげることがで
きる。As the method of impregnating the tin oxide particle gaps with these organosilicon compounds, a usual coating impregnation method such as spraying, spin coating, dip coating can be used. At this time, the concentration of the organic silicon compound is appropriately adjusted, and the tin oxide fine particle gaps are filled to bind them,
Further, it is preferable to coat the tin oxide film by making it 100 to 2000 Å thicker than the thickness of the tin oxide film, which can increase the strength of the heat ray shielding film.
【００２８】このような構成を有する本発明の熱線遮蔽
ガラス板の断面説明図を図１に示す。図１において、ガ
ラス板１上に、酸化スズ微粒子２により皮膜が形成さ
れ、これら酸化スズ微粒子２の間隙を充填し、かつその
皮膜を被覆するマトリックス３が形成され、この酸化ス
ズ微粒子２の皮膜と、マトリックス３とにより熱線遮蔽
性皮膜４が形成されている。FIG. 1 shows a cross sectional explanatory view of the heat ray shielding glass plate of the present invention having such a constitution. In FIG. 1, a film is formed on the glass plate 1 by the tin oxide particles 2, and a matrix 3 is formed which fills the gaps between the tin oxide particles 2 and covers the film. And the matrix 3 form the heat ray shielding film 4.
【００２９】本発明の熱線遮蔽ガラス板において、必要
に応じさらに膜の耐摩耗性を改善するために、熱線遮蔽
性皮膜上に、さらに保護膜を積層してもよい。保護膜を
形成する材料としては、耐摩耗性、耐薬品性、耐候性等
の耐久性が優れた材料が望ましく、前記有機Ｓｉ化合物
を用いることが出来る。特に、ポリシロキサン、ポリシ
ラザン、およびポリメタロシロキサン化合物は、それか
ら形成される膜硬度が硬く好適である。保護膜の膜厚
は、皮膜の硬度、耐摩耗性、酸化スズ層との密着性等を
考慮して、５００Å以上であることが好ましく、特に１
０００〜５０００Åが好ましい。In the heat ray-shielding glass plate of the present invention, a protective film may be further laminated on the heat ray-shielding film, if necessary, in order to further improve the abrasion resistance of the film. As a material for forming the protective film, a material having excellent durability such as abrasion resistance, chemical resistance, and weather resistance is desirable, and the organic Si compound can be used. In particular, polysiloxane, polysilazane, and polymetallosiloxane compounds are suitable because the film formed from them is hard. The thickness of the protective film is preferably 500 Å or more in consideration of hardness of the film, abrasion resistance, adhesion to the tin oxide layer, etc., and particularly 1
000 to 5000Å is preferable.
【００３０】保護膜を積層した熱線遮蔽ガラスの断面図
を図２に示す。図２に示された熱線遮蔽ガラス板におい
て、熱線遮蔽性皮膜４の上に、保護膜５が積層形成され
ている。FIG. 2 shows a cross-sectional view of a heat ray shielding glass having a protective film laminated thereon. In the heat ray shielding glass plate shown in FIG. 2, a protective film 5 is laminated on the heat ray shielding film 4.
【００３１】本発明の熱線遮蔽性皮膜の熱線遮蔽度は、
皮膜の厚さにおおむね比例するので、必要とする性能に
応じ皮膜の厚さを適宜に設定する。図３に皮膜の厚さ
と、日射透過率との関係を示す。また、図４に皮膜の厚
さと、可視光透過率との関係を示す。さらに図５に、日
射遮蔽率と、可視光透過率との関係を示す。ここで日射
透過率、および可視光透過率はＪＩＳ Ｒ ３１０６の
方法により測定した。また、日射遮蔽率は１００−日射
透過率により算出した。The heat ray shielding degree of the heat ray shielding film of the present invention is
Since it is roughly proportional to the thickness of the coating, the thickness of the coating is set appropriately according to the required performance. FIG. 3 shows the relationship between the film thickness and the solar radiation transmittance. Further, FIG. 4 shows the relationship between the film thickness and the visible light transmittance. Further, FIG. 5 shows the relationship between the solar radiation shielding rate and the visible light transmittance. Here, the solar radiation transmittance and the visible light transmittance were measured by the method of JIS R3106. The solar radiation shielding rate was calculated by 100-solar radiation transmittance.
【００３２】図３によれば、皮膜の厚さが１０００Å以
上になれば日射遮蔽率は５％以上になる。従って、熱線
遮蔽ガラスとして必要な最低の皮膜の厚さは１０００Å
である。なぜなら、日射遮蔽率が５％未満では乗り物用
または建物用の窓ガラスとして用いた場合、冷房負荷の
低減にほとんど寄与しないからである。皮膜の厚さの上
限については特に制限はないが、皮膜の厚さが厚くなる
と可視光の透過率が低下するので乗り物用の窓ガラスの
ように高い可視光透過率が必要な用途にはおのづから適
当な範囲がある。According to FIG. 3, when the thickness of the film is 1000 Å or more, the solar radiation shielding rate is 5% or more. Therefore, the minimum film thickness required for heat ray shielding glass is 1000Å
Is. This is because if the solar radiation shielding ratio is less than 5%, it will hardly contribute to the reduction of the cooling load when it is used as a window glass for vehicles or buildings. There is no particular upper limit on the thickness of the film, but as the film thickness increases, the visible light transmittance decreases, so it is recommended for applications requiring high visible light transmittance such as window glass for vehicles. There is an appropriate range.
【００３３】例えば、乗り物用のうち自動車用ガラス
は、安全性から７０％以上の可視光透過率が必要である
が、この場合例えば、可視光透過率が９０％のガラス板
を使用する場合、皮膜の可視光透過率は７８％以上でな
ければならず、この場合皮膜の厚さは１５０００Å以下
であることが好ましい。しかし建物用の窓ガラスでは高
い可視光透過率は必要ではなく、冷房負荷低減のために
高い熱線遮蔽性が求められる。このような用途には皮膜
の厚さを厚くすることにより、可視光透過率を下げるこ
とも可能である。For example, automobile glass among vehicles is required to have a visible light transmittance of 70% or more for safety. In this case, for example, when a glass plate having a visible light transmittance of 90% is used, The visible light transmittance of the coating must be 78% or more, and in this case, the thickness of the coating is preferably 15000Å or less. However, window glass for buildings does not require a high visible light transmittance, and a high heat ray shielding property is required to reduce the cooling load. For such applications, the visible light transmittance can be lowered by increasing the thickness of the film.
【００３４】本発明の熱線遮蔽性皮膜が好適なのは、次
のような理由による。本発明においては、熱線を反射す
る性質のある酸化スズ微粒子のゾル状分散液を用いて皮
膜を形成するため、高密度の酸化スズ皮膜を形成するこ
とができ、しかも皮膜の厚さを１０００Å以上に厚くす
ることができるので、皮膜に入射する熱線は、まず皮膜
表面の粒子により反射され、さらに皮膜内に侵入した熱
線は、粒子間において反射を繰り返し、一部は皮膜外に
射出され、一部は皮膜内に吸収され、最終的に皮膜を透
過する熱線はごくわずかとなるからである。The heat ray-shielding film of the present invention is suitable for the following reasons. In the present invention, since a film is formed using a sol-like dispersion liquid of tin oxide fine particles having a property of reflecting heat rays, a high-density tin oxide film can be formed, and the film thickness is 1000 Å or more. Since the heat rays incident on the film are first reflected by the particles on the surface of the film, the heat rays that have penetrated into the film are repeatedly reflected between the particles and some are emitted outside the film. This is because the part is absorbed in the film, and the number of heat rays that finally penetrates the film is very small.
【００３５】本発明の熱線遮蔽ガラス板において、粒径
５００Å以下の酸化スズ微粒子が高度な分散状態で皮膜
に形成されているため、可視光における透明性および熱
線遮蔽性の両方に優れた皮膜を形成することができる。In the heat ray-shielding glass plate of the present invention, since tin oxide fine particles having a particle size of 500Å or less are formed in a highly dispersed state in the film, a film excellent in both transparency in visible light and heat ray shielding property is obtained. Can be formed.
【００３６】本発明において酸化スズ微粒子を単独で用
いてもよく、または、他の熱線遮蔽性のある物質と組み
合わせて用いてもよい。酸化スズ微粒子の比較的遮蔽力
の弱い波長、すなわち７８０nm〜１０００nmの波長の放
射線を遮蔽する物質と組み合わせることにより、さらに
熱線遮蔽性の高い透明皮膜を得ることができる。また、
他の機能性透明膜を積層して多層膜とすることも可能で
ある。例えば、紫外線吸収膜や、反射防止膜との多層膜
が考えられる。In the present invention, the tin oxide fine particles may be used alone or in combination with another substance having a heat ray shielding property. By combining with a substance that shields the radiation of the tin oxide fine particles having a relatively weak shielding power, that is, the wavelength of 780 nm to 1000 nm, a transparent film having a further high heat ray shielding property can be obtained. Also,
It is also possible to stack other functional transparent films to form a multilayer film. For example, a multilayer film including an ultraviolet absorbing film and an antireflection film can be considered.
【００３７】次に、本発明を実施例によりさらに詳しく
説明する。実施例１ ４６．２重量部のＳｂＣｌ3 と、６７０重量部のＳｎＣ
ｌ・５Ｈ2 Ｏとを、３０００重量部の６Ｎ塩酸に溶解
し、これに２５％のアンモニア液２０００重量部を添加
して反応させ、反応生成物を塩化アンモニウムが検出出
来なくなるまで、ろ過洗浄した。この反応生成物含有液
を密閉容器で３５０℃に加熱し、５時間保持した後、冷
却過程で水蒸気を放出し、固形分２５重量％まで濃縮
し、粒径１０〜１００Åのアンチモン含有酸化スズ（以
下、ＡＴＯと記す）のゾル状分散液を得た。この分散液
３００重量部に、水６９７重量部とポリビニルアルコー
ル３重量部とを混合して、ＡＴＯ固形分含有率７．５％
のゾルを調製した。このゾルに３mm厚の板ガラスを浸漬
してガラス両面に前記ゾルを塗布し、５００℃で１０分
間焼成してＡＴＯ皮膜を作製した。次に、ＳｉＯ2 分含
有率１０．０％のポリシロキサンのアルコール溶液を前
記ＡＴＯ皮膜にディップコートにより塗布含浸し、これ
を大気中で５８０℃で焼き付けて、ガラス板の両面に熱
線遮蔽性皮膜を形成した。この皮膜の各々は０．４５μ
ｍの厚さを有していた。得られた熱線遮蔽ガラス板の分
光透過特性を図６に示し、また、その皮膜の厚さ、可視
光透過率、日射透過率、および耐摩耗性を表１に示す。Next, the present invention will be described in more detail with reference to examples. Example 1 46.2 parts by weight of SbCl 3 and 670 parts by weight of SnC
1 · 5H 2 O was dissolved in 3000 parts by weight of 6N hydrochloric acid, 2000 parts by weight of 25% ammonia solution was added and reacted, and the reaction product was filtered and washed until ammonium chloride could not be detected. . The reaction product-containing liquid was heated to 350 ° C. in a closed container and kept for 5 hours, then, in the cooling process, water vapor was released, and the solid content was concentrated to 25% by weight to obtain an antimony-containing tin oxide having a particle size of 10 to 100Å ( Hereinafter, a sol dispersion liquid of ATO) was obtained. 300 parts by weight of this dispersion was mixed with 697 parts by weight of water and 3 parts by weight of polyvinyl alcohol to give an ATO solid content of 7.5%.
Was prepared. A plate glass having a thickness of 3 mm was dipped in this sol to apply the sol to both surfaces of the glass and baked at 500 ° C. for 10 minutes to form an ATO film. Next, an alcohol solution of polysiloxane having a SiO 2 content of 10.0% is applied and impregnated on the ATO film by dip coating, and this is baked at 580 ° C. in the air to form a heat ray shielding film on both surfaces of the glass plate. Was formed. Each of these films is 0.45μ
It had a thickness of m. FIG. 6 shows the spectral transmission characteristics of the obtained heat ray-shielding glass plate, and Table 1 shows the film thickness, visible light transmittance, solar radiation transmittance, and abrasion resistance.
【００３８】実施例２ 実施例１のＡＴＯ皮膜に、ポリシロキサンの代りにポリ
シラザンの５％キシレン溶液をディップコート法により
塗布し、これを大気中５００℃で焼き付けて保護膜を形
成し、熱線遮蔽ガラスを得た。この熱線遮蔽ガラスの膜
厚、可視光透過率、日射透過率、耐摩耗性を表１に示
す。 Example 2 The ATO film of Example 1 was coated with a 5% xylene solution of polysilazane in place of polysiloxane by a dip coating method, and this was baked at 500 ° C. in the atmosphere to form a protective film, which was shielded from heat rays. I got a glass. Table 1 shows the film thickness, visible light transmittance, solar radiation transmittance, and abrasion resistance of this heat ray shielding glass.
【００３９】実施例３ 実施例１の熱線遮蔽性皮膜に、５％のポリシロキサンの
アルコール溶液をディップコート法により塗布し、大気
中５５０℃で焼成して、２０００Åの厚さを有する保護
膜を形成し、熱線遮蔽ガラスを得た。この熱線遮蔽ガラ
スの各皮膜の厚さ、可視光透過率、日射透過率、耐摩耗
性を表１に示す。 Example 3 The heat ray-shielding film of Example 1 was coated with a 5% alcohol solution of polysiloxane by a dip coating method and baked at 550 ° C. in the atmosphere to form a protective film having a thickness of 2000 Å. It formed and obtained the heat ray shielding glass. Table 1 shows the thickness, visible light transmittance, solar radiation transmittance, and abrasion resistance of each film of this heat ray shielding glass.
【００４０】実施例４ 実施例１の熱線遮蔽性皮膜に、５％のポリシラザンのキ
シレン溶液をディップコート法により塗布し、大気中５
００℃で焼成して、２０００Åの厚さを有する保護膜を
積層し、熱線遮蔽ガラスを得た。この熱線遮蔽ガラスの
各皮膜の厚さ、可視光透過率、日射透過率、耐摩耗性を
表１に示す。 Example 4 A 5% xylene solution of polysilazane was applied to the heat ray-shielding film of Example 1 by a dip coating method, and the coating was applied in air at 5%.
It was fired at 00 ° C. and a protective film having a thickness of 2000 Å was laminated to obtain a heat ray shielding glass. Table 1 shows the thickness, visible light transmittance, solar radiation transmittance, and abrasion resistance of each film of this heat ray shielding glass.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【発明の効果】従来法は基材に成膜する時点では非晶質
か低結晶性のため、加熱してある基材に成膜するか、成
膜後加熱することにより結晶性を上げる必要があり、加
熱時に結晶構造が変化するため皮膜の厚さを厚くするこ
とができず熱線遮蔽性の高いガラスを得ることができな
かった。これに対し、本発明では、結晶度の高い酸化ス
ズのゾル状分散液を塗布するため、成膜後、乾燥程度の
加熱処理で皮膜が形成され、体積変化がないためかなり
厚い皮膜を成膜できる。しかも皮膜の厚さは分散液の固
形分、塗布方法により自由に設定できるので熱線遮蔽性
の高い皮膜を容易に形成できる。さらに、酸化スズ粒子
の間隙を、Ｓｉ−Ｏ結合を主体として含有するマトリッ
クスで充填し、粒子を結着するため強度の高い皮膜を形
成することが出来る。また本発明の熱線遮蔽ガラス板
は、通常の塗布方法を用いて製造することができるた
め、従来のスパッタリング法、蒸着法などを用いる方法
に対し、量産性に優れ、安価な熱線遮蔽ガラスを提供す
ることが可能となる。EFFECTS OF THE INVENTION Since the conventional method is amorphous or low crystalline at the time of forming a film on a substrate, it is necessary to increase the crystallinity by forming a film on a heated substrate or by heating after forming the film. However, since the crystal structure changes during heating, the thickness of the film cannot be increased, and glass having a high heat ray shielding property cannot be obtained. On the other hand, in the present invention, since the sol-like dispersion liquid of tin oxide having a high degree of crystallinity is applied, a film is formed by a heat treatment of about dryness after film formation, and a considerably thick film is formed because there is no volume change. it can. Moreover, since the thickness of the film can be freely set by the solid content of the dispersion and the coating method, a film having a high heat ray shielding property can be easily formed. Furthermore, the gap between the tin oxide particles is filled with a matrix containing Si—O bonds as a main component, and the particles are bound to each other, so that a film having high strength can be formed. Further, the heat ray-shielding glass plate of the present invention can be produced by using an ordinary coating method, and therefore, it is possible to provide an inexpensive heat ray-shielding glass with excellent mass productivity as compared with the conventional sputtering method, vapor deposition method and the like. It becomes possible to do.
【図１】図１は、本発明の熱線遮蔽ガラス板の一例の断
面説明図。FIG. 1 is a sectional explanatory view of an example of a heat ray shielding glass plate of the present invention.
【図２】図２は、本発明の熱線遮蔽ガラス板の他の例の
断面説明図。FIG. 2 is a sectional explanatory view of another example of the heat ray shielding glass plate of the present invention.
【図３】図３は、本発明の熱線遮蔽ガラス板の、熱線遮
蔽性皮膜の厚さとその日射遮蔽率又は日射透過率との関
係の一例を示すグラフ。FIG. 3 is a graph showing an example of the relationship between the thickness of a heat ray-shielding film and its solar radiation shielding rate or solar radiation transmittance of the heat ray shielding glass plate of the present invention.
【図４】図４は本発明の熱線遮蔽ガラス板の熱線遮蔽性
皮膜の厚さと、その可視光透過率との関係の一例を示す
グラフ。FIG. 4 is a graph showing an example of the relationship between the thickness of the heat ray shielding film of the heat ray shielding glass plate of the present invention and its visible light transmittance.
【図５】図５は、本発明の熱線遮蔽ガラス板の熱線遮蔽
性皮膜の日射遮蔽率と可視光透過率との関係を示すグラ
フ。FIG. 5 is a graph showing the relationship between the solar radiation shielding rate and the visible light transmittance of the heat ray shielding film of the heat ray shielding glass plate of the present invention.
【図６】図６は実施例１に記載の熱線遮蔽ガラス板の、
波長と可視光〜熱線透過率との関係を示すグラフ。FIG. 6 is a view of the heat ray shielding glass plate described in Example 1,
The graph which shows the relationship between a wavelength and visible light-heat ray transmittance.
１…ガラス板 ２…酸化スズ微粒子 ３…マトリックス ４…熱線遮蔽性皮膜 ５…保護膜 1 ... Glass plate 2 ... Tin oxide fine particles 3 ... Matrix 4 ... Heat ray shielding film 5 ... Protective film
Claims (7)
成された熱線遮蔽性皮膜とを有し、 前記熱線遮蔽性皮膜が、５００Å以下の粒径を有する酸
化スズ微粒子により形成され、かつ１０００Å以上の厚
さを有する皮膜と、有機シリコン化合物の焼成物から形
成され、かつ前記酸化スズ微粒子の間隙を充填している
マトリックスとにより形成されている、ことを特徴とす
る、熱線遮蔽ガラス板。1. A transparent glass plate, and a heat ray-shielding film formed on the glass plate, wherein the heat ray-shielding film is formed of tin oxide fine particles having a particle size of 500 Å or less, and A heat ray shielding glass plate, characterized in that it is formed by a film having a thickness of 1000 Å or more and a matrix formed from a fired product of an organic silicon compound and filling the gaps of the tin oxide fine particles. .
ドープされており、かつ５００Å以下の粒径を有する、
請求項１に記載の熱線遮蔽ガラス板。2. The tin oxide fine particles are doped with antimony and have a particle size of 500 Å or less.
The heat ray shielding glass plate according to claim 1.
有機シリコン化合物の焼成物からなる保護膜をさらに有
する、請求項１又は２に記載の熱線遮蔽ガラス板。3. The heat ray shielding glass plate according to claim 1, further comprising a protective film formed on the heat ray shielding film and made of a fired product of an organic silicon compound.
径を有する酸化スズ微粒子からなり、１０００Å以上の
厚さを有する皮膜を形成し、前記酸化スズ微粒子皮膜
に、前記酸化スズ微粒子の間隙を充填するように、有機
シリコン化合物を含有する処理液を含浸させ、これに３
５０℃以上の温度における焼成を施し、それによって、
前記有機シリコン化合物の焼成物からなるマトリックス
と、このマトリックス中に分散している前記酸化スズ微
粒子とからなる熱線遮蔽性皮膜を形成する、ことを特徴
とする熱線遮蔽ガラス板の製造方法。4. A film made of tin oxide fine particles having a particle size of 500 Å or less and having a thickness of 1000 Å or more is formed on a transparent glass plate, and the tin oxide fine particle film has a gap between the tin oxide fine particles. So that it is filled with a treatment liquid containing an organosilicon compound, and
Subject to calcination at a temperature above 50 ° C., whereby
A method for producing a heat ray-shielding glass plate, which comprises forming a heat ray-shielding film comprising a matrix made of the baked product of the organosilicon compound and the tin oxide fine particles dispersed in the matrix.
下の粒径を有し、かつアンチモンによりドープされた酸
化スズ微粒子を含むゾル状水性分散液を、前記ガラス板
上に塗布し乾燥して形成する、請求項４に記載の熱線遮
蔽ガラス板の製造方法。5. The tin oxide fine particle film is formed by applying a sol-like aqueous dispersion liquid having a particle diameter of 500 Å or less and containing tin oxide fine particles doped with antimony onto the glass plate and drying it. The method for manufacturing the heat ray shielding glass plate according to claim 4.
有ゾル状水性分散液が熱分解性水溶性高分子材料を含
む、請求項５に記載の熱線遮蔽ガラス板の製造方法。6. The method for producing a heat ray-shielding glass plate according to claim 5, wherein the antimony-doped tin oxide fine particle-containing sol-like aqueous dispersion contains a thermally decomposable water-soluble polymer material.
化合物を含有する処理液を塗布し、これを焼成して保護
膜を形成することをさらに含む、請求項４，５又は６に
記載の熱線遮蔽ガラス板の製造方法。7. The heat ray shielding film according to claim 4, further comprising applying a treatment liquid containing an organic silicon compound and baking the treatment liquid to form a protective film. Method for manufacturing heat ray shielding glass plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10452693A JP3408578B2 (en) | 1993-04-30 | 1993-04-30 | Method of manufacturing heat ray shielding glass plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10452693A JP3408578B2 (en) | 1993-04-30 | 1993-04-30 | Method of manufacturing heat ray shielding glass plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06316439A true JPH06316439A (en) | 1994-11-15 |
| JP3408578B2 JP3408578B2 (en) | 2003-05-19 |
Family
ID=14382942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10452693A Expired - Lifetime JP3408578B2 (en) | 1993-04-30 | 1993-04-30 | Method of manufacturing heat ray shielding glass plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3408578B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11181336A (en) * | 1997-09-30 | 1999-07-06 | Sumitomo Metal Mining Co Ltd | Coating fluid for permselective membrane, permselective membrane, and multi layered permselective membrane |
| EP0887179A4 (en) * | 1996-12-09 | 2000-08-30 | Nippon Sheet Glass Co Ltd | Non-fogging article and process for the production thereof |
| EP1031642A1 (en) * | 1999-02-26 | 2000-08-30 | Agfa-Gevaert N.V. | Conductive metal oxide based layer |
| US8038786B2 (en) | 2003-03-17 | 2011-10-18 | Hae-Wook Lee | Composition for cutting off heat-ray, film formed therefrom, and method for forming the composition and the film |
| CN102775073A (en) * | 2012-07-09 | 2012-11-14 | 华尔润玻璃产业股份有限公司 | Process for producing heat-insulated glass by roller coating method |
| JP2018535905A (en) * | 2015-09-09 | 2018-12-06 | ピルキントン グループ リミテッド | Deposition method |
| CN112501560A (en) * | 2020-11-13 | 2021-03-16 | 江西善纳新材料科技有限公司 | Preparation method of high-heat-reflectivity black coating |
-
1993
- 1993-04-30 JP JP10452693A patent/JP3408578B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0887179A4 (en) * | 1996-12-09 | 2000-08-30 | Nippon Sheet Glass Co Ltd | Non-fogging article and process for the production thereof |
| JPH11181336A (en) * | 1997-09-30 | 1999-07-06 | Sumitomo Metal Mining Co Ltd | Coating fluid for permselective membrane, permselective membrane, and multi layered permselective membrane |
| EP1031642A1 (en) * | 1999-02-26 | 2000-08-30 | Agfa-Gevaert N.V. | Conductive metal oxide based layer |
| US8038786B2 (en) | 2003-03-17 | 2011-10-18 | Hae-Wook Lee | Composition for cutting off heat-ray, film formed therefrom, and method for forming the composition and the film |
| CN102775073A (en) * | 2012-07-09 | 2012-11-14 | 华尔润玻璃产业股份有限公司 | Process for producing heat-insulated glass by roller coating method |
| JP2018535905A (en) * | 2015-09-09 | 2018-12-06 | ピルキントン グループ リミテッド | Deposition method |
| CN112501560A (en) * | 2020-11-13 | 2021-03-16 | 江西善纳新材料科技有限公司 | Preparation method of high-heat-reflectivity black coating |
| CN112501560B (en) * | 2020-11-13 | 2022-09-20 | 江西善纳新材料科技有限公司 | Preparation method of high-heat-reflectivity black coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3408578B2 (en) | 2003-05-19 |
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