JP3144951B2 - Method of manufacturing heat reflection window - Google Patents
Method of manufacturing heat reflection windowInfo
- Publication number
- JP3144951B2 JP3144951B2 JP10385293A JP10385293A JP3144951B2 JP 3144951 B2 JP3144951 B2 JP 3144951B2 JP 10385293 A JP10385293 A JP 10385293A JP 10385293 A JP10385293 A JP 10385293A JP 3144951 B2 JP3144951 B2 JP 3144951B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- indium
- organic
- tin
- heat ray
- 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 - Fee Related
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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/253—Coating containing SnO2
-
- 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
- C03C2217/231—In2O3/SnO2
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
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)
- Electric Ovens (AREA)
- Surface Treatment Of Glass (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は電子レンジやオーブンに
用いる熱線反射窓の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a heat reflecting window used in a microwave oven or an oven.
【0002】[0002]
【従来の技術】一般に電子レンジや電子オーブンには、
その加熱調理時の熱効率を向上するために、前面ガラス
窓の表面に熱線反射材料膜が形成されている。2. Description of the Related Art Generally, a microwave oven and an electronic oven include:
In order to improve the thermal efficiency during the heating and cooking, a heat ray reflective material film is formed on the surface of the front glass window.
【0003】このような熱線反射材料として、酸化スズ
・酸化アンチモン系(ATO)や酸化インジウム・酸化
スズ系(ITO)などが知られており、これらの金属酸
化物をガラス基板上に被膜形成すると、透明な熱線反射
膜とすることができる。As such heat ray reflecting materials, tin oxide / antimony oxide (ATO), indium oxide / tin oxide (ITO), and the like are known. When these metal oxides are formed on a glass substrate, a film is formed. And a transparent heat ray reflective film.
【0004】これらの熱線反射膜の形成方法としては、
次の方法が知られている。 (1) 真空蒸着法 (2) スパッタリング法 (3) CVD法 (4) 塗布法[0004] As a method of forming these heat ray reflection films,
The following methods are known. (1) Vacuum evaporation method (2) Sputtering method (3) CVD method (4) Coating method
【0005】[0005]
【発明が解決しようとする課題】しかし、上記の(1) 、
(2) 、(3) の方法は、装置が複雑かつ高価で、コストと
量産性に問題がある。また、(4) の方法は、上記の(1)
、(2) 、(3) の方法の問題点を解決する可能性を有し
ているものの、実用に耐えうる膜を形成することが困難
であった。However, the above (1),
The methods (2) and (3) have complicated and expensive devices and have problems in cost and mass productivity. The method (4) is based on the above (1)
Although there is a possibility of solving the problems of the methods (2) and (3), it has been difficult to form a film that can withstand practical use.
【0006】たとえば、硝酸インジウム、塩化インジウ
ム、塩化第2スズ等の無機化合物の有機溶液を使用した
場合は、形成された膜に白濁を生じたり、得られた膜の
機械的強度が不足で容易に傷がつく等の欠点がある。ま
た、オクチル酸インジウム等のイオン結合性の強い有機
酸インジウムを用いる方法においては、有機酸インジウ
ムが加水分解し易く、比較的容易に化学変化するため
に、塗布液のゲル化が生じる等の欠点がある。さらに、
インジウムやスズの有機錯体を使用する方法も提案され
ているが、この方法では基板に塗布した後の塗膜の熱分
解時において、スズ化合物の蒸散等により、膜の均一化
が阻害されるために、低抵抗の均質膜が得られない等の
欠点がある。For example, when an organic solution of an inorganic compound such as indium nitrate, indium chloride, stannic chloride or the like is used, the formed film becomes cloudy, or the obtained film lacks mechanical strength and is easily used. Has disadvantages such as scratching. In addition, in the method using an organic acid having a strong ionic bond such as indium octylate, since the organic acid indium is easily hydrolyzed and relatively easily chemically changed, gelling of a coating solution occurs. There is. further,
A method using an organic complex of indium or tin has also been proposed, but in this method, during thermal decomposition of a coating film after being applied to a substrate, evaporation of a tin compound or the like hinders uniformity of the film. However, there is a disadvantage that a low-resistance homogeneous film cannot be obtained.
【0007】ところで膜の電気抵抗値と熱線反射特性は
図2に示すように反比例の関係がある。このため、前記
の従来の酸化物膜は熱線反射特性が低く、電子レンジや
電子オーブン等の熱線反射膜としては機能として不十分
であった。The electrical resistance of the film and the heat ray reflection characteristic have an inversely proportional relationship as shown in FIG. For this reason, the above-mentioned conventional oxide film has low heat ray reflection characteristics, and is insufficient in function as a heat ray reflection film for a microwave oven or an electronic oven.
【0008】本発明は、上記課題を解決するもので、低
抵抗、高可視光透過率、高熱線反射特性を有する電子レ
ンジやオーブン用の熱線反射窓の製造法を提供すること
を目的とする。An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a method for manufacturing a heat-reflection window for a microwave oven or an oven having low resistance, high visible light transmittance, and high heat-ray reflection characteristics. .
【0009】[0009]
【課題を解決するための手段】本発明は、上記目的を達
成するために、無機インジウム化合物と有機スズ化合物
と、インジウムとスズのいずれにも配位可能な有機化合
物とからなる有機溶液を加熱処理して、前記有機溶液を
部分的に加水分解することでインジウムと錫の中間複合
化合物を形成し、前記有機溶液に多価アルコール類を混
合して得られた組成物の熱分解による可視光透過膜をガ
ラス基板の片面または両面に形成する熱線反射窓の製造
方法、とする。In order to achieve the above object, the present invention provides a method for heating an organic solution comprising an inorganic indium compound, an organic tin compound, and an organic compound capable of coordinating with both indium and tin. Treating the organic solution
Intermediate complex of indium and tin by partial hydrolysis
Manufacture of a heat reflection window for forming a compound and forming a visible light transmitting film on one or both surfaces of a glass substrate by thermal decomposition of a composition obtained by mixing a polyhydric alcohol with the organic solution.
Method .
【0010】[0010]
【作用】本発明は、無機インジウム化合物と有機スズ化
合物と、インジウムとスズのいずれとも配位可能な有機
化合物とからなる有機溶液を加熱処理することにより、
有機化合物が1部配位した無機インジウム化合物と有機
スズ化合物と無機インジウム化合物が含有する結晶水が
反応し、有機スズ化合物が部分的に加水分解されて、イ
ンジウムとスズの中間複合化合物を形成し、これによっ
て従来の課題であったスズの蒸散による膜の不均一化を
抑え、得られる膜の高熱線反射特性、低抵抗率、高可視
光透過率を与えるものである。また、多価アルコール類
の添加により、溶液の増粘効果と、前記組成物を基板に
塗布・乾燥して得られる被膜の安定性を与えるものであ
る。According to the present invention, an organic solution comprising an inorganic indium compound, an organic tin compound, and an organic compound capable of coordinating with both indium and tin is subjected to heat treatment.
The inorganic indium compound in which one part of the organic compound is coordinated reacts with the water of crystallization contained in the organic tin compound and the inorganic indium compound, and the organic tin compound is partially hydrolyzed to form an intermediate composite compound of indium and tin. This suppresses the nonuniformity of the film due to the evaporation of tin, which is a conventional problem, and gives the obtained film high heat ray reflection characteristics, low resistivity, and high visible light transmittance. The addition of polyhydric alcohols also provides a thickening effect of the solution and the stability of a film obtained by applying and drying the composition on a substrate.
【0011】[0011]
【実施例】以下に、本発明の実施例を詳細に説明する。
本実施例における透明導電膜形成用組成物は以下のよう
にして合成される。まず最初に、無機インジウム化合物
をインジウムとスズのいずれとも配位可能な有機化合物
と混合する。ここで、前記無機インジウム化合物は、イ
ンジウムやスズと配位可能な有機化合物と、置換できる
ような配位子を持つものであればよい。たとえば、硝酸
インジウム、塩化インジウムが挙げられ、さらに結晶水
を有しているものが好ましい。また、インジウムとスズ
のいずれとも配位可能な有機化合物は、インジウムとス
ズに1部配位して、それらの中間化合物の形成を助け、
有機溶剤に対する溶解性をもたせるために必要であり、
たとえば、β−ジケトン類、α−またはβ−ケトン酸
類、前記ケトン酸類のエステル類、α−またはβ−アミ
ノアルコール類が挙げられる。Embodiments of the present invention will be described below in detail.
The composition for forming a transparent conductive film in this example is synthesized as follows. First, an inorganic indium compound is mixed with an organic compound capable of coordinating with both indium and tin. Here, the inorganic indium compound may be any compound having an organic compound capable of coordinating with indium or tin and having a ligand that can be substituted. For example, indium nitrate and indium chloride are mentioned, and those having crystallization water are preferable. In addition, an organic compound capable of coordinating with both indium and tin coordinates one part with indium and tin to help form an intermediate compound between them.
It is necessary to have solubility in organic solvents,
Examples include β-diketones, α- or β-ketone acids, esters of the ketone acids, and α- or β-amino alcohols.
【0012】次に、前記溶液に有機溶剤と有機スズ化合
物を加え、それらの有機溶液を加熱処理する。ここで、
前記有機スズ化合物としては、空気中では比較的安定で
あるが、加熱処理により容易に加水分解し易いものであ
ればよい。たとえば、カルボン酸スズやジカルボン酸ス
ズが挙げられ、炭素数が小さい、ギ酸スズ、酢酸スズ、
シュウ酸スズが好ましい。また、前記有機溶剤として
は、本実施例で用いる有機化合物や無機化合物を溶解す
るものであればよい。たとえば、トルエン、キシレン等
の芳香族炭化水素、エタノール、イソプロパノール等の
アルコール類、酢酸エチル、酢酸ブチル等の酢酸エステ
ル類、アセトン、ジエチルケトン等のケトン類、メトキ
シエタノール、エトキシエタノール等のエーテル類、テ
トラヒドロフラン等が挙げられる。さらに、加熱処理の
温度としては、無機インジウム化合物と有機スズ化合物
と、それらと配位可能な有機化合物とからなる有機溶液
の還流温度もしくは還流温度付近が好ましい。Next, an organic solvent and an organic tin compound are added to the solution, and the organic solution is heated. here,
The organotin compound may be any compound that is relatively stable in air, but is easily hydrolyzed by heat treatment. For example, tin carboxylate and tin dicarboxylate are mentioned, and the carbon number is small, tin formate, tin acetate,
Tin oxalate is preferred. The organic solvent may be any solvent that dissolves the organic compound and the inorganic compound used in this embodiment. For example, toluene, aromatic hydrocarbons such as xylene, ethanol, alcohols such as isopropanol, ethyl acetate, acetates such as butyl acetate, acetone, ketones such as diethyl ketone, methoxyethanol, ethers such as ethoxyethanol, Tetrahydrofuran and the like. Further, the temperature of the heat treatment is preferably at or near the reflux temperature of an organic solution comprising an inorganic indium compound, an organic tin compound, and an organic compound capable of coordinating with the compound.
【0013】そして、加熱処理後の有機溶液を室温付近
まで冷却し、多価アルコール類を加えて、混合した有機
溶液を熱分解性組成物とする。ここで、多価アルコール
類は、有機溶液の増粘効果と、熱分解性組成物をガラス
基板に塗布・乾燥して得られる被膜の安定性を与えるも
のであり、たとえばグリコール類や3価のアルコール類
が挙げられるが、炭素数が小さく、熱分解時の炭素残留
の恐れの少ない、エチレングリコールやグリセリンが好
ましい。Then, the organic solution after the heat treatment is cooled to around room temperature, a polyhydric alcohol is added, and the mixed organic solution is made a thermally decomposable composition. Here, the polyhydric alcohol gives the effect of thickening the organic solution and the stability of the coating obtained by applying and drying the thermally decomposable composition on the glass substrate. Alcohols may be mentioned, but ethylene glycol and glycerin, which have a small number of carbon atoms and are less likely to remain carbon during thermal decomposition, are preferred.
【0014】このようにして、得られた熱分解性組成物
をガラス基板に塗布・乾燥した後、焼成して、熱線反射
膜を形成する。ここで、熱分解性組成物の塗布には、ス
クリーン印刷法、ロールコート法、ディップコート法、
スピンコート法等を用いることができるが、ディップコ
ート法、スピンコート法が好ましい。また、焼成温度と
しては、熱分解性組成物が分解する温度以上で、かつガ
ラス基板の変形温度以下であればよく、400〜700
℃が好ましい。The heat-decomposable composition thus obtained is applied to a glass substrate, dried, and fired to form a heat ray reflective film. Here, the application of the thermally decomposable composition includes a screen printing method, a roll coating method, a dip coating method,
Although a spin coating method or the like can be used, a dip coating method or a spin coating method is preferable. The firing temperature is not less than the temperature at which the thermally decomposable composition decomposes and not more than the deformation temperature of the glass substrate.
C is preferred.
【0015】以下、さらに詳細な実施例によって本発明
を説明するが、本発明はこれらの実施例によって限定さ
れるものではない。 (実施例1)三角フラスコに、45gの硝酸インジウム
In(NO3 )3 ・3H2 Oを秤量し、50gのアセチ
ルアセトンを加えて、室温で混合・溶解させた。その溶
液に、0[Sn/In+Sn)×100でOwt%]〜
8.1g[Sn/(In+S)n)×100で30wt
%〕のシュウ酸第1スズ(SnC2 O4 )とアセトンを
加えて還流した。その還流後の溶液を、室温付近まで冷
却し、5gのグリセリンを加えて、撹拌・混合し、熱分
解性組成物を合成した。その熱分解性組成物に、SiO
2 コート並ガラス基板を60cm/minの引き上げ速
度でディップコートした。その基板を5分間室温で放置
し、100℃で5分間乾燥した後、500℃で1時間焼
成した。得られた膜の厚みは0.10μmであった。
(実施例2)無機インジウム化合物として、塩化インジ
ウムInCl3 ・3H2 Oを、有機スズ化合物として、
シュウ酸第1スズを用い、[Sn/(In+Sn)×1
00]で10wt%となるようにした。他は実施例1に
同じ。 (実施例3)有機スズ化合物として、酢酸第1スズを用
い、[Sn/(In+Sn)×100]で10wt%と
なるようにした。他は実施例1に同じ。 (実施例4)実施例1と同じ熱分解性組成物を用いてガ
ラス基板へのディップ熱分解を3回繰り返した。他は、
実施例1と同じ。得られた反射窓の赤外線反射特性を図
1に示す。 (比較例1)三角フラスコに、45gの硝酸インジウム
In(NO3 )3 ・3H2 Oと5.4g[Sn/(In
+Sn)×100で10wt%]の塩化第2スズSnC
l4・5H2 Oとアセトンを加えて、撹拌・混合し、熱
分解性組成物を合成した。その熱分解性組成物に、Si
O2 コート並ガラス基板を60cm/minの引き上げ
速度でディップコートした。その基板を5分間室温で放
置し、100℃で5分間乾燥した後、500℃で1時間
焼成した。Hereinafter, the present invention will be described with reference to more detailed examples, but the present invention is not limited to these examples. (Example 1) In an Erlenmeyer flask, 45 g of indium nitrate In (NO 3 ) 3 .3H 2 O was weighed, 50 g of acetylacetone was added, and mixed and dissolved at room temperature. In the solution, 0 [Sn / In + Sn) × 100 and Owt%] %
8.1 g [Sn / (In + S) n) × 100 30 wt
%] Of stannous oxalate (SnC 2 O 4 ) and acetone were added and refluxed. The solution after the reflux was cooled to around room temperature, 5 g of glycerin was added, and the mixture was stirred and mixed to synthesize a thermally decomposable composition. The thermally decomposable composition contains SiO 2
The two- coated glass substrate was dip-coated at a pulling rate of 60 cm / min. The substrate was left at room temperature for 5 minutes, dried at 100 ° C. for 5 minutes, and baked at 500 ° C. for 1 hour. The thickness of the obtained film was 0.10 μm.
Example 2 Indium chloride InCl 3 .3H 2 O was used as an inorganic indium compound, and as an organic tin compound,
Using stannous oxalate, [Sn / (In + Sn) × 1
00] to 10 wt%. Others are the same as Example 1. (Example 3) Stannous acetate was used as an organotin compound, and [Sn / (In + Sn) x 100] was adjusted to 10 wt%. Others are the same as Example 1. (Example 4) Using the same thermally decomposable composition as in Example 1, dip pyrolysis to a glass substrate was repeated three times. Others
Same as Example 1. FIG. 1 shows the infrared reflection characteristics of the obtained reflection window. Comparative Example 1 In an Erlenmeyer flask, 45 g of indium nitrate In (NO 3 ) 3 .3H 2 O and 5.4 g [Sn / (In
+ Sn) × 100 wt%] Stannic chloride SnC
added l 4 · 5H 2 O and acetone, stirred and mixed to synthesize a thermally decomposable composition. The thermally decomposable composition contains Si
The O 2 -coated glass substrate was dip-coated at a pulling rate of 60 cm / min. The substrate was left at room temperature for 5 minutes, dried at 100 ° C. for 5 minutes, and baked at 500 ° C. for 1 hour.
【0016】表1に実施例1〜4、比較例1の結果を示
す。Table 1 shows the results of Examples 1 to 4 and Comparative Example 1.
【0017】[0017]
【表1】 [Table 1]
【0018】本実施例においては、ガラス基板の両面に
熱線反射膜をディップ熱分解形成した例を述べたが、片
方の面にレジスト形成するなどして片面のみに熱線反射
膜を形成することも可能である。In this embodiment, an example is described in which the heat ray reflective film is formed by dip pyrolysis on both surfaces of the glass substrate. However, the heat ray reflective film may be formed on only one surface by forming a resist on one surface. It is possible.
【0019】また、形成された熱線反射膜に一対の電極
を形成し、これに交流または直流の電界を印加すること
により、この部分を面状の発熱体として作用させ、飛散
して付着した物の表面クリーニングも可能になる。Further, a pair of electrodes is formed on the formed heat ray reflection film, and an AC or DC electric field is applied to the pair of electrodes to cause this portion to function as a planar heating element, and to scatter and adhere to the portion. Surface cleaning becomes possible.
【0020】[0020]
【発明の効果】上記実施例の説明より明らかなように、
本発明によれば熱線反射特性と可視領域における透過性
に優れた透明導電膜を容易にかつ安価で得ることがで
き、電子レンジや電気オーブンの熱線反射用窓として適
するものが提供できる。As is clear from the description of the above embodiment,
ADVANTAGE OF THE INVENTION According to this invention, the transparent conductive film excellent in the heat ray reflection characteristic and the transmittance | permeability in a visible region can be obtained easily and cheaply, and what is suitable as a window for heat rays reflection of a microwave oven or an electric oven can be provided.
【図1】本発明の熱線反射窓の赤外線反射特性を示す図FIG. 1 is a diagram showing infrared reflection characteristics of a heat ray reflection window of the present invention.
【図2】膜の電気抵抗と熱線反射特性との相関性を示す
図FIG. 2 is a diagram showing a correlation between electric resistance of a film and heat ray reflection characteristics.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平5−32917(JP,A) (58)調査した分野(Int.Cl.7,DB名) C03C 15/00 - 23/00 ────────────────────────────────────────────────── (5) References JP-A-5-32917 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C03C 15/00-23/00
Claims (6)
と、インジウムとスズいずれにも配位可能な有機化合物
とからなる有機溶液を加熱処理して、前記有機溶液を部
分的に加水分解することでインジウムと錫の中間複合化
合物を形成し、前記有機溶液に多価アルコール類を混合
して得られた組成物の熱分解による可視光透過膜をガラ
ス基板の片面または両面に形成する熱線反射窓の製造方
法。 1. An organic solution comprising an inorganic indium compound and an organic tin compound, and an organic compound capable of coordinating with both indium and tin, is subjected to a heat treatment to partially remove the organic solution.
Intermediate complexation of indium and tin by partial hydrolysis
A method for manufacturing a heat ray reflective window, wherein a visible light transmitting film is formed on one or both surfaces of a glass substrate by thermal decomposition of a composition obtained by forming a compound and mixing the polyhydric alcohol with the organic solution.
化合物の配合比(Sn/(In+Sn)×100)が5
〜20wt%の範囲にあることを特徴とする請求項1記
載の熱線反射窓の製造方法。2. The compounding ratio of an organotin compound to an inorganic indium compound (Sn / (In + Sn) × 100) is 5
The method for producing a heat ray reflective window according to claim 1, wherein the content is in the range of 20 wt% to 20 wt%.
ムまたは塩化インジウムであることを特徴とする請求項
1記載の熱線反射窓の製造方法。3. The method according to claim 1, wherein the inorganic indium compound is indium nitrate or indium chloride.
ジカルボン酸塩であることを特徴とする請求項1記載の
熱線反射窓の製造方法。4. The method according to claim 1, wherein the organotin compound is a carboxylate or a dicarboxylate.
ン類、α- またはβ−ケトン酸類、前記ケトン酸類のエ
ステル類、α- またはβ−アミノアルコール類からなる
群から選ばれるものであることを特徴とする請求項1記
載の熱線反射窓の製造方法。5. The coordinable organic compound is selected from the group consisting of β-diketones, α- or β-ketone acids, esters of the ketone acids, and α- or β-amino alcohols. The method for manufacturing a heat ray reflection window according to claim 1, wherein:
後、焼成することを特徴とする請求項1記載の熱線反射
窓の製造方法。6. The method according to claim 1, wherein the composition is applied to a glass substrate, dried, and then fired.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10385293A JP3144951B2 (en) | 1993-04-30 | 1993-04-30 | Method of manufacturing heat reflection window |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10385293A JP3144951B2 (en) | 1993-04-30 | 1993-04-30 | Method of manufacturing heat reflection window |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06316441A JPH06316441A (en) | 1994-11-15 |
JP3144951B2 true JP3144951B2 (en) | 2001-03-12 |
Family
ID=14364978
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10385293A Expired - Fee Related JP3144951B2 (en) | 1993-04-30 | 1993-04-30 | Method of manufacturing heat reflection window |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3144951B2 (en) |
-
1993
- 1993-04-30 JP JP10385293A patent/JP3144951B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH06316441A (en) | 1994-11-15 |
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