JP2518129B2 - Heat-treated coated glass and method for producing the same - Google Patents
Heat-treated coated glass and method for producing the sameInfo
- Publication number
- JP2518129B2 JP2518129B2 JP4309338A JP30933892A JP2518129B2 JP 2518129 B2 JP2518129 B2 JP 2518129B2 JP 4309338 A JP4309338 A JP 4309338A JP 30933892 A JP30933892 A JP 30933892A JP 2518129 B2 JP2518129 B2 JP 2518129B2
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- JP
- Japan
- Prior art keywords
- film
- oxide
- coated glass
- heat
- protective film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Optical Filters (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
- Surface Treatment Of Glass (AREA)
Description
【０００１】本発明は、熱処理被覆ガラスおよびその製
造方法にかかり、特に、曲げ加工前後の特性変化を最小
限にとどめることのできる熱処理ガラスの製造方法に関
する。[0001] The present invention relates to a method for producing a heat-treated coated glass and its, in particular to a method of manufacturing a heat treatment glass that can minimize the bending properties before and after the change.
【０００２】[0002]
【従来の技術】曲げ被覆ガラスは、従来、曲げ加工を既
に行ったガラスに被覆を施すことにより製造されたり、
保護されるべき金属膜、あるいは、金属窒化物膜をタン
タル等の酸化しやすい金属ではさむように被覆したガラ
スを曲げ加工し、曲げ加工時は、酸化しやすい金属がも
っぱら酸化されることにより、上記保護されるべき膜を
保護して製造していた。あるいは、曲げ加工時の雰囲気
を非酸化性雰囲気に保つことにより、上記保護されるべ
き膜の酸化を防いで製造していた。2. Description of the Related Art Bending-coated glass is conventionally manufactured by applying a coating to glass that has already been bent,
The metal film to be protected, or the metal nitride film is bent so as to be sandwiched by a metal such as tantalum which is easily oxidized, and the glass is bent. It was manufactured with the membrane to be protected protected. Alternatively, the atmosphere during the bending process is kept in a non-oxidizing atmosphere to prevent the above-mentioned film to be protected from being oxidized.
【０００３】[0003]
【発明が解決しようとする課題】前記した技術のうち、
曲げガラスに被覆を行う方法では、曲げガラスの形状に
合わせて、被覆工程と被覆条件を調整しなければ、曲げ
ガラス上に一様な被覆を行うことができず、高品質で、
同一性能を持つ製品を得ることは困難である。Among the above-mentioned techniques,
In the method of coating bent glass, according to the shape of the bent glass, unless the coating process and the coating conditions are adjusted, uniform coating cannot be performed on the bent glass, and high quality,
It is difficult to obtain products with the same performance.
【０００４】一方、保護すべき層を容易に酸化する金属
ではさむ方法では、曲げ加工前後でかかる被覆ガラスの
特性が変化するために、得られる曲げガラスと同一特性
を持つ平面ガラスは、別の膜構成で用意するか、あるい
は、曲げ加工と同じ加熱処理をしなければならず、その
製品管理に大きな無駄が存在する。また、曲げ加工時の
雰囲気を非酸化性雰囲気に保つ方法では、通常の曲げ加
工装置の改造が必要となり、コストが高くなる。ガラス
の熱処理として曲げ加工と同様に一般的に強化加工が行
われているが、強化加工された被覆ガラスについても、
曲げ被覆ガラスの場合と同様である。On the other hand, in the method of sandwiching the layer to be protected with a metal that easily oxidizes, the characteristics of the coated glass change before and after bending, so that the flat glass having the same characteristics as the obtained bent glass is different from the flat glass. The film must be prepared or the same heat treatment as bending must be performed, and there is a great waste in product management. Further, in the method of maintaining the atmosphere during the bending process in a non-oxidizing atmosphere, it is necessary to modify the ordinary bending device, which increases the cost. Generally, tempering is performed as heat treatment for glass as in bending, but also for tempered coated glass,
This is similar to the case of bend-coated glass.
【０００５】[0005]
【課題を解決するための手段】本発明は、通常の平面ガ
ラスの被覆技術を用いて、低コストで、均一性の高い被
覆平面ガラスを製造し、ついで、一般に行われている平
易な、雰囲気制御の不必要な、大気中での加熱による曲
げ加工かつ／または強化加工を行い、光学特性などを主
に左右する、保護されるべき被覆層の変化がほとんどな
い熱処理被覆ガラスの製造方法を提供するものである。SUMMARY OF THE INVENTION The present invention uses a conventional flat glass coating technique to produce a low cost, highly uniform coated flat glass, which is then subjected to the commonly used simple atmosphere. Provided is a method for producing heat-treated coated glass which is subjected to bending and / or strengthening by heating in the air without control, and which has almost no change in the coating layer to be protected, which mainly influences optical properties. To do.
【０００６】すなわち、本発明は、ガラス基板上に、熱
線遮断膜または導電膜を形成し、次いで可視光領域にお
いて透明な、非酸化物膜または完全には酸化されていな
い膜であって、かつ酸化されても透明である第１の保護
膜を形成して、少なくとも２層からなる多層膜を有する
被覆ガラスを製造し、その後、かかる被覆ガラスに熱処
理を施す熱処理被覆ガラスの製造方法において、第１の
保護膜は、ケイ素またはホウ素の窒化物、あるいは、ケ
イ素、ホウ素、アルミニウム、ジルコニウム、スズのう
ち少なくとも２種以上の窒化物、を主成分とする膜であ
ることを特徴とする熱処理被覆ガラスの製造方法を提供
するものである。また本発明は、第１の保護膜上に、さ
らに、金属酸化物からなり透明な第２の保護膜を形成し
て、少なくとも３層からなる多層膜を有する被覆ガラス
を製造し、その後、かかる被覆ガラスに熱処理を施すこ
とを特徴とする上記熱処理被覆ガラスの製造方法を提供
するものである。That is, according to the present invention , a heat ray-shielding film or a conductive film is formed on a glass substrate, and then a transparent non-oxide film or a film which is not completely oxidized in the visible light region, and A method for producing a heat-treated coated glass, which comprises forming a first protective film that is transparent even when oxidized to produce a coated glass having a multilayer film composed of at least two layers, and then subjecting the coated glass to a heat treatment , One
The protective film may be a nitride of silicon or boron, or a
Silicon, boron, aluminum, zirconium, tin oxide
A film containing at least two kinds of nitrides as a main component
There is provided a method for manufacturing a heat treatment coated glass, characterized in that that. Further, according to the present invention, a transparent second protective film made of a metal oxide is further formed on the first protective film to manufacture a coated glass having a multilayer film made of at least three layers, and thereafter manufacturing method of the heat treatment the coated glass, wherein the heat treatment to the coated glass is to provide.
【０００７】図１は、本発明で製造される熱処理被覆ガ
ラスの一例の断面図であり、図２および図３は、本発明
による熱処理被覆ガラスの他の例の断面図である。図に
おいて、１は熱線遮断膜、２は第１の保護膜、３は第２
の保護膜、４はガラス基板である。FIG. 1 is a cross-sectional view of an example of the heat-treated coated glass manufactured by the present invention, and FIGS. 2 and 3 are cross-sectional views of other examples of the heat-treated coated glass according to the present invention. In the figure, 1 is a heat ray blocking film, 2 is a first protective film, and 3 is a second
The protective films 4 and 4 are glass substrates.
【０００８】本発明において、熱線遮断膜１としては、
太陽光の波長領域の少なくとも一部において光吸収特性
を有する、太陽エネルギー吸収性能を有する膜や、主に
近赤外域において光反射特性を有する膜などが挙げられ
る。In the present invention, as the heat ray blocking film 1,
Examples thereof include a film having a solar energy absorption performance, which has a light absorption property in at least a part of the wavelength range of sunlight, and a film which has a light reflection property mainly in the near infrared region.
【０００９】具体的には、ステンレス、チタン、クロ
ム、ジルコニウム、タンタル、ハフニウムのうち少なく
とも一種（以下、金属Ｍとする）、金属Ｍの窒化物、金
属Ｍのホウ化物、金属Ｍの炭化物、あるいはこれらの混
合物を主成分とする膜や、銀、アルミニウム、クロム等
の金属を主成分とする膜が挙げられる。窒化物、ホウ化
物、炭化物等の場合は、熱線遮断特性を得るために、そ
の厚さは、１００〜８００Å程度にするのが好ましく、
金属膜の場合は、同様に２０〜３００Åの膜厚にするの
が好ましい。Specifically, at least one of stainless steel, titanium, chromium, zirconium, tantalum, and hafnium (hereinafter referred to as metal M), a metal M nitride, a metal M boride, a metal M carbide, or A film containing a mixture of these as a main component and a film containing a metal such as silver, aluminum, or chromium as a main component can be given. In the case of nitrides, borides, carbides, etc., the thickness thereof is preferably about 100 to 800Å in order to obtain the heat ray blocking property.
Similarly, in the case of a metal film, it is preferable to set the film thickness to 20 to 300Å.
【００１０】本発明は、上記熱線遮断膜の代わりに、酸
素欠損あるいは金属過剰により導電性が生じている、金
属酸化物からなる導電膜についても適用できる。かかる
導電膜としては、低比抵抗なものとしては、スズを添加
した酸化インジウム、アンチモンあるいはフッ素を添加
した酸化スズ、アルミニウム、ホウ素、ケイ素等を添加
した酸化亜鉛等が挙げられ、その他に、酸化亜鉛、酸化
チタン、酸化スズ、酸化トリウム、酸化バナジウム、酸
化ニオブ、酸化タンタル、酸化モリブデン、酸化タング
ステン、酸化マンガン、鉛−クロムの酸化物、等が挙げ
られる。The present invention can also be applied to a conductive film made of a metal oxide, which has conductivity due to oxygen deficiency or excess metal, instead of the heat ray blocking film. Examples of such a conductive film having a low specific resistance include indium oxide to which tin is added, tin oxide to which antimony or fluorine is added, zinc oxide to which aluminum, boron, silicon and the like are added, and the like. Examples thereof include zinc, titanium oxide, tin oxide, thorium oxide, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, manganese oxide, and lead-chromium oxide.
【００１１】以上の導電膜は、熱線遮断性能も兼ね備え
ているものが多い。特に低比抵抗のものは、近赤外領域
の反射特性が良好で、優れた熱線遮断性能を有する。導
電膜の膜厚は、反射率等の所望の光学特性に応じて、決
定される。以下、本明細書においては、“熱線遮断膜”
は、かかる導電膜も含むものとする。Many of the above-mentioned conductive films also have a heat ray shielding property. Particularly, those having a low specific resistance have good reflection characteristics in the near infrared region and have excellent heat ray shielding performance. The film thickness of the conductive film is determined according to desired optical characteristics such as reflectance. Hereinafter, in the present specification, "heat ray blocking film"
Also includes such a conductive film.
【００１２】第１の保護膜２は、可視光領域で透明な、
非酸化物膜または完全には酸化されていない膜であっ
て、かつ酸化されても可視光領域で透明な膜である。第
１の保護膜２は、熱処理時に加熱されても酸素が熱線遮
断膜１へ拡散するのを防ぎ、また、第１の保護膜２自身
が酸素を含んでいてもその酸素を熱線遮断膜１へ放出す
ることがない膜である。かかる第１の保護膜は、酸化さ
れても屈折率が変化するだけで、吸収が生じず、透明で
あるため、熱処理後の光学特性に大きな影響は与えな
い。The first protective film 2 is transparent in the visible light region,
It is a non-oxide film or a film that is not completely oxidized, and is a film that is transparent in the visible light region even if it is oxidized. The first protective film 2 prevents oxygen from diffusing into the heat ray blocking film 1 even when it is heated during heat treatment, and even if the first protective film 2 itself contains oxygen, the oxygen is absorbed by the heat ray blocking film 1. It is a film that does not release to. The first protective film does not absorb light and changes its refractive index even when it is oxidized, and is transparent, so that it does not significantly affect the optical characteristics after heat treatment.
【００１３】第１の保護膜２としては、ケイ素またはホ
ウ素の窒化物を主成分とする膜、あるいは、ケイ素、ホ
ウ素、アルミニウム、ジルコニウム、スズのうち少なく
とも２種以上の窒化物を主成分とする膜、なかでも、ケ
イ窒化ジルコニウム膜、ケイ窒化スズ膜などが代表的な
例として挙げられる。以上のうちで、窒化ケイ素、ケイ
窒化ジルコニウムは、特に酸素バリヤ性能が良好であ
る。The first protective film 2 is a film containing a nitride of silicon or boron as a main component, or a nitride containing at least two kinds of silicon, boron, aluminum, zirconium and tin as a main component. A typical example is a film, especially a zirconium silicon nitride film, a tin silicon nitride film, or the like . Of the more than, silicon nitride, silicon zirconium nitride has good especially oxygen burrs ya performance.
【００１４】以上で述べた第１の保護膜としての窒化物
膜等においては、窒化物が化学量論的に最も一般的な割
合で結合していなくても、可視光領域で透明であればよ
い。例えば、窒化ケイ素の場合、Ｓｉ3 Ｎ4 が一般的で
あるが、可視光領域で透明であるために、Ｓｉに対する
Ｎの比が１．２５以上であることが好ましい。In the nitride film or the like as the first protective film described above, even if the nitrides are not bound in the most general stoichiometric ratio, as long as they are transparent in the visible light region. Good. For example, in the case of silicon nitride, Si 3 N 4 is generally used, but since it is transparent in the visible light region, the ratio of N to Si is preferably 1.25 or more.
【００１５】この第１の保護膜２の厚さは、最外層の第
２の保護膜を形成する場合には、その酸素バリヤ性に依
存し、熱処理時にこの第２の保護膜を通して内部に拡散
される酸素量を考慮して決定されるが、通常の熱処理で
は、少なくとも１０Å程度以上、特に２０Å以上である
ことが好ましい。本発明においては、第２の保護膜を形
成せず、ある程度厚い膜厚で第１の保護膜を形成するだ
けでもよい。膜厚は熱処理中に酸化される分の膜厚を考
慮して決定すればよい。The thickness of the first protective film 2 depends on its oxygen barrier property when the outermost second protective film is formed, and diffuses inward through the second protective film during heat treatment. It is determined in consideration of the amount of oxygen to be generated, but in a normal heat treatment, it is preferably at least about 10Å or more, and particularly preferably 20Å or more. In the present invention, the second protective film may not be formed, and only the first protective film may be formed to have a relatively large film thickness. The film thickness may be determined in consideration of the film thickness that is oxidized during the heat treatment.
【００１６】第２の保護膜３は、金属酸化物からなり、
可視光領域において透明な膜であり、酸素バリヤ性の高
いものが好ましい。具体的には、酸化スズ、酸化タンタ
ル、酸化ニオブ、酸化チタン、酸化ケイ素、酸化ジルコ
ニウム、酸化亜鉛などが挙げられる。かかる第２の保護
膜３の厚さは、第１の保護膜２の厚さや、被覆ガラス全
体としての光学特性などを考慮して決定される。The second protective film 3 is made of a metal oxide,
A film that is transparent in the visible light region and has a high oxygen barrier property is preferable. Specifically, tin oxide, tantalum oxide, niobium oxide, titanium oxide, silicon oxide, zirconium oxide, zinc oxide and the like can be mentioned. The thickness of the second protective film 3 is determined in consideration of the thickness of the first protective film 2 and the optical characteristics of the entire coated glass.
【００１７】本発明の方法においては、ガラス基板４中
から微量拡散してくる酸素を遮断するために、熱線遮断
膜１とガラス基板４の間に、第１の保護膜と同様の機能
を発揮しうる膜、即ち、非酸化物膜または完全に酸化さ
れていない膜であって、かつ酸化されても透明である
膜、を、図２のように、第１の下地膜５として形成する
ことが好ましい。第１の下地膜５の材料としては、第１
の保護膜と同様の材料が使用できる。In the method of the present invention, in order to block a small amount of oxygen diffused from the glass substrate 4, the same function as that of the first protective film is exerted between the heat ray blocking film 1 and the glass substrate 4. A possible film, that is, a non-oxide film or a film that is not completely oxidized and that is transparent even when oxidized, as the first base film 5 as shown in FIG. Is preferred. The material of the first base film 5 is the first
The same material as the protective film of can be used.
【００１８】さらに、本発明の方法においては、光の干
渉を用いて所望の光学特性（透過率、反射率、色調等）
を得るために、あるいは密着性等の耐久性向上のため
に、図３のように、金属酸化物からなり、透明な膜を、
第２の下地膜６として、ガラス基板４と第１の下地膜５
との間に形成してもよい。第２の下地膜６としては、第
１の保護膜として例示した膜も使用できる。また、これ
らの膜に限らず、所望の膜をガラス基板４と第１の下地
膜５との間に形成してよい。Further, in the method of the present invention, desired optical characteristics (transmittance, reflectance, color tone, etc.) are obtained by using light interference.
In order to obtain the above or to improve durability such as adhesion, as shown in FIG. 3, a transparent film made of a metal oxide,
The glass substrate 4 and the first base film 5 are used as the second base film 6.
It may be formed between and. As the second base film 6, the film exemplified as the first protective film can also be used. Further, not limited to these films, a desired film may be formed between the glass substrate 4 and the first base film 5.
【００１９】ガラス基板４は、特に限定されない。ソー
ダライムガラス板、熱線吸収ガラス板など、各種のガラ
ス板が使用できる。The glass substrate 4 is not particularly limited. Various glass plates such as soda lime glass plate and heat ray absorbing glass plate can be used.
【００２０】熱処理としての曲げ加工方法は、特に限定
されず、大気中で、上記被覆ガラスを５８０〜７００℃
程度に加熱し、曲げ成形する、通常行われている方法で
よい。もちろん、非酸化性雰囲気で曲げ加工してもよい
が、装置の改造等が必要となり、コストが高くなる。熱
処理としての強化加工としては、やはり特に限定され
ず、大気中で、上記被覆ガラスを５００〜７００℃程度
に加熱した後、急冷する、通常の方法でよい。曲げ加工
後、連続して強化加工を行うこともできる。なお、かか
る強化加工は full temper（全強化）であってもよい
し、あるいは semitemper（半強化）であってもよい。
なお、上述の各熱処理温度は、ガラスの組成に依存す
る。The bending method as the heat treatment is not particularly limited, and the above coated glass is heated to 580 to 700 ° C. in the atmosphere.
A commonly used method of heating to a certain degree and bending may be used. Of course, the bending process may be performed in a non-oxidizing atmosphere, but the device needs to be modified and the cost is increased. The tempering process as the heat treatment is not particularly limited, and may be a usual method in which the above coated glass is heated to about 500 to 700 ° C. in the air and then rapidly cooled. After the bending process, the strengthening process can be continuously performed. The tempering process may be a full temper or a semitemper.
The heat treatment temperatures described above depend on the glass composition.
【００２１】熱処理後の被覆ガラスにおいては、第１の
保護膜は、第２の保護膜の酸素バリヤ性が高い場合に、
酸化が進まず組成変化がほとんど生じていないこともあ
るが、熱処理時の加熱により酸化が進み、熱処理前より
酸素をより多く含んでいることが多い。ときには、第１
の保護膜中の窒素や炭素が熱処理中に放出され、酸化物
に変化していることもある。あるいは、第２の保護膜を
形成しない場合には第１の保護膜の表面からある程度酸
化されているが、熱線遮断膜と接する部分までは酸化さ
れていない状態となっている。In the coated glass after the heat treatment, when the first protective film has a high oxygen barrier property of the second protective film,
In some cases, the composition does not change due to the fact that the oxidation does not progress, but the oxidation progresses due to the heating during the heat treatment, and often contains more oxygen than before the heat treatment. Sometimes the first
Nitrogen and carbon in the protective film may be released during the heat treatment and changed into oxides. Alternatively, when the second protective film is not formed, the surface of the first protective film is oxidized to some extent, but the portion contacting the heat ray blocking film is not oxidized.
【００２２】[0022]
【作用】ガラスに被覆された熱線遮断膜１は通常、熱処
理時に、これを保護する酸化物膜を通して内部に拡散す
る雰囲気ガス（大気）中の酸素と、隣接する酸化物膜中
の化合酸素により酸化され、その光学特性、特に熱線遮
断性能、可視光透過率（導電膜の場合は、導電性能）等
が大きく変化する。The heat ray-shielding film 1 coated on glass is usually formed by oxygen in the atmospheric gas (atmosphere) that diffuses inside through the oxide film that protects it during heat treatment and combined oxygen in the adjacent oxide film. It is oxidized, and its optical characteristics, especially heat ray blocking performance, visible light transmittance (in the case of a conductive film, conductive performance), etc., change greatly.
【００２３】本発明では、保護のための第２の保護膜３
に酸素バリヤ性の高いものを選んで内部に拡散する酸素
を大きく減少せしめ、さらに、第２の保護膜３と熱線遮
断膜１との間に第１の保護膜２を設けたため、かかる第
１の保護膜２が、第２の保護膜を通ってわずかに内部に
拡散してくる酸素や第２の保護膜中の化合酸素ともっぱ
ら反応し、これらの拡散してくる酸素と化合酸素を、保
護すべき熱線遮断膜１まで達することを防止したことに
より、熱線遮断膜１がほとんど変化しない。また、第２
の保護膜３を形成しない場合においても、第１の保護膜
が熱処理時に大気中から入ってくる酸素を十分に吸収
し、酸素バリヤの働きをするため、熱線遮断膜１はほと
んど変化しない。In the present invention, the second protective film 3 for protection is used.
Since a material having a high oxygen barrier property is selected to greatly reduce the amount of oxygen diffused inward, the first protective film 2 is provided between the second protective film 3 and the heat ray blocking film 1. The protective film 2 of No. 2 reacts exclusively with oxygen that slightly diffuses inside through the second protective film and combined oxygen in the second protective film, and these diffused oxygen and combined oxygen are Since the heat ray blocking film 1 to be protected is prevented from reaching the heat ray blocking film 1, the heat ray blocking film 1 hardly changes. Also, the second
Even when the protective film 3 is not formed, since the first protective film sufficiently absorbs oxygen coming from the atmosphere during the heat treatment and acts as an oxygen barrier, the heat ray blocking film 1 hardly changes.
【００２４】したがって、ガラスに被覆された多層膜全
体でみても、熱線遮断膜１はほとんど変化せず、第１の
保護膜の屈折率が若干変化するだけで、膜全体として、
通常の熱処理によって生じる光学特性変化を生じること
はない。Therefore, even if the entire multilayer film coated with glass is viewed, the heat ray-shielding film 1 hardly changes, and the refractive index of the first protective film slightly changes.
There is no change in optical characteristics caused by ordinary heat treatment.
【００２５】[0025]
［実施例１］平板状ガラス基板４上に、スズ・ターゲッ
トを酸素とアルゴン混合気体中で反応性スパッタリング
を行い、酸化スズからなる第２の下地膜６（２５０Å）
を形成し、ついで、ケイ化ジルコニウム合金ターゲット
を窒素ガス中で反応性スパッタリングして、ケイ窒化ジ
ルコニウムからなる第１の下地膜５（５０Å）を形成し
た。[Example 1] On a flat glass substrate 4, a tin target was reactively sputtered in a mixed gas of oxygen and argon to form a second underlayer film 6 (250 Å) made of tin oxide.
Then, a zirconium silicide alloy target was reactively sputtered in nitrogen gas to form a first underlayer film 5 (50 Å) made of zirconium silicide nitride.
【００２６】つぎに、クロム・ターゲットを窒素ガス中
で反応性スパッタリングして窒化クロムからなる熱線遮
断膜１（１００Å）を形成した後、膜５と同様にして、
ケイ窒化ジルコニウムからなる第１の保護膜２（５０
Å）、さらに、膜６と同様にして酸化スズからなる第２
の保護膜３（３００Å）を形成し、図３のような構成の
被覆ガラスを得た。Next, a chromium target is reactively sputtered in nitrogen gas to form a heat ray blocking film 1 (100 Å) of chromium nitride, and then the same process as for the film 5 is performed.
The first protective film 2 (50
Å), and a second layer made of tin oxide in the same manner as the film 6.
A protective film 3 (300 Å) was formed to obtain a coated glass having a structure as shown in FIG.
【００２７】この平板状被覆ガラスを電気炉に入れ、大
気雰囲気中で約６３０℃に加熱して曲げ加工を行った。
曲げ加工後の熱線遮断膜１、第２の保護膜３、および第
２の下地膜６は曲げ加工前と変化がなく、曲げ加工後の
第１の保護膜２および第１の下地膜５は、部分的に酸化
されていた。加熱処理前後の被覆ガラスの光学特性を表
１に示す。This plate-shaped coated glass was placed in an electric furnace and heated at about 630 ° C. in the air atmosphere to be bent.
The heat ray blocking film 1, the second protective film 3, and the second base film 6 after the bending process are the same as those before the bending process, and the first protective film 2 and the first base film 5 after the bending process are , Was partially oxidized. Table 1 shows the optical characteristics of the coated glass before and after the heat treatment.
【００２８】［比較例１］平板状ガラス基板上に、順
に、酸化スズ膜（２５０Å）、窒化クロム膜（１００
Å）、酸化スズ膜（３００Å）を実施例１と同様のスパ
ッタリング法により形成した。得られた平板状被覆ガラ
スを実施例１と同様に加熱処理を行い、加熱前後の光学
特性を測定した。結果を表１に示す。Comparative Example 1 A tin oxide film (250 Å) and a chromium nitride film (100
Å) and a tin oxide film (300 Å) were formed by the same sputtering method as in Example 1. The obtained flat coated glass was heat-treated in the same manner as in Example 1, and the optical characteristics before and after heating were measured. The results are shown in Table 1.
【００２９】［比較例２］平板状ガラス基板上に、窒化
クロム膜（１００Å）を実施例１と同様のスパッタリン
グ法により形成した。得られた平面被覆ガラスを実施例
１と同様に加熱処理を行った。加熱前後の光学特性を表
１に与える。Comparative Example 2 A chromium nitride film (100 Å) was formed on a flat glass substrate by the same sputtering method as in Example 1. The obtained flat-coated glass was heat-treated in the same manner as in Example 1. The optical properties before and after heating are given in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】［実施例２］第１の下地膜５、および第１
の保護膜２として、ケイ素ターゲットを窒素ガス中で反
応性スパッタリングして、窒化ケイ素膜を形成した以外
は実施例１と同様の方法で図３のような被覆ガラス（即
ち、ガラス基板／酸化スズ（３２０Å）／窒化ケイ素／
窒化クロム（１３６Å）／窒化ケイ素／酸化スズ（２８
０Å）の構成の被覆ガラス）を得た。[Embodiment 2] First base film 5 and first
As the protective film 2 of Example 1, a coated glass as shown in FIG. 3 (that is, a glass substrate / tin oxide) was formed in the same manner as in Example 1 except that a silicon target was reactively sputtered in a nitrogen gas to form a silicon nitride film. (320Å) / silicon nitride /
Chromium nitride (136Å) / Silicon nitride / Tin oxide (28
A coated glass having a composition of 0Å) was obtained.
【００３２】第１の下地膜５および第１の保護膜２とし
ての窒化ケイ素の膜厚を、３０Å、２０Å、０Å（即
ち、窒化ケイ素を形成しなかった場合）、の３種類につ
き、加熱処理温度を変化させたときの光学特性の変化を
表２に示す。本実施例の窒化ケイ素膜におけるケイ素に
対する窒素の原子比は１．３５であった。Heat treatment is performed for each of three types of film thicknesses of silicon nitride as the first undercoat film 5 and the first protective film 2, that is, 30Å, 20Å, and 0Å (that is, when silicon nitride is not formed). Table 2 shows changes in optical characteristics when the temperature is changed. The atomic ratio of nitrogen to silicon in the silicon nitride film of this example was 1.35.
【００３３】実施例１、比較例１、２の結果の比較、お
よび表２より、本発明による被覆ガラスは大気中での熱
処理の際に光学特性変化が少なく、本発明の方法の有意
性が明らかである。From the comparison of the results of Example 1, Comparative Examples 1 and 2, and Table 2, the coated glass according to the present invention shows little change in the optical characteristics during the heat treatment in the atmosphere, and the significance of the method of the present invention is significant. it is obvious.
【００３４】[0034]
【表２】 [Table 2]
【００３５】[0035]
【発明の効果】通常用いられる平板状ガラス基板用被覆
装置により、被覆処理を行うことができ、このため被覆
制御が極めて容易で、これにより、高品質で、一様な膜
が被覆されたガラスを低コストで得ることができる。EFFECTS OF THE INVENTION A coating apparatus for a flat glass substrate which is usually used can perform a coating treatment, and therefore, coating control is extremely easy, which results in high quality and uniform film coated glass. Can be obtained at low cost.
【００３６】さらに雰囲気制御の不必要な大気雰囲気で
熱処理を行うことができるため、加工費が極めて安価で
あり、さらに、熱処理後の光学特性の変化がないため、
平板ガラスと曲げガラスかつ／または強化ガラスを組み
合わせて使用する際も、同一品種の被覆ガラスを、前者
には熱処理をしないもの、後者には曲げ加工かつ／また
は強化ガラスを施したものを使うことができる。したが
って、従来のように、熱処理による変化後の光学特性を
持つ平板ガラスを、曲げガラスや強化ガラスと別構成の
膜で用意する必要がない。Further, since the heat treatment can be performed in an air atmosphere that does not require atmosphere control, the processing cost is extremely low, and further, there is no change in the optical characteristics after the heat treatment,
When using flat glass and bent glass and / or tempered glass in combination, use the same type of coated glass, the former without heat treatment, and the latter with bent and / or tempered glass You can Therefore, unlike the conventional case, it is not necessary to prepare a flat glass having optical characteristics after being changed by heat treatment with a film having a different structure from the bent glass or the tempered glass.
【図１】本発明の曲げ被覆ガラスの膜構成の一例を示す
断面図FIG. 1 is a cross-sectional view showing an example of a film structure of bend-coated glass of the present invention.
【図２】本発明の曲げ被覆ガラスの膜構成の他の一例を
示す断面図FIG. 2 is a cross-sectional view showing another example of the film structure of the bend-coated glass of the present invention.
【図３】本発明の曲げ被覆ガラスの膜構成の他の一例を
示す断面図FIG. 3 is a cross-sectional view showing another example of the film structure of the bend-coated glass of the present invention.
１：熱線遮断膜または導電膜 ２：第１の保護膜 ３：第２の保護膜 ４：ガラス基板 ５：第１の下地膜 ６：第２の下地膜 1: Heat ray blocking film or conductive film 2: First protective film 3: Second protective film 4: Glass substrate 5: First base film 6: Second base film
Claims (10)
を形成し、次いで可視光領域において透明な、非酸化物
膜または完全には酸化されていない膜であって、かつ酸
化されても透明である第１の保護膜を形成して、少なく
とも２層からなる多層膜を有する被覆ガラスを製造し、
その後、かかる被覆ガラスに熱処理を施す熱処理被覆ガ
ラスの製造方法において、第１の保護膜は、ケイ素また
はホウ素の窒化物、あるいは、ケイ素、ホウ素、アルミ
ニウム、ジルコニウム、スズのうち少なくとも２種以上
の窒化物、を主成分とする膜であることを特徴とする熱
処理被覆ガラスの製造方法。1. A heat ray-shielding film or a conductive film is formed on a glass substrate, and is a non-oxide film or a film that is not completely oxidized and is transparent in the visible light region. Forming a transparent first protective film to produce a coated glass having a multilayer film composed of at least two layers,
Thereafter, heat treatment coating gas is subjected to a heat treatment such coated glass
In the method for manufacturing lath, the first protective film is made of silicon or
Is boron nitride, or silicon, boron, aluminum
At least two or more of titanium, zirconium, and tin
A process for producing heat-treated coated glass, characterized in that the film is mainly composed of the above-mentioned nitride .
明な第２の保護膜を形成して、少なくとも３層からなる
多層膜を有する被覆ガラスを製造し、その後、かかる被
覆ガラスに熱処理を施すことを特徴とする請求項１の熱
処理被覆ガラスの製造方法。2. A transparent second protective film made of a metal oxide is formed on a first protective film to produce a coated glass having a multi-layered film having at least three layers, and then the coated glass. The method for producing heat-treated coated glass according to claim 1, wherein the glass is heat-treated.
ム、ジルコニウム、タンタル、ハフニウムのうち少なく
とも一種（以下、金属Ｍとする）、金属Ｍの窒化物、金
属Ｍのホウ化物、金属Ｍの炭化物、あるいはこれらの混
合物を主成分とする膜であることを特徴とする請求項１
の熱処理被覆ガラスの製造方法。3. The heat ray blocking film comprises at least one of stainless steel, titanium, chromium, zirconium, tantalum, and hafnium (hereinafter referred to as metal M), a metal M nitride, a metal M boride, and a metal M carbide. Or a film whose main component is a mixture thereof.
Method for producing heat-treated coated glass according to.
あることを特徴とする請求項２の熱処理被覆ガラスの製
造方法。4. The method for producing heat-treated coated glass according to claim 2, wherein the second protective film is a film having a high oxygen barrier property.
ル、酸化ニオブ、酸化チタン、酸化ケイ素、酸化ジルコ
ニウム、酸化亜鉛のうち少なくとも一種を主成分とする
膜であることを特徴とする請求項２の熱処理被覆ガラス
の製造方法。5. The second protective film is a film containing at least one of tin oxide, tantalum oxide, niobium oxide, titanium oxide, silicon oxide, zirconium oxide, and zinc oxide as a main component. Item 2. A method for producing heat-treated coated glass according to item 2.
形成する前に、ガラス基板上に非酸化物膜または完全に
は酸化されていない膜であって、かつ酸化されても透明
である第１の下地膜を形成することを特徴とする請求項
１の熱処理被覆ガラスの製造方法。6. A non-oxide film or a film which is not completely oxidized on a glass substrate and is transparent even if it is oxidized before forming a heat ray shielding film or a conductive film on the glass substrate. The method for producing heat-treated coated glass according to claim 1, wherein a first underlayer film is formed.
に、ガラス基板上に金属酸化物からなり透明な第２の下
地膜を形成することを特徴とする請求項６の熱処理被覆
ガラスの製造方法。7. The heat treatment coating according to claim 6, wherein a transparent second undercoating film made of a metal oxide is formed on the glass substrate before forming the first undercoating film on the glass substrate. Glass manufacturing method.
加工のための加熱処理を施すことを特徴とする請求項１
の熱処理被覆ガラスの製造方法。8. The heat treatment is a heat treatment for bending and / or strengthening.
Method for producing heat-treated coated glass according to.
処理されたガラス基板上に、酸化されていない熱線遮断
膜または導電膜と、可視光領域において透明な、非酸化
物あるいは酸化物からなる第１の保護膜であって、ケイ
素またはホウ素の窒化物、あるいは、ケイ素、ホウ素、
アルミニウム、ジルコニウム、スズのうち少なくとも２
種以上の窒化物、を主成分とする第１の保護膜と、の少
なくとも２層が順次積層された多層膜を有することを特
徴とする被覆ガラス。9. A heat-ray shielding film or a conductive film which is not oxidized and a non-oxide or an oxide which is transparent in a visible light region on a glass substrate having a curved surface shape or a glass substrate which has been strengthened. 1 is a protective film ,
Elemental or boron nitride, or silicon, boron,
At least 2 of aluminum, zirconium and tin
A coated glass having a multilayer film in which at least two layers of a first protective film containing at least one kind of nitride as a main component are sequentially laminated.
透明な第２の保護膜が形成されていることを特徴とする
請求項９の被覆ガラス。10. The coated glass according to claim 9, wherein a transparent second protective film made of a metal oxide is formed on the first protective film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4309338A JP2518129B2 (en) | 1991-10-30 | 1992-10-23 | Heat-treated coated glass and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31172391 | 1991-10-30 | ||
| JP3-311723 | 1991-10-30 | ||
| JP4309338A JP2518129B2 (en) | 1991-10-30 | 1992-10-23 | Heat-treated coated glass and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05213632A JPH05213632A (en) | 1993-08-24 |
| JP2518129B2 true JP2518129B2 (en) | 1996-07-24 |
Family
ID=26565924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4309338A Expired - Fee Related JP2518129B2 (en) | 1991-10-30 | 1992-10-23 | Heat-treated coated glass and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2518129B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009084442A1 (en) | 2007-12-27 | 2009-07-09 | Asahi Glass Company, Limited | Heat reflecting glass and process for producing heat reflecting glass |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07333423A (en) * | 1994-06-08 | 1995-12-22 | Hitachi Maxell Ltd | Permselective membrane |
| FR2766174B1 (en) | 1997-07-21 | 1999-08-20 | Saint Gobain Vitrage | TRANSPARENT SUBSTRATE COATED WITH AT LEAST ONE THIN FILM |
| FR2799005B1 (en) * | 1999-09-23 | 2003-01-17 | Saint Gobain Vitrage | GLAZING PROVIDED WITH A STACK OF THIN FILMS ACTING ON THE SOLAR RADIATION |
| JP4682473B2 (en) * | 2000-07-21 | 2011-05-11 | 旭硝子株式会社 | Substrate with tin oxynitride film and method for producing the same |
| US6689475B1 (en) * | 2002-11-20 | 2004-02-10 | Guardian Industries Corp. | Heat treatable coated articles with boride layer of titanium and/or zirconium and methods of making same |
| FR2858816B1 (en) * | 2003-08-13 | 2006-11-17 | Saint Gobain | TRANSPARENT SUBSTRATE HAVING ANTIREFLECTION COATING |
| KR102096053B1 (en) * | 2013-07-25 | 2020-04-02 | 삼성디스플레이 주식회사 | Method for manufacturing organic luminescence emitting display device |
| CN113998900B (en) * | 2021-11-30 | 2023-06-20 | 太仓耀华玻璃有限公司 | Manufacturing method of magnetron sputtering solar control film toughened glass |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63265846A (en) * | 1987-04-22 | 1988-11-02 | Nippon Sheet Glass Co Ltd | Bent heat ray reflection glass and production thereof |
-
1992
- 1992-10-23 JP JP4309338A patent/JP2518129B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63265846A (en) * | 1987-04-22 | 1988-11-02 | Nippon Sheet Glass Co Ltd | Bent heat ray reflection glass and production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009084442A1 (en) | 2007-12-27 | 2009-07-09 | Asahi Glass Company, Limited | Heat reflecting glass and process for producing heat reflecting glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05213632A (en) | 1993-08-24 |
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