JPH0632635A - Heat shielding glass having low reflecting characteristic of electrical radiation - Google Patents
Heat shielding glass having low reflecting characteristic of electrical radiationInfo
- Publication number
- JPH0632635A JPH0632635A JP18961292A JP18961292A JPH0632635A JP H0632635 A JPH0632635 A JP H0632635A JP 18961292 A JP18961292 A JP 18961292A JP 18961292 A JP18961292 A JP 18961292A JP H0632635 A JPH0632635 A JP H0632635A
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- Prior art keywords
- thin film
- glass
- layer
- film
- thickness
- 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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- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、太陽輻射エネルギーを
遮蔽する主として建築物等の窓ガラスに用いる被膜付き
の熱線遮蔽ガラスであって、とりわけ冷暖房効果を向上
せしめるようにできるとともに比較的低い可視光透過率
を有するものであり、しかも電波の透過性が通常すなわ
ち未加工のフロート板ガラス並であって、ビル周囲の住
宅等においてＴＶ画像でのゴースト現象等の電波の障害
を低減でき、さらにとりわけガラス面側からの反射色調
がシルバ−系色調である、特に高層建築用窓ガラスとし
て有用な電波低反射特性を有する熱線遮蔽ガラスに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray-shielding glass with a film for shielding solar radiation energy, which is mainly used for window glass of buildings, etc. It has a light transmittance, and its radio wave transmission is similar to that of a normal or unprocessed float plate glass, which can reduce radio wave interference such as a ghost phenomenon in a TV image in a house around a building. The present invention relates to a heat ray-shielding glass having a reflection tone from the glass surface side of a silver color tone, and particularly having a low radio wave reflection characteristic useful as a window glass for high-rise buildings.
【０００２】[0002]
【従来技術】近年、ビル、住宅、自動車等の窓ガラスに
太陽光線を反射する熱線反射ガラスが使用されている。
熱線反射ガラスは、太陽輻射熱を反射し、室内への侵入
をカットして温度上昇を防ぐ省エネルギ−効果や、直射
日光を遮断して眩しさを防いだり、外部の視線からプラ
イバシ−を守る等の機能の他、ミラ−効果により建物等
に美観を付与するなどの効果も有し、各種窓ガラス材と
してことに注目を集めている。また、近年、テレビ電波
の受信にあたり、ビルの反射によるゴースト障害が問題
になり、ビルのコンクリート壁などにフェライト電波吸
収体を設けることが実用化されつつあり、一方、省エネ
や冷暖房効率の向上等から、例えば高層ビルなどの窓ガ
ラスにおいても金属、金属窒化物、金属酸化物などの膜
をコーティングしたり、このような膜を有するフイルム
を貼付けた断熱性能などの機能を付与したものが増加し
ており、ガラスより電波に対して反射率が高い膜をコー
ティングしたり、フイルムを貼付けると電波反射率が例
えばガラスより高い値となり、ことにシルバ−系色調を
呈する熱線反射ガラスとしては電波障害は避けられない
面があった。2. Description of the Related Art In recent years, heat ray-reflecting glass that reflects sun rays has been used for window glass of buildings, houses, automobiles and the like.
The heat ray reflective glass reflects the solar radiation heat, cuts the invasion into the room to prevent temperature rise, saves energy, cuts off direct sunlight to prevent glare, protects privacy from the outside line of sight, etc. In addition to its function, it also has the effect of giving a beautiful appearance to buildings and the like due to the mirror effect, and is attracting attention as a window glass material of various types. Also, in recent years, when receiving TV radio waves, ghost damage due to building reflection has become a problem, and it is becoming practical to install ferrite radio wave absorbers on concrete walls of buildings, while energy saving and improvement of cooling and heating efficiency, etc. Therefore, for example, even in windowpanes of high-rise buildings, the number of those that are coated with a film of metal, metal nitride, metal oxide, etc., or have a function such as heat insulation performance by sticking a film having such a film, has increased. Therefore, if a film with a higher reflectance for radio waves than glass is coated or a film is attached, the radio reflectance will be higher than that of glass, for example, as a heat ray reflective glass exhibiting a silver color tone, it will cause radio interference. There was an unavoidable aspect.
【０００３】例えば、特開昭60ー36355 号公報には可視
スペクトル帯域で５〜40％の透過率および熱線に対する
反射性能を有する板の製法について記載されており、ガ
ラス基板の上に第１層であるSn、Ti、Al等の酸化物層の
光学的厚さ20〜280nm 、第２層であるCrの窒化物層の膜
厚10〜40nmであること、あるいはさらに第３層として誘
電体層をそれぞれスパッタ法で成膜してなるものであ
り、ガラス基板からの反射色調がシルバー色系を得るた
めには、第１層である酸化物層の膜厚を調節することに
より得られる。即ちその光学的厚さが20nmであることが
開示されている。For example, Japanese Patent Application Laid-Open No. 60-36355 discloses a method for producing a plate having a transmittance of 5 to 40% in the visible spectrum band and a reflection property for heat rays. The first layer is formed on a glass substrate. The optical thickness of the oxide layer of Sn, Ti, Al or the like is 20 to 280 nm, the thickness of the second layer of Cr nitride is 10 to 40 nm, or the third layer is a dielectric layer. Are formed by a sputtering method, and in order to obtain a silver-based reflection color tone from the glass substrate, it is obtained by adjusting the film thickness of the oxide layer which is the first layer. That is, it is disclosed that the optical thickness is 20 nm.
【０００４】[0004]
【発明が解決しようとする問題点】前述したような、例
えば特開昭60-36355号公報では、シルバ−色を得るため
の２層構成については、最外層であるCrN 膜の耐摩耗性
が劣るため３層構成にする必要がある。また第１層の膜
厚が比較的厚いため、生産性が悪くまた、膜面の反射率
も高く室内の居住性に優れているとは言いがたい。ま
た、表面抵抗率が比較的低く、その電波低反射性能は充
分とは言いがたく、近年、ことに今日ではさらなる電波
低反射性能に優れているものが望まれつつある。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in Japanese Patent Laid-Open No. 60-36355, in the two-layer structure for obtaining a silver color, the wear resistance of the CrN film as the outermost layer is high. Since it is inferior, it is necessary to use a three-layer structure. Further, since the thickness of the first layer is relatively large, it is difficult to say that the productivity is poor, the reflectance of the film surface is high, and the habitability in the room is excellent. Further, the surface resistivity is relatively low, and it cannot be said that the low radio wave reflection performance is sufficient. In recent years, in particular, there is a demand for a further excellent radio wave low reflection performance.
【０００５】[0005]
【問題点を解決するための手段】本発明は、このような
点に鑑みてなされたものであり、特定膜厚で表面抵抗率
が少なくとも１ｋΩ／口以上である特定した窒化物薄膜
を被膜して、その上に特定膜厚の特定した窒素酸化物薄
膜または酸素窒化物薄膜を被膜して、その上に特定膜厚
の特定した酸化物薄膜または酸素窒化物薄膜を積層被膜
することで、光の干渉作用を巧みに利用することによっ
てシルバ−系色調を発現させたものであって、またさら
に、シルバ−系色調を発現させることが可能な特定膜厚
のCrの窒化物薄膜を第１層として、第１層と第３層との
密着力を向上せしめるCrの窒素酸化物薄膜または酸素窒
化物薄膜を第２層として用いる積層膜構成とすること
で、可視光透過率等を特定範囲、例えば10〜60％で任意
に調整せしめることを可能とし、さらにはそれらの膜を
巧みに組み合わせることにより、膜面の反射率を低くし
かつ膜面の色調をニュ−トラル化させ、ガラス面の反射
色調がシルバ−系色調であって、しかも電波反射率をTV
電波帯、ことに周波数150MHz付近において約５％以下と
フロ−トガラス並に低くすることができ、断熱性能を保
持しつつ、ことに特定酸化物をオ−バ−コ−トしている
ので耐摩耗性や耐久性をより頑固に向上せしめるものと
なり、かつ色調を微妙にコントロ−ルできることを可能
とした。単板で充分使用することができる電波低反射特
性を有する熱線遮蔽ガラスを提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and it coats a specified nitride thin film having a specific film thickness and a surface resistivity of at least 1 kΩ / port or more. Then, by coating a specified nitrogen oxide thin film or oxynitride thin film with a specific thickness on it, and by laminating a specific oxide thin film or oxygen nitride thin film with a specific thickness on it, The first layer of a Cr nitride thin film having a specific thickness capable of developing a silver-based color tone by skillfully utilizing the interference action of As a laminated film structure using a nitrogen oxide thin film of Cr or an oxynitride thin film of Cr for improving the adhesion between the first layer and the third layer as the second layer, the visible light transmittance and the like are within a specific range, For example, 10-60% can be adjusted arbitrarily. Function, and by skillfully combining these films, the reflectance of the film surface is lowered and the color tone of the film surface is neutralized, and the reflection color tone of the glass surface is a silver color tone, and TV reflectivity
It can be reduced to about 5% or less in the radio wave band, especially around 150MHz, which is as low as that of float glass. In particular, the specific oxide is overcoated while maintaining the heat insulation performance. This makes it possible to stubbornly improve the wear resistance and durability, and to enable delicate control of the color tone. (EN) Provided is a heat ray shielding glass having a low reflection property of a radio wave which can be sufficiently used as a single plate.
【０００６】すなわち、本発明は、透明なガラス基板の
−方の表面上に、表面抵抗率が１ｋΩ／口以上でかつ膜
厚が５〜50nmのCrの窒化物薄膜を第１層として被膜した
後、該第１層の上に、膜厚が１〜10nmのCrの窒素酸化物
薄膜または酸素窒化物薄膜を第２層として被膜した後、
該第２層の上に、膜厚が５〜30nmのTi、TiSi、Ta、Sn、
Al、Siの酸化物薄膜または酸素窒化物薄膜のうち、少な
くとも１種を選択し積層被膜したことを特徴とする電波
低反射特性を有する熱線遮蔽ガラス。That is, in the present invention, a Cr nitride thin film having a surface resistivity of 1 kΩ / mouth or more and a film thickness of 5 to 50 nm is coated as the first layer on the negative surface of a transparent glass substrate. After that, a nitrogen oxide thin film or an oxynitride thin film of Cr having a film thickness of 1 to 10 nm is coated on the first layer as a second layer,
On the second layer, Ti, TiSi, Ta, Sn having a film thickness of 5 to 30 nm,
A heat ray-shielding glass having a low radio wave reflection characteristic, which is obtained by selecting at least one of an oxide thin film of Al and Si or an oxynitride thin film and performing a laminated coating.
【０００７】ならびに、前記電波低反射特性を有する熱
線遮蔽ガラスにおいて、前記被膜した熱線遮蔽性能膜の
表面抵抗率が１ｋΩ／口以上で、かつ該ガラス面側から
の反射色調がシルバ−系色調を呈することを特徴とする
上述した電波低反射特性を有する熱線遮蔽ガラスをそれ
ぞれ提供するものである。Further, in the heat ray shielding glass having the low radio wave reflection characteristic, the surface resistivity of the coated heat ray shielding performance film is 1 kΩ / mouth or more, and the reflection color tone from the glass surface side is a silver type tone. The present invention provides the heat ray-shielding glass having the above-mentioned low radio wave reflection characteristic, which is characterized by being exhibited.
【０００８】ここで、前記表面抵抗率が1ｋΩ／口以上
でかつ膜厚が５〜50nmのCrの窒化物薄膜である第１層と
して被膜したのは、表面抵抗率が１ｋΩ／口以上、特に
好ましくは５ｋΩ／口以上で、該ガラス面側からの反射
色調がシルバ−系色調を発現させるためであり、膜面の
反射率を低減し、膜面の色調をニュ−トラル化するため
であり、また可視光線透過率を例えば10〜60％の範囲内
で任意に調整せしめることを可能とするためであり、好
ましくは膜厚は10〜40nm程度である。Here, the first layer, which is a Cr nitride thin film having a surface resistivity of 1 kΩ / port or more and a film thickness of 5 to 50 nm, has a surface resistivity of 1 kΩ / port or more, particularly It is preferably 5 kΩ / mouth or more, for the reflection color tone from the glass surface side to develop a silver-based color tone, for reducing the reflectance of the film surface and for neutralizing the color tone of the film surface. Also, the visible light transmittance can be arbitrarily adjusted within the range of, for example, 10 to 60%, and the film thickness is preferably about 10 to 40 nm.
【０００９】また、前記第１層の上に、第２層として膜
厚が１〜10nmのCrの窒素酸化物薄膜または酸素窒化物薄
膜としたのは、第１層のCrの窒化物薄膜と第３層の特定
した酸化物薄膜または酸素窒化物薄膜とのなじみを良く
する効果があって、積層薄膜の密着性を高めるためであ
り、好ましくは膜厚は３〜７nm程度である。On the first layer, a Cr nitrogen oxide thin film or an oxynitride thin film having a film thickness of 1 to 10 nm is used as the second layer because the first layer is a Cr nitride thin film. This is because it has the effect of improving compatibility with the specified oxide thin film or oxynitride thin film of the third layer and enhances the adhesion of the laminated thin film, and preferably the film thickness is about 3 to 7 nm.
【００１０】さらに、前記第２層の上に、第３層として
膜厚が５〜30nmのTi，TiSi，Ta、Sn、Al、Siの酸化物薄
膜または酸素窒化物薄膜のうち少なくとも１種を選択し
積層被膜したのは、光の干渉作用を巧みに組み合わせる
ことで、シルバ−色系色調をより強く効果的に発現させ
るためであり、さらに耐久性等が格別に向上し、かつガ
ラス面からの反射色調を微妙にコントロ−ルできること
が可能とでき得るものとなるためであり、好ましくは10
〜25nm程度である。Further, on the second layer, at least one of an oxide thin film or an oxygen nitride thin film of Ti, TiSi, Ta, Sn, Al, Si having a film thickness of 5 to 30 nm is formed as a third layer. The reason why the film was selected and laminated was to skillfully combine the interference effect of light so as to more strongly and effectively develop the silver color tone, and further, the durability and the like were further improved, and from the glass surface. This is because it is possible and possible to subtly control the reflection color tone of, and preferably 10
It is about 25 nm.
【００１１】さらにまた、前記被膜した熱線遮蔽性能膜
の表面抵抗率が１ｋΩ／口以上、特に好ましくは５ｋΩ
／口以上で、かつ該ガラス面側からの反射色調がシルバ
−系色調を呈するものとしたのは、充分な電波反射性能
を有し、ＴＶ映像でのゴ−スト現象等の電波障害をより
確実に発現しないようにするためであり、またガラス面
側からの反射色調がシルバ−系色調を呈することにより
ビル等が意匠性に優れ環境に優しいものとなるためであ
る。Furthermore, the surface resistivity of the heat-shielding film coated above is 1 kΩ / port or more, particularly preferably 5 kΩ.
/ Mouth or more, and the color tone reflected from the glass surface side exhibits a silver color tone, because it has sufficient radio wave reflection performance and prevents radio wave interference such as the ghost phenomenon in TV images. This is because it surely does not occur, and because the reflection color tone from the glass surface side exhibits a silver color tone, the building and the like have excellent design and are environmentally friendly.
【００１２】つぎに、ガラス基板としては、無機質はも
ちろん有機質でも透明ガラスであればよく、無色あるい
は着色等でも電波透過性を損なわない基板であればより
好ましいものである。また単板で使用できることはもと
より、複層ガラスあるいは合せガラス、強化ガラスとう
各種板ガラス製品として使用できることは言うまでもな
い。Next, as the glass substrate, an inorganic material as well as an organic material may be used as long as it is transparent glass, and it is more preferable if it is a substrate which is colorless or colored and does not impair radio wave transmission. It goes without saying that it can be used not only as a single plate but also as a laminated glass, laminated glass, or various types of plate glass products such as tempered glass.
【００１３】[0013]
【作用】前述したとおり、本発明の電波低反射特性を有
する熱線遮蔽ガラスは、表面抵抗率が１ｋΩ／口以上で
かつ特定膜厚のCrの窒化物薄膜を第１層として被膜し、
該第１層の上に、特定膜厚のCrの窒素酸化物薄膜または
酸素窒化物薄膜を第２層として被膜積層し、該第２層の
上に、特定膜厚のTi、TiSi、Ta、Sn、Al、Siの酸化物薄
膜または酸素窒化物薄膜のうち少なくとも１種を被膜積
層し、第１層から第３層を巧みに組み合わせるものとし
たものであり、その表面抵抗率が１ｋΩ／口以上と高
く、可視光線透過率を10〜60％程度の範囲内で任意にコ
ントロ−ルすることでき膜面からの反射を低くかつその
反射色調のニュ−トラル化を可能にせしめ、とりわけガ
ラス面側からの反射色調がシルバ−系色調を呈すること
となり、各薄膜の密着性を高め、積層した多層膜全体の
耐摩耗性ならびに耐食性が向上し、耐久性に優れ、単板
として充分採用できるものとなることはもちろん、ＴＶ
帯での電波低反射性能が格段に優れて通常のフロ−トガ
ラス並であることから、高層建築物等に使用されても、
その周囲において従来発現していたＴＶ画像におけるゴ
−スト現象等の電波障害を低減することができ、さらに
適度の干渉効果でもって熱線反射を持たせて断熱機能を
充分有するものとなって冷暖房の効果を高め、透視性を
適宣抑えてより色調に富むものとすることができる等、
建築物内外の居住性ならびに景観性等環境をより優れた
ものとすることができる、有用な電波低反射特性を有す
る熱線遮蔽ガラスを提供するものである。As described above, the heat ray shielding glass of the present invention having a radio wave low reflection characteristic is coated with a nitride thin film of Cr having a surface resistivity of 1 kΩ / mouth or more and a specific film thickness as the first layer,
A nitrogen oxide thin film or an oxygen nitride thin film of Cr having a specific film thickness is laminated on the first layer as a second layer, and Ti, TiSi, Ta having a specific film thickness is formed on the second layer. At least one of Sn, Al, and Si oxide thin films or oxygen nitride thin films is laminated to form a film, and the first to third layers are skillfully combined, and the surface resistivity is 1 kΩ / port. Higher than the above, the visible light transmittance can be arbitrarily controlled within the range of about 10 to 60%, the reflection from the film surface is low, and the reflection color tone can be made neutral, and particularly the glass surface The color tone reflected from the side will show a silver color tone, the adhesion of each thin film will be improved, the abrasion resistance and corrosion resistance of the entire laminated multilayer film will be improved, the durability will be excellent, and it can be sufficiently adopted as a single plate. Of course, TV
Since the radio wave low reflection performance in the band is remarkably excellent and is similar to ordinary float glass, even when used for high-rise buildings,
It is possible to reduce the radio interference such as the ghost phenomenon in the TV image that has been conventionally generated in the surroundings, and further to provide the heat ray reflection with an appropriate interference effect so as to have a sufficient heat insulating function, thereby providing a cooling and heating function. The effect can be enhanced, the transparency can be properly suppressed, and the color tone can be made richer.
(EN) Provided is a heat ray shielding glass having useful low-reflection characteristics of radio waves, which can improve the environment such as habitability in and outside a building and landscape.
【００１４】なお、電波低反射のため、衛星放送帯の電
波も透過できることは言うまでもなく、室内での衛星放
送受信等も可能である。そのため、自動車用のル−フ熱
線遮蔽ガラス等として有効である。It is needless to say that radio waves in the satellite broadcasting band can be transmitted due to low reflection of radio waves, and it is possible to receive satellite broadcasting indoors. Therefore, it is effective as a roof heat ray shielding glass for automobiles.
【００１５】[0015]
【実施例】以下、実施例により本発明を具体的に説明す
る。ただし本発明は係る実施例に限定されるものではな
い。EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.
【００１６】実施例１ 大きさ約600mmx600mm 、厚さ約6mm のクリアーガラス
(FL6)を中性洗剤、水すすぎ、イソプロピルアルコール
で順次洗浄し、乾燥した後、DCマグネトロンスパッタリ
ング装置の真空槽内にセットしてあるCr，Tiのターゲッ
トに対向して上方を往復できるようセットし、つぎに前
記槽内を真空ポンプで5x10-6Torr以下までに排気した
後、該真空槽内にN2ガス（但し、ArとN2の流量比は1:1
から0:1 の範囲にあればよい。）を導入して真空度を2x
10-3Torrに保持し、前記Crのターゲットに約1.2kw の電
力を印加し、N2ガスによるDCマグネトロン反応スパッタ
の中を、前記Crターゲット上方においてスピ−ド約146m
m/min で前記板ガラスを搬送することによって、約30nm
厚さのCrNx薄膜を第１層として成膜した。成膜が完了し
た後、Crターゲットへの印加を停止する。 Example 1 Clear glass having a size of about 600 mm x 600 mm and a thickness of about 6 mm
(FL6) is washed with a neutral detergent, water rinse, isopropyl alcohol in order, dried, and then set so that it can reciprocate upwards facing the Cr and Ti targets set in the vacuum chamber of the DC magnetron sputtering system. Then, after the inside of the chamber was evacuated to 5 × 10 −6 Torr or less by a vacuum pump, N 2 gas (however, the flow ratio of Ar and N 2 was 1: 1 was evacuated into the vacuum chamber.
It should be in the range 0 to 0: 1. ) Is introduced to increase the degree of vacuum to 2x
Hold at 10 -3 Torr, apply a power of about 1.2 kw to the Cr target, and in the DC magnetron reaction sputter with N 2 gas, speed about 146 m above the Cr target.
By conveying the plate glass at m / min, about 30 nm
A CrNx thin film having a thickness was formed as the first layer. After the film formation is completed, the application to the Cr target is stopped.
【００１７】次に、板ガラスを前記真空槽内に置いたま
ま、該真空槽内を5x10-6Torr以下までに排気した後、該
真空槽内に、N2、O2の混合ガス（N2:O2=99:1）を導入し
て真空度を2x10-3Torrに保持し、Crターゲットに約1.2k
w の電力を印加し、前記Crターゲット上方においてスピ
−ド約1320mm/minで前記板ガラスを搬送することによっ
て、前記板ガラスのCrNx薄膜表面上に約３nm厚さのCrNx
Oy薄膜を第２層として積層成膜した。成膜が完了した
後、Crターゲットへの印加を停止する。Next, while the plate glass was left in the vacuum chamber, the inside of the vacuum chamber was evacuated to 5 × 10 −6 Torr or less, and then the mixed gas of N 2 and O 2 (N 2 : O 2 = 99: 1) and maintain the vacuum at 2x10 -3 Torr, about 1.2k on the Cr target.
By applying the electric power of w and conveying the plate glass at a speed of about 1320 mm / min above the Cr target, the CrNx thin film surface of the plate glass has a thickness of about 3 nm.
The Oy thin film was laminated as a second layer. After the film formation is completed, the application to the Cr target is stopped.
【００１８】さらに板ガラスを前記真空槽内に置いたま
ま、該真空槽内を5x10-6Torr以下までに排気した後、該
真空槽内にO2ガス（但し、ArとO2の流量比は1:1 から0:
1 の範囲にあればよい。）を導入して真空度を2x10-3To
rrに保持し、Tiターゲットに約1.9kw の電力を印加し、
前記Tiターゲット上方においてスピ−ド約56mm/minで前
記板ガラスを搬送することによって、前記板ガラスのCr
NxOy薄膜表面上に約20nm厚さのTiOx薄膜を第３層として
積層成膜した。成膜が完了した後、Tiターゲットへの印
加を停止する。すなわち、表１の実施例１に示す薄膜構
成である。Further, while the plate glass was placed in the vacuum chamber, the inside of the vacuum chamber was evacuated to 5 × 10 −6 Torr or less, and then O 2 gas (however, the flow ratio of Ar and O 2 was 1: 1 to 0:
It should be in the range of 1. ) Is introduced to adjust the degree of vacuum to 2x10 -3 To
Hold it at rr and apply a power of about 1.9kw to the Ti target,
By conveying the plate glass at a speed of about 56 mm / min above the Ti target, the Cr of the plate glass is
A TiOx thin film having a thickness of about 20 nm was laminated and formed as a third layer on the surface of the NxOy thin film. After the film formation is completed, the application to the Ti target is stopped. That is, it is the thin film structure shown in Example 1 of Table 1.
【００１９】得られた３層膜を有する電波低反射特性を
有する熱線遮蔽ガラスについて、可視光透過率(380nm〜
780nm)、可視光反射率(380nm〜780nm)ならびに日射透過
率(340nm〜1800nm) についてはU-4000型自記分光光度計
（日立製作所製）とJISZ8722、JISR3106によってそれぞ
れの光学的特性を求めた。さらにテ−バ−試験によるヘ
−ズ（曇り具合）値の変化量（△Ｈ％）については、テ
−バ−試験機（MODEL503 、TABER 社製）に膜面を上に
した10cm角試験片をセットし、膜面に荷重500gのかかっ
た摩耗輪(CS-10F)が２箇所で当たるようになっているも
ので、300 回回転した後、ヘーズメーター（日本電色工
業製、NDH-20D ）によって測定し、試験前の測定値と対
比し、その変化量（△Ｈ％）をもって表した数値であ
る。With respect to the heat ray shielding glass having the radio wave low reflection property having the obtained three-layer film, the visible light transmittance (380 nm-
780 nm), visible light reflectance (380 nm to 780 nm), and solar radiation transmittance (340 nm to 1800 nm), optical characteristics were determined by a U-4000 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and JISZ8722, JISR3106. Regarding the amount of change in haze value (△ H%) by the taper test, a 10 cm square test piece with the membrane surface facing up on a taper tester (MODEL503, TABER) The wear wheel (CS-10F) with a load of 500g applied to the film surface hits it in two places. After rotating 300 times, the haze meter (NDH-20D manufactured by Nippon Denshoku Industries Co., Ltd.) ), Compared with the measured value before the test, and represented by the amount of change (ΔH%).
【００２０】次に、耐薬品性のうち耐酸試験について
は、常温で１規定のHCl 溶液中に前記試験片を約６時間
浸漬した後、膜の劣化状態を見て判断したものであり、
耐アルカリ試験については、常温で１規定のNaOH溶液中
に試験片を約６時間浸漬した後、膜の劣化状態を見てJI
SR3221により判断したものであり、それぞれ○印はほと
んど劣化が見られなかったもの、×印は劣化が明らかに
目立ったものである。Next, regarding the acid resistance test of the chemical resistance, it was judged by observing the deterioration state of the film after immersing the test piece in a 1N HCl solution at room temperature for about 6 hours,
Regarding the alkali resistance test, after immersing the test piece in 1N NaOH solution at room temperature for about 6 hours, check the deterioration state of the film and see
It was judged according to SR3221. In each case, the ○ marks show almost no deterioration, and the X marks clearly show the deterioration.
【００２１】さらに表面抵抗率については、105 Ω／口
以下のものは四探針抵抗測定装置RT-8（NAPSON社製）に
よって、105 Ω／口〜105 ＭΩ／口のものは三菱油化製
表面高抵抗計（HIRESTA HT-210）によって測定したもの
である。Further, regarding the surface resistivity, those having a resistance of 10 5 Ω / port or less are measured with a four-point probe resistance measuring device RT-8 (manufactured by NAPSON), and those having a surface resistivity of 10 5 Ω / port to 10 5 MΩ / port are Mitsubishi. It is measured by a surface high resistance meter (HIRESTA HT-210) made by Yuka.
【００２２】またさらに、電波反射率については、大型
導波管法によって測定することで得た。表２の実施例１
に示すことより明らかなように、従来の熱線反射ガラス
とほぼ同等の断熱性能を示し、優れた居住性をもって、
耐摩耗性、耐食性、耐候性、耐久性を有し、電波を充分
透過するものであって、電波低反射特性を有する熱線遮
蔽ガラスとして高層建築物等の窓ガラスに有用なものと
なり、ことにガラス面側からの反射色調がシルバ−系色
調で所期のめざすものを得た。Further, the radio wave reflectivity was obtained by measuring with the large waveguide method. Example 1 in Table 2
As is clear from the above, the heat insulation performance is almost the same as that of the conventional heat ray reflective glass, and it has excellent habitability.
It has abrasion resistance, corrosion resistance, weather resistance, durability, and is capable of sufficiently transmitting radio waves, and is useful as a window glass for high-rise buildings, etc. as a heat-shielding glass with low radio wave reflection characteristics. A desired color tone with a silver-based color tone reflected from the glass surface side was obtained.
【００２３】実施例２ 実施例１と同様の方法で、処理したガラスを使用し、DC
マグネトロンスパッタリング装置内の真空槽内にCr、Ta
のターゲットをセットし、前記槽内を真空ポンプで5x10
-6Torr以下までに排気た後、該真空槽内にN2ガス（但
し、ArとN2の流量比は1:1 から0:1 の範囲にあればよ
い。）を導入して実施例１と同真空度、同N2ガス、同印
加電力にて、DCマグネトロン反応スパッタの中を、前記
Crのターゲット上方においてスピ−ド約218mm/min で前
記板ガラスを搬送することによって、約20nm厚さのCrNx
薄膜を第１層として成膜した。 Example 2 In the same manner as in Example 1, the treated glass was used and DC
Cr and Ta are placed in the vacuum chamber of the magnetron sputtering system.
Set the target of, and the inside of the tank with a vacuum pump 5x10
After evacuation to -6 Torr or less, N 2 gas (provided that the flow rate ratio of Ar and N 2 is in the range of 1: 1 to 0: 1) is introduced into the vacuum chamber. At the same vacuum degree, the same N 2 gas, and the same applied power as in 1, the inside of the DC magnetron reactive sputtering was
By conveying the plate glass at a speed of about 218 mm / min above the Cr target, CrNx with a thickness of about 20 nm was formed.
A thin film was formed as the first layer.
【００２４】次に前記板ガラスを前記真空槽内に置いた
まま、該真空槽内を5x10-6Torr以下までに排気した後、
該真空槽内に、O2、N2の混合ガス（O2:N2=6:4 ）を導入
して真空度を2x10-3Torrに保持し、Crターゲットに約1.
8kw の電力を印加し、前記Crターゲット上方においてス
ピ−ド約960mm/min で前記板ガラスを搬送することによ
って、前記板ガラスのCrNx薄膜表面上に約５nm厚さのCr
OxNy薄膜を第２層として積層成膜した。成膜が完了した
後、Crターゲットへの印加を停止する。Next, while the plate glass was left in the vacuum chamber, the inside of the vacuum chamber was evacuated to 5 × 10 −6 Torr or less,
A mixed gas of O 2 and N 2 (O 2 : N 2 = 6: 4) was introduced into the vacuum chamber to maintain the degree of vacuum at 2 × 10 −3 Torr, and the Cr target had a pressure of about 1.
By applying an electric power of 8 kw and transporting the plate glass at a speed of about 960 mm / min above the Cr target, a CrNx thin film surface of the plate glass having a thickness of about 5 nm was formed.
The OxNy thin film was laminated as a second layer. After the film formation is completed, the application to the Cr target is stopped.
【００２５】さらに前記板ガラスを前記真空槽内に置い
たまま、該真空槽内を5x10-6Torr以下までに排気した
後、該真空槽内にO2ガス（但し、ArとO2の流量比は1:1
から0:1 の範囲にあればよい。）を導入して真空度を2x
10-3Torrに保持し、Taターゲットに約1.3kw の電力を印
加し、前記Taターゲット上方においてスピ−ド約28mm/m
inで前記板ガラスを搬送することによって、前記板ガラ
スのCrOxNy薄膜表面上に約30nm厚さのTaOx薄膜を第３層
として積層成膜した。すなわち表１の実施例２に示す薄
膜構成である。Further, while the plate glass was placed in the vacuum chamber, the inside of the vacuum chamber was evacuated to 5 × 10 −6 Torr or less, and then O 2 gas (however, the flow rate ratio of Ar and O 2 was changed into the vacuum chamber). Is 1: 1
It should be in the range 0 to 0: 1. ) Is introduced to increase the degree of vacuum to 2x
The Ta target was kept at 10 -3 Torr and a power of about 1.3 kw was applied to the Ta target.
The TaOx thin film having a thickness of about 30 nm was laminated and formed as a third layer on the surface of the CrOxNy thin film of the plate glass by transporting the plate glass in in. That is, it has the thin film structure shown in Example 2 of Table 1.
【００２６】表２の実施例２に示すように、得られた３
層膜を有する電波低反射特性を有する熱線遮蔽ガラスは
その膜構成において実施例１で示した測定法等によって
同様の評価手段で行ない、その結果は実施例１と同様に
優れた所期の光学特性等各物性を示すものであった。As shown in Example 2 of Table 2, obtained 3
The heat ray-shielding glass having a layered film and having a low radio wave reflection characteristic is subjected to the same evaluation means in the film structure by the measuring method and the like shown in Example 1, and the result is similar to that of Example 1, and the desired optical properties are obtained. It showed various physical properties such as characteristics.
【００２７】実施例３〜５ 前記実施例と同様の方法で、表１に示す３層膜の各膜厚
を得て、その膜構成において実施例１で示した測定法等
によって同様の評価手段で行ない、その結果を表２に示
す。 Examples 3 to 5 Each film thickness of the three-layer film shown in Table 1 was obtained in the same manner as in the above examples, and the same evaluation means was used in the film structure by the measuring method shown in Example 1 and the like. The results are shown in Table 2.
【００２８】得られた３層膜を有する電波低反射特性を
有する熱線遮蔽ガラスは、実施例１と同様に優れた所期
の光学特性等各物性を示すものであった。なお、TiSixO
y 薄膜については同装置でTiSiターゲットを用い、同真
空度、O2ガス、印加電1.8kw において、例えば板ガラス
搬送スピ−ド約276mm/min で膜厚約５nmのTiSixOy 薄膜
を得た。The heat ray-shielding glass having a low radio wave reflection characteristic having the three-layer film thus obtained exhibited excellent physical properties such as desired optical characteristics as in Example 1. In addition, TiSixO
With respect to the y thin film, a TiSi target was used in the same apparatus to obtain a TiSixOy thin film with a film thickness of about 5 nm at the same vacuum degree, O 2 gas, and applied voltage of 1.8 kw, for example, at a plate glass conveying speed of about 276 mm / min.
【００２９】さらになお、上記各実施例は、例えば刺激
純度が５％程度以下、ガラス面反射率が20％程度以上、
あるいは主波長が460 〜490nm 程度とより好ましいもの
であった。Furthermore, in each of the above examples, for example, the stimulus purity is about 5% or less, the glass surface reflectance is about 20% or more,
Alternatively, it was more preferable that the dominant wavelength was about 460 to 490 nm.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】比較例１〜３ 実施例１と同様に処理したガラスを用い、同装置にTi、
Cr、Tiターゲットをセットし、真空槽内を約5x10-6Torr
以下に排気した後、該真空槽内にO2ガスを導入し、真空
度を約2x10-3Torrに保持し、前記Tiのターゲットに約1.
9kw の電力を印加し、板ガラス搬送スピード約112mm/mi
n で膜厚約10nmのTiOx薄膜を第１層として成膜した。次
いでCrのターゲットを用い、同真空度、ArとN2の混合ガ
ス（Ar:N 2=7:3 ）、印加電力約1.2kw において、ガラス
搬送スピード約506mm/min で膜厚約15nmのCrNx薄膜を得
た。さらに第１層と同様して板ガラス搬送スピード約3
7.3mm/minで膜厚約30nmのTiOx薄膜を第３層として成膜
積層した。[0032]Comparative Examples 1-3 Using the glass treated in the same manner as in Example 1, Ti,
Cr and Ti targets are set and the inside of the vacuum chamber is approximately 5x10-6Torr
After evacuating to below, O in the vacuum chamber2Introduce gas, vacuum
About 2x10 degrees-3Hold on to Torr and target about 1.
Applying 9kw power, plate glass transfer speed is about 112mm / mi
A TiOx thin film with a film thickness of about 10 nm was formed as the first layer. Next
And use a Cr target with the same vacuum, Ar and N2A mixed moth
Space (Ar: N 2= 7: 3), glass with applied power of about 1.2kw
Obtain CrNx thin film with a film thickness of about 15 nm at a transfer speed of about 506 mm / min.
It was Further, as with the first layer, the plate glass transport speed is about 3
A TiOx thin film with a thickness of about 30 nm is formed as a third layer at 7.3 mm / min.
Laminated.
【００３３】また、SnOx薄膜については、同装置でSnタ
ーゲットを用い、同真空度、O2ガス、印加電力約0.4kw
において、例えば板ガラス搬送スピード約330mm/min で
膜厚約10nmのSnOx薄膜を得た。Regarding the SnOx thin film, a Sn target was used in the same apparatus, the same vacuum degree, O 2 gas, and applied power of about 0.4 kw.
In, for example, a SnOx thin film having a film thickness of about 10 nm was obtained at a plate glass conveying speed of about 330 mm / min.
【００３４】このような方法によって、表３に示すよう
な１〜３層の積層膜を得、その膜構成において、実施例
１と同様の測定法、同様の評価手段で行い、その結果を
表４にそれぞれ示す。By such a method, a laminated film of 1 to 3 layers as shown in Table 3 was obtained, and in the film constitution, the same measurement method and the same evaluation means as in Example 1 were used, and the results are shown in the table. 4 respectively.
【００３５】それぞれ、各実施例に比して、従来の熱線
反射ガラスであるこれらにおいては、例えば表面抵抗率
が低く、150 Ω／口以下であって、電波反射率も20％以
上となり、従来のフロートガラスの電波反射率より悪
く、建築物の周辺に電波障害を発現し易いものまたは発
現するものである。In each of these conventional heat ray-reflecting glasses, for example, the surface resistivity is low, 150 Ω / port or less, and the radio wave reflectance is 20% or more. It is worse than the radio wave reflectivity of the float glass, and is likely to or will develop radio wave interference around the building.
【００３６】[0036]
【表３】 [Table 3]
【００３７】[0037]
【表４】 [Table 4]
【００３８】[0038]
【発明の効果】以上前述したように、本発明はスパッタ
法で、特定膜厚の高表面抵抗率を有するCrの窒化物薄膜
を第１層とし、該第１層の上に特定膜厚のCrの窒素酸化
物薄膜または酸素窒化物薄膜を第２層とし、該第２層の
上に特定膜厚のTi、TiSi、Ta、Sn、Al、Siの酸化物薄膜
または酸素窒化物薄膜のうち１種を被膜積層し、特異に
適宜巧みに組み合わせることで構成せしめたことによ
り、断熱ガラスであって、耐摩耗性、耐食性ならびに耐
久性に優れ、適宜膜面の反射色調をニュートラル化する
ことができ、電波透過がよく、通常のフロートガラス並
の電波低反射率であり、高層建築物周辺に対し電波障害
を発現するようなこともなく、ガラス面側からの反射色
調がシルバ−系色調を呈する居住性のよい、単板ガラス
はもちろん合せガラスあるいは複層ガラス等として使用
し得る、有用な電波低反射特性を有する熱線遮蔽ガラス
を効率よく提供するものである。As described above, according to the present invention, a sputtering method is used to form a Cr nitride thin film having a specific film thickness and a high surface resistivity as a first layer, and to form a specific film thickness on the first layer. A nitrogen oxide thin film or an oxygen nitride thin film of Cr is used as a second layer, and an oxide thin film or an oxygen nitride thin film of Ti, TiSi, Ta, Sn, Al, Si having a specific film thickness is formed on the second layer. It is a heat-insulating glass with excellent abrasion resistance, corrosion resistance and durability, and the reflection color tone of the film surface can be neutralized as appropriate by laminating one kind by coating and combining it appropriately and skillfully. It has good radio wave transmission, low radio wave reflectance similar to that of normal float glass, and does not cause radio wave interference in the vicinity of high-rise buildings, and the color tone reflected from the glass surface is a silver color tone. There is laminated glass as well as veneered glass that presents good comfort. Can be used as double glazing or the like, is intended to provide efficient solar control glass having a useful wave low reflection characteristics.
Claims (2)
面抵抗率が１ｋΩ／口以上でかつ膜厚が５〜50nmのCrの
窒化物薄膜を第１層として被膜した後、該第１層の上に
膜厚が１〜10nmのCrの窒素酸化物薄膜または酸素窒化物
薄膜を第２層として被膜した後、該第２層の上に膜厚が
５〜30nmのTi、Ta、TiSi、Sn、Al、Siの酸化物薄膜また
は酸素窒化物薄膜のうち、少なくとも一種選択し積層被
膜したことを特徴とする電波低反射特性を有する熱線遮
蔽ガラス。1. A transparent thin glass substrate is coated on one surface thereof with a nitride thin film of Cr having a surface resistivity of 1 kΩ / port or more and a thickness of 5 to 50 nm as a first layer, and then the first layer is formed. After coating a nitrogen oxide thin film or an oxygen nitride thin film of Cr having a film thickness of 1 to 10 nm as a second layer on the layer, Ti, Ta, TiSi having a film thickness of 5 to 30 nm is provided on the second layer. , Sn, Al, Si oxide thin film or oxynitride thin film, and at least one of them is laminated and coated to form a laminated film.
ラスにおいて、前記被膜した熱線遮蔽性能膜の表面抵抗
率が１ｋΩ／口以上で、かつ該ガラスのガラス面側から
の反射色調がシルバー系色調を呈することを特徴とする
請求項１記載の電波低反射特性を有する熱線遮蔽ガラ
ス。2. The heat ray shielding glass having the low radio wave reflection property, wherein the coated heat ray shielding performance film has a surface resistivity of 1 kΩ / mouth or more, and a reflection tone from the glass surface side of the glass is a silver tone. The heat ray-shielding glass having a low radio wave reflection characteristic according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18961292A JPH0632635A (en) | 1992-07-16 | 1992-07-16 | Heat shielding glass having low reflecting characteristic of electrical radiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18961292A JPH0632635A (en) | 1992-07-16 | 1992-07-16 | Heat shielding glass having low reflecting characteristic of electrical radiation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0632635A true JPH0632635A (en) | 1994-02-08 |
Family
ID=16244222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18961292A Pending JPH0632635A (en) | 1992-07-16 | 1992-07-16 | Heat shielding glass having low reflecting characteristic of electrical radiation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0632635A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135342A (en) * | 1997-07-15 | 1999-02-09 | Central Glass Co Ltd | Polyfunctional glass and its production |
| CN112941463A (en) * | 2020-12-31 | 2021-06-11 | 广东振华科技股份有限公司 | Nano multilayer oxynitride corrosion-resistant protective coating on titanium alloy surface and preparation method and application thereof |
-
1992
- 1992-07-16 JP JP18961292A patent/JPH0632635A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135342A (en) * | 1997-07-15 | 1999-02-09 | Central Glass Co Ltd | Polyfunctional glass and its production |
| CN112941463A (en) * | 2020-12-31 | 2021-06-11 | 广东振华科技股份有限公司 | Nano multilayer oxynitride corrosion-resistant protective coating on titanium alloy surface and preparation method and application thereof |
| CN112941463B (en) * | 2020-12-31 | 2024-01-23 | 广东振华科技股份有限公司 | Nano multilayer oxynitride corrosion-resistant protective coating and preparation method and application thereof |
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