JPH08295540A - Glass for cutting off heat ray - Google Patents
Glass for cutting off heat rayInfo
- Publication number
- JPH08295540A JPH08295540A JP7119035A JP11903595A JPH08295540A JP H08295540 A JPH08295540 A JP H08295540A JP 7119035 A JP7119035 A JP 7119035A JP 11903595 A JP11903595 A JP 11903595A JP H08295540 A JPH08295540 A JP H08295540A
- Authority
- JP
- Japan
- Prior art keywords
- film
- glass
- wsio
- transparent protective
- nitride
- 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.)
- Pending
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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- 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
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- 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
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/365—Coating different sides of a glass substrate
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)
- Special Wing (AREA)
- Surface Treatment Of Glass (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は熱線を遮断するガラスに
関し、さらに詳しくは、例えば、車両用窓ガラス、建材
用ガラス等に有用である熱線遮断性および電波透過性に
優れたガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass which blocks heat rays, and more particularly to a glass which is useful as a window glass for vehicles, a glass for building materials and the like and has an excellent heat ray blocking property and radio wave transmission property.
【0002】[0002]
【従来の技術】従来、自動車用窓ガラス等において直射
日光等による室内への熱の侵入および蓄積を防止するた
めに、窓ガラス面に熱線反射膜を形成することが行われ
ている。これらの従来の熱線反射膜は窒化チタンや銀、
アルミニウムの如き比較的導電性の高い物質を蒸着やス
パッタリング法等でガラス面に形成している。2. Description of the Related Art Conventionally, in an automobile window glass or the like, a heat ray reflective film is formed on the surface of the window glass in order to prevent heat from entering and accumulating in the room due to direct sunlight or the like. These conventional heat ray reflective films are titanium nitride, silver,
A relatively highly conductive substance such as aluminum is formed on the glass surface by vapor deposition or sputtering.
【0003】[0003]
【発明が解決しようとしている問題点】上記従来の熱線
反射板ガラスは、その熱線反射膜の導電性が高く、その
性質上電磁波遮蔽性が高く、電波が透過しないために室
内アンテナやガラスプリントアンテナ、携帯電話等の通
信機器が十分に機能しないという問題があった。また、
上記窒化チタン、銀、アルミニウム等からなる膜は、あ
る程度の厚みとなると可視光線に対する反射性が高くな
り可視光線透過率が低下し、車両の窓ガラスとしては使
用できなくなる。また、十分な透明性になる程膜を薄く
すると、十分な熱線反射性能が得られないという問題が
ある。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the above-mentioned conventional heat ray reflector glass, the heat ray reflection film has high conductivity, has a high electromagnetic wave shielding property due to its nature, and does not allow radio waves to pass therethrough. There is a problem that communication devices such as mobile phones do not function sufficiently. Also,
When the film made of titanium nitride, silver, aluminum or the like has a certain thickness, it has a high reflectance for visible light and a low visible light transmittance, and cannot be used as a window glass for vehicles. Further, if the film is thin enough to have sufficient transparency, there is a problem that sufficient heat ray reflection performance cannot be obtained.
【0004】また、タングステンと珪素の混合物の複合
酸化物から、電波透過性であり、かつ熱線遮断性にも優
れており、可視光線に対して十分な透明性、透過性を持
つ膜を形成することができる。この膜を使用して種々の
環境下で使用するには、熱、紫外線などに対する十分な
耐環境性を付与するために有効な保護膜を設ける必要が
ある。従って、本発明の目的は、熱線遮断性および電波
透過性に優れ、車両用窓ガラスや建材用ガラスとして有
用な熱線を遮断するガラスを提供することである。Further, a composite oxide of a mixture of tungsten and silicon is formed into a film which is radio wave permeable and has an excellent heat ray shielding property, and which is sufficiently transparent and permeable to visible light. be able to. In order to use this film in various environments, it is necessary to provide a protective film effective for imparting sufficient environment resistance to heat, ultraviolet rays and the like. Therefore, an object of the present invention is to provide a glass which has excellent heat ray shielding properties and radio wave transparency and which shields heat rays and is useful as a window glass for vehicles and a glass for building materials.
【0005】[0005]
【問題点を解決するための手段】上記目的は以下の本発
明によって達成される。即ち、本発明は、ガラス基体の
少なくとも一方の面に、タングステン珪素複合酸化物膜
および酸化物誘電体膜とが順次形成してなり、該タング
ステン珪素複合酸化物膜の少なくとも一方の面には、金
属および/または窒化物からなる透明保護膜が設けられ
たことを特徴とする熱線を遮断するガラスである。The above object can be achieved by the present invention described below. That is, according to the present invention, a tungsten silicon composite oxide film and an oxide dielectric film are sequentially formed on at least one surface of a glass substrate, and at least one surface of the tungsten silicon composite oxide film, A glass for shielding heat rays, which is characterized in that a transparent protective film made of metal and / or nitride is provided.
【0006】[0006]
【作用】タングステン珪素複合酸化物膜(以下WSiO
膜という)を熱線遮断膜とする熱線を遮断するガラスに
おいて、WSiO膜の少なくとも一方の面に透明保護膜
を設けることによって、熱線遮断性および電波透過性に
優れ、車両用窓ガラスや建材用ガラスとして有用な高耐
久の熱線を遮断するガラスを提供することができる。Function: Tungsten-silicon composite oxide film (hereinafter WSiO)
(A film) as a heat ray-shielding film that blocks heat rays. By providing a transparent protective film on at least one surface of the WSiO film, it has excellent heat ray-shielding properties and radio wave transmission properties, and is used for vehicle window glass and building material glass. It is possible to provide a highly durable glass that shields heat rays.
【0007】[0007]
【好ましい実施態様】次に好ましい実施態様を挙げて本
発明をさらに詳しく説明する。本発明の熱線を遮断する
ガラスは、その断面を図1に図解的に示す様に、基体で
ある板ガラス1(1’)の少なくとも一方の表面に、少
なくとも1層のWSiO膜2と、該WSiO膜2の少な
くとも一方の面に、透明保護膜3を設けたことを特徴と
している。図1aに示す例は、本発明を合わせガラスに
応用した例であり、この例では基体である外板ガラス
1’と内板ガラス1との間に、WSiO膜2、透明保護
膜3、誘電体膜4およびポリビニルブチラール樹脂等か
らなる中間膜5が図示の順序で積層されている。図1b
の例は、WSiO膜2の両側に透明保護膜3が形成され
た例であり、図1cに示す例は、図1bの例においてさ
らに誘電体膜4と中間膜5との間にも透明保護膜3が形
成された例である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The glass for blocking heat rays of the present invention has at least one layer of a WSiO film 2 and the WSiO film 2 on at least one surface of a plate glass 1 (1 ′) as a substrate, as shown in a schematic cross section in FIG. The transparent protective film 3 is provided on at least one surface of the film 2. The example shown in FIG. 1a is an example in which the present invention is applied to a laminated glass. In this example, a WSiO film 2, a transparent protective film 3 and a dielectric film are provided between an outer plate glass 1 ′ which is a substrate and an inner plate glass 1. 4 and an intermediate film 5 made of polyvinyl butyral resin or the like are laminated in the order shown. Figure 1b
In the example shown in FIG. 1C, the transparent protective films 3 are formed on both sides of the WSiO film 2. In the example shown in FIG. 1C, the transparent protective film 3 is further provided between the dielectric film 4 and the intermediate film 5 in the example shown in FIG. 1B. This is an example in which the film 3 is formed.
【0008】以上の例は、合わせガラスに本発明を適用
した例であるが、本発明は合わせガラスに限定されず、
単板ガラスおよび複層ガラス等の他のガラス基体にも適
用し得ることは云うまでもない。本発明において使用さ
れるガラス基体とは、普通ガラス、強化板ガラス、部分
強化板ガラス等であって、透明性を損なわない程度に着
色されたものあってもよい。これらのガラス基体は平板
状のものに限られず、種々の形状および曲率に加工され
た曲面状であってもよく、形状的にも特に限定されない
が、特に各種車両のフロント、リヤ、サイド、ルーフ等
の窓ガラス等において有用である。また、これらのガラ
ス基体の厚みは特に限定されないが、通常は約1.5〜
5mm程度の厚みが一般的である。The above example is an example in which the present invention is applied to laminated glass, but the present invention is not limited to laminated glass,
It goes without saying that the present invention can also be applied to other glass substrates such as single glass and double glazing. The glass substrate used in the present invention may be ordinary glass, tempered glass plate, partially tempered glass plate, etc., and may be colored to such an extent that transparency is not impaired. These glass substrates are not limited to flat plates, and may have curved surfaces processed into various shapes and curvatures, and the shape is not particularly limited, but particularly the front, rear, side, and roof of various vehicles. It is useful for window glass and the like. The thickness of these glass substrates is not particularly limited, but is usually about 1.5 to
A thickness of about 5 mm is common.
【0009】本発明において使用されるWSiO膜は、
タングステン(W)と珪素(Si)とを、例えば、W1
00原子当たりSiを約3〜20原子の割合で混合して
加圧焼結したターゲットを酸素雰囲気中でスパッタリン
グする方法、真空蒸着法、ゾルゲル法、フレキソ印刷
法、スプレー法等の公知の方法でガラス基体の表面に堆
積および成膜することによって形成することができる。
この様にして成膜されるWSiO膜の好ましい組成は、
Wに対してSiを5〜15原子%含む複合酸化物であ
る。また、形成されるWSiO膜の厚みとしては、薄す
ぎると所望の性能が得られず、また、厚すぎるとガラス
の透明性が低下するので、好ましい厚みは約100〜1
300Åである。The WSiO film used in the present invention is
Tungsten (W) and silicon (Si) are, for example, W1
A known method such as a method of sputtering a target obtained by mixing Si at a ratio of about 3 to 20 atoms per 100 atoms and pressure sintering in an oxygen atmosphere, a vacuum vapor deposition method, a sol-gel method, a flexo printing method, a spray method and the like. It can be formed by depositing and forming a film on the surface of a glass substrate.
The preferred composition of the WSiO film thus formed is
It is a composite oxide containing 5 to 15 atomic% of Si with respect to W. In addition, as the thickness of the WSiO film formed, if the thickness is too thin, desired performance cannot be obtained, and if it is too thick, the transparency of the glass decreases, so a preferable thickness is about 100 to 1
It is 300Å.
【0010】本発明おいて、上記WSiO膜の耐久性を
向上させる透明保護膜としては、IVa族元素、Va族元
素、IIIb族元素およびIVb族元素の金属またはこれら
の金属の窒化物または複合窒化物が好ましく用いられ、
好ましい具体的な金属としては、例えば、チタン、ジル
コニウム、アルミニウム、および珪素からなる群から選
ばれる少なくとも1種の金属および/または該金属の窒
化物が挙げられる。より具体的には、特に好ましい例と
して、ZrSI2Nx(X=2〜4)、TixSiyNz(T
i:Si=90:10〜33:67原子比)、TiN
x(X=0.5〜1.3)、SiNx(X=0.5〜1.
3)、AlNx(X=0.5〜1.0)、Ti、Ti/T
iNx(X=0.5〜1.3)(2層)、ZrSi2/Zr
Si2Nx(X=2〜4)(2層)等が挙げられる。In the present invention, as the transparent protective film for improving the durability of the WSiO film, a metal of group IVa element, a group Va element, a group IIIb element and a group IVb element, or a nitride or complex nitride of these metals is used. Is preferably used,
Preferred specific metals include, for example, at least one metal selected from the group consisting of titanium, zirconium, aluminum, and silicon and / or a nitride of the metal. More specifically, as particularly preferable examples, ZrSI 2 N x (X = 2~4), Ti x Si y N z (T
i: Si = 90: 10 to 33:67 atomic ratio), TiN
x (X = 0.5 to 1.3), SiN x (X = 0.5 to 1.
3), AlN x (X = 0.5 to 1.0), Ti, Ti / T
iN x (X = 0.5 to 1.3) (two layers), ZrSi 2 / Zr
Si 2 N x (X = 2~4 ) (2 layers), and the like.
【0011】これらの透明保護層は、例えば、膜形成元
素または2種以上の元素を所望の割合で混合して加圧焼
結したターゲットを不活性雰囲気または窒素雰囲気中で
スパッタリングする方法、真空蒸着法等の公知の方法
で、図1aの場合は前記WSiO膜の少なくとも一方の
面、他の例の場合には所望の面に、元素膜および/また
は窒化物膜として堆積および成膜することによって形成
することができる。この様にして成膜される透明保護膜
の厚みとしては、例えば、図1aに示す例では約10〜
200Åであり、図1bに示す例では1層として約5〜
100Åであり、図1cに示す例では1層として約5〜
150Åであり、透明保護膜全体の合計厚みとしては約
10〜200Åであることが好ましい。これらの透明保
護膜が薄すぎると所望の性能が得られず、また、厚すぎ
るとガラスの透明性が低下するので好ましくない。These transparent protective layers can be formed by, for example, a method of sputtering a target obtained by mixing a film-forming element or two or more kinds of elements in a desired ratio and sintering the mixture under pressure in an inert atmosphere or a nitrogen atmosphere, or vacuum deposition. By a known method such as a method, by depositing and forming an elemental film and / or a nitride film on at least one surface of the WSiO film in the case of FIG. 1a and a desired surface in the other example. Can be formed. The thickness of the transparent protective film thus formed is, for example, about 10 in the example shown in FIG.
It is 200Å, and in the example shown in FIG.
100 Å, and in the example shown in FIG.
It is preferably 150Å, and the total thickness of the entire transparent protective film is preferably about 10 to 200Å. If these transparent protective films are too thin, the desired performance cannot be obtained, and if they are too thick, the transparency of the glass decreases, which is not preferable.
【0012】本発明においては前記WSiO膜のガラス
基体とは反対側に誘電体膜を形成する。誘電体膜として
は、例えば、Zn、Sn、Al、Si、Ti、Zr、T
a、Nb、Bi等の元素の酸化物や複合酸化物が好まし
く、前記WSiO膜と同様にスパッタリング方法等の公
知の製膜技術により形成される。誘電体膜は、図1a〜
cに示す例ではいずれも中間膜に接する位置に形成され
ているが、該誘電体膜は図示の位置には限定されない。
また、該誘電体膜をガラス基体とWSiO膜との間にさ
らに形成してもよい。これらの誘電体膜は可視光線遮断
率の低減或は反射色調調整等の目的で形成され、形成さ
れる誘電体膜の厚みとしては、WSiO層と誘電体層と
の合計で約900〜1700Åである。In the present invention, a dielectric film is formed on the side of the WSiO film opposite to the glass substrate. As the dielectric film, for example, Zn, Sn, Al, Si, Ti, Zr, T
Oxides and complex oxides of elements such as a, Nb, and Bi are preferable, and are formed by a known film forming technique such as a sputtering method like the WSiO film. The dielectric film is shown in FIG.
In each of the examples shown in c, the dielectric film is formed at a position in contact with the intermediate film, but the dielectric film is not limited to the illustrated position.
Further, the dielectric film may be further formed between the glass substrate and the WSiO film. These dielectric films are formed for the purpose of reducing the visible light blocking rate or adjusting the reflection color tone, and the thickness of the dielectric film formed is about 900 to 1700Å in total for the WSiO layer and the dielectric layer. is there.
【0013】また、本発明おける熱線を遮断するガラス
が合わせガラスである場合に使用される中間樹脂膜と
は、合わせガラスにした場合において、その両面に配設
される二枚の板ガラスを強固に接着させると共に、合わ
せガラスが破損した場合にも、ガラスの破片が飛び散ら
ない作用及び耐貫通作用を有するものであって、通常は
接着性、耐光性、耐熱性等の諸物性が改良されたポリビ
ニルブチラール樹脂シートが好ましく使用される。これ
らの中間樹脂膜の厚みも特に限定されないが、通常は約
0.2〜0.9mm程度の厚みが一般的である。The intermediate resin film used when the glass for blocking heat rays in the present invention is a laminated glass means, when the laminated glass is used, the two sheet glasses disposed on both sides of the laminated glass are solidified. Along with bonding, even when the laminated glass is broken, it has a function of preventing glass fragments from scattering and a penetration resistance, and generally has improved physical properties such as adhesion, light resistance, and heat resistance. Butyral resin sheet is preferably used. The thickness of these intermediate resin films is not particularly limited, but is generally about 0.2 to 0.9 mm.
【0014】合わせガラスの製造方法自体は公知の方法
でよく、例えば、二枚の所定形状の板ガラスを必要に応
じて曲げ加工し、洗浄乾燥後に一方の板ガラスの面に上
記の如きWSiO膜、透明保護層および誘電体膜等を形
成する。一方、中間樹脂膜も洗浄および乾燥させた後所
定形状に裁断する。上記二枚の板ガラスを、樹脂シート
を挟持する様に貼り合わせ、予備接着、オートクレーブ
処理、洗浄・乾燥等の工程によって所望の合わせガラス
が製造される。The method for producing the laminated glass may be a known method, for example, two sheet glasses having a predetermined shape are bent as required, and after washing and drying, one of the sheet glasses has the WSiO film and the transparent layer as described above. A protective layer and a dielectric film are formed. On the other hand, the intermediate resin film is also washed and dried and then cut into a predetermined shape. A desired laminated glass is manufactured by laminating the above two sheets of glass so as to sandwich a resin sheet, and performing steps such as pre-adhesion, autoclave treatment, washing and drying.
【0015】[0015]
【実施例】次に比較例および実施例を挙げて本発明をさ
らに具体的に説明する。 比較例1 ガラス基体として十分に洗浄したグリーンガラス(10
cm×10cm×2mm厚)を使用し、W中にSiを
4.8原子%添加し、1,500℃前後の温度で不活性
ガス雰囲気中で加圧焼結させたターゲットを用いて、直
流スパッタ法により、上記基板上にスパッタ時の圧力
1.0mTorr、Ar:O2 =30:16の比率で混
合したガス雰囲気中で膜厚500ÅのW 95Si5Ox(X
は未測定)からなる透明WSiO膜を成膜し、次に大気
開放を経ずに連続してZn金属ターゲットを用いて、ス
パッタ時の圧力=4.0mTorr、Ar:O2=2
0:40の比率で混合したガス雰囲気中で膜厚700Å
のZnO透明誘電体膜を成膜した。尚、成膜中に基板の
加熱は行わなかった。EXAMPLES Next, the present invention will be described with reference to Comparative Examples and Examples.
Will be specifically described. Comparative Example 1 Green glass (10
cm × 10 cm × 2 mm thickness) and Si in W
Adds 4.8 atom% and is inactive at temperatures around 1,500 ° C
Using a target that has been pressure-sintered in a gas atmosphere,
Pressure during sputtering on the above substrate by the flow sputtering method.
1.0 mTorr, Ar: O2 = Mixed at a ratio of 30:16
W with a film thickness of 500Å in a combined gas atmosphere 95SiFiveOx(X
A transparent WSiO film consisting of
Using a Zn metal target continuously without opening,
Pressure at putter = 4.0 mTorr, Ar: O2= 2
Film thickness 700Å in gas atmosphere mixed with 0:40 ratio
ZnO transparent dielectric film of was formed. In addition, during film formation
No heating was done.
【0016】上記の被膜が形成されたガラスと、別の2
mmのグリーンガラスとをポリビニルブチラールシート
(0.76mm厚)を挟んで積層し、予備圧着し、次に
オートクレーブにより加熱加圧圧着して合わせガラスと
した。尚、上記WSiO膜の膜抵抗は10MΩ/□以上
であった。この膜付き合わせガラスの可視光線透過率は
72%であり、太陽光線透過率は47%であった。一
方、上記方法においてWSiO膜およびZnO膜を設け
ない以外は同様にして作製した通常の膜無し合わせガラ
スの可視光線透過率は79%であり、太陽光線透過率は
54%であった。[0016] The glass coated with the above-mentioned
A polyvinyl butyral sheet (thickness: 0.76 mm) was laminated with a green glass sheet having a thickness of 0.7 mm, pre-pressed, and then heat-pressed by an autoclave to obtain a laminated glass. The film resistance of the WSiO film was 10 MΩ / □ or more. The visible light transmittance of this laminated glass with a film was 72%, and the solar light transmittance was 47%. On the other hand, the visible light transmittance of ordinary glass having no film formed in the same manner as above except that the WSiO film and the ZnO film were not provided was 79%, and the solar light transmittance was 54%.
【0017】上記膜付き合わせガラスについて耐熱テス
トを行ったところ、110℃の恒温槽に24時間放置し
たところ、WSiO膜による微吸収発色は消失してお
り、ほぼ完全に無色透明化していた。また、熱線遮断性
能も殆ど失われていた。その後30日間放置して観察し
たが、透明化したままで変化は認められなかった。上記
膜付き合わせガラスの着色の経時変化を図2に示した。
図2におけるΔTは試験開始前後の可視光線透過率の変
化率である。次に上記膜付き合わせガラスについて紫外
線による影響を調べた。上記膜付きガラスをJIS−R
3212に準拠してカーボンアークランプで中間膜の反
対面から紫外線を100時間照射したところ、WSiO
膜による微吸収発色濃度が高くなり可視光線透過率が7
0.2%まで低下していた。その後300時間経過後に
はWSiO膜による着色濃度はさらに高くなり可視光線
透過率は68%となって、その後さらに1000時間ま
で評価を継続したが、WSiOによる濃色化は進行し、
最終的には可視光線透過率は67%にまで低下した。こ
れらの経時変化を図2に示す。A heat resistance test was conducted on the laminated glass with a film, and when it was allowed to stand in a constant temperature bath at 110 ° C. for 24 hours, the slightly absorbed coloring due to the WSiO film disappeared, and it was almost completely colorless and transparent. Also, the heat ray blocking performance was almost lost. After that, it was left for 30 days for observation, but no change was observed while it remained transparent. FIG. 2 shows changes with time in coloring of the laminated glass with a film.
ΔT in FIG. 2 is the change rate of the visible light transmittance before and after the start of the test. Next, the influence of ultraviolet rays was examined on the laminated glass with a film. The above glass with film is JIS-R
In accordance with 3212, when a carbon arc lamp was used to irradiate ultraviolet rays from the opposite surface of the intermediate film for 100 hours,
The slightly absorbed color density of the film is increased and the visible light transmittance is 7
It had dropped to 0.2%. After 300 hours, the coloring density by the WSiO film was further increased and the visible light transmittance was 68%. After that, the evaluation was continued for 1000 hours, but the darkening by WSiO proceeded.
Finally, the visible light transmittance dropped to 67%. These changes with time are shown in FIG.
【0018】実施例1 図1cに示す如く、WSiO膜とグリーンガラス(外板
ガラス)との間、WSiO膜とZnO膜との間およびZ
nO膜とポリビニルブチラール膜との間に透明保護膜を
形成した以外は比較例1と同様にして合わせガラスを作
製した。上記3層の夫々の透明保護膜としては、Zrと
SiとをZr:Si=1:2の割合で混合し、1,50
0℃前後の温度で不活性ガス雰囲気中で加圧焼結したタ
ーゲットを用いて、スパッタ時の圧力=3.0mTor
r、Ar:N2 =20:20の比率で混合したガス雰囲
気中で膜厚50ÅのZrSi2Nx膜(X=約4)をスパ
ッタ成膜により設けた。尚、上記WSiO膜の膜抵抗は
10MΩ/□以上であった。この膜付き合わせガラスの
可視光線透過率は72%であり、太陽光線透過率は47
%であった。Example 1 As shown in FIG. 1c, between the WSiO film and the green glass (outer plate glass), between the WSiO film and the ZnO film and Z
A laminated glass was produced in the same manner as in Comparative Example 1 except that a transparent protective film was formed between the nO film and the polyvinyl butyral film. For each of the three layers of transparent protective films, Zr and Si were mixed at a ratio of Zr: Si = 1: 2, and
Using a target pressure-sintered in an inert gas atmosphere at a temperature of around 0 ° C., the pressure during sputtering = 3.0 mTorr
A ZrSi 2 N x film (X = about 4) having a film thickness of 50Å was formed by sputtering in a gas atmosphere mixed with r and Ar: N 2 = 20: 20. The film resistance of the WSiO film was 10 MΩ / □ or more. This film-coated laminated glass has a visible light transmittance of 72% and a solar light transmittance of 47%.
%Met.
【0019】上記膜付き合わせガラスについて耐熱テス
トを行ったところ、110℃の恒温槽に24時間放置し
たところ、WSiO膜による微吸収発色は殆ど変化して
おらず、また、熱線遮断性能も殆ど変化していなかっ
た。その後30日間放置して観察したが微吸収発色の変
化は認められなかった。上記膜付き合わせガラスの着色
の経時変化を図2に示した。次に上記膜付き合わせガラ
スについて比較例1と同様にして紫外線による影響を調
べたところ、30日および1000時間経過後において
も可視光線透過率および太陽光線透過率は殆ど変化は認
められず、その変化の絶対値は0.5%以内であった。
これらのテストの結果を図2に示す。A heat resistance test was conducted on the laminated glass with a film, and when it was left in a constant temperature bath at 110 ° C. for 24 hours, the slight absorption color development by the WSiO film was hardly changed, and the heat ray blocking performance was also almost changed. I didn't. After that, the sample was left for 30 days for observation, but no change in slightly absorbed color was observed. FIG. 2 shows changes with time in coloring of the laminated glass with a film. Next, with respect to the laminated glass with a film, the effect of ultraviolet rays was examined in the same manner as in Comparative Example 1. As a result, visible light transmittance and sunlight transmittance were hardly changed even after 30 days and 1000 hours. The absolute value of the change was within 0.5%.
The results of these tests are shown in FIG.
【0020】実施例2 図1aに示す様に、WSiO膜と誘電体膜との間にのみ
実施例1と同様にして膜厚50ÅのZrSi2Nx膜を透
明保護膜としてスパッタ成膜により設けた以外は比較例
1と同様にして合わせガラスを作製した。尚、上記WS
iO膜の膜抵抗は10MΩ/□以上であった。この膜付
き合わせガラスの可視光線透過率は72%であり、太陽
光線透過率は47%であった。上記膜付き合わせガラス
について耐熱テストおよび耐紫外線テストを行ったとこ
ろ、実施例1と同様にガラスの光学特性の変化はほとん
どなく、その変化の絶対値は1%以内であった。上記耐
熱テストおよび耐紫外線テストの結果を図2に示す。Example 2 As shown in FIG. 1a, a ZrSi 2 N x film having a film thickness of 50 Å was provided as a transparent protective film between the WSiO film and the dielectric film by sputtering as in Example 1. A laminated glass was produced in the same manner as in Comparative Example 1 except for the above. The above WS
The film resistance of the iO film was 10 MΩ / □ or more. The visible light transmittance of this laminated glass with a film was 72%, and the solar light transmittance was 47%. When a heat resistance test and an ultraviolet resistance test were conducted on the above laminated glass with a film, there was almost no change in the optical characteristics of the glass as in Example 1, and the absolute value of the change was within 1%. The results of the heat resistance test and the ultraviolet light resistance test are shown in FIG.
【0021】実施例3 前記実施例2におけるZrSi2Nx膜に代えて直流スパ
ッタ法により、膜厚25Åのチタン金属膜を成膜した以
外は実施例2と同様にして合わせガラスを作製した。こ
の膜付合わせガラスの可視光線透過率は70%であり、
太陽光線透過率は45%であった。上記25Åのチタン
膜付き合わせガラスについて、実施例1と同様に耐熱テ
ストおよび耐紫外線テストを行ったところ、可視光線透
過率および太陽光線透過率の変化の絶対値は1%以内で
あった。上記耐熱テストの結果を図2に示す。Example 3 A laminated glass was produced in the same manner as in Example 2 except that a titanium metal film having a film thickness of 25 Å was formed by DC sputtering instead of the ZrSi 2 N x film in Example 2. The visible light transmittance of this laminated glass with a film is 70%,
The solar ray transmittance was 45%. When the heat resistance test and the ultraviolet light resistance test were performed on the above 25Å titanium film-coated laminated glass in the same manner as in Example 1, the absolute values of changes in the visible light transmittance and the sunlight transmittance were within 1%. The results of the above heat resistance test are shown in FIG.
【0022】[0022]
【発明の効果】以上説明の通り、本発明によれば、WS
iO膜を熱線遮断膜とする熱線を遮断するガラスにおい
て、WSiO膜の少なくとも一方の面に透明保護膜を設
けることによって、熱線遮断性および電波透過性に優
れ、車両用窓ガラスや建材用ガラスとして有用な高耐久
の熱線を遮断するガラスを提供することができる。As described above, according to the present invention, WS
In a glass for blocking heat rays using an io film as a heat ray blocking film, by providing a transparent protective film on at least one surface of the WSiO film, it has excellent heat ray blocking properties and radio wave transmission properties, and is used as a window glass for vehicles or a glass for building materials. It is possible to provide a useful highly durable glass that blocks heat rays.
【図1】本発明の熱線を遮断するガラスの断面を図形的
に示す図。FIG. 1 is a diagram schematically showing a cross section of glass for blocking heat rays according to the present invention.
【図2】比較例および実施例の結果を示す図。FIG. 2 is a diagram showing the results of comparative examples and examples.
1:内板ガラス 1’:外板ガラス 2:WSiO膜 3:透明保護膜 4:誘電体膜 5:中間膜 1: Inner plate glass 1 ': Outer plate glass 2: WSiO film 3: Transparent protective film 4: Dielectric film 5: Intermediate film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西出 利一 神奈川県横浜市神奈川区宝町2番地 日産 自動車株式会社内 (72)発明者 柴田 格 神奈川県横浜市神奈川区宝町2番地 日産 自動車株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Riichi Nishide 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (72) Inventor Shibata 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. Within
Claims (4)
グステン珪素複合酸化物膜および酸化物誘電体膜とが順
次形成してなり、該タングステン珪素複合酸化物膜の少
なくとも一方の面には、金属および/または窒化物から
なる透明保護膜が設けられたことを特徴とする熱線を遮
断するガラス。1. A glass substrate is provided with a tungsten silicon composite oxide film and an oxide dielectric film formed on at least one surface of the glass substrate, and a metal film is formed on at least one surface of the tungsten silicon composite oxide film. A glass for blocking heat rays, which is characterized in that a transparent protective film made of and / or nitride is provided.
ム、アルミニウム、および珪素からなる群から選ばれる
少なくとも1種の金属、および/または該金属の窒化物
からなることを特徴とする請求項1記載の熱線を遮断す
るガラス。2. The transparent protective film is made of at least one metal selected from the group consisting of titanium, zirconium, aluminum, and silicon, and / or a nitride of the metal. A glass that blocks the heat rays of.
されてなる合せガラスにおいて、少なくとも一方のガラ
ス基体と中間樹脂膜との間には、タングステン珪素複合
酸化物膜および酸化物誘電体膜とがガラス基体側から順
次形成され、かつ、該タングステン珪素複合酸化物膜の
少なくとも一方の面には、金属および/または窒化物か
らなる透明保護膜が設けられたことを特徴とする合せガ
ラス。3. A laminated glass in which two glass substrates are laminated via an intermediate resin film, and a tungsten silicon composite oxide film and an oxide dielectric film are provided between at least one of the glass substrates and the intermediate resin film. Is sequentially formed from the glass substrate side, and a transparent protective film made of a metal and / or a nitride is provided on at least one surface of the tungsten silicon composite oxide film.
ム、アルミニウム、および珪素からなる群から選ばれる
少なくとも1種の金属、および/または該金属の窒化物
からなることを特徴とする請求項3記載の合せガラス。4. The transparent protective film comprises at least one metal selected from the group consisting of titanium, zirconium, aluminum and silicon, and / or a nitride of the metal. Laminated glass.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7119035A JPH08295540A (en) | 1995-04-21 | 1995-04-21 | Glass for cutting off heat ray |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7119035A JPH08295540A (en) | 1995-04-21 | 1995-04-21 | Glass for cutting off heat ray |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH08295540A true JPH08295540A (en) | 1996-11-12 |
Family
ID=14751356
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7119035A Pending JPH08295540A (en) | 1995-04-21 | 1995-04-21 | Glass for cutting off heat ray |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH08295540A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100419781B1 (en) * | 2001-03-09 | 2004-02-21 | 주식회사 엘지화학 | Shading Film for the Roll-Type Shading Screen to Be Hung at Indoor Windows and the Method of Manufacturing thereof |
JP2010216081A (en) * | 2009-03-13 | 2010-09-30 | Bridgestone Corp | Heat ray shielding glass louver and window structure including the same |
DE102012106518A1 (en) * | 2012-07-18 | 2014-01-23 | H2 Solar Gmbh | Coating of substrates with silicides and their oxides |
-
1995
- 1995-04-21 JP JP7119035A patent/JPH08295540A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100419781B1 (en) * | 2001-03-09 | 2004-02-21 | 주식회사 엘지화학 | Shading Film for the Roll-Type Shading Screen to Be Hung at Indoor Windows and the Method of Manufacturing thereof |
JP2010216081A (en) * | 2009-03-13 | 2010-09-30 | Bridgestone Corp | Heat ray shielding glass louver and window structure including the same |
DE102012106518A1 (en) * | 2012-07-18 | 2014-01-23 | H2 Solar Gmbh | Coating of substrates with silicides and their oxides |
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