JPH08143335A - Ultraviolet ray absorbing glass - Google Patents
Ultraviolet ray absorbing glassInfo
- Publication number
- JPH08143335A JPH08143335A JP28682894A JP28682894A JPH08143335A JP H08143335 A JPH08143335 A JP H08143335A JP 28682894 A JP28682894 A JP 28682894A JP 28682894 A JP28682894 A JP 28682894A JP H08143335 A JPH08143335 A JP H08143335A
- Authority
- JP
- Japan
- Prior art keywords
- film
- glass
- ultraviolet absorbing
- ultraviolet
- refractive index
- 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
- C03C17/3411—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
- C03C17/3417—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 all coatings being oxide coatings
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- 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)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は紫外線吸収ガラスに関す
る。FIELD OF THE INVENTION This invention relates to ultraviolet absorbing glass.
【０００２】[0002]
【従来の技術】室内や車内等へ入射する紫外線の遮蔽
は、人体の日焼けを防ぐばかりでなく、室内や車内の装
飾品等の劣化を防ぐことができるという点で重要であ
る。2. Description of the Related Art Shielding of ultraviolet rays entering a room or a car is important not only to prevent sunburn of the human body but also to prevent deterioration of ornaments and the like in the room and the car.
【０００３】また、可視光線より長い波長を有する赤外
線（熱線）の遮蔽も室内、車内の冷房効率を高めるため
に重要である。Further, shielding of infrared rays (heat rays) having a wavelength longer than visible light is also important in order to improve the cooling efficiency in the room and the inside of the vehicle.
【０００４】従来より、紫外線吸収ガラス、熱線遮蔽ガ
ラスは数多く提案されており、これら両方を具備させた
ガラスが特開平６−１３５７４７号公報で提案されてい
る。しかし、該公報で提案のガラスは、中間膜として、
透明導電膜を用いるため、電波透過性能を必要とされる
車両用ガラスなどに使用する場合、シート抵抗値の制約
上、十分な熱線遮蔽性を発揮できない問題があった。Conventionally, many ultraviolet absorbing glasses and heat ray shielding glasses have been proposed, and a glass provided with both of them has been proposed in Japanese Patent Application Laid-Open No. 6-135747. However, the glass proposed in this publication, as an intermediate film,
Since a transparent conductive film is used, there is a problem in that when used for vehicle glass or the like that requires radio wave transmission performance, sufficient heat ray shielding properties cannot be exhibited due to the restriction of the sheet resistance value.
【０００５】この問題を解決しうる方法として、導電性
酸化物の超微粒子を分散させた導電膜の使用があげられ
る。しかし、該導電膜を使用すると電波透過性は発現す
るが、中間膜が多孔質になることにより、耐摩耗性に問
題が生じる欠点があった。As a method capable of solving this problem, use of a conductive film in which ultrafine particles of a conductive oxide are dispersed can be mentioned. However, when the conductive film is used, radio wave transparency is exhibited, but the interlayer film is porous, which causes a problem in abrasion resistance.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、優れた熱線
遮蔽性と高い耐摩耗性とを有する紫外線吸収ガラスの提
供を目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide an ultraviolet absorbing glass having excellent heat ray shielding properties and high abrasion resistance.
【０００７】[0007]
【課題を解決するための手段】本発明は、ガラスの表面
に、中間膜、紫外線吸収膜が順次形成された紫外線吸収
ガラスにおいて、該中間膜は、Ｒｕ、Ｃｏ、Ｃｕ、Ｆ
ｅ、ＮｉおよびＶからなる群から選ばれる少なくとも１
種の金属の酸化物を含む膜であることを特徴とする紫外
線吸収ガラスを提供する。The present invention provides an ultraviolet absorbing glass in which an intermediate film and an ultraviolet absorbing film are sequentially formed on the surface of glass, wherein the intermediate film is Ru, Co, Cu or F.
at least 1 selected from the group consisting of e, Ni and V
Provided is an ultraviolet absorbing glass, which is a film containing an oxide of one kind of metal.
【０００８】中間膜としては、特に近赤外線領域の消衰
係数が高いＲｕおよび／またはＣｏの酸化物を含む膜で
あることが好ましい。The intermediate film is preferably a film containing an oxide of Ru and / or Co, which has a particularly high extinction coefficient in the near infrared region.
【０００９】紫外線吸収膜の材質は、特に限定されず、
紫外線吸収性能の観点から酸化セリウム（ＣｅＯ2 ）お
よび／または酸化チタン（ＴｉＯ2 ）を主成分とする膜
が好ましい。特に、ＣｅＯ2 とＴｉＯ2 とを主成分とす
る膜が好ましく、その組成比がＣｅＯ2 ／ＴｉＯ2 ＝
１．０〜５．０（重量比）の範囲において優れた紫外線
吸収性能を有する。The material of the ultraviolet absorbing film is not particularly limited,
From the viewpoint of ultraviolet absorption performance, a film containing cerium oxide (CeO 2 ) and / or titanium oxide (TiO 2 ) as a main component is preferable. In particular, a film containing CeO 2 and TiO 2 as main components is preferable, and the composition ratio thereof is CeO 2 / TiO 2 =
It has excellent ultraviolet absorption performance in the range of 1.0 to 5.0 (weight ratio).
【００１０】また、ＣｅＯ2 および／またはＴｉＯ2 の
みで構成される紫外線吸収膜では屈折率が高くなり、可
視光透過率が低下するおそれがあるので、ＳｉＯ2 など
の低屈折率成分を含ませて、紫外線吸収膜の屈折率を低
下させることも好ましい。Further, since an ultraviolet absorbing film composed only of CeO 2 and / or TiO 2 may have a high refractive index and a low visible light transmittance, a low refractive index component such as SiO 2 should be contained. It is also preferable to lower the refractive index of the ultraviolet absorbing film.
【００１１】紫外線吸収膜の膜厚は、特に限定されず、
紫外線吸収性能や成膜性の観点から、１００〜８００ｎ
ｍであることが好ましい。The thickness of the ultraviolet absorbing film is not particularly limited,
From the viewpoint of ultraviolet absorption performance and film formability, 100 to 800 n
It is preferably m.
【００１２】紫外線吸収膜の成分であるＣｅＯ2 とＴｉ
Ｏ2 はいずれも屈折率が高く、ＣｅＯ2 および／または
ＴｉＯ2 を含有する紫外線吸収膜は単層膜では膜厚を１
μｍ程度まで厚くしない限り光の干渉による反射光の着
色（光彩）は不可避である。よって、中間膜の屈折率
を、紫外線吸収膜の屈折率とガラスの屈折率との中間の
屈折率とし、かつ、その光学膜厚を４００〜７００ｎｍ
の１／４とするように設計することが、光彩を減少させ
うるので好ましい。CeO 2 and Ti which are components of the ultraviolet absorbing film
O 2 has a high refractive index, and the ultraviolet absorption film containing CeO 2 and / or TiO 2 has a thickness of 1 in a single layer film.
Unless the thickness is increased to about μm, coloring (light) of reflected light due to light interference is unavoidable. Therefore, the refractive index of the intermediate film is set to an intermediate refractive index between the refractive index of the ultraviolet absorbing film and the refractive index of glass, and the optical film thickness thereof is 400 to 700 nm.
It is preferable to design it to be 1/4 of the above because the iris can be reduced.
【００１３】また、前述のように光彩を減少させる膜構
成とすることにより、可視光線に関しては無反射条件が
成立し可視光線よりも波長の長い近赤外線では無反射条
件が成立しなくなり、結果として近赤外領域の反射率を
高くすることができる。In addition, by adopting the film structure for reducing the iris as described above, the non-reflective condition is satisfied with respect to visible light and the non-reflective condition is not satisfied with near infrared light having a wavelength longer than that of visible light. The reflectance in the near infrared region can be increased.
【００１４】中間膜の形成方法は特に限定されず、通常
用いられている真空蒸着法やスパッタリング法、ＣＶＤ
法等の乾式法のほか、スプレー熱分解法やゾルゲル法等
の湿式法等、幅広い方法が用いられる。The method for forming the intermediate film is not particularly limited, and a vacuum deposition method, a sputtering method, a CVD method ordinarily used.
In addition to a dry method such as a method, a wide range of methods such as a spray pyrolysis method and a wet method such as a sol-gel method are used.
【００１５】中間膜には、先に列記した金属酸化物以外
の他の成分を含ませうる。例えば、比較的低屈折率な酸
化物をマトリックスとして含むことにより、屈折率を低
減でき、光彩減少に有効であることから好ましい。ま
た、中間膜に添加することによって、紫外線吸収ガラス
としての摩耗や薬品に対する耐久性を向上させうるマト
リックス成分の添加も好ましい。The intermediate film may contain components other than the metal oxides listed above. For example, it is preferable to include an oxide having a relatively low refractive index as a matrix because the refractive index can be reduced and it is effective for reducing the iris. It is also preferable to add a matrix component that can improve durability against abrasion and chemicals as the ultraviolet absorbing glass by adding it to the intermediate film.
【００１６】[0016]
【実施例】以下の実施例（例１〜３）および比較例（例
４〜５）において得られた膜の評価は、外観は目視によ
り、紫外線透過率（Ｔuv）はＩＳＯ ９０５０により、
可視光線透過率（Ｔv ）はＪＩＳ Ｒ３１０６により、
日射透過率（ＴE ）はＪＩＳ Ｒ３１０６により、耐摩
耗性はＪＩＳ Ｒ３２１２により行った。EXAMPLES The films obtained in the following Examples (Examples 1 to 3) and Comparative Examples (Examples 4 to 5) were evaluated by visual observation, and the ultraviolet transmittance (T uv ) was measured by ISO 9050.
The visible light transmittance (T v ) is according to JIS R3106,
The solar radiation transmittance (T E ) was measured according to JIS R3106, and the abrasion resistance was measured according to JIS R3212.
【００１７】（例１）エタノール２８．０ｇに塩化ルテ
ニウム水和物（Ｒｕ：４０重量％）２．０ｇを混合し、
３０分撹拌して溶解させた（Ａ液）。Example 1 2.0 g of ruthenium chloride hydrate (Ru: 40% by weight) was mixed with 28.0 g of ethanol,
It was dissolved by stirring for 30 minutes (solution A).
【００１８】エタノール２６ｇ、アセチルアセトン１．
１ｇに、エチルシリケート４０の１．１ｇ、ジルコニウ
ム ｎ−プロポキシド（（ｎ−ＰｒＯ）4 Ｚｒ）の２．
４ｇ、０．１Ｎ塩酸水溶液の０．４ｇを混合して３０分
撹拌後、Ａ液を８．０ｇ混合してさらに３０分撹拌し、
塗布液Ｂとした。26 g of ethanol, acetylacetone 1.
1.1 g of ethyl silicate 40 and 2. g of zirconium n-propoxide ((n-PrO) 4 Zr) were added to 1 g.
After mixing 4 g and 0.4 g of a 0.1 N hydrochloric acid aqueous solution and stirring for 30 minutes, 8.0 g of solution A was mixed and further stirred for 30 minutes,
This was coating liquid B.
【００１９】塗布液Ｂを厚さ２ｍｍのソーダライムガラ
ス（屈折率１．５２、Ｔuv７０％、Ｔv ９０％、ＴE ８
７％）の上にスピンコータを用いて塗布し、２００℃で
１０分焼き付け、中間膜を得た。この中間膜の屈折率は
１．７、光学膜厚は１２０ｎｍであった。The coating liquid B was soda lime glass having a thickness of 2 mm (refractive index 1.52, T uv 70%, T v 90%, T E 8
7%) was applied using a spin coater and baked at 200 ° C. for 10 minutes to obtain an intermediate film. The refractive index of this intermediate film was 1.7, and the optical film thickness was 120 nm.
【００２０】硝酸セリウム６水和物１５ｇにアセチルア
セトン１０ｇを加え、撹拌しながら９０℃で１時間反応
させ、濃黄色粘稠液を得た（Ｃ液）。10 g of acetylacetone was added to 15 g of cerium nitrate hexahydrate and reacted at 90 ° C. for 1 hour with stirring to obtain a dark yellow viscous liquid (liquid C).
【００２１】テトライソプロピルチタネート５ｇにアセ
チルアセトン１．８ｇを加えて室温で１２時間反応さ
せ、モノアセチルアセトナトチタントリイソプロポキシ
ドのイソプロパノール溶液を得た（Ｄ液）。1.8 g of acetylacetone was added to 5 g of tetraisopropyl titanate and reacted at room temperature for 12 hours to obtain an isopropanol solution of monoacetylacetonato titanium triisopropoxide (solution D).
【００２２】Ｃ液３．５ｇとＤ液１．２ｇを混合し、イ
ソプロパノールで固形分濃度が８．３％になるように希
釈して紫外線吸収膜形成用塗布液Ｅとした。Liquid C (3.5 g) and liquid D (1.2 g) were mixed and diluted with isopropanol to a solid content concentration of 8.3% to obtain an ultraviolet absorbing film forming coating liquid E.
【００２３】塗布液Ｅを、前記中間膜上にスピンコータ
を用いて塗布し、１５０℃で５分乾燥後、６００℃で５
分間焼き付けた。この紫外線吸収膜膜の屈折率は２．
３、光学膜厚は１７０ｎｍであった。The coating solution E was applied onto the intermediate film by using a spin coater, dried at 150 ° C. for 5 minutes, and then dried at 600 ° C. for 5 minutes.
Baked for a minute. The refractive index of this ultraviolet absorbing film is 2.
3, the optical film thickness was 170 nm.
【００２４】得られた膜の透過色はブロンズ色をおび、
透明で光彩も目だたなかった。また、Ｔuvは５％、Ｔv
は８０％、ＴE は７１％であった。また、テーバー摩耗
試験を行ったところ、１０００回後のヘイズ値変化は
３．７％であり、十分な耐摩耗性を示した。The transmitted color of the obtained film is bronze,
It was transparent and the glow was inconspicuous. Also, T uv is 5%, T v
Was 80% and T E was 71%. Further, when a Taber abrasion test was carried out, the change in haze value after 1000 times was 3.7%, showing sufficient abrasion resistance.
【００２５】（例２）例１のＡ液における塩化ルテニウ
ム２．０ｇを硝酸コバルト（Ｃｏ（ＮＯ3 ）3 ・６Ｈ2
Ｏ）４．３ｇに変更した以外は例１と同様にして行っ
た。本例における中間膜は屈折率１．７、膜厚１２０ｎ
ｍであった。Example 2 2.0 g of ruthenium chloride in the liquid A of Example 1 was added to cobalt nitrate (Co (NO 3 ) 3 .6H 2
O) The same procedure as in Example 1 was repeated except that the amount was changed to 4.3 g. The intermediate film in this example has a refractive index of 1.7 and a film thickness of 120 n.
It was m.
【００２６】得られた膜付きガラスは透明で光彩も目だ
たず、また、Ｔuvは５％、Ｔv は７８％、ＴE は７０％
であった。また、テーバー摩耗試験を行ったところ、１
０００回後のヘイズ値変化は３．５％であり、十分な耐
摩耗性を示した。The film-coated glass obtained was transparent and had no brilliance, and T uv was 5%, T v was 78%, and T E was 70%.
Met. Also, when the Taber abrasion test was conducted, it was 1
The change in haze value after 000 times was 3.5%, indicating sufficient abrasion resistance.
【００２７】（例３）例１のＢ液でアセチルアセトン
１．１ｇとジルコニウム ｎ−プロポキシド２．４ｇを
硝酸セリウム６水和物１．５ｇに変更する以外は例１と
同様にして行った。本例における中間膜は屈折率１．
７、膜厚１２０ｎｍであった。(Example 3) The procedure of Example 1 was repeated except that 1.1 g of acetylacetone and 2.4 g of zirconium n-propoxide were changed to 1.5 g of cerium nitrate hexahydrate in the liquid B of Example 1. The intermediate film in this example has a refractive index of 1.
7. The film thickness was 120 nm.
【００２８】得られた膜付きガラスは透明で光彩も目だ
たず、また、Ｔuvは５％、Ｔv は８０％、ＴE は７３％
であった。また、テーバー摩耗試験を行ったところ、１
０００回後のヘイズ値変化は３．２％であり、十分な耐
摩耗性を示した。The obtained film-coated glass was transparent and had no brilliance, and T uv was 5%, T v was 80%, and T E was 73%.
Met. Also, when the Taber abrasion test was conducted, it was 1
The change in haze value after 000 times was 3.2%, indicating sufficient abrasion resistance.
【００２９】（例４）例１のＢ液の代わりに、アンチモ
ンを１０重量％含む酸化錫（平均粒径１０ｎｍ）をサン
ドミル装置によって水中に分散させた液（固形分５％）
５ｇとケイ酸エチル１ｇ、エタノール４ｇ、０．２Ｎ塩
酸１．２ｇ、ビスアセチルアセトナトチタンジイソプロ
ポキシド０．２ｇとを混合し、超音波照射して酸化錫が
分散した塗布液Ｆを用いた以外は例１と同様にして行っ
た。Example 4 A liquid in which tin oxide containing 10% by weight of antimony (average particle size 10 nm) was dispersed in water by means of a sand mill instead of the liquid B of Example 1 (solid content 5%)
5 g of ethyl silicate, 1 g of ethanol, 4 g of ethanol, 1.2 g of 0.2N hydrochloric acid, and 0.2 g of bisacetylacetonato titanium diisopropoxide were mixed, and the coating liquid F in which tin oxide was dispersed by ultrasonic irradiation was used. Example 1 was repeated except that
【００３０】得られた膜付きガラスは透明で光彩も目だ
たず、また、Ｔuvは９％、Ｔv は８７％、ＴE は７２％
であったが、テーバー摩耗試験を行ったところ、１００
０回後には、塗膜は完全に剥離していた。The obtained glass with a film was transparent and had no brilliance, and T uv was 9%, T v was 87%, and T E was 72%.
However, when the Taber abrasion test was performed, it was 100
After 0 times, the coating film was completely peeled off.
【００３１】（例５）例１のＥ液を中間膜の付いていな
いガラス基板上にスピンコートし、６００℃で５分間焼
き付けた。得られた膜は透明であったが、干渉により反
射光は緑色に着色しており、Ｔuvは５％、Ｔv は８４
％、ＴE は８２％であった。また、テーバー摩耗試験を
行ったところ、１０００回後のヘイズ値変化は４．０％
であった。Example 5 Solution E of Example 1 was spin-coated on a glass substrate having no intermediate film and baked at 600 ° C. for 5 minutes. The obtained film was transparent, but the reflected light was colored green due to interference, T uv was 5% and T v was 84.
%, T E was 82%. Further, when a Taber abrasion test was conducted, the change in haze value after 1000 times was 4.0%.
Met.
【００３２】[0032]
【発明の効果】本発明の紫外線吸収ガラスは、優れた熱
線遮蔽性を併わせ持つとともに、光彩を減少させうる。EFFECT OF THE INVENTION The ultraviolet absorbing glass of the present invention has not only excellent heat ray shielding properties but also reduced brilliance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森本 剛 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Go Morimoto 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory
Claims (3)
順次形成された紫外線吸収ガラスにおいて、該中間膜
は、Ｒｕ、Ｃｏ、Ｃｕ、Ｆｅ、ＮｉおよびＶからなる群
から選ばれる少なくとも１種の金属の酸化物を含む膜で
あることを特徴とする紫外線吸収ガラス。1. An ultraviolet-absorbing glass in which an intermediate film and an ultraviolet-absorbing film are sequentially formed on the surface of the glass, wherein the intermediate film is at least one selected from the group consisting of Ru, Co, Cu, Fe, Ni and V. An ultraviolet absorbing glass, which is a film containing an oxide of one kind of metal.
／または酸化チタンを主成分とする膜であることを特徴
とする請求項１記載の紫外線吸収ガラス。2. The ultraviolet absorbing glass according to claim 1, wherein the ultraviolet absorbing film is a film containing cerium oxide and / or titanium oxide as a main component.
ラスの屈折率との中間の屈折率を有し、かつ、４００〜
７００ｎｍの１／４の光学膜厚を有することを特徴とす
る請求項１または２記載の紫外線吸収ガラス。3. The intermediate film has a refractive index intermediate between that of the ultraviolet absorbing film and that of glass, and 400 to 400.
The ultraviolet absorbing glass according to claim 1 or 2, which has an optical film thickness of 1/4 of 700 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28682894A JPH08143335A (en) | 1994-11-21 | 1994-11-21 | Ultraviolet ray absorbing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28682894A JPH08143335A (en) | 1994-11-21 | 1994-11-21 | Ultraviolet ray absorbing glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08143335A true JPH08143335A (en) | 1996-06-04 |
Family
ID=17709571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28682894A Pending JPH08143335A (en) | 1994-11-21 | 1994-11-21 | Ultraviolet ray absorbing glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08143335A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6060154A (en) * | 1997-09-30 | 2000-05-09 | Sumitomo Metal Mining Co., Ltd. | Coating liquid for selective permeable membrane, selective permeable membrane and selective permeable multilayered membrane |
-
1994
- 1994-11-21 JP JP28682894A patent/JPH08143335A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6060154A (en) * | 1997-09-30 | 2000-05-09 | Sumitomo Metal Mining Co., Ltd. | Coating liquid for selective permeable membrane, selective permeable membrane and selective permeable multilayered membrane |
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