JPH05345638A - Ultraviolet-absorbing glass and its production - Google Patents
Ultraviolet-absorbing glass and its productionInfo
- Publication number
- JPH05345638A JPH05345638A JP18313692A JP18313692A JPH05345638A JP H05345638 A JPH05345638 A JP H05345638A JP 18313692 A JP18313692 A JP 18313692A JP 18313692 A JP18313692 A JP 18313692A JP H05345638 A JPH05345638 A JP H05345638A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- ultraviolet absorbing
- absorbing glass
- compound
- producing
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は建築用、自動車用をはじ
めとするガラスの表面に膜を形成することによって紫外
線吸収性を具備させたガラスに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass having a UV-absorbing property by forming a film on the surface of the glass for buildings and automobiles.
【０００２】[0002]
【従来の技術】室内、および車内等へ入射する紫外線を
遮蔽することは、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。従来より、紫外線吸収剤としては、ベン
ゾフェノン、ベンゾトリアゾールなどの有機化合物が主
に知られているが、これらの有機化合物は紫外線の吸収
にともなって劣化が起り易いという問題点があった。2. Description of the Related Art It is important to shield ultraviolet rays entering the interior of a vehicle or the interior of a vehicle, in addition to preventing sunburn of the human body and preventing deterioration of ornaments and the like in the interior and the interior of the vehicle. Conventionally, organic compounds such as benzophenone and benzotriazole have been mainly known as ultraviolet absorbers, but these organic compounds have a problem that they are easily deteriorated due to absorption of ultraviolet rays.
【０００３】また、無機化合物で紫外線吸収性能が高い
として知られている酸化亜鉛を用いた紫外線吸収膜も特
開平１−２１７０８４号公報などで提案されているが、
酸化亜鉛は化学的に耐久性に乏しく、一般ガラス表面処
理用としては使用が困難であるといった問題点があっ
た。An ultraviolet absorbing film using zinc oxide, which is known as an inorganic compound and has a high ultraviolet absorbing performance, is proposed in Japanese Patent Laid-Open No. 1-217084.
Zinc oxide has a problem that it is chemically poor in durability and is difficult to use for general glass surface treatment.
【０００４】[0004]
【発明が解決しようとする課題】本発明は従来技術が有
していた前述の問題点を解消しようとするものであり、
表面に酸化セリウム、酸化チタンおよび酸化珪素の３成
分を主成分としてなる、劣化がなく高耐久性を有する紫
外線吸収膜を形成させた紫外線吸収ガラスを新規に提供
することを目的とするものである。SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems that the prior art has.
It is an object of the present invention to provide a novel ultraviolet absorbing glass on the surface of which an ultraviolet absorbing film having three components of cerium oxide, titanium oxide and silicon oxide as main components and having no deterioration and high durability is formed. ..
【０００５】[0005]
【課題を解決するための手段】本発明は前述の問題点を
解決すべくなされたものであり、キレート配位子と錯体
を形成したセリウム塩と、珪素化合物と、チタン化合物
とを主成分として含む塗布液をガラス基体上に塗布した
後、３００℃以上に加熱することによって紫外線吸収膜
を形成することを特徴とする紫外線吸収ガラスの製造方
法を提供するものである。The present invention has been made to solve the above-mentioned problems, and contains a cerium salt complexed with a chelate ligand, a silicon compound, and a titanium compound as main components. The present invention provides a method for producing an ultraviolet absorbing glass, which comprises forming an ultraviolet absorbing film by applying a coating liquid containing the same on a glass substrate and then heating it to 300 ° C. or higher.
【０００６】原料セリウム塩としては塩化セリウム、硝
酸セリウム、硫酸セリウム等が使用できるが、アルコー
ル等の有機溶剤に溶解させ易いという点で塩化セリウ
ム、硝酸セリウムが比較的好適に使用できる。As the raw material cerium salt, cerium chloride, cerium nitrate, cerium sulfate and the like can be used, but cerium chloride and cerium nitrate are relatively suitable because they are easily dissolved in an organic solvent such as alcohol.
【０００７】原料セリウム塩は、キレート配位子と錯体
を形成させて使用することが重要である。セリウム無機
塩をそのまま用いると乾燥、加熱時に酸化セリウムの結
晶が析出し易くなり、膜の透明性が損なわれるおそれが
ある。該キレート配位子としては、β−ジケトンの１種
であるアセチルアセトンを用いると、そのキレート環の
安定性故に塗布後の乾燥時に酸化セリウムの結晶が析出
して白化するのを防止できる。配位させる配位子の量と
しては、Ｃ5 Ｈ8 Ｏ2 ／Ｃｅのモル比で１以上３以下と
するとよい。アセチルアセトンがこれより少ないと白化
しやすくなり、またこれより多くてもセリウムと反応で
きないため、無駄になる。It is important that the raw material cerium salt is used by forming a complex with a chelate ligand. If the cerium inorganic salt is used as it is, cerium oxide crystals are likely to precipitate during drying and heating, which may impair the transparency of the film. When acetylacetone, which is one of β-diketones, is used as the chelate ligand, it is possible to prevent cerium oxide crystals from being deposited and whitening due to the stability of the chelate ring during the drying after coating. The amount of the ligand to be coordinated is preferably 1 or more and 3 or less in terms of the molar ratio of C 5 H 8 O 2 / Ce. If the amount of acetylacetone is less than this, whitening is likely to occur, and if more than this amount, it cannot react with cerium, which is wasted.
【０００８】キレート配位子と錯体を形成したセリウム
塩は、原料セリウム塩とキレート配位子となる有機化合
物とを反応させることによって容易に得られる。この時
に、無溶剤中で直接配位子とセリウム塩を反応させても
良いし、生成物の溶媒となるアルコール等の有機溶剤中
で反応させても良い。また、反応が進みにくい時には、
加熱するなどして反応を促進させることもできる。The cerium salt complexed with the chelate ligand can be easily obtained by reacting the raw material cerium salt with an organic compound serving as the chelate ligand. At this time, the ligand and the cerium salt may be directly reacted in the absence of a solvent, or may be reacted in an organic solvent such as alcohol which is a solvent for the product. Also, when the reaction is difficult to proceed,
The reaction can be promoted by heating.
【０００９】珪素化合物としては、ＳｉＲm （ＯＲ’）
4-m （ただし、Ｒ、Ｒ’はアルキル基、ｍ＝０〜３）で
表される珪素化合物、およびこれらの重合物の中から選
ばれる少なくとも１種が挙げられる。これら珪素化合物
はそのまま用いてもよく、また酸触媒下等で加水分解し
て用いてもよい。As the silicon compound, SiR m (OR ')
4-m (where R and R ′ are alkyl groups, m = 0 to 3), and a silicon compound represented by at least one selected from these polymers. These silicon compounds may be used as they are, or may be hydrolyzed and used in the presence of an acid catalyst or the like.
【００１０】チタン化合物としては、ＴｉＬm （ＯＲ）
4-m （ただし、Ｌ＝キレート配位子、Ｒ＝アルキル基、
ｍ＝０〜２）の形で表されるチタンアルコキシド、チタ
ンキレート化合物、およびこれらの重合物から選ばれる
少なくとも１種が挙げられる。As the titanium compound, TiL m (OR)
4-m (where L = chelate ligand, R = alkyl group,
At least one selected from a titanium alkoxide represented by the form of m = 0 to 2), a titanium chelate compound, and a polymer thereof is used.
【００１１】例として挙げればテトライソプロポキシチ
タンＴｉ（ＯＣ3 Ｈ7 ）4 、モノアセチルアセトナトチ
タントリイソプロポキシドＴｉ（Ｃ3 Ｈ7 Ｏ2 ）（ＯＣ
3 Ｈ7 ）3 、ジアセチルアセトナトチタンジイソプロポ
キシドＴｉ（Ｃ3 Ｈ7 Ｏ2 ）2 （ＯＣ3 Ｈ7 ）2 、ジエ
チルアセトアセタトチタンジイソプロポキシドＴｉ（Ｃ
6 Ｈ9 Ｏ2 ）2 （ＯＣ3 Ｈ7 ）2 あるいはそれらのブト
キシドなどである。As an example, tetraisopropoxy titanium Ti (OC 3 H 7 ) 4 , monoacetylacetonato titanium triisopropoxide Ti (C 3 H 7 O 2 ) (OC
3 H 7 ) 3 , diacetylacetonato titanium diisopropoxide Ti (C 3 H 7 O 2 ) 2 (OC 3 H 7 ) 2 , diethyl acetoacetato titanium diisopropoxide Ti (C
6 H 9 O 2 ) 2 (OC 3 H 7 ) 2 or butoxides thereof.
【００１２】これらの中でも、キレート配位子が少なく
とも１つ配位したものを用いる方が製造される膜がより
白濁しにくくなり、また液の保存安定性もより良くなる
ので好ましい。チタン化合物はそのまま用いてもよく、
また加水分解して用いてもよい。Of these, it is preferable to use one in which at least one chelate ligand is coordinated, because the film to be produced is less likely to become cloudy and the storage stability of the liquid is better. The titanium compound may be used as it is,
It may also be used after being hydrolyzed.
【００１３】本発明の塗布液において、液中のＴｉ／Ｓ
ｉの存在比は、モル比で１．０以上３．０以下であるこ
とが望ましい。Ｔｉの存在比がこれより低いと紫外線吸
収能が低くなり、また膜の透明性も悪化する。またこれ
より高いと、可視光の反射率が非常に高くなり、可視光
透過率が低下するとともに、成膜性も悪化する。In the coating solution of the present invention, Ti / S in the solution is
The abundance ratio of i is preferably 1.0 or more and 3.0 or less in terms of molar ratio. If the abundance ratio of Ti is lower than this range, the ultraviolet absorptivity becomes low and the transparency of the film also deteriorates. On the other hand, if it is higher than this, the reflectance of visible light becomes very high, the transmittance of visible light is lowered, and the film forming property is deteriorated.
【００１４】また、本発明の塗布液において、液中のＴ
ｉ／Ｃｅ存在比は、モル比で０．５以上１．５以下、好
ましくは０．５以上１．０以下であることが望ましい。
Ｔｉの存在比がこれより低いと膜の透明性が損なわれ易
くなるばかりでなく、紫外線吸収能も低下する。またこ
れより高くても紫外線吸収能が低下し、また成膜性も低
下するので好ましくない。In the coating solution of the present invention, T in the solution is
The i / Ce abundance ratio is 0.5 or more and 1.5 or less, preferably 0.5 or more and 1.0 or less in terms of molar ratio.
If the abundance ratio of Ti is lower than this, not only the transparency of the film tends to be impaired, but also the ultraviolet absorptivity is lowered. Further, if it is higher than this, the ultraviolet absorbing ability is lowered and the film forming property is also lowered, which is not preferable.
【００１５】本発明の塗布液は、酸化物換算の総固形分
量として１．０％以上１５．０％以下であることが好ま
しい。固形分量がこれ以下では、１回の塗布で得られる
膜の膜厚が薄くなり、所望の紫外線吸収能を有する膜を
得るためには数回塗布を行わなくてはならず不便であ
り、また固形分量がこれより高いと塗布液の寿命が短く
なり易い。希釈用の溶剤としては通常のアルコールや炭
化水素、エステル、エーテルアルコール、グリコール等
の有機溶剤が適宜使用できる。また、ガラスとの濡れ性
を向上させるために種々の界面活性剤を添加してもよ
い。The coating solution of the present invention preferably has a total solid content of oxide of 1.0% or more and 15.0% or less. If the solid content is less than this, the thickness of the film obtained by one-time coating becomes thin, and it is inconvenient to perform coating several times in order to obtain a film having a desired ultraviolet absorption ability. When the solid content is higher than this range, the life of the coating solution tends to be shortened. As the solvent for dilution, an ordinary organic solvent such as alcohol, hydrocarbon, ester, ether alcohol or glycol can be appropriately used. Further, various surfactants may be added to improve wettability with glass.
【００１６】このようにして得られた塗布液をガラス基
体上へ塗布する際の塗布方法としては、従来用いられて
きた方法、すなわちディップコート法、スピンコート
法、スプレーコート法、ロールコート法、メニスカスコ
ート法、スクリーン印刷法、フレキソ印刷法等が利用で
きる。As a coating method for coating the coating liquid thus obtained on a glass substrate, a conventionally used method, that is, a dip coating method, a spin coating method, a spray coating method, a roll coating method, A meniscus coating method, a screen printing method, a flexo printing method, etc. can be used.
【００１７】塗布された膜は乾燥の後、加熱することに
よって金属化合物が酸化物になり、緻密な透明無機膜と
なるが、このときの加熱温度は３００℃〜ガラスの軟化
点の間で選ぶことができる。温度がこれ以下では金属有
機化合物から酸化物への分解が充分に進行しないため
に、紫外線吸収能が劣るばかりでなく、膜の強度も不足
する。When the applied film is dried and then heated, the metal compound becomes an oxide and becomes a dense transparent inorganic film, and the heating temperature at this time is selected between 300 ° C. and the softening point of the glass. be able to. If the temperature is lower than this, the decomposition of the metal organic compound to the oxide does not proceed sufficiently, so that not only the ultraviolet absorption ability is deteriorated but also the strength of the film is insufficient.
【００１８】また、本発明の製造方法によって得られた
紫外線吸収膜は、更にその上に酸化珪素やフッ化マグネ
シウムのような低屈折率の透明膜を形成させて反射防止
性能を持たせることもできる。Further, the ultraviolet absorbing film obtained by the manufacturing method of the present invention may be further provided with an antireflection property by forming a transparent film having a low refractive index such as silicon oxide or magnesium fluoride thereon. it can.
【００１９】[0019]
【実施例】以下に本発明の実施例を挙げ更に説明を行う
が、本発明はこれらに限定されるものではない。以下の
実施例および比較例において得られた膜の評価は、外観
（目視）、紫外線透過率（Ｔuv：ＩＳＯ９０５０）、可
視光線透過率（Ｔv ：ＪＩＳ３１０６）、耐摩耗性試験
（テーバー試験：ＪＩＳ３２２１）、耐薬品試験（０．
１Ｎ−ＮａＯＨ、Ｈ2 ＳＯ4 １０日間浸漬）によって行
った。The present invention will be further described below with reference to examples of the present invention, but the present invention is not limited thereto. The films obtained in the following Examples and Comparative Examples were evaluated by appearance (visual inspection), ultraviolet transmittance (T uv : ISO9050), visible light transmittance (T v : JIS3106), and abrasion resistance test (Taber test: JIS 3221), chemical resistance test (0.
1N-NaOH, H 2 SO 4 10 days immersion).
【００２０】［実施例１および比較例１］硝酸セリウム
６水和物１５０ｇにアセチルアセトン１０４ｇを加え、
撹拌しながら９０℃で１時間反応させ、濃黄色粘ちょう
液を得た。（アセチルアセトン／Ｃｅ＝３（モル比）、
Ａ液とする。） 珪酸エチル重合物（エチルシリケート４０）５０ｇに、
イソプロパノール４４ｇ、０．２Ｎ塩酸水溶液６ｇを加
え、室温で１２時間反応させた（Ｂ液）。[Example 1 and Comparative Example 1] To 150 g of cerium nitrate hexahydrate, 104 g of acetylacetone was added,
The mixture was reacted for 1 hour at 90 ° C. with stirring to obtain a dark yellow viscous liquid. (Acetylacetone / Ce = 3 (molar ratio),
Use liquid A. ) 50 g of ethyl silicate polymer (ethyl silicate 40),
44 g of isopropanol and 6 g of 0.2N aqueous hydrochloric acid solution were added, and the mixture was reacted at room temperature for 12 hours (solution B).
【００２１】テトラプロピルチタネート５０ｇにアセチ
ルアセトン１８ｇ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（Ｃ液）。Ａ，Ｂ，Ｃ液をそ
れぞれ金属が以下の表１の組成になるように混合し、イ
ソプロパノールで総固形分が８．３％になるように希釈
した。18 g of acetylacetone was added to 50 g of tetrapropyl titanate and reacted at room temperature for 12 hours to obtain an isopropanol solution of monoacetylacetonato titanium triisopropoxide (solution C). The liquids A, B, and C were mixed so that the metals had the compositions shown in Table 1 below, and diluted with isopropanol so that the total solid content was 8.3%.
【００２２】[0022]
【表１】 [Table 1]
【００２３】この塗布液を図１に示すようなディップコ
ート装置を用いて、片面をマスキングしたソーダライム
ガラス表面に引き上げ塗布し、１５０℃で５分乾燥させ
た後６００℃の電気炉で５分間焼成を行った。形成され
た紫外線吸収膜の膜厚はいずれも２００ｎｍであった。
得られた膜の特性を表２に示す。Using a dip coater as shown in FIG. 1, this coating solution was pulled up and coated on the surface of soda lime glass with one side masked, dried at 150 ° C. for 5 minutes, and then dried in an electric furnace at 600 ° C. for 5 minutes. Firing was performed. The formed ultraviolet absorbing films each had a thickness of 200 nm.
The characteristics of the obtained film are shown in Table 2.
【００２４】[0024]
【表２】 [Table 2]
【００２５】ここで、耐摩耗性試験はテーバー試験３０
０回転後、および耐薬品試験は１０日間浸漬後の膜の状
態を示しており、○は試験後も膜の剥離がないことを示
す。また、外観の○はクラックや白濁がなく、透明であ
ることを示す。（以下同じ）Here, the abrasion resistance test is Taber test 30.
After 0 rotation and the chemical resistance test, the state of the film after immersion for 10 days is shown, and ◯ means that the film does not peel off even after the test. In addition, ◯ in the appearance means that there is no crack or white turbidity and it is transparent. (same as below)
【００２６】［実施例２および比較例２］硝酸セリウム
６水和物１５０ｇにアセチルアセトン６９ｇを加え、撹
拌しながら９０℃で１時間反応させ、黄色粘ちょう液を
得た。（アセチルアセトン／Ｃｅ＝２（モル比）、Ｄ液
とする。）[Example 2 and Comparative Example 2] To 150 g of cerium nitrate hexahydrate, 69 g of acetylacetone was added, and the mixture was reacted at 90 ° C for 1 hour with stirring to obtain a yellow viscous liquid. (Acetylacetone / Ce = 2 (molar ratio), referred to as liquid D.)
【００２７】テトラプロピルチタネート５０ｇにアセチ
ルアセトン３６ｇを加えて室温で１２時間反応させ、ジ
アセチルアセトナトチタンジイソプロポキシドのイソプ
ロパノール溶液を得た（Ｅ液）。Ｄ、Ｅおよび実施例１
に示したＢ液をそれぞれ金属が以下の表３の組成になる
ように混合し、エタノールで総固形分が１０．０％にな
るように希釈した。36 g of acetylacetone was added to 50 g of tetrapropyl titanate and reacted at room temperature for 12 hours to obtain an isopropanol solution of diacetylacetonato titanium diisopropoxide (solution E). D, E and Example 1
The solutions B shown in 1 above were mixed so that the metals had the compositions shown in Table 3 below, and diluted with ethanol so that the total solid content was 10.0%.
【００２８】[0028]
【表３】 [Table 3]
【００２９】この塗布液を図１に示すようなディップコ
ート装置で、ソーダライムガラスの両面に引き上げ塗布
し、１５０℃で５分乾燥させた後３００℃で３０分間焼
成を行った。試料を室温まで冷却した後、該紫外線吸収
膜の上に、Ｂ液をイソプロパノールで酸化珪素換算固形
分４重量％に希釈した液を、同じディップコート装置で
両面に引き上げ塗布し、１５０℃で５分乾燥した後再度
３００℃で３０分間焼成を行った。形成された下層膜
（紫外線吸収膜）の膜厚はいずれも２００ｎｍ、上層膜
（酸化珪素膜）の膜厚はいずれも１００ｎｍであった。
得られた膜の特性を表４に示す。This coating solution was pulled up and coated on both sides of soda lime glass by a dip coater as shown in FIG. 1, dried at 150 ° C. for 5 minutes, and then baked at 300 ° C. for 30 minutes. After cooling the sample to room temperature, a solution prepared by diluting solution B with isopropanol to a solid content of 4% by weight of silicon oxide on the ultraviolet absorbing film was pulled up on both sides by the same dip coating apparatus and applied at 150 ° C. After minute drying, baking was performed again at 300 ° C. for 30 minutes. The formed lower layer film (ultraviolet absorbing film) had a film thickness of 200 nm, and the upper layer film (silicon oxide film) had a film thickness of 100 nm.
The characteristics of the obtained film are shown in Table 4.
【００３０】[0030]
【表４】 [Table 4]
【００３１】［実施例３および比較例３］硝酸セリウム
６水和物１５０ｇにアセチルアセトン３４．５ｇとヘキ
シレングリコール１００ｇを加え、撹拌しながら９０℃
で１時間反応させ、淡黄色粘ちょう液を得た。（アセチ
ルアセトン／Ｃｅ＝１（モル比）、Ｆ液とする。）Example 3 and Comparative Example 3 To 150 g of cerium nitrate hexahydrate, 34.5 g of acetylacetone and 100 g of hexylene glycol were added, and the mixture was stirred at 90 ° C.
And reacted for 1 hour to obtain a pale yellow viscous liquid. (Acetylacetone / Ce = 1 (molar ratio), liquid F)
【００３２】珪酸エチル重合物（エチルシリケート４
０）５０ｇに、ヘキシレングリコール４４ｇ、０．２Ｎ
塩酸水溶液６ｇを加え、室温で１２時間反応させた（Ｇ
液）。Ｆ，Ｇおよびテトラブチルチタネートをそれぞれ
金属が以下の表５の組成になるように混合し、ヘキシレ
ングリコールで総固形分が１２％になるように希釈し
た。Ethyl silicate polymer (ethyl silicate 4
0) 50 g, hexylene glycol 44 g, 0.2N
6 g of hydrochloric acid aqueous solution was added, and the mixture was reacted at room temperature for 12 hours (G
liquid). F, G and tetrabutyl titanate were mixed so that the metals had the compositions shown in Table 5 below, and diluted with hexylene glycol so that the total solid content was 12%.
【００３３】[0033]
【表５】 [Table 5]
【００３４】この塗布液をソーダライムガラス上にフレ
キソ印刷機を用いて印刷塗布し、１５０℃で５分乾燥さ
せた後５００℃の電気炉で１０分間焼成を行った。形成
された紫外線吸収膜の膜厚はいずれも１６０ｎｍであっ
た。得られた膜の特性を表６に示す。This coating solution was applied on soda lime glass by printing using a flexographic printing machine, dried at 150 ° C. for 5 minutes, and then baked at 500 ° C. in an electric furnace for 10 minutes. The formed ultraviolet absorbing films each had a thickness of 160 nm. The characteristics of the obtained film are shown in Table 6.
【００３５】[0035]
【表６】 [Table 6]
【００３６】［比較例４］実施例１に示されるＡ液の代
わりに、硝酸セリウムのエタノール溶液（ＣｅＯ2 換算
１０重量％）を用いて、表１の実施例１−ｂおよび１−
ｄの組成で合成した塗布液を用いる以外は実施例１と同
様に行った。得られた膜の特性を表７に示す。[Comparative Example 4] An ethanol solution of cerium nitrate (10% by weight in terms of CeO 2 ) was used in place of the solution A shown in Example 1, and Examples 1-b and 1-in Table 1 were used.
The same procedure as in Example 1 was performed except that the coating solution synthesized with the composition of d was used. The characteristics of the obtained film are shown in Table 7.
【００３７】[0037]
【表７】 [Table 7]
【００３８】[0038]
【発明の効果】本発明によれば、紫外線を９０％以上遮
蔽でき、劣化がなく、外観も良好な紫外線吸収ガラスを
提供できる。また、耐久性も優れているので建築用や自
動車用の窓ガラスに使用可能である。According to the present invention, it is possible to provide an ultraviolet absorbing glass which can shield 90% or more of ultraviolet rays, is not deteriorated and has a good appearance. Further, since it has excellent durability, it can be used as a window glass for construction and automobiles.
【図１】実施例１で用いたディップコート装置の概略斜
視図FIG. 1 is a schematic perspective view of a dip coating device used in Example 1.
１：ガラス基板 ２：液だめ ３：塗布液 ４：フード ５：プーリー 1: Glass substrate 2: Liquid reservoir 3: Coating liquid 4: Hood 5: Pulley
Claims (8)
塩と、珪素化合物と、チタン化合物とを主成分として含
む塗布液をガラス基体上に塗布した後、３００℃以上に
加熱することによって表面に紫外線吸収膜を形成するこ
とを特徴とする紫外線吸収ガラスの製造方法。1. A surface of a glass substrate coated with a coating liquid containing a cerium salt complexed with a chelate ligand, a silicon compound and a titanium compound as main components, and then heated to 300 ° C. or higher. A method for producing an ultraviolet absorbing glass, which comprises forming an ultraviolet absorbing film on the substrate.
セトンであることを特徴とする請求項１記載の紫外線吸
収ガラスの製造方法。2. The method for producing an ultraviolet absorbing glass according to claim 1, wherein the chelating ligand of the cerium salt is acetylacetone.
4-m （ただし、Ｒ、Ｒ’はアルキル基、ｍ＝０〜３）の
形で表される珪素化合物、およびこれらの重合物から選
ばれる少なくとも１種を含むことを特徴とする請求項１
記載の紫外線吸収ガラスの製造方法。3. SiR m (OR ′) as a silicon compound
4. A silicon compound represented by the form of 4-m (wherein R and R ′ are alkyl groups, m = 0 to 3), and at least one selected from polymers thereof.
A method for producing the ultraviolet-absorbing glass described.
4-m （ただし、Ｌ＝キレート配位子、Ｒ＝アルキル基、
ｍ＝０〜２）の形で表されるチタンアルコキシド、チタ
ンキレート化合物、およびこれらの重合物から選ばれる
少なくとも１種を含むことを特徴とする請求項１記載の
紫外線吸収ガラスの製造方法。4. TiL m (OR) as a titanium compound
4-m (where L = chelate ligand, R = alkyl group,
The method for producing an ultraviolet absorbing glass according to claim 1, further comprising at least one selected from titanium alkoxide represented by the form of m = 0 to 2), a titanium chelate compound, and a polymer thereof.
上３．０以下であることを特徴とする請求項１記載の紫
外線吸収ガラスの製造方法。5. The method for producing an ultraviolet absorbing glass according to claim 1, wherein the molar ratio of Ti / Si in the coating liquid is 1.0 or more and 3.0 or less.
上１．５以下であることを特徴とする請求項１記載の紫
外線吸収ガラスの製造方法。6. The method for producing an ultraviolet absorbing glass according to claim 1, wherein the molar ratio of Ti / Ce in the coating liquid is 0.5 or more and 1.5 or less.
線吸収ガラス。7. An ultraviolet absorbing glass manufactured by the manufacturing method according to claim 1.
収ガラスの表面に更に酸化珪素を主成分とする低屈折率
膜が形成され、反射防止性が付与された紫外線吸収ガラ
ス。8. An ultraviolet absorbing glass having an antireflection property, which is obtained by further forming a low refractive index film containing silicon oxide as a main component on the surface of the ultraviolet absorbing glass produced by the method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18313692A JP3357090B2 (en) | 1992-06-17 | 1992-06-17 | Manufacturing method of ultraviolet absorbing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18313692A JP3357090B2 (en) | 1992-06-17 | 1992-06-17 | Manufacturing method of ultraviolet absorbing glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05345638A true JPH05345638A (en) | 1993-12-27 |
| JP3357090B2 JP3357090B2 (en) | 2002-12-16 |
Family
ID=16130433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18313692A Expired - Fee Related JP3357090B2 (en) | 1992-06-17 | 1992-06-17 | Manufacturing method of ultraviolet absorbing glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3357090B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08104544A (en) * | 1994-09-30 | 1996-04-23 | Central Glass Co Ltd | Heat ray reflecting and ultraviolet ray absorbing glass and its production |
| WO2008133773A1 (en) * | 2007-04-27 | 2008-11-06 | Guardian Industries Corp. | Coated glass substrate with heat treatable ultraviolet blocking characteristics |
| JP2016191003A (en) * | 2015-03-31 | 2016-11-10 | 日揮触媒化成株式会社 | Coating liquid for forming transparent film, method for producing the same, and transparent film-fitted base material |
-
1992
- 1992-06-17 JP JP18313692A patent/JP3357090B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08104544A (en) * | 1994-09-30 | 1996-04-23 | Central Glass Co Ltd | Heat ray reflecting and ultraviolet ray absorbing glass and its production |
| WO2008133773A1 (en) * | 2007-04-27 | 2008-11-06 | Guardian Industries Corp. | Coated glass substrate with heat treatable ultraviolet blocking characteristics |
| US8409663B2 (en) | 2007-04-27 | 2013-04-02 | Guardian Industries Corp. | Method of making a coated glass substrate with heat treatable ultraviolet blocking characteristics |
| JP2016191003A (en) * | 2015-03-31 | 2016-11-10 | 日揮触媒化成株式会社 | Coating liquid for forming transparent film, method for producing the same, and transparent film-fitted base material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3357090B2 (en) | 2002-12-16 |
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