JPH0624794A - Production of ultraviolet-shielding glass - Google Patents
Production of ultraviolet-shielding glassInfo
- Publication number
- JPH0624794A JPH0624794A JP20447792A JP20447792A JPH0624794A JP H0624794 A JPH0624794 A JP H0624794A JP 20447792 A JP20447792 A JP 20447792A JP 20447792 A JP20447792 A JP 20447792A JP H0624794 A JPH0624794 A JP H0624794A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- cucl
- chlorine
- fine particles
- mother glass
- 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.)
- Withdrawn
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、紫外線をシャープにカ
ットする紫外線カットガラスの製造方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ultraviolet cut glass which sharply cuts ultraviolet rays.
【０００２】[0002]
【従来の技術】ＣｕＣｌは紫外線領域にシャープな吸収
をもつことが知られている。このようなＣｕＣｌ微粒子
を析出したガラスとして、特公昭４６−３４６４号公報
や特開平３−１７４３３７号公報に記載のものが知られ
ている。これらのガラスは、ＣｕＣｌ成分を含む原料を
高温で溶解して、まずＣｕＣｌ成分を含有するガラスを
作製し、このガラスを所定の温度で熱処理を行なうこと
によってガラス中にＣｕＣｌ微粒子を析出させる、いわ
ゆる溶融析出法によって製造される。CuCl is known to have sharp absorption in the ultraviolet region. As glass in which such CuCl fine particles are deposited, those described in JP-B-46-3464 and JP-A-3-174337 are known. In these glasses, a raw material containing a CuCl component is melted at a high temperature to first produce a glass containing a CuCl component, and the glass is heat-treated at a predetermined temperature to precipitate CuCl fine particles in the glass. It is manufactured by the melt precipitation method.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記方
法は、ガラスを高温で溶融するというプロセスが含まれ
るため、揮散しやすいＣｕＣｌ成分をガラス中に含有さ
せるためには比較的低温で溶解する必要があり、そのた
めＣｕＣｌ微粒子が析出可能なガラス組成は限定される
という課題があった。However, since the above method includes a process of melting glass at a high temperature, it is necessary to melt the glass at a relatively low temperature in order to contain a CuCl component which is easily volatilized in the glass. Therefore, there is a problem that the glass composition in which the CuCl fine particles can be deposited is limited.
【０００４】[0004]
【課題を解決するための手段】本発明は、前述の課題を
解決するためになされたもので、塩素を含有する母ガラ
スを製造し、母ガラスへ銅イオンを拡散してガラス中に
ＣｕＣｌ微粒子を析出することを特徴とする紫外線カッ
ト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 produces a mother glass containing chlorine, diffuses copper ions into the mother glass to form CuCl fine particles in the glass. The present invention provides a method for producing an ultraviolet cut glass, which comprises depositing
【０００５】本発明の紫外線カットガラスの製造方法
は、母ガラスへ銅イオンを拡散する工程が比較的低温で
行なえるため、高温でＣｕＣｌ成分をガラス中に溶融さ
せるプロセスを必要とせず、幅広い組成の母ガラス中に
ＣｕＣｌ微粒子を析出させることができる。したがっ
て、母ガラスの組成としては塩素を含有することを除き
特に限定されない。母ガラスとしては、後記するよう
に、塩素を原料に混合しそれをガラス化したものであっ
てもよく、塩素を含有しない多孔質ガラスを製造しその
細孔に塩素を導入し無孔化したものであってもよい。In the method for producing the ultraviolet cut glass of the present invention, the step of diffusing copper ions into the mother glass can be carried out at a relatively low temperature, so that the process of melting the CuCl component into the glass at a high temperature is not required and the composition of a wide range can be obtained. CuCl fine particles can be deposited in the mother glass of. Therefore, the composition of the mother glass is not particularly limited except that it contains chlorine. As the mother glass, as will be described later, it may be one obtained by mixing chlorine with a raw material and vitrifying it, producing a chlorine-free porous glass and introducing chlorine into its pores to make it non-porous. It may be one.
【０００６】母ガラスへの銅イオンの拡散方法として
は、銅イオンを単独で母ガラスに拡散させてもよいし、
母ガラスのイオンとのイオン交換によって銅イオンを母
ガラスに拡散させてもよい。イオン交換は、塩素を含有
する母ガラスを、銅を含む溶融塩やペーストと接触させ
ることにより行なうことが好ましいが、銅を含有する水
溶液と接触させることによっても行なえる。As a method of diffusing copper ions into the mother glass, copper ions may be diffused into the mother glass alone,
Copper ions may be diffused into the mother glass by ion exchange with ions of the mother glass. The ion exchange is preferably carried out by bringing the mother glass containing chlorine into contact with a molten salt or paste containing copper, but can also be carried out by bringing it into contact with an aqueous solution containing copper.
【０００７】イオン交換は、母ガラスに存在する、例え
ばＮａ+ 、Ｌｉ+ 、Ｋ+ 、Ｒｂ+ などの１価イオンまた
はＣａ2+、Ｍｇ2+、Ｓｒ2+、Ｂａ2+などの２価イオン
と、銅化合物の溶融塩、ペースト、水溶液などに存在す
るＣｕ+ イオンまたはＣｕ2+イオンとのイオン交換によ
って母ガラスへ銅イオンが拡散し、母ガラスの塩素と結
合することによってＣｕＣｌ微粒子を析出する。この場
合、イオン交換によって母ガラスに銅イオンが拡散する
ため、１μｍ以上の深さまで母ガラスに銅イオンを導入
させることが可能となり、したがって、１μｍ以上の深
さまでＣｕＣｌ微粒子を析出させることが可能となる。Ion exchange is a molten salt of a copper compound with a monovalent ion such as Na +, Li +, K +, Rb + or a divalent ion such as Ca2 +, Mg2 +, Sr2 +, Ba2 + existing in the mother glass. Copper ions diffuse into the mother glass by ion exchange with Cu + ions or Cu2 + ions present in the paste, aqueous solution, etc., and bond with chlorine in the mother glass to precipitate CuCl fine particles. In this case, since copper ions diffuse into the mother glass by ion exchange, it is possible to introduce the copper ions into the mother glass to a depth of 1 μm or more, and thus it is possible to deposit CuCl fine particles to a depth of 1 μm or more. Become.
【０００８】また、塩素を含有する母ガラスと銅イオン
の拡散を行なった後に、ガラスの転移温度以上の温度で
熱処理を行なうことによって、さらに多量のＣｕＣｌ微
粒子をガラスに析出することも可能である。It is also possible to deposit a larger amount of CuCl fine particles on the glass by diffusing the mother glass containing chlorine and the copper ions and then performing a heat treatment at a temperature higher than the transition temperature of the glass. .
【０００９】母ガラス中の塩素の含有量は０．００１〜
１０重量％であることが好ましい。塩素の含有量が０．
００１重量％未満の場合、ＣｕＣｌ微粒子のガラス中へ
の析出が得られ難く好ましくない。逆に、１０重量％を
超える場合は、ＣｕＣｌ微粒子の粒径の制御が困難にな
るとともにガラスの耐候性が劣化してしまうため好まし
くない。そして、この範囲のうち、塩素の含有量が０．
０１〜５重量％の場合、均一で制御されたＣｕＣｌ微粒
子が容易に析出しうるので特に好ましい。The content of chlorine in the mother glass is 0.001-
It is preferably 10% by weight. The chlorine content is 0.
When it is less than 001% by weight, it is difficult to obtain CuCl fine particles in the glass, which is not preferable. On the contrary, if it exceeds 10% by weight, it becomes difficult to control the particle diameter of the CuCl fine particles and the weather resistance of the glass deteriorates, which is not preferable. In this range, the chlorine content is 0.
The amount of 01 to 5% by weight is particularly preferable because uniform and controlled CuCl fine particles can be easily deposited.
【００１０】塩素を含有する母ガラスの製造法としては
特に制限がないが、例えば、ＮａＣｌなどの塩化物を含
むガラス原料バッチを溶融して、ガラス化することによ
り製造する方法、分相後、酸溶出して作製した多孔質ガ
ラス、ゾルゲル法により作製した多孔質ガラス、または
ＣＶＤ法で作製した多孔質ガラスを高温で塩素処理後焼
結して無孔化することによって製造する方法等がある。The method for producing the mother glass containing chlorine is not particularly limited, but for example, a method for producing by melting and vitrifying a glass raw material batch containing a chloride such as NaCl, after phase separation, There is a method in which a porous glass produced by elution with an acid, a porous glass produced by a sol-gel method, or a porous glass produced by a CVD method is treated by chlorine treatment at a high temperature and then sintered to render it non-porous. .
【００１１】銅イオンは、ＣｕＣｌ、ＣｕＣｌ2 、Ｃｕ
Ｂｒ、ＣｕＢｒ2 、ＣｕI 、ＣｕＳＯ4 、Ｃｕ（ＮＯ3
）2 、Ｃｕ2 Ｏ、ＣｕＯ、ＣｕＳのうち少なくとも１
つの化合物で形成されることがイオン交換を効率的に行
なう上で好ましい。銅を含有する溶融塩やペーストとガ
ラスとの間でイオン交換を行なう温度としては、塩素を
含むガラスのガラス転移温度以上軟化温度以下の温度範
囲でイオン交換を行なう場合と、ガラス転移温度以下の
温度で行なう場合があるが、いずれでもよい。Copper ions are CuCl, CuCl2, Cu
Br, CuBr2, CuI, CuSO4, Cu (NO3
) 2, at least 1 of Cu2 O, CuO, CuS
It is preferable that the two compounds are formed for efficient ion exchange. As the temperature at which ion exchange is performed between the molten salt or paste containing copper and the glass, when performing ion exchange in the temperature range of the glass transition temperature of the glass containing chlorine or more and the softening temperature or less, and the glass transition temperature or less It may be carried out at temperature, but either may be used.
【００１２】これらの化合物の融点等の熱特性は表１に
示したとおりで、各種ガラスの適正なイオン交換温度に
応じた融点等の熱特性をもつ化合物を選べばよい。ま
た、この化合物の融点を制御するために、例えばＮａＣ
ｌ、ＮａＮＯ3 、Ｎａ2 ＳＯ4などの他の塩を適宜混合
することも可能である。The thermal characteristics such as melting point of these compounds are as shown in Table 1, and it suffices to select the compound having the thermal characteristics such as melting point corresponding to the appropriate ion exchange temperature of various glasses. In order to control the melting point of this compound, for example, NaC
It is also possible to appropriately mix other salts such as 1, NaNO3 and Na2 SO4.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
［実施例１〜１０］表２に示す組成（単位：重量％）を
有する母ガラスを溶融法により製造し、１０×１０×１
ｍｍの大きさの板状試料を作製した。これらの試料を表
２に示す溶融塩（単位：重量％）中で表２に示すイオン
交換温度、イオン交換時間でイオン交換を行なった。得
られた試料の表面を洗浄後、試料を２つに割り、その断
面をＥＰＭＡを用いて分析し、ガラス表面からの銅の拡
散深さを求めた。[Examples 1 to 10] A mother glass having a composition (unit: wt%) shown in Table 2 was produced by a melting method, and 10 x 10 x 1
A plate-shaped sample having a size of mm was prepared. These samples were subjected to ion exchange in the molten salt shown in Table 2 (unit: wt%) at the ion exchange temperature and ion exchange time shown in Table 2. After washing the surface of the obtained sample, the sample was divided into two, and the cross section was analyzed using EPMA to determine the diffusion depth of copper from the glass surface.
【００１５】また、得られた試料の分光スペクトルの測
定を行なうとともに、透過型電子顕微鏡観察を行なうこ
とによってガラスに析出するＣｕＣｌ微粒子の粒径を測
定した。その結果、いずれの試料にもＣｕＣｌに特有な
吸収構造が現れ、ガラスに表２に示す粒径のＣｕＣｌ微
粒子が析出していることがわかった。また、銅の拡散深
さは表２に示すように５〜４００μｍであることがわか
った。またこれらのガラスは、紫外線をシャープにカッ
トする性能を有することがわかった。The particle size of the CuCl fine particles deposited on the glass was measured by measuring the spectral spectrum of the obtained sample and observing it with a transmission electron microscope. As a result, it was found that the absorption structure peculiar to CuCl appeared in any of the samples, and CuCl fine particles having the particle sizes shown in Table 2 were deposited on the glass. Further, it was found that the diffusion depth of copper was 5 to 400 μm as shown in Table 2. It was also found that these glasses have a property of sharply cutting ultraviolet rays.
【００１６】［実施例１１〜１２］表２に示す組成のガ
ラスを実施例１と同様に作製し、表２に示す溶融塩中で
表２に示す温度・時間でイオン交換を行なった。イオン
交換終了後に試料を６００℃で３０分間熱処理を行なっ
た。得られた試料の評価は実施例１と同様に行なった。
その結果、これらの試料にはＣｕＣｌに特有な吸収構造
が現れ、ガラス中に表２に示す粒径のＣｕＣｌ微粒子が
析出していることがわかった。また、銅の拡散深さは表
１に示すように８〜１０μｍであることがわかった。ま
たこれらのガラスは、紫外線をシャープにカットする性
能を有することがわかった。[Examples 11 to 12] Glasses having the compositions shown in Table 2 were prepared in the same manner as in Example 1 and subjected to ion exchange in the molten salt shown in Table 2 at the temperature and time shown in Table 2. After completion of the ion exchange, the sample was heat-treated at 600 ° C. for 30 minutes. Evaluation of the obtained sample was performed in the same manner as in Example 1.
As a result, it was found that an absorption structure peculiar to CuCl appeared in these samples, and CuCl fine particles having a particle size shown in Table 2 were precipitated in the glass. Further, it was found that the diffusion depth of copper was 8 to 10 μm as shown in Table 1. It was also found that these glasses have a property of sharply cutting ultraviolet rays.
【００１７】[0017]
【表２】 [Table 2]
【００１８】［実施例１３］溶融・分相法により作製し
た平均細孔径４００ｎｍ、厚さ１．２ｍｍの多孔質ガラ
ス（ガラス組成；ＳｉＯ2 ：９６重量％、Ｂ2 Ｏ3 ：３
重量％、Ａｌ2 Ｏ3：０．３重量％、Ｎａ2 Ｏ：０．１
５重量％）を、５％Ｃｌ2 含有のＮ2 雰囲気中で１２０
０℃に加熱し、無孔化し、塩素を含有する母ガラスを作
製した。蛍光Ｘ線分析の結果、母ガラスには約０．３重
量％のＣｌが均一に含まれていることがわかった。この
塩素を含有する母ガラスをＣｕＣｌ溶融塩中に、１００
０℃で３０分間保持することによりイオン交換を行なっ
た。得られた試料の評価は実施例１と同様に行なった。
その結果、ＣｕＣｌに特有な吸収構造が現れ、ガラスに
粒径３．５ｎｍのＣｕＣｌ微粒子が析出していることが
わかった。また、銅は深さ方向に表面より中央部までほ
ぼ均一に拡散しており、その含有量は０．５重量％拡散
であった。またこのガラスは、紫外線をシャープにカッ
トする性能を有することがわかった。[Example 13] Porous glass (glass composition; SiO2: 96% by weight, B2 O3: 3) having an average pore diameter of 400 nm and a thickness of 1.2 mm produced by the melting / phase separation method.
% By weight, Al2 O3: 0.3% by weight, Na2 O: 0.1
5% by weight) in an N2 atmosphere containing 5% Cl2.
A mother glass containing chlorine was prepared by heating to 0 ° C. to make it non-porous. As a result of fluorescent X-ray analysis, it was found that the mother glass uniformly contained about 0.3% by weight of Cl. The mother glass containing chlorine was added to CuCl molten salt in an amount of 100
Ion exchange was performed by holding at 0 ° C. for 30 minutes. Evaluation of the obtained sample was performed in the same manner as in Example 1.
As a result, it was found that an absorption structure peculiar to CuCl appeared and CuCl fine particles having a particle diameter of 3.5 nm were deposited on the glass. Further, copper was diffused almost uniformly in the depth direction from the surface to the central portion, and its content was 0.5% by weight. It was also found that this glass has a property of sharply cutting ultraviolet rays.
【００１９】［実施例１４］実施例２と同様の方法で作
製した塩素含有母ガラスをＣｕ2 Ｏ溶融塩中に、１２５
０℃で３０間保持した。得られたガラスの評価は実施例
１〜１２と同様に行なった。その結果、ＣｕＣｌに特有
な吸収構造が現れ、ガラス中に粒径６ｎｍのＣｕＣｌ微
粒子が析出していることがわかった。また、銅は深さ方
向に表面より中央部までほぼ均一に拡散しており、その
含有量は０．６重量％であった。またこのガラスは、紫
外線をシャープにカットする性能を有することがわかっ
た。[Embodiment 14] A chlorine-containing mother glass prepared in the same manner as in Embodiment 2 was added to a molten Cu 2 O salt at a concentration of 125
Hold at 0 ° C. for 30 minutes. The obtained glass was evaluated in the same manner as in Examples 1-12. As a result, it was found that an absorption structure peculiar to CuCl appeared and CuCl fine particles having a particle diameter of 6 nm were deposited in the glass. Further, copper diffused almost uniformly from the surface to the central portion in the depth direction, and its content was 0.6% by weight. It was also found that this glass has a property of sharply cutting ultraviolet rays.
【００２０】［実施例１５］Ｓｉ（ＯＣＨ3 ）4 および
ＮａＯＣＨ3 を原料に用い、ゾルゲル法により１０Ｎａ
2 Ｏ−９５ＳｉＯ2 組成の多孔質ゲルを作製した。得ら
れた多孔質ゲルを空気中に４００℃で２時間保持後、５
％Ｃｌ2 含有のＮ2 雰囲気中に６００℃で２時間保持
し、５０ｍｍφ×５ｍｍ厚の塩素含有母ガラスを作製し
た。蛍光Ｘ線分析の結果、この母ガラスは約１重量％の
Ｃl を含有していることがわかった。この塩素含有母ガ
ラスをＣｕＢｒ溶融塩中に５００℃で３０分間保持し
た。得られたガラスの評価は実施例１と同様に行なっ
た。その結果、ＣｕＣｌに特有な吸収構造が現れ、ガラ
ス中に粒径４．５ｎｍのＣｕＣｌ微粒子が析出している
ことがわかった。また、銅の拡散深さは４００μｍであ
ることがわかった。またこのガラスは、紫外線をシャー
プにカットする性能を有することがわかった。[Example 15] Si (OCH3) 4 and NaOCH3 were used as raw materials and 10 Na was obtained by the sol-gel method.
A porous gel having a composition of 2 O-95 SiO 2 was prepared. The obtained porous gel was kept in air at 400 ° C. for 2 hours, and then 5
It was kept at 600 ° C. for 2 hours in a N 2 atmosphere containing% Cl 2 to prepare a chlorine-containing mother glass having a thickness of 50 mmφ × 5 mm. As a result of X-ray fluorescence analysis, this mother glass was found to contain about 1% by weight of Cl. This chlorine-containing mother glass was kept in molten CuBr salt at 500 ° C. for 30 minutes. The obtained glass was evaluated in the same manner as in Example 1. As a result, it was found that an absorption structure peculiar to CuCl appeared and CuCl fine particles having a particle diameter of 4.5 nm were precipitated in the glass. It was also found that the diffusion depth of copper was 400 μm. It was also found that this glass has a property of sharply cutting ultraviolet rays.
【００２１】[0021]
【発明の効果】本発明によれば、高温でＣｕＣｌ成分を
ガラス中に溶融するプロセスを必要としないので、幅広
い組成のガラスにＣｕＣｌ微粒子を析出した紫外線カッ
トガラスを製造することができる。According to the present invention, the process of melting the CuCl component in the glass at a high temperature is not required, so that it is possible to produce an ultraviolet cut glass in which CuCl fine particles are deposited on a glass having a wide range of compositions.
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【手続補正書】[Procedure amendment]
【提出日】平成４年９月１１日[Submission date] September 11, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項４[Name of item to be corrected] Claim 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】イオン交換は、母ガラスに存在する、例え
ばＮａ+ 、Ｌｉ+ 、Ｋ+ 、Ｒｂ+ などの１価イオンまた
はＣａ2+、Ｍｇ2+、Ｓｒ2+、Ｂａ2+などの２価イオン
と、銅化合物の溶融塩、ペースト、水溶液などに存在す
るＣｕ+ イオンまたはＣｕ2+イオンとのイオン交換によ
って母ガラスへ銅イオンが拡散し、母ガラスの塩素と結
合することによってＣｕＣｌ微粒子を析出する。この場
合、イオン交換によって母ガラスに銅イオンが拡散する
ため、１μｍ以上の深さまで母ガラスに銅イオンを導入
させることが可能となり、したがって、１μｍ以上の深
さまでＣｕＣｌ微粒子を析出させることが可能となる。Ion exchange is carried out by using monovalent ions existing in the mother glass such as Na + , Li + , K + and Rb + or divalent ions such as Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+. an ion, a molten salt of a copper compound, paste, diffused copper ions into the base glass by ion exchange with Cu + ions or Cu 2+ ions present in such solution, the CuCl fine particles by combining with chlorine mother glass To deposit. In this case, since copper ions diffuse into the mother glass by ion exchange, it is possible to introduce the copper ions into the mother glass to a depth of 1 μm or more, and thus it is possible to deposit CuCl fine particles to a depth of 1 μm or more. Become.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】銅イオンは、ＣｕＣｌ、ＣｕＣｌ2 、Ｃｕ
Ｂｒ、ＣｕＢｒ2 、ＣｕＩ、ＣｕＳＯ4 、Ｃｕ（ＮＯ
3 ）2 、Ｃｕ2 Ｏ、ＣｕＯ、ＣｕＳのうち少なくとも１
つの化合物で形成されることがイオン交換を効率的に行
なう上で好ましい。銅を含有する溶融塩やペーストとガ
ラスとの間でイオン交換を行なう温度としては、塩素を
含むガラスのガラス転移温度以上軟化温度以下の温度範
囲でイオン交換を行なう場合と、ガラス転移温度以下の
温度で行なう場合があるが、いずれでもよい。Copper ions are CuCl, CuCl 2 , Cu
Br, CuBr 2 , CuI, CuSO 4 , Cu (NO
3 ) 2 , at least 1 of Cu 2 O, CuO, CuS
It is preferable that the two compounds are formed for efficient ion exchange. As the temperature at which ion exchange is performed between the molten salt or paste containing copper and the glass, when performing ion exchange in the temperature range of the glass transition temperature of the glass containing chlorine or more and the softening temperature or less, and the glass transition temperature or less It may be carried out at temperature, but either may be used.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】これらの化合物の融点等の熱特性は表１に
示したとおりで、各種ガラスの適正なイオン交換温度に
応じた融点等の熱特性をもつ化合物を選べばよい。ま
た、この化合物の融点を制御するために、例えばＮａＣ
ｌ、ＮａＮＯ3 、Ｎａ2 ＳＯ4などの他の塩を適宜混合
することも可能である。The thermal characteristics such as melting point of these compounds are as shown in Table 1, and it suffices to select the compound having the thermal characteristics such as melting point corresponding to the appropriate ion exchange temperature of various glasses. In order to control the melting point of this compound, for example, NaC
It is also possible to appropriately mix other salts such as 1, NaNO 3 , and Na 2 SO 4 .
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１３】[0013]
【表１】 [Table 1]
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１８】［実施例１３］溶融・分相法により作製し
た平均細孔径４００ｎｍ、厚さ１．２ｍｍの多孔質ガラ
ス（ガラス組成；ＳｉＯ2 ：９６重量％、Ｂ2 Ｏ3 ：３
重量％、Ａｌ2 Ｏ3：０．３重量％、Ｎａ2 Ｏ：０．１
５重量％）を、５％Ｃｌ2 含有のＮ2 雰囲気中で１２０
０℃に加熱し、無孔化し、塩素を含有する母ガラスを作
製した。蛍光Ｘ線分析の結果、母ガラスには約０．３重
量％のＣｌが均一に含まれていることがわかった。この
塩素を含有する母ガラスをＣｕＣｌ溶融塩中に、１００
０℃で３０分間保持することによりイオン交換を行なっ
た。得られた試料の評価は実施例１と同様に行なった。
その結果、ＣｕＣｌに特有な吸収構造が現れ、ガラスに
粒径３．５ｎｍのＣｕＣｌ微粒子が析出していることが
わかった。また、銅は深さ方向に表面より中央部までほ
ぼ均一に拡散しており、その含有量は０．５重量％拡散
であった。またこのガラスは、紫外線をシャープにカッ
トする性能を有することがわかった。[Example 13] Porous glass having an average pore diameter of 400 nm and a thickness of 1.2 mm produced by the melting / phase separation method (glass composition; SiO 2 : 96% by weight, B 2 O 3 : 3).
% By weight, Al 2 O 3 : 0.3% by weight, Na 2 O: 0.1
5% by weight) in an N 2 atmosphere containing 5% Cl 2
A mother glass containing chlorine was prepared by heating to 0 ° C. to make it non-porous. As a result of fluorescent X-ray analysis, it was found that the mother glass uniformly contained about 0.3% by weight of Cl. The mother glass containing chlorine was added to CuCl molten salt in an amount of 100
Ion exchange was performed by holding at 0 ° C. for 30 minutes. Evaluation of the obtained sample was performed in the same manner as in Example 1.
As a result, it was found that an absorption structure peculiar to CuCl appeared and CuCl fine particles having a particle diameter of 3.5 nm were deposited on the glass. Further, copper was diffused almost uniformly in the depth direction from the surface to the central portion, and the content thereof was 0.5% by weight diffusion. It was also found that this glass has a property of sharply cutting ultraviolet rays.
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１９】［実施例１４］実施例２と同様の方法で作
製した塩素含有母ガラスをＣｕ2 Ｏ溶融塩中に、１２５
０℃で３０間保持した。得られたガラスの評価は実施例
１〜１２と同様に行なった。その結果、ＣｕＣｌに特有
な吸収構造が現れ、ガラス中に粒径６ｎｍのＣｕＣｌ微
粒子が析出していることがわかった。また、銅は深さ方
向に表面より中央部までほぼ均一に拡散しており、その
含有量は０．６重量％であった。またこのガラスは、紫
外線をシャープにカットする性能を有することがわかっ
た。[Embodiment 14] A chlorine-containing mother glass prepared in the same manner as in Embodiment 2 is added to a Cu 2 O molten salt in an amount of 125
Hold at 0 ° C. for 30 minutes. The obtained glass was evaluated in the same manner as in Examples 1-12. As a result, it was found that an absorption structure peculiar to CuCl appeared and CuCl fine particles having a particle diameter of 6 nm were deposited in the glass. Further, copper diffused almost uniformly from the surface to the central portion in the depth direction, and its content was 0.6% by weight. It was also found that this glass has a property of sharply cutting ultraviolet rays.
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２０】［実施例１５］Ｓｉ（ＯＣＨ3 ）4 および
ＮａＯＣＨ3 を原料に用い、ゾルゲル法により１０Ｎａ
2 Ｏ−９５ＳｉＯ2 組成の多孔質ゲルを作製した。得ら
れた多孔質ゲルを空気中に４００℃で２時間保持後、５
％Ｃｌ2 含有のＮ2 雰囲気中に６００℃で２時間保持
し、５０ｍｍφ×５ｍｍ厚の塩素含有母ガラスを作製し
た。蛍光Ｘ線分析の結果、この母ガラスは約１重量％の
Ｃｌを含有していることがわかった。この塩素含有母ガ
ラスをＣｕＢｒ溶融塩中に５００℃で３０分間保持し
た。得られたガラスの評価は実施例１と同様に行なっ
た。その結果、ＣｕＣｌに特有な吸収構造が現れ、ガラ
ス中に粒径４．５ｎｍのＣｕＣｌ微粒子が析出している
ことがわかった。また、銅の拡散深さは４００μｍであ
ることがわかった。またこのガラスは、紫外線をシャー
プにカットする性能を有することがわかった。[Example 15] Si (OCH 3 ) 4 and NaOCH 3 were used as raw materials and 10 Na was obtained by the sol-gel method.
A porous gel having a composition of 2 O-95SiO 2 was prepared. The obtained porous gel was kept in air at 400 ° C. for 2 hours, and then 5
It was kept at 600 ° C. for 2 hours in a N 2 atmosphere containing% Cl 2 to prepare a chlorine-containing mother glass having a thickness of 50 mmφ × 5 mm. As a result of X-ray fluorescence analysis, this mother glass was found to contain about 1% by weight of Cl. This chlorine-containing mother glass was kept in molten CuBr salt at 500 ° C. for 30 minutes. The obtained glass was evaluated in the same manner as in Example 1. As a result, it was found that an absorption structure peculiar to CuCl appeared and CuCl fine particles having a particle diameter of 4.5 nm were precipitated in the glass. It was also found that the diffusion depth of copper was 400 μm. It was also found that this glass has a property of sharply cutting ultraviolet rays.
Claims (4)
スへ銅イオンを拡散してガラス中にＣｕＣｌ微粒子を析
出することを特徴とする紫外線カットガラスの製造方
法。1. A method for producing an ultraviolet cut glass, which comprises producing a mother glass containing chlorine and diffusing copper ions into the mother glass to deposit CuCl fine particles in the glass.
換することにより母ガラスへ銅イオンを拡散する請求項
１の紫外線カットガラスの製造方法。2. The method for producing an ultraviolet cut glass according to claim 1, wherein the copper ions are diffused into the mother glass by ion-exchanging the ions of the mother glass with the copper ions.
１０重量％であることを特徴とする請求項１または２の
紫外線カットガラスの製造方法。3. The chlorine content of the mother glass is 0.001 to 0.001.
It is 10% by weight, and the method for producing the ultraviolet cut glass according to claim 1 or 2.
ｒ、ＣｕＢｒ2 、ＣｕI 、ＣｕＳＯ4 、Ｃｕ（ＮＯ3 ）
2 、Ｃｕ2 Ｏ、ＣｕＯ、ＣｕＳのうち少なくとも１つの
化合物より形成される請求項１、２または３の紫外線カ
ットガラスの製造方法。4. Copper ions are CuCl, CuCl2, CuB
r, CuBr2, CuI, CuSO4, Cu (NO3)
The method for producing an ultraviolet cut glass according to claim 1, 2 or 3, which is formed of at least one compound selected from the group consisting of 2, Cu2 O, CuO and CuS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20447792A JPH0624794A (en) | 1992-07-08 | 1992-07-08 | Production of ultraviolet-shielding glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20447792A JPH0624794A (en) | 1992-07-08 | 1992-07-08 | Production of ultraviolet-shielding glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0624794A true JPH0624794A (en) | 1994-02-01 |
Family
ID=16491180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20447792A Withdrawn JPH0624794A (en) | 1992-07-08 | 1992-07-08 | Production of ultraviolet-shielding glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0624794A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006078569A (en) * | 2004-09-07 | 2006-03-23 | Japan Science & Technology Agency | Ultraviolet light filter |
| JPWO2005033031A1 (en) * | 2003-10-06 | 2006-12-14 | 日本板硝子株式会社 | UV transmitting glass and microplate using the same |
| WO2007058185A1 (en) | 2005-11-15 | 2007-05-24 | Isuzu Glass Co., Ltd. | Blue-violet light blocking glass |
| WO2008123378A1 (en) | 2007-03-29 | 2008-10-16 | Isuzu Glass Co., Ltd. | Method for production of distributed refractive index-type optical element having ultraviolet ray-absorbing ability |
| WO2022131275A1 (en) * | 2020-12-18 | 2022-06-23 | Ａｇｃ株式会社 | Glass plate, laminated glass, window glass for building, and window glass for vehicle |
-
1992
- 1992-07-08 JP JP20447792A patent/JPH0624794A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2005033031A1 (en) * | 2003-10-06 | 2006-12-14 | 日本板硝子株式会社 | UV transmitting glass and microplate using the same |
| JP2006078569A (en) * | 2004-09-07 | 2006-03-23 | Japan Science & Technology Agency | Ultraviolet light filter |
| WO2007058185A1 (en) | 2005-11-15 | 2007-05-24 | Isuzu Glass Co., Ltd. | Blue-violet light blocking glass |
| WO2008123378A1 (en) | 2007-03-29 | 2008-10-16 | Isuzu Glass Co., Ltd. | Method for production of distributed refractive index-type optical element having ultraviolet ray-absorbing ability |
| WO2022131275A1 (en) * | 2020-12-18 | 2022-06-23 | Ａｇｃ株式会社 | Glass plate, laminated glass, window glass for building, and window glass for vehicle |
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