JPS62297232A - Production of thin glass film - Google Patents
Production of thin glass filmInfo
- Publication number
- JPS62297232A JPS62297232A JP13913386A JP13913386A JPS62297232A JP S62297232 A JPS62297232 A JP S62297232A JP 13913386 A JP13913386 A JP 13913386A JP 13913386 A JP13913386 A JP 13913386A JP S62297232 A JPS62297232 A JP S62297232A
- Authority
- JP
- Japan
- Prior art keywords
- solution
- drum
- metal alkoxide
- film
- thin film
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 25
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 239000010409 thin film Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 108010025899 gelatin film Proteins 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 229920000609 methyl cellulose Polymers 0.000 abstract description 3
- 239000001923 methylcellulose Substances 0.000 abstract description 3
- 235000010981 methylcellulose Nutrition 0.000 abstract description 3
- 239000004034 viscosity adjusting agent Substances 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 12
- -1 silicon alkoxide Chemical class 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/60—Silica-free oxide glasses
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
（産業上の利用分野）
本発明は金属アルコキシドから、連続した薄膜状のガラ
スを製造する方法に関する。Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a continuous thin film of glass from a metal alkoxide.
（従来技術〉
金属アルコキシドを主成分とし、ガラス状の非晶質物質
を製造する方法は、分子レベルの均質混合が可能であり
、また溶融温度が高いものあるいは結晶化傾向が大きい
もの等、従来の溶融法では得られ難い組成のガラス状物
質も低温で合成できる事から近年注目をあび、汎く研究
が行なわれている。(Prior art) The method for producing a glass-like amorphous material containing metal alkoxide as the main component enables homogeneous mixing at the molecular level, and also allows for the production of materials with a high melting temperature or a strong tendency to crystallize. Glass-like materials with compositions that are difficult to obtain using the melting method can be synthesized at low temperatures, so they have attracted attention in recent years and are being widely studied.
しかるに金属アルコキシドから薄膜状ガラスを得ようと
した場合、必ずしも必要とする寸法、あるいは性状の薄
膜状のガラスは得られなかった。However, when attempting to obtain thin film glass from metal alkoxides, it has not always been possible to obtain thin film glass with the required dimensions or properties.
例えば特開昭５１−３４２１９号公報には部分重合させ
たシリコンアルコキシド含有溶液を水面に滴下し、水面
上に溶液を拡散させてゲル化し、できた膜を加熱してガ
ラスフィルムを得る方法が開示されている。For example, JP-A-51-34219 discloses a method of obtaining a glass film by dropping a partially polymerized silicon alkoxide-containing solution onto the water surface, causing the solution to diffuse onto the water surface to form a gel, and heating the resulting film. has been done.
しかるにこの方法においては支持体が水であるため、水
面との接触面において加水分解によるゲル化が急速に進
行するため、他の一方の面との間に加水分解速度、ゲル
化速度等にお論て差異を生じるものであυ、その結果物
理的、化学的に均一な膜とはなし得す、その後の加熱工
程において破壊を生じ大きなガラスフィルムを製造する
事は困難であった。ｔた水面との接触面において急速に
進行するゲル化のため、膜に白濁が生じるという問題が
あシ、必ずしも好ましい方法ではなかった。However, in this method, since the support is water, gelation due to hydrolysis proceeds rapidly on the surface in contact with the water surface, so there is a difference in the hydrolysis rate, gelation rate, etc. between the surface and the other surface. As a result, a physically and chemically uniform film could not be obtained, but it would break during the subsequent heating process, making it difficult to produce a large glass film. This was not necessarily a preferable method because gelation rapidly progresses at the surface in contact with the water surface, resulting in clouding of the membrane.
一方、ガラス融液のブローイングによって薄膜状ガラス
を得る方法も知られているが、この方法では組成にもよ
るが、例えばＳｉＯ□、５ｉｏ２−Ｔ１０．系、Ｂ１０
ｚ −Ｚｒ０１系では２０００℃に近い高温を要し、薄
膜状に成形することが難しく、また得られる膜は湾曲し
ており、充分な平面度が得られないものである。On the other hand, a method of obtaining thin film glass by blowing a glass melt is also known, but this method depends on the composition, for example, SiO□, 5io2-T10. Series, B10
The z-Zr01 system requires a high temperature close to 2000°C, making it difficult to form into a thin film, and the resulting film is curved, making it impossible to obtain sufficient flatness.
また基板へ薄膜を蒸着し、その後基板を溶解除去する方
法もあるが、この方法では単一成分の場合にはよいが、
多成分の場合にはその組成が限定され、しかも均一な膜
とはなりにくいばかりでなく、操作が煩雑で、かつ充分
な膜厚を得ることが困鑵で連続的な薄膜を・得ることが
できない欠点を有している。There is also a method of depositing a thin film on a substrate and then dissolving and removing the substrate, but this method is good for single components, but
In the case of multiple components, the composition is limited, and it is difficult to obtain a uniform film, and the operation is complicated, and it is difficult to obtain a sufficient film thickness, making it difficult to obtain a continuous thin film. It has the disadvantage that it cannot be used.
また金属、ガラス板、プラスチック等の平坦な基板上く
形成させる方法も研究されているが、これまでのところ
基板と接触面において発生する白濁あるいは剥離の内鑵
性等の問題点が解決されておらず、所望の寸法、物性を
有する薄膜状ガラスの製造はできていない。Research is also being conducted into methods of forming the film on flat substrates such as metal, glass plates, plastic, etc., but so far, problems such as cloudiness that occurs at the contact surface with the substrate, or problems with peeling, etc., have not been solved. Therefore, it has not been possible to manufacture thin film glass having the desired dimensions and physical properties.
（問題点を解決するための手段）
本発明者らは上記の問題点に鑑み鋭意研究を行ない１本
発明を完成したものである。(Means for Solving the Problems) In view of the above-mentioned problems, the present inventors conducted intensive research and completed the present invention.
すなわち本発明は、円柱状のドラムの円周面の一端を金
属アルコキシドを含む加水分解過程にある溶液に浸漬し
つつ、回転させることによりトラム面上に金属アルコキ
シド溶液層を形成し、該溶液の加水分解を進行させ加水
分解の進行により回転するドラム上よシ剥離した連続し
たリボン状の薄膜ゲルを乾燥し焼結することを特徴とす
る薄膜状ガラスの製造法である。That is, the present invention forms a metal alkoxide solution layer on the tram surface by immersing one end of the circumferential surface of a cylindrical drum in a solution containing a metal alkoxide in the hydrolysis process and rotating it. This method of producing thin film glass is characterized by proceeding with hydrolysis and drying and sintering a continuous ribbon-shaped thin film gel that is peeled off on a rotating drum as the hydrolysis progresses.
本発明で用いられる円柱状ドラムの表面は金属アルコキ
シド溶液が付着し易く、かつゲル化の進行により ＩＪ
ボン状のゲルが剥離し易いことが必要であシ、かかる観
点から、目安として臨界表面張力（γＣ）が２５〜３５
知Ｘｃｒａ度の素材を用いることが好ましい。かかる材
料としては、プラスチックがちシ、特にポリスチレン、
ポリプロピレン、ポリエチレン等が最適に用いられる。The metal alkoxide solution easily adheres to the surface of the cylindrical drum used in the present invention, and as gelation progresses, IJ
It is necessary that the bong-shaped gel is easily peeled off, and from this point of view, the critical surface tension (γC) is 25 to 35.
It is preferable to use materials of high quality. Such materials include plastics, especially polystyrene;
Polypropylene, polyethylene, etc. are optimally used.
またこれ以外のプラスチックであっても、表面に金属ア
ルコキシドとの親和力が弱く、かつ平坦度に優れた物質
層を設けたものは、本目的に充分供し得る。上記物質層
としては、その物性および基板上への層形成方法の谷易
さから、離型剤が適しており、この中でも特にワックス
系の離型剤が最適に用いられる。しかし、このものは、
変性を受は易く、連続使用には適していない。Other plastics can also be used for this purpose if they have a layer of material on the surface that has a low affinity with metal alkoxides and has excellent flatness. A mold release agent is suitable for the material layer in view of its physical properties and the ease of forming the layer on the substrate, and among these, a wax-based mold release agent is particularly suitable. But this one is
It is susceptible to denaturation and is not suitable for continuous use.
さらに本発明において金属アルコキシドは必ずしも限定
されるものではなく、代表的なシリコンアルコキシドと
しては、テトラメチルシリケート（５ｉ（ＱＣ！Ｈｓ）
４）、 テトラエチルシリケート（５ｉ（ＯＯｔ＆）４
Ｗ カ６す、またシリコンアルコキシド以外の金属アル
コキシドとしては荷に限定されるものではないが、薄膜
状ガラスの物性向上という面から考え、耐熱性向上のた
めにはチタンのアルコキシド、耐化学薬品性向上のため
にはジルコニウムのアルコキシド、その他アルミニウム
のアルコキシド等が必要に応じて選択される。より具体
的にはチタニウムブトキシド（Ｔｉ（ＯＣｓＨ７）４
）、チタニウムブトキシド（Ｔｉ（００４ＨＩ）４ ）
、ジルコニウムブトキシド（ｚｒ（ｏｃ、ｎ、）、
） ｓ ジルコニウムブトキシド（Ｚｒ（ＱＣ！４Ｈ
＊）＊ ） 、アルミニウムブトキシド（ＡＩＣＯＣ！
４Ｈｓ）ｓ ）が挙げられる。Further, in the present invention, the metal alkoxide is not necessarily limited, and typical silicon alkoxides include tetramethyl silicate (5i (QC!Hs)
4), Tetraethyl silicate (5i(OOt&)4
In addition, metal alkoxides other than silicon alkoxides are not limited to loading, but from the perspective of improving the physical properties of thin film glass, titanium alkoxides, chemical resistance, etc. are recommended to improve heat resistance. For improvement, zirconium alkoxide, other aluminum alkoxide, etc. are selected as necessary. More specifically, titanium butoxide (Ti(OCsH7)4
), titanium butoxide (Ti(004HI)4)
, zirconium butoxide (zr(oc,n,),
) s Zirconium butoxide (Zr(QC!4H
*) * ), aluminum butoxide (AICOC!
4Hs)s).
基板上に金属アルコキシドの溶液層を形成するに当って
は、その溶液粘度および当該溶液の加水分解状態が極め
て大きな意味を有するものである。In forming a metal alkoxide solution layer on a substrate, the viscosity of the solution and the state of hydrolysis of the solution are extremely important.
すなわち、ゾル状の金属アルコキシド層をドラム面上に
形成するに際し、溶液粘度が低きに過ぎれば過剰な流動
性によって金属アルコキシド層の形成は内鑵であシ、高
きに過ぎれば薄膜の製造が困鑵でちるばかりでなく、そ
の平坦度についても必ずしも望ましいものではない。In other words, when forming a sol-like metal alkoxide layer on the drum surface, if the solution viscosity is too low, the metal alkoxide layer will not be formed due to excessive fluidity, and if it is too high, it will be difficult to form a thin film. Not only is it difficult and dry, but its flatness is also not necessarily desirable.
従がって、一般的には金属アルコキシド溶液が加水分解
し脱水縮合が進行しである程度粘稠になったものを用い
ると良い。詳しくは金属アル；キシド溶液の粘度が１０
ｐｓ（ポアズ）以上、１０００ ｐθ以下の範囲のもの
を用いると艮い。Therefore, it is generally best to use a metal alkoxide solution that has become viscous to some extent due to hydrolysis and dehydration condensation. For details, the viscosity of metal alkoxide solution is 10
It is best to use something in the range of ps (poise) or more and 1000 pθ or less.
ｔｆｃ必要に応じて金属アルコキシド溶液に適量の粘度
調節剤を添加しても良い。特に本目的にはヒドロキシグ
ロビルセルロース、ヒドロキシエチルセルロース、とド
ロ中シグロビルメチルセルロース、メチルセルロース、
エチルセルロース等の水溶性セルロースエーテルは安定
性等に優れ、好適に用いられる。この粘度調節剤は、金
属アルコキシド溶液中への均一な分散を考慮して、１〜
３チ程度のアルコール溶液として添加する。その添加量
は混合溶液の組成、水溶性高分子の種類によって異なる
。TFC An appropriate amount of viscosity modifier may be added to the metal alkoxide solution if necessary. In particular, for this purpose, hydroxyglobil cellulose, hydroxyethyl cellulose, and siglobil methyl cellulose, methyl cellulose,
Water-soluble cellulose ethers such as ethyl cellulose have excellent stability and are preferably used. This viscosity modifier is selected from 1 to
Add as an alcoholic solution of about 3 g. The amount added varies depending on the composition of the mixed solution and the type of water-soluble polymer.
円柱状ドラムの円筒部表面への前記金属アルコキシド溶
液の塗布は、円周方向にゆつくシ回転する該ドラムを、
金属アルコキシド溶液に接することによって行なう。溶
液と接したドラム面上には該溶液層が形成されこれがド
ラムの回転に伴い徐々に加水分解を受はゲル化が進行す
る。ドラムがある程度まで回転した時点でゲル膜はドラ
ム面から剥離するため、ドラムが回転して新しい溶液層
が形成されていくに従ってゲル膜は連続した状態で供給
される。Application of the metal alkoxide solution to the surface of the cylindrical portion of the cylindrical drum involves rotating the drum slowly in the circumferential direction.
This is done by contacting with a metal alkoxide solution. A solution layer is formed on the drum surface in contact with the solution, and as the drum rotates, this solution layer is gradually hydrolyzed and gelatinized. Since the gel film is peeled off from the drum surface when the drum rotates to a certain extent, the gel film is continuously supplied as the drum rotates and a new solution layer is formed.
この際、回転ドラムの一部を適当な容器で覆い、加熱蒸
気雰囲気やヒーター等による加熱雰囲気等に保って、溶
液ノーの乾燥、ゲル化の条件を厳密にコントロールする
ような方法を用いることも好適である。At this time, a method may be used in which a part of the rotating drum is covered with a suitable container and maintained in a heated steam atmosphere or a heated atmosphere using a heater, etc., to strictly control the drying and gelation conditions of the solution. suitable.
ゲル膜は連続した状態で供給され続けるため、該ゲル膜
を引き続き加熱炉に導入し所望の温度、雰囲気で加熱す
るようにすれば、最終的に連続したリボン状の薄膜状ガ
ラスを得ることが可能となる。Since the gel film is continuously supplied, if the gel film is continuously introduced into the heating furnace and heated at the desired temperature and atmosphere, it is possible to finally obtain a continuous ribbon-shaped thin film glass. It becomes possible.
（実施例） 以下本発明を実施例により説明する。(Example) The present invention will be explained below with reference to Examples.
実施例１
テトラエチルシリケート（ｓｉ（ＯＯＩＨｓ ）４ ）
、エタ／ −ル（Ｃ！、Ｈ，０）Ｉ）、水、塩酸（Ｈｃ
ｘ）が４Ａ／比で１ ： １ ： １ ： ０，１とな
る金属アルコキシド溶液を調製した。調製の方法として
はテトラエチルシリケート（Ｓｉ（００ｓＨｉ）ｉ ）
をエタノールと宣温にて混合し、次に水、塩酸および含
水エタノールの混合溶液を加え混合攪拌した。この溶液
を宣温で加水分解し、粘度が５０〜６０ ｐａに達した
時点で、ポリプロピレンで円筒部表面を積った直径５０
部、巾７３の回転ドラムを該溶液に接しながら３０分間
で１回転の速度で回転させた。Example 1 Tetraethylsilicate (si(OOIHs)4)
, ethyl (C!,H,0)I), water, hydrochloric acid (Hc
A metal alkoxide solution was prepared in which x) was 4A/ratio of 1:1:1:0.1. The preparation method is tetraethyl silicate (Si(00sHi)i)
was mixed with ethanol at room temperature, and then a mixed solution of water, hydrochloric acid, and aqueous ethanol was added and mixed and stirred. This solution is hydrolyzed at room temperature, and when the viscosity reaches 50 to 60 pa, the surface of the cylindrical part is covered with polypropylene.
A rotary drum having a width of 73 mm was rotated at a speed of 1 revolution per 30 minutes while in contact with the solution.
さらにこの回転ドラムの上半分を樹脂性の容器で覆いこ
の内部をヒーターで加熱し６０℃に保った。ポリプロピ
レン上に形成された溶液層は回転に従い徐々にゲル化し
、上記樹脂容器を通過後、該ゲル膜はポリプロピレンよ
シ自然に剥離し、連続した巾７国のリボン状ゲルが得ら
れた。Furthermore, the upper half of this rotating drum was covered with a resinous container and the inside was heated with a heater to maintain the temperature at 60°C. The solution layer formed on the polypropylene gradually gelled as it rotated, and after passing through the resin container, the gel film was naturally peeled off from the polypropylene, yielding a continuous ribbon-shaped gel with a width of 7 mm.
このゲルを３０３の長さに切って巾７傷×長さ３０謝の
帯状のゲルとした。このゲルの厚みはおよそ３００μｍ
であった。このゲルを電気炉に入れ冨温から１ ’Ｃ／
ｍｉｎの昇温速度で１１００℃まで昇温し１時間保持し
て焼結し透明な薄膜状石英ガラスを得九。得られたガラ
スは巾５備×長さ２０傷、厚み約２００μｍであった。This gel was cut into a length of 30 cm to obtain a band-shaped gel with a width of 7 scratches and a length of 30 cm. The thickness of this gel is approximately 300 μm
Met. Put this gel in an electric furnace and heat it to 1'C/
The temperature was raised to 1100° C. at a heating rate of 10 min, and sintered by holding for 1 hour to obtain a transparent thin film of quartz glass. The resulting glass had a width of 5 mm, a length of 20 scratches, and a thickness of approximately 200 μm.
実施例２
実施例Ｉにおいて、金属アルコキシド溶液の粘度が約３
０ｐｓのときにヒドロキシグロビルセルロースの２ｖｔ
％エタノール溶液を、金属アルコキシド溶液に対し１ｗ
ｔ％添加したところ溶液の粘度は約５０ ｐｓとなった
。Example 2 In Example I, the viscosity of the metal alkoxide solution is about 3
2vt of hydroxyglobil cellulose at 0ps
% ethanol solution to 1w of metal alkoxide solution.
When t% was added, the viscosity of the solution was about 50 ps.
この溶液を用い、実施例１（ただし、回転ドラムの表面
はポリエチレンで被覆した）と同じ操作を行なったとこ
ろ巾約４．５ （ｍ、長さ約１８ｃｒｎ。Using this solution, the same operation as in Example 1 (however, the surface of the rotating drum was coated with polyethylene) resulted in a drum with a width of about 4.5 m and a length of about 18 crn.
厚み１７０μｍの薄膜状石英ガラスを得た。A thin film of quartz glass with a thickness of 170 μm was obtained.
実施例３
ガラスの組成が５０ Ｓｉｎ、・５０ＴｉＯｔとなるよ
うに室温でエチルシリケート１０４ｇｒとテトライソプ
ロビルチタネート１４２ｇｒをよく混合し９９．５％エ
タノールを１０００ｄ加えた。この溶液を攪拌しながら
２Ｎ塩酸を１２ｇｒ滴下し、均一な透明溶液を得な。こ
の溶液を７０℃恒温槽に入れ加水分解させ、粘度が約１
００ｐａになったととるで、実施例１と同様にポリスチ
レンで円筒部を覆った直径約５０ｃ１ｎ、巾７ｃＩＩＬ
の回転ドラムを該溶液に接しながら３０分間に１回転の
速さで回転させた。この結果実施例１と同様リボン状の
ゲルを得これを１１００℃で２時間焼結して透明な薄膜
状Ｔｉｅ、・ＳｉＯ茸ガラスを得た。Example 3 104 gr of ethyl silicate and 142 gr of tetraisoprobyl titanate were thoroughly mixed at room temperature so that the composition of the glass was 50 Sin, 50 TiOt, and 1000 d of 99.5% ethanol was added thereto. Add 12g of 2N hydrochloric acid dropwise to this solution while stirring to obtain a homogeneous and transparent solution. This solution was placed in a 70°C constant temperature bath and hydrolyzed until the viscosity was approximately 1.
Assuming that the pressure reached 00 pa, the cylindrical part was covered with polystyrene as in Example 1, with a diameter of about 50 c1n and a width of 7 cIIL.
A rotating drum was rotated at a rate of 1 rotation per 30 minutes while in contact with the solution. As a result, a ribbon-like gel was obtained as in Example 1, and this was sintered at 1100° C. for 2 hours to obtain a transparent thin film of Tie.SiO mushroom glass.
（本発明の効果）
本発明によれば円柱ドラムを用いるためゲル化により自
然にゲル膜が剥離し、クラック、割れの発生を抑えるこ
とができ、連続したガラス薄膜を容易に得ることができ
る。(Effects of the Present Invention) According to the present invention, since a cylindrical drum is used, the gel film naturally peels off due to gelation, the occurrence of cracks and breaks can be suppressed, and a continuous glass thin film can be easily obtained.
Claims (1)
む加水分解過程にある溶液に浸漬しつつ回転させること
により、ドラム面上に金属アルコキシド溶液層を形成し
、該溶液の加水分解を進行させ、加水分解の進行により
回転するドラム上より剥離した連続したリボン状の薄膜
ゲルを乾燥し、焼結することを特徴とする薄膜状ガラス
の製造法。By rotating one end of the circumferential surface of a cylindrical drum while immersing it in a solution containing metal alkoxide that is undergoing hydrolysis, a layer of metal alkoxide solution is formed on the drum surface, and the hydrolysis of the solution proceeds. A method for producing thin film glass, characterized by drying and sintering a continuous ribbon-shaped thin film gel peeled off from a rotating drum as hydrolysis progresses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13913386A JPS62297232A (en) | 1986-06-17 | 1986-06-17 | Production of thin glass film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13913386A JPS62297232A (en) | 1986-06-17 | 1986-06-17 | Production of thin glass film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62297232A true JPS62297232A (en) | 1987-12-24 |
Family
ID=15238299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13913386A Pending JPS62297232A (en) | 1986-06-17 | 1986-06-17 | Production of thin glass film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62297232A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02120247A (en) * | 1988-10-28 | 1990-05-08 | Shin Etsu Chem Co Ltd | Silica-titania glass and method producing the same |
| JPH03193633A (en) * | 1989-12-19 | 1991-08-23 | Reiko Co Ltd | Glassy filmlike spacer |
| WO1997011035A1 (en) * | 1995-09-19 | 1997-03-27 | Institut für Neue Materialien Gemeinnützige GmbH | THIN SiO2 FILMS, A PROCESS FOR PRODUCING THEM AND THEIR USE |
-
1986
- 1986-06-17 JP JP13913386A patent/JPS62297232A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02120247A (en) * | 1988-10-28 | 1990-05-08 | Shin Etsu Chem Co Ltd | Silica-titania glass and method producing the same |
| JPH03193633A (en) * | 1989-12-19 | 1991-08-23 | Reiko Co Ltd | Glassy filmlike spacer |
| WO1997011035A1 (en) * | 1995-09-19 | 1997-03-27 | Institut für Neue Materialien Gemeinnützige GmbH | THIN SiO2 FILMS, A PROCESS FOR PRODUCING THEM AND THEIR USE |
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