JPH01138136A - Production of silica glass - Google Patents
Production of silica glassInfo
- Publication number
- JPH01138136A JPH01138136A JP29445287A JP29445287A JPH01138136A JP H01138136 A JPH01138136 A JP H01138136A JP 29445287 A JP29445287 A JP 29445287A JP 29445287 A JP29445287 A JP 29445287A JP H01138136 A JPH01138136 A JP H01138136A
- Authority
- JP
- Japan
- Prior art keywords
- gel
- silica glass
- cracks
- silica
- silica sol
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- -1 silicon alkoxide Chemical class 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 150000004703 alkoxides Chemical class 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract 2
- 239000000499 gel Substances 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 229960001231 choline Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000120 polyethyl acrylate Polymers 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- CRNJBCMSTRNIOX-UHFFFAOYSA-N methanolate silicon(4+) Chemical compound [Si+4].[O-]C.[O-]C.[O-]C.[O-]C CRNJBCMSTRNIOX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
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)
- Glass Melting And Manufacturing (AREA)
- Silicon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は光学用、半導体工業用、電子工業用、理化学用
等に使用されるシリカガラスを製造する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention produces silica glass used for optics, semiconductor industry, electronic industry, physics and chemistry, etc.
（従来の技術）
シリカガラスは耐熱性、耐食性および光学的性質に優れ
ていることから、半導体 製造に欠かせない重要な材料
であり、さらには光ファイバやＩＣ製造用フォトマスク
基板、ＴＰＴ基板などに使用され、その用途はますます
拡大されている。(Prior technology) Silica glass has excellent heat resistance, corrosion resistance, and optical properties, so it is an important material indispensable for semiconductor manufacturing, and is also used in optical fibers, photomask substrates for IC manufacturing, TPT substrates, etc. It has been used for many years, and its applications are being expanded more and more.
従来のシリカガラスの製造法には、天然石英を電気炉ま
たは酸水素炎により溶解する方法、あるいは四塩化ケイ
素を酸水素炎又はプラズマ炎中で高温酸化し溶解する方
法があるが、いずれの方法も製造工程に２０００℃ある
いはそれ以上の高温を必要とするため大量のエネルギー
を消費し、また製造時にそのような高温に耐える材料が
必要であり、また高純度のものが得にくいなど経済的１
品質的にいくつかの問題点をもっている。Conventional methods for manufacturing silica glass include melting natural quartz in an electric furnace or oxyhydrogen flame, or oxidizing and melting silicon tetrachloride at high temperature in an oxyhydrogen flame or plasma flame. However, the manufacturing process requires high temperatures of 2000°C or higher, which consumes a large amount of energy, and materials that can withstand such high temperatures are required during manufacturing, and it is difficult to obtain high-purity materials, making it an economical problem.
There are some quality issues.
これに対し、近年ゾル−ゲル法と呼ばれるシリカガラス
を低温で合成する方法が注目されている。その概要を簡
単に述べる。On the other hand, in recent years, a method of synthesizing silica glass at low temperature called the sol-gel method has been attracting attention. The outline will be briefly described below.
一般式Ｓ ｉ （ＯＲ） ａ （Ｒ：アルキル基）で
表わされるシリコンアルキシド（本発明に於いては、そ
の重縮合物を含む）５例えば（ＲＯ）、Ｓ ｉ・ （Ｏ
Ｓ ｉ （ＯＲ）ｚｌ−・Ｏ３ｉ（ＯＲ）３． （ｎ
＝ｏ〜８．Ｒ：アルキル基）に水（アルカリまたは酸で
ｐＨを調整してもよい）を加え、加水分解し、シリカヒ
ドロシル（本発明に於いてはシリカゾルという）とする
。この時、シリコンアルコキシドと水が均一な系となる
様、一般には溶媒として適当なアルコールが添加されて
いる。このシリカゾルを静置、昇温、ゲル化剤の添加等
によってゲル化させる。その後ゲルを蒸発乾燥すること
によりシリカ乾燥ゲルとする。この乾燥ゲルを適当な雰
囲気中で焼結することによりシリカガラスを得る。Silicon alkoxide (including its polycondensate in the present invention) represented by the general formula S i (OR) a (R: alkyl group) 5 For example, (RO), S i (O
S i (OR)zl-・O3i(OR)3. (n
=o~8. R: alkyl group) is added with water (pH may be adjusted with an alkali or acid) and hydrolyzed to produce silica hydrosil (referred to as silica sol in the present invention). At this time, an appropriate alcohol is generally added as a solvent so that the silicon alkoxide and water form a homogeneous system. This silica sol is gelled by standing still, increasing the temperature, adding a gelling agent, etc. Thereafter, the gel is evaporated to dryness to obtain a dry silica gel. Silica glass is obtained by sintering this dried gel in a suitable atmosphere.
（発明が解決しようとする問題点）
しかし、ゾル−ゲル法によるシリカガラスの製造にはま
だ未解決の問題が残されている。(Problems to be Solved by the Invention) However, there are still unresolved problems in the production of silica glass by the sol-gel method.
特にゲルを乾燥していく過程でゲルにクランクや割れが
発生し易く、クランクや割れのないモノリシックな大形
の乾燥ゲルを歩留り良く製造することが困難となること
である。In particular, during the process of drying the gel, cracks and cracks are likely to occur in the gel, making it difficult to produce a monolithic large-sized dried gel without any cracks or cracks with a good yield.
本発明はクランクや割れの発生することのないシリカガ
ラスの製造法を提供するものである。The present invention provides a method for manufacturing silica glass that does not cause cracks or cracks.
（問題点を解決するための手段）
本発明は、ゾル−ゲル法によるシリカガラスの製造法に
於て、ゾル調整時に、ポリアクリル酸エステルを添加す
ることを特徴とするものである。(Means for Solving the Problems) The present invention is characterized in that a polyacrylic acid ester is added during sol preparation in a method for producing silica glass by a sol-gel method.
本発明において、シリコンアルコキシドのアルキル基に
ついて、特に制限はないが、加水分解のし易さ、ゲル化
時間の点から、メチル基、エチル基、プロピル基、ブチ
ル基を有するシリコンアルコキシドを使用することが好
ましい。シリコンアルコキシドに水又は水とアルコール
の混合溶液を加えて加水分解してシリカゾルを生成させ
る際、アルコール。In the present invention, there are no particular restrictions on the alkyl group of silicon alkoxide, but from the viewpoint of ease of hydrolysis and gelation time, silicon alkoxide having a methyl group, ethyl group, propyl group, or butyl group is used. is preferred. When silicon alkoxide is hydrolyzed by adding water or a mixed solution of water and alcohol to produce silica sol, alcohol.
又は水とアルコールの混合溶液にあらかじめポリアクリ
ル酸エステルを添加、均一に溶解させてお（。Alternatively, add polyacrylic acid ester to a mixed solution of water and alcohol in advance and dissolve it uniformly (.
ポリアクリル酸エステルとしては、水と相溶性のある有
機溶媒に溶解するものが望ましい。ポリアクリル酸エス
テルのアルキル基としてはメチル基、エチル基等が望ま
しい。The polyacrylic ester is preferably one that dissolves in an organic solvent that is compatible with water. As the alkyl group of the polyacrylic ester, a methyl group, an ethyl group, etc. are preferable.
添加するポリアクリル酸エステルの分子量は、ポリアク
リル酸エステルをアルコール。The molecular weight of the polyacrylic ester to be added is that of polyacrylic ester and alcohol.
又は水とアルコールの混合溶液にあらかじめ添加、均一
に溶解させておく点等を考慮して選定される。Alternatively, it is selected by adding it to a mixed solution of water and alcohol in advance and dissolving it uniformly.
添加するポリアクリル酸エステルの量は用いるシリコン
アルコキシドの種類等、及び加水分解速度によって適宜
調整する。The amount of polyacrylic ester to be added is appropriately adjusted depending on the type of silicon alkoxide used and the rate of hydrolysis.
水と共に加える触媒は、塩基、酸等特に制限しないが、
ゲル化時間、また得られる乾燥ゲルの焼結のし易すさの
点から塩基の方が好ましい結果が得られる。水と共に加
えるアルコールについては特に制限しないが、水、アル
コキシドの両者に対する溶解性の点より。The catalyst added with water is not particularly limited, such as bases and acids, but
From the viewpoint of gelation time and ease of sintering of the resulting dry gel, a base gives more preferable results. There are no particular restrictions on the alcohol added together with water, but from the viewpoint of solubility in both water and alkoxide.
メチルアルコール、エチルアルコール、１−プロピルア
ルコール、２−プロピルアルコール等のアルコール類を
使用するのが好ましい。Preferably, alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol are used.
シリカガラスは、上記のようにして調整したシリカゾル
をシャーレ等の容器に移し、室温〜７０℃に保って、ゲ
ル化し３次いで室温以上の温度で数週間乾燥して、乾燥
ゲルとし。Silica glass is obtained by transferring the silica sol prepared as described above to a container such as a petri dish, keeping it at room temperature to 70°C to gel it, and then drying it at a temperature above room temperature for several weeks to form a dry gel.
更に公知の方法１例えば、空気中で１０００〜１４００
℃に昇温しで焼結することにより得られる。Further known method 1, for example, 1000 to 1400 in air
It is obtained by sintering at elevated temperature to ℃.
（作用）
ポリアクリル酸エステルの添加効果の原因については、
詳細は不明であるが、ゾル中でのシリカ微粒子の生成の
制御、ゲル中でのこれらのシリカ徽粒子間の結合、乾燥
過程でゲル中に発生する応力の緩和等に寄与し、ゲルの
大形化が可能となったものと考えられる。(Effect) Regarding the cause of the effect of adding polyacrylic ester,
Although the details are unknown, it contributes to controlling the generation of silica particles in the sol, bonding between these silica particles in the gel, and alleviating the stress generated in the gel during the drying process, and increases the size of the gel. It is thought that this made it possible to take shape.
実施例 １
３モルのメチルアルコールにポリアクリル酸エチルを７
．６ｇ充分に溶解させ、３モルの水と０．０００５モル
のコリンを混合た。得られた溶液を１モルのシリコンメ
トキシド（Ｓｉ（ＯＣＨｓ） ４）にゆっくりと加え、
さらに充分混合しシリカゾルを得た。これを直径１５０
１のテフロンでコーティングしたガラス製シャーレに入
れ、アルミ箔で密封し、室温でゲル化した。その後、蓋
に孔を開け、５０℃の恒温槽中で２週間乾燥し、その後
１２０℃の恒温槽に移して１日乾燥して、直径約１２０
ｍｍの乾燥ゲルを得た。こうして得られた乾燥ゲルのか
さ密度は約０．６ｇ／ｃＪであり、クラックや割れは全
（なかった。Example 1 7 mols of polyethyl acrylate in 3 mol of methyl alcohol
．． 6g was fully dissolved and 3 moles of water and 0.0005 moles of choline were mixed. The resulting solution was slowly added to 1 mol of silicon methoxide (Si(OCHs)4),
The mixture was further thoroughly mixed to obtain a silica sol. This has a diameter of 150
The mixture was placed in a glass Petri dish coated with Teflon (No. 1), sealed with aluminum foil, and allowed to gel at room temperature. After that, a hole was made in the lid and dried in a constant temperature bath at 50℃ for two weeks, then transferred to a constant temperature bath at 120℃ and dried for one day.
A dry gel of mm was obtained. The bulk density of the dry gel thus obtained was about 0.6 g/cJ, and there were no cracks or breaks.
得られたゲルを空気中１２００°Ｃまで加熱焼結したと
ころ直径約８（１ｍｍ、 ＩＩさ５ｍｍのクラックや割
れのない透明なシリカガラスが得られた。このシリカガ
ラスは分析の結果、そのシリカガラスと一致した。When the resulting gel was heated and sintered in air to 1200°C, transparent silica glass with a diameter of approximately 8 mm (1 mm, II 5 mm) with no cracks or breaks was obtained.As a result of analysis, this silica glass was found to be Matched with glass.
実施例 ２
ポリアクリル酸エチル３．０ｇを３モルのメチルアルコ
ールに充分に溶解させた後、３モルの水、０．０００５
モルのコリンとを混合した。以下実施例１と同様の操作
を行って乾燥ゲルを得た。得られた乾燥ゲルにはクラン
クや割れは全くなかった。Example 2 After fully dissolving 3.0 g of polyethyl acrylate in 3 mol of methyl alcohol, 3 mol of water, 0.0005
Mixed with mole of choline. Thereafter, the same operation as in Example 1 was performed to obtain a dry gel. The dried gel obtained had no cracks or cracks.
実施例 ３
ポリアクリル酸エチル１５．２ ｇを３モルのメチルア
ルコールに充分に溶解させた後、３モルの水、ｏ、ｏｏ
ｏｓモルのコリンとを混合した。以下実施例１と同様の
操作を行って乾燥ゲルを得た。得られた乾燥ゲルにはク
ランクや割れは全くなかった。Example 3 After fully dissolving 15.2 g of polyethyl acrylate in 3 mol of methyl alcohol, 3 mol of water, o, oo
and osmol of choline. Thereafter, the same operation as in Example 1 was performed to obtain a dry gel. The dried gel obtained had no cracks or cracks.
（発明の効果）
本発明によれば、クラックや割れのない大形のシリカガ
ラスをヅルゲール法により容易に製造可能となる。その
大きさは基本的には制約がなく、形状も板状、棒状、管
状等のいずれでも製造できる。(Effects of the Invention) According to the present invention, large-sized silica glass without cracks or cracks can be easily produced by the Dugel method. There are basically no restrictions on its size, and it can be manufactured in any shape such as a plate, rod, or tube.
Claims (1)
し、次いで焼結するシリカガラスの製造法に於て、シリ
コンアルキシドを加水分解してシリカゾルとする段階で
、ポリアクリル酸エステルを添加することを特徴とする
シリカガラスの製造法。[Scope of Claims] 1. In a method for producing silica glass in which silicon alkoxide is hydrolyzed to form silica sol, this is gelled, dried to form a dry gel, and then sintered, silicon alkoxide is hydrolyzed. A method for producing silica glass characterized by adding polyacrylic acid ester at the step of preparing silica sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29445287A JPH01138136A (en) | 1987-11-20 | 1987-11-20 | Production of silica glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29445287A JPH01138136A (en) | 1987-11-20 | 1987-11-20 | Production of silica glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01138136A true JPH01138136A (en) | 1989-05-31 |
Family
ID=17807965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29445287A Pending JPH01138136A (en) | 1987-11-20 | 1987-11-20 | Production of silica glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01138136A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9030427B2 (en) | 2009-11-20 | 2015-05-12 | Sharp Kabushiki Kaisha | Flexible display panel with touch sensor function |
-
1987
- 1987-11-20 JP JP29445287A patent/JPH01138136A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9030427B2 (en) | 2009-11-20 | 2015-05-12 | Sharp Kabushiki Kaisha | Flexible display panel with touch sensor function |
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