JPH02149431A - Production of silica glass - Google Patents
Production of silica glassInfo
- Publication number
- JPH02149431A JPH02149431A JP30335688A JP30335688A JPH02149431A JP H02149431 A JPH02149431 A JP H02149431A JP 30335688 A JP30335688 A JP 30335688A JP 30335688 A JP30335688 A JP 30335688A JP H02149431 A JPH02149431 A JP H02149431A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- silicon alkoxide
- added
- polyethylene glycol
- water
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000010419 fine particle Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 239000000499 gel Substances 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 230000007547 defect Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 4
- 229960001231 choline Drugs 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004017 vitrification Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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)
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、理工学用
等に使用されるシリカガラスを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing silica glass used in optics, semiconductor industry, electronic industry, science and engineering, and the like.
（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 art) 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 for 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熔解する方
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嵩に耐える材料
が必要であり、また高純度のものが得にくいなど経済的
、品質的にいくつかの問題点をもっている。Conventional methods for producing silica glass include a method in which natural quartz is melted in an electric furnace or an oxyhydrogen flame, or a method in which silicon tetrachloride is oxidized and melted at high temperature in an oxyhydrogen flame or a plasma flame. 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 bulk are required during manufacturing, and it is difficult to obtain high-purity materials, making it economically difficult. There are some problems in terms of performance and quality.
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。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.
その概要を面単に述べる。I will give a simple overview of it.
シリコンアルコキシドの加水分解、重合によって、ある
いは四塩化ケイ素の気相加水分解によって作製した５ｔ
ｏｔ１粒子を分散させた水、有機溶剤、あるいは水−有
ｍ熔剤混合溶液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、ゲルを芸発、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
を適当に雰囲気中で焼結することによりシリカガラスを
得る。5T prepared by hydrolysis or polymerization of silicon alkoxide or by gas phase hydrolysis of silicon tetrachloride
A silica sol containing water, an organic solvent, or a mixed solution of water and a molten solvent in which ot1 particles are dispersed is gelled by standing still, raising the temperature, adding a gelling agent, or the like. Thereafter, the gel is dried to obtain a dry silica gel. Silica glass is obtained by sintering this dried gel in an appropriate atmosphere.
上記のゾル−ゲル法によるシリカガラスの製造法には次
の問題がある。すなわち、５ｉＯｚ微粒子を水、有機溶
剤等に均一に分散させることは非常に困難であり、シリ
カゾル中にＳｉｎｇ微粒子の大きな凝集体が残りやすい
。このような凝集体はゲルを焼結して作製したガラス中
の欠陥（空孔）の原因となり、品質の低下を生じさせる
。このため５ｉＯｘａ粒子の分散を良くするために、シ
リカゾルに超音波を照射する方法、凝集体により生ずる
ガラス中の欠陥（空孔）を消すために焼結ガラスを更に
加圧下で焼結する方法が提案されているが、いずれも工
程数の増加、不純物混入の機会の増加を引き起こす。The above sol-gel method for producing silica glass has the following problems. That is, it is very difficult to uniformly disperse 5iOz fine particles in water, organic solvents, etc., and large aggregates of Sing fine particles tend to remain in the silica sol. Such aggregates cause defects (pores) in the glass produced by sintering the gel, resulting in a decrease in quality. Therefore, in order to improve the dispersion of 5iOxa particles, there is a method of irradiating silica sol with ultrasonic waves, and a method of sintering the sintered glass under pressure to eliminate defects (vacancies) in the glass caused by aggregates. However, all of these methods increase the number of steps and increase the chance of contamination with impurities.
液相へのＳｉｎ、微粒子の分数工程をなくすため、シリ
コンアルコキシドを塩基触媒の存在下で加水分解してＳ
ｉＯア微粒子を含むゾルを作製し、これを直接、ゲル化
させる方法が提案されている。In order to eliminate the fractional step of introducing Sin and fine particles into the liquid phase, silicon alkoxide is hydrolyzed in the presence of a base catalyst to form S.
A method has been proposed in which a sol containing iO particles is prepared and the sol is directly gelled.
（発明が解決しようとする課題）
しかしこの方法では、乾燥過程でゲルにクラックや割れ
が発生しやすい。このようなゲルの破壊を防ぐためには
、ゾル中に含まれるｓｌｏ、ｉ粒子径を大きくする必要
があり、このためアルコキシドの加水分解の際に用いる
水は、アルコキシドに対して大過剰でかつ濃厚な塩基を
含む必要がある。したがってゾルをゲル化する前に、大
過剰の水を除去する濃縮工程を入れる必要が生じ、工程
数の増加を引き起こした。またゾルをゲル化に適当にｐ
Ｈにするため、酸を加える必要があるが、これによって
ゾル中に多量に生成する塩は乾燥過程でゲル中に析出し
、ガラス化した際に空孔の発生を引き起こすという問題
が生ずる。(Problems to be Solved by the Invention) However, with this method, cracks and breaks are likely to occur in the gel during the drying process. In order to prevent such destruction of the gel, it is necessary to increase the slo and i particle diameters contained in the sol, and for this reason, the water used for hydrolyzing the alkoxide must be in large excess and concentrated with respect to the alkoxide. It must contain a base. Therefore, before gelling the sol, it became necessary to include a concentration step to remove a large excess of water, resulting in an increase in the number of steps. In addition, to gel the sol, adjust the p
It is necessary to add an acid to make the gel H, but this causes a problem in that a large amount of salt produced in the sol is precipitated in the gel during the drying process, causing the formation of pores when it is vitrified.
本発明は、ゲル化前にＳｉＯ□微粒子の分数工程、また
ゾルの濃縮工程を必要としないシリカガラスの製造方法
を堤供するものである。The present invention provides a method for producing silica glass that does not require a fractional SiO□ particle step or a sol concentration step before gelation.
（課題を解決するための手段）
本発明は、シリコンアルコシキドを塩基性触媒を用いて
加水分解して５ｉｆｔ微粒子を含むシリカゾルを得、そ
のゾルを乾燥、焼結するシリカガラスの製造法に於いて
、シコンアルコシキドをポリエチレングリコール及び／
又はその誘導体の存在化で加水分解すると共に５ｉｏｚ
ａ＆粒子を含むシリカゾルに酸を加えることを特徴とす
るものである。(Means for Solving the Problems) The present invention provides a method for producing silica glass in which silicon alkoxide is hydrolyzed using a basic catalyst to obtain a silica sol containing 5ift fine particles, and the sol is dried and sintered. In the process, shicon alkoxide is mixed with polyethylene glycol and/or
or its derivatives, it is hydrolyzed and 5ioz
This method is characterized by adding an acid to a silica sol containing particles.
本発明において、シリコンアルコキシドについては特に
制限を設けないが、加水分解のしやすさの点から、メチ
ル基、エチル基、プロピル基、ブチル基を有するシリコ
ンアルコキシド又はこれらが部分的に重縮合したシリコ
ンアルコキシドの少なくとも一種を使用することが好ま
しい。In the present invention, silicon alkoxide is not particularly limited, but from the viewpoint of ease of hydrolysis, silicon alkoxide having a methyl group, ethyl group, propyl group, butyl group, or silicon partially polycondensed with these Preferably, at least one alkoxide is used.
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、
水、アルコール、又は水とアルコールの混合溶液にあら
かじめポリエチレングリコール及び／又はそのｍＨ体を
添加、均一に溶解させておく。When adding water or a mixed solution of water and alcohol to silicon alkoxide and hydrolyzing it to generate silica sol,
Polyethylene glycol and/or its mH form is added in advance to water, alcohol, or a mixed solution of water and alcohol, and is uniformly dissolved therein.
添加するポリエチレングリコール及び／又はその誘導体
の分子量については特に制限を設けないが、シリカゾル
中でのＳｉＯ□微粒子の成長を実現するという点から、
平均分子ｆｆ１１０００〜５０００００のもの、好まし
くは５０００〜２０００００のもの、最も好ましくは８
０００〜５００００の範囲のものが使用でき、これは単
独でも混合物でもよい。分子量が１０００未満の場合は
、シリカゾル中でＳ ｉＯｚ ｇ粒子の適切な成長がで
きず、一方５ｏｏｏｏｏを超える場合は、シリカゾル中
にＳ ＋ Ｏを微粒子の大きな凝集体が発生し、均一な
シリカゾル及びゲルが得られない傾向にある。但しポリ
エチレングリコール及び／又はその誘導体の適切な分子
量は、使用するシリコンアルコキシドの種類、共存する
アルコールの種類、塩基の濃度によって変化するため、
上記の分子量の範囲に必ずしも限定されるものはない。There is no particular restriction on the molecular weight of polyethylene glycol and/or its derivatives to be added, but from the point of view of realizing the growth of SiO□ fine particles in silica sol,
Average molecular ff of 11,000 to 500,000, preferably 5,000 to 200,000, most preferably 8
000 to 50,000, which may be used alone or in mixtures. If the molecular weight is less than 1000, proper growth of SiOzg particles cannot occur in the silica sol, while if it exceeds 5oooooo, large aggregates of S + O particles will occur in the silica sol, resulting in a uniform silica sol and Gel tends not to be obtained. However, the appropriate molecular weight of polyethylene glycol and/or its derivatives varies depending on the type of silicon alkoxide used, the type of coexisting alcohol, and the concentration of the base.
The above molecular weight ranges are not necessarily limited.
ポリエチレングリコール及び／又はその誘導体の添加量
については特に制限を設けないが、シリコンアルコキシ
ド重量１００重量部に対して０．０５〜１０重量部とす
ることが好ましい。添加量が０．０５重置部未満の場合
は、分子量が小さい場合にはシリカゾル中でのＳｉＯ□
微粒子の成長に所望の効果が得られない、あるいは分子
量が大きい場合には著しい凝集体の生成を引き起こす傾
向にある。一方添加量が１０重量部を超える場合は、シ
リカゾル中でのＳｉＯ□微粒子の成長に所望の効果が得
られない、ゲルを焼結ガラス化する際、ポリエチレング
リコール及び／又はその誘導体の熱分解、燃焼、離脱に
よりクランクや割れが発生しやすくなる等の問題が発生
する。但しポリエチレングリコール及び／又はその誘導
体の適切な添加量は、使用するシリコンアルコキシドの
種類、共存するアルコールの種類、塩基の濃度によって
変化するため、上記の添加量の範囲に必ずしも限定され
るものではない。The amount of polyethylene glycol and/or its derivative added is not particularly limited, but it is preferably 0.05 to 10 parts by weight per 100 parts by weight of silicon alkoxide. If the amount added is less than 0.05 parts, if the molecular weight is small, SiO□ in the silica sol
If the desired effect on the growth of fine particles cannot be obtained, or if the molecular weight is large, there is a tendency to cause the formation of significant aggregates. On the other hand, if the amount added exceeds 10 parts by weight, the desired effect on the growth of SiO□ fine particles in the silica sol may not be obtained, and when the gel is sintered and vitrified, thermal decomposition of polyethylene glycol and/or its derivatives may occur. Problems such as cranking and cracking are likely to occur due to combustion and separation. However, the appropriate amount of polyethylene glycol and/or its derivatives to be added varies depending on the type of silicon alkoxide used, the type of coexisting alcohol, and the concentration of the base, so it is not necessarily limited to the range of the amount added above. .
ポリエチレングリコールの誘導体としては、ポリエチレ
ングリコールモノ （ジ）メチルエーテル、ポリエチレ
ングリコールモノ （ジ）エチルエーテル、ポリエチレ
ングリコールモノ （ジ）プロピルエーテル、ポリエチ
レングリコールモノ（ジ）ブチルエーテル等が使用され
、それらは混合物でも、あるいはポリエチレングリコー
ルと混合して使用することができる。As derivatives of polyethylene glycol, polyethylene glycol mono (di) methyl ether, polyethylene glycol mono (di) ethyl ether, polyethylene glycol mono (di) propyl ether, polyethylene glycol mono (di) butyl ether, etc. are used, and they can also be used as a mixture. Alternatively, it can be used in combination with polyethylene glycol.
市販のポリエチレングリコール及び／又はその誘導体に
は、しばしば、Ｎａ、に等のアルカリ金属、Ｃａ、Ｍｇ
等のアルカリ土類金属、Ｆ ｅ ％Ｔｉ等の遷移金属が
不純物として含有されており、これらはゲル中に残留し
、得られるガラスの結晶化、着色等の問題を生じさせる
。このような場合には、ポリエチレングリコール及び／
又はその誘導体を熔解させた水、あるいは水とアルコー
ルの混合溶液をイオン交換樹脂と接触させて、不純物金
属を除去させた後、使用すると好適な結果が得られる。Commercially available polyethylene glycol and/or its derivatives often contain alkali metals such as Na, Ca, Mg, etc.
Alkaline earth metals such as Fe and transition metals such as Ti are contained as impurities, and these remain in the gel and cause problems such as crystallization and coloring of the resulting glass. In such cases, polyethylene glycol and/or
Suitable results can be obtained by contacting water in which a compound or a derivative thereof is dissolved, or a mixed solution of water and alcohol with an ion exchange resin to remove impurity metals before use.
本発明において、シリコンアルコキシドを加水分解する
ために添加する水の量については特に制限は設けないが
、シリコンアルコキシドを完全に加水分解するのに必要
な水の０．５〜２．０倍の範囲にあることが好ましい。In the present invention, there is no particular restriction on the amount of water added to hydrolyze silicon alkoxide, but it is in the range of 0.5 to 2.0 times the amount of water required to completely hydrolyze silicon alkoxide. It is preferable that the
添加する水の量がこの範囲未満では、一般にゾル及びゲ
ルが不均一となりやすい、一方、水の添加量がこの範囲
を超えるとシリカゾル中でのＳｉＯ，ｌｉ顆粒子成長が
抑制され、得られるゲルは乾燥過程で割れやすくなる。If the amount of water added is less than this range, the sols and gels generally tend to be non-uniform; on the other hand, if the amount of water added exceeds this range, the growth of SiO,li granules in the silica sol is suppressed, and the resulting gel becomes susceptible to cracking during the drying process.
本発明において、シリコンアルコキシドを加水分解する
際に水にアルコールを加えるのが好ましいが、アルコー
ルとしては、水、アルコキシドの両者に対する溶解性の
点より、メチルアルコール、エチルアルコール、ｌ−プ
ロピルアルコール、２−プロピルアルコール等を使用す
るのが好ましい、またアルコールの添加量は、特に制限
しないがシリコンアルコキシドの体積の０．７〜２．０
倍の範囲にあることが好ましい。In the present invention, it is preferable to add alcohol to water when hydrolyzing silicon alkoxide, but from the viewpoint of solubility in both water and alkoxide, examples of alcohol include methyl alcohol, ethyl alcohol, l-propyl alcohol, - It is preferable to use propyl alcohol, etc., and the amount of alcohol added is not particularly limited, but is 0.7 to 2.0 of the volume of silicon alkoxide.
Preferably, the range is twice that.
シリコンアルコキシドを加水分解する際に添加する塩基
触媒としては、アンモニア、コリン、各種アミノ類が使
用できる。As the base catalyst added when hydrolyzing silicon alkoxide, ammonia, choline, and various aminos can be used.
本発明に於ては、シリコンアルコキシドを加水分解して
得られたＳｉＯよ微粒子を含むシリカゾルに酸を加える
。添加する酸としては、塩酸、硝酸、硫酸、ギ酸、酢酸
、プロピオン酸等が使用できる。これらの酸の添加量は
シリカゾルのｐＨが２．０〜５．０となるように調節す
ると好適である。In the present invention, an acid is added to a silica sol containing SiO fine particles obtained by hydrolyzing silicon alkoxide. As the acid to be added, hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, propionic acid, etc. can be used. The amount of these acids added is preferably adjusted so that the pH of the silica sol is 2.0 to 5.0.
これらの酸は濃厚な液としてシリカゾルに添加するより
は、水、あるいはアルコール、あるいはこれらの混合溶
液で希釈して使用するとよい。Rather than adding these acids to the silica sol as a concentrated liquid, it is preferable to use them after diluting them with water, alcohol, or a mixed solution thereof.
さらにホルムアミド、ジメチルホルムアミド、ジメチル
アセトアミド、テトラヒドロフルフリルアルコール、メ
チルセロソルブ、エチルセロソルブ、ブチルセロソルブ
、ジエチレングリコールモノメチルエーテル、ジエチレ
ングリコールモノメチルエーテル、ジエチレングリコー
ルモノブチルエーテル、エチレングリコールジメチルエ
ーテル、エチレングリコールジエチルエーテル、ジエチ
レングリコールジメチルエーテル、ジエチレングリコー
ルジエチルエーテル、モルホリン、Ｎ−メチルピロリド
ン等の高沸点かつ小さな表面張力を有する溶剤を溶解さ
せた水、アルコール、水とアルコールの混合溶液で酸を
希釈した後、シリカゾルに添加すると、上記の高沸点、
かつ小さな表面張力を有する溶剤の存在により乾燥過程
でのゲルの破壊が防止される効果が期待できる。Furthermore, formamide, dimethylformamide, dimethylacetamide, tetrahydrofurfuryl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, If the acid is diluted with water, alcohol, or a mixed solution of water and alcohol in which a solvent with a high boiling point and low surface tension such as morpholine or N-methylpyrrolidone is dissolved, and then added to the silica sol, the above-mentioned high boiling point,
Moreover, the presence of a solvent having a small surface tension can be expected to have the effect of preventing gel destruction during the drying process.
更にシリカゾルに対して酸と共にシリコンアルコキシド
を添加しても乾燥過程でのゲルの割れに対して好適な結
果が得られる。シリコンアルコキシドとしては、テトラ
メトキシシラン、テトラエトキシシラン、テトラプロポ
キシシラン、テトラブトキシシラン又はこれらが部分的
に重縮合したものを用いることができる。シリカゾルに
対するシリコンアルコキシドの添加及び先に示した高沸
点でかつ小さな表面張力を有する溶剤の添加を組合わせ
ても良い。Furthermore, adding a silicon alkoxide to the silica sol together with an acid can also provide favorable results in preventing cracking of the gel during the drying process. As the silicon alkoxide, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or a partial polycondensation thereof can be used. The addition of silicon alkoxide to the silica sol and the addition of the above-mentioned solvent having a high boiling point and low surface tension may be combined.
酸を添加する前に、シリカゾルに対して熟成操作を加え
る（数時間〜数日の放置）、また超音波を照射する等の
工程をはさむことも好適な効果を生む。A suitable effect can also be produced by subjecting the silica sol to a ripening operation (leaving it for several hours to several days) or by irradiating it with ultrasonic waves before adding the acid.
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、次いで室温以上の温度で乾燥して、乾燥ゲルと
し、更に公知の方法、例えば、空気中で１，０００〜１
４．０００℃に昇温しで焼結することにより得られる。Silica glass is produced 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, and then drying it at a temperature above room temperature to form a dry gel, and then using a known method. For example, 1,000 to 1 in air
It is obtained by sintering at a temperature of 4.000°C.
実施例１
２−プロピルアルコール７１ｇと０．０１Ｍコリン水溶
ｆＬ４０ｇを混合し、これに４．２ｇのポリエチレング
リコール（分子１２００００）を添加し溶解させた。得
られた溶液を８５ｇのテトラメチルオルソシリケート
（Ｓ ｉ （ＯＣＨ）） 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。Example 1 71 g of 2-propyl alcohol and 40 g of 0.01 M choline aqueous solution fL were mixed, and 4.2 g of polyethylene glycol (molecules 120,000) was added and dissolved therein. The resulting solution was mixed with 85 g of tetramethyl orthosilicate.
It was slowly added to (S i (OCH)) 4) and mixed thoroughly to obtain a silica sol.
これを室温で１晩静置して熟成させた。次いでシ゛リカ
ゾルに０．１Ｍ塩酸水溶液２ｍｌを激しく攪拌しながら
添加した。これを直径１５０ｍｍ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４０
℃でゲル化させた。その後蓋に孔を開け６０℃の恒温槽
中で１週間乾燥し、その後１２０℃まで昇温しで１日乾
燥して、直径約１１０ｍｍの乾燥ゲルを得た。得られた
乾燥ゲルには、クランクや割れは全くなかった。得られ
た乾燥ゲルを空気中１，３００’Ｃまで加熱乾燥し、シ
リカガラスを得た。得られたシリカガラスには空孔等の
欠陥は全くなかった。This was allowed to stand overnight at room temperature to age. Next, 2 ml of 0.1M hydrochloric acid aqueous solution was added to the silica sol with vigorous stirring. This was placed in a Teflon-coated glass petri dish with a diameter of 150 mm and sealed with aluminum foil.
Gelled at ℃. Thereafter, a hole was made in the lid and the gel was dried for one week in a constant temperature bath at 60°C, and then the temperature was raised to 120°C and dried for one day to obtain a dried gel with a diameter of about 110 mm. The dried gel obtained had no cracks or cracks. The obtained dried gel was dried by heating to 1,300'C in air to obtain silica glass. The obtained silica glass had no defects such as pores.
実施例２
実施例１と同様にして作製したシリカゾルに、０、１
Ｍ塩酸水溶液２ｍｊ！を１９ｇの水で希釈した後、激し
く攪拌しながら添加した。これを実施例１と同様にして
ゲル化、乾燥、焼結ガラス化した。Example 2 A silica sol prepared in the same manner as in Example 1 was added with 0, 1
M hydrochloric acid aqueous solution 2 mj! was diluted with 19 g of water and added with vigorous stirring. This was gelled, dried, and sintered into vitrification in the same manner as in Example 1.
乾燥ゲルには、クラックや割れは全くながった。There were no cracks or splits in the dried gel.
また得られたシリカガラスにも、空孔等の欠陥は全くな
かった。The obtained silica glass also had no defects such as pores.
実施例３
実施例１と同様にして作製したシリカゾルに、０、．１
Ｍ塩酸水溶液２ｍｌを２４ｇのテトラヒトフルフリルア
ルコールで希釈した後、激しく撹拌しながら添加した。Example 3 A silica sol prepared in the same manner as in Example 1 was mixed with 0, . 1
After diluting 2 ml of M hydrochloric acid aqueous solution with 24 g of tetrahydrofurfuryl alcohol, it was added with vigorous stirring.
これを実施例１と同様にしてゲル化、乾燥、焼結ガラス
化した。乾燥ゲルには、クラックや割れは全くなく、ま
た得られたシリカガラスにも空孔等の欠陥は全くなかっ
た。This was gelled, dried, and sintered into vitrification in the same manner as in Example 1. The dried gel had no cracks or breaks, and the obtained silica glass had no defects such as pores.
実施例４
１−プロピルアルコール７１ｇと０．０１Ｍコリン水溶
液４０ｇを混合し、これに２．６ｇのポリエチレングリ
コール（分子１５００００）を添加し溶解させた。得ら
れた溶液を８５ｇのテトラメチルオルソシリケートにゆ
っくりと加え、さらに充分混合し、シリカゾルを得た。Example 4 71 g of 1-propyl alcohol and 40 g of 0.01M choline aqueous solution were mixed, and 2.6 g of polyethylene glycol (molecules 150,000) was added and dissolved therein. The obtained solution was slowly added to 85 g of tetramethyl orthosilicate and mixed thoroughly to obtain a silica sol.
これを室温で１晩静置して熟成させた。次いで、シリカ
ゾルに、０、１モル塩酸水溶液２ｍｌを激しく攪拌しな
がら添加した。以下、実施例１と同様にしてゲル化、乾
燥、焼結ガラス化した。乾燥ゲルには、クランクや割れ
は全くなく、また得られたシリカガラスにも空孔等の欠
陥は全くなかった。This was allowed to stand overnight at room temperature to age. Then, 2 ml of a 0.1 molar aqueous hydrochloric acid solution was added to the silica sol with vigorous stirring. Thereafter, gelation, drying, and sintering and vitrification were performed in the same manner as in Example 1. The dried gel had no cracks or cracks, and the obtained silica glass had no defects such as pores.
実施例５
２−プロピルアルコール７１ｇと０．０１Ｍコリン水溶
液４０ｇを混合し、これに０．８５ ｇのポリエチレン
グリコール（分子量８０００）を添加し溶解させた。得
られた溶液を８５ｇのテトラメチルオルソシリケートに
ゆっくりと加え、さらに充分混合しシリカゾルを得た。Example 5 71 g of 2-propyl alcohol and 40 g of 0.01M choline aqueous solution were mixed, and 0.85 g of polyethylene glycol (molecular weight 8000) was added and dissolved therein. The obtained solution was slowly added to 85 g of tetramethyl orthosilicate and thoroughly mixed to obtain a silica sol.
これを室温で１晩静置して熟成させた０次いでシリカゾ
ルに、０．１ Ｍ塩酸水溶液２ｍｆｆを激しく撹拌しな
がら添加した。This was allowed to stand overnight at room temperature to age, and then 2 mff of a 0.1 M hydrochloric acid aqueous solution was added to the silica sol with vigorous stirring.
以下、実施例１と同様にしてゲル化、乾燥、焼結し、シ
リカガラスを得た。乾燥ゲルにはクランクや割れは全く
なく、また、得られたシリカガラスには空孔等の欠陥は
全くなかった。Thereafter, gelation, drying, and sintering were performed in the same manner as in Example 1 to obtain silica glass. The dried gel had no cracks or cracks, and the obtained silica glass had no defects such as pores.
実施例６
実施例１と同様にして作製したシリカゾルに、０．１Ｍ
塩酸水溶液２ｍｌを６ｍｆの水で希釈した後、激しく攪
拌しながら添加した。次いで８．５ｇのテトラメトキシ
シランを添加した。これを実施例１と同様にしてゲル化
、乾燥、焼結ガラス化した。乾燥ゲルには、クランクや
割れは全くなく、また得られたシリカガラスにも空孔等
の欠陥は全くなかった。Example 6 0.1M was added to the silica sol prepared in the same manner as in Example 1.
After diluting 2 ml of an aqueous hydrochloric acid solution with 6 mf of water, it was added with vigorous stirring. Then 8.5g of tetramethoxysilane was added. This was gelled, dried, and sintered into vitrification in the same manner as in Example 1. The dried gel had no cracks or cracks, and the obtained silica glass had no defects such as pores.
（発明の効果）
本発明によれば、クランクや割れがなく、また空孔等の
欠陥の少ない大形のシリカガラスをゲル−ゾル法により
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 and with few defects such as pores can be easily produced by a gel-sol method. There are basically no restrictions on its size, and it can be manufactured in any shape such as a plate, rod, or tube.
また、本発明によればシリカガラスは、従来よりも安価
に製造できめため、従来から使用されてきたＩＣ製造用
フォトマスク基材等の分解はもちろん、
液晶表示基材等にも応用が拡大できる。In addition, according to the present invention, silica glass can be produced at a lower cost than before, so its application is expanding not only to decomposition of photomask substrates for IC manufacturing, which have been conventionally used, but also to liquid crystal display substrates, etc. can.
代理人 弁理士 廣 瀬 章Agent Patent Attorney Akira Hirose
Claims (1)
解してＳｉＯ＿２微粒子を含むシリカゾルを得、そのゾ
ルを乾燥、焼結するシリカガラスの製造法に於いて、シ
コンアルコシキドをポリエチレングリコール及び／又は
その誘導体の存在化で加水分解すると共にＳｉＯ＿２微
粒子を含むシリカゾルに酸を加えることを特徴とするシ
リカガラスの製造法。1. In a method for producing silica glass in which silicon alkoxide is hydrolyzed using a basic catalyst to obtain a silica sol containing SiO_2 fine particles, and the sol is dried and sintered, silicon alkoxide is mixed with polyethylene glycol and A method for producing silica glass characterized by adding an acid to a silica sol that is hydrolyzed in the presence of/or a derivative thereof and also contains SiO_2 fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30335688A JP2504148B2 (en) | 1988-11-30 | 1988-11-30 | Method for producing silica glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30335688A JP2504148B2 (en) | 1988-11-30 | 1988-11-30 | Method for producing silica glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02149431A true JPH02149431A (en) | 1990-06-08 |
| JP2504148B2 JP2504148B2 (en) | 1996-06-05 |
Family
ID=17919994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30335688A Expired - Lifetime JP2504148B2 (en) | 1988-11-30 | 1988-11-30 | Method for producing silica glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2504148B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1061050A1 (en) * | 1999-06-17 | 2000-12-20 | Lucent Technologies Inc. | Process for fabricating an article via sol-gel processing |
| JP2001049178A (en) * | 1999-06-01 | 2001-02-20 | Jsr Corp | Film-forming composition, formation of film and low- density film |
| EP1215180A1 (en) * | 2000-12-14 | 2002-06-19 | Lucent Technologies Inc. | Process for fabricating sol-gel article involving low-shrinkage formulation |
-
1988
- 1988-11-30 JP JP30335688A patent/JP2504148B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049178A (en) * | 1999-06-01 | 2001-02-20 | Jsr Corp | Film-forming composition, formation of film and low- density film |
| EP1061050A1 (en) * | 1999-06-17 | 2000-12-20 | Lucent Technologies Inc. | Process for fabricating an article via sol-gel processing |
| EP1215180A1 (en) * | 2000-12-14 | 2002-06-19 | Lucent Technologies Inc. | Process for fabricating sol-gel article involving low-shrinkage formulation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2504148B2 (en) | 1996-06-05 |
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