JPH0791070B2 - Glass molded body and manufacturing method thereof - Google Patents
Glass molded body and manufacturing method thereofInfo
- Publication number
- JPH0791070B2 JPH0791070B2 JP4146935A JP14693592A JPH0791070B2 JP H0791070 B2 JPH0791070 B2 JP H0791070B2 JP 4146935 A JP4146935 A JP 4146935A JP 14693592 A JP14693592 A JP 14693592A JP H0791070 B2 JPH0791070 B2 JP H0791070B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- silane compound
- general formula
- molded body
- glass molded
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明はいわゆるゾル・ゲル法に
よるガラス成型体とその製造方法の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a so-called sol-gel method for forming a glass body and improving its production method.
【０００２】[0002]
【従来の技術】ガラス成型体は、従来、ガラス原料とな
るシリカやソーダ灰などを溶融してガラス化しこれを所
定の型に流し込むか、成型することによって作られてき
ているが、この方法では、ガラス製造工程で数１００℃
以上の高温を必要とするため大量の熱エネルギーを消費
し、経済的に好ましくないのに加え、成型加工も熟練を
要するなど多くの問題がある。2. Description of the Related Art Conventionally, glass moldings have been manufactured by melting silica or soda ash, which is a raw material for glass, and then vitrifying it into a predetermined mold or molding it. , Glass manufacturing process at several 100 ℃
Since the above high temperature is required, a large amount of heat energy is consumed, which is not economically preferable, and there are many problems such as the molding process requires skill.
【０００３】これに対し、近年、ゾル・ゲル法と呼ばれ
るガラスの低温での製造方法が注目されている。ゾル・
ゲル法は、一般式Ｓｉ（ＯＲ）4 （ここでＲは、メチル
またはエチル基）で示されるアルキルシリケートを主成
分とし、これに水、溶剤、触媒などを加えたゾルを加水
分解・重縮合によってゲル化させ、さらに乾燥させて乾
燥ゲルとしこれを加熱焼結してガラスを得る方法であ
る。On the other hand, in recent years, a method for producing glass at a low temperature, which is called a sol-gel method, has attracted attention. Sol
The gel method is based on an alkyl silicate represented by the general formula Si (OR) 4 (where R is a methyl or ethyl group) as a main component, and water, a solvent, a catalyst, etc. are added to the resulting sol for hydrolysis / polycondensation. This is a method of obtaining a glass by gelling and further drying to obtain a dried gel, which is heat-sintered.
【０００４】[0004]
【発明が解決しようとする課題】ゾル・ゲル法によるガ
ラス製造においては、ゾルがゲル化したあと乾燥ゲルに
移行する段階で、ゲル中の溶剤や縮合反応生成物が大量
に気散するため、その分の容積が減ることによりゲルに
クラックやワレを生じやすいという問題があり、特に大
型の乾燥ゲルを作り難く、したがってまた、大型ガラス
成型体を得ることは困難であった。In the glass production by the sol-gel method, a large amount of the solvent and condensation reaction product in the gel are vaporized at the stage when the sol is gelated and then transferred to a dry gel. There is a problem that cracks and cracks are likely to occur in the gel due to the decrease in volume, and it is particularly difficult to make a large dry gel, and it is also difficult to obtain a large glass molded body.
【０００５】本発明は、ゾル・ゲル法によるガラス製造
におけるかかる欠点を改善し、光学用、電子・電気工業
用、産業廃棄物処理用、装飾用、学術・医療用等であっ
て、かつ、耐熱性の各種標本を封じ込め保存するために
使用するのに有用なガラス成型体の提供を目的とする。The present invention has improved such drawbacks in the production of glass by the sol-gel method and has optical, electronic and electrical industries, industrial waste treatment, decoration, academic and medical use, and An object of the present invention is to provide a glass molded body which is useful for containing and storing various heat-resistant specimens.
【０００６】[0006]
【課題を解決するための手段】この発明は、一般式
（１）で示されるアルキルシリケート及び一般式（２）
で示されるシラン化合物をリン酸と、または、一般式
（２）で示されるシラン化合物をリン酸と、低級アルコ
ールを溶剤として共縮合させることによって、上記の問
題を解決することを知見し、完成に至ったものである。 Ｓｉ（ＯＲ）４ （１） ここで、Ｒはメチルまたはエチル基を表す。 Ｒ′ｎＳｉ（ＯＲ″）４−ｎ （２） ここで、Ｒ′、Ｒ″はメチルまたはエチル基、ｎは１ま
たは２を表す。The present invention has the general formula
The alkyl silicate represented by (1) and the general formula (2)
A silane compound represented by phosphoric acid or a general formula
The inventors have found that the above problems can be solved by cocondensing the silane compound represented by (2) with phosphoric acid and a lower alcohol as a solvent, and have completed the invention. Si (OR) 4 (1) Here, R represents a methyl or ethyl group. R'n Si (OR ") 4-n (2) Here, R'and R" represent a methyl or ethyl group, and n represents 1 or 2.
【０００７】アルキルシリケート（１）及びシラン化合
物（２）に対するリン酸の割合、または、シラン化合物
（２）に対するリン酸の割合は、アルコキシ（ＯＲ基）
または（ＯＲ″基）の１モルに対してリン酸が１／３〜
１モルの範囲で組み合わされる。リン酸が少なければゲ
ル化に長い時間を要し、多くなればゲル化時間が短くな
る。 Alkyl silicate (1) and silane compound
Ratio of phosphoric acid to substance (2) or silane compound
The ratio of phosphoric acid to (2) is alkoxy (OR group)
Or phosphoric acid is 1/3 to 1 mol of (OR "group)
Combined in the range of 1 mole. If the amount of phosphoric acid is small, it takes a long time to gel, and if it is large, the gelling time is short.
【０００８】シラン化合物（γ−グリシドキシプロピル
トリアルコキシシラン及び／又はメチルトリメトキシシ
ラン）６０％とエチルシルケートの加水分解物（ＳｉＯ
2 として１０％含む）４０％の混合液をＸ液とする。一
方、８５％リン酸１０％とイソプロピルアルコール９０
％との混合物をＹ液とする。Ｘ液及びＹ液それぞれの比
率によってゾルから湿潤ゲルまでの時間は表１のように
変化した。60% of a silane compound (γ-glycidoxypropyltrialkoxysilane and / or methyltrimethoxysilane) and a hydrolyzate of ethyl silicate (SiO 2
A mixed solution of 40% (including 10% as 2 ) is designated as solution X. On the other hand, 85% phosphoric acid 10% and isopropyl alcohol 90
The mixture with 10% is referred to as liquid Y. The time from the sol to the wet gel changed as shown in Table 1 depending on the ratio of each of the X liquid and the Y liquid.
【０００９】[0009]
【表１】 [Table 1]
【００１０】リン酸としては化学用純８５％リン酸が好
ましいが７５％、８９％、１００％のリン酸や１０５
％、１１５〜１１６％のポリリン酸も使用できる。Chemically pure 85% phosphoric acid is preferred as phosphoric acid, but 75%, 89%, 100% phosphoric acid or 105
%, 115-116% polyphosphoric acid can also be used.
【００１１】アルキルシリケート（１）及びシラン化合
物（２）、または、シラン化合物（２）に対するリン酸
の反応は複雑で正確な表現は困難であるが、例えば、ア
ルキルシリケート（１）及びシラン化合物（２）のアル
コキシ基とリン酸が反応して Alkyl silicate (1) and silane compound
Although the reaction of phosphoric acid with the compound (2) or the silane compound (2) is complicated and accurate expression is difficult, for example, the alkoxy group of the alkyl silicate (1) and the silane compound (2) reacts with phosphoric acid. do it
【００１２】これが、さらにアルキルシリケート（１）
及びシラン化合物（２）のアルコキシ基と反応して、 This is the alkyl silicate (1)
And it reacts with the alkoxy groups of the silane compound (2),
【００１３】また、さらにリン酸と反応して、 のような反応が繰り返されることによって、次式の構造
を含む無機ポリマーが完成されるものと考えられる。Further, by further reacting with phosphoric acid, It is considered that the inorganic polymer containing the structure of the following formula is completed by repeating the above reaction.
【００１４】 [0014]
【００１５】本発明において、必要に応じて染料、顔料
などの着色剤、無機フィラー、あるいは消泡剤、チクソ
性付与剤などを併用することもできる。In the present invention, a coloring agent such as a dye or a pigment, an inorganic filler, an antifoaming agent, a thixotropy-imparting agent, or the like can be used in combination, if necessary.
【００１６】[0016]
【作用】本発明によるゾル・ゲル法によるガラス製造に
おいては、ゾルがゲル化するまでの時間を調節すること
ができ、しかも、ゲル化したあと乾燥ゲルに移行する段
階でゲル中の溶剤や縮合反応生成物の気散に起因するク
ラックやワレを生じにくく、したがって、大型のガラス
成型体も得ることができる。本発明の共縮合物は、水溶
性物質の縮合反応で得られる物質であるため、適当な解
析手段がなく、上記クラックやワレが生じにくくなる理
由が、今のところ立証できる程に明らかではないが、次
のように推測される。すなわち、本発明のアルキルシリ
ケート及びシラン化合物とリン酸の共縮合物は、前記の
ように若干のアルキル基を有する極めて親水性の無機ポ
リマーとなっており、したがって、本発明のゲル体は、
イ）水溶性無機ポリマーから溶媒の水が揮発してゆくよ
うなメカニズムで脱水・脱アルコールが進行して乾燥ゲ
ルが得られ、ロ）無機ポリマーの親水度が高いために、
ゲル中の水が完全には取り除けないが、このような含有
水状態でも見かけ上、乾燥した状態になっていると考え
られ、クラックやワレを生じにくくする。In the glass production by the sol-gel method according to the present invention, the time until the sol gels can be adjusted, and the solvent and condensation in the gel at the stage of transition to gel after gelation Cracks and cracks due to vaporization of the reaction product are unlikely to occur, and thus a large glass molded body can be obtained. The cocondensate of the present invention is water-soluble.
Since it is a substance obtained by the condensation reaction of a volatile substance,
The reason why there is no analysis means and the above cracks and cracks are less likely to occur
The reason is not yet clear enough to prove, but next
Is speculated as . That is, the alkylsilyl of the present invention
The co-condensation products of phosphoric acid with silicates and silane compounds are
Is a very hydrophilic inorganic polymer with some alkyl groups.
Therefore, the gel body of the present invention is
B) The solvent water evaporates from the water-soluble inorganic polymer
Dehydration / dealcoholization progresses by a mechanism like that
Is obtained, and b) because of the high hydrophilicity of the inorganic polymer,
Although water in the gel cannot be completely removed,
Considered to be dry even in water
To prevent cracks and cracks .
【００１７】[0017]
【実施例】実施例１ γ−グリシドキシプロピルトリアルコキシシラン４００
ｇにメチルトリメトキシシラン１００ｇを加え良く撹拌
・混合した（Ａ液という）。一方、エチルシリケートの
加水分解物（ＳｉＯ2 として１０％含む）３００ｇと８
５％リン酸１００ｇをＩＰＡ（イソプロピルアルコー
ル）１００ｇに溶解した（Ｂ液という）。EXAMPLES Example 1 γ-glycidoxypropyltrialkoxysilane 400
100 g of methyltrimethoxysilane was added to g and well mixed and stirred (referred to as solution A). On the other hand, 300 g of a hydrolyzate of ethyl silicate (containing 10% as SiO 2 ) and 8
100 g of 5% phosphoric acid was dissolved in 100 g of IPA (isopropyl alcohol) (referred to as solution B).
【００１８】Ａ液とＢ液を静かに混合して得られたゾル
を、密閉のできるポリエチレン容器に入れ室温に静置し
た。このゾルは４８時間後にはゲル化し流動性がなくな
った。ポリエチレン容器の蓋の一部に穴を開けることに
よってこの容器を外部に対して開放とし、室温で４週間
静置することにより湿潤ゲルを乾燥ゲルとした。その
後、この乾燥ゲルを容器から取り出し、６０℃で２週
間、１２０℃で１日加熱乾燥を行った。このようにして
得られた乾燥ゲルにはクラックやワレが全く認められな
かった。この乾燥ゲルを空気中で１３００℃まで加熱し
焼結して無色透明のガラスを得た。The sol obtained by gently mixing the liquids A and B was placed in a sealable polyethylene container and allowed to stand at room temperature. The sol gelled after 48 hours and lost fluidity. This container was opened to the outside by making a hole in a part of the lid of the polyethylene container, and the wet gel was made into a dry gel by allowing it to stand at room temperature for 4 weeks. Then, the dried gel was taken out of the container and heated and dried at 60 ° C. for 2 weeks and 120 ° C. for 1 day. No cracks or cracks were found in the dried gel thus obtained. The dried gel was heated to 1300 ° C. in air and sintered to obtain colorless transparent glass.
【００１９】実施例２ 蒸留水９９ｇに酢酸１ｇを加えて撹拌し、これをγ−グ
リシドキシプロピルトリアルコキシシラン４００ｇに滴
下し、撹拌混合した（Ａ2 液という）。一方、８５％リ
ン酸１００ｇを蒸留水４００ｇに溶解した（Ｂ2 液とい
う）。Ａ2 液とＢ2 液を静かに混合して得られたゾル
を、実施例１と同様に処理し無色透明のガラスを得た。Example 2 1 g of acetic acid was added to 99 g of distilled water and stirred, which was added dropwise to 400 g of γ-glycidoxypropyltrialkoxysilane and mixed by stirring (referred to as A 2 solution). On the other hand, 100 g of 85% phosphoric acid was dissolved in 400 g of distilled water (referred to as solution B 2 ). The sol obtained by gently mixing the liquid A 2 and the liquid B 2 was treated in the same manner as in Example 1 to obtain a colorless transparent glass.
【００２０】実施例３ γ−グリシドキシプロピルトリアルコキシシラン４００
ｇにメチルトリメトキシシラン１００ｇを加え、良く撹
拌・混合した（Ａ3 液という）。一方、エチルシリケー
トの加水分解物（ＳｉＯ2 として１０％含む）４８０ｇ
に８５％リン酸８０ｇを良く混合撹拌した（Ｂ3 液とい
う）。Ａ3 液とＢ3 液を静かに混合して得られたゾル
を、実施例１と同様に処理し無色透明のガラスを得た。Example 3 γ-glycidoxypropyltrialkoxysilane 400
100 g of methyltrimethoxysilane was added to g, and well stirred and mixed (referred to as A 3 solution). On the other hand, ethyl silicate hydrolyzate (containing 10% as SiO 2 ) 480 g
80 g of 85% phosphoric acid was thoroughly mixed and stirred (referred to as solution B 3 ). The sol obtained by gently mixing the liquid A 3 and the liquid B 3 was treated in the same manner as in Example 1 to obtain a colorless transparent glass.
【００２１】[0021]
【発明の効果】本発明によるゾル・ゲル法によるガラス
製造においては、ゾルがゲル化するまでの時間を適宜調
節することができる。しかも、ゲル化したあと乾燥ゲル
に移行する段階で、ゲル中の溶剤や縮合反応生成物の気
散によるクラックやワレを生じにくく、大型のガラス成
型体を容易に得ることができる。このガラス成型体は、
光学用、電子・電気工業用、産業廃棄物処理用、装飾
用、学術・医療用等であって、かつ、耐熱性の各種標本
を封じ込め保存するために使用するのに有用である。In the glass production by the sol-gel method according to the present invention, the time until the sol gels can be adjusted appropriately. Moreover, cracks and cracks due to vaporization of the solvent and condensation reaction product in the gel are unlikely to occur at the stage of gelation and then transfer to a dry gel, and a large glass molding can be easily obtained. This glass molding is
It is useful for optics, electronic / electric industry, industrial waste treatment, decoration, academic / medical use, etc., and for containing and storing various heat-resistant specimens.
【００２２】なお、上記各種標本の封じ込めは、２液混
合ゾル中に当該標本を没入固定しておくことによって行
うものである。Incidentally, the containment of the various specimens is carried out by immersing and fixing the specimens in the two-liquid mixed sol.
Claims (4)
ト及び一般式（２）で示されるシラン化合物とリン酸と
の共縮合物、または、一般式（２）で示されるシラン化
合物とリン酸との共縮合物からなることを特徴とするガ
ラス成型体。 Ｓｉ（ＯＲ）４ （１） ここで、Ｒはメチルまたはエチル基を表す。 Ｒ′ｎＳｉ（ＯＲ″）４−ｎ （２） ここで、Ｒ′、Ｒ″はメチルまたはエチル基、ｎは１ま
たは２を表す。1. An alkyl silicate represented by the general formula (1) :
And a silane compound represented by the general formula (2) and phosphoric acid
Cocondensation product or silanization represented by the general formula (2)
A glass molded body comprising a co-condensate of a compound and phosphoric acid . Si (OR) 4 (1) Here, R represents a methyl or ethyl group. R'n Si (OR ") 4-n (2) Here, R'and R" represent a methyl or ethyl group, and n represents 1 or 2.
ト及び一般式（２）で示されるシラン化合物をリン酸と
共縮合させて得られた共縮合物、または、一般式（２）
で示されるシラン化合物をリン酸と共縮合させて得られ
た共縮合物を密閉状態で静置してゲル化し、さらに、そ
れを乾燥ゲルとした後、加熱焼結することを特徴とする
ガラス成型体の製造方法。 Ｓｉ（ＯＲ）４ （１） ここで、Ｒはメチルまたはエチル基を表す。 Ｒ′ｎＳｉ（ＯＲ″）４−ｎ （２） ここで、Ｒ′、Ｒ″はメチルまたはエチル基、ｎは１ま
たは２を表す。2. An alkyl silicate represented by the general formula (1) :
And a silane compound represented by the general formula (2) with phosphoric acid
Cocondensation product obtained by cocondensation or general formula (2)
Obtained by co-condensing a silane compound represented by
A method for producing a glass molded body, characterized in that the co-condensate is allowed to stand in a sealed state to be gelled, and the dried gel is dried and then sintered. Si (OR) 4 (1) Here, R represents a methyl or ethyl group. R'n Si (OR ") 4-n (2) Here, R'and R" represent a methyl or ethyl group, and n represents 1 or 2.
たは、シラン化合物のアルコキシ基１モルに対してリン
酸が１／３〜１モルである請求項１記載の共縮合物から
なるガラス成型体。3. An alkyl silicate and a silane compound, or
Alternatively, a glass molded body comprising the cocondensate according to claim 1, wherein phosphoric acid is 1/3 to 1 mol per 1 mol of the alkoxy group of the silane compound .
たは、シラン化合物のアルコキシ基１モルに対してリン
酸が１／３〜１モルである請求項２記載のガラス成型体
の製造方法。4. An alkyl silicate and a silane compound, or
The method for producing a glass molded body according to claim 2, wherein the phosphoric acid is 1/3 to 1 mol per 1 mol of the alkoxy group of the silane compound .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4146935A JPH0791070B2 (en) | 1992-05-13 | 1992-05-13 | Glass molded body and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4146935A JPH0791070B2 (en) | 1992-05-13 | 1992-05-13 | Glass molded body and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05319861A JPH05319861A (en) | 1993-12-03 |
| JPH0791070B2 true JPH0791070B2 (en) | 1995-10-04 |
Family
ID=15418901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4146935A Expired - Lifetime JPH0791070B2 (en) | 1992-05-13 | 1992-05-13 | Glass molded body and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791070B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100619379B1 (en) * | 2003-06-27 | 2006-09-05 | 삼성전자주식회사 | Method for Producing Quantum Dot Silicate Thin Film for Light Emitting Device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6225616A (en) * | 1985-07-24 | 1987-02-03 | Shimizu Constr Co Ltd | Blade built-in type auger excavator |
-
1992
- 1992-05-13 JP JP4146935A patent/JPH0791070B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05319861A (en) | 1993-12-03 |
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