JPS6346095B2 - - Google Patents
Info
- Publication number
- JPS6346095B2 JPS6346095B2 JP60091124A JP9112485A JPS6346095B2 JP S6346095 B2 JPS6346095 B2 JP S6346095B2 JP 60091124 A JP60091124 A JP 60091124A JP 9112485 A JP9112485 A JP 9112485A JP S6346095 B2 JPS6346095 B2 JP S6346095B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- och
- solvent
- silica
- silanol oligomer
- 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
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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Formation Of Insulating Films (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、シリコン、ガラス、セラミツク、ア
ルミ等の基体表面上に厚いシリカ系被膜を容易に
形成可能なシラノールオリゴマー液の製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a silanol oligomer liquid that can easily form a thick silica-based coating on the surface of a substrate such as silicon, glass, ceramic, or aluminum.
（従来の技術）
従来、ハロゲン化シラン、アルコキシシラン等
の溶液もしくは、その部分加水分解物を基体上に
塗布し、焼成してシリカ系の被膜を形成する方法
はよく知られており、特公昭52−16488号公報、
同52−20825号公報、特開昭55−34258号公報等に
提案されている。しかし、ハロゲン化シランを用
いる方法によれば、加水分解によつてハロゲン化
水素が発生し、系が強い酸性となるため反応のコ
ントロールが非常に困難である。また生成物にハ
ロゲン化水素が多量に残存するため、液の安定性
が著しくそこなわれるほか、電子部品等に用いた
場合、部品の耐湿信頼性が著しく低下するという
欠点を有する。一方アルコキシシランとしては従
来テトラエトキシシラン（エチルシリケート）等
の四官能シランを用いた系が最も良く検討されて
いるが、これらの四官能シランを用いた系では焼
成してシリカ系被膜を形成する際に、三次元架橋
構造が非常に密になり、剛直になるため、膜厚が
厚くなるとクラツクが発生するという欠点を有す
る。そこでこれらの欠点を改良するため種々の試
みがなされており、米国特許第4408009号明細書、
特開昭58−28850号公報等に見られる様な三官能、
二官能シランを共加水分解する方法が開示されて
いる。しかし、これらの公知例においては、用い
るアルコキシシランのアルコキシ基の種類および
用いる溶媒についてほとんど検討がなされていな
い。(Prior Art) Conventionally, a method of coating a solution of halogenated silane, alkoxysilane, etc. or a partially hydrolyzed product thereof on a substrate and baking it to form a silica-based film is well known. Publication No. 52-16488,
This method has been proposed in Japanese Patent Publication No. 52-20825, Japanese Patent Application Laid-Open No. 55-34258, etc. However, according to the method using halogenated silane, hydrogen halide is generated by hydrolysis and the system becomes strongly acidic, making it very difficult to control the reaction. Furthermore, since a large amount of hydrogen halide remains in the product, the stability of the liquid is significantly impaired, and when used in electronic components, etc., the moisture resistance reliability of the components is significantly reduced. On the other hand, as alkoxysilanes, systems using tetrafunctional silanes such as tetraethoxysilane (ethyl silicate) have been the most studied, but systems using these tetrafunctional silanes require firing to form a silica-based film. However, since the three-dimensional crosslinked structure becomes very dense and rigid, it has the disadvantage that cracks occur when the film thickness increases. Various attempts have been made to improve these drawbacks, including US Pat. No. 4,408,009;
Trisensory, as seen in Japanese Patent Application Laid-open No. 58-28850, etc.
A method of cohydrolyzing difunctional silanes is disclosed. However, in these known examples, little consideration has been given to the type of alkoxy group of the alkoxysilane used and the solvent used.
（発明が解決しようとする問題点）
本発明は、焼成後の成膜性および膜質は用いる
アルコキシ基と、溶媒の種類に大きく依存するこ
とを見出してなされたもので上記の問題点を解決
するものである。(Problems to be Solved by the Invention) The present invention was made based on the discovery that the film formability and film quality after firing largely depend on the alkoxy group used and the type of solvent, and thus solves the above problems. It is something.
（問題点を解決するための手段）
本発明は、溶媒の存在下でメチルメトキシシラ
ンと水とを溶媒を用いて加水分解縮合させる際
に、溶媒としてアミド系溶媒を用いるシラノール
オリゴマー液の製造法に関する。(Means for Solving the Problems) The present invention provides a method for producing a silanol oligomer liquid using an amide solvent as a solvent when methylmethoxysilane and water are hydrolyzed and condensed using a solvent in the presence of a solvent. Regarding.
アルコキシシランは一般式 RnSi（OR）4-oで
表わされ、次式
RnSi（OR）4-o＋(4-o)H2O →RnSi（OH）4-o
（ただしｎは０〜３の整数）
の様に加水分解し、次にシラノール基（≡Si−
OH）が縮合してSi−Ｏ−Si結合を生成して最終
的にはシリカ系重合体となる。溶媒中で加水分解
反応を行なつた場合これらの反応は即座に完結す
るわけではなく、部分的に加水分解されたシラノ
ールオリゴマー液を作製することが可能である。
このシラノールオリゴマー液を基体上に塗布し、
400℃以上の温度で焼成するとさらに加水分解、
縮合が進行しシリカ系被膜を形成するわけである
が、この際アルコキシ基が大きい、すなわち炭素
数が多いと、アルコキシ基の脱離による収縮歪が
大きくなりクラツクが発生する。また、膜中に多
量の炭素残渣が残存し、完全なシリカ系被膜とな
らない。本発明者らの詳細な検討によれば、アル
コキシ基として使用可能なのはメトキシ基のみで
ある。同様にしてアルキル基についてもメチル基
のみが用いられる。 Alkoxysilane is represented by the general formula RnSi(OR) 4-o , and the following formula: RnSi(OR) 4-o + (4-o) H 2 O → RnSi(OH) 4-o (where n is 0 to 3 (an integer of ), and then the silanol group (≡Si−
OH) condenses to form Si-O-Si bonds, ultimately forming a silica-based polymer. When hydrolysis reactions are carried out in a solvent, these reactions are not completed immediately, and it is possible to prepare a partially hydrolyzed silanol oligomer liquid.
Apply this silanol oligomer liquid onto the substrate,
When fired at a temperature of 400℃ or higher, further hydrolysis occurs.
Condensation progresses to form a silica-based film, but if the alkoxy group is large, that is, the number of carbon atoms is large, shrinkage strain due to elimination of the alkoxy group becomes large and cracks occur. Further, a large amount of carbon residue remains in the film, and a complete silica-based film cannot be obtained. According to detailed studies by the present inventors, only methoxy group can be used as the alkoxy group. Similarly, for alkyl groups, only methyl groups are used.
次に本発明に用いるメチルメトキシシランの共
重合組成としては前述した成膜性と炭素残渣の観
点からSi（OCH3）420〜40モル％、CH3Si
（OCH3）340〜60モル％、（CH3）2Si（OCH3）210〜
20モル％の範囲のものが好ましい。Si（OCH3）4
が40モル％以上になるとクラツクが入りやすくな
り、またCH3Si（OCH3）3および（CH3）2Si
（OCH3）2が多いと、炭素残渣の量が多くなる。 Next, the copolymerization composition of methylmethoxysilane used in the present invention is 20 to 40 mol% of Si(OCH 3 ) 4 , CH 3 Si
( OCH3 ) 3 40~60 mol%, ( CH3 ) 2Si ( OCH3 ) 2 10~
A range of 20 mol% is preferred. Si( OCH3 ) 4
When CH 3 Si (OCH 3 ) 3 and (CH 3 ) 2 Si
When (OCH 3 ) 2 is high, the amount of carbon residue increases.
次に、これらアルコキシシランの種類および組
成を最適化した場合でも、公知例のごとく溶媒と
してエチルアルコール、ｉ−プロピルアルコール
や、エチレングリコール等炭素数の大きいアルコ
ール系溶媒を用いた場合、目的とする厚いシリカ
系被膜をクラツクなく得ることは不可能である。 Next, even if the type and composition of these alkoxysilanes are optimized, if an alcoholic solvent with a large number of carbon atoms such as ethyl alcohol, i-propyl alcohol, or ethylene glycol is used as a solvent as in the known example, the target It is impossible to obtain thick silica-based coatings without cracks.
本発明者らの詳細な検討によれば、例えばアル
コキシシランとしてテトラメトキシシランを用
い、溶媒としてプロピルアルコールを用いた場
合、溶液中で次式
Si（OCH3）4＋4i−C3H9OH
→Si（OC3H9）4＋4CH3OH
のごとき交換反応が生じ、実質上テトライソプロ
ポキシシランを用いた場合と同様の結果となり、
成膜性が著しくそこなわれる。従つて本発明に用
いられる溶媒はメトキシシランとこの様な交換反
応を生じないアミド系溶媒に限定される。アミド
系溶媒としては、Ｎ，Ｎ−ジメチルホルムアミ
ド，Ｎ，Ｎ−ジメチルアセトアミド，Ｎ−メチル
−２−ピロリドン等が好ましい。 According to detailed studies by the present inventors, for example, when tetramethoxysilane is used as the alkoxysilane and propyl alcohol is used as the solvent, the following formula Si(OCH 3 ) 4 + 4i−C 3 H 9 OH is formed in solution.
→Si(OC 3 H 9 ) 4 +4CH 3 OH An exchange reaction occurs, and the result is essentially the same as when tetraisopropoxysilane is used.
Film formability is significantly impaired. Therefore, the solvents used in the present invention are limited to amide solvents that do not cause such an exchange reaction with methoxysilane. Preferred amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.
次に本発明に用いられる反応触媒としては、塩
酸、硫酸、リン酸、ホウ酸等の無機酸や、五酸化
リン、酸化ホウ素等の酸化物等を用いることが可
能であるが、シラノールオリゴマー液を電子部品
関係に用いる場合には、リン酸、ホウ酸等が好ま
しい。 Next, as the reaction catalyst used in the present invention, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid, and oxides such as phosphorus pentoxide and boron oxide can be used, but silanol oligomer liquid When used in connection with electronic components, phosphoric acid, boric acid, etc. are preferred.
また、触媒の添加量は、メチルメトキシシラン
に対して0.1〜５重量％の範囲が好ましい。 Further, the amount of the catalyst added is preferably in the range of 0.1 to 5% by weight based on methylmethoxysilane.
本発明のシラノールオリゴマー液は、前述した
溶媒中にメチルメトキシシランを溶解した後、触
媒と水を添加することにより、容易に得られる。
また、このシラノールオリゴマー液から、シリカ
系被膜を形成するには、基体上にスピナー、ハ
ケ、スプレー等でシラノールオリゴマー液を塗布
したのち50〜200℃好ましくは100〜150℃の温度
で乾燥し、次に400〜800℃好ましくは500〜600℃
温度で焼成を行なえばよい。 The silanol oligomer liquid of the present invention can be easily obtained by dissolving methylmethoxysilane in the above-mentioned solvent and then adding a catalyst and water.
In addition, in order to form a silica-based film from this silanol oligomer liquid, the silanol oligomer liquid is applied onto the substrate with a spinner, brush, spray, etc., and then dried at a temperature of 50 to 200°C, preferably 100 to 150°C. Then 400-800℃ preferably 500-600℃
It is sufficient to perform the firing at a certain temperature.
（発明の効果）
本発明のシラノールオリゴマー液を用いると、
シリコン、ガラス、セラミツク等の基体上に最高
2μmまでのクラツクのないシリカ系被膜を形成可
能であり、電子部品、特に半導体の多層配線にお
ける層間段差の被膜、磁気バブルメモリー等の素
子表面の平坦化等に非常に有効である。(Effect of the invention) When the silanol oligomer liquid of the invention is used,
Ideal for use on substrates such as silicon, glass, and ceramics
It is possible to form crack-free silica-based coatings up to 2 μm in thickness, and is extremely effective for coating interlayer steps in electronic components, especially semiconductor multilayer wiring, and for flattening the surfaces of devices such as magnetic bubble memories.
（実施例）
以下、実施例、比較例により本発明をより具体
的に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例
Si（OCH3）4 17ｇ，CH3Si（OCH3）3 25ｇ，
（CH3）2Si（OCH3）2 ５ｇをＮ，Ｎ−ジメチルホル
ムアミド40ｇ、メタノール５ｇ中に溶解し、リン
酸0.5ｇを溶解した水20ｇを添加して、加水分解、
縮合を行ない、シラノールオリゴマー液を作製し
た。Example Si(OCH 3 ) 4 17g, CH 3 Si(OCH 3 ) 3 25g,
5 g of (CH 3 ) 2 Si(OCH 3 ) 2 was dissolved in 40 g of N,N-dimethylformamide and 5 g of methanol, and 20 g of water in which 0.5 g of phosphoric acid was dissolved was added for hydrolysis.
Condensation was performed to prepare a silanol oligomer liquid.
この溶液をスピナーを用いて1000rpmでSiウエ
ーハ上に塗布した後120℃で１時間乾燥した。そ
の後電気炉中で500℃で１時間焼成したところ、
無色透明、クラツクフリーのシリカフイルムが得
られた。表面あらさ計（商品名，タリステツプ，
ランクテーラーホブソン社製）を用いてこのシリ
カフイルムの膜厚を測定したところ2.0μmであつ
た。また、赤外分光光度計を用いて吸収スペクト
ルを測定したところ完全なSiO2の膜であること
が確認された。 This solution was applied onto a Si wafer at 1000 rpm using a spinner, and then dried at 120° C. for 1 hour. After that, it was fired at 500℃ for 1 hour in an electric furnace.
A colorless, transparent, crack-free silica film was obtained. Surface roughness meter (product name, Talystep,
The thickness of this silica film was measured using a silica film (manufactured by Rank Taylor Hobson) and found to be 2.0 μm. Furthermore, when the absorption spectrum was measured using an infrared spectrophotometer, it was confirmed that it was a complete SiO 2 film.
比較例 １
Si（OCH3）4 17ｇ，CH3Si（OCH3）3 25ｇ，
（CH3）2Si（OCH3）2 ５ｇをイソプロピルアルコー
ル40ｇ，メタノール５ｇ中に溶解し、リン酸0.5
ｇを溶解した水20ｇを添加して加水分解、縮合を
行ないシラノールオリゴマー液を作製した。Comparative example 1 Si(OCH 3 ) 4 17g, CH 3 Si(OCH 3 ) 3 25g,
Dissolve 5 g of (CH 3 ) 2 Si(OCH 3 ) 2 in 40 g of isopropyl alcohol and 5 g of methanol, and add 0.5 g of phosphoric acid.
20 g of water was added to perform hydrolysis and condensation to prepare a silanol oligomer liquid.
この溶液を実施例と同様にして塗布、焼成した
ところ同じく約2μmの膜が得られたが、多数のク
ラツクが発生し、膜が白化してしまつた。次にこ
の溶液をガスクロマトグラフによつて分析したと
ころ、Si（OCH3）o（OC3H9）4-o（ｎは０〜４の整
数、CH3Si（OCH3）o（OC3H9）3-o（ｎは０〜３の
整数）、（CH3）2Si（OCH3）o（OC3H9）2-o（ｎは０
〜２の整数）のピークが存在することが確認され
た。 When this solution was applied and baked in the same manner as in the example, a film of approximately 2 μm was obtained, but many cracks were generated and the film turned white. Next, this solution was analyzed by gas chromatography, and it was found that Si(OCH 3 ) o (OC 3 H 9 ) 4-o (n is an integer from 0 to 4, CH 3 Si(OCH 3 ) o (OC 3 H 9 ) 3-o (n is an integer from 0 to 3), (CH 3 ) 2 Si (OCH 3 ) o (OC 3 H 9 ) 2-o (n is 0
It was confirmed that a peak (integer of ~2) was present.
また、120℃で乾燥した粉末を作製し、500℃で
１時間の焼成を行なつたところ茶かつ色の粉末が
得られ炭素残渣が残存することがわかつた。 Furthermore, when a powder dried at 120°C was prepared and fired at 500°C for 1 hour, a brown powder was obtained, indicating that carbon residue remained.
比較例 ２
Si（OCH3）4、Si（OC2H5）4、Si（OC3H7）4の各１
種のみを用いて実施例と同様にしてＮ，Ｎ−ジメ
チルホルムアミドと、それぞれのアルコキシ基に
対応するアルコールを用いてシラノールオリゴマ
ー液を作製し、成膜性を評価したところいずれ
も、1μm以下の膜厚でクラツクが発生した。Comparative Example 2 One each of Si(OCH 3 ) 4 , Si(OC 2 H 5 ) 4 , and Si(OC 3 H 7 ) 4
Using only seeds, silanol oligomer liquids were prepared using N,N-dimethylformamide and alcohols corresponding to the respective alkoxy groups in the same manner as in the example, and film forming properties were evaluated. Cracks occurred due to film thickness.
Claims (1)
を触媒を用いて加水分解縮合させる際に、溶媒と
して、アミド系溶媒を用いることを特徴とするシ
ラノールオリゴマー液の製造法。1. A method for producing a silanol oligomer liquid, which comprises using an amide solvent as a solvent when methylmethoxysilane and water are hydrolyzed and condensed using a catalyst in the presence of a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9112485A JPS61250032A (en) | 1985-04-30 | 1985-04-30 | Preparation of silanol origomer liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9112485A JPS61250032A (en) | 1985-04-30 | 1985-04-30 | Preparation of silanol origomer liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61250032A JPS61250032A (en) | 1986-11-07 |
| JPS6346095B2 true JPS6346095B2 (en) | 1988-09-13 |
Family
ID=14017773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9112485A Granted JPS61250032A (en) | 1985-04-30 | 1985-04-30 | Preparation of silanol origomer liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61250032A (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791509B2 (en) * | 1985-12-17 | 1995-10-04 | 住友化学工業株式会社 | Insulating film forming coating solution for semiconductors |
| US4999397A (en) * | 1989-07-28 | 1991-03-12 | Dow Corning Corporation | Metastable silane hydrolyzates and process for their preparation |
| JPH03221577A (en) * | 1990-01-26 | 1991-09-30 | Sumitomo Chem Co Ltd | Coating solution for insulating film formation |
| US5332429A (en) * | 1991-05-31 | 1994-07-26 | Minnesota Mining And Manufacturing Company | Method for treating fluoroaluminosilicate glass |
| JP3262334B2 (en) | 1992-07-04 | 2002-03-04 | トリコン ホルディングズ リミテッド | Method for processing semiconductor wafers |
| BE1008724A3 (en) * | 1994-09-27 | 1996-07-02 | Couttenier Andre | COMPOSITION FOR PROTECTING WATER REPELLENT AND MAKING A siliceous substrate. |
| JP6612563B2 (en) | 2014-12-26 | 2019-11-27 | 日東電工株式会社 | Silicone porous body and method for producing the same |
| JP6604781B2 (en) | 2014-12-26 | 2019-11-13 | 日東電工株式会社 | Laminated film roll and method for producing the same |
| JP6599699B2 (en) | 2014-12-26 | 2019-10-30 | 日東電工株式会社 | Void structure film bonded through catalytic action and method for producing the same |
| TWI691559B (en) * | 2014-12-26 | 2020-04-21 | 日商日東電工股份有限公司 | Paint and its manufacturing method |
| JP6563750B2 (en) | 2014-12-26 | 2019-08-21 | 日東電工株式会社 | Paint and production method thereof |
| JP6713871B2 (en) | 2015-07-31 | 2020-06-24 | 日東電工株式会社 | Optical laminate, method for producing optical laminate, optical member, image display device, method for producing optical member, and method for producing image display device |
| JP6713872B2 (en) | 2015-07-31 | 2020-06-24 | 日東電工株式会社 | Laminated film, laminated film manufacturing method, optical member, image display device, optical member manufacturing method, and image display device manufacturing method |
| JP6892744B2 (en) | 2015-08-24 | 2021-06-23 | 日東電工株式会社 | Laminated optical film, manufacturing method of laminated optical film, optical members, and image display device |
| JP7152130B2 (en) | 2015-09-07 | 2022-10-12 | 日東電工株式会社 | Low refractive index layer, laminated film, method for producing low refractive index layer, method for producing laminated film, optical member, and image display device |
| JP6615552B2 (en) * | 2015-09-25 | 2019-12-04 | 日本ペイント・オートモーティブコーティングス株式会社 | Cationic electrodeposition coating composition |
| EP3178884B1 (en) * | 2015-12-08 | 2018-02-07 | Evonik Degussa GmbH | Aqueous [3- (2,3-dihydroxyprop-1-oxy) propyl] silanololigomer containing composition, method for their preparation and their use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3842110A (en) * | 1973-10-11 | 1974-10-15 | Gen Electric | Process for producing octaphenyltetracyclosiloxane |
| JPS5739659A (en) * | 1980-08-21 | 1982-03-04 | Nec Corp | Calling out system for private branch of exchanger |
| FR2523590B1 (en) * | 1982-03-16 | 1984-06-29 | Inst Nat Rech Chimique | BASIC LIQUID COMPOSITION SUITABLE FOR PRODUCING TRANSPARENT OR VARNISHED COATINGS ON SOLID SURFACES, PROCESS FOR OBTAINING VARNISHES AND VARNISHES THEREFROM |
-
1985
- 1985-04-30 JP JP9112485A patent/JPS61250032A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61250032A (en) | 1986-11-07 |
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