JP3163579B2 - Coating liquid for film formation - Google Patents
Coating liquid for film formationInfo
- Publication number
- JP3163579B2 JP3163579B2 JP06225590A JP6225590A JP3163579B2 JP 3163579 B2 JP3163579 B2 JP 3163579B2 JP 06225590 A JP06225590 A JP 06225590A JP 6225590 A JP6225590 A JP 6225590A JP 3163579 B2 JP3163579 B2 JP 3163579B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- silica sol
- alkoxysilane
- silica
- coating
- 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
Description
【発明の詳細な説明】 発明の技術分野 本発明は、被膜形成用塗布液に関し、さらに詳しく
は、ボイドの少ない緻密な被膜が得られるような被膜形
成用塗布液に関する。Description: TECHNICAL FIELD The present invention relates to a coating solution for forming a film, and more particularly to a coating solution for forming a film capable of obtaining a dense film having few voids.
発明の技術的背景 シリカゾルと、アルコキシシランの部分加水分解物と
が含まれた塗布液は、従来より知られている（特開昭63
−117,074号公報、特開平１−170,668号公報、特開昭63
−278,977号公報、特開昭51−2,736号公報、特開昭62−
105,987号公報参照）。Technical Background of the Invention A coating solution containing a silica sol and a partial hydrolyzate of an alkoxysilane has been conventionally known (Japanese Patent Application Laid-Open (JP-A) No.
-117,074, JP-A-1-170,668, JP-A-63
-278,977, JP-A-51-2736, JP-A-62-2
No. 105,987).
しかしながら、これらの塗布液に含まれているシリカ
ゾルは、いずれも、アルカリ金属ケイ酸塩を脱アルカリ
してなる液状のケイ酸化合物を重合させることにより得
られており、このような方法で得られたシリカゾルには
微量のアルカリが含有されてしまう。However, the silica sols contained in these coating solutions are all obtained by polymerizing a liquid silicate compound obtained by dealkalizing an alkali metal silicate, and are obtained by such a method. The silica sol contains a small amount of alkali.
従って、このような方法で得られたシリカゾルを、半
導体用絶縁膜などの用途に適用しようとすると、塗布液
中に含まれた微量のアルカリのために、半導体の機能が
低下する虞があり、従って、このような用途には、上記
の方法で得られた塗布液を用いることはできない。Therefore, when the silica sol obtained by such a method is applied to an application such as a semiconductor insulating film, the function of the semiconductor may be reduced due to a trace amount of alkali contained in the coating solution, Therefore, the coating liquid obtained by the above method cannot be used for such applications.
発明の目的 本発明は、上記のような従来技術に鑑みて完成された
ものであって、ピンホールあるいはボイドなどが発生す
ることがなく、緻密であって、密着性、機械的強度、耐
薬品性、耐湿性、絶縁性などに優れ、さらに比誘電率の
低いシリカ系被膜を形成することができるようなシリカ
系被膜形成用塗布液を提供することを目的としている。Object of the Invention The present invention has been completed in view of the prior art as described above, has no pinholes or voids, is dense, has high adhesion, mechanical strength, and chemical resistance. It is an object of the present invention to provide a coating liquid for forming a silica-based film, which is excellent in water resistance, moisture resistance, insulation properties, etc. and can form a silica-based film having a low relative dielectric constant.
発明の概要 本発明に係る被膜形成用塗布液には、 一般式RnSi（OR′）4-n（式中、Ｒ、Ｒ′は炭素数１
〜８のアルキル基、アリール基またはビニル基を表わ
し、ｎは０〜３の整数である）で示されるアルコキシシ
ランを、アンモニア、アミン、第４級アンモニウム化合
物またはアミン系カップリング剤の存在下、pH7〜12の
条件で加水分解重縮合して得られるものであり、かつ平
均粒径が100〜500Åの範囲内の均一なシリカ粒子が分散
したシリカゾルと、 アルコキシシランの部分加水分解物とを 酸、アンモニア、アミン、第４級アンモニウム化合物
またはアミン系カップリング剤の存在下で100℃以下の
温度で反応させて得られた反応物が含まれている。SUMMARY OF THE INVENTION The coating solution for forming a film according to the present invention includes a general formula R n Si (OR ′) 4-n (where R and R ′ each have 1 carbon atom).
To an alkyl group, an aryl group or a vinyl group, and n is an integer of 0 to 3) in the presence of ammonia, an amine, a quaternary ammonium compound or an amine-based coupling agent. A silica sol obtained by hydrolytic polycondensation under the condition of pH 7 to 12 and in which uniform silica particles having an average particle size in the range of 100 to 500 mm are dispersed, and a partially hydrolyzed product of alkoxysilane are acidified. And a reaction product obtained by reacting at a temperature of 100 ° C. or lower in the presence of ammonia, an amine, a quaternary ammonium compound or an amine-based coupling agent.
本発明に係る被膜形成用塗布液の好ましい製造液は、
一般式RnSi（OR′）4-n（式中、ｎは０〜３の整数、
Ｒ、Ｒ′は炭素数１〜８のアルキル基、アリール基また
はビニル基を表わし、ＲとＲ′とは同一であっても異な
っていてもよい）で示されるアルコキシシランを、水、
有機溶媒およびアルカリ触媒の存在下で加水分解重縮合
させて、平均粒系50〜500Åのシリカ粒子が分散したシ
リカゾルを得る工程と、前記のアルコキシシランまたは
このアルコキシシランの部分加水分解物と、上記シリカ
ゾルとを混合し、30℃以上の温度で反応させる工程 とからなる。Preferred production liquid of the coating liquid for forming a film according to the present invention,
General formula R n Si (OR ′) 4-n (where n is an integer of 0 to 3,
R and R 'each represent an alkyl group, an aryl group or a vinyl group having 1 to 8 carbon atoms, and R and R' may be the same or different.
Hydrolytic polycondensation in the presence of an organic solvent and an alkali catalyst to obtain a silica sol in which silica particles having an average particle size of 50 to 500 ° are dispersed, and the alkoxysilane or a partial hydrolyzate of the alkoxysilane, Mixing with silica sol and reacting at a temperature of 30 ° C. or higher.
本発明に係る被膜形成用塗布液は、好ましくは上記の
ような製造法を採用することにより得られ、例えば半導
体用絶縁膜、プラスチック、ガラスの表面保護膜などの
用途に適用すると、ピンホールあるいはボイドなどが発
生することがなく、緻密であって、密着性、機械的強
度、耐薬品性、耐湿性、絶縁性などに優れ、さらに比誘
電率の低いシリカ系被膜を形成することができる。The coating liquid for forming a film according to the present invention is preferably obtained by adopting the above-mentioned production method.For example, when applied to applications such as an insulating film for semiconductor, plastic, and a surface protective film of glass, a pinhole or It is possible to form a silica-based coating which is dense without generating voids and the like, is excellent in adhesion, mechanical strength, chemical resistance, moisture resistance, insulation and the like, and has a low relative dielectric constant.
発明の具体的説明 以下、本発明に係る被膜形成用塗布液およびその製造
方法について具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the coating liquid for forming a coating film according to the present invention and a method for producing the same will be specifically described.
被膜形成用塗布液 本発明に係る被膜形成用塗布液には、 一般式 RnSi（OR′）4-n （式中、ｎは０〜３の整数、Ｒ、Ｒ′は炭素数１〜８の
アルキル基、アリール基またはビニル基）で示されるア
ルコキシシランを加水分解重縮合して得られるシリカゾ
ルと、 前記したアルコキシシランの部分加水分解物との反応
物が含まれている。The film-forming coating liquid according to the coating liquid for forming a coating film present invention, the general formula R n Si (OR ') in 4-n (wherein, n is an integer of from 0 to 3, R, R' is 1 to the number of carbon atoms (Alkyl group, aryl group or vinyl group of No. 8), and a reaction product of a silica sol obtained by hydrolytic polycondensation of an alkoxysilane represented by the above formula (2) and a partial hydrolyzate of the alkoxysilane.
本発明に係る被膜形成用塗布液には、上記のような成
分が含まれているため、ピンホールあるいはボイドなど
が発生することがなく、緻密であって、密着性、機械的
強度、耐薬品性、耐湿性、絶縁性などに優れ、さらに比
誘電率の低いシリカ系被膜を形成することができる。Since the coating liquid for forming a film according to the present invention contains the above-described components, it is dense without pinholes or voids, and is dense, and has high adhesion, mechanical strength, and chemical resistance. It is possible to form a silica-based film having excellent properties, moisture resistance, insulation properties, etc. and a low relative dielectric constant.
被膜形成用塗布液の製法 上記のような本発明に係る被膜形成用塗布液は、好ま
しくは以下のような方法で得られる。Method for Producing Coating Solution for Forming Film The coating solution for forming a film according to the present invention as described above is preferably obtained by the following method.
まず、シリカゾルは、下記一般式で示されるアルコキ
シシランを、水、有機溶媒およびアルカリ触媒の存在下
に加水分解重縮合させることにより得られ、このような
シリカゾルの調製法としては、従来より公知の方法を採
用することができる。First, a silica sol is obtained by subjecting an alkoxysilane represented by the following general formula to hydrolysis and polycondensation in the presence of water, an organic solvent, and an alkali catalyst.A method for preparing such a silica sol has been conventionally known. A method can be adopted.
RnSi（OR′）4-n 式中、ｎは０〜３の整数を表わし、Ｒ、Ｒ′は炭素数
１〜８のアルキル基、アリール基またはビニル基を表わ
している。R n Si (OR ') in 4-n formula, n represents an integer of 0 to 3, R, R' represents an alkyl group, an aryl group or a vinyl group having 1 to 8 carbon atoms.
アルコキシシランの具体例としては、テトラメトキシ
シラン、テトラエトキシシラン、テトライソプロポキシ
シラン、テトラブトキシシラン、テトラオクチルシラ
ン、メチルトリメトキシシラン、メチルトリエトキシシ
ラン、エチルトリエトキシシラン、メチルトリイソプロ
ポキシシラン、ジメチルジメトキシシラン、メチルトリ
ブトキシシラン、オクチルトリエトキシシラン、フェニ
ルトリメトキシシラン、ビニルトリメトキシシラン等が
挙げられる。Specific examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraoctylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltriisopropoxysilane, Examples thereof include dimethyldimethoxysilane, methyltributoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, and vinyltrimethoxysilane.
本発明においては、これらのアルコキシシランを単独
で用いてもよく、２種以上組合せて用いてもよい。In the present invention, these alkoxysilanes may be used alone or in combination of two or more.
有機溶媒としては、アルコール類、ケトン類、エーテ
ル類、エステル類等が挙げられ、より具体的には、例え
ばメタノール、エタノール、プロパノール、ブタノール
などのアルコール類、メチルセロソルブ、エチルセロソ
ルブなどのエチレングリコールエーテル類、エチレング
リコール、プロピレングリコールなどのグリコール類、
酢酸メチル、酢酸エチル、乳酸メチルなどのエステル類
等が用いられる。Examples of the organic solvent include alcohols, ketones, ethers, esters and the like.More specifically, for example, alcohols such as methanol, ethanol, propanol and butanol, and ethylene glycol ethers such as methyl cellosolve and ethyl cellosolve , Glycols such as ethylene glycol and propylene glycol,
Esters such as methyl acetate, ethyl acetate, and methyl lactate are used.
アルカリ触媒としては、アンモニア、アミン、、第４
級アンモニウム化合物、アミン系カップリング剤など、
水溶液中でアルカリ性を示す化合物が用いられ、反応混
合物のpHが７〜12、好ましくは８〜11となるような量で
用いられる。Examples of the alkali catalyst include ammonia, amine, and quaternary.
Grade ammonium compounds, amine coupling agents, etc.
A compound exhibiting alkalinity in an aqueous solution is used in such an amount that the pH of the reaction mixture becomes 7 to 12, preferably 8 to 11.
シリカゾルの調製法をさらに詳細に説明すると、例え
ば、水−アルコール混合溶媒を攪拌しながら、この混合
溶媒にアルコキシシランおよび、例えばアンモニア水の
ようなアルカリ触媒を添加し、反応させる。The method of preparing the silica sol will be described in more detail. For example, while stirring a water-alcohol mixed solvent, an alkoxysilane and an alkali catalyst such as ammonia water are added to the mixed solvent and reacted.
この際、水は、アルコキシシランを構成するSi−OR基
１モル当り５〜50モル、好ましくは５〜25モルとなるよ
うな量で用いられ、アンモニアは、前記のpH範囲となる
量で、例えば0.01〜1.0モル/SiO2モル、好ましくは0.05
〜0.8モル/SiO2モルとなるような量で配合される。At this time, water is used in such an amount as to be 5 to 50 mol, preferably 5 to 25 mol, per 1 mol of the Si-OR group constituting the alkoxysilane, and ammonia is used in such an amount as to have the above pH range. For example, 0.01 to 1.0 mol / SiO 2 mol, preferably 0.05
It is blended in such an amount that it becomes 0.80.8 mol / SiO 2 mol.
反応は、通常、常圧下における用いられる溶媒の沸点
以下の温度で、好ましくは沸点より５〜10℃程度低い温
度で行なわれるが、オートクレーブ等の耐熱耐圧容器を
用いる場合には、この温度よりもさらに高い温度で行な
うこともできる。The reaction is usually carried out at a temperature not higher than the boiling point of the solvent used under normal pressure, preferably at a temperature lower by about 5 to 10 ° C. than the boiling point, but when using a heat-resistant pressure vessel such as an autoclave, the temperature is lower than this temperature. It can be performed at a higher temperature.
上記のような条件で加水分解すると、アルコキシシラ
ンの重縮合が三次元的に進行し、シリカ粒子が生成、成
長する。When hydrolysis is performed under the above conditions, the polycondensation of alkoxysilane proceeds three-dimensionally, and silica particles are generated and grown.
また、上記のように、例えば攪拌下の水−アルコール
混合溶媒に、アルコキシシランとアンモニアとを添加
し、水−アルコール混合溶媒の沸点以下の温度、すなわ
ち約100℃以下の温度で反応を進行させて、シリカ粒子
を生成・成長させ、その後、上記温度を溶媒の沸点以上
の温度、すなわち約100℃以上の温度に加圧下で昇温
し、一定時間保持する加熱処理を行なっても良い。In addition, as described above, for example, to a water-alcohol mixed solvent under stirring, an alkoxysilane and ammonia are added, and the reaction proceeds at a temperature lower than the boiling point of the water-alcohol mixed solvent, that is, at a temperature of about 100 ° C. or lower. Then, silica particles may be generated and grown, and thereafter, a heat treatment may be performed in which the temperature is raised to a temperature higher than the boiling point of the solvent, that is, a temperature higher than about 100 ° C. under pressure and maintained for a certain period of time.
このような加熱処理を行なうと、アルコキシシランの
重縮合が一層促進され、密度の大きいシリカ粒子が分散
したシリカゾルが得られる。By performing such a heat treatment, the polycondensation of the alkoxysilane is further promoted, and a silica sol in which silica particles having a high density are dispersed is obtained.
このようにして得られたシリカゾルのうち、本発明に
おいて用いられるシリカゾルは、その平均粒径が約100
〜500Å、好ましくは100〜300Åの範囲内の均一なシリ
カ粒子が分散したゾルである。この粒径が100Å未満で
は、得られる被膜形成用塗布液を用いた膜成形時に、膜
面にクラックが発生する傾向があり、一方、500Åを越
えると膜にボイドが多発し、緻密な膜が得られない。Of the silica sol thus obtained, the silica sol used in the present invention has an average particle size of about 100
It is a sol in which uniform silica particles in the range of from 500 to 500, preferably from 100 to 300, are dispersed. When the particle size is less than 100 mm, cracks tend to occur on the film surface during film formation using the obtained coating liquid for forming a film, whereas when it exceeds 500 mm, voids are frequently generated in the film, and a dense film is formed. I can't get it.
シリカ粒子は、シリカゾル中に、SiO2として約50重量
％以下、好ましくは40重量％以下となるような量で含ま
れていることが望ましい。シリカ含量が50重量％を越え
るとゲル化し易い傾向がある。The silica particles are desirably contained in the silica sol in an amount such that the content of SiO 2 is about 50% by weight or less, preferably 40% by weight or less. If the silica content exceeds 50% by weight, gelation tends to occur.
本発明においては、後述するようにシリカゾルとアル
コキシシランとを反応させるが、その際に、前述の方法
で得られた未精製のシリカゾルをそのまま用いてもよい
が、そのように両者を反応させるに先立ち、予めシリカ
ゾルから、限外濾過等の手段により分散媒の水−有機溶
媒系を水系に溶媒置換させておくことが好ましい。In the present invention, the silica sol and the alkoxysilane are reacted as described below. At that time, the unpurified silica sol obtained by the above-described method may be used as it is, but in such a case, the two are reacted. Prior to this, it is preferable that the water-organic solvent system of the dispersion medium is previously solvent-replaced from the silica sol by means such as ultrafiltration.
この溶媒置換操作は、前述のシリカゾルの加熱処理前
に行なっても良い。This solvent replacement operation may be performed before the above-mentioned heat treatment of the silica sol.
本発明においては、上記のようにしても、まずシリカ
ゾルを調製したのち、さらにこのシリカゾルと新たなア
ルコキシシランまたはその部分加水分解物とを反応させ
る。シリカゾルと反応させるアルコキシシランは、シリ
カゾルの調製に用いられたものと同一のものでも良く、
または前述のシリカゾル調製に用いられるアルコキシシ
ランであれば必ずしも同一のものでなくても良い。この
反応においては、シリカゾル中のシリカ粒子の成長ある
いは新たなシリカ粒子の生成は起らず、シリカ粒子の表
面で、このシリカ粒子と新たなアルコキシシランとの結
合反応が起り、その結果、本発明の目的にかなった塗布
液が得られる。In the present invention, as described above, after preparing a silica sol, the silica sol is further reacted with a new alkoxysilane or a partial hydrolyzate thereof. The alkoxysilane to be reacted with the silica sol may be the same as that used for preparing the silica sol,
Alternatively, the same alkoxysilane may not necessarily be used as long as it is used in the above-mentioned silica sol preparation. In this reaction, the growth of the silica particles in the silica sol or the formation of new silica particles does not occur, and a bonding reaction between the silica particles and the new alkoxysilane occurs on the surface of the silica particles. A coating solution suitable for the purpose of (1) is obtained.
本発明においては、シリカゾルと反応させるアルコキ
シシランはそのまま用いても良いが、常法に従って予め
部分加水分解させた後、得られた部分加水分解物とシリ
カゾルとを混合することが好ましく、このようにする
と、ゾルの凝集、ゲル化が起こり難くなる傾向がある。In the present invention, the alkoxysilane to be reacted with the silica sol may be used as it is, but it is preferable to partially hydrolyze in advance according to a conventional method, and then to mix the obtained partial hydrolyzate with the silica sol. Then, sol aggregation and gelation tend to be less likely to occur.
このようにアルコキシシランの部分加水分解を行なう
際には、通常、水、有機溶媒、酸またはアルカリ触媒が
用いられる。有機溶媒およびアルカリ触媒としては、前
述したものが挙げられる。酸触媒としては、具体的に
は、塩酸、硝酸、硫酸などの無機酸、酢酸、シュウ酸な
どの有機酸または金属石ケンなど水溶液中で酸性を示す
化合物が用いられる。When partial hydrolysis of the alkoxysilane is performed as described above, usually, water, an organic solvent, an acid or an alkali catalyst is used. Examples of the organic solvent and the alkali catalyst include those described above. Specific examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, organic acids such as acetic acid and oxalic acid, and compounds that show acidity in an aqueous solution such as metallic soap.
水は、アルコキシシランを構成するSi−OR基１モル当
り、通常、0.1〜２モル、好ましくは0.5〜２モルの量で
用いられる。酸触媒が用いられる場合には、反応液のpH
が、通常、０〜６、好ましくは１〜３となるような量
で、また、アルカリ触媒が用いられる場合には、反応液
のpHが、通常、７〜10、好ましくは７〜８となるような
量で用いられる。Water is used in an amount of usually 0.1 to 2 mol, preferably 0.5 to 2 mol, per 1 mol of the Si-OR group constituting the alkoxysilane. If an acid catalyst is used, the pH of the reaction solution
However, the amount is usually from 0 to 6, preferably from 1 to 3, and when an alkali catalyst is used, the pH of the reaction solution is usually from 7 to 10, preferably from 7 to 8. Used in such amounts.
上記のような条件で得られるアルコキシシラン部分加
水分解物の分子量は、約100〜10,000、好ましくは500〜
5000（ポリスチレン換算分子量）であることが望まし
い。The molecular weight of the alkoxysilane partial hydrolyzate obtained under the above conditions is about 100 to 10,000, preferably 500 to
It is desirable to be 5000 (polystyrene equivalent molecular weight).
本発明においては、このような方法でアルコキシシラ
ンの部分加水分解物が得られるが、さらに、先に出願し
た特願平１−189,046号あるいは特願平１−253,580号記
載の方法により得られる塗布液を本発明の部分加水分解
物として用いることもできる。すなわち、特願平１−18
9,046号に記載されているように、一般式R1 nSi（OR2）
4-n（式中、R1は炭化水素基であり、R2は炭化数１〜４
のアルキル基であり、ｎは０〜３である）で示されるア
ルコキシシランの１種または２種以上を、有機溶媒、水
およびアルカリ触媒の存在下で部分加水分解し、 次いで得られた部分加水分解液を、水および酸触媒の
存在下でさらに部分加水分解してなる、アルコキシシラ
ン部分加水分解物の縮重合物を含む シリカ系被膜形成用塗布液を本発明における部分加水
分解物として用いることができる。あるいは、特願平１
−253,580号に記載されているよに、一般式R1 nSi（O
R2）4-n（式中、R1は炭化水素基であり、R2は炭化数１
〜４のアルキル基であり、ｎは０〜３である）で示され
るアルコキシシランの１種または２種以上を、有機溶
媒、水および酸の存在下で部分加水分解し、 次いで得られた部分加水分解液をアルカリと接触さ
せ、得られた塗布液にさらに必要に応じて酸を加えて酸
性にしてなる、アルコキシシラン部分加水分解物の縮重
合物を含むシリカ系被膜形成用塗布液を、本発明におけ
る部分加水分解物として用いることもできる。In the present invention, a partial hydrolyzate of alkoxysilane is obtained by such a method, and further, a coating obtained by the method described in Japanese Patent Application No. 1-189,046 or Japanese Patent Application No. 1-253,580 filed earlier. The liquid can also be used as the partial hydrolyzate of the present invention. That is, Japanese Patent Application No. 1-18
As described in 9,046, the general formula R 1 n Si (OR 2 )
4-n (wherein, R 1 is a hydrocarbon group, and R 2 is a carbon number of 1-4.
One or two or more of the alkoxysilanes represented by n) is partially hydrolyzed in the presence of an organic solvent, water and an alkali catalyst; A silica-based film forming coating solution containing a condensation polymerized product of an alkoxysilane partially hydrolyzed product obtained by further partially hydrolyzing the decomposition solution in the presence of water and an acid catalyst is used as the partial hydrolyzate in the present invention. Can be. Or, Japanese Patent Application No. 1
−253,580, the general formula R 1 n Si (O
R 2 ) 4-n (wherein, R 1 is a hydrocarbon group, and R 2 is a carbon number of 1)
And at least one of the alkoxysilanes represented by the formula (1), wherein n is 0 to 3), in the presence of an organic solvent, water and an acid. The hydrolysis solution is brought into contact with an alkali, and the obtained coating solution is made acidic by further adding an acid, if necessary, a coating solution for forming a silica-based film containing a condensation polymerization product of an alkoxysilane partial hydrolyzate, It can also be used as a partial hydrolyzate in the present invention.
本発明においては、シリカゾルと、アルコキシシラン
あるいはその部分加水分解物とを、 シリカゾル中のSiO2（Ａ）の重量／アルコキシシラン
あるいはその部分加水分解物中のSiO2（Ｂ）の重量＝0.
1〜10.0、好ましくは0.25〜4.0となるような重量比で混
合させることが望ましい。In the present invention, the silica sol and the alkoxysilane or the partial hydrolyzate thereof are obtained by dividing the weight of SiO 2 (A) in the silica sol / the weight of SiO 2 (B) in the alkoxysilane or the partial hydrolyzate = 0.
It is desirable to mix them in a weight ratio of from 1 to 10.0, preferably from 0.25 to 4.0.
成分（Ａ）の量が多くなると、得られるシリカ系被膜
は、耐熱性、耐湿性には優れるが、厚い膜厚を有するシ
リカ系被膜を形成するとクラックが発生しやすくなる傾
向が生じ、一方成分（Ｂ）の量が多くなると、得られる
シリカ系被膜は耐熱性、耐湿性に劣る傾向が生ずる。When the amount of the component (A) is large, the obtained silica-based coating is excellent in heat resistance and moisture resistance, but when a silica-based coating having a large film thickness is formed, cracks tend to occur easily. When the amount of (B) increases, the resulting silica-based coating tends to have poor heat resistance and moisture resistance.
本発明においては、上記のようにシリカゾルとアルコ
キシシラン部分加水分解物とを混合した後、約100℃以
下、好ましくは80℃以下の温度で、また温度条件等によ
り変動するが、通常、0.5〜５時間、好ましくは１〜３
時間加熱処理を行なう。このような処理を行なうと、本
発明に係る被膜形成用塗布液が得られる。なお、処理温
度の下限には特に制限はないが、低温になる程反応時間
が長くなり、生産性に劣る。一方、100℃を越えると、
アルコキシシランの加水分解反応が進行し過ぎるため好
ましくない。In the present invention, after mixing the silica sol and the alkoxysilane partial hydrolyzate as described above, at a temperature of about 100 ° C. or less, preferably at a temperature of 80 ° C. or less, and it fluctuates depending on temperature conditions and the like. 5 hours, preferably 1-3
Heat treatment is performed for a time. By performing such treatment, the coating liquid for forming a film according to the present invention is obtained. The lower limit of the processing temperature is not particularly limited, but the lower the temperature, the longer the reaction time and the lower the productivity. On the other hand, if it exceeds 100 ° C,
It is not preferable because the hydrolysis reaction of alkoxysilane proceeds too much.
なお、被膜を形成するには、上記のようにして得られ
た被膜形成用塗布液を基板上に塗布し、次いで乾燥、焼
成すれば基板上に被膜が形成される。なお、該塗布液を
基板上に塗布するには、スプレー法、スピンコート法、
ディップコート法、ロールコート法、スクリーン印刷
法、転写印刷法など通常の方法を採用することができ
る。In order to form a coating, the coating liquid for forming a coating obtained as described above is applied to a substrate, followed by drying and baking to form a coating on the substrate. In addition, in order to apply the coating liquid on a substrate, a spray method, a spin coating method,
Conventional methods such as a dip coating method, a roll coating method, a screen printing method, and a transfer printing method can be employed.
上記の焼成温度は、通常、150〜800℃、好ましくは20
0〜800℃程度である。The above firing temperature is usually 150 to 800 ° C., preferably 20
It is about 0-800 ° C.
このようにして得られた被膜は、用途によっても異な
るが、通常、膜厚0.05〜２μｍ、好ましくは0.1〜１μ
ｍ程度であり、膜形成時にはクラックの発生が見られ
ず、密着性に優れ、耐アルカリ性、耐湿性に優れ、特に
比誘電率が著しく低い。従って、本発明に係る塗布液は
各種保護膜、半導体用絶縁膜等の形成用として広く用い
られる。The film thus obtained varies depending on the application, but usually has a thickness of 0.05 to 2 μm, preferably 0.1 to 1 μm.
m, no cracks are observed at the time of film formation, excellent adhesion, excellent alkali resistance and moisture resistance, and particularly low relative permittivity. Therefore, the coating liquid according to the present invention is widely used for forming various protective films, insulating films for semiconductors and the like.
なお、ガラス基板にITO膜等の電極膜が形成された液
晶素子において、ガラス基板中のアルカリ成分（Na）に
よるITO膜アタックを防止するため、ガラス基板とITO膜
との間に、本発明に係る塗布液により被膜を設けると、
ITO膜のアルカリアタックを防止することができるの
で、いわゆるアルカリパッシベーション用膜としても有
用である。Note that, in a liquid crystal element in which an electrode film such as an ITO film is formed on a glass substrate, in order to prevent an attack of the ITO film due to an alkali component (Na) in the glass substrate, the present invention is applied between the glass substrate and the ITO film. When a coating is provided with such a coating solution,
Since the alkali attack of the ITO film can be prevented, it is also useful as a so-called alkali passivation film.
発明の効果 本発明によれば、ピンホールあるいはボイドなどが発
生することがなく、緻密であって、密着性、機械的強
度、耐薬品性、耐湿性、絶縁性などに優れ、さらに比誘
電率の低いシリカ系被膜を形成することができるような
シリカ系被膜形成用塗布液が提供される。Advantageous Effects of the Invention According to the present invention, pinholes or voids are not generated, and it is dense and excellent in adhesion, mechanical strength, chemical resistance, moisture resistance, insulation, and the like, and furthermore, its relative dielectric constant. The present invention provides a coating liquid for forming a silica-based film capable of forming a silica-based film having a low viscosity.
［実施例］ 以下、本発明を実施例によりさらに具体的に説明する
が、本発明はこれらの実施例に何ら制約されるものでは
ない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
1.（シリカゾルの調製） （１）純水101.5gとメタノール406.1gの混合溶液にエチ
ルシリケート−28（多摩化学工業製）110.4gを加えたの
ち、65℃に加熱し、この温度を保持しながら５％アンモ
ニア水89.5gを３時間かけて添加した。添加終了後、さ
らにこの温度で１時間熟成した。熟成後、この反応液を
限外濾過で未反応エチルシリケート、メタノール、アン
モニアを除去すると同時に純水を加えた。その結果SiO2
濃度５重量％、平均粒径約100ÅのSiO2粒子が分散した
シリカゾル（Ａ）を得た。1. (Preparation of silica sol) (1) After adding 110.4 g of ethyl silicate-28 (manufactured by Tama Chemical Industry) to a mixed solution of 101.5 g of pure water and 406.1 g of methanol, the mixture was heated to 65 ° C. and maintained at this temperature. 89.5 g of 5% aqueous ammonia was added over 3 hours. After the addition was completed, the mixture was further aged at this temperature for 1 hour. After aging, the reaction solution was subjected to ultrafiltration to remove unreacted ethyl silicate, methanol and ammonia, and at the same time pure water was added. As a result, SiO 2
A silica sol (A) in which SiO 2 particles having a concentration of 5% by weight and an average particle size of about 100 ° were dispersed was obtained.
（２）純水203.0gとメタノール812.2gの混合溶液にメチ
ルシリケート−51（多摩化学工業製）121.6gを加えたの
ち、45℃に加熱し、この温度を保持しながら５％アンモ
ニア水150gを５時間かけて添加した。添加終了後、さら
にこの温度で１時間熟成した。その後、未反応メチルシ
リケート、メタノール、アンモニアを除去すると同時に
純水を加え、SiO2濃度５重量％、平均粒径約110ÅのSiO
2粒子が分散したシリカゾル（Ｂ）を得た。(2) To a mixed solution of 203.0 g of pure water and 812.2 g of methanol was added 121.6 g of methyl silicate-51 (manufactured by Tama Chemical Industry), and the mixture was heated to 45 ° C., and 150 g of 5% aqueous ammonia was added while maintaining the temperature. Added over 5 hours. After the addition was completed, the mixture was further aged at this temperature for 1 hour. Thereafter, pure water was added at the same time as removing unreacted methyl silicate, methanol and ammonia, and the SiO 2 concentration was 5% by weight and the average particle size was about 110 °.
A silica sol (B) in which two particles were dispersed was obtained.
（３）純水139.1gとメタノール169.9gの混合溶液を60℃
に保持し、これに、エチルシリケート−28の水−メタノ
ール溶液（重量比2/8の水／メタノール混合液2450gにエ
チルシリケート−28を532.5g加えたもの）2982.5gおよ
び0.25％アンモニア水596.4gを同時に52時間かけて添加
した。添加終了後、さらにこの温度で３時間熟成した。
その後、限外濾過法で同様の操作を行ない、SiO2濃度10
重量％、平均粒径約250ÅのSiO2粒子が分散したシリカ
ゾル（Ｃ）を得た。(3) A mixed solution of 139.1 g of pure water and 169.9 g of methanol was heated at 60 ° C.
2982.5 g of a water-methanol solution of ethyl silicate-28 (532.5 g of ethyl silicate-28 added to 2450 g of a water / methanol mixture having a weight ratio of 2/8) and 596.4 g of 0.25% ammonia water Was added simultaneously over 52 hours. After the addition was completed, the mixture was further aged at this temperature for 3 hours.
After that, the same operation was performed by ultrafiltration, and the SiO 2 concentration was 10
A silica sol (C) in which SiO 2 particles having a weight percentage of about 250 ° and an average particle diameter of about 50% were dispersed was obtained.
（４）エチルシリケート−28の代わりにエチルシリケー
ト−40（多摩化学工業製）を372.8g用いた以外は、シリ
カゾル（Ｃ）と同様の条件で水分散ゾルを得た。この水
分散ゾルをオートクレーブで150℃、12時間処理し、SiO
2濃度10重量％、平均粒径約270ÅのSiO2粒子が分散した
シリカゾル（Ｄ）を得た。(4) An aqueous dispersion sol was obtained under the same conditions as for the silica sol (C), except that 372.8 g of ethyl silicate-40 (manufactured by Tama Chemical Industry) was used instead of ethyl silicate-28. This aqueous dispersion sol was treated in an autoclave at 150 ° C. for 12 hours,
2 A silica sol (D) in which SiO 2 particles having a concentration of 10% by weight and an average particle size of about 270 ° were dispersed was obtained.
（５）エチルシリケート−40の代わりに、メチルトリメ
トキシシラン169.4gとエチルシリケート−28 266.3gの
混合液を用いた以外は、シリカゾル（Ｄ）と同様の条件
で調製し、SiO2濃度10重量％、平均粒径約250ÅのSiO2
粒子が分散したシリカゾル（Ｅ）を得た。(5) Except for using a mixed solution of 169.4 g of methyltrimethoxysilane and 266.3 g of ethyl silicate-28 instead of ethyl silicate-40, it was prepared under the same conditions as the silica sol (D), and the SiO 2 concentration was 10% by weight. %, SiO 2 with average particle size of about 250Å
A silica sol (E) in which particles were dispersed was obtained.
（６）シリカゾル（Ａ）をオートクレーブで150℃、12
時間処理して、シリカゾル（Ｆ）を得た。（SiO2濃度、
粒子の平均粒径はシリカゾル（Ａ）と同じ。） 2.（アルコキシシラン部分加水分解物の調製） （１）エチルシリケート−28（多摩化学工業製）357.1
g、エタノール402.9gおよび純水240.0gの混合溶液に濃
硝酸を添加し、pHを1.5に調整した。この溶液を50℃、
１時間反応させることによって部分加水分解物（Ａ）を
得た。(6) Silica sol (A) is autoclaved at 150 ° C, 12
After a time treatment, a silica sol (F) was obtained. (SiO 2 concentration,
The average particle size of the particles is the same as that of the silica sol (A). 2.) (Preparation of partial hydrolysis product of alkoxysilane) (1) Ethylsilicate-28 (manufactured by Tama Chemical Industry) 357.1
g, 402.9 g of ethanol and 240.0 g of pure water, concentrated nitric acid was added to adjust the pH to 1.5. This solution is at 50 ° C,
By reacting for 1 hour, a partial hydrolyzate (A) was obtained.
（２）メチルシリケート−51（多摩化学工業製）196.1
g、エタノール683.9gおよび純水120.0gの混合溶液に１
％アンモニア水を添加し、pHを8.0に調整した。これを5
0℃、１時間加水分解させ、その後、濃硝酸でpHを2.5に
調整し、さらに50℃、30分間処理した（部分加水分解物
（Ｂ））。(2) Methyl silicate-51 (manufactured by Tama Chemical Industry) 196.1
g, 683.9 g of ethanol and 120.0 g of pure water
% Ammonia water was added to adjust the pH to 8.0. This is 5
The mixture was hydrolyzed at 0 ° C. for 1 hour, then adjusted to pH 2.5 with concentrated nitric acid, and further treated at 50 ° C. for 30 minutes (partial hydrolyzate (B)).
（３）メチルトリメトキシシラン454.5g、エタノール18
5.5gおよび純水360.0gの混合溶液を濃硝酸でpH 1.0に
調整したのち、50℃、２時間加水分解させた。その後、
１％アンモニア水を添加し、pHを7.0に調整したのち、
さらに50℃で２時間処理した。（部分加水分解物
（Ｃ））。(3) 454.5 g of methyltrimethoxysilane, 18 ethanol
A mixed solution of 5.5 g and 360.0 g of pure water was adjusted to pH 1.0 with concentrated nitric acid, and then hydrolyzed at 50 ° C. for 2 hours. afterwards,
After adding 1% ammonia water and adjusting the pH to 7.0,
Further treatment was performed at 50 ° C. for 2 hours. (Partial hydrolyzate (C)).
（４）メチルトリエトキシシラン227.3g、エチルシリル
ケート−28 3571g、エタノール175.0gおよび純水240.0
gの混合溶液を１％アンモニア水でpH 8.5に調整し、50
℃、２時間加水分解させた。次いで、95％酢酸水溶液で
pH ４に調整したのち、さらに50℃で５時間処理した。
（部分加水分解物（Ｄ））。(4) 227.3 g of methyltriethoxysilane, 3571 g of ethylsilylcate-28, 175.0 g of ethanol and 240.0 g of pure water
g of the mixed solution was adjusted to pH 8.5 with 1% aqueous ammonia, and
The mixture was hydrolyzed at 2 ° C. for 2 hours. Then, with 95% acetic acid aqueous solution
After adjusting to pH 4, it was further treated at 50 ° C. for 5 hours.
(Partial hydrolyzate (D)).
（５）メチルトリメトキシシラン272.7g、メチルシリケ
ート−51 156.9g、エタノール330.4gおよび純水240.0g
の混合溶液を濃硝酸でpH 2.0に調整し、50℃、１時間
加水分解させた。次いで、１％トリエタノールアミン水
溶液でpHを7.0に調整したのち、さらに50℃で２時間処
理した。（部分加水分解物（Ｅ））。(5) 272.7 g of methyltrimethoxysilane, 156.9 g of methyl silicate-51, 330.4 g of ethanol and 240.0 g of pure water
Was adjusted to pH 2.0 with concentrated nitric acid and hydrolyzed at 50 ° C. for 1 hour. Next, the pH was adjusted to 7.0 with a 1% aqueous solution of triethanolamine, followed by treatment at 50 ° C. for 2 hours. (Partial hydrolyzate (E)).
3.（塗布液の調製） １（シリカゾルの調製）で得られたシリカゾルと２
（アルコキシシラン部分加水分解物の調製）で得られた
アルコキシシラン部分加水分解物を表１記載の所定の割
合で混合し、50℃で１時間加熱処理した。次いで、ロー
タリーエバポレーターで、水、アルコールを留去し、エ
チルセルソルブまたはプロピレングリコールモノプロピ
ルエーテルと溶媒置換し、SiO2濃度10重量％の塗布液Ｉ
〜VIを調製した。3. (Preparation of coating liquid) The silica sol obtained in 1 (Preparation of silica sol) and 2
The partially hydrolyzed alkoxysilane obtained in (Preparation of partially hydrolyzed alkoxysilane) was mixed at a predetermined ratio shown in Table 1, and heat-treated at 50 ° C. for 1 hour. Then, in a rotary evaporator, water, the alcohol was distilled off, ethyl cellosolve or propylene glycol monopropyl ether and solvent substitution, SiO 2 concentration of 10% by weight of the coating solution I
~ VI was prepared.
次いで、これらの塗布液をガラス基板にスピナー法で
塗布し、乾燥後、350℃、30分間焼成して膜厚2.0μｍの
被膜を形成した。得られた被膜について、次の如き評価
を行なった。Next, these coating solutions were applied to a glass substrate by a spinner method, dried, and baked at 350 ° C. for 30 minutes to form a film having a thickness of 2.0 μm. The following evaluation was performed about the obtained film.
（１）クラックの有無：目視観察。(1) The presence or absence of cracks: visual observation.
（２）密着性：市販のセロハンテープを膜面にはり付
け、その端部を膜面に対して直角に保ち、瞬間的に引き
はがす。そのときの膜の剥離状態を観察。(2) Adhesion: A commercially available cellophane tape is stuck to the film surface, and its end is kept perpendicular to the film surface, and is instantaneously peeled off. Observe the state of peeling of the film at that time.
（３）耐アルカリ性:30℃の５重量％NaOH水溶液に24時
間浸したのちの膜面の状態を観察。(3) Alkali resistance The state of the film surface after immersion in a 5% by weight NaOH aqueous solution at 30 ° C. for 24 hours was observed.
（４）絶縁性：絶縁抵抗計で測定。(4) Insulation: Measured with an insulation resistance meter.
（５）アルカリパッシベーション能：それぞれの被膜の
うえにさらにNESA膜を、CVD法で設けたのち、450℃で加
熱処理し、加熱前後の膜の抵抗変化を評価。(5) Alkali passivation ability: An NESA film was further formed on each of the films by a CVD method, and then heat-treated at 450 ° C., and the resistance change of the film before and after heating was evaluated.
さらに、各塗布液をシリコンウエハに２μｍの厚さに
なるように、スピナー法で塗布、乾燥し、350℃、30分
間、窒素気流中で焼成して被膜を形成した。さらにこの
SiO2膜の上にAlの蒸着膜を形成して、比誘電率を測定し
た。それぞれの結果を表１に示す。Further, each coating solution was applied to a silicon wafer to a thickness of 2 μm by a spinner method, dried, and fired at 350 ° C. for 30 minutes in a nitrogen stream to form a coating. Furthermore this
An Al deposited film was formed on the SiO 2 film, and the relative dielectric constant was measured. Table 1 shows the results.
フロントページの続き (56)参考文献 特開 昭63−278977（ＪＰ，Ａ) 特開 平１−170668（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09D 1/00 - 201/10 Continuation of the front page (56) References JP-A-63-278977 (JP, A) JP-A-1-170668 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C09D 1 / 00-201/10
Claims (1)
は炭素数１〜８のアルキル基、アリール基またはビニル
基を表わし、ｎは０〜３の整数である）で示されるアル
コキシシランを、アンモニア、アミン、第４級アンモニ
ウム化合物またはアミン系カップリング剤の存在下、pH
7〜12の条件で加水分解重縮合して得られるものであ
り、かつ平均粒径が100〜500Åの範囲内の均一なシリカ
粒子が分散したシリカゾルと、 アルコキシシランの部分加水分解物とを 酸、アンモニア、アミン、第４級アンモニウム化合物ま
たはアミン系カップリング剤の存在下で100℃以下の温
度で反応させて得られた反応物を含む被膜形成用塗布
液。A compound of the formula R n Si (OR ') 4-n wherein R, R'
Represents an alkyl group, an aryl group or a vinyl group having 1 to 8 carbon atoms, and n is an integer of 0 to 3), by converting ammonia, amine, quaternary ammonium compound or amine-based coupling agent PH in the presence of
A silica sol obtained by hydrolysis and polycondensation under the conditions of 7 to 12 and in which uniform silica particles having an average particle size in the range of 100 to 500 mm are dispersed, and a partially hydrolyzed product of alkoxysilane are acidified. A coating liquid for forming a film containing a reaction product obtained by reacting at a temperature of 100 ° C. or less in the presence of ammonia, an amine, a quaternary ammonium compound or an amine-based coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06225590A JP3163579B2 (en) | 1990-03-13 | 1990-03-13 | Coating liquid for film formation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06225590A JP3163579B2 (en) | 1990-03-13 | 1990-03-13 | Coating liquid for film formation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03263476A JPH03263476A (en) | 1991-11-22 |
| JP3163579B2 true JP3163579B2 (en) | 2001-05-08 |
Family
ID=13194854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06225590A Expired - Lifetime JP3163579B2 (en) | 1990-03-13 | 1990-03-13 | Coating liquid for film formation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3163579B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011181939A (en) * | 2009-06-24 | 2011-09-15 | Asahi Kasei E-Materials Corp | Method of forming trench-filling insulating film using polysiloxane condensation product |
| US8906153B2 (en) | 2009-06-24 | 2014-12-09 | Asahi Kasei E-Materials Corporation | Product of polysiloxane condensation |
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|---|---|---|---|---|
| JPH04233732A (en) * | 1990-08-16 | 1992-08-21 | Motorola Inc | Spin on derivative used in manufacturing process of semiconductor |
| JP3320440B2 (en) * | 1992-03-17 | 2002-09-03 | 触媒化成工業株式会社 | Coating liquid for film formation and method for producing the same |
| JP3517890B2 (en) * | 1993-02-18 | 2004-04-12 | 日産化学工業株式会社 | Coating liquid for insulating film formation for liquid crystal display element |
| JP3813268B2 (en) | 1996-03-25 | 2006-08-23 | 触媒化成工業株式会社 | Coating liquid for forming low dielectric constant silica-based film and substrate with low dielectric constant film |
| EP1026213B1 (en) * | 1998-09-01 | 2014-11-05 | JGC Catalysts and Chemicals Ltd. | Coating fluid for forming low-permittivity silica-based coating film and substrate with low-permittivity coating film |
| EP1035183B1 (en) * | 1998-09-25 | 2009-11-25 | JGC Catalysts and Chemicals Ltd. | Coating fluid for forming low-permittivity silica-based coating film and substrate with low-permittivity coating film |
| JP2007138144A (en) * | 2005-10-18 | 2007-06-07 | Hitachi Chem Co Ltd | Silica-based coated film-forming composition |
| JP5063161B2 (en) * | 2007-03-30 | 2012-10-31 | シャープ株式会社 | Coating liquid for forming interlayer insulating film and substrate having interlayer insulating film |
| JP5695290B2 (en) * | 2007-09-20 | 2015-04-01 | 日揮触媒化成株式会社 | Method for preparing a coating solution for forming a silica-based film |
| JP5709351B2 (en) * | 2008-12-25 | 2015-04-30 | 日揮触媒化成株式会社 | Method for producing coating solution for forming silica-based transparent coating on microlens array |
| JP5596960B2 (en) * | 2009-11-06 | 2014-09-24 | 旭化成イーマテリアルズ株式会社 | Insulating film formation method |
| JP2012131859A (en) * | 2010-12-20 | 2012-07-12 | Asahi Kasei E-Materials Corp | Coating liquid for formation of silica-based insulating film |
| JP6144001B2 (en) * | 2011-06-02 | 2017-06-07 | 日立化成株式会社 | Silver and silver alloy surface treatment agent, substrate with light reflecting film, and light emitting device |
-
1990
- 1990-03-13 JP JP06225590A patent/JP3163579B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011181939A (en) * | 2009-06-24 | 2011-09-15 | Asahi Kasei E-Materials Corp | Method of forming trench-filling insulating film using polysiloxane condensation product |
| US8906153B2 (en) | 2009-06-24 | 2014-12-09 | Asahi Kasei E-Materials Corporation | Product of polysiloxane condensation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03263476A (en) | 1991-11-22 |
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