JPH02145414A - Production of liquefied coating material for improved silica-based coating film - Google Patents
Production of liquefied coating material for improved silica-based coating filmInfo
- Publication number
- JPH02145414A JPH02145414A JP29894788A JP29894788A JPH02145414A JP H02145414 A JPH02145414 A JP H02145414A JP 29894788 A JP29894788 A JP 29894788A JP 29894788 A JP29894788 A JP 29894788A JP H02145414 A JPH02145414 A JP H02145414A
- Authority
- JP
- Japan
- Prior art keywords
- alkoxysilane
- reaction
- inorganic acid
- group
- solution
- 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 description 44
- 238000000576 coating method Methods 0.000 title claims description 37
- 239000011248 coating agent Substances 0.000 title claims description 34
- 239000000377 silicon dioxide Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000463 material Substances 0.000 title description 3
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 24
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract 2
- 229910052733 gallium Inorganic materials 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 3
- 229910003480 inorganic solid Inorganic materials 0.000 abstract 2
- 230000002265 prevention Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000011521 glass Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 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 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910019752 Mg2Si Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- -1 RGa(OH) Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Landscapes
- Glass Melting And Manufacturing (AREA)
- Silicon Compounds (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野コ
本発明は厚膜でもクラックの生じなく、Ｎａ”イオン等
の溶出防止に効果のあるシリカ系被膜形成用塗布液の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a coating liquid for forming a silica-based film that does not cause cracks even in thick films and is effective in preventing elution of Na'' ions and the like.
シリカ系被膜を形成させる方法としては、気相成長法、
真空蒸着法、スパッター法や塗布方法が知られている。Methods for forming a silica-based film include vapor phase growth,
Vacuum deposition methods, sputtering methods, and coating methods are known.
気相成長法、真空蒸着法及びスパッター法は特殊な装置
を必要とし、被膜を形成させる基板の大きさに制限があ
り、且つ量産が難しいという欠点がある。そこで近年塗
布による方法が注目され、電子材料部品の絶縁膜や液晶
表示素子材料の表面安定化膜（パッシベーション膜）等
に使用されている。これらに加えて最近はより厚膜での
用途が種々提案されておシ、厚膜でクラックが生じない
シリカ系被膜が要求されている。The vapor phase growth method, the vacuum evaporation method, and the sputtering method require special equipment, have limitations on the size of the substrate on which the film is formed, and have drawbacks such as difficulty in mass production. Therefore, in recent years, coating methods have attracted attention and are used for insulating films of electronic material parts, surface stabilizing films (passivation films) of liquid crystal display element materials, and the like. In addition to these, various applications for thicker films have recently been proposed, and there is a demand for thick silica-based films that do not cause cracks.
従来用途に使用されているシリカ系塗布液に関しては、
既に多くの製造方法が提案されている。例えば特公昭４
８−２４６６５号公報、同５２−１６４８８号公報、同
５６−３４２３４号公報、特開昭５４−２４８３１号公
報、同５５−３４２５８号公報、同５６−３８３６２号
公報、同５６−１１９７７４号公報、同５７一７４３７
０号公報、同５７−９４０５７号公報、同６２−２３０
８２８号公報等があり、アルコキシシランを有機溶剤中
で水や酢酸を用いて加水分解してシリカ系被膜形成用塗
布液を得る製造方法が一般的であった。Regarding silica-based coating liquids used in conventional applications,
Many manufacturing methods have already been proposed. For example, Tokuko Sho 4
JP 8-24665, JP 52-16488, JP 56-34234, JP 54-24831, JP 55-34258, JP 56-38362, JP 56-119774, 57-7437
Publication No. 0, Publication No. 57-94057, Publication No. 62-230
No. 828, etc., and a common manufacturing method involves hydrolyzing alkoxysilane in an organic solvent using water or acetic acid to obtain a coating solution for forming a silica-based film.
（発明が解決しようとする課題〕
しかしながら、これら従来技術で得られる塗布液上石英
ガラス、或いはシリコンウェハー上に塗布し、５００°
Ｃ以上の焼成を行うと、膜厚が０．５μｍ以上で気泡の
生成やクラックの発生が生じる。(Problems to be Solved by the Invention) However, when coating liquids obtained using these conventional techniques are coated on quartz glass or silicon wafers,
If baking is performed at a temperature of C or higher, bubbles and cracks will occur if the film thickness is 0.5 μm or more.
本発明は、かかる欠点を克服し、反応工程が極めて簡単
で且つ５００℃以上の焼成においても膜厚が０．５μｆ
ｒｉヲ越えてもクラックや気泡の生じ々いシリカ被膜を
形成し得る塗布液の製造方法を提供することである。The present invention overcomes these drawbacks, has an extremely simple reaction process, and has a film thickness of 0.5 μf even when fired at 500°C or higher.
It is an object of the present invention to provide a method for producing a coating liquid that can form a silica film that does not easily generate cracks or bubbles even if the temperature exceeds RI.
即ち、本発明は、一般弐Ｒ’ｎ５ｉ（ＯＲ）＋−ｎ （
ことにＲ′はメチル基、エチル基又はフェニル基を表わ
し、ＲＦｉメチル基、エチル基、ｎ−プロピル基又はｉ
−プロピル基を表わし、ｎ ”’ Ｏ％ １又は２であ
る。）で表わされる化合物及びこれらの部分縮合物であ
るアルコキシシランの内少なくとも１種と、一般式
％式％
（ここに、ＹはＯＨ又はＯＲ（ここにＲはメチル基、エ
チル基又はｎ−プロピル基又はｉ−プロピル基を表わす
。以下同じ。）を表わし、ＭはＢ、Ｐ、Ａｓ、ｓｂ又は
Ｇａｋ表わし、ＸはＲ′２はＨ又はＲ１−ＷＥわし、Ｘ
′はＲ′、ＯＲ，ＯＨ又はＯＴ’を表わし、前記Ｔは２
又は
は各々１〜１００の整数を表わし、前記Ｘ、Ｙ及び２の
うち少なくとも１つはＸがＯＨ，ＹがＯＨ及び２がＨで
ある。）
で表わされる無機酸の少なくとも１種とを予め反応溶媒
中で反応させておき、次いで前記アルコキシシランと前
記無機酸のうち少なくとも該アルコキシシランの中に残
存するアルコキシル基を加水分解・縮合させ、前記あら
かじめの反応の後又は前記加水分解・縮合の後前記無機
酸記反応溶媒の一部を除去し又は有機溶媒を前記反応生
成液に加えることによりシリカ系被膜形成用塗布液を製
造する方法全要旨とする。That is, the present invention provides general 2R'n5i(OR)+-n (
In particular R' is methyl, ethyl or phenyl; RFi methyl, ethyl, n-propyl or i
- represents a propyl group and is 1 or 2) and at least one alkoxysilane which is a partial condensate thereof, and a compound represented by the general formula % formula % (wherein, Y is OH or OR (herein R represents a methyl group, ethyl group, n-propyl group or i-propyl group; the same applies hereinafter), M represents B, P, As, sb or Gak, and X represents R' 2 is H or R1-WE, X
' represents R', OR, OH or OT', and T is 2
or each represents an integer from 1 to 100, and in at least one of the above-mentioned X, Y, and 2, X is OH, Y is OH, and 2 is H. ) is reacted in advance with at least one inorganic acid represented by the following in a reaction solvent, and then the alkoxysilane and the alkoxyl group remaining in at least the alkoxysilane of the inorganic acid are hydrolyzed and condensed, A method for producing a coating solution for forming a silica-based film by removing a part of the inorganic acid reaction solvent or adding an organic solvent to the reaction product solution after the above-mentioned preliminary reaction or after the above-mentioned hydrolysis/condensation. This is the summary.
本発明者らは、反応の初期段階においてＳｉ−０−Ｍの
結合を生成させておくことがクラック防止、更にはＮａ
イオン等の溶出防止に効果があることを見い出し、
本発明を完成したのである。The present inventors have found that forming Si-0-M bonds in the initial stage of the reaction prevents cracking and furthermore
We discovered that it is effective in preventing the elution of ions, etc.
The present invention was completed.
本発明に用いるアルコキシシランとしては、Ｓｉ（ＯＭ
ｅ）ａ、５ｉ（ＯＥｔ）４、Ｓ ｉ （ＯＰｒ ）４、
ＭｅＳｉ（ＯＭｅ）ｓ、Ｍｇ２Ｓｉ（ＯＭｅ）ｔ、Ｍａ
ｓｔ（ＯＥｔ）ｓ −ＭｅｚＳｉ（ＯＥｔ）２、ＭｅＳ
ｉ（ＯＰｒ）ｍ、Ｍｇ２Ｓｉ（ＯＰｒ）ｔ、ＰｈＳｉ（
ＯＭｅ）ｓ、Ｐｈ Ｓ ｉ （ＯＥｔ ）イＰｈｔＳ
ｉ （ＯＥｔ ）を等（但しここにＭｅはメチル基、
Ｅｔはエチル基、Ｐｒ１ｄプロピル基、ｐｈはフェニル
基を表わす。The alkoxysilane used in the present invention is Si(OM
e) a, 5i (OEt) 4, S i (OPr ) 4,
MeSi(OMe)s, Mg2Si(OMe)t, Ma
st(OEt)s-MezSi(OEt)2, MeS
i(OPr)m, Mg2Si(OPr)t, PhSi(
OMe)s, Ph S i (OEt)i PhtS
i (OEt) etc. (where Me is a methyl group,
Et represents an ethyl group, Pr1d represents a propyl group, and ph represents a phenyl group.
以下同様とする。）及びこれらの部分縮合物並びにこれ
らの２種以上の混合物を挙げることができる。The same shall apply hereinafter. ), partial condensates thereof, and mixtures of two or more thereof.
本発明に用いる無機酸としては、Ｐ （ＯＨ）ｓ、（Ｒ
Ｏ） Ｐ （ＯＨ）！、（ＲＯ）２Ｐ（ＯＨ）、ＲＡＰ
（ＯＨ）、Ｒ’Ｐ （ＯＨ）ｔ、ＰＯ（ＯＨ）ｓ−（Ｒ
Ｏ）ＰＯ（ＯＨ）ｔ−（ＲＯ）ｚＰｏ （ＯＨ） 、
Ｒ’ＰＯ（ＯＨ）ｔ 、 ＲＳＰＯ（ＯＨ）
、（ＨＯ） Ｂ （ＯＲ）ｚ、（ＨＯ）ｔＢ （ＯＲ
）、Ｂ（ＯＨ）いＲ’Ｂ （ＯＨ）ｔ、Ｒ’Ｂ（ＯＲ）
（ＯＨ）、Ａ ｓ （ＯＨ）ｓ ％５ｂ（ＯＨ）ｓ −
ＲＧａ（ＯＨ）を等の化合物、ＰｔＯｓとＥｔＯＨとの
反応生成物、ＢｔｕｓとＥｔＯＨとの反応生成物及びこ
れらの２種以上の混合物を挙げることができる。Inorganic acids used in the present invention include P (OH)s, (R
O) P (OH)! , (RO)2P(OH), RAP
(OH), R'P (OH)t, PO(OH)s-(R
O)PO(OH)t-(RO)zPo(OH),
R'PO(OH)t, RSPO(OH)
, (HO) B (OR)z, (HO)tB (OR
), B(OH)iR'B (OH)t, R'B(OR)
(OH), As (OH)s %5b(OH)s −
Examples include compounds such as RGa(OH), reaction products of PtOs and EtOH, reaction products of Btus and EtOH, and mixtures of two or more of these.
前記無機酸は反応混合物中において液体であ ９ 一
つても固体であってもよいが、液体であることが好まし
い。前記無機酸が反応混合物中において固体であるとき
は、前記予めの反応の進行と共に徐々に溶解して行き、
通常は完全に溶解してしまう。しかし完全に溶解せず固
体のままで残存することがある。この場合、この予めの
反応が終了した時点で炉別してもよいが、これを残存さ
せたまま次の加水分解・縮合を行なってもよい。この加
水分解・縮合反応の進行中にも固体の無機酸線溶解して
行く。この加水分解・縮合が終了したときにも未だ固体
の無機酸が残存しているときは該固体ｔ−ｐ別する。こ
の炉別を行なわないと、最終的に塗布液として使用した
とき、生成する塗膜に凸部が生じて好ましくないからで
ある。The inorganic acid may be liquid or solid in the reaction mixture, but is preferably liquid. When the inorganic acid is solid in the reaction mixture, it gradually dissolves as the pre-reaction progresses,
Usually it dissolves completely. However, it may not dissolve completely and remain as a solid. In this case, the reactor may be separated from the furnace upon completion of this preliminary reaction, but the reactor may be left to carry out the next hydrolysis/condensation. During the progress of this hydrolysis/condensation reaction, solid inorganic acid rays continue to dissolve. If solid inorganic acid still remains after this hydrolysis/condensation is completed, the solid is separated t-p. This is because, if this furnace separation is not carried out, when the coating solution is finally used as a coating solution, the resulting coating film will have convex portions, which is undesirable.
従来技術においても、ガラス質形成剤（例えばＰｒｏｓ
、ＢｔＯｓ ）’を塗布液に混合する例があるが、単に
塗布液に混合するだけではＳｉ−０−Ｍ結合の生成量が
少なく、塗布液焼成時にＭ−０−Ｍ結合のｔま蒸発、揮
散し、有効に働ｌＯ−
かず、膜厚０．５μｍ以下でクラックが発生したり、Ｎ
ａ イオン等の溶出防止効果にとぼしいという欠点が
おる。これに対し、本発明の製造方法に因れば、初期の
段階でＳ！−０−Ｍ結合が生成しているので５００°Ｃ
以上の焼成時においても膜中に残存し、有効に働き、膜
厚０，５μｍ以上であってもクラック発生は生じない。In the prior art, glass-forming agents (e.g. Pros
, BtOs)' is mixed into the coating solution, but simply mixing it with the coating solution produces a small amount of Si-0-M bonds, and when the coating solution is fired, the M-0-M bonds evaporate, It volatilizes and does not work effectively, cracks occur when the film thickness is less than 0.5 μm, and N
a) It has the disadvantage that it has limited effectiveness in preventing the elution of ions, etc. On the other hand, according to the manufacturing method of the present invention, S! -0-M bond is generated, so 500°C
Even during the above firing, it remains in the film and works effectively, and no cracks occur even if the film thickness is 0.5 μm or more.
又Ｎａ＋イオン等の溶出防止効果にすぐれている。It also has an excellent effect of preventing the elution of Na+ ions, etc.
前記反応溶媒としては１価アルコール（例えばメタノー
ル、エタノール、プロパツール、エチレングリコールモ
ノメチルエーテル、エチレンクリコールモノエチルエー
テル、フロピレンゲリコールモノメチルエーテル、プロ
ピレングリコールモノエチルエーテル、）これらの混合
アルコール）、ジオキサン、酢酸エステル（例工ば酢酸
メチル、酢酸エチル）、又はこれらの混合物が好適で、
ケトン（例えばメチルエチルケトン、アセトン等）も一
部使用できる。Examples of the reaction solvent include monohydric alcohols (for example, methanol, ethanol, propatool, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene gelicol monomethyl ether, propylene glycol monoethyl ether, and mixed alcohols thereof), dioxane. , acetic esters (e.g. methyl acetate, ethyl acetate), or mixtures thereof are preferred;
Ketones (eg methyl ethyl ketone, acetone, etc.) can also be used in some cases.
本発明の塗布液は次のようにして製造できる。The coating liquid of the present invention can be manufactured as follows.
第１段階で前記反応溶媒中にアルコキシシラン１以下と
ガるように配合し反応させる。第２段階で未反応のアル
コキシシラｙ’ｌ従末法（例えば特開昭５７−９４０５
７号公報）に従って加水分解・縮合させる。第１段階で
の反応速度は、溶液中のアルコキシル基及び無機酸の濃
度、無機酸の酸強度及び反応温度に比例する。溶液中の
官能基濃度が大きすぎると３次元化を起こす場合がある
のでアルコキシシラン濃度は好ましくは５モル／ｌ以下
更に好ましくは４−ｆニル／ｌ以下がよい。無機酸の酸
強度が小さい場合は触媒（例えば強酸性イオン交換樹脂
等）を少量加えることで反応時間を短縮できる。一方該
無機酸は、好ましくは０．５そル／１以上更に好ましく
は０．７モル／１以上がよい。反応温度は２０〜１００
℃、好ましくは２０〜８０℃がよい。In the first step, 1 or less alkoxysilane is mixed in the reaction solvent and reacted. In the second step, unreacted alkoxysilane y'l is processed (e.g., JP-A-57-9405
7)). The reaction rate in the first stage is proportional to the concentration of alkoxyl groups and inorganic acid in the solution, the acid strength of the inorganic acid, and the reaction temperature. If the concentration of functional groups in the solution is too high, three-dimensionalization may occur, so the alkoxysilane concentration is preferably 5 mol/l or less, more preferably 4-f nyl/l or less. When the acid strength of the inorganic acid is low, the reaction time can be shortened by adding a small amount of a catalyst (for example, a strongly acidic ion exchange resin). On the other hand, the inorganic acid is preferably 0.5 mol/1 or more, more preferably 0.7 mol/1 or more. Reaction temperature is 20-100
℃, preferably 20 to 80℃.
反応時間は３０分〜３０時間、好ましくは１〜１０時間
がよい。無機酸の使用量はアルコキシシランに対し１〜
２０モ２ル％、好ましくは１〜ましくけ０．２〜０．５
である。第２段階は従来技術と同様に第１段階で反応に
関与しなかったアルコキシル基を水を加えて加水分解さ
せ、縮合反応を進行させる。加える水の量は第１段階で
反応に関与しなかったアルコキシル基１当量に対して０
．５〜１モルが好ましい。The reaction time is 30 minutes to 30 hours, preferably 1 to 10 hours. The amount of inorganic acid used is 1 to 1 per alkoxysilane.
20 mole%, preferably 1 to 0.2 to 0.5
It is. In the second step, as in the prior art, water is added to hydrolyze the alkoxyl groups that did not participate in the reaction in the first step, and the condensation reaction proceeds. The amount of water added is 0 per equivalent of alkoxyl group that did not participate in the reaction in the first step.
．． 5 to 1 mol is preferred.
以上のように第１段及び第２段の反応を行なうが、各段
階の反応終了時に固体の無機酸が残存しているときは、
前述のようにいずれかの段階の反応終了時にこれ全濾過
し除去する。尚、第２段の反応終了後は他の固体夾雑物
を除くためにも濾過を行うのが好ましい。そしてシリカ
被膜形成用塗布液として保存し又は使用するに際して、
前記第１・２段の反応生成物の濃度が低過ぎるときは、
反応溶媒の一部を蒸発除去し、高過ぎるときは有機溶媒
を加える。この有機溶媒としては前記反応溶媒を使用す
ることができる。The first and second stage reactions are carried out as described above, but if solid inorganic acid remains at the end of each stage of reaction,
As mentioned above, at the end of any stage of the reaction, all of this is filtered and removed. Incidentally, after the completion of the second stage reaction, it is preferable to perform filtration in order to remove other solid impurities. When storing or using it as a coating solution for forming a silica film,
When the concentration of the reaction products in the first and second stages is too low,
Part of the reaction solvent is evaporated off, and if the temperature is too high, organic solvent is added. As this organic solvent, the above reaction solvent can be used.
このようにしてシリカ系被膜形成用塗布液が得られる。In this way, a coating liquid for forming a silica-based film is obtained.
こうして得られた塗布液は高純度でｃｔ−Ｆｄ−含有し
ないのでτ１子材料用として用いることができる。又こ
の塗布液の使用可能な時間は、シリカ濃度８ｗｔ％の時
、室温で３ケ月以上である。The coating liquid thus obtained has high purity and does not contain ct-Fd-, so it can be used as a τ1 child material. Further, the usable time of this coating liquid is 3 months or more at room temperature when the silica concentration is 8 wt%.
次にこうして得られた塗布液ｔｆ板ガラス、硬値ガラス
又はシリコンウェハー等に浸漬又はスピンコーターで塗
布し、Ｎｔ 、空気、酸素ガス等の雰囲気中で５００°
Ｃ以上に加熱して焼成する。こうして得られた焼成膜は
０．５μｍ以上の膜厚であってもクラックは発生しない
。又Ｎａ＋イオン尋の溶出防止に効果がある。Next, the coating solution obtained in this way is applied to tf plate glass, hard value glass, silicon wafer, etc. by dipping or spin coater, and heated at 50° in an atmosphere of Nt, air, oxygen gas, etc.
Heat to C or above and bake. The fired film thus obtained does not develop cracks even if it has a thickness of 0.5 μm or more. It is also effective in preventing the elution of Na+ ions.
本発明で製造した塗布液を用いれば表面に段差、凹凸を
有する基材に塗布・焼成した場合に、表面段差を埋め、
平滑化することができるので電子部品用の多層配線の絶
縁膜として好適に使用することができ、又従来用途の表
面安定化膜、液晶セル用配向膜等にも好適に使用できる
。If the coating liquid produced according to the present invention is used to coat and bake a substrate with steps or irregularities on the surface, it will fill the surface steps and
Since it can be smoothed, it can be suitably used as an insulating film for multilayer wiring for electronic components, and can also be suitably used as a surface stabilizing film for conventional purposes, an alignment film for liquid crystal cells, etc.
（実施例）
以下に実施例を示すが、本発明はこれら実施例によって
限定されるものではない。(Examples) Examples are shown below, but the present invention is not limited by these Examples.
実施例１
撹拌機、冷却器及び温度計を付けた５ ００ ｗｔｌの
三つロフラスコにＳｉ （ＯＥｔ）４６９ ｆ 。Example 1 Si (OEt) 469 f was placed in a 500 wtl three-necked flask equipped with a stirrer, condenser and thermometer.
ＭｅＳｉ（ＯＥｔ）ｓ ２４ ｆ 、 ジオキサン４０
ｇ、ホウ酸８．２ｆｋ入れ、攪拌しつつ７０°Ｃで２時
間反応させる。次いでこれに強酸性イオン交換樹脂３０
ｇ＋／とエタノール１３７ｆｋ加え、７０℃とし、この
溶液に水１６．３Ｆ”５約２時間で滴下し、更に７０°
Ｃで５時間反応を継続した。その後、この反応液を室温
に冷却し、デカンテーションでイオン交換樹脂を分離し
、溶液全０．２μｍフィルターでろ過し、無色透明の液
を得た。得られた溶液の固形分濃度（１５０°Ｃで３時
間加熱後の重量％）は１１．４％で、その不純物濃度は
表１に示す通りであった。MeSi(OEt)s24f, dioxane40
g and 8.2fk of boric acid were added, and the mixture was allowed to react at 70°C for 2 hours with stirring. Next, strong acidic ion exchange resin 30
Add 137fk of ethanol and 137fk of ethanol, heat to 70°C, add water 16.3F”5 dropwise to this solution over about 2 hours, and heat to 70°C.
The reaction was continued for 5 hours at C. Thereafter, this reaction solution was cooled to room temperature, the ion exchange resin was separated by decantation, and the entire solution was filtered through a 0.2 μm filter to obtain a colorless and transparent solution. The solid content concentration (weight % after heating at 150°C for 3 hours) of the obtained solution was 11.4%, and the impurity concentration was as shown in Table 1.
次いでこの溶液を５０ｆｆｘ５０ｆｌｘｌｎの硬質ガラ
ス板上にスピンナーを用いて回転数を種々変えて塗布し
、空気中で１５０″Ｃ／３０分、更に５００℃／１時間
焼成し、シリカ系被膜を形成した。この種々の膜厚のシ
リカ系被膜全光学顕微鏡で観察した所、膜厚０．７〜０
．８μｍのものにもピンホール及びクラックの発生は認
められなかった。Next, this solution was applied onto a 50 ff x 50 fl x ln hard glass plate using a spinner at various rotation speeds, and baked in air at 150''C for 30 minutes and then at 500°C for 1 hour to form a silica-based coating. When this silica-based coating with various thicknesses was observed with a full-optical microscope, the thickness was 0.7 to 0.
．． No pinholes or cracks were observed even in the case of 8 μm.
実施例２
実施例１と同様のフラスコに５ｉ（ＯＥｔ）＋ ６７９
、 ＭｅＳｉ（ＯＥｔ）ｓ ２９ ｆ 、 エタノー
ル１８６ノ及びリン酸４．２ｆ？入れ、攪拌しっつ６０
’Ｃで２時間反応させた。次いでこの反応液中に約２時
間で水１８．３ｆｖＩ−滴下し、更に５時間反応を継続
した。その後、この反応液を室温に冷却し、溶液全０．
２μｍフィルターでろ過し、無色透明な液を得た。得ら
れた溶液の固形分濃度（実施例１と同じ方法による。）
は１２．８％であった。Example 2 In a flask similar to Example 1, 5i(OEt)+679
, MeSi(OEt)s 29 f, ethanol 186 and phosphoric acid 4.2 f? Add and stir for 60 minutes.
'C for 2 hours. Next, 18.3 fvI of water was added dropwise into this reaction solution over about 2 hours, and the reaction was continued for an additional 5 hours. Thereafter, the reaction solution was cooled to room temperature, and the solution totaled 0.
It was filtered through a 2 μm filter to obtain a colorless and transparent liquid. Solid content concentration of the obtained solution (according to the same method as Example 1)
was 12.8%.
次いでこの溶液を実施例１と同様に硬質ガラス板上に回
転数を種々変えて塗布し、空気中で１５０°Ｃ／３０分
、更に５００°Ｃ／１時間焼成し、シリカ系被膜を形成
した。これら種々の膜厚のシリカ系被膜を光学顕微鏡で
観察した所、膜厚０．７４〜０．８４μｍのものにもピ
ンホール及びクラックの発生は認められなかった。Next, this solution was applied onto a hard glass plate at various rotation speeds in the same manner as in Example 1, and baked in air at 150°C for 30 minutes and then at 500°C for 1 hour to form a silica-based film. . When these silica-based coatings with various thicknesses were observed using an optical microscope, no pinholes or cracks were observed even in those with a thickness of 0.74 to 0.84 μm.
尚、焼成膜中のＰ含量を螢光Ｘ線で測定した所、初期に
配合したＰの７８％が膜中に存在していることがわかっ
た。When the P content in the fired film was measured using fluorescent X-rays, it was found that 78% of the P added initially was present in the film.
比較例１
実施例１と同様のフラスコに５ｉ（ＯＥｔ）＋ ６７９
、 ＭｅＳｉ（ＯＥｔ）ｓ ２９ （１、エタノール
１８６ｆ及びイオン交換樹脂３（Ｊｓｌｋ入れ、攪拌し
つつ６０°Ｃとした。次にこの溶液に水１８．３ｇ’を
約２時間で滴下し、更に６０°Ｃで５時間反応を継続し
た。この反応液全室温に冷却し、デカンテ−シヨンでイ
オン交換樹脂を分離し、溶液を０．２μｍフィルターで
ろ過し、無色透明な液を得た。得られた溶液の固形分濃
度は１２．０％であった。次にこの溶液に、Ｂ２Ｏ３２
，５ｆをＥｔＯＨｓｏｙに溶解させた溶液を加え、堕布
液を調整した。Comparative Example 1 5i (OEt) + 679 was added to the same flask as in Example 1.
, MeSi(OEt)s 29 (1, ethanol 186f and ion exchange resin 3 (Jslk) were added and heated to 60°C while stirring.Next, 18.3g' of water was added dropwise to this solution over about 2 hours, and further heated to 60°C. The reaction was continued at °C for 5 hours.The reaction solution was cooled to room temperature, the ion exchange resin was separated by decantation, and the solution was filtered through a 0.2 μm filter to obtain a colorless and transparent liquid. The solid content concentration of the solution was 12.0%.Next, B2O32 was added to this solution.
, 5f dissolved in EtOHsoy was added to prepare a droplet solution.
次いでこの液を実施例１と同様に神々の厚さに硬質ガラ
ス板上にスピン塗布し、空気中で１５０″Ｃ／３０分、
更に５００℃／１時間焼成し、シリカ系被膜を形成した
。この種々の膜厚の被膜を光学顕微鏡で観察した所０．
４５μｍでクラックが発生していた。Next, this solution was spin-coated onto a hard glass plate to a divine thickness in the same manner as in Example 1, and heated at 150"C/30 minutes in air.
It was further baked at 500° C. for 1 hour to form a silica-based film. When these films with various thicknesses were observed with an optical microscope, they were 0.
Cracks occurred at 45 μm.
比較例２
比較例１と同じ溶液（１２，０％固形分）にＰｚＯｓ
８．０１″’ｔＥｔＯＨ３０ｆ Ｋ溶解して加え、塗布
液を作成した。Comparative Example 2 PzOs was added to the same solution (12.0% solids) as Comparative Example 1.
8.01'''tEtOH30fK was dissolved and added to prepare a coating liquid.
次いでこの塗布液を比較例１と同様に塗布及び焼成し形
成した被膜を光学顕微鏡で観察した所、０．４０μｍの
膜厚のものにクラックの発生が見られた。又、実施例２
と同様にこの被膜中−屈 −
のＰ含量を螢光Ｘ線で測定した所、塗布液に添加したＰ
含量の４３％が焼成膜中に存在しているにすぎなかった
。Next, this coating solution was applied and baked in the same manner as in Comparative Example 1, and the formed film was observed under an optical microscope, and cracks were observed in the film having a thickness of 0.40 μm. Also, Example 2
Similarly, when the P content in this coating was measured using fluorescent X-rays, it was found that the P content added to the coating solution was
Only 43% of the content was present in the fired film.
実施例３
実施例２と同じ溶液（１２，８％固形分） １００ｆバ
ー上にポリシリサイドで巾１．０μｍ、深さ１．０μｍ
の段差全１．０μｍ間隙で形成し、先に調整した塗布液
をスピンナーを用いて塗布し、空気中で１５０″Ｃ／３
０分、更に５００″Ｃ／３０分、更に９００″Ｃ／３０
分焼成し、シリカ系被膜を形成した。このウエノ・−全
破断し、溝の代理性及び平坦性をｓＥＭで観察した所、
溝ハ０．８μｍの厚みで埋まっており、ピンホール及び
クラックの発生は認められなかった。Example 3 Same solution as Example 2 (12.8% solids) Polysilicide on a 100f bar with a width of 1.0 μm and a depth of 1.0 μm
The steps were formed with a total gap of 1.0 μm, and the previously prepared coating liquid was applied using a spinner, and then heated at 150″C/3 in air.
0 minutes, then 500″C/30 minutes, then 900″C/30
A silica-based coating was formed by firing separately. When this Ueno was completely fractured and the agency and flatness of the groove were observed using sEM,
The groove was filled to a thickness of 0.8 μm, and no pinholes or cracks were observed.
実施例４
実施例１と同様の５００ ｍｌの三つロフラスコに５ｔ
（ＯＥｔ）＋ １２５９ 、 エタノール１３１ｆ及
びＰ２Ｏ５の１０重量％エタノール溶液２１ｆ’ｉ入れ
、攪拌しつつ６０°Ｃで２時間反応させた。次いでこの
反応液中に約２時間で水２５ｆｔ−滴下し、更に５時間
反応を継続した。その後、この反応液を室温に冷却し、
０．２μｍフィルターでろ過し、無色透明な液を得た。Example 4 5 tons was placed in a 500 ml three-necked flask similar to Example 1.
(OEt)+1259, 131f of ethanol, and 21f'i of a 10% by weight ethanol solution of P2O5 were added, and the mixture was reacted at 60°C for 2 hours with stirring. Next, 25 feet of water was added dropwise into the reaction solution over a period of about 2 hours, and the reaction was continued for an additional 5 hours. Then, the reaction solution was cooled to room temperature,
It was filtered through a 0.2 μm filter to obtain a colorless and transparent liquid.
更にこの液にエタノールを加え、固形分濃度？４ｉｉＣ
量％に調整した。次いでこの溶液を実施例１と同様にガ
ラス板上にスピン塗布し、空気中で１５０″Ｃ／３０分
、更に５００℃／１時間焼成しシリカ系被膜を形成した
。次にこの膜のエツチング速度を測定した所２６０人／
分であった。Furthermore, add ethanol to this liquid and check the solid content concentration. 4iiC
The amount was adjusted to %. Next, this solution was spin-coated on a glass plate in the same manner as in Example 1, and baked in air at 150''C for 30 minutes and then at 500℃ for 1 hour to form a silica-based film.Next, the etching rate of this film was determined. 260 people/
It was a minute.
尚、前記エツチング速度は、前記シリカ系被膜を形成し
たガラス板の半分にアピエドンワックス（商標）を塗り
乾燥させ、得られたガラス板の全体を、１モル％のＨＦ
水溶液に１分間浸漬しエツチング処理した後引上げ、水
洗し、前記ワックスをトルエンで溶解除去し、エツチン
グされた部分とされなかった部分との段差を触針段差針
で測定することにより求めた。The etching rate is determined by applying Apiedon Wax (trademark) to half of the glass plate on which the silica-based coating is formed, drying it, and then drying the entire glass plate with 1 mol% HF.
After being immersed in an aqueous solution for 1 minute and subjected to etching treatment, it was pulled up, washed with water, the wax was dissolved and removed with toluene, and the level difference between the etched area and the unetched area was measured using a stylus.
比較例３
実施例１と同様の５００−の三つロフラスコにＳｉ （
ＯＥｔ ）４１２５ ｆ、エタノール１３１ｆ及び強酸
性イオン交換樹脂３０ｇ１ｋ入れ、攪拌しつつ６０°Ｃ
とした。次にこの溶液に水２５Ｆを約２時間で滴下し、
更に６０℃で５時間反応を継続した。その後、この反応
液を室温に冷却し、０．２μｍフィルターでろ過し、無
色透明の液を得た。次にこの溶液にＰ２Ｏ３の１０重量
％エタノール溶液２１ｆＴｈ加え、更にエタノール管加
えて固形分濃度を４重量％に調整した。次いで、この溶
液を実施例４と同様にガラス板上に塗布、焼成しシリカ
系被膜を得た。次にこの膜のエツチング速度を実施例４
と同様にして測定した所４５０人／ｍｉｎであった。Comparative Example 3 Si (
Add OEt) 4125f, 131f ethanol, and 30g/k of strong acidic ion exchange resin, and heat to 60°C while stirring.
And so. Next, 25F water was added dropwise to this solution over a period of about 2 hours.
The reaction was further continued at 60°C for 5 hours. Thereafter, this reaction solution was cooled to room temperature and filtered through a 0.2 μm filter to obtain a colorless and transparent solution. Next, 21 fTh of a 10% by weight ethanol solution of P2O3 was added to this solution, and an ethanol tube was added to adjust the solid content concentration to 4% by weight. Next, this solution was applied onto a glass plate and fired in the same manner as in Example 4 to obtain a silica-based coating. Next, the etching rate of this film was determined in Example 4.
It was measured in the same manner as above and found to be 450 people/min.
実施例４と比較例３を比較すると実施例４の被膜の方が
はるかにエツチング速度が遅く、これ社実施例４の被膜
中のアルカリイオンがはる（発明の効果〕
本発明の塗布液は、その製造方法が極めて簡単であり、
ガラス、石英ガラス、シリコンウェハー等の上に塗布し
焼成して被膜を形成するとある。Comparing Example 4 and Comparative Example 3, the coating of Example 4 has a much slower etching rate, and the alkali ions in the coating of Example 4 increase (effects of the invention). , the manufacturing method is extremely simple,
It is said that it is applied onto glass, quartz glass, silicon wafers, etc. and baked to form a film.
以上that's all
Claims (11)
にＲ′はメチル基、エチル基又はフェニル基を表わし、
Ｒはメチル基、エチル基、ｎ−プロピル基又はｉ−プロ
ピル基を表わし、ｎ＝０、１又は２である。）で表わさ
れる化合物及びこれらの部分縮合物であるアルコキシシ
ランの内少なくとも１種と、一般式 ▲数式、化学式、表等があります▼又は▲数式、化学式
、表等があります▼ （ここに、ＹはＯＨ又はＯＲ（ここにＲはメチル基、エ
チル基又はｎ−プロピル基又はｉ−プロピル基を表わす
。以下同じ。）を表わし、ＭはＢ、Ｐ、Ａｓ、Ｓｂ又は
Ｇａを表わし、ＸはＲ′（ここにＲ′はメチル基、エチ
ル基又はフェニル基を表わす。以下同じ。）、ＯＲ、Ｏ
Ｈ又はＯＴを表わし、ＺはＨ又はＲを表わし、Ｘ′はＲ
′、ＯＲ、ＯＨ又ＯＴ′を表わし、前記ＴはＺ又は▲数
式、化学式、表等があります▼を 表わし、前記Ｔ′はＺ又は▲数式、化学式、表等があり
ます▼を表わし、前記ｋ、ｌ、ｉ及びｊは各々１〜１０
０の整数を表わし、前記Ｘ、Ｙ及びＺのうち少なくとも
１つはＸがＯＨ、ＹがＯＨ及びＺがＨである。）で表わ
される無機酸の少なくとも１種とを予め反応溶媒中で反
応させておき、次いで前記アルコキシシランと前記無機
酸のうち少なくとも該アルコキシシランの中に残存する
アルコキシル基を加水分解・縮合させ、前記あらかじめ
の反応の後又は前記加水分解・縮合の後前記無機酸の固
体が残つているときは、該反応の後又は該加水分解・縮
合の後該固体を除去し、所望により、前記反応溶媒の一
部を除去し又は有機溶媒を前記反応生成溶液に加えるこ
とを特徴とするシリカ系被膜形成用塗布液の製造方法。(1) General formula R'_nSi(OR)_4_-_n (where R' represents a methyl group, ethyl group or phenyl group,
R represents a methyl group, ethyl group, n-propyl group or i-propyl group, and n=0, 1 or 2. ) and at least one type of alkoxysilane which is a partial condensate of these, and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, Y represents OH or OR (herein R represents a methyl group, ethyl group, n-propyl group or i-propyl group; the same applies hereinafter), M represents B, P, As, Sb or Ga, and X represents R' (here R' represents a methyl group, ethyl group or phenyl group. The same applies hereinafter), OR, O
represents H or OT, Z represents H or R, X' represents R
', OR, OH or OT', the above T represents Z or ▲there are mathematical formulas, chemical formulas, tables, etc.▼, the above T' represents Z or ▲there are mathematical formulas, chemical formulas, tables, etc.▼, and the above k , l, i and j are each 1 to 10
represents an integer of 0, and in at least one of the X, Y, and Z, X is OH, Y is OH, and Z is H. ) is reacted in advance in a reaction solvent with at least one type of inorganic acid represented by the formula (2), and then the alkoxysilane and the alkoxyl group remaining in at least the alkoxysilane of the inorganic acid are hydrolyzed and condensed, If the solid of the inorganic acid remains after the preliminary reaction or the hydrolysis/condensation, the solid is removed after the reaction or after the hydrolysis/condensation, and if desired, the reaction solvent is removed. A method for producing a coating liquid for forming a silica-based film, comprising removing a part of the reaction product solution or adding an organic solvent to the reaction product solution.
のＲ′の量がＳｉに対してＲ′／Ｓｉの比（モル）比）
で、平均して０〜１であることを特徴とする前記方法。(2) In claim (1), the amount of R' in the alkoxysilane used is the ratio (mole) of R'/Si to Si)
and on average between 0 and 1.
のＲ′の量がＳｉに対してＲ′／Ｓｉの比（モル比）で
、平均して０．２〜０．５であることを特徴とする前記
方法。(3) Claim (2) is characterized in that the amount of R' in the alkoxysilane used is on average 0.2 to 0.5 in terms of the ratio (molar ratio) of R'/Si to Si. The said method.
る無機酸の量が前記アルコキシシランに対して１〜２０
モル％であることを特徴とする前記方法。(4) In claim (1), (2) or (3), the amount of the inorganic acid used is 1 to 20% based on the alkoxysilane.
The above method, characterized in that the mole %.
アルコキシシランに対して１〜１０モル％であることを
特徴とする前記方法。(5) The method according to claim 4, characterized in that the amount of inorganic acid used is 1 to 10 mol % based on the alkoxysilane.
前記アルコキシシランと無機酸とを反応させるときの反
応温度を２０〜１００℃とすることを特徴とする前記方
法。(6) In any of claims (1) to (5),
The method described above, characterized in that the reaction temperature when reacting the alkoxysilane and the inorganic acid is 20 to 100°C.
０℃とすることを特徴とする前記方法。(7) In claim (6), the reaction temperature is 20 to 8
The above method, characterized in that the temperature is 0°C.
前記アルコキシシランと無機酸とを反応させるときの反
応時間を３０分〜３０時間とすることを特徴とする前記
方法。(8) In any of claims (1) to (7),
The method described above, characterized in that the reaction time when the alkoxysilane and the inorganic acid are reacted is 30 minutes to 30 hours.
時間とすることを特徴とする前記方法。(9) In claim (8), the reaction time is 1 to 10
The said method, characterized in that it is a time period.
、前記アルコキシシランと無機酸とを反応させるにあた
つて、アルコキシシランの濃度を０．５〜５モル／ｌと
することを特徴とする前記方法。(10) In any one of claims (1) to (9), when reacting the alkoxysilane and the inorganic acid, the concentration of the alkoxysilane is set to 0.5 to 5 mol/l. The said method.
ンの濃度を０．７〜４モル％とすることを特徴とする前
記方法。(11) The method according to claim (10), characterized in that the concentration of the alkoxysilane is 0.7 to 4 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29894788A JP2678380B2 (en) | 1988-11-26 | 1988-11-26 | Method for producing improved coating liquid for forming silica film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29894788A JP2678380B2 (en) | 1988-11-26 | 1988-11-26 | Method for producing improved coating liquid for forming silica film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02145414A true JPH02145414A (en) | 1990-06-04 |
| JP2678380B2 JP2678380B2 (en) | 1997-11-17 |
Family
ID=17866241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29894788A Expired - Fee Related JP2678380B2 (en) | 1988-11-26 | 1988-11-26 | Method for producing improved coating liquid for forming silica film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2678380B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0625532A1 (en) * | 1993-05-17 | 1994-11-23 | Dow Corning Corporation | Precursor for ceramic coatings |
| JP2010525466A (en) * | 2007-04-20 | 2010-07-22 | フィッシャー コントロールズ インターナショナル リミテッド ライアビリティー カンパニー | Pressure averaging detector tube for gas flow regulator |
-
1988
- 1988-11-26 JP JP29894788A patent/JP2678380B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0625532A1 (en) * | 1993-05-17 | 1994-11-23 | Dow Corning Corporation | Precursor for ceramic coatings |
| JP2010525466A (en) * | 2007-04-20 | 2010-07-22 | フィッシャー コントロールズ インターナショナル リミテッド ライアビリティー カンパニー | Pressure averaging detector tube for gas flow regulator |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2678380B2 (en) | 1997-11-17 |
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