JPH03263476A - Coating dope for coating film formation - Google Patents
Coating dope for coating film formationInfo
- Publication number
- JPH03263476A JPH03263476A JP6225590A JP6225590A JPH03263476A JP H03263476 A JPH03263476 A JP H03263476A JP 6225590 A JP6225590 A JP 6225590A JP 6225590 A JP6225590 A JP 6225590A JP H03263476 A JPH03263476 A JP H03263476A
- Authority
- JP
- Japan
- Prior art keywords
- film
- alkoxysilane
- silica sol
- coating
- silica
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 abstract description 7
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000011800 void material Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000003513 alkali Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 9
- -1 silicic acid compound Chemical class 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RWHPJDQRXPFAJG-UHFFFAOYSA-N ethoxy(octyl)silane Chemical compound CCCCCCCC[SiH2]OCC RWHPJDQRXPFAJG-UHFFFAOYSA-N 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- VDXTYGONCKJCPN-UHFFFAOYSA-N methyl(2-methylpropoxy)silane Chemical compound C[SiH2]OCC(C)C VDXTYGONCKJCPN-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Formation Of Insulating Films (AREA)
Abstract
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。DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a coating liquid for film formation, and more specifically,
The present invention relates to a coating liquid for forming a film that allows a dense film with few voids to be obtained.
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８３
−１１．７．０７４号公報、特開平１−１７０，８８８
号公報、特開昭６３−２７８，９７７号公報、特開昭５
１−２，７３８号公報、特開昭６２−１０５，９８７号
公報参照）。Technical Background of the Invention Coating liquids containing silica sol and partially hydrolyzed alkoxysilane have been known (Japanese Patent Laid-Open No. 83
-11.7.074 publication, JP-A-1-170,888
Publication No. 63-278,977, Japanese Patent Application Laid-open No. 1983-278,977
1-2,738, JP-A-62-105,987).
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 silicic acid compound obtained by dealkalizing an alkali metal silicate; The silica sol contains a trace 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, if the silica sol obtained by such a method is applied to applications such as insulating films for semiconductors, there is a risk that the functionality of the semiconductor will deteriorate due to the trace amount of alkali contained in the coating solution. Therefore, the coating liquid obtained by the above method cannot be used for such uses.
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、絶縁性なとに優れ、さらに比誘電率の低
いシリカ系被膜を形成することかできるよ・うなシリカ
系被膜形成用塗布液を提供することをＬ−１的と１゛Ｃ
いる。Purpose of the Invention The present invention has been completed in view of the above-mentioned prior art. L-1's objective is to provide a coating solution for forming a silica-based film that has excellent properties, moisture resistance, and insulation properties, and is also capable of forming a silica-based film with a low dielectric constant.
There is.
発明の概要
本発明に係る被膜形成用＊ ｒｒＩ液には、−形成Ｒ８
１（ＯＲ”） （式中、＋１はＯｎ
４−ｎ
〜３の整数、Ｒ，Ｒ，’ は炭素数１〜８のアル−ギル
基、アリール、！！またはビニル基を表わ（２、Ｒ，Ｒ
’は同一・であっても異ム′っていても良い）で示され
るアル：１ギシシー）ンを加水分解ｊｎ縮、ＡＩ、 し
て得られるシリカゾルと、
前記のアル二■キンンランの部分加水分解物との反応物
が含まれこ〜いる。Summary of the Invention The *rrI solution for film formation according to the present invention contains -formation R8
1(OR”) (in the formula, +1 is On
4-n is an integer of 3 to 3, R, R,' is an ar-gyl group having 1 to 8 carbon atoms, aryl,! ! or represents a vinyl group (2, R, R
The silica sol obtained by hydrolyzing Al (1), represented by '' may be the same or different, and the partial hydration of the above-mentioned Al2, Contains reactants with decomposition products.
本発明に係る被膜形成用塗布液の好ましい製造法は、−
形成Ｒ８１（ＯＲ′）４−ｎ （式中、１１ｎ
４−ｎ
はＯ〜・３の整数、ＲＳＲ’ 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“
とは同一であツーζも異なっ′Ｃいてもよい）で示さ
れるアルコキンシランを、水、ａ機溶媒およびアルカリ
触媒のＩＴ （＋−下−Ｃ加水分解重縮合さ（４で、平
均粒径１５０へ５５００人のシリカ粒子がり〕散したシ
リカゾルを得る［、程と、１１０記の）′ル“Ｊキシシ
ランまたはこのアルＴ１キシシランの部分加水分解物と
、Ｌ記シリカゾルさを混合１７．３ （′）４−ｎ ℃
以」−４の温度で反応させる才程
とからなる。A preferred method for producing the film-forming coating liquid according to the present invention is -
Formation R81(OR')4-n (wherein, 11n
4-n represents an integer of O to .3, RSR' represents an alkyl group, aryl group, or vinyl group having 1 to .8 carbon atoms, and R and R"
The alkoxysilane represented by ζ may be the same and different from ζ and C) is subjected to the hydrolytic polycondensation of water, a solvent and an alkali catalyst (+-lower-C hydrolytic polycondensation (with 4, average particle size) 17.3. Mixing the partial hydrolyzate of 17.3. (')4-n ℃
It consists of a step of reacting at a temperature of -4.
本発明に係る被膜形成用塗布液は、好ま１．＜は］−記
のような製造法を採用することにより得られ、例えば゛
１′、導体用絶縁膜、プラスデック、ノＩラスの表面保
護膜などの用途に適用すると、ピン；１、−ルあるいは
ボイドなどが発４１８することがなく、緻密Ｃあって、
密着性、機械的強度、耐薬品性、耐湿性、絶縁性なとに
優れ、さらに比誘電率の低いシリカ系被膜を形成するこ
とかできる。The film-forming coating liquid according to the present invention is preferably 1. < is] - It can be obtained by adopting the manufacturing method described below, and when applied to applications such as insulating films for conductors, plus decks, and surface protective films for Nori glass, pins;1, - There are no gaps or voids, and there is a dense C.
It is possible to form a silica-based film that has excellent adhesion, mechanical strength, chemical resistance, moisture resistance, and insulation, and also has a low dielectric constant.
発明の詳細な説明
以下、本発明に係る被膜形成用塗布液およびその製造法
についで具体的に説明４″る。DETAILED DESCRIPTION OF THE INVENTION The film-forming coating liquid and method for producing the same according to the present invention will be specifically explained below.
被膜形成用塗布液
本発明に係る被膜形成用塗布液には、
−・形成 ＲＳ ｉ （ＯＲ’ ） ４□（式中、＋１
は０〜３の整数、ＲＳＲ’ は炭素数１〜８のアルキル
基、アリール基またはビニル基）て示されるアルコキシ
シランを加水分解重縮合１．。Coating liquid for forming a film The coating liquid for forming a film according to the present invention includes -・Formation RS i (OR' ) 4□ (in the formula, +1
is an integer of 0 to 3, and RSR' is an alkyl group, aryl group, or vinyl group having 1 to 8 carbon atoms). .
て得られるシリカゾルと、
前記［、たアル：１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。It contains a reaction product of the silica sol obtained by the process and the partial hydrolyzate of the above-mentioned [,taal:1-xysilane].
本発明に係る被膜形成用塗布液には、」−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
どが発ルすることがなく、緻密てあっ°Ｃ１密着性、機
械的強度、耐薬品性、耐ん１性、絶縁性なとに優れ、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 solution for forming a film according to the present invention contains the components listed below, so it does not generate pinholes or voids, and has a dense film with excellent C1 adhesion and mechanical properties. It is possible to form a silica-based film that has excellent physical strength, chemical resistance, corrosion resistance, and insulation properties, and also has a low 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
くは以ドのような方法で得られる。Method for producing coating liquid for film formation The coating liquid for film formation according to the present invention as described above is preferably obtained by the following method.
まず、シリカゾルは、ド記−・形成で示されるアルコキ
シシランを１．水、ｒｆ機溶媒およびアルカリ触媒の存
ｒ１．下に加水分解重縮合させることにより得られ、こ
の、Ｊ二うなシリカゾルの１凋製ａ、とし、では、従来
より公知の方法を採用することかできる。First, the silica sol is prepared by adding an alkoxysilane as shown in the following formula to 1. Presence of water, RF solvent and alkaline catalyst r1. In this case, a conventionally known method can be used to prepare the silica sol obtained by hydrolytic polycondensation.
【３
ＲＳ ］（ＯＲ） ４−ｎ
口
式中、「〕は（−〕〜３の整数を表わ＋７、Ｉで、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°ζいる。[3 RS ] (OR) 4-n In the expression, "] represents an integer from (-) to 3, +7, I, R'
represents an alkyl group having 1 to 8 carbon atoms, an aryl group or a vinyl group.
アル：１キシシランの具体例と（２ては、テトラメトキ
シシラン、テＩ・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トラオクチルシラン
、メチルトリメｌ− Ｖジシラン、メチルトリエトキシ
シラン、エチルトリエｌーキシシラン、メチルトリイソ
プロポ片ジシラン、ジメチルジメトキシシラン、メチル
ｉ・リブトキシシラン、オクチルＩ・リエトキシシラン
、フゴ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。Al: Specific examples of 1-xysilane and (2) include tetramethoxysilane, te-laethoxysilane, tetraisopropoxysilane, tetrabutoxysilanetraoctylsilane, methyltrimethyl-Vdisilane, methyltriethoxysilane, ethyltriethoxysilane. , methyltriisopropodisilane, dimethyldimethoxysilane, methyl i-butoxysilane, octyl-I-ethoxysilane, fugonyltrimethoxysilane, vinyltrimethoxysilane and the like.
本発明においては、これらのアルコキシシランを１１１
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 are 111
They 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、ブロバノール、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 organic solvents include alcohols, ketones, ethers, esters, and more specifically, alcohols such as methanol, ethanol, brobanol, 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、アルカリ
金属水酸化物、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〜］、２、好ましく
は８〜１１となるような量で用いられる。As the alkali catalyst, compounds that exhibit alkalinity in aqueous solution, such as ammonia, amines, alkali metal hydroxides, quaternary ammonium compounds, and amine coupling agents, are used, and the pH of the reaction mixture is 7~], 2, It is preferably used in an amount of 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。To explain the method for preparing silica sol in more detail, for example, while stirring a water-alcohol mixed solvent, an alkoxysilane and an alkali catalyst such as aqueous ammonia 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５ｔ−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、例えば屹 ０１〜１．０モル／ Ｓ Ｌ
０２モル、好ましくは０．０５〜０．８モル／ Ｓ
ｉ ０２モルとなるような量で配合される。At this time, water is 5t-OR constituting the alkoxysilane.
Ammonia is used in an amount of 5 to 50 mol, preferably 5 to 25 mol, per 1 mol of the group, and ammonia is used in an amount that provides the above pH range, for example, 01 to 1.0 mol/S L
02 mol, preferably 0.05-0.8 mol/S
It is blended in an amount such that i02 moles.
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 below the boiling point of the solvent used under normal pressure, preferably at a temperature about 5 to 10°C lower than the boiling point; however, when using a heat-resistant and pressure-resistant container such as an autoclave, the temperature is lower than this temperature. It is also possible to carry out the process at higher temperatures.
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 hydrolyzed under the above conditions, polycondensation of alkoxysilane proceeds three-dimensionally, producing and growing silica particles.
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℃以上の温度に昇温し、一定時
間保持する加熱処理を行なっても良い。Alternatively, as described above, for example, by adding alkoxysilane and ammonia to a water-alcohol mixed solvent under stirring,
The reaction is allowed to proceed at a temperature below the boiling point of the water-alcohol mixed solvent, i.e., at a temperature below about 100°C, to generate and grow silica particles, and then the temperature is reduced to a temperature above the boiling point of the solvent, i.e., at about 100°C or above. A heat treatment may be performed in which the temperature is raised to a temperature of and held 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。When such a heat treatment is performed, the polycondensation of the alkoxysilane is further promoted, and a silica sol in which high-density silica particles are dispersed can be 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５０〜
５００人、好ましくは１００〜３００人の範囲内の均一
なシリカ粒子が分散したゾルである。この粒径が５０人
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、５０
０人を越えると膜にボイドが多発し、緻密な膜が得られ
ない。Among the silica sols obtained in this way, the silica sol used in the present invention has an average particle size of about 50 to
It is a sol in which 500, preferably 100 to 300, uniform silica particles are dispersed. If the particle size is less than 50%, cracks tend to occur on the film surface during film forming using the resulting film-forming coating solution;
When the number exceeds 0, voids occur frequently in the film and a dense film cannot be obtained.
シリカ粒子は、シリカゾル中に、Ｓ １０２として約５
０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。The silica particles are present in the silica sol as S102 of about 5
It is desirable that the content is 0% by weight or less, preferably 40% by weight or less.
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。When 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
、こ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, silica sol and alkoxysilane are reacted as described below. At that time, the unpurified silica sol obtained by the above method may be used as it is, but in order to react the two in this way, It is preferable to first replace the water-organic solvent system of the dispersion medium with an aqueous system 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 heat treatment of the silica sol described above.
本発明においては、上記のようにして、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。In the present invention, after first preparing a silica sol as described above, this silica sol is further reacted with a new alkoxysilane or a partially hydrolyzed product thereof.
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。The alkoxysilane to be reacted with the silica sol may be the same as that used for preparing the silica sol, or may not necessarily be the same as the alkoxysilane used for preparing the silica sol described above. In this reaction, the silica particles in the silica sol do not grow or new silica particles are generated, but a bonding reaction between the silica particles and new alkoxysilane occurs on the surface of the silica particles, and as a result, the present invention A coating solution suitable for the purpose can be obtained.
本発明においては、シリカゾルと反応させるア０
ルコキシシランはそのＪ、ま用いても良いが、常法ＩＪ
従って予め部分加水分解さゼた後、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 in the conventional IJ or IJ method.
Therefore, it is preferable to perform partial hydrolysis in advance and then mix the obtained partial hydrolyzate with silica sol. In this way, aggregation and gelation of the sol tend to be less likely to occur.
このようにアル−１キシシランの部分加水分解を行なう
際には、通常、水、イｊ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ｊ、たちのが挙げられる。酸触媒とし、では、具体
的には、塩酸、硝酸、硫酸などの無機酸、ｉ′）酸、ン
コウ酸などの有機酸または金属石ケンなと水溶ｌｌ＆中
で酸性を示す化合物が用いられる。When performing partial hydrolysis of al-1-xysilane in this manner, water, an organic solvent, and an acid or alkali catalyst are generally used. As organic solvents and alkaline catalysts,
The above-mentioned J and Tachino are mentioned. As the acid catalyst, specifically, an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, an organic acid such as i' acid, oric acid, or a compound exhibiting acidity in aqueous solution such as metal soap is used.
水は、アルコキシシランを構成するＳ ｉ −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ｐ Ｈが、通常、０〜６、好ま［７，＜は１
〜−３となるような量で、また、アルカリ触媒か用いら
れる場合には、反応液の１〕Ｉ（が、通常、７〜１０、
好ま【、＜は７〜８とな１す
るような量で用いられる。Water is the S i -OR group 1 constituting the alkoxysilane
Usually 0.1 to 2 mol, preferably 0.5 to 2 mol per mol
It is used in an amount of 2 molar. When an acid catalyst is used, the pH of the reaction solution is usually 0 to 6, preferably [7, < is 1
-3, and when an alkali catalyst is used, 1]I (of the reaction solution is usually 7 to 10,
Preferably, < and < are used in an amount of 7 to 8.
」−記のような条件Ｃ得られる１ルコフ１−ジシラン部
分加水分解物のり〕重量は、約１００−・１．０．００
０、好ま１．＜は５００〜・５０００ （ボリスチ１ノ
ン換算分子量）であることが望ま＋７い。- The weight of the 1-Lukov 1-disilane partial hydrolyzate obtained under conditions C is approximately 100-1.0.00
0, preferred 1. < is preferably 500 to 5000 (molecular weight in terms of Boristi 1 non) +7.
本発明においては、このような方法でアルコ１′−ジシ
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１−１８９，０４８号あるいは特願平１−２
５３．５８０号記載の方法により得られる塗イ［Ｉ液を
本発明の部分加水分解物として用いることもてきる。す
なわち、特願平１ｉ、８９．０４１３月に記載されＣＣ
ＪＩＥ中、Ｒ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、ｒ］は０〜３°Ｃある）で示さ
れるアルコキシシランの１種または２種以」、を、有機
溶媒、水およびアルカリ触媒のイｊ−（＋’、ドて部分
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ＦＣさらに部分加水分解しζ゛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２
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１２で用いることができる。あるいは、特願平１
−２５８．５８ｆ１号に記載されているように、一般式
Ｒ，５ｉ（ＯＲ） （式中、Ｒ１は２
ｎ ４−口炭化水素基で
あり、Ｒ２は炭化数１〜４の゛ア月ｌ−ルｈ（であり、
＋１は０〜３である＞ ＝Ｃ示されるアルコキシ：／ラ
ンの１種または２種以」−を、有機溶媒、水および酸の
存（Ｅ ”１’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−Ｃ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（
、、て用いることもできる。In the present invention, a partial hydrolyzate of alco-1'-disilane can be obtained by such a method.
The coating solution I obtained by the method described in No. 53.580 can also be used as the partial hydrolyzate of the present invention. That is, it was written in Patent Application Hei 1i, March 89.04 and CC
In JIE, R is a hydrocarbon group, and R2 has a carbon number of 1-.
4, and r] is 0 to 3°C), in an organic solvent, water and an alkali catalyst. Partially hydrolyzed, and then the resulting partially hydrolyzed solution is further partially hydrolyzed in the presence of water and an acid catalyst to form a 2 silica-based film-forming coating containing a condensation product of an alkoxysilane partial hydrolyzate. The liquid can be used as a partial hydrolyzate in the present invention.
-258.58f1, the general formula R, 5i (OR) (wherein, R1 is a 2 n 4-mouth hydrocarbon group, and R2 is a carbon number of 1 to 4). -leh(and
+1 is from 0 to 3>=C The alkoxy represented by:/one or more of the runs is partially hydrolyzed in the presence of an organic solvent, water and an acid (E "1', and then the obtained A coating solution for forming a silica-based film containing a condensation product of an alkoxysilane partial hydrolyzate, which is made by contacting a partial hydrolyzate with an alkali and making the resulting coating solution acidic by adding an acid as necessary to form -C. , and the partial hydrolyzate in the present invention (
, , can also be used.
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Ｓ ｉ
０２ （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８１０２ （Ｂ）の重量−（
，１，１〜１０ 、 （、）、好ましくは０．２５〜４
．、Ｏとなるような重量比で混 ３
合させることが望まし５い。In the present invention, silica sol and alkoxysilane or its partial hydrolyzate are combined into Si
Weight of 02 (A)/weight of 8102 (B) in alkoxysilane or its partial hydrolyzate - (
,1,1-10, (,), preferably 0.25-4
．． , O, and O at a weight ratio of 3 to 5 is desirable.
成分（Ａ）の瓜か多くなると、得られるシリカ系被膜は
、耐熱性、耐湿性には優れるが、１ｖ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、−力成分（Ｂ）の瓜が多くなると、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 quantity of component (A) increases, the resulting silica-based coating has excellent heat resistance and moisture resistance, but when a silica-based coating is formed with a thickness of 1V, cracks tend to occur easily, - When the amount of melon in the force component (B) increases, the resulting silica-based coating tends to be inferior in 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。−）ｊ 、 １．、
ＯＯ’Ｃ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, the temperature is about 100° C. or less, preferably 80° C. or less, and although it varies depending on the temperature conditions etc., it is usually 0. 5 to 5 hours, preferably 1
~・Heat treatment is performed for 3 hours. When such a treatment is performed, a film-forming coating liquid according to the present invention is obtained. In addition,
Although there is no particular restriction on the lower limit of the treatment temperature, the lower the temperature, the longer the reaction time and the lower the productivity. −)j, 1. ,
If it exceeds OO'C, the hydrolysis reaction of the 'alkoxysilane will proceed too much, which is not preferable.
なお、被膜を形成するには、」上記のように＋２て得ら
れた被膜形成用塗布液を基板Ｌｌ、：塗布（２、次４
いで乾燥、焼成すれば基板上に被膜が形成される。In order to form the film, the film forming coating solution obtained in step 2 as described above is applied to the substrate L1 (2, then dried and fired in steps 4 and 4) to form a film on the substrate.
なお、該塗布液を基板上に塗布するには、スプレー法、
スピンコード法、ディップコ−１・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 addition, in order to apply the coating liquid onto the substrate, a spray method,
Usual methods such as a spin code method, a dip coat 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２００〜８００℃程度である。The above firing temperature is usually about 150 to 800°C, preferably about 200 to 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０．０５〜２μｍ１好ましくは０．１〜
１μｍ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 obtained in this way usually has a thickness of 0.05 to 2 μm, preferably 0.1 to 2 μm, although it varies depending on the application.
The film has a diameter of about 1 μm, no cracks are observed during film formation, excellent adhesion, excellent alkali resistance and moisture resistance, and particularly a significantly low dielectric constant. 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膜アシアタツク止するため、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５
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。In addition, in a liquid crystal element in which an electrode film such as an ITO film is formed on a glass substrate, an alkali component (Na) in the glass substrate
In order to prevent the ITO film from being attacked by alkali, if a film is provided between the glass substrate and the ITO film using the coating liquid according to the present invention, it is possible to prevent the ITO film from being attacked by alkali. It is also useful as a membrane.
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。Effects of the Invention According to the present invention, pinholes or voids do not occur, the structure is dense, and has good adhesion, mechanical strength, and
A coating liquid for forming a silica-based film is provided that can form a silica-based film that has excellent chemical resistance, moisture resistance, insulation, etc., and has a low dielectric constant.
［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 explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
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１−２８（多摩化学工業型）
１１．０．４＋ｒ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６
反応液を限外濾過で未反応エチルンリケ−１・、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Ｓ ｉＯ２濃度５重量％、平均粒径約１００人の
８１０２粒子が分散したシリカゾル（Ａ）を得た。1. (Preparation of silica sol) (1) Pure water 101. ．． Ethyl silica 1-28 (Tama Chemical Industry type) in a mixed solution of 5 g and 406.1 g of methanol.
After adding 11.0.4+r, it was heated to 65° C., and while maintaining 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 alcohol 1., methanol, and ammonia, and at the same time, pure water was added. As a result, a silica sol (A) was obtained in which SiO2 concentration was 5% by weight and 8102 particles having an average particle size of about 100 particles were dispersed.
（２）純水２０３．Ｏｇとメタノール８１．２．２ｇの
混合溶液にメチルシリケート−５１，（多摩化学工業型
）１．２１．６＋ｒ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、８１
０２濃度５重量％、平均粒径約１１０人の５ｌＯ３粒子
が分散したシリカゾル（Ｂ）を得た。(2) Pure water 203. After adding methyl silicate-51, (Tama Chemical Industry type) 1.21.6+r to a mixed solution of Og and 81.2.2 g of methanol, it was heated to 45°C, and while maintaining this temperature, 150 g of 5% ammonia water was added. was added over 5 hours. After the addition was completed, the mixture was further aged at this temperature for 1 hour. After that, unreacted methyl silicate, methanol, and ammonia were removed, and pure water was added at the same time.
A silica sol (B) was obtained in which 5 lO3 particles having a concentration of 5% by weight and an average particle diameter of about 110 particles were dispersed.
（３）純水］、３９．１ｇとメタノール１．．６９．９
ｇの混合溶液を６０℃に保持し、これに、エチルシリケ
ー１−２８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５３２．５に加えたもの）２９８２．５７
ｇ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、Ｓ Ｌ ０２６度１０重量％、平均粒径約２５
０人のＳｉＯ□粒子が分散したシリカゾル（Ｃ）を得た
。(3) pure water], 39.1 g and methanol 1. ．． 69.9
g of mixed solution was kept at 60°C, and a water-methanol solution of ethyl silica 1-28 (water/methanol solution of 2/8 weight ratio) was added to this.
Ethyl silicate-28 to 2450 g of methanol mixture
2982.57 g (added to 532.5 g) and 596.4 g of 0.25% aqueous ammonia were simultaneously added 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 using the ultrafiltration method, and the S L 026 degrees was 10% by weight and the average particle size was about 25.
A silica sol (C) in which 0 SiO□ particles were dispersed was obtained.
（４）エチルシリケー１−２８の代わりにエチルシリケ
ー１−４０（多摩化学工業型）を３７２．８ｇＪＴＩ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、Ｓ ｓ Ｏ２濃度１０重量％、平均粒
径約２７０人のＳ 五〇 ２粒子が分散したシリカゾル
（Ｄ）を得た。(4) A water-dispersed sol was obtained under the same conditions as silica sol (C), except that 372.8 g of JTI ethyl silica 1-40 (Tama Chemical Industries type) was used instead of ethyl silica 1-28. This water-dispersed sol was heated at 150°C in an autoclave.
The treatment was carried out for 12 hours to obtain a silica sol (D) in which S 502 particles with an S s O 2 concentration of 10% by weight and an average particle size of about 270 were dispersed.
（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
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、Ｓ １ ０
２濃度１０重量９６、乎均粒径約２５０人のＳ ｉＯ
２粒子が分散したシリカゾル（Ｅ）を得た。(5) Prepared under the same conditions as silica sol (D) except that a mixture of 266 and 3 g of methyltrimethoxysilanate-28 was used instead of ethyl silicate-40, and S 10
2 concentration 10 weight 96, average particle size about 250 SiO
A silica sol (E) in which two particles were dispersed was obtained.
（６）シリカゾル（Ａ）をオートクレーブで８
１５０℃、１２時間処理し７、で、Ｓ／リカゾル（Ｆ）
を得た。（Ｓ ＋、 ０２ ／ａ、痕、粒子の甲均拉径
はシリカゾル（Ａ）と同じ。）
２゜（アルコ１ギシシラン部分加水分解物の調製）（１
）エチルシラン１゛−１・−２８（多摩化学１−梨型）
３５ ”？、 １． ｇ、エタノール４Ｃ，）２．９
ｇおよび純水２４０．０ｇの混合溶液に濃硝酸を添加（
，５、ｐＨを１．５に調整し１．た。この溶ｌ（ｋを５
０℃、１時間反応させることによって部分加水分解物（
Ａ）を （＋３ ）こ 。(6) Silica sol (A) was treated in an autoclave at 150°C for 12 hours.
I got it. (S +, 02 /a, trace, average diameter of particles are the same as silica sol (A).) 2゜ (Preparation of alco-1 silane partial hydrolyzate) (1
) Ethylsilane 1゛-1・-28 (Tama Chemical 1-Pear shape)
35 ”?, 1. g, ethanol 4C,) 2.9
Add concentrated nitric acid to a mixed solution of g and 240.0 g of pure water (
, 5, adjust the pH to 1.5 and 1. Ta. This solution (k is 5
By reacting at 0°C for 1 hour, a partial hydrolyzate (
A) (+3).
（２）メチルシラン１ｙ−１−５１（多摩化学−１４業
製）１９６ 、 １．、 ｇ ％ ”−タノール０８３
、Ｃ′）ｇおよび純水１２０、□ ｇの混合溶液に１０
６アンモニア水を添加し１、ｐ Ｈを８ 、 （１１
） １ｍ調整（また。これを５０ ”Ｃ１１時間加水分
解させ、その後、濃硝酸でｐ Ｈを２．５に調整し１、
さらに５０°Ｃ，３０分間処伸した（部分加水分解物（
Ｂ））。(2) Methylsilane 1y-1-51 (manufactured by Tama Kagaku-14 Gyo) 196, 1. , g %”-tanol 083
, C′) g and pure water 120, □ g in a mixed solution of 10
6 Add ammonia water to 1, pH to 8, (11
) Adjust to 1 m (Also. Hydrolyze this at 50"C for 11 hours, then adjust the pH to 2.5 with concentrated nitric acid.
It was further processed at 50°C for 30 minutes (partial hydrolyzate (
B)).
（３）メチルトリメトキシシラン４５４．５ｇ。(3) 454.5 g of methyltrimethoxysilane.
エタノール１．８５．５ｇおよび純水３６０．Ｏｇの混
合溶液を濃硝酸でｐＨ１、（）に１規整１．だの１（９
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Ｉ５、■）丁■逢’１．０ζ４−調整］
またのち、さらに５０℃で２時間処理り戸、＝。 （部
分加水分解物（Ｃ））。1.85.5 g of ethanol and 360 g of pure water. A mixed solution of Og was adjusted to pH 1 () with concentrated nitric acid. Dano 1 (9) Hydrolyzed at 50°C for 2 hours. Then, 1% ammonia water was added I5,
After that, it was further treated at 50℃ for 2 hours. (Partial hydrolyzate (C)).
（４）メチルトリーｌ−キシシラン２２’７．３ｇ。(4) Methyl tri-l-xysilane 22'7.3 g.
ゴヂルシリノト ｌ・ ２８′３５７．１ｇ、エタノル
１−７５．０ｇおよび純水２４０．Ｏｇの？Ｉ１．合溶
液を１％アンＴ：二Ｔ水で￥）Ｈ８，５に調整し５．５
０℃、２時間加水分解させた。次いで、９１５％酢酸水
溶液でｐＨ４に調整し７たのぢ、さらに５０ ”Ｃて５
時間処理した。（部分加水分解物（Ｄ））。Godil Sirinoto 1.28'357.1g, ethanol 1-75.0g and pure water 240. Of Og? I1. The combined solution was adjusted to 5.5 with 1% AnT:2T water.
Hydrolysis was carried out at 0°C for 2 hours. Next, the pH was adjusted to 7 with a 915% acetic acid aqueous solution, and further heated at 50"C.
Time processed. (Partial hydrolyzate (D)).
（５）メチルトリメトキシシラン２７２．７ｇ。(5) 272.7 g of methyltrimethoxysilane.
メチルシリゲ−１・〜５１ １５６．９に、 丁、タ
ノール３′３０．４ｇおよび純水２４．０．０ｇの混合
溶液を濃硝酸でＩＩ）Ｈ２，Ｏに調整し１．５０℃、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−ｒ ｐ Ｈを７．０に調整１．たのち、さ
らに５０℃で２時間処理した。（部分加水分解物（Ｅ）
）。Methylsilige-1.~51 156.9, a mixed solution of 30.4 g of tanol 3' and 24.0.0 g of pure water was adjusted to II) H2,O with concentrated nitric acid and heated at 1.50°C.
Hydrolyzed for hours. Next, 1% triethanol'amine aqueous solution - r pH adjusted to 7.01. Afterwards, the mixture was further treated at 50°C for 2 hours. (Partial hydrolyzate (E)
).
０
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時間加熱処理しまた。次いで、ロ
ータリー毛バボレー、−夕で、水、アルコールを留ノく
し、て−チルセルソルブまたはブｒ７ビ１ノングリコー
ルモノプロビル上・、チルと溶媒置換し２、ＳｉＯ□濃
度１．、 ＯＸｎ ｍ ９６のす重液１〜■を調製し５
た。0 3, (Preparation of coating liquid) The silica sol obtained in 1 (Preparation of silica sol) and 2 (
The alkoxysilane partial hydrolyzate obtained in (Preparation of alkoxysilane partial hydrolyzate) was mixed at the predetermined ratio shown in Table 1, and heat treated at 50° C. for 1 hour. Next, water and alcohol were removed using a rotary vaporizer, and the solvent was replaced with chill on Til Cell Solsolve or B1 Non-Glycol Monoprobil, and the SiO□ concentration was 1. , Prepare OXn m 96 heavy liquids 1 to 5.
Ta.
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７、乾燥後、３５０ ℃、３ （１分間焼成：、チ
ー膜厚２．Ｃ］／！ｍの被膜を形成］、た。得られた被
膜につい０１次の如き評価を行な７．た。Next, these coating solutions were applied to a glass substrate using a spinner method, and after drying, they were heated at 350° C. for 1 minute to form a film with a thickness of 2.C]/!m. The following evaluations were made on the coated film.
（１）クラックのｆ」−無＋ １１１１：ｌ ′ｆ１．
Ｊ、観察。(1) Crack f''-no+ 1111:l'f1.
J. Observation.
（２）密着性・中成のｂ ＋：：ｙハンチ ブを膜面に
はりイ・ｊけ、その端部を膜面に灼１７で直角に保ち、
瞬間的に引き（、ｔが４゛。そのときの膜の剥離状態を
観察。(2) Adhesiveness/Medium b+::y Glue the haunch onto the membrane surface, keep the end perpendicular to the membrane surface with a cauter 17,
Pull it instantaneously (t is 4゛. Observe the peeling state of the film at that time.
（３）−ノ“ルカリ性 ０℃の５銀量％Ｎ ａ ＯＨ水
１
溶液に２４時間浸したのちの膜面の状態を観察。(3) - Alkalinity The state of the membrane surface was observed after 24 hours of immersion in a solution of 5% NaOH water at 0°C.
（４）絶縁性：絶縁抵抗１−１で測定。(4) Insulation: Measured with insulation resistance 1-1.
（５）アルカリパッシベーション能：４５０℃で加熱処
理し、加熱前後の膜の抵抗変化を評価。(5) Alkaline passivation ability: Heat treated at 450°C and evaluated the change in resistance of the film before and after heating.
さらに、各塗布液をシリコンウェハに２ ｆｔ ＋］）
の厚さになるように、スピナー法で塗布、乾燥（７，３
５０℃、３０分間、窒素気流中で焼成１２て被膜を形成
１，５た。さらにこのＳ ｉ ０２膜の」−にＡΩの蒸
着膜を形成り、 −Ｃ” 、比誘電率を測定した。それ
ぞれの結果を表１に示す。Furthermore, apply each coating solution to a silicon wafer by 2 ft +])
Apply with a spinner method and dry (7, 3
A film was formed by baking at 50° C. for 30 minutes in a nitrogen stream. Further, an AΩ vapor-deposited film was formed on the ``-'' of this Si02 film, and the ``-C'' and relative permittivity were measured.The respective results are shown in Table 1.
（以Ｆ余白）
２
手続中ｒｙｙ Ｊ−Ｔ二書
］、事件の表示
平成 ２年 特 許 願 第６２，２５５号平成 ２年
３月１３日提出の特許願
２、発明の名称
被膜形成用塗布液
３、補正をする者
事件との関係 特許出願人
住 所 東京都千代田区大手町２丁［１６番２号名称
触媒化成］二業株式会社
代表者 綱島 建吉
４、代 理 人 （郵便番号１４１）
住 所 東京部品用区西五反田二丁目１９番２号荒
久ビル ３階
６゜
７゜
補正の対象
明細書の「発明の詳細な説明」の欄
補正の内容
別紙の通り（補正の対象の欄に記載した事項以外は内容
に変更なし）
補正の内容
１）明細書第８頁第１９行において、
「約１００℃以上の温度に昇温し」とあるのを、「約１
００℃以上の温度に加圧下で昇温し」と補正します。(Herein F margin) 2 In the proceedings ryy J-T 2 books], Indication of the case 1990 Patent Application No. 62,255 Patent application 2 filed on March 13, 1990, Title of invention Coating for film formation Solution 3: Relationship with the person making the amendment Patent applicant address 2-chome Otemachi, Chiyoda-ku, Tokyo [Name 16-2]
Catalyst Chemicals] Nigyo Co., Ltd. Representative: Kenkichi Tsunashima 4, Agent (zip code: 141) Address: 3rd floor, Araku Building, 2-19-2 Nishigotanda, Parts Ward, Tokyo 6° 7° Specification subject to amendment Contents of the amendment in the "Detailed Description of the Invention" column of "Detailed Description of the Invention" As shown in the attached sheet (no change in content other than the matters stated in the column subject to amendment) Contents of the Amendment 1) In line 19 of page 8 of the specification, "about The phrase ``raise the temperature to 100℃ or more'' is replaced by ``about 1
The temperature is raised under pressure to a temperature of 00℃ or higher.''
２）明細書第２１頁第２０行において、［０℃の５重量
％Ｎａ０ＨＪとあるのを、１３０℃の５重量％Ｎａ０Ｈ
Ｊと補正します。2) On page 21, line 20 of the specification, [5 wt% Na0HJ at 0°C is replaced with 5 wt% Na0H at 130°C.
Correct it with J.
３）明細書第２２頁第３行において、
［アルカリパッシベーション能：４５ｏ℃で」とあるの
を、
「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」と補正します。3) In the third line of page 22 of the specification, the phrase [Alkali passivation ability: at 45oC] was replaced with "Alkali passivation ability: After further providing a NESA film on each film using the CVD method,
℃” is corrected.
以 上that's all
Claims (1)
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加水分解重縮合して得られるシ
リカゾルと、 前記アルコキシシランの部分加水分解物との反応物を含
む被膜形成用塗布液。[Claims] 1) General formula R_nSi(OR')_4_-_n (wherein,
R and R' represent an alkyl group having 1 to 8 carbon atoms, an aryl group, or a vinyl group, and n is an integer of 0 to 3) A silica sol obtained by hydrolyzing and polycondensing an alkoxysilane; A film-forming coating solution containing a reaction product with a partially hydrolyzed product of alkoxysilane.
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 true JPH03263476A (en) | 1991-11-22 |
| JP3163579B2 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) |
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| WO1997035939A1 (en) * | 1996-03-25 | 1997-10-02 | Catalysts & Chemicals Industries Co., Ltd. | Coating fluid for low-permittivity silica coating and substrate provided with low-permittivity coating |
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| WO2000018847A1 (en) * | 1998-09-25 | 2000-04-06 | Catalysts & Chemicals Industries Co., Ltd. | Coating fluid for forming low-permittivity silica-based coating film and substrate with low-permittivity coating film |
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| WO2010150861A1 (en) * | 2009-06-24 | 2010-12-29 | 旭化成イーマテリアルズ株式会社 | Product of polysiloxane condensation |
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| JP2011100858A (en) * | 2009-11-06 | 2011-05-19 | Asahi Kasei E-Materials Corp | Method for forming insulating film |
| JP2012131859A (en) * | 2010-12-20 | 2012-07-12 | Asahi Kasei E-Materials Corp | Coating liquid for formation of silica-based insulating film |
| JP2012251204A (en) * | 2011-06-02 | 2012-12-20 | Hitachi Chemical Co Ltd | Surface treatment agent for silver and silver alloy, substrate coated with light-reflective film, and light-emitting device |
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1990
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04233732A (en) * | 1990-08-16 | 1992-08-21 | Motorola Inc | Spin on derivative used in manufacturing process of semiconductor |
| JPH05263045A (en) * | 1992-03-17 | 1993-10-12 | Catalysts & Chem Ind Co Ltd | Film-forming coating liquid and its production |
| US5700391A (en) * | 1993-02-18 | 1997-12-23 | Nissan Chemical Industries, Ltd. | Liquid coating composition forming a liquid crystal display element insulating film |
| WO1997035939A1 (en) * | 1996-03-25 | 1997-10-02 | Catalysts & Chemicals Industries Co., Ltd. | Coating fluid for low-permittivity silica coating and substrate provided with low-permittivity coating |
| US6261357B1 (en) | 1996-03-25 | 2001-07-17 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming low-permittivity silica film and substrate having low-permittivity coating film |
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| JP2007138144A (en) * | 2005-10-18 | 2007-06-07 | Hitachi Chem Co Ltd | Silica-based coated film-forming composition |
| JP2008248130A (en) * | 2007-03-30 | 2008-10-16 | Sharp Corp | Coating liquid for forming interlayer insulation film, and substrate having interlayer insulation film |
| JP2009091545A (en) * | 2007-09-20 | 2009-04-30 | Jgc Catalysts & Chemicals Ltd | Application liquid for forming silica-based coating film, preparation method for application liquid, and silica-based insulation film obtained from application liquid |
| JP2010150361A (en) * | 2008-12-25 | 2010-07-08 | Jgc Catalysts & Chemicals Ltd | Coating liquid for forming silica based transparent coating film |
| WO2010150861A1 (en) * | 2009-06-24 | 2010-12-29 | 旭化成イーマテリアルズ株式会社 | Product of polysiloxane condensation |
| JP2011026570A (en) * | 2009-06-24 | 2011-02-10 | Asahi Kasei E-Materials Corp | Polysiloxane condensation reaction product |
| EP2447303A4 (en) * | 2009-06-24 | 2012-10-10 | Asahi Kasei E Materials Corp | Product of polysiloxane condensation |
| US8906153B2 (en) | 2009-06-24 | 2014-12-09 | Asahi Kasei E-Materials Corporation | Product of polysiloxane condensation |
| JP2011100858A (en) * | 2009-11-06 | 2011-05-19 | Asahi Kasei E-Materials Corp | Method for forming insulating film |
| JP2012131859A (en) * | 2010-12-20 | 2012-07-12 | Asahi Kasei E-Materials Corp | Coating liquid for formation of silica-based insulating film |
| JP2012251204A (en) * | 2011-06-02 | 2012-12-20 | Hitachi Chemical Co Ltd | Surface treatment agent for silver and silver alloy, substrate coated with light-reflective film, and light-emitting device |
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