JPH062155A - Formation of silicon dioxide coating film on metal body - Google Patents
Formation of silicon dioxide coating film on metal bodyInfo
- Publication number
- JPH062155A JPH062155A JP16462892A JP16462892A JPH062155A JP H062155 A JPH062155 A JP H062155A JP 16462892 A JP16462892 A JP 16462892A JP 16462892 A JP16462892 A JP 16462892A JP H062155 A JPH062155 A JP H062155A
- Authority
- JP
- Japan
- Prior art keywords
- silicon dioxide
- film
- metal body
- dioxide film
- substrate
- 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.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 62
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000000576 coating method Methods 0.000 title abstract description 26
- 239000011248 coating agent Substances 0.000 title abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 22
- 229910052681 coesite Inorganic materials 0.000 abstract 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract 5
- 229910052682 stishovite Inorganic materials 0.000 abstract 5
- 229910052905 tridymite Inorganic materials 0.000 abstract 5
- 229910003638 H2SiF6 Inorganic materials 0.000 abstract 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 abstract 2
- 239000002585 base Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 150000003377 silicon compounds Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- -1 fluorine ions Chemical class 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000005361 soda-lime glass Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-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
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、二酸化珪素被膜を形成
する方法に関し、特に基材として金属体を用いる場合に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a silicon dioxide film, and more particularly to the case of using a metal body as a substrate.
【０００２】[0002]
【従来の技術】今日、金属はその良導体としての特徴を
生かし、幅広い産業分野に利用されている。しかしなが
ら、金属を良導体として扱う場合、例えば電線として使
用する場合、安全上絶縁被覆が必要である。また、金属
の腐食防止も必要とされ、陽極酸化膜や塗料等が腐食防
止用保護膜として使用されている。特に高温環境あるい
は特殊目的としてのＳｉＯ2被覆が必要な分野、例えば
コンパクトディスクのプリント基板、鉄鋼関係の圧延ロ
ールの腐食摩耗防止用被膜、光磁気ヘッドの基板保護、
太陽電池用アモルファスシリコンをつけるステンレス基
板の保護膜、あるいは各種陽極酸化膜の代替等の分野が
ある。また、半導体の分野では層間絶縁膜等に二酸化珪
素膜が使用されている。2. Description of the Related Art Today, metal is utilized in a wide range of industrial fields by taking advantage of its characteristics as a good conductor. However, when treating a metal as a good conductor, for example, when using it as an electric wire, an insulating coating is required for safety. Further, it is also necessary to prevent metal corrosion, and an anodic oxide film, paint, etc. are used as a protective film for corrosion prevention. Especially in fields requiring SiO 2 coating for high-temperature environments or special purposes, such as compact disk printed circuit boards, coatings for preventing corrosion and wear of steel-related rolling rolls, substrate protection for magneto-optical heads,
There is a field such as a protective film for a stainless steel substrate on which amorphous silicon for solar cells is attached, or a substitute for various anodic oxide films. In the field of semiconductors, a silicon dioxide film is used as an interlayer insulating film or the like.
【０００３】従来、二酸化珪素膜形成方法として、二酸
化珪素が飽和状態となった珪弗化水素酸を含む水溶液
に、水または試薬（ホウ酸、塩化アルミニウム、金属ア
ルミニウム、その他）を添加するか、温度を上昇させる
等の手段で、二酸化珪素の過飽和状態とした水溶液に、
基材を浸漬して基材表面に二酸化珪素被膜を形成する方
法（以後、二酸化珪素が飽和状態となった珪弗化水素酸
を含む水溶液を「処理液」、成膜方法を「析出法」と呼
ぶ）が知られている（例えば、特開昭５７−１９６７４
４号、特開昭６１−２８１０４７号、特開昭６２−２０
８７６号）。Conventionally, as a method for forming a silicon dioxide film, water or a reagent (boric acid, aluminum chloride, aluminum metal, etc.) is added to an aqueous solution containing hydrosilicofluoric acid in which silicon dioxide is saturated, or To a supersaturated aqueous solution of silicon dioxide by means such as raising the temperature,
A method of forming a silicon dioxide film on the surface of a base material by immersing the base material (hereinafter, an aqueous solution containing hydrofluoric acid in which silicon dioxide is saturated is a "treatment liquid", and a film formation method is a "precipitation method"). Is called) (for example, JP-A-57-19674).
4, JP-A-61-281047, JP-A-62-20
876).
【０００４】上記析出法では、低温成膜が可能である、
真空系を必要としないため成膜コストが安価である、大
面積・大量成膜が可能である、等の利点があるが、処理
液である珪弗化水素酸が強酸であり、かつ弗素イオンを
含有するため、金属等の基材（特に水素よりイオン化傾
向が大である金属、弗素イオンと反応しやすい金属等）
は容易に溶解してしまい、基材として使用できないとい
う問題点があった。The above-mentioned deposition method enables low-temperature film formation,
Since it does not require a vacuum system, it has the advantages of low film formation cost, large area, large volume film formation, etc., but hydrosilicofluoric acid, which is the processing liquid, is a strong acid and it also contains fluorine ions. Since it contains, it is a base material such as a metal (especially a metal that has a greater ionization tendency than hydrogen, a metal that easily reacts with fluorine ions, etc.)
However, there is a problem in that it dissolves easily and cannot be used as a substrate.
【０００５】上記問題点を解決するために該基材表面に
あらかじめ真空蒸着、スパッター、ＣＶＤ等の方法で二
酸化珪素被膜を形成した後、上記析出法により二酸化珪
素被膜を形成する方法（特開昭６０−２１８１０号、以
後改良法１と呼ぶ）や、該基材を陽極として電解析出を
行う方法（特開平１−８２９６号、以後改良法２と呼
ぶ）が知られている。また、該基材と処理液との反応を
抑制する条件である低温下で二酸化珪素被膜を形成し、
該基材をこの被膜で処理液から保護した状態にしてから
従来の析出法で再度二酸化珪素被膜を形成する方法（特
開平３−１７０３１７号、以後改良法３と呼ぶ）が提案
されている。In order to solve the above problems, a method of forming a silicon dioxide film on the surface of the substrate in advance by a method such as vacuum vapor deposition, sputtering or CVD, and then forming the silicon dioxide film by the above-mentioned precipitation method (Japanese Patent Laid-Open No. SHO11-86). 60-21810, hereinafter referred to as improvement method 1) and a method of performing electrolytic deposition using the substrate as an anode (JP-A-1-8296, hereinafter referred to as improvement method 2). Further, a silicon dioxide film is formed at a low temperature which is a condition for suppressing the reaction between the base material and the treatment liquid,
A method has been proposed in which the base material is protected from the treatment liquid by this coating and then a silicon dioxide coating is formed again by a conventional deposition method (JP-A-3-170317, hereinafter referred to as improvement method 3).
【０００６】[0006]
【発明が解決しようとする課題】しかし、上記改良法１
では、該基材表面にあらかじめ真空蒸着、スパッター、
ＣＶＤ等の方法で二酸化珪素を含む被膜を形成するた
め、装置が簡便でなく二酸化珪素被膜に要するコストが
高い、大面積の基材を処理することが困難である等の問
題点があった。However, the above-mentioned improved method 1
Then, vacuum deposition, sputtering,
Since a film containing silicon dioxide is formed by a method such as CVD, there are problems that the apparatus is not simple, the cost required for the silicon dioxide film is high, and it is difficult to process a large-area substrate.
【０００７】また、改良法２では、そのメカニズムから
推定されるようにＳｉＯ2に近い形の粒子、錯イオン、
ゾル、ゲル、コロイド等が表面あるいは全体として負に
帯電しており電気的に陽極に引きつけられて成膜するた
め、膜表面の平坦性が悪い、ピンホールが発生しやす
い、等の問題点があった。Further, in the improved method 2, as estimated from the mechanism, particles having a shape close to SiO 2 , complex ions,
Since sol, gel, colloid, etc. are negatively charged on the surface or as a whole and are electrically attracted to the anode to form a film, there are problems such as poor flatness of the film surface and easy occurrence of pinholes. there were.
【０００８】さらに、改良法３では、基材表面に珪弗化
水素酸中の珪素化学種との反応拠点が存在しないため、
析出初期には二酸化珪素粒子が基材表面に不均一に付着
し、この粒子を拠点として二酸化珪素が成長するといっ
た過程を経て成膜していくので、成膜まで長時間を要す
る、そのため低温とはいえ基材が長時間強酸にさらされ
る、得られた二酸化珪素被膜は密着性が悪くポーラスで
不均一に白濁している等の問題があった。Further, in the improved method 3, since there is no reaction site with the silicon chemical species in hydrofluoric acid on the surface of the substrate,
At the initial stage of deposition, silicon dioxide particles are non-uniformly adhered to the surface of the base material, and the film is formed through the process in which silicon dioxide grows from these particles as a base, so it takes a long time to form the film. However, there are problems that the substrate is exposed to a strong acid for a long time, the obtained silicon dioxide coating has poor adhesion, and is porous and nonuniformly clouded.
【０００９】[0009]
【課題を解決するための手段】本発明は、上記従来の問
題点を解決し、金属体を均一厚さの二酸化珪素被膜で覆
う方法を提供するものである。SUMMARY OF THE INVENTION The present invention solves the above problems of the prior art and provides a method of covering a metal body with a silicon dioxide film having a uniform thickness.
【００１０】本発明は、有機珪素化合物被膜で金属体を
被覆することにより、強酸である珪弗化水素酸水溶液へ
の溶解を防ぎ、二酸化珪素の過飽和状態の珪弗化水素酸
を含む水溶液と接触させて形成する二酸化珪素被膜の成
膜性を向上させ、また上記行程において加熱処理を行う
ことにより付着力を向上させることを要旨とする。According to the present invention, by coating a metal body with an organic silicon compound film, it is possible to prevent dissolution in a hydrosilicofluoric acid solution which is a strong acid, and to provide an aqueous solution containing hydrofluoric acid in a supersaturated state of silicon dioxide. The gist of the invention is to improve the film-forming property of the silicon dioxide film formed by contact and improve the adhesive force by performing the heat treatment in the above process.
【００１１】以下に本発明を詳細に説明する。The present invention will be described in detail below.
【００１２】本発明において、金属体を被覆する有機化
合物は、一般式（Ｉ）Ｒ1 nＳｉ（ＯＲ2）4-nで示される
珪素化合物の１種または２種以上の部分加水分解物を被
覆硬化してなる層が用いられる。In the present invention, the organic compound coating the metal body is one or more partial hydrolyzates of the silicon compound represented by the general formula (I) R 1 n Si (OR 2 ) 4-n. A layer formed by coating and curing is used.
【００１３】式中Ｒ1 は炭素数１〜６の炭化水素基、ビ
ニル基、メタクリロキシ基、エポシキ基、アミノ基、メ
タカプト基、フッ素を有する有機基または塩素を有する
有機基を示し、Ｒ2はアルキル基、アシル基またはアル
コキシアルキル基から選ばれる１種もしくは複数の結合
基である。ｎは０または１である。In the formula, R 1 represents a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, an epoxy group, an amino group, a metacapto group, an organic group having fluorine or an organic group having chlorine, and R 2 is It is one or more bonding groups selected from an alkyl group, an acyl group or an alkoxyalkyl group. n is 0 or 1.
【００１４】該一般式（Ｉ）で示される珪素化合物とし
ては、テトラメトキシシラン、テトラエトキシシラン、
テトラアセトキシシラン、メチルトリエトキシシラン、
フェニルトリメトキシシラン、ビニルトリス（β−メト
キシエトキシ）シラン、ビニルトリメトキシシラン、γ
−クロロプロピルトリメトキシシラン、γ−メルカプト
プロピルトリメトキシシラン、γ−グリシドキシプロピ
ルトリメトキシシラン、γ−メタクリロキシプロピルト
リメトキシシラン、γ−アミノプロピルトリエトキシシ
ラン、Ｎ−（β−アミノエチル）−γ−アミノプロピル
トリメトキシシラン等が挙げられる。As the silicon compound represented by the general formula (I), tetramethoxysilane, tetraethoxysilane,
Tetraacetoxysilane, methyltriethoxysilane,
Phenyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, γ
-Chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) Examples include -γ-aminopropyltrimethoxysilane and the like.
【００１５】これらの加水分解物とは、該一般式（Ｉ）
で示される珪素化合物中のアルコキシ基、アルコキシア
ルコキシ基、アセトキシ基の一部または全部が水酸基で
置換されたもの、更に、置換された水酸基同志が一部自
然に縮合されたものを含んでいる。これらの加水分解物
は、例えば、水およびアルコールのような混合溶媒中に
て酸の存在下で加水分解することによって容易に得るこ
とができる。These hydrolysates mean the compounds of the general formula (I)
The alkoxy compound, the alkoxyalkoxy group, and the acetoxy group in the silicon compound represented by are partially or entirely substituted with a hydroxyl group, and further, the substituted hydroxyl groups are partially condensed with each other. These hydrolysates can be easily obtained by hydrolysis in the presence of an acid in a mixed solvent such as water and alcohol.
【００１６】これらの加水分解物は、１種を単独で用い
ても２種以上を併用してもよいが、２種以上を併用する
場合には、一般式（Ｉ）で示される珪素化合物を２種以
上混合して共加水分解したものの使用が好ましい。These hydrolysates may be used alone or in combination of two or more. When two or more of them are used in combination, the silicon compound represented by the general formula (I) is used. It is preferable to use a mixture of two or more kinds which are cohydrolyzed.
【００１７】有機珪素化合物被膜は前記珪素化合物の部
分加水分解物を各種有機溶剤に溶解して塗布液を作製
し、金属体に塗布後、熱、紫外線あるいは電子線を用い
て硬化させ得ることができる。The organosilicon compound coating can be prepared by dissolving the above-mentioned partial hydrolyzate of a silicon compound in various organic solvents to prepare a coating solution, coating the coating on a metal body, and then curing it by using heat, ultraviolet rays or electron beams. it can.
【００１８】該有機珪素化合物被膜を設ける目的は、析
出法による二酸化珪素被覆前の金属体表面をガラス表面
に対する二酸化珪素被膜形成のような好ましい状況に近
づけるための処置である。また、金属体を、強酸である
珪弗化水素酸水溶液との直接接触から保護し、珪弗化水
素酸水溶液への溶解を防ぐ役割を果たしている。該有機
珪素化合物被膜を形成した金属体上に析出法にて成膜を
行うと、均一厚さの二酸化珪素被膜が得られるが付着力
が必ずしも充分ではないという欠点を有する。The purpose of providing the organic silicon compound coating is a treatment for bringing the surface of the metal body before the silicon dioxide coating by the deposition method to a preferable condition such as the formation of the silicon dioxide coating on the glass surface. In addition, it protects the metal body from direct contact with a hydrosilicofluoric acid aqueous solution which is a strong acid, and plays a role of preventing dissolution in the hydrosilicofluoric acid aqueous solution. When a film is formed on the metal body on which the organic silicon compound film is formed by a precipitation method, a silicon dioxide film having a uniform thickness can be obtained, but there is a drawback that the adhesive force is not always sufficient.
【００１９】しかし、得られた二酸化珪素で被覆された
金属体に加熱処理を施すと、二酸化珪素の付着力が向上
する。また、有機珪素化合物被膜層を形成した段階の金
属体に加熱処理を施し、その上に析出法にて成膜を行う
と、付着力の強い二酸化珪素被膜が得られる。However, when the obtained metal body coated with silicon dioxide is subjected to heat treatment, the adhesion of silicon dioxide is improved. Further, when the metal body at the stage of forming the organic silicon compound coating layer is subjected to heat treatment and a film is formed thereon by a precipitation method, a silicon dioxide coating having a strong adhesive force is obtained.
【００２０】本発明における加熱処理とは、有機珪素化
合物を塗布した際に乾燥する加熱手段を指すのではなく
て、積極的にそれより高い温度を加えるものである。The heat treatment in the present invention does not refer to a heating means for drying an organic silicon compound when applied, but means to positively apply a temperature higher than that.
【００２１】上記の加熱処理温度は、２５０〜４５０℃
程度が好ましい。この温度が２５０℃より低い場合に
は、析出法によって得られる二酸化珪素被膜の付着力が
向上しない。また４５０℃より高い場合には、該有機化
合物被膜の分解等によりピンホール等の欠点が発生す
る。The heat treatment temperature is 250 to 450 ° C.
A degree is preferable. If this temperature is lower than 250 ° C., the adhesion of the silicon dioxide film obtained by the precipitation method will not be improved. On the other hand, when the temperature is higher than 450 ° C., defects such as pinholes occur due to decomposition of the organic compound film.
【００２２】以上のようにして得られる有機化合物被膜
層の厚さは、特に限定されないが、通常、０．００５〜
０．２μｍがより好ましい。この被覆層の厚さが０．０
０５μｍより薄いと透明均一な二酸化珪素被膜が得られ
にくくなり、逆に０．２μｍより厚くなると、該有機化
合物被膜へのクラックの発生原因となるため適当でな
い。The thickness of the organic compound coating layer obtained as described above is not particularly limited, but usually 0.005 to 0.005.
0.2 μm is more preferable. The thickness of this coating layer is 0.0
If it is thinner than 05 μm, it is difficult to obtain a transparent and uniform silicon dioxide coating, and if it is thicker than 0.2 μm, cracks may occur in the organic compound coating, which is not suitable.
【００２３】本発明の基材としては、ほとんどの金属体
に適用されるが、特に、表面に酸化層を形成させると二
酸化珪素被膜の成膜性が向上する。したがってＣｒのよ
うに、表面に自然酸化膜を容易に形成する金属体がより
好ましい。また、その他の金属体の場合には、そのまま
基材として用いても良いが、金属体上に効率よく二酸化
珪素被膜を得るためには、好ましくは、その上に、Ｃｒ
等の金属を蒸着法、スパッター法等により被覆して基材
として用いるとより望ましい結果が得られる。The base material of the present invention is applied to most metal bodies, and in particular, when an oxide layer is formed on the surface, the film forming property of the silicon dioxide film is improved. Therefore, a metal body such as Cr that easily forms a natural oxide film on its surface is more preferable. Further, in the case of other metal bodies, they may be used as they are as a base material, but in order to efficiently obtain a silicon dioxide film on the metal body, it is preferable to add Cr on it.
More desirable results can be obtained by coating such a metal as a substrate by vapor deposition, sputtering or the like.
【００２４】[0024]
【作用】本発明によれば、金属体への二酸化珪素被膜形
成および加熱処理を行うことにより、金属体を均一の厚
さで、ピンホールのない、二酸化珪素被膜で覆うことが
できる。According to the present invention, by forming a silicon dioxide film on a metal body and performing heat treatment, the metal body can be covered with a silicon dioxide film having a uniform thickness and having no pinhole.
【００２５】[0025]
【実施例】以下に実施例、比較例及び参考例を挙げて本
発明を詳細に説明するが、本発明はその要旨を越えない
限り、以下の実施例に限定されるものではない。EXAMPLES The present invention will be described in detail below with reference to Examples, Comparative Examples and Reference Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.
【００２６】（実施例１）基材として、縦１００ｍｍ、
横１００ｍｍ、厚さ１ｍｍのソーダライムガラスに蒸着
した、厚さ２００ｎｍのＣｒ膜を有するものを用いた。(Example 1) As a base material, a length of 100 mm,
A soda lime glass having a width of 100 mm and a thickness of 1 mm, which had a Cr film with a thickness of 200 nm, was used.
【００２７】このＣｒ膜表面に、テトラエチルシリケー
トを主成分とする加水分解物溶液（商品名ＣＳＧ−Ｌ−
０８０３Ｐ、チッソ（株）製）をエタノール：２ープロ
パノール：ｎ−ブタノール＝３：１：１の割合で含む溶
液を用いて、２％に希釈しこれを用いて、ディッピング
法にて１０ｎｍの厚さになるように塗布し、１５０℃の
温度で加熱乾燥した。On the surface of the Cr film, a hydrolyzate solution containing tetraethyl silicate as a main component (trade name CSG-L-
0803P, manufactured by Chisso Co., Ltd.) was diluted to 2% with a solution containing ethanol: 2-propanol: n-butanol = 3: 1: 1, and was diluted with this solution to a thickness of 10 nm by a dipping method. And was dried by heating at a temperature of 150 ° C.
【００２８】その後、図１に示す二酸化珪素被膜製造装
置を用いて、上記の処理を行った基材上に、二酸化珪素
被膜を以下の手順にて作製した。After that, a silicon dioxide film was produced on the base material subjected to the above treatment by the following procedure using the silicon dioxide film production apparatus shown in FIG.
【００２９】二酸化珪素被膜製造装置は、外槽（１）と
内槽（２）からなり、内槽と外槽の間には水（３）が満
たしてある。本実施例ではこの水の温度が３５℃となる
よう、温度調節器（４）で調節した。また、水（３）は
温度均一化のため、攪拌機（５）により攪拌されてい
る。内槽は前部（６）、中部（７）、後部（８）からな
り、各部にはシリカゲル粉末を溶解飽和した３モル／リ
ットルの濃度の珪弗化水素酸水溶液が処理液として満た
してある。The silicon dioxide film manufacturing apparatus comprises an outer tank (1) and an inner tank (2), and water (3) is filled between the inner tank and the outer tank. In this example, the temperature of the water was adjusted to 35 ° C. by the temperature controller (4). Further, the water (3) is stirred by the stirrer (5) in order to make the temperature uniform. The inner tank was composed of a front part (6), a middle part (7) and a rear part (8), and each part was filled with a hydrosilicofluoric acid aqueous solution having a concentration of 3 mol / liter in which silica gel powder was dissolved and saturated as a treatment liquid. .
【００３０】ここでまず循環ポンプ（１０）を始動さ
せ、内槽後部（８）の処理液を一定量ずつくみ出してフ
ィルター（１１）で濾過し、内槽前部（６）へ戻す処理
液循環を開始した。処理液を二酸化珪素の過飽和状態に
するために、その後、内槽後部（８）に添加物として金
属Ａｌ板（１２）を浸漬し、１６時間保持した。この状
態で処理液は適度な二酸化珪素過飽和度を有する処理液
となった。Here, first, the circulation pump (10) is started, the treatment liquid in the rear part (8) of the inner tank is pumped out by a fixed amount, filtered by the filter (11), and returned to the front part (6) of the inner tank. Started. In order to make the treatment liquid a supersaturated state of silicon dioxide, a metal Al plate (12) as an additive was then immersed in the rear part (8) of the inner tank and kept for 16 hours. In this state, the treatment liquid became a treatment liquid having an appropriate degree of supersaturation of silicon dioxide.
【００３１】その後、上記の基材（９）を内槽中部
（７）に垂直に浸漬し、８時間保持した。Then, the above-mentioned base material (9) was vertically dipped in the middle part (7) of the inner tank and held for 8 hours.
【００３２】上記処理で得られた二酸化珪素被膜の膜厚
は、５００ｎｍであった。電子顕微鏡による観察の結
果、二酸化珪素被膜の表面は比較的平坦であり、ピンホ
ール等は観察されなかった。また上記処理した基材を３
００℃で１ｈｒ、加熱処理すると該二酸化珪素被膜の表
面状態には変化なく、引っ張り試験法による付着力は６
００ｋｇｆ／ｃｍ2 以上であった。The film thickness of the silicon dioxide film obtained by the above treatment was 500 nm. As a result of observation with an electron microscope, the surface of the silicon dioxide film was relatively flat, and pinholes and the like were not observed. In addition, the treated substrate is 3
When heat-treated at 00 ° C. for 1 hr, the surface state of the silicon dioxide film does not change, and the adhesion force by the tensile test method is 6
It was at least 00 kgf / cm 2 .
【００３３】（比較例１）二酸化珪素被膜形成後、加熱
処理を行なわなかった場合の引っ張り試験による二酸化
珪素被膜の付着力は２００ｋｇｆ／ｃｍ2以下であっ
た。また、有機珪素化合物の被膜で被覆されていない試
料について、図１の装置を用いて二酸化珪素の被覆を行
なった場合は、目的とする透明な二酸化珪素被膜は得ら
れず、基材表面は白濁しており、電子顕微鏡による観察
の結果、二酸化珪素の粒子で基材表面が覆われていた。(Comparative Example 1) The adhesion of the silicon dioxide film obtained by a tensile test without heat treatment after forming the silicon dioxide film was 200 kgf / cm 2 or less. When a sample not coated with a coating of an organosilicon compound was coated with silicon dioxide using the apparatus shown in FIG. 1, the desired transparent silicon dioxide coating was not obtained, and the surface of the substrate became cloudy. As a result of observation with an electron microscope, the surface of the base material was covered with particles of silicon dioxide.
【００３４】（実施例２）金属基材として、縦１００ｍ
ｍ、横１００ｍｍ、厚さ１ｍｍのソーダライムガラスに
蒸着した厚さ２００ｎｍのＣｒ膜を有するものを用い
た。(Example 2) 100 m in length as a metal substrate
A soda lime glass having a thickness of 200 nm and a thickness of 200 nm was deposited on a soda-lime glass having a thickness of 100 mm, a width of 100 mm and a thickness of 1 mm.
【００３５】このＣｒ膜表面に、テトラエチルシリケー
トを主成分とする加水分解物溶液（商品名ＣＳＧ−Ｌ−
０８０３Ｐ、チッソ（株）製）をエタノール：２ープロ
パノール：ｎ−ブタノール＝３：１：１の割合で含む溶
液を用いて、２％に希釈しこれを用いて、ディッピング
法にて１０ｎｍの厚さになるように塗布し、１５０℃の
温度で加熱乾燥した。On the surface of the Cr film, a hydrolyzate solution containing tetraethyl silicate as a main component (trade name CSG-L-
0803P, manufactured by Chisso Co., Ltd.) was diluted to 2% with a solution containing ethanol: 2-propanol: n-butanol = 3: 1: 1, and was diluted with this solution to a thickness of 10 nm by a dipping method. And was dried by heating at a temperature of 150 ° C.
【００３６】その後、窒素雰囲気中にて３００℃、１ｈ
ｒ加熱処理し、図１の装置を用いて、上記の処理を行っ
た基材上に、二酸化珪素被膜を形成した。Then, in a nitrogen atmosphere at 300 ° C. for 1 hour
r A heat treatment was performed, and a silicon dioxide film was formed on the substrate that had been subjected to the above treatment using the apparatus shown in FIG.
【００３７】基材（９）を内槽中部（７）に垂直に浸漬
し、実施例１と同一条件で基材を８時間保持した。The substrate (9) was vertically dipped in the middle part (7) of the inner tank, and the substrate was held for 8 hours under the same conditions as in Example 1.
【００３８】上記処理で得られた二酸化珪素被膜の膜厚
は、５００ｎｍであった。電子顕微鏡による観察の結
果、二酸化珪素被膜の表面は比較的平坦であり、ピンホ
ール等は観察されなかった。また引っ張り試験法により
得られた該二酸化珪素被膜の付着力は６００ｋｇｆ／ｃ
ｍ2以上であった。The film thickness of the silicon dioxide film obtained by the above treatment was 500 nm. As a result of observation with an electron microscope, the surface of the silicon dioxide film was relatively flat, and pinholes and the like were not observed. The adhesion of the silicon dioxide film obtained by the tensile test method is 600 kgf / c.
It was m 2 or more.
【００３９】[0039]
【発明の効果】本発明により、析出法を用いて、金属体
表面に均一の厚さで、ピンホールのない、強固な付着力
を有する二酸化珪素被膜を形成することができる。その
結果、金属体の耐久性を向上させることが可能である。EFFECTS OF THE INVENTION According to the present invention, a silicon dioxide film having a uniform thickness, pinhole-free and strong adhesion can be formed on the surface of a metal body by using a deposition method. As a result, it is possible to improve the durability of the metal body.
【図１】本発明の実施例に使用した二酸化珪素被膜製造
装置の系統説明図である。FIG. 1 is a system explanatory view of a silicon dioxide film manufacturing apparatus used in an example of the present invention.
１…外槽 ２…内槽 ３…水 ４…温度調節器 ５，１３…攪拌器 ６…内槽前部 ７…内槽中部 ８…内槽後部 ９…基材 １０…循環ポンプ １１…フィルター １２…Ａｌ板 DESCRIPTION OF SYMBOLS 1 ... Outer tank 2 ... Inner tank 3 ... Water 4 ... Temperature controller 5, 13 ... Stirrer 6 ... Inner tank front part 7 ... Inner tank middle part 8 ... Inner tank rear part 9 ... Base material 10 ... Circulation pump 11 ... Filter 12 ... Al plate
Claims (3)
を二酸化珪素の過飽和状態の珪弗化水素酸を含む水溶液
と接触させ金属体へ二酸化珪素被膜を形成方法させた
後、加熱処理することを特徴とする金属体への二酸化珪
素被膜形成方法。1. A method of forming a silicon dioxide film on a metal body by bringing a metal body coated with an organosilicon compound film into contact with an aqueous solution containing hydrofluoric acid in a supersaturated state of silicon dioxide, followed by heat treatment. A method for forming a silicon dioxide film on a metal body, comprising:
を加熱処理した後、二酸化珪素被膜を形成することを特
徴とする請求項１記載の金属体への二酸化珪素被膜形成
方法。2. The method for forming a silicon dioxide film on a metal body according to claim 1, wherein the silicon dioxide film is formed after heat-treating the metal body coated with the organosilicon compound film.
ある請求項１〜２のいずれか１項に記載の金属体への二
酸化珪素被膜形成方法。3. The method for forming a silicon dioxide film on a metal body according to claim 1, wherein the heat treatment temperature is 250 to 450 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16462892A JPH062155A (en) | 1992-06-23 | 1992-06-23 | Formation of silicon dioxide coating film on metal body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16462892A JPH062155A (en) | 1992-06-23 | 1992-06-23 | Formation of silicon dioxide coating film on metal body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH062155A true JPH062155A (en) | 1994-01-11 |
Family
ID=15796820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16462892A Pending JPH062155A (en) | 1992-06-23 | 1992-06-23 | Formation of silicon dioxide coating film on metal body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH062155A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019085459A (en) * | 2017-11-02 | 2019-06-06 | 株式会社放電精密加工研究所 | Surface-coated base material that can be used as a substitute material for alumite material, coating composition for forming a top coat layer on the surface of the substrate |
-
1992
- 1992-06-23 JP JP16462892A patent/JPH062155A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019085459A (en) * | 2017-11-02 | 2019-06-06 | 株式会社放電精密加工研究所 | Surface-coated base material that can be used as a substitute material for alumite material, coating composition for forming a top coat layer on the surface of the substrate |
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