JP2520834B2 - Inorganic film forming method and film forming article - Google Patents
Inorganic film forming method and film forming articleInfo
- Publication number
- JP2520834B2 JP2520834B2 JP4358030A JP35803092A JP2520834B2 JP 2520834 B2 JP2520834 B2 JP 2520834B2 JP 4358030 A JP4358030 A JP 4358030A JP 35803092 A JP35803092 A JP 35803092A JP 2520834 B2 JP2520834 B2 JP 2520834B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- inorganic
- inorganic film
- forming
- titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、無機系被膜形成方法と
その無機系被膜を形成した物品に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an inorganic coating and an article formed with the inorganic coating.
【0002】[0002]
【従来の技術】従来、シラン化合物の加水分解・重縮合
反応物を主成分とする無機系コーテイング組成物、さら
に詳しくは、有機溶剤系シリカゾルの加水分解・重縮合
物とアルキルチタネートとを主成分とする無機系被膜形
成用組成物と、これを耐熱性基材に塗布して乾燥した
後、室温ないし数100℃で熱処理して無機系被膜を形
成することは公知であった。2. Description of the Related Art Conventionally, an inorganic coating composition containing a hydrolysis / polycondensation reaction product of a silane compound as a main component, more specifically, a hydrolysis / polycondensation product of an organic solvent silica sol and an alkyl titanate as main components It has been known that the above-mentioned composition for forming an inorganic coating film, and that the composition is applied to a heat resistant substrate, dried, and then heat-treated at room temperature to several 100 ° C. to form an inorganic coating film.
【0003】[0003]
【発明が解決しようとする課題】しかし、上記したシラ
ン化合物の加水分解・重縮合反応物を主成分とする無機
系コーテイング組成物を用いて得られる被膜は、電気絶
縁性の高いものであり、非絶縁性すなわち導電性または
半導電性(半導体)のものを得ることができなかった。
本発明の目的は、耐熱性基材に、電気的に半導体レベル
の電導性を有する非絶縁性であって、かつ、耐食性、耐
薬品性、耐熱性、耐磨耗性を有する透明な無機系被膜を
形成できるようにすることにある。However, a coating film obtained by using the above-mentioned inorganic coating composition containing the hydrolysis / polycondensation reaction product of a silane compound as a main component has a high electric insulation property. It was not possible to obtain non-insulating, ie conductive or semi-conductive (semiconductor) materials.
An object of the present invention is to provide a heat-resistant substrate with a transparent inorganic system which is electrically non-insulating having electrical conductivity at a semiconductor level, and which has corrosion resistance, chemical resistance, heat resistance, and abrasion resistance. It is to be able to form a film.
【0004】本発明は、特定のシラン化合物の加水分解
・重縮合反応物と特定アルキルチタネートを主成分とす
る無機系コーテイング組成物を耐熱性基材に塗布して乾
燥した後、特定の熱処理条件で処理し得られた無機系被
膜が、従来の技術で得られたものに比べて、より高い導
電性無機系被膜であるとの知見を得たことに基づいてな
された。According to the present invention, a hydrolysis / polycondensation reaction product of a specific silane compound and an inorganic coating composition containing a specific alkyl titanate as a main component are applied to a heat resistant substrate and dried, followed by specific heat treatment conditions. It was made based on the finding that the inorganic coating film obtained by the treatment of 1. is a higher conductive inorganic coating film than that obtained by the conventional technique.
【0005】本発明による無機系被膜は、ステンレス、
鉄、真鍮などの金属や、レンガ、スレート、アルミナ基
板などのセラミックスあるいはガラス、石英などのよう
な耐熱性基材に塗布、乾燥、熱処理によって形成され、
最終熱処理温度が300℃以上では、透明で緻密な被膜
を与えられ、表面保護や帯電防止機能が付与されるので
工業的に極めて有用である。The inorganic coating according to the present invention is made of stainless steel,
Formed by coating, drying and heat treatment on metals such as iron and brass, ceramics such as bricks, slate and alumina substrates, or heat resistant substrates such as glass and quartz.
When the final heat treatment temperature is 300 ° C. or higher, a transparent and dense coating film is provided, and surface protection and antistatic functions are provided, which is industrially extremely useful.
【0006】[0006]
【課題を解決するための手段】本発明の無機系被膜形成
用組成物は、有機溶剤系シリカゾルの加水分解・重縮合
物とアルキルチタネートとを主成分とする無機系被膜形
成用組成物であって、SiO2/Tiの比が重量換算で
100/0.1〜100/3であることを特徴とする。The composition for forming an inorganic film of the present invention is a composition for forming an inorganic film containing a hydrolysis / polycondensation product of an organic solvent-based silica sol and an alkyl titanate as main components. Then, the ratio of SiO 2 / Ti is 100 / 0.1 to 100/3 in terms of weight.
【0007】ここで、シラン化合物としては、数多くの
ものが市販されているが、本願発明に用いられるシラン
化合物は、次式(1)で示されるように、シリコンの4
つの結合がアルコキシであることが好ましい。 Si(OR)4 (1) ここで、RはCnH2n+1で示されるアルキル基で、 n=1〜4、好ましくはn=1〜2である。式(1)に
おいて、ORの一部を−CH3などのアルキル基、ある
いはγ−グリシドキシプロピルやγ−アミノプロピルな
どで置換された構造をもつ各種シラン化合物も多くの市
販品があるが、本発明に使用することができない。Although many silane compounds are commercially available, the silane compound used in the present invention is a silicon silane compound represented by the following formula (1).
It is preferred that one bond is alkoxy. Si (OR) 4 (1) Here, R is an alkyl group represented by C n H 2n + 1 , and n = 1 to 4, preferably n = 1 to 2. In the formula (1), various silane compounds having a structure in which a part of OR is substituted with an alkyl group such as —CH 3 or γ-glycidoxypropyl or γ-aminopropyl are available on the market. , Cannot be used in the present invention.
【0008】このように、本発明に使用することができ
るシラン化合物が特定のものに限定される理由は、本発
明の無機系被膜形成用組成物を耐熱性基材に塗布して乾
燥した後、特定の熱処理条件で熱処理することによって
形成される無機系被膜の透明性を確保するための条件に
なるからである。As described above, the reason why the silane compound which can be used in the present invention is limited to a particular one is that the composition for forming an inorganic film of the present invention is applied to a heat resistant substrate and dried. The reason is that the heat treatment is performed under a specific heat treatment condition to ensure the transparency of the inorganic coating film formed.
【0009】式(1)で示されるシラン化合物でRが、
例えばC8H17のものや、CH3Si(OCH3)3
で示されるシラン化合物を用いた場合、熱処理後の被膜
が茶色ないし褐色かかった色に着色してしまう問題があ
り好ましくない。また、特定シラン化合物の加水分解・
重縮合物に組み合わせて本発明に用いられる特定アルキ
ルチタネートとしては、アルコール可溶性であるアルコ
キシチタンが好ましい。特にテトラブチルチタネートの
単量体あるいは2量体、3量体などのオリゴマーまたは
ポリマーが好ましい。In the silane compound represented by the formula (1), R is
For example, C 8 H 17 or CH 3 Si (OCH 3 ) 3
The use of the silane compound represented by is not preferable because there is a problem that the coating film after heat treatment is colored brown or brownish. In addition, hydrolysis of specific silane compounds
As the specific alkyl titanate used in the present invention in combination with the polycondensate, alcohol-soluble alkoxy titanium is preferable. Particularly preferred are tetrabutyl titanate monomers or oligomers or polymers such as dimers and trimers.
【0010】特定シラン化合物の加水分解・重縮合物と
特定アルキルチタネートの比率は、SiO2/Ti(重
量比)で示して、100/0.1〜100/5、好まし
くは100/0.2〜100/3がよい。この比率より
Tiが少ないと得られた無機系被膜は電気絶縁性が高く
なり好ましくない。またこの比率よりTiが多くなると
無機系コーテイング組成物自身の安定性が悪く、ゲル状
物となり塗布して均一な膜を形成することができない。The ratio of the hydrolysis / polycondensation product of the specific silane compound to the specific alkyl titanate is 100 / 0.1 to 100/5, preferably 100 / 0.2, expressed as SiO 2 / Ti (weight ratio). ~ 100/3 is preferable. When the content of Ti is less than this ratio, the obtained inorganic coating film has high electric insulation and is not preferable. On the other hand, if the content of Ti is larger than this ratio, the stability of the inorganic coating composition itself is poor, and a gel-like material cannot be applied to form a uniform film.
【0011】本発明の無機系被膜形成用組成物の熱処理
条件も本発明の効果を引き出すために重要な要素であ
る。本発明の無機系被膜形成用組成物を浸漬、ロールコ
ート、スプレー、スピンコート、刷毛塗り、印刷など任
意の方法で耐熱性基材に塗布し、室温ないし150℃以
下の温度で加熱乾燥した後、少なくとも最高温度が30
0℃以上で焼成することが必要である。この温度が低い
場合には、被膜は電気絶縁性のままである。The heat treatment conditions of the composition for forming an inorganic coating film of the present invention are also important factors for bringing out the effects of the present invention. After applying the composition for forming an inorganic film of the present invention to a heat resistant substrate by any method such as dipping, roll coating, spraying, spin coating, brush coating, printing, and after heating and drying at room temperature to 150 ° C. or lower , At least the maximum temperature is 30
It is necessary to bake at 0 ° C or higher. When this temperature is low, the coating remains electrically insulating.
【0012】本発明によって電気的に非絶縁性の無機系
被膜が形成される原理は、明らかではないが、本発明の
SiとTiを含む無機系コーテイング組成物が300℃
以上の熱処理によって、SiとTiを含む炭化物が形成
されるためではないかと推定している。The principle of forming an electrically non-insulating inorganic coating film according to the present invention is not clear, but the inorganic coating composition containing Si and Ti according to the present invention is 300 ° C.
It is presumed that the above heat treatment may be due to the formation of carbides containing Si and Ti.
【0013】本発明に用いられる基材としては、上記の
製膜条件に耐えられる耐熱性の基材である必要があり、
たとえば、ステンレス、鉄、真鍮などの金属や、レン
ガ、スレート、アルミナ基板、素焼などのセラミックス
あるいはガラス、石英などがあげられる。The base material used in the present invention must be a heat resistant base material that can withstand the above film forming conditions.
Examples thereof include metals such as stainless steel, iron, and brass, bricks, slate, alumina substrates, ceramics such as unglazed ceramics, glass, and quartz.
【0014】[0014]
【作用】本発明によって、耐熱性基材に、電気的に非絶
縁性であって、かつ、耐食性、耐薬品性、耐熱性、耐磨
耗性の無機系無色透明被膜を形成でき、その被膜は帯電
防止性能をもった各種保護膜などとして極めて有用であ
る。According to the present invention, an inorganic colorless transparent coating which is electrically non-insulating, and has corrosion resistance, chemical resistance, heat resistance and abrasion resistance can be formed on a heat resistant substrate. Is extremely useful as various protective films having antistatic properties.
【0015】[0015]
【実施例】以下、本発明を実施例で説明するが、本発明
が以下の実施例に限定されるものではない。 実施例1 まず、ブチルチタネート(松本製薬工業製、オルガチッ
クスT−25、Tiとして17wt%を含むイソプロピ
ルアルコール溶液)4gをイソプロピルアルコール19
6gに希釈した。これをエチルシリケートの加水分解・
重縮合物として市販されているHAS−10(コルコー
ト(株)製、SiO2として10wt%を含む)800
g中に除々に添加し、室温に24時間放置し無機系コー
テイング組成物を得た。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. Example 1 First, 4 g of butyl titanate (manufactured by Matsumoto Pharmaceutical Co., Organix T-25, an isopropyl alcohol solution containing 17 wt% as Ti) was added to 19 g of isopropyl alcohol.
Diluted to 6 g. This is the hydrolysis of ethyl silicate
HAS-10 commercially available as a polycondensate (manufactured by Colcoat Co., Ltd., containing 10 wt% as SiO 2 ) 800
Gradually added to g, the mixture was allowed to stand at room temperature for 24 hours to obtain an inorganic coating composition.
【0016】これを石英ガラスに浸漬塗布(引上げ速度
5cm/分)した後、80℃で30分乾燥した。これを
420℃に設定したマッフル炉に入れ、1時間熱処理を
行って膜厚約0.5ミクロンの無機系被膜を形成した。
得られた塗膜は、干渉色は認められるものの無色透明被
膜で、表面をスチールウールで擦っても何らのキズが付
かず、また、沸騰水中に240時間放置しても被膜に剥
離、白濁など何らの変化も認められなかった。これの電
気絶縁性を超絶縁計で測定したところ2×108Ωであ
った。This was applied to quartz glass by dipping (pulling speed: 5 cm / min) and then dried at 80 ° C. for 30 minutes. This was placed in a muffle furnace set at 420 ° C. and heat-treated for 1 hour to form an inorganic coating film having a thickness of about 0.5 μm.
The obtained coating film is a colorless and transparent coating film although interference color is recognized, and it is not scratched even if the surface is rubbed with steel wool, and it is peeled off or clouded even if left in boiling water for 240 hours. No change was observed. The electrical insulation of this product was measured by a super-insulation meter and found to be 2 × 10 8 Ω.
【0017】比較例1 実施例1において、HAS−10のみをコーテイング剤
として用い、実施例1と同様な手順で得た無機系被膜
は、無色透明であるが電気絶縁性は1011Ωであっ
た。Comparative Example 1 The inorganic coating obtained by the same procedure as in Example 1 except that HAS-10 was used as the coating agent in Example 1 was colorless and transparent, but had an electrical insulation property of 10 11 Ω. It was
【0018】ブチルチタネート(松本製薬工業製、オル
ガチックスT−25、Tiとして17wt%を含むイソ
プロピルアルコール溶液)5gをイソプロピルアルコー
ル195gに希釈した。これをエチルシリケートの加水
分解・重縮合物として市販されているHAS−10(コ
ルコート(株)製、SiO2として10wt%含む)3
00g中に除々に添加し、室温にて150時間養生して
無機系コーテイング組成物を得た。5 g of butyl titanate (manufactured by Matsumoto Pharmaceutical Co., Ltd., Organix T-25, isopropyl alcohol solution containing 17 wt% as Ti) was diluted with 195 g of isopropyl alcohol. This is commercially available as a hydrolysis / polycondensation product of ethyl silicate, HAS-10 (manufactured by Colcoat Co., Ltd., containing 10 wt% as SiO 2 ) 3
It was gradually added to 00 g and cured at room temperature for 150 hours to obtain an inorganic coating composition.
【0019】これをアルミナ系セラミックス製ピンセッ
トに浸漬塗布した後、室温で15分、80℃で30分乾
燥した。、これを450℃に設定したマッフル炉に入
れ、1時間熱処理を行って膜厚約1ミクロンの無機系被
膜を形成した。得られた塗膜は、無色透明被膜で、10
9Ωの電気絶縁性であり、帯電防止効果のあるピンセッ
トとして、半導体などのチップの取扱いに好適であっ
た。After this was dipped and coated on alumina-based ceramic tweezers, it was dried at room temperature for 15 minutes and at 80 ° C. for 30 minutes. This was placed in a muffle furnace set at 450 ° C. and heat-treated for 1 hour to form an inorganic coating film having a thickness of about 1 micron. The resulting coating film was a colorless transparent film and had a thickness of 10
The tweezers having an electric insulation property of 9 Ω and having an antistatic effect were suitable for handling chips such as semiconductors.
【0020】[0020]
【発明の効果】本発明によって、耐熱性基材に、電気的
に非絶縁性であって、かつ、耐食性、耐薬品性、耐熱
性、耐磨耗性の無機系透明被膜を形成できる。それは、
ステンレス、鉄、真鍮などの金属や、レンガ、スレー
ト、アルミナ基板、素焼などのセラミックスあるいはガ
ラス、石英などのような耐熱性基材に塗布乾燥後、30
0℃以上の最終熱処理によって容易に形成され、それ
は、帯電防止効果のある耐火物の保護膜として極めて有
用である。Industrial Applicability According to the present invention, an inorganic transparent coating film which is electrically non-insulating, corrosion resistant, chemical resistant, heat resistant and abrasion resistant can be formed on a heat resistant substrate. that is,
After coating and drying on metals such as stainless steel, iron, and brass, bricks, slate, alumina substrates, ceramics such as unglazed, or heat-resistant substrates such as glass and quartz, 30
It is easily formed by a final heat treatment at 0 ° C or higher, and it is extremely useful as a protective film for a refractory material having an antistatic effect.
Claims (4)
し、nは1ないし4である)を有するシラン化合物を加
水分解・重縮合して得られる有機溶剤系シリカゾルとア
ルキルチタネートとを主成分とし、SiO2/Tiの比
が重量換算で100/0.1〜100/3である無機系
被膜形成用組成物を、耐熱性基材に塗布して乾燥した
後、300℃以上で熱処理することを特徴とする無機系
被膜形成方法。1. A silane compound having the general formula Si (OR) 4 (1) (wherein R represents an alkyl group represented by C n H 2n + 1 and n is 1 to 4) is hydrolyzed and deuterated. A heat-resistant inorganic film-forming composition comprising an organic solvent-based silica sol obtained by condensation and an alkyl titanate as main components and having a SiO 2 / Ti ratio of 100 / 0.1 to 100/3 in terms of weight. A method for forming an inorganic coating, which comprises heat-treating at 300 ° C. or higher after being applied to a substrate, dried.
し、nは1ないし4である)を有するシラン化合物を加
水分解・重縮合して得られる有機溶剤系シリカゾルとア
ルキルチタネートとを主成分とし、そのアルキルチタネ
ートがアルコール可溶性のテトラブチルチタネートの単
量体あるいは2量体、3量体などのオリゴマーまたはポ
リマーであり、SiO2/Tiの比が重量換算で100
/0.1〜100/3である無機系被膜形成用組成物
を、耐熱性基材に塗布して乾燥した後、300℃以上で
熱処理することを特徴とする無機系被膜形成方法。2. A silane compound having the general formula Si (OR) 4 (1) (wherein R represents an alkyl group represented by C n H 2n + 1 and n is 1 to 4) is hydrolyzed and deuterated. An organic solvent-based silica sol obtained by condensation and an alkyl titanate as main components, the alkyl titanate being an alcohol-soluble tetrabutyl titanate monomer or dimer, trimer or other oligomer or polymer, SiO 2 / Ti ratio is 100 in terms of weight
/0.1 to 100/3 of the composition for forming an inorganic film, which is applied to a heat resistant substrate, dried, and then heat-treated at 300 ° C or higher.
し、nは1ないし4である)を有するシラン化合物を加
水分解・重縮合して得られる有機溶剤系シリカゾルとア
ルキルチタネートとを主成分とし、SiO2/Tiの比
が重量換算で100/0.1〜100/3である無機系
被膜形成用組成物を、耐熱性基材に塗布して乾燥した
後、300℃以上で熱処理することによって形成された
無機系被膜を有することを特徴とする無機系被膜形成物
品。3. A silane compound having the general formula Si (OR) 4 (1) (wherein R represents an alkyl group represented by C n H 2n + 1 and n is 1 to 4) is hydrolyzed and deuterated. A heat-resistant inorganic film-forming composition comprising an organic solvent-based silica sol obtained by condensation and an alkyl titanate as main components and having a SiO 2 / Ti ratio of 100 / 0.1 to 100/3 in terms of weight. An inorganic film-forming article having an inorganic film formed by applying a heat treatment at 300 ° C. or higher after being applied to a substrate, dried.
し、nは1ないし4である)を有するシラン化合物を加
水分解・重縮合して得られる有機溶剤系シリカゾルとア
ルキルチタネートとを主成分とし、そのアルキルチタネ
ートがアルコール可溶性のテトラブチルチタネートの単
量体あるいは2量体、3量体などのオリゴマーまたはポ
リマーであり、SiO2/Tiの比が重量換算で100
/0.1〜100/3である無機系被膜形成用組成物
を、耐熱性基材に塗布して乾燥した後、300℃以上で
熱処理することによって形成された無機系被膜を有する
ことを特徴とする無機系被膜形成物品。4. A silane compound having the general formula Si (OR) 4 (1) (wherein R represents an alkyl group represented by C n H 2n + 1 and n is 1 to 4) is hydrolyzed and deuterated. An organic solvent-based silica sol obtained by condensation and an alkyl titanate as main components, the alkyl titanate being an alcohol-soluble tetrabutyl titanate monomer or dimer, trimer or other oligomer or polymer, SiO 2 / Ti ratio is 100 in terms of weight
/0.1 to 100/3 of the inorganic coating forming composition is applied to a heat resistant substrate, dried, and then heat treated at 300 ° C. or higher to have an inorganic coating formed. And an inorganic film-forming article.
Priority Applications (1)
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JP4358030A JP2520834B2 (en) | 1992-12-25 | 1992-12-25 | Inorganic film forming method and film forming article |
Applications Claiming Priority (1)
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---|---|---|---|
JP4358030A JP2520834B2 (en) | 1992-12-25 | 1992-12-25 | Inorganic film forming method and film forming article |
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Publication Number | Publication Date |
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JPH06192620A JPH06192620A (en) | 1994-07-12 |
JP2520834B2 true JP2520834B2 (en) | 1996-07-31 |
Family
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5477635A (en) * | 1977-12-01 | 1979-06-21 | Kansai Paint Co Ltd | Surface treating composition for metal |
US4725501A (en) * | 1985-05-28 | 1988-02-16 | Ppg Industries, Inc. | Primer for adherence to plastic substrates |
-
1992
- 1992-12-25 JP JP4358030A patent/JP2520834B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH06192620A (en) | 1994-07-12 |
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