JPH06306329A - Composition and method for coating - Google Patents

Composition and method for coating

Info

Publication number
JPH06306329A
JPH06306329A JP21426893A JP21426893A JPH06306329A JP H06306329 A JPH06306329 A JP H06306329A JP 21426893 A JP21426893 A JP 21426893A JP 21426893 A JP21426893 A JP 21426893A JP H06306329 A JPH06306329 A JP H06306329A
Authority
JP
Japan
Prior art keywords
polysilazane
group
coating
acetylacetonato complex
silicon
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
Application number
JP21426893A
Other languages
Japanese (ja)
Other versions
JP3307471B2 (en
Inventor
Hideki Matsuo
英樹 松尾
Haruo Hashimoto
晴夫 橋本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tonen General Sekiyu KK
Original Assignee
Tonen Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tonen Corp filed Critical Tonen Corp
Priority to JP21426893A priority Critical patent/JP3307471B2/en
Publication of JPH06306329A publication Critical patent/JPH06306329A/en
Application granted granted Critical
Publication of JP3307471B2 publication Critical patent/JP3307471B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials

Abstract

PURPOSE:To obtain a coating compsn. which gives, by low-temp. baking, a dense coating film excellent in resistances to heat, abrasion, and corrosion and in adhesion to a substrate by incorporating a specific acetylacetonate complex adduct of polysilazane into the compsn. CONSTITUTION:A coating compsn. contains an acetylacetonate complex adduct of polysilazane which has a number-average mol.wt. of about 200-500,000 and is obtd. by reacting polysilazane having a number-average mol.wt. of 100-50,000 and a backbone consisting of structural units of the formula wherein R<1>, R<2>, and R<3> are each H, (cyclo)alkyl, alkenyl, aryl, a group other than the foregoing groups and attached to Si through C, alkylsilyl, alkylamino, or alkoxy provided at least one of them is H with an acetylacetonate complex of the formula: (CH3COCH2COCH3)nM wherin M is an n-valent metal in a wt. ratio of the complex to polysilazane of 0.000001-2.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、変性ポリシラザンを必
須成分とし、耐熱性、耐摩耗性、耐食性に優れた被覆膜
を形成できるコーティング用組成物、及びこれを用いた
コーティング方法に関する。TECHNICAL FIELD The present invention relates to a coating composition containing a modified polysilazane as an essential component and capable of forming a coating film excellent in heat resistance, abrasion resistance and corrosion resistance, and a coating method using the same.

【０００２】[0002]

【従来の技術】高度の耐熱、耐摩耗、耐食性を得るため
には、有機系塗料では不十分であり、セラミックス系コ
ーティングが用いられる。従来、セラミックス系コーテ
ィングの形成方法としては、ＰＶＤ（スパッタ法等）、
ＣＶＤ、ゾル−ゲル法、ポリチタノカルボシラン系塗
料、ポリ（ジシル）シラザン系塗料、ポリシラザン系塗
料、ポリメタロシラザン系塗料などが知られている。2. Description of the Related Art Organic paints are not sufficient for obtaining high heat resistance, wear resistance and corrosion resistance, and ceramic coatings are used. Conventionally, as a method of forming a ceramic coating, PVD (sputtering method, etc.),
Known are CVD, sol-gel method, polytitanocarbosilane-based paint, poly (dicyl) silazane-based paint, polysilazane-based paint, polymetallosilazane-based paint, and the like.

【０００３】[0003]

【発明が解決しようとする課題】上記の如きセラミック
ス系コーティング法が知られているが、いずれも問題が
ある。すなわち、ＰＶＤ，ＣＶＤ法では装置が高価であ
る。ゾル−ゲル法では、必要焼成温度が５００℃以上と
高い。ポリチタノカルボシラン系塗料では低温焼成（４
００℃以下）における表面強度が不十分である。ポリ
（ジシル）シラザン系重合体を用いたものは、施工に難
があり、クラックが発生する。ポリシラザン、ポリメタ
ロシラザンコーティングでは、２００〜５００℃で焼成
できるが、３００℃未満の焼成では膜質が必ずしも良好
でない。The above-mentioned ceramics-based coating methods are known, but all have problems. That is, the PVD and CVD methods are expensive. In the sol-gel method, the required firing temperature is as high as 500 ° C or higher. Low-temperature baking (4
The surface strength at 00 ° C. or lower) is insufficient. Those using a poly (disyl) silazane-based polymer are difficult to apply and cracks occur. Polysilazane and polymetallosilazane coatings can be fired at 200 to 500 ° C, but firing at less than 300 ° C does not necessarily give good film quality.

【０００４】そこで、本発明は、上記の如き従来技術に
おける問題を解決し、低温（５０℃〜３５０℃）焼成に
より、または焼成せずに５０℃未満の温度で保持するこ
とにより、耐熱性、耐摩耗性、耐食性に優れ、クラック
のない緻密な塗膜を与えるコーティング用組成物とその
施工法を提供すること、特に、低温焼成という特長によ
り、従来不可能であった、電子部品、プラスチック等へ
のコーティングを可能とすることを目的とする。Therefore, the present invention solves the problems in the prior art as described above, heat resistance by low temperature (50 ° C. to 350 ° C.) firing, or by holding at a temperature of less than 50 ° C. without firing, To provide a coating composition having excellent wear resistance and corrosion resistance, which gives a dense coating film without cracks, and a construction method therefor, in particular, electronic components, plastics, etc. The purpose is to enable coating on.

【０００５】[0005]

【課題を解決するための手段】本発明者らは、上記問題
点を解決するために鋭意検討した結果、ポリシラザンに
金属を含むアセチルアセトナト錯体を付加させることに
より、該付加物の塗膜を空気中で焼成する際の硬化反応
が促進され、従来よりも低い焼成温度で良好な被覆が形
成されることを見出した。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a coating film of the adduct is formed by adding an acetylacetonato complex containing a metal to polysilazane. It has been found that the curing reaction is promoted when firing in air, and a good coating is formed at a firing temperature lower than before.

【０００６】こうして、本発明によれば、主として一般
式（Ｉ）：Thus, according to the present invention, the general formula (I):

【０００７】[0007]

【化２】 [Chemical 2]

【０００８】（但し、Ｒ1 ，Ｒ2 ，Ｒ3 はそれぞれ独立
に水素原子、アルキル基、アルケニル基、シクロアルキ
ル基、アリール基、またはこれらの基以外でケイ素に直
結する基が炭素である基、アルキルシリル基、アルキル
アミノ基、アルコキシ基を表わす。ただし、Ｒ1 ，
Ｒ2 ，Ｒ3 のうち少なくとも１つは水素原子である。）
で表わされる単位からなる主骨格を有する数平均分子量
が１００〜５万のポリシラザンと一般式（ＣＨ3 ＣＯＣ
ＨＣＯＣＨ3 ）n Ｍ〔式中、Ｍはｎ価の金属を表わす〕
で示されるアセチルアセトナト錯体を反応させて得られ
る、アセチルアセトナト錯体／ポリシラザン重量比が
０．０００００１〜２の範囲内かつ数平均分子量が約２
００〜５０万のアセチルアセトナト錯体付加ポリシラザ
ンを少なくとも含有するコーティング用組成物が提供さ
れる。(However, R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups in which the group directly bonded to silicon is carbon. , An alkylsilyl group, an alkylamino group, and an alkoxy group, provided that R 1 ,
At least one of R 2 and R 3 is a hydrogen atom. )
A polysilazane having a main skeleton composed of a unit represented by the following formula and a number average molecular weight of 100 to 50,000, and a general formula (CH 3 COC
HCOCH 3 ) n M [wherein M represents an n-valent metal]
The acetylacetonato complex / polysilazane weight ratio, which is obtained by reacting the acetylacetonato complex represented by, is in the range of 0.000001 to 2 and the number average molecular weight is about 2.
Provided is a coating composition containing at least 100,000 to 500,000 acetylacetonato complex-added polysilazane.

【０００９】本発明で用いるアセチルアセトナト錯体付
加ポリシラザンの数平均分子量は２００〜５０万、好ま
しくは５００〜１０，０００の範囲内である。本発明に
用いるアセチルアセトナト錯体付加ポリシラザンを製造
する方法は、ポリシラザンとアセチルアセトナト錯体を
無溶媒または溶媒中で、かつ反応に対して不活性な雰囲
気下で反応させることからなる。The acetylacetonato complex-added polysilazane used in the present invention has a number average molecular weight of 200 to 500,000, preferably 500 to 10,000. The method for producing the acetylacetonato complex-added polysilazane used in the present invention comprises reacting the polysilazane and the acetylacetonato complex with or without a solvent and in an atmosphere inert to the reaction.

【００１０】用いるポリシラザンは、分子内に少なくと
もＳｉ−Ｈ結合、あるいはＮ−Ｈ結合を有するポリシラ
ザンであればよく、ポリシラザン単独は勿論のこと、ポ
リシラザンと他のポリマーとの共重合体やポリシラザン
と他の化合物との混合物でも利用できる。用いるポリシ
ラザンには、鎖状、環状、あるいは架橋構造を有するも
の、あるいは分子内にこれら複数の構造を同時に有する
ものがあり、これら単独でもあるいは混合物でも利用で
きる。The polysilazane to be used may be any polysilazane having at least a Si--H bond or an N--H bond in the molecule. Not only polysilazane alone, but also a copolymer of polysilazane and another polymer or polysilazane and other It can also be used as a mixture with the compound of. The polysilazanes to be used include those having a chain structure, a cyclic structure, or a crosslinked structure, or those having a plurality of these structures simultaneously in the molecule, and these can be used alone or in a mixture.

【００１１】用いるポリシラザンの代表例としては下記
のようなものがあるが、これらに限定されるものではな
い。一般式（Ｉ）でＲ1 ，Ｒ2 、及びＲ3 に水素原子を
有するものは、ペルヒドロポリシラザンであり、その製
造法は例えば特開昭６０−１４５９０３号公報、D.Seyf
erthらCommunication of Am.Cer.Soc., C-１３,January
１９８３．に報告されている。これらの方法で得られ
るものは、種々の構造を有するポリマーの混合物である
が、基本的には分子内に鎖状部分と環状部分を含み、Typical examples of the polysilazane to be used are as follows, but are not limited thereto. The one having hydrogen atoms in R 1 , R 2 and R 3 in the general formula (I) is perhydropolysilazane, and its production method is described in, for example, JP-A-60-145903 and D. Seyf.
erth et al Communication of Am.Cer.Soc., C-13, January
1983. Has been reported to. What is obtained by these methods is a mixture of polymers having various structures, but basically contains a chain portion and a cyclic portion in the molecule,

【００１２】[0012]

【化３】 [Chemical 3]

【００１３】の化学的で表わすことができる。ペルヒド
ロポリシラザンの構造の一例を示すと下記の如くであ
る。It can be represented by the chemical formula: An example of the structure of perhydropolysilazane is as follows.

【００１４】[0014]

【化４】 [Chemical 4]

【００１５】一般式（Ｉ）でＲ1 及びＲ2 に水素原子、
Ｒ3 にメチル基を有するポリシラザンの製造方法は、D.
SeyferthらPolym.Prepr.,Am.Chem.Soc.,Div.Polym.Che
m,.２５，１０（１９８４） に報告されている。この
方法により得られるポリシラザンは、繰り返し単位が−
（ＳｉＨ2 ＮＣＨ3 ）−の鎖状ポリマーと環状ポリマー
であり、いずれも架橋構造をもたない。In the general formula (I), R 1 and R 2 are hydrogen atoms,
A method for producing polysilazane having a methyl group in R 3 is described in D.
Seyferth et al. Polym.Prepr., Am.Chem.Soc., Div.Polym.Che
m ,. 25 , 10 (1984). The polysilazane obtained by this method has a repeating unit of −
(SiH 2 NCH 3) - is a chain polymer and a cyclic polymer, either no cross-linked structure.

【００１６】一般式（Ｉ）でＲ1 及びＲ3 に水素原子、
Ｒ2 に有機基を有するポリオルガノ（ヒドロ）シラザン
の製造法は、D.SeyferthらPolym.Prepr.,Am.Chem.Soc.,
Div.Polym.Chem.,２５，１０（１９８４）、特開昭６１
−８９２３０号公報に報告されている。これらの方法に
より得られるポリシラザンには、−（Ｒ2 ＳｉＨＮＨ）
−を繰り返し単位として、主として重合度が３〜５の環
状構造を有するものや（Ｒ3 ＳｉＨＮＨ）X 〔（Ｒ2 Ｓ
ｉＨ）1.5 Ｎ〕1-X （０．４＜ｘ＜１）の化学式で示せ
る分子内に鎖状構造と環状構造を同時に有するものがあ
る。In the general formula (I), R 1 and R 3 are hydrogen atoms,
A method for producing a polyorgano (hydro) silazane having an organic group in R 2 is described in D. Seyferth et al., Polym.Prepr., Am.Chem.Soc.,
Div. Polym. Chem., 25 , 10 (1984), JP-A-61.
-89230. Polysilazanes obtained by these methods include-(R 2 SiHNH)
-Having a cyclic structure having a degree of polymerization of 3 to 5 as a repeating unit, or (R 3 SiHNH) x [(R 2 S
iH) 1.5 N] 1−X (0.4 <x <1) has a chain structure and a cyclic structure at the same time in the molecule.

【００１７】一般式（Ｉ）でＲ1 に水素原子、Ｒ2 及び
Ｒ3 に有機基を有するポリシラザン、またＲ1 及びＲ2
に有機基、Ｒ3 に水素原子を有するものは−（Ｒ1 Ｒ2
ＳｉＮＲ3 ）−を繰り返し単位として、主に重合度が３
〜５の環状構造を有している。次に用いるポリシラザン
の内、一般式（Ｉ）以外のものの代表例をあげる。In the general formula (I), polysilazane having a hydrogen atom at R 1 and an organic group at R 2 and R 3 , and R 1 and R 2
An organic group for R 3 and a hydrogen atom for R 3 is — (R 1 R 2
SiNR 3 ) -is a repeating unit and the degree of polymerization is mainly 3
It has a cyclic structure of ~ 5. Among the polysilazanes used next, typical examples other than those of the general formula (I) will be given.

【００１８】ポリオルガノ（ヒドロ）シラザンの中に
は、D.SeyferthらCommunication of Am.Cer.Soc., C-１
３２, July １９８４．が報告されている様な分子内に
架橋構造を有するものもある。一例を示すと下記の如く
である。Among the polyorgano (hydro) silazanes are D. Seyferth et al. Communication of Am. Cer. Soc., C-1.
32, July 1984. There are also those having a cross-linked structure in the molecule as reported in. An example is as follows.

【００１９】[0019]

【化５】 [Chemical 5]

【００２０】また、特開昭４９−６９７１７に報告され
ている様なＲ1 ＳｉＸ3(Ｘ：ハロゲン）のアンモニア分
解によって得られる架橋構造を有するポリシラザン（Ｒ
1 Ｓｉ（ＮＨ）X ）、あるいはＲ1 ＳｉＸ3 及びＲ2 2Ｓ
ｉＸ2 の共アンモニア分解によって得られる下記の構造
を有するポリシラザンも出発材料として用いることがで
きる。Further, polysilazane (R having a crosslinked structure obtained by ammonia decomposition of R 1 SiX 3 (X: halogen) as reported in JP-A-49-69717 (R
1 Si (NH) x ), or R 1 SiX 3 and R 2 2 S
Polysilazane having the following structure obtained by co-ammonia decomposition of iX 2 can also be used as a starting material.

【００２１】[0021]

【化６】 [Chemical 6]

【００２２】用いるポリシラザンは、上記の如く一般式
（Ｉ）で表わされる単位からなる主骨格を有するが、一
般式（Ｉ）で表わされる単位は、上記にも明らかな如く
環状化することがあり、その場合にはその環状部分が末
端基となり、このような環状化がされない場合には、主
骨格の末端はＲ1 ，Ｒ2 ，Ｒ3 と同様の基又は水素であ
ることができる。The polysilazane to be used has a main skeleton consisting of the unit represented by the general formula (I) as described above, but the unit represented by the general formula (I) may be cyclized as is apparent from the above. In that case, the cyclic portion serves as a terminal group, and when such cyclization is not carried out, the terminal of the main skeleton can be a group similar to R 1 , R 2 and R 3 or hydrogen.

【００２３】用いるポリシラザンの分子量に特に制約は
なく、入手可能なものを用いることができるが、アセチ
ルアセトナト錯体との反応性の点で、式（Ｉ）における
Ｒ1，Ｒ2 、及びＲ3 は立体障害の小さい基が好まし
い。即ち、Ｒ1 ，Ｒ2 及びＲ3としては水素原子及びＣ
1 〜Ｃ5 のアルキル基が好ましく、水素原子及びＣ1 〜
Ｃ2 のアルキル基がさらに好ましい。用いるアセチルア
セトナト錯体は、アセチルアセトン（２，４−ペンタジ
オン）から酸解離により生じた陰イオンａｃａｃ- が金
属原子に配位した錯体であり、一般的には式（ＣＨ3 Ｃ
ＯＣＨＣＯＣＨ3 ）n Ｍ 〔式中、Ｍはイオン価ｎの金
属を表す。〕で表わされる。好適な金属Ｍとしては、例
えば、ニッケル、白金、パラジウム、アルミニウム、ロ
ジウムなどを挙げることができる。例えば金属Ｍとして
ニッケルを用いた場合次式の如き構造を有する。The molecular weight of the polysilazane to be used is not particularly limited and any available polysilazane can be used, but R 1 , R 2 and R 3 in the formula (I) can be used in view of reactivity with the acetylacetonato complex. Is preferably a group having a small steric hindrance. That is, R 1 , R 2 and R 3 are hydrogen atoms and C
1 to C 5 alkyl groups are preferable, and a hydrogen atom and C 1 to
More preferred is a C 2 alkyl group. Acetylacetonato complex used is acetylacetone (2,4-pentanedione) Yin caused by acid dissociation from ion acac - are complex coordinated to a metal atom, typically formula (CH 3 C
OCHCOCH 3) in n M [wherein, M represents a metal ion valence n. ] Is represented. Examples of suitable metal M include nickel, platinum, palladium, aluminum, rhodium, and the like. For example, when nickel is used as the metal M, it has the following structure.

【００２４】[0024]

【化７】 [Chemical 7]

【００２５】ポリシラザンとアセチルアセトナト錯体と
の混合比は、アセチルアセトナト錯体／ポリシラザン重
量比が０．０００００１から２になるように、好ましく
は０．００１から１になるように、さらに好ましくは
０．０１から０．５になる様に加える。アセチルアセト
ナト錯体の添加量をこれより増やすとポリシラザンの分
子量が上がり過ぎてゲル化し、また、少ないと十分な効
果が得られない。The mixing ratio of polysilazane and acetylacetonato complex is such that the acetylacetonato complex / polysilazane weight ratio is 0.000001 to 2, preferably 0.001 to 1, and more preferably 0. Add from 0.01 to 0.5. If the amount of the acetylacetonato complex added is increased beyond this range, the molecular weight of the polysilazane increases too much to cause gelation, and if it is too low, a sufficient effect cannot be obtained.

【００２６】反応は、無溶媒で行なうこともできるが、
有機溶媒を使用する時に比べて、反応制御が難しく、ゲ
ル状物質が生成する場合もあるので、一般に有機溶媒を
用いた方が良い。溶媒としては、芳香族炭化水素、脂肪
族炭化水素、脂環式炭化水素の炭化水素溶媒、ハロゲン
化炭化水素、脂肪族エーテル、脂環式エーテル類、芳香
族アミン類が使用できる。好ましい溶媒としては、例え
ばベンゼン、トルエン、キシレン、塩化メチレン、クロ
ロホルム、ｎ−ヘキサン、エチルエーテル、テトラヒド
ロフラン、ピリジン、メチルピリジン等があり、特に好
ましい溶媒としてはキシレン、ピリジン、メチルピリジ
ン等があげられる。また反応に対して不活性な雰囲気、
例えば、窒素、アルゴン等の雰囲気中において反応を行
なうことが好ましいが、空気中のような酸化性雰囲気中
でも可能である。Although the reaction can be carried out without solvent,
Compared to the case of using an organic solvent, it is generally preferable to use an organic solvent because it is difficult to control the reaction and a gelled substance may be generated. As the solvent, aromatic hydrocarbons, aliphatic hydrocarbons, hydrocarbon solvents of alicyclic hydrocarbons, halogenated hydrocarbons, aliphatic ethers, alicyclic ethers, and aromatic amines can be used. Preferred solvents include, for example, benzene, toluene, xylene, methylene chloride, chloroform, n-hexane, ethyl ether, tetrahydrofuran, pyridine, methylpyridine and the like, and particularly preferred solvents include xylene, pyridine, methylpyridine and the like. Also, an atmosphere inert to the reaction,
For example, the reaction is preferably carried out in an atmosphere of nitrogen, argon or the like, but it is also possible in an oxidizing atmosphere such as air.

【００２７】反応温度は広い範囲にわたって変更するこ
とができ、例えば有機溶媒を使用する場合には、その有
機溶媒の沸点以下の温度に加熱してもよいが、数平均分
子量の高い固体を得るには、引続き有機溶媒の沸点以上
に加熱して有機溶媒を留去させて反応を行なうこともで
きる。反応温度は、一般に１５０℃以下にするのが好ま
しい。The reaction temperature can be varied over a wide range. For example, when an organic solvent is used, it may be heated to a temperature below the boiling point of the organic solvent, but in order to obtain a solid having a high number average molecular weight. Alternatively, the reaction can be carried out by subsequently heating the organic solvent to a boiling point or higher to distill off the organic solvent. Generally, the reaction temperature is preferably 150 ° C. or lower.

【００２８】反応時間は特に重要ではないが、通常、１
〜５０時間程度である。反応は一般に常圧付近で行なう
のが好ましい。本発明において、前記アセチルアセトナ
ト錯体付加ポリシラザンを用いてコーティング用組成物
を調製するには、通常アセチルアセトナト錯体付加ポリ
シラザンを溶剤に溶解させればよい。The reaction time is not particularly important, but is usually 1
It is about 50 hours. It is generally preferable to carry out the reaction at around normal pressure. In the present invention, in order to prepare a coating composition using the acetylacetonato complex-added polysilazane, usually, the acetylacetonato complex-added polysilazane may be dissolved in a solvent.

【００２９】溶剤としては、脂肪族炭化水素、脂環式炭
化水素、芳香族炭化水素の炭化水素溶媒、ハロゲン化メ
タン、ハロゲン化エタン、ハロゲン化ベンゼン等のハロ
ゲン化炭化水素、脂肪族エーテル、脂環式エーテル等の
エーテル類が使用できる。好ましい溶媒は、塩化メチレ
ン、クロロホルム、四塩化炭素、ブロモホルム、塩化エ
チレン、塩化エチリデン、トリクロロエタン、テトラク
ロロエタン等のハロゲン化炭化水素、エチルエーテル、
イソプロピルエーテル、エチルブチルエーテル、ブチル
エーテル、１，２−ジオキシエタン、ジオキサン、ジメ
チルジオキサン、テトラヒドロフラン、テトラヒドロピ
ラン等のエーテル類、ペンタンヘキサン、イソヘキサ
ン、メチルペンタン、ヘプタン、イソヘプタン、オクタ
ン、イソオクタン、シクロペンタン、メチルシクロペン
タン、シクロヘキサン、メチルシクロヘキサン、ベンゼ
ン、トルエン、キシレン、エチルベンゼン等の炭化水素
等である。Examples of the solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, hydrocarbon solvents of aromatic hydrocarbons, halogenated hydrocarbons such as halogenated methane, halogenated ethane and halogenated benzene, aliphatic ethers, and fats. Ethers such as cyclic ethers can be used. Preferred solvents are halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane and tetrachloroethane, ethyl ether,
Ethers such as isopropyl ether, ethylbutyl ether, butyl ether, 1,2-dioxyethane, dioxane, dimethyldioxane, tetrahydrofuran, tetrahydropyran, pentanehexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane And hydrocarbons such as cyclohexane, methylcyclohexane, benzene, toluene, xylene and ethylbenzene.

【００３０】これらの溶剤を使用する場合、前記アセチ
ルアセトナト錯体付加ポリシラザンの溶解度や溶剤の蒸
発速度を調節するために、２種類以上の溶剤を混合して
もよい。溶剤の使用量（割合）は採用するコーティング
方法により作業性がよくなるように選択され、またアセ
チルアセトナト錯体付加ポリシラザンの平均分子量、分
子量分布、その構造によって異なるので、コーティング
用組成物中溶剤は９０重量％程度まで混合することがで
き、好ましくは１０〜５０重量％の範囲で混合すること
ができる。When these solvents are used, two or more kinds of solvents may be mixed in order to adjust the solubility of the acetylacetonato complex-added polysilazane and the evaporation rate of the solvent. The amount (ratio) of the solvent used is selected so as to improve the workability depending on the coating method adopted, and it depends on the average molecular weight, the molecular weight distribution, and the structure of the acetylacetonato complex-added polysilazane. It is possible to mix up to about 10% by weight, preferably 10 to 50% by weight.

【００３１】また溶剤濃度はアセチルアセトナト錯体付
加ポリシラザンの平均分子量、分子量分布、その構造に
よって異なるが、通常０〜９０重量％の範囲で良い結果
が得られる。また、本発明においては、必要に応じて適
当な充填剤を加えてもよい。充填剤の例としてはシリ
カ、アルミナ、ジルコニア、マイカを始めとする酸化物
系無機物あるいは炭化珪素、窒化珪素等の非酸化物系無
機物の微粉等が挙げられる。また用途によってはアルミ
ニウム、亜鉛、銅等の金属粉末の添加も可能である。さ
らに充填剤の例を詳しく述べれば、ケイ砂、石英、ノバ
キュライト、ケイ藻土などのシリカ系：合成無定形シリ
カ：カオリナイト、雲母、滑石、ウオラストナイト、ア
スベスト、ケイ酸カルシウム、ケイ酸アルミニウム等の
ケイ酸塩：ガラス粉末、ガラス球、中空ガラス球、ガラ
スフレーク、泡ガラス球等のガラス体：窒化ホウ素、炭
化ホウ素、窒化アルミニウム、炭化アルミニウム、窒化
ケイ素、炭化ケイ素、ホウ化チタン、窒化チタン、炭化
チタン等の非酸化物系無機物：炭酸カルシウム：酸化亜
鉛、アルミナ、マグネシア、酸化チタン、酸化ベリリウ
ム等の金属酸化物：硫酸バリウム、二硫化モリブデン、
二硫化タングステン、弗化炭素その他無機物：アルミニ
ウム、ブロンズ、鉛、ステンレススチール、亜鉛等の金
属粉末：カーボンブラック、コークス、黒鉛、熱分解炭
素、中空カーボン球等のカーボン体等があげられる。The solvent concentration varies depending on the average molecular weight, the molecular weight distribution and the structure of the acetylacetonato complex-added polysilazane, but good results are usually obtained in the range of 0 to 90% by weight. Further, in the present invention, a suitable filler may be added if necessary. Examples of the filler include fine powders of oxide-based inorganic materials such as silica, alumina, zirconia, and mica, or non-oxide-based inorganic materials such as silicon carbide and silicon nitride. Depending on the application, it is also possible to add metal powders such as aluminum, zinc and copper. More specifically, examples of fillers include silica-based materials such as silica sand, quartz, novaculite, and diatomaceous earth: synthetic amorphous silica: kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, aluminum silicate. Silicates such as: glass powder, glass spheres, hollow glass spheres, glass flakes, glass spheres such as foam glass spheres: boron nitride, boron carbide, aluminum nitride, aluminum carbide, silicon nitride, silicon carbide, titanium boride, nitride Non-oxide inorganic substances such as titanium and titanium carbide: calcium carbonate: zinc oxide, alumina, magnesia, titanium oxide, beryllium oxide and other metal oxides: barium sulfate, molybdenum disulfide,
Tungsten disulfide, carbon fluoride, and other inorganic substances: metal powders such as aluminum, bronze, lead, stainless steel, zinc: carbon black, coke, graphite, pyrolytic carbon, carbon bodies such as hollow carbon spheres, and the like.

【００３２】これら充填剤は、針状（ウィスカーを含
む。）、粒状、鱗片状等種々の形状のものを単独又は２
種以上混合して用いることができる。又、これら充填剤
の粒子の大きさは１回に塗布可能な膜厚よりも小さいこ
とが望ましい。また充填剤の添加量はアセチルアセトナ
ト錯体付加ポリシラザン１重量部に対し、０．０５重量
部〜１０重量部の範囲であり、特に好ましい添加量は
０．２重量部〜３重量部の範囲である。又、充填剤の表
面をカップリング剤処理、蒸着、メッキ等で表面処理し
て使用してもよい。These fillers have various shapes such as needle-like shape (including whiskers), granular shape, and scale-like shape, either alone or in 2 pieces.
A mixture of two or more species can be used. Further, it is desirable that the particle size of these fillers is smaller than the film thickness that can be applied at one time. The amount of the filler added is in the range of 0.05 parts by weight to 10 parts by weight with respect to 1 part by weight of acetylacetonato complex-added polysilazane, and the particularly preferable amount of addition is in the range of 0.2 parts by weight to 3 parts by weight. is there. Further, the surface of the filler may be surface-treated by a coupling agent treatment, vapor deposition, plating or the like for use.

【００３３】コーティング用組成物には、必要に応じて
各種顔料、レベリング剤、消泡剤、帯電防止剤、紫外線
吸収剤、pH調整剤、分散剤、表面改質剤、可塑剤、乾燥
促進剤、流れ止め剤を加えてもよい。本発明によれば、
同様にして、上記の如きコーティング用組成物を用いた
コーティング方法が提供され、このコーティング方法は
上記のコーティング用組成物を基盤に１回又は２回以上
繰り返し塗布した後、焼成し珪素−窒素−酸素−金属元
素系又は珪素−窒素−酸素−炭素−金属元素系セラミッ
クスから成る被覆膜を形成させることを特徴とするもの
である。The coating composition may contain various pigments, leveling agents, defoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, surface modifiers, plasticizers, and drying accelerators, if necessary. Alternatively, anti-flow agents may be added. According to the invention,
In the same manner, there is provided a coating method using the coating composition as described above, which comprises applying the coating composition to a substrate once or more than once and then baking the silicon-nitrogen-containing material. It is characterized in that a coating film made of oxygen-metal element ceramics or silicon-nitrogen-oxygen-carbon-metal element ceramics is formed.

【００３４】また本発明は上記のごとく焼成した被覆膜
を５０℃未満の条件で長時間保持し、被覆膜の性質を向
上させることを特徴とするコーティング方法を提供す
る。更に本発明は上記のごときコーティング用組成物を
基板に１回または２回以上繰り返し塗布した後、被覆膜
を５０℃未満の条件で長時間保持し、珪素−窒素−酸素
−金属元素系又は珪素−窒素−酸素−炭素−金属元素系
セラミックスから成る被覆膜を形成させることを特徴と
するコーティング方法を提供する。The present invention also provides a coating method characterized in that the coating film baked as described above is kept at a temperature of less than 50 ° C. for a long time to improve the properties of the coating film. Further, the present invention further comprises applying the coating composition as described above to the substrate once or twice or more, and then holding the coating film at a temperature of less than 50 ° C. for a long time to obtain a silicon-nitrogen-oxygen-metal element system or Provided is a coating method, which comprises forming a coating film made of silicon-nitrogen-oxygen-carbon-metal element ceramics.

【００３５】コーティング組成物を塗布する基盤は、特
に限定されず、金属、セラミックス、プラスチックス等
のいずれでもよい。コーティングとしての塗布手段とし
ては、通常の塗布方法、つまり浸漬、ロール塗り、バー
塗り、刷毛塗り、スプレー塗り、フロー塗り等が用いら
れる。又、塗布前に基盤をヤスリがけ、脱脂、各種ブラ
スト等で表面処理しておくとコーティング組成物の付着
性能は向上する。The substrate on which the coating composition is applied is not particularly limited and may be any of metal, ceramics, plastics and the like. As a coating means for coating, a usual coating method, that is, dipping, roll coating, bar coating, brush coating, spray coating, flow coating or the like is used. Further, if the substrate is sanded, degreased, and surface-treated with various blasts before coating, the adhesion performance of the coating composition is improved.

【００３６】このような方法でコーティングし、充分乾
燥させた後、加熱・焼成する。この焼成によってアセチ
ルアセトナト錯体付加ポリシラザンは架橋、縮合、ある
いは、焼成雰囲気によっては酸化、加水分解して硬化
し、強靱な被覆を形成する。上記焼成条件はアセチルア
セトナト錯体付加ポリシラザンの分子量や構造によって
異なる。昇温速度は特に限定しないが、０．５〜１０℃
／分の緩やかな昇温速度が好ましい。好ましい焼成温度
は２５０℃〜３５０℃の範囲である。焼成雰囲気は酸素
中、空気中あるいは不活性ガス等のいずれであってもよ
いが、空気中がより好ましい。空気中での焼成によりア
セチルアセトナト錯体付加ポリシラザンの酸化、あるい
は空気中に共存する水蒸気による加水分解が進行し、上
記のような低い焼成温度てＳｉ−Ｏ結合あるいはＳｉ−
Ｎ結合を主体とする強靱な被覆の形成が可能となる。After being coated by such a method and sufficiently dried, it is heated and baked. By this firing, the acetylacetonato complex-added polysilazane is crosslinked, condensed, or is oxidized and hydrolyzed depending on the firing atmosphere to be cured to form a tough coating. The firing conditions differ depending on the molecular weight and structure of the acetylacetonato complex-added polysilazane. The heating rate is not particularly limited, but is 0.5 to 10 ° C.
A slow heating rate of / min is preferred. The preferred firing temperature is in the range of 250 ° C to 350 ° C. The firing atmosphere may be oxygen, air, or an inert gas, but the air is more preferable. Oxidation of acetylacetonato complex-added polysilazane by hydrolysis in air or hydrolysis by water vapor coexisting in air progresses, and Si—O bond or Si—
It is possible to form a tough coating mainly composed of N bonds.

【００３７】コーティングするアセチルアセトナト錯体
付加ポリシラザンの種類によっては、限られた焼成条件
ではセラミックスへの転化が不完全である場合があり、
この場合には焼成後の被覆膜を５０℃未満の条件で長時
間保持し、被覆膜の性質を向上させることが可能であ
る。この場合の保持雰囲気は空気中が好ましく、また水
蒸気圧を高めた湿潤空気中でも更に好ましい。保持する
時間は特に限定されるものではないが、１０分以上３０
日以内が現実的に適当である。また保持温度は特に限定
されるものではないが、０℃以上５０℃未満が現実的に
適当である。ここで５０℃以上で保持することも当然有
効であるが、本文では５０℃以上での加熱操作を「焼
成」と定義している。即ち、ある温度で一定時間焼成し
た後、温度を例えば５０℃に下げて長時間焼成すること
も有効であるが、この操作は前述の「加熱・焼成」操作
の一類型である。Depending on the type of acetylacetonato complex-added polysilazane to be coated, conversion to ceramics may be incomplete under limited firing conditions.
In this case, the properties of the coating film can be improved by keeping the coating film after firing at a temperature of less than 50 ° C. for a long time. In this case, the holding atmosphere is preferably air, and more preferably wet air having an increased water vapor pressure. The holding time is not particularly limited, but 10 minutes or more and 30
Within a day is realistically appropriate. The holding temperature is not particularly limited, but 0 ° C or more and less than 50 ° C is practically appropriate. Here, it is naturally effective to hold at 50 ° C. or higher, but in the present text, the heating operation at 50 ° C. or higher is defined as “baking”. That is, it is also effective to bake at a certain temperature for a certain period of time and then lower the temperature to, for example, 50 ° C. and bake for a long time, but this operation is one type of the above-mentioned “heating / baking” operation.

【００３８】この空気中での保持によりアセチルアセト
ナト錯体付加ポリシラザンの酸化、あるいは空気中に共
存する水蒸気による加水分解が更に進行し、セラミック
スへの転化が完了して、性質のより向上した、より強靱
な被覆膜の形成が可能となる。以上の方法によれば焼成
温度が低下でき、高い焼成温度に起因する種々の問題を
軽減することができる。By this retention in air, oxidation of acetylacetonato complex-added polysilazane or hydrolysis by water vapor coexisting in air further progresses, conversion to ceramics is completed, and properties are further improved. A tough coating film can be formed. According to the above method, the firing temperature can be lowered and various problems caused by the high firing temperature can be alleviated.

【００３９】更に、コーティングするアセチルアセトナ
ト錯体付加ポリシラザンの種類によっては、５０℃以上
での焼成を全く行なわず、塗布後の被覆膜を５０℃未満
の条件で長時間保持し、被覆膜の性質を向上させること
が可能である。この場合の保持雰囲気は空気中が好まし
く、また水蒸気圧を高めた湿潤空気中でも更に好まし
い。保持する時間は特に限定されるものではないが、１
０分以上３０日以内が現実的に適当である。また保持温
度は特に限定されるものではないが、０℃以上５０℃未
満が現実的に適当である。ここで５０℃以上で保持する
ことも当然有効であるが、本文では５０℃以上での加熱
操作を「焼成」と定義している。この空気中での保持に
よりアセチルアセトナト錯体付加ポリシラザンの酸化、
あるいは空気中に共存する水蒸気による加水分解が進行
し、セラミックスへの転化が完了して、Ｓｉ−Ｏ結合あ
るいはＳｉ−Ｎ結合を主体とした強靱な被覆膜の形成が
可能となる。以上の方法によれば高い焼成温度に起因す
る種々の問題を大幅に軽減することができ、場合によっ
ては室温付近でのセラミックスへの転化が可能となる。Further, depending on the kind of the acetylacetonato complex-added polysilazane to be coated, baking at 50 ° C. or higher is not performed at all, and the coating film after coating is kept for a long time at a temperature of less than 50 ° C. It is possible to improve the property of. In this case, the holding atmosphere is preferably air, and more preferably wet air having an increased water vapor pressure. The holding time is not particularly limited, but 1
0 minutes or more and 30 days or less is practically appropriate. The holding temperature is not particularly limited, but 0 ° C or more and less than 50 ° C is practically appropriate. Here, it is naturally effective to hold at 50 ° C. or higher, but in the present text, the heating operation at 50 ° C. or higher is defined as “baking”. Oxidation of acetylacetonato complex-added polysilazane by holding in air,
Alternatively, hydrolysis by water vapor coexisting in the air progresses, conversion to ceramics is completed, and it becomes possible to form a tough coating film mainly composed of Si—O bond or Si—N bond. According to the above method, various problems caused by the high firing temperature can be significantly reduced, and in some cases, conversion to ceramics near room temperature becomes possible.

【００４０】[0040]

〔原料ペルヒドロポリシラザンの製造〕[Production of raw material perhydropolysilazane]

内容積１１の四つ口フラスコにガス吹きこみ管、メカニ
カルスターラー、ジュワーコンデンサーを装置した。反
応器内部を脱酸素した乾燥窒素で置換した後、四つ口フ
ラスコに脱気した乾燥ピリジン４９０mlを入れ、これを
氷冷した。次にジクロロシラン５１．６ｇを加えると白
色固体状のアダクト（ＳｉＨ2 Ｃｌ・２Ｃ5 Ｈ5 Ｎ）が
生成した。反応混合物を氷冷し、攪拌しながら、水酸化
ナトリウム管及び活性炭管を通して精製したアンモニア
５１．０ｇを吹き込んで加熱した。A four-necked flask having an inner volume of 11 was equipped with a gas blowing tube, a mechanical stirrer, and a dewar condenser. After replacing the inside of the reactor with deoxygenated dry nitrogen, 490 ml of degassed dry pyridine was put into a four-necked flask, and this was ice-cooled. Next, 51.6 g of dichlorosilane was added to produce a white solid adduct (SiH 2 Cl · 2C 5 H 5 N). The reaction mixture was ice-cooled, and while stirring, 51.0 g of purified ammonia was bubbled through the sodium hydroxide tube and the activated carbon tube to heat.

【００４１】反応終了後、反応混合物を遠心分離し、乾
燥ピリジンを用いて洗浄した後、更に窒素雰囲気下でろ
過してろ液８５０mlを得た。ろ液５mlから溶媒を減去留
去すると樹脂状固体ペルヒドロポリシラザン０．１ｇが
得られた。得られたポリマーの数平均分子量は、凝固点
降下法（溶媒：乾燥ベンゼン）により測定したところ、
９０３であった。ＩＲ（赤外吸収）スペクトル（溶媒：
乾燥ｏ−キシレン；ペルヒドロポリシラザンの濃度：１
０．２ｇ／１）は、波数（cm-1）３３４０（見かけの吸
光係数ε＝０．５５７１ｇ-1cm-1）、及び１１７５のＮ
Ｈに基づく吸収；２１６０（ε＝３．１４）のＳｉＨに
基づく吸収；１０２０〜８２０のＳｉＨ及びＳｉＮＳｉ
に基づく吸収を示した。 1ＨＮＭＲ（プロトン核磁気共
鳴）スペクトル（６０MHz 、溶媒ＣＤＣｌ3 ／基準物質
ＴＭＳ）は、いずれも幅広い吸収を示している。即ち、
δ４．８及び４．４（ｂｒ．，ＳｉＨ）；１．５（ｂ
ｒ．，ＮＨ）の吸収が観測された。After the reaction was completed, the reaction mixture was centrifuged, washed with dry pyridine, and then filtered under a nitrogen atmosphere to obtain 850 ml of a filtrate. The solvent was removed from the filtrate (5 ml) by distillation, and 0.1 g of a resinous solid perhydropolysilazane was obtained. The number average molecular weight of the obtained polymer was measured by the freezing point depression method (solvent: dry benzene),
It was 903. IR (infrared absorption) spectrum (solvent:
Concentration of dry o-xylene; perhydropolysilazane: 1
0.2 g / 1) is a wave number (cm −1 ) 3340 (apparent extinction coefficient ε = 0.5571 g −1 cm −1 ), and N of 1175.
H-based absorption; SiH-based absorption of 2160 (ε = 3.14); SiH and SiNSi of 1024-820
Showed absorption based on. The 1 H NMR (proton nuclear magnetic resonance) spectra (60 MHz, solvent CDCl 3 / reference material TMS) all show broad absorption. That is,
δ 4.8 and 4.4 (br., SiH); 1.5 (b
r. , NH) absorption was observed.

【００４２】比較例１ （焼成時のセラミックス化の評価）一般にポリシラザン
の焼成時には、Ｓｉ−Ｒ1 ，Ｎ−Ｒ2 （Ｒ1 ，Ｒ2 は水
素原子、またはアルキル基等を示す）結合の切断と、Ｓ
ｉ−Ｎ，Ｓｉ−Ｏ結合の生成（後者は酸化性雰囲気下で
の焼成時に限る）が起こり、ポリシラザンは窒化珪素、
シリコンオキシナイトライド、シリカなどのセラミック
スに転化する。この過程をセラミックス化と称する。本
比較例または実施例では焼成を大気雰囲気下で行なった
ためポリシラザンは主にシリカに変化したが、このセラ
ミックス化の進行の半定量的評価をＩＲ法にて行なっ
た。 Comparative Example 1 (Evaluation of Ceramization during Firing) Generally, when polysilazane is fired, Si—R 1 and N—R 2 (R 1 and R 2 represent a hydrogen atom or an alkyl group) bond is broken. And S
Formation of i-N and Si-O bonds (the latter is limited to firing in an oxidizing atmosphere) occurs, polysilazane is silicon nitride,
Converts to ceramics such as silicon oxynitride and silica. This process is called ceramization. In this Comparative Example or Example, since the polysilazane was mainly changed to silica because the firing was performed in the air atmosphere, the semi-quantitative evaluation of the progress of the ceramization was performed by the IR method.

【００４３】ＳｉＨ残存率＝（加熱後のＳｉＨ吸光度／
加熱前のＳｉＮ吸光度）×１００（％） ＳｉＯ／ＳｉＮ比＝加熱後のＳｉＯ吸光度／加熱後のＳ
ｉＮ吸光度 両者の数値はセラミックス化進行の指標となるものであ
り、ＳｉＨ残存率が小さいほど、またＳｉＯ／ＳｉＮ比
が大きいほどセラミックス化が進んでいる事を示す。SiH residual rate = (SiH absorbance after heating /
(SiN absorbance before heating) × 100 (%) SiO / SiN ratio = SiO absorbance after heating / S after heating
iN Absorbance Both numerical values serve as indicators of the progress of ceramization, and the smaller the SiH residual rate and the larger the SiO / SiN ratio, the more advanced the ceramization.

【００４４】なおここでＳｉＮ，ＳｉＯ，ＳｉＨの特性
吸収はそれぞれ約８４０，１１６０，２１６０cm-1のも
のを用いた。また吸光度は、 吸光度＝ｌｏｇ（Ｉo ／Ｉ） にて算出した。（Ｉo ，Ｉの定義は図１参照）The characteristic absorptions of SiN, SiO, and SiH used here are about 840, 1160, and 2160 cm -1 , respectively. The absorbance was calculated by the equation: absorbance = log (I o / I). (See FIG. 1 for the definition of I o and I)

【００４５】実施例１ 東燃製ペルヒドロポリシラザンＴｙｐｅ−１（ＰＨＰＳ
−１；数平均分子量６００〜９００）の４．４％ピリジ
ン溶液１１３．６ｇにパラジウムアセチルアセトネート
（Strem Chemicals.Inc.製、純度９９％）０．０５ｇを
添加し、窒素雰囲気中、５０℃で２時間攪拌しながら反
応を行った。この溶液を減圧し溶媒を除去した後、キシ
レンにて希釈し、１０％キシレン溶液とした。本溶液の
数平均分子量はＧＰＣにより測定したところ１２６７で
あった。また、そのＩＲスペクトル分析の結果パラジウ
ムアセチルアセトネートとの反応前と比較して波数（cm
-1）２９６０，２９４０のＣＨに基づく吸収が確認され
た。また、 1ＨＮＭＲスペクトル（ＣＤＣｌ3 ）分析の
結果δ＝１．４の吸収が確認された。この溶液をコーテ
ィング液とし、直径４インチ、厚さ０．５mmのシリコン
ウェハー上にスピンコーターを用いて塗布（１０００rp
m 、２０秒）し、大気雰囲気下３５０℃で１時間加熱
し、膜厚３１３２Åの塗膜を得た。この塗膜のセラミッ
クス化の進行度をＩＲで評価したところ、（評価法はグ
リシドール系と同様）ＳｉＨ残存率６％、ＳｉＯ／Ｓｉ
Ｎ比＝６．１であった（図２）。更にこの塗膜を４９％
フッ酸（ダイキン工業株式会社製）１８ml、６１％硝酸
（小宗化学株式会社製）１７６３mlの混合溶液で処理し
たところ、エッチングレートは１０７８Å／min.であっ
た。一方パラジウムアセチルアセトネートを付加しない
ポリシラザンのコーティング液を同様のプロセスで施
工、評価したところ、ＳｉＨ残存率２１％、ＳｉＯ／Ｓ
ｉＮ比＝１．１、エッチングレートは２３３５Å／min.
以上であった。（図３）。（表１参照） Example 1 Tonen Perhydropolysilazane Type-1 (PHPS
-1; 0.05 g of palladium acetylacetonate (manufactured by Strem Chemicals. Inc., purity 99%) was added to 113.6 g of a 4.4% pyridine solution having a number average molecular weight of 600 to 900), and the temperature was 50 ° C. in a nitrogen atmosphere. The reaction was carried out with stirring for 2 hours. This solution was depressurized to remove the solvent and then diluted with xylene to give a 10% xylene solution. The number average molecular weight of this solution was 1267 as measured by GPC. In addition, as a result of the IR spectrum analysis, the wave number (cm) was compared with that before the reaction with palladium acetylacetonate.
-1 ) CH2 absorption of 2960 and 2940 was confirmed. As a result of 1 H NMR spectrum (CDCl 3 ) analysis, absorption of δ = 1.4 was confirmed. This solution is used as a coating solution and applied on a silicon wafer having a diameter of 4 inches and a thickness of 0.5 mm by using a spin coater (1000 rp).
m 2 for 20 seconds) and heated at 350 ° C. for 1 hour in an air atmosphere to obtain a coating film having a film thickness of 3132Å. When the degree of progress of ceramization of this coating film was evaluated by IR (the evaluation method is the same as that of glycidol system), the SiH residual ratio is 6%, SiO / Si
The N ratio was 6.1 (Fig. 2). Furthermore, this coating film is 49%
When treated with a mixed solution of 18 ml of hydrofluoric acid (manufactured by Daikin Industries, Ltd.) and 1763 ml of 61% nitric acid (manufactured by Kosou Chemical Co., Ltd.), the etching rate was 1078 Å / min. On the other hand, a coating solution of polysilazane to which palladium acetylacetonate was not added was applied and evaluated in the same process. SiH residual ratio was 21%, SiO / S
iN ratio = 1.1, etching rate 2335Å / min.
That was all. (Figure 3). (See Table 1)

【００４６】実施例２ 白金アセチルアセトネートを用いて実施例１と全く同様
に反応、施工、評価を行った。この溶液の数平均分子量
は１０８６であった。また、そのＩＲスペクトル分析の
結果白金アセチルアセトネートとの反応前と比較して波
数（cm-1）２９６０，２９４０のＣＨに基づく吸収が確
認された。また、 1ＨＮＭＲスペクトル（ＣＤＣｌ3 ）
分析の結果δ＝１．４の吸収が確認された。更に、加熱
後の塗膜は膜厚３４３５Å、ＳｉＨ残存率６％、ＳｉＯ
／ＳｉＮ比＝３．１４、エッチングレートは１２９０Å
／min.であった。（表１参照） Example 2 Using platinum acetylacetonate, the reaction, construction and evaluation were performed in exactly the same manner as in Example 1. The number average molecular weight of this solution was 1086. As a result of the IR spectrum analysis, CH-based absorption of wave numbers (cm −1 ) 2960 and 2940 was confirmed as compared with that before reaction with platinum acetylacetonate. In addition, 1 H NMR spectrum (CDCl 3 )
As a result of the analysis, absorption of δ = 1.4 was confirmed. Furthermore, the coating film after heating has a film thickness of 3435Å, SiH residual ratio 6%, SiO
/ SiN ratio = 3.14, etching rate is 1290Å
/ Min. (See Table 1)

【００４７】実施例３ ロジウムアセチルアセトネートを用いて実施例１と全く
同様に反応、施工、評価を行った。この溶液の数平均分
子量は９０１であった。加熱後の塗膜は膜厚３６９３
Å、ＳｉＨ残存率２％、ＳｉＯ／ＳｉＮ比＝３．１８、
エッチングレートは１０８６Å／min.であった。（表１
参照） Example 3 Using rhodium acetylacetonate, the reaction, construction and evaluation were performed in exactly the same manner as in Example 1. The number average molecular weight of this solution was 901. Film thickness after heating is 3693
Å, SiH residual rate 2%, SiO / SiN ratio = 3.18,
The etching rate was 1086Å / min. (Table 1
reference)

【００４８】[0048]

【表１】 [Table 1]

【００４９】[0049]

【発明の効果】本発明によれば、耐熱性、耐摩耗性、耐
食性に優れ、基材との密着性の良い被覆が、従来にない
低温での焼成で得られる。本発明の組成物は、金属、セ
ラミックス等はもちろん、高温処理に不適なプラスチッ
ク材料、電子部品等の表面保護剤として好適である。特
にプラスチックのハードコーティング剤、合成樹脂フィ
ルムや容器のガス透過抑制用コーティング剤、半導体の
保護膜や絶縁膜、即ちパシベーション膜、層間絶縁膜、
チップコート膜など、また半導体の封止剤、液晶表示体
のアンダーコート膜や配向膜としても利用することがで
きる。EFFECTS OF THE INVENTION According to the present invention, a coating having excellent heat resistance, abrasion resistance, corrosion resistance and good adhesion to a substrate can be obtained by firing at a low temperature which has never been seen before. The composition of the present invention is suitable as a surface protective agent for not only metals and ceramics but also plastic materials unsuitable for high temperature treatment and electronic parts. In particular, plastic hard coating agents, synthetic resin films and coatings for gas permeation suppression of containers, semiconductor protective films and insulating films, that is, passivation films, interlayer insulating films,
It can be used as a chip coat film, a semiconductor sealant, an undercoat film or an alignment film for liquid crystal displays.

【図面の簡単な説明】[Brief description of drawings]

【図１】比較例のセラミックスを評価したＩＲスペクト
ル図である。FIG. 1 is an IR spectrum diagram evaluating a ceramic of a comparative example.

【図２】実施例１のセラミックスを評価したＩＲスペク
トル図である。2 is an IR spectrum diagram for evaluating the ceramic of Example 1. FIG.

【図３】実施例１のセラミックスを評価したＩＲスペク
トル図である。3 is an IR spectrum diagram for evaluating the ceramic of Example 1. FIG.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 主として一般式（Ｉ）： 【化１】 （但し、Ｒ1 ，Ｒ2 ，Ｒ3 はそれぞれ独立に水素原子、
アルキル基、アルケニル基、シクロアルキル基、アリー
ル基、またはこれらの基以外でケイ素に直結する基が炭
素である基、アルキルシリル基、アルキルアミノ基、ア
ルコキシ基を表わす。ただし、Ｒ1 ，Ｒ2 ，Ｒ3 のうち
少なくとも１つは水素原子である。）で表わされる単位
からなる主骨格を有する数平均分子量が１００〜５万の
ポリシラザンと、一般式（ＣＨ3 ＣＯＣＨＣＯＣＨ3 ）
n Ｍ〔式中、Ｍはイオン価ｎの金属を表わす〕で示され
るアセチルアセトナト錯体を反応させて得られる、アセ
チルアセトナト錯体／ポリシラザン重量比が０．０００
００１〜２の範囲内かつ数平均分子量が約２００〜５０
万のアセチルアセトナト錯体付加ポリシラザンを少なく
とも含有するコーティング用組成物。1. Mainly represented by the general formula (I): (However, R 1 , R 2 and R 3 are each independently a hydrogen atom,
An alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups in which the group directly bonded to silicon is carbon, an alkylsilyl group, an alkylamino group, and an alkoxy group. However, at least one of R 1 , R 2 and R 3 is a hydrogen atom. The number average molecular weight having a main skeleton and 100-50000 polysilazane comprising units represented by), the general formula (CH 3 COCHCOCH 3)
acetylacetonato complex / polysilazane weight ratio obtained by reacting an acetylacetonato complex represented by n M [wherein M represents a metal having an ionic valence n] of 0.000.
In the range of 001 to 2 and a number average molecular weight of about 200 to 50
A coating composition containing at least acetylacetonato complex-added polysilazane. 【請求項２】 前記アセチルアセトナト錯体の金属Ｍが
ニッケル、白金、パラジウム、アルミニウム、ロジウム
から選択される少なくとも１種である請求項１記載のコ
ーティング用組成物。2. The coating composition according to claim 1, wherein the metal M of the acetylacetonato complex is at least one selected from nickel, platinum, palladium, aluminum and rhodium. 【請求項３】 請求項１又は２記載のコーティング用組
成物を基板に１回または２回以上繰り返し塗布した後、
５０℃以上の温度で焼成し珪素−窒素−酸素−金属元素
系又は珪素−窒素−酸素−炭素−金属元素系セラミック
スから成る被覆膜を形成させることを特徴とするコーテ
ィング方法。3. The coating composition according to claim 1 or 2 is repeatedly applied to a substrate once or twice or more,
A coating method comprising forming a coating film made of silicon-nitrogen-oxygen-metal element ceramics or silicon-nitrogen-oxygen-carbon-metal element ceramics by firing at a temperature of 50 ° C or higher.
JP21426893A 1993-02-24 1993-08-30 Composition for ceramic coating and coating method Expired - Lifetime JP3307471B2 (en)

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