JP2613787B2 - Inorganic silazane high polymer, production method thereof and use thereof - Google Patents
Inorganic silazane high polymer, production method thereof and use thereofInfo
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- JP2613787B2 JP2613787B2 JP63074918A JP7491888A JP2613787B2 JP 2613787 B2 JP2613787 B2 JP 2613787B2 JP 63074918 A JP63074918 A JP 63074918A JP 7491888 A JP7491888 A JP 7491888A JP 2613787 B2 JP2613787 B2 JP 2613787B2
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- inorganic silazane
- inorganic
- high polymer
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Description
【発明の詳細な説明】 〔技術分野〕 本発明は無機シラザン高重合体、その製造方法及びそ
の用途に関し、更に詳しくは窒化珪素および窒化珪素含
有セラミックスの前駆体として使用することのできる無
機シラザン高重合体、その製造方法及び該無機シラザン
高重合体を必須成分としたコーティング剤及びバインダ
ーに関する。Description: TECHNICAL FIELD The present invention relates to a high inorganic silazane polymer, a method for producing the same, and uses thereof. More specifically, the present invention relates to a high inorganic silazane which can be used as a precursor of silicon nitride and a silicon nitride-containing ceramic. The present invention relates to a polymer, a method for producing the polymer, and a coating agent and a binder containing the inorganic silazane high polymer as an essential component.
従来、窒化珪素の製造方法としては、金属シリコン
粉末を窒素又はアンモニア気流中で、1300℃〜1500℃で
加熱して直接窒化するシリコン直接窒化法、シリカ又
は含シリカ物質を炭素と共に窒素雰囲気下で加熱し、尿
素でシリカを還元して、生成するケイ素と窒素とを反応
させるシリカ還元法、四塩化珪素とアンモニアとを高
温で直接反応せしめる気相合成法、四塩化珪素をアン
モノリシスして得られるシリコンジイミドを非酸化性雰
囲気中で加熱して窒化珪素を得るイミド熱分解法等が採
用されている。Conventionally, as a method for producing silicon nitride, a metal silicon powder is heated directly at 1300 ° C. to 1500 ° C. in a stream of nitrogen or ammonia, and is directly nitrided by silicon. It is obtained by heating, reducing silica with urea, and reducing the silica with nitrogen to react with the generated silicon, a gas phase synthesis method in which silicon tetrachloride and ammonia are directly reacted at a high temperature, and ammonolysis of silicon tetrachloride. An imide thermal decomposition method of heating silicon diimide in a non-oxidizing atmosphere to obtain silicon nitride is employed.
しかしながら、上記の方法の場合には、反応時間が
長く、加熱工程が煩雑である上、得られる窒化珪素は粗
大で不純物を多く含むβ型窒化珪素が主体であり、の
方法の場合には、原料の精製が困難なばかりでなく、反
応時間が長く、得られる生成物はα型窒化珪素とβ型窒
化珪素の混合系であり、の方法の場合には、生成した
窒化珪素は一般に非晶質であり、の方法の場合には、
高純度のα型窒化珪素を収率よく製造し得るという利点
が有るものの、窒化珪素前駆体であるシリコンジイミド
〔Si（NH）２〕ｘは溶媒に溶けないために実質的に用途
が限定されざるを得ない等の欠点があった。However, in the case of the above method, the reaction time is long, the heating step is complicated, and the obtained silicon nitride is mainly β-type silicon nitride containing a large amount of impurities and a large amount of impurities. Not only is the purification of the raw materials difficult, but the reaction time is long, and the product obtained is a mixed system of α-type silicon nitride and β-type silicon nitride. Quality, and in the case of the method,
Although there is an advantage that high-purity α-type silicon nitride can be produced with high yield, silicon diimide [Si (NH) 2 ] x which is a silicon nitride precursor is practically limited because it is insoluble in a solvent. There were drawbacks, such as the necessity.
更に、最近、有機ポリシラザンを熱分解して得られる
ポリシラザンを800〜2000℃で加熱して窒化珪素を合成
する方法も提案されている（斉藤肇、繊維学会誌 Vol
38 No.1第65頁〜第72頁〔1982年〕）が、この方法では
窒化珪素と同時に炭化珪素や遊離の炭素が生成するとい
う欠点が有った。Furthermore, recently, a method of synthesizing silicon nitride by heating polysilazane obtained by thermally decomposing organic polysilazane at 800 to 2000 ° C. has been proposed (Hajime Saito, Vol.
38 No. 1, pp. 65-72 (1982)), this method has the disadvantage that silicon carbide and free carbon are formed simultaneously with silicon nitride.
一方、溶媒に可溶である無機ポリシラザンは、1921年
にStock（Ber.54.（1921）.p740）等によって合成され
ており、1983年にはSeyferth〔Comm.Am.Ceram.Soc.C−1
3/14,（83）〕等によって、これが窒化珪素前駆体とし
て有用であることが証明されている。本発明者等は、か
かる観点に注目し無機ポリシラザンを加熱処理すること
により、高純度のα型窒化珪素を得る方法を提案した
（特開昭59−207812号）。On the other hand, an inorganic polysilazane soluble in a solvent was synthesized by Stock (Ber. 54. (1921). P740) in 1921 and the like, and in 1983 Seyferth [Comm. Am. Ceram. Soc. 1
3/14, (83)] and the like prove that this is useful as a silicon nitride precursor. The present inventors have paid attention to such a viewpoint and have proposed a method of obtaining high-purity α-type silicon nitride by subjecting an inorganic polysilazane to a heat treatment (Japanese Patent Application Laid-Open No. 59-207812).
しかしながら、従来の無機ポリシラザンの製造方法に
おいては、何れの場合も気化性の高いジクロロシランを
原料として用いるために、反応装置のガス配管又は反
応器壁に生成したポリシラザンが固着してガス流路を閉
塞する恐れがある、上記弊害を防止するためには反応
温度を低温に維持してジクロロシランの飛散を防止する
必要が有る、ジクロロシランは毒性及び引火性が強い
ので低温密閉容器に入れて利用せねばならないなど取扱
が煩雑である等の欠点があった。更に、合成されたポリ
シラザンはStock等の場合には、−（SiH2NH）ｎ−の構
造を有するｎ＝７〜８のオリゴマーにすぎず常温では粘
性のある液体であり、Seyferth等の場合には、Stock等
の場合より複雑な構造を有し、Si−H/N−Ｈのプロトン
比が約3.3のオイル状液体であるが、約200℃で加熱する
か室温で３日〜５日放置することにより固化するもので
あり、いずれのポリシラザンの場合であっても、常温で
賦形化した窒化珪素焼結体のための前駆体として十分な
性質を有していると言えるものではなかった。However, in the conventional method for producing an inorganic polysilazane, in each case, since highly volatile dichlorosilane is used as a raw material, polysilazane generated on a gas pipe or a reactor wall of a reactor is fixed and a gas flow path is formed. There is a risk of clogging. In order to prevent the above adverse effects, it is necessary to maintain the reaction temperature at a low temperature to prevent scattering of dichlorosilane.Dichlorosilane is highly toxic and flammable, so it is used in a low-temperature closed container. There are drawbacks such as complicated handling such as the necessity of handling. Further, in the case of such combined polysilazane Stock is, - (SiH 2 NH) n - at normal temperature only n = 7 to 8 of the oligomer having the structure of a viscous liquid, in the case of such Seyferth Is an oily liquid having a more complex structure than that of Stock et al. And having a proton ratio of Si-H / N-H of about 3.3, but heated at about 200 ° C. or left at room temperature for 3 to 5 days. Therefore, in any case of polysilazane, it cannot be said that the polysilazane has sufficient properties as a precursor for a shaped silicon nitride sintered body at normal temperature. .
したがって、より高い分子量と曳糸性を有する窒化珪
素の前駆体として有用な無機シラザン及びこのものをよ
り収率よくかつより容易に合成できる方法の開発が望ま
れていた。Therefore, development of an inorganic silazane useful as a precursor of silicon nitride having higher molecular weight and spinnability and a method capable of synthesizing the same in a higher yield and more easily has been desired.
一方、金属材料や無機材料の表面のコーティング剤と
しては、シリコン系塗料、ポリチタノカルボシラン系塗
料、更にはポリ（ジシリル）シラザン重合体等（特公昭
61−38933号公報）を使用する方法が知られている。On the other hand, as a coating agent for the surface of a metal material or an inorganic material, a silicon-based paint, a polytitanocarbosilane-based paint, and a poly (disilyl) silazane polymer (for example,
No. 61-38933).
しかしながら、シリコーン系塗料は200℃以上の高温
雰囲気下でも耐熱効果に優れた被膜を与えるものの、ピ
ンホールが発生し易く、またこのピンホールの発生を防
止するためにその被膜の膜厚を厚くすると焼成中に被膜
にクラックやブリスターが生じたり剥離が生ずる場合が
ある。このような現象は300℃以上の温度領域下におい
て特に顕著にみられるため、シリコーン系塗料を用いる
場合には、シリコーン樹脂の架橋密度を減少させる必要
があり、このため形成被膜の表面硬度が低下するという
難点が生じる。However, although silicone-based paints provide films with excellent heat resistance even in a high-temperature atmosphere of 200 ° C or higher, pinholes are likely to occur, and when the film thickness is increased to prevent the occurrence of pinholes, Cracks, blisters, or peeling may occur in the coating during firing. Since such a phenomenon is particularly remarkable in a temperature range of 300 ° C. or more, when a silicone-based paint is used, it is necessary to reduce the crosslink density of the silicone resin. The difficulty arises.
また、ポリチタノカルボシラン系塗料は低温焼成（40
0℃以下）における表面硬度が充分でない上、原料製造
工程が複雑であり、その製造コストが高価となるという
欠点がある。In addition, polytitanocarbosilane-based paints are fired at low temperatures (40
(0 ° C. or lower), the surface hardness is not sufficient, and the raw material production process is complicated, and the production cost is high.
また、ポリ（ジシル）シラザン系重合体を用いる方法
は、750℃以上の高温下で不活性雰囲気又は真空中で熱
分解を行うプロセスを採る必要があり、その施行性に多
く困難さを伴う。同様にポリシラザンから得られた窒化
珪素の被覆膜についての報告もなされているが、クラッ
クが生じており十分実用的価値を有するものが得られて
いない（W.S.Cobling et al,“Formation of Ceramic C
ompositions Utilizing Polymer Pyrolysis",p271〜28
5、Materials Science Research voll,Emergent Proces
s Methods For High−Technology Ceramics edited by
R.F.Dabis et.al,Plenun Press N.Y.）。In addition, the method using a poly (disyl) silazane-based polymer requires a process of performing thermal decomposition in an inert atmosphere or vacuum at a high temperature of 750 ° C. or higher, which involves many difficulties in its workability. Similarly, there has been a report on a coating film of silicon nitride obtained from polysilazane, but cracks have occurred and a film having sufficient practical value has not been obtained (WSCobling et al, “Formation of Ceramic C
ompositions Utilizing Polymer Pyrolysis ", p271-28
5, Materials Science Research voll, Emergent Proces
s Methods For High-Technology Ceramics edited by
RFDabis et.al, Plenun Press NY).
本発明の第１の目的は、窒化珪素前駆体として好適な
新規な無機シラザン高重合体及びこのものを工業的に有
利に製造する方法を提供することにあり、第２の目的は
耐熱性、耐摩耗性及び耐薬品性に優れると共に、表面硬
度の高い被膜を形成し得るコーティング剤を提供するこ
とにある。更に第３の目的は、セラミックス成形体、特
にセラミックス成形焼結体用のバインダーを提供するこ
とにある。A first object of the present invention is to provide a novel inorganic silazane high polymer suitable as a silicon nitride precursor and a method for industrially producing the same, and a second object is to provide heat resistance, An object of the present invention is to provide a coating agent which is excellent in abrasion resistance and chemical resistance and can form a film having a high surface hardness. Still another object of the present invention is to provide a binder for a ceramic molded body, particularly a ceramic molded sintered body.
本発明によれば、第１の発明として、数平均分子量が
200〜500000であり、１分子中のSiH3基とSiH2基の比（S
iH2基/SiH3基）が2.5〜8.4であって、しかも元素比率が
Si:59重量％〜70重量％、N:20重量％〜34重量％、H:5重
量％〜９重量％である無機シラザン高重合体が提供さ
れ、第２の発明として、無機シラザンを塩基性溶媒中又
は塩基性化合物を含む溶媒中で加熱することを特徴とす
る数平均分子量が200〜500000であり、１分子中のSiH3
基とSiH2基の比（SiH2基/SiH3基）が2.5〜8.4であっ
て、しかも元素比率がSi:59重量％〜70重量％、N:20重
量％〜34重量％、H:5重量％〜９重量％である無機シラ
ザン高重合体の製造方法が提供され、第３の発明とし
て、数平均分子量が200〜500000であり、１分子中のSiH
3基とSiH2基の比（SiH2基/SiH3基）が2.5〜8.4であっ
て、しかも元素比率がSi:59重量％〜70重量％、N:20重
量％〜34重量％、H:5重量％〜９重量％である無機シラ
ザン高重合体を必須成分としたコーティング剤が提供さ
れる。更に、第４の発明として数平均分子量が200〜500
000であり、１分子中のSiH3基とSiH2基の比（SiH2基/Si
H3基）が2.5〜8.4であって、しかも元素比率がSi:59重
量％〜70重量％、N:20重量％〜34重量％、H:5重量％〜
９重量％である無機シラザン高重合体を必須成分とした
バインダーが提供される。According to the present invention, as a first invention, the number average molecular weight is
200 to 500,000, and the ratio of SiH 3 groups to SiH 2 groups in one molecule (S
iH 2 groups / SiH 3 groups) is 2.5 to 8.4, and the element ratio is
The present invention provides an inorganic silazane high polymer in which Si: 59% to 70% by weight, N: 20% to 34% by weight, and H: 5% to 9% by weight. The number average molecular weight is 200 to 500,000 characterized by heating in a basic solvent or a solvent containing a basic compound, and SiH 3 in one molecule
The ratio of the group to the SiH 2 group (SiH 2 group / SiH 3 group) is 2.5 to 8.4, and the element ratio is Si: 59% to 70% by weight, N: 20% to 34% by weight, H: A method for producing an inorganic silazane polymer having a weight average molecular weight of 200 to 500,000 and a SiH content in one molecule is provided as a third invention.
The ratio of three groups to SiH 2 groups (SiH 2 groups / SiH 3 groups) is 2.5 to 8.4, and the element ratio is Si: 59% to 70% by weight, N: 20% to 34% by weight, : A coating agent containing an inorganic silazane high polymer in an amount of 5 to 9% by weight as an essential component is provided. Further, as a fourth invention, the number average molecular weight is 200 to 500.
000, and the ratio of SiH 3 groups to SiH 2 groups in one molecule (SiH 2 groups / SiH
A H 3 group) is 2.5 to 8.4, yet elemental ratio Si: 59 wt% to 70 wt%, N: 20 wt% to 34 wt%, H: 5% to
A binder containing an inorganic silazane high polymer of 9% by weight as an essential component is provided.
本発明の無機シラザン高重合体の出発材料として用い
られる原料無機シラザンは、次の一般式で表わされる骨
格を有するものである。The raw material inorganic silazane used as a starting material for the inorganic silazane high polymer of the present invention has a skeleton represented by the following general formula.
本発明の原料無機シラザンは、100〜50,000の数平均
分子量を有するもので、環状無機シラザン、鎖状無機シ
ラザンあるいはそれらの混合物から構成される。本発明
において好ましく用いられる原料無機シラザンは、数平
均分子量300〜2000好ましくは600〜1400の鎖状無機シラ
ザンである。 The raw material inorganic silazane of the present invention has a number average molecular weight of 100 to 50,000, and is composed of cyclic inorganic silazane, chain inorganic silazane, or a mixture thereof. The raw material inorganic silazane preferably used in the present invention is a chain inorganic silazane having a number average molecular weight of 300 to 2,000, preferably 600 to 1,400.
前記で示した無機シラザンは、下記に示す如き従来公
知の方法で合成することができる。The inorganic silazane shown above can be synthesized by a conventionally known method as shown below.
本発明者特許出願（特開60−145903） ・SiH2Cl2＋2Py→SiH2Cl2・2Py adduct ・SiH2Cl2・2Py adduct＋3NH→SiH2NHｎ ＋2NH4Cl＋2Py 本発明においては、前記出発原料である無機シラザン
を塩基性溶媒又は塩基性化合物を添加した溶媒中で加熱
し、脱水素重縮合反応（以下、単に重縮合反応とも言
う）させる。この場合、塩基性化合物としては、窒素や
リンの如き塩基性元素を含有する化合物、例えば、第３
級アミン類や、立体障害性の基を有する２級アミン類、
フォスフィン等を用いることができる。本発明で用いる
反応溶媒は、非塩基性溶媒にこのような塩基性化合物を
添加した溶媒あるいは塩基性化合物自体からなる溶媒で
ある。非塩基性溶媒に塩基性化合物を添加する場合、塩
基性化合物の添加量は、非塩基性溶媒100重量部に対し
少なくとも５重量部、好ましくは20重量部以上である。
塩基性化合物の添加量がこれより少なくなると、重縮合
反応が円滑に促進されない。The present inventor patent application (JP 60-145903) · SiH 2 Cl 2 + 2Py → SiH 2 Cl 2 · 2Py adduct · SiH 2 Cl 2 · 2Py adduct + 3NH → SiH 2 NH n + 2NH 4 Cl + 2Py In the present invention, the inorganic silazane as the starting material is heated in a basic solvent or a solvent to which a basic compound has been added to cause a dehydrogenation polycondensation reaction (hereinafter, also simply referred to as a polycondensation reaction). In this case, as the basic compound, a compound containing a basic element such as nitrogen or phosphorus, for example,
Secondary amines, secondary amines having a sterically hindered group,
Phosphine or the like can be used. The reaction solvent used in the present invention is a solvent obtained by adding such a basic compound to a non-basic solvent or a solvent consisting of the basic compound itself. When the basic compound is added to the non-basic solvent, the amount of the basic compound added is at least 5 parts by weight, preferably 20 parts by weight or more based on 100 parts by weight of the non-basic solvent.
If the amount of the basic compound is less than this, the polycondensation reaction is not smoothly promoted.
前記塩基性化合物又は塩基性溶媒としては、出発原料
である無機シラザンを分解しないものであれば任意のも
のが使用できる。このようなものとしては、例えば、ト
リメチルアミン、ジメチルエチルアミン、ジエチルメチ
ルアミン及びトリエチルアミン等のトリアルキルアミ
ン、ピリジン、ピコリン、ジメチルアニリン、ピラジ
ン、ピリミジン、ピリダジン及びこれらの誘導体等の第
３級アミン類の他、ピロール、３−ピロリン、ピラゾー
ル、２−ピラゾリン、及びそれらの混合物等を挙げるこ
とができる。また、非塩基性溶媒としては、例えば、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。As the basic compound or basic solvent, any one can be used as long as it does not decompose the inorganic silazane as a starting material. Such compounds include, for example, tertiary amines such as trialkylamines such as trimethylamine, dimethylethylamine, diethylmethylamine and triethylamine, pyridine, picoline, dimethylaniline, pyrazine, pyrimidine, pyridazine and derivatives thereof. , Pyrrole, 3-pyrroline, pyrazole, 2-pyrazoline, and mixtures thereof. Examples of the non-basic solvent include, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene; Ethers such as aromatic ethers and alicyclic ethers can be used. Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, halogenated hydrocarbons such as ethylidene chloride, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, dioxane , Ethers such as dimethyldioxane, tetrahydrofuran, tetrahydropyran, pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, etc. And the like.
本発明の重縮合反応は、前記した如き溶媒中で実施さ
れるが、この場合、原料無機シラザンの溶媒中濃度は0.
1重量％〜50重量％、好ましくは１重量％〜12重量％で
ある。無機シラザンの濃度がこれより低いと分子間重縮
合反応が十分進行せず、またそれより高いと分子間重縮
合反応が進みすぎてゲルを生成するようになる。反応温
度は、−78℃〜300℃、好ましくは−40℃〜200℃であ
り、それより低い温度では重縮合反応が十分進行せず、
それより高い温度では重縮合反応が進みすぎてゲルを生
成する。反応雰囲気としては、大気の使用が可能である
が、好ましくは、水素雰囲気や、乾燥窒素、乾燥アルゴ
ン等の不活性ガス雰囲気あるいはそれらの混合雰囲気が
使用される。本発明における重縮合反応においては、副
生物の水素によって反応の際圧力がかかるが、必ずしも
加圧は必要でなく、常圧を採用することができる。な
お、反応時間は、出発原料の無機シラザンの種類、濃度
および塩基性化合物又は塩基性溶媒の種類、濃度、重縮
合反応温度など諸条件により異なるが、一般的に0.5時
間〜20時間の範囲とすれば充分である。The polycondensation reaction of the present invention is carried out in a solvent as described above.In this case, the concentration of the raw material inorganic silazane in the solvent is 0.
It is 1% to 50% by weight, preferably 1% to 12% by weight. When the concentration of the inorganic silazane is lower than this, the intermolecular polycondensation reaction does not sufficiently proceed, and when it is higher than this, the gel is generated due to excessive progress of the intermolecular polycondensation reaction. The reaction temperature is from −78 ° C. to 300 ° C., preferably from −40 ° C. to 200 ° C. At a lower temperature, the polycondensation reaction does not proceed sufficiently,
At a higher temperature, the polycondensation reaction proceeds too much to form a gel. As the reaction atmosphere, air can be used, but preferably, a hydrogen atmosphere, an inert gas atmosphere such as dry nitrogen or dry argon, or a mixed atmosphere thereof is used. In the polycondensation reaction of the present invention, pressure is applied during the reaction due to hydrogen as a by-product, but pressurization is not necessarily required, and normal pressure can be employed. The reaction time varies depending on various conditions such as the type and concentration of the inorganic silazane as the starting material and the type and concentration of the basic compound or the basic solvent, and the polycondensation reaction temperature, but generally ranges from 0.5 hours to 20 hours. That is enough.
重縮合反応の最適条件は出発原料の無機シラザンの平
均分子量、分子量分布等によって異なる。条件設定の一
般的な考慮は、出発原料のポリシラザンの平均分子量が
低い程よりきびしい条件（温度、反応時間）が必要とさ
れるということである。Optimum conditions for the polycondensation reaction differ depending on the average molecular weight, molecular weight distribution, and the like of the starting inorganic silazane. A general consideration in setting conditions is that the lower the average molecular weight of the starting polysilazane, the more stringent conditions (temperature, reaction time) are required.
本発明の重縮合反応においては、無機シラザン高重合
体、即ち、高分子量化された無機シラザンを含む溶媒溶
液が得られるが、この場合、その溶液組成を調整して、
塩基性化合物又は塩基性溶媒含量を、全溶媒中30重量％
以下、好ましくは５重量％以下にするのがよい。塩基性
化合物又は塩基性溶媒は、無機シラザン高重合体の分子
間重縮合反応触媒として作用するため、その全溶媒に対
する割合が余りにも多くなると、室温で長時間保存して
いる間にゲルを生成する。この溶液組成の調整は、例え
ば、前記重縮合反応で得られた無機シラザン高重合体溶
液を蒸発処理して、それに含まれる塩基性化合物もしく
は溶媒を蒸発除去した後、非塩基性（非反応性）溶媒を
添加することによって行うことができる。溶液中の塩基
性化合物の含量が高い場合や、反応溶媒として塩基性化
合物自体を用いる場合は、前記した塩基性化合物の蒸発
除去と非塩基性溶媒添加とからなる溶液組成調整操作を
行うことによって安定性の良い溶液組成とすることがで
きる。本発明において無機シラザン高重合体の安定溶液
を形成するための非塩基性溶媒としては、前記で示した
如き脂肪族炭化水素、脂環式炭化水素、芳香族炭化水
素、ハロゲン化炭化水素、脂肪族エーテル、脂環式エー
テル等を用いることができる。In the polycondensation reaction of the present invention, an inorganic silazane high polymer, that is, a solvent solution containing a high molecular weight inorganic silazane is obtained.In this case, by adjusting the solution composition,
30% by weight of basic compound or basic solvent in all solvents
Or less, preferably 5% by weight or less. Since the basic compound or the basic solvent acts as a catalyst for the intermolecular polycondensation reaction of the inorganic silazane high polymer, if the ratio to the total solvent becomes too large, a gel is generated during long-term storage at room temperature. I do. The adjustment of the solution composition can be performed, for example, by evaporating the inorganic silazane high polymer solution obtained by the polycondensation reaction to remove the basic compound or the solvent contained therein by evaporation and then removing the non-basic (non-reactive ) Can be carried out by adding a solvent. When the content of the basic compound in the solution is high, or when the basic compound itself is used as the reaction solvent, by performing a solution composition adjustment operation including the above-described evaporation and removal of the basic compound and addition of a non-basic solvent. A stable solution composition can be obtained. In the present invention, the non-basic solvent for forming a stable solution of the inorganic silazane high polymer includes aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and aliphatic hydrocarbons as described above. Group ethers, alicyclic ethers and the like can be used.
本発明における無機シラザンの重縮合反応は、次の如
き素反応を含んでいるものと考えられる。The polycondensation reaction of the inorganic silazane in the present invention is considered to include the following elementary reaction.
（１） 前記一般式（Ｉ）において、 本発明の無機シラザン高重合体は、前記のように原料
無機シラザンの重縮合反応によって生成された重合体で
あり、無機シラザン分子中に新しい架橋結合が生じて高
分子量化されたものである。即ち、本発明の無機シラザ
ン高重合体は、前記のように数平均分子量100〜50,000
の無機シラザンを原料として用い、これを架橋高分子化
することによって形成されることから、その分子量は、
当然のことながら、原料無機シラザンの分子量よりも増
加されたものとなる。一般的には、本発明の目的とする
無機シラザン高重合体は、数平均分子量200〜500,000、
好ましくは、1,500〜10,000を有する。(1) In the general formula (I), The inorganic silazane high polymer of the present invention is a polymer produced by the polycondensation reaction of the raw material inorganic silazane as described above, and has a high molecular weight due to a new cross-linking occurring in the inorganic silazane molecule. That is, the inorganic silazane high polymer of the present invention has a number average molecular weight of 100 to 50,000 as described above.
Is formed by using an inorganic silazane as a raw material and cross-linking it into a polymer, so that its molecular weight is
Naturally, the molecular weight of the starting inorganic silazane is increased. In general, the inorganic silazane high polymer intended for the present invention has a number average molecular weight of 200 to 500,000,
Preferably, it has between 1,500 and 10,000.
本発明の無機シラザン高重合体は、分子構造的には前
記の如き特徴を有し、原料無機シラザンと区別されるも
のであるが、その他、多くの枝分れ構造を有する点もそ
の特徴の１つである。この枝分れ構造のために、本発明
の無機シラザン高重合体は、原料無機シラザンに比して
高分子量化されたものでありながら、むしろ溶媒可溶性
において改善された結果を与える。例えば、Seyferth等
が先に提案した無機シラザンは、−Si−H/N−Ｈのプロ
トン比が約3.3のオイル状液体であるが、約200℃で加熱
するか室温で３〜５日放置することにより固化するもの
であった。これに対し、本発明の無機シラザン高重合体
は、200〜500,000の分子量を持ち、１分子中のSiH3基の
数は、通常、原料無機シラザンの２倍以上に増加し、溶
媒再可溶性を有する。本発明の無機シラザン高重合体が
原料無機シラザンに比してより多くの枝分れ構造を有す
る理由は、本発明における重縮合反応では、重縮合反応
以外に、例えば、次のような反応が起ることによるもの
と考えられる。The inorganic silazane high polymer of the present invention has the characteristics as described above in terms of molecular structure and is distinguished from the raw material inorganic silazane, but in addition, it has many branched structures. One. Due to this branched structure, the inorganic silazane high polymer of the present invention has a higher molecular weight than the raw inorganic silazane, but gives improved results in solvent solubility. For example, the inorganic silazane previously proposed by Seyferth et al. Is an oily liquid having a proton ratio of -Si-H / N-H of about 3.3, but is heated at about 200 ° C or left at room temperature for 3-5 days. This caused the solidification. On the other hand, the inorganic silazane high polymer of the present invention has a molecular weight of 200 to 500,000, and the number of SiH 3 groups in one molecule usually increases twice or more as compared with the raw material inorganic silazane, thereby reducing solvent resolubility. Have. The reason that the inorganic silazane high polymer of the present invention has a more branched structure than the raw material inorganic silazane is that, in the polycondensation reaction of the present invention, in addition to the polycondensation reaction, for example, the following reaction is performed. It is thought to be caused.
本発明の無機シラザン高重合体の枝分れ構造は、例え
ば、1HNMRスペクトル測定により得られる（SiH2）／（S
iH3）〔（SiH2）：δ4.8におけるSi−Ｈ共鳴の面積の1/
2、（SiH3）：δ4.4におけるSi−Ｈ共鳴面積の1/3〕比
によって評価することができる。原料無機シラザンの場
合、（SiH2）／（SiH3）比は、5.0〜19.0の範囲である
が、本発明の無機シラザン高重合体の場合、それぞれ、
2.5〜8.4の低められた値となる。無機シラザン高重合体
のSiH2/SiH3比が上記範囲でない場合、凝固性、賦形性
等が劣り、本発明の所期の目的を達成することができな
い。 The branched structure of the inorganic silazane high polymer of the present invention can be obtained by, for example, 1 HNMR spectrum measurement, (SiH 2 ) / (S
iH 3 ) [(SiH 2 ): 1 / of the area of the Si-H resonance at δ 4.8
2, (SiH 3): it can be evaluated by 1/3] ratio of SiH resonance area in Deruta4.4. In the case of the raw inorganic silazane, the (SiH 2 ) / (SiH 3 ) ratio is in the range of 5.0 to 19.0, but in the case of the inorganic silazane high polymer of the present invention,
This is a reduced value of 2.5 to 8.4. If the SiH 2 / SiH 3 ratio of the inorganic silazane high polymer is not in the above range, the solidification properties and the shapeability are poor, and the intended object of the present invention cannot be achieved.
本発明の無機シラザン高重合体は、前記の如き分子構
造的特徴を有するとともに、物性的には、架橋結合を有
しながら、有機溶媒に可溶であり、特に溶液から溶媒を
除去して得られた固体重合体は、溶媒に対して再可溶性
を有するという大きな特徴を示す。従来の無機シラザン
の場合、安定性が悪く、その溶液から溶媒を除去すると
樹脂状固体を生成し、このものは溶媒に不溶であった
が、本発明の無機シラザン高重合体はこのような傾向を
示さない。従って、従来の無機シラザンの場合、固体重
合体としての取扱いが不可能ないし著しく困難であった
のに対し、本発明の無機シラザン高重合体は固体重合体
として容易に取扱うことができる。The inorganic silazane high polymer of the present invention has the molecular structural characteristics as described above, and is physically soluble in an organic solvent while having a cross-linking bond, and is particularly obtained by removing the solvent from the solution. The obtained solid polymer has a great feature of having resolubility in a solvent. In the case of the conventional inorganic silazane, the stability is poor, and when the solvent is removed from the solution, a resinous solid is formed, which is insoluble in the solvent, but the inorganic silazane high polymer of the present invention has such a tendency. Is not shown. Therefore, in the case of the conventional inorganic silazane, it was impossible or extremely difficult to handle it as a solid polymer, whereas the inorganic silazane high polymer of the present invention can be easily handled as a solid polymer.
更に本発明の無機シラザン高重合体は元素比率がSi:5
9重量％〜70重量％、N:20重量％〜34重量％、H:5重量％
〜９重量％であることを特徴とする。Further, the inorganic silazane high polymer of the present invention has an element ratio of Si: 5
9% to 70% by weight, N: 20% to 34% by weight, H: 5% by weight
-9% by weight.
本発明の無機シラザン高重合体の好ましい元素比率は
Si:61重量％〜68重量％、N:25重量％〜33重量％、H:5重
量％〜８重量％であり、更に好ましい元素比率はSi:64
重量％〜68重量％、N:27重量％〜33重量％、H:5重量％
〜７重量％である。The preferred element ratio of the inorganic silazane high polymer of the present invention is
Si: 61% to 68% by weight, N: 25% to 33% by weight, H: 5% to 8% by weight, and a more preferable element ratio is Si: 64%.
Wt% to 68 wt%, N: 27 wt% to 33 wt%, H: 5 wt%
~ 7% by weight.
無機シラザン高重合体の元素比率が上記範囲を満たさ
ないと固体重合体として容易に取り扱うことが困難とな
って本発明の所期の目的を達成することができない。If the elemental ratio of the inorganic silazane high polymer does not satisfy the above range, it is difficult to handle it as a solid polymer, and the intended object of the present invention cannot be achieved.
本発明において、前記無機シラザン高重合体を用いて
コーティング剤を形成するには、通常無機シラザン高重
合体を溶剤に溶解させればよい。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、シオキサン、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。In the present invention, in order to form a coating agent using the inorganic silazane high polymer, the inorganic silazane high polymer may be usually dissolved in a solvent. As the solvent, aliphatic hydrocarbons, alicyclic hydrocarbons, hydrocarbon solvents of aromatic hydrocarbons, halogenated methane, halogenated ethane, halogenated hydrocarbons such as halogenated benzene, aliphatic ethers,
Ethers such as alicyclic ethers can be used. Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, halogenated hydrocarbons such as ethylidene chloride, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, and siloxane. , Dimethyldioxane, tetrahydrofuran, ethers such as tetrahydropyran, pentanehexane, isohexane, methylpentane, heptane, isoptan, octane, isooctane, cyclopentane,
Hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene.
これらの溶剤を使用する場合、前記無機シラザン高重
合体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、また無機シラザン高重合体の平均分子
量、分子量分布、その構造によって異なるが、コーティ
ング剤中溶剤は90重量％程度まで混合することができ、
好ましくは10重量％〜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 inorganic silazane high polymer and the evaporation rate of the solvent. Amount of solvent used (ratio)
Is selected so that the workability is improved by the coating method employed.Although it depends on the average molecular weight, molecular weight distribution and structure of the inorganic silazane high polymer, the solvent in the coating agent can be mixed up to about 90% by weight,
Preferably, it can be mixed in the range of 10% by weight to 50% by weight.
また、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。Further, an appropriate filler may be added as needed. Examples of the filler include fine powders of oxide-based inorganic substances such as silica, alumina, zirconia, and mica, and non-oxide-based inorganic substances such as silicon carbide and silicon nitride. Depending on the application, metal powder such as aluminum, zinc, and copper can be added. Further examples of fillers include silica silica, quartz, novacurite, diatomaceous earth, and other silica-based materials: synthetic amorphous silica: kaolinite, mica, talc, wollastonite, asbestos, calcium silicate, aluminum silicate Glass bodies such as glass powder, glass spheres, hollow glass spheres, glass flakes, 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: metal oxides such as zinc oxide, alumina, magnesia, titanium oxide, beryllium oxide: barium sulfate, molybdenum disulfide, tungsten disulfide, carbon fluoride and other inorganic substances: Metal powders such as aluminum, bronze, lead, stainless steel, zinc, etc .: carb Black, coke, graphite, pyrolytic carbon, carbon and the like of the hollow carbon spheres and the like.
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無機シラザン高重合体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 may be of various shapes such as needles (including whiskers), granules, and scales, or may be used alone or in combination of two or more. 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 addition amount of the filler is in the range of 0.05 to 10 parts by weight, and particularly preferably 0.2 to 3 parts by weight, based on 1 part by weight of the inorganic silazane high polymer.
Further, the surface of the filler may be surface-treated by coupling agent treatment, vapor deposition, plating or the like before use.
更に、コーティング剤には、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。Further, the coating agent, if necessary, various pigments,
Leveling agent, defoamer, antistatic agent, ultraviolet absorber, PH
Adjusters, dispersants, surface modifiers, plasticizers, drying accelerators, flow inhibitors may be added.
このように調製されたコーティング剤は均一に溶解、
分解させて金属、セラミックス、プラスチック等の基盤
にコーティングされる。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。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
って無機シラザン高重合体は架橋、縮合して硬化し、強
靭な被覆を形成する。The coating agent prepared in this way dissolves uniformly,
Decomposed and coated on a base of metal, ceramics, plastic, etc. As a coating means as a coating, a normal coating method, that is, dipping, roll coating,
Bar coating, brush coating, spray coating, flow coating and the like are used. In addition, if the substrate is sanded, degreased, or surface-treated with various types of blasting before application, the adhesion performance of the coating composition is improved. After coating by such a method and sufficiently drying, heating and baking are performed. By this calcination, the inorganic silazane high polymer is cross-linked, condensed and cured to form a tough coating.
上記焼成条件は無機シラザン高重合体の分子量や構造
によって異なるが0.5〜10℃／分の緩やかな昇温速度で1
00℃〜1000℃の範囲の温度で焼成する。好ましい焼成温
度は200℃〜500℃の範囲である。焼成雰囲気は空気中あ
るいは不活性ガスのいずれであってもよいが、非酸化性
雰囲気であればSi−Ｎ結合を、酸化又は加水解性雰囲気
であればSi−Ｏ結合の被膜を形成するので、基盤に応じ
て雰囲気を適当に選択することができる。The above calcination conditions vary depending on the molecular weight and structure of the inorganic silazane high polymer, but are controlled at a gradual heating rate of 0.5 to 10 ° C / min.
Baking at a temperature in the range of 00C to 1000C. Preferred firing temperatures range from 200 ° C to 500 ° C. The firing atmosphere may be either air or an inert gas.Since a non-oxidizing atmosphere forms a Si-N bond, and an oxidizing or hydrolyzing atmosphere forms a Si-O bond film. The atmosphere can be appropriately selected according to the base.
したがって、本発明のコーティング剤は、鉄、アルミ
ニウム、銅、ステンレス鋼、黄銅等の金属類やセラミッ
クスの表面保護剤として更には電子部品用の多属配線の
絶縁膜としても好適なものである。Therefore, the coating agent of the present invention is suitable as a surface protective agent for metals such as iron, aluminum, copper, stainless steel, brass and the like and ceramics, and also as an insulating film for multi-part wiring for electronic components.
前記無機シラザン高重合体を用いてバインダーとして
使用するためには通常以下に述べる手法が用いられる。
即ち、無機シラザン高重合体は、キシレン等の有機溶剤
に可溶である。In order to use the inorganic silazane high polymer as a binder, the following method is usually used.
That is, the inorganic silazane high polymer is soluble in an organic solvent such as xylene.
したがって、このような溶剤中に、各種セラミックス
粉末と無機シラザン高重合体とを添加し、混合すること
によって、容易にセラミックス粉体中に、バインダーと
して均一に分散させることが可能である。ここで、無機
シラザン高重合体は、解こう剤（分散剤）としても作用
するため、本スラリーは造粒用あるいはスラリー成形用
に連した均質なスラリーとなる。故に、成形法として
は、金型プレス法、ラバープレス法などのプレス成形
法、押出し法、シート法、持込み法などのスラリー成形
法を適用することができる。Therefore, by adding and mixing various ceramic powders and an inorganic silazane high polymer into such a solvent, it is possible to easily and uniformly disperse them as a binder in the ceramic powders. Here, since the inorganic silazane high polymer also acts as a peptizer (dispersant), the present slurry is a homogeneous slurry connected for granulation or slurry molding. Therefore, as a molding method, a press molding method such as a mold press method and a rubber press method, and a slurry molding method such as an extrusion method, a sheet method, and a carry-in method can be applied.
以上のようにして得られらた成形体を焼結すると、無
機シラザン高重合体は、熱分解し、水素が揮散し、活性
度の高いSiとＮがセラミックス粒子と反応し、焼結用バ
インダーとして作用し、粒子間を強固に結合する。ここ
で、この結合力は、熱分解収率の高いプレセラミックポ
リマーを用いる程、さらに、結合に関与しない過剰の炭
素を残存させないプレセラミックポリマーを用いる程強
固であるため、本質的に有機基を有することなく、熱分
解後、高純度なSi3N4組成となる無機シラザン高重合体
は、焼結用バインダーとして適したプレセラミックポリ
マーと言える。また、このSi3N4の形態は、通常、非晶
質あるいは1000Å以下という極めて小さな結晶粒子とい
う形でセラミックス粒子間を充てんするため、粒成量抑
制剤としての役割をも果す。When the molded body obtained as described above is sintered, the inorganic silazane high polymer is thermally decomposed, hydrogen is volatilized, and highly active Si and N react with the ceramic particles to form a binder for sintering. And strongly binds between the particles. Here, since the bonding strength is so strong that the preceramic polymer having a high thermal decomposition yield is used and further the preceramic polymer which does not leave an excess of carbon which does not participate in the bonding is used, the organic group essentially has an organic group. An inorganic silazane high polymer that does not have a high purity Si 3 N 4 composition after pyrolysis can be said to be a preceramic polymer suitable as a binder for sintering. In addition, since the form of Si 3 N 4 usually fills the space between ceramic particles in the form of amorphous or extremely small crystal particles of 1000 ° or less, it also serves as a granulation amount inhibitor.
以上の反応は、約400℃より始まり、約1500℃で完了
する。故に、Si3N4、SiCなどの非酸化物に代表される無
機焼結セラミックスにおいては、従来、1700℃以上とい
う高温焼結が行われてきたが、本発明によれば1300〜15
00℃程度で、比較的低密度であるにもかかわらず、機械
的特性に優れたセラミックス成形焼結体が得られる。The above reaction starts at about 400 ° C. and is completed at about 1500 ° C. Therefore, in the case of inorganic sintered ceramics represented by non-oxides such as Si 3 N 4 and SiC, conventionally, high-temperature sintering of 1700 ° C. or more has been performed.
At about 00 ° C., a ceramic molded sintered body having excellent mechanical properties despite relatively low density can be obtained.
また、無機シラザン高重合体の添加量は、目的とする
焼結体の特性、例えば、強度、密度、加工性などに応
じ、制限なく増減することが可能である。これは、従来
のプレセラミックポリマーと異なり、重合度をコントロ
ールすることにより、融解の度合いを低減し、多量添加
時においても成形体の軟化を防止することができるため
である。Further, the amount of the inorganic silazane high polymer added can be increased or decreased without limitation according to the properties of the target sintered body, for example, strength, density, workability, and the like. This is because, unlike the conventional preceramic polymer, by controlling the degree of polymerization, the degree of melting can be reduced, and the softening of the molded body can be prevented even when a large amount is added.
このようなバインダーを用いてセラミックスを成形す
るには、前記の如く、溶剤中にセラミックス粉末と無機
シラザン高重合体を添加し混合してスラリーを作成して
スラリー成形するか、あるいはこのスラリーから溶剤を
蒸発させて造粒粉を作成してプレス成形すればよい。In order to form ceramics using such a binder, as described above, a ceramic powder and an inorganic silazane high polymer are added to a solvent and mixed to form a slurry, and the slurry is formed. May be evaporated to form granulated powder and press-molded.
一例として、プレス法を適用するためには、スプレー
ドライヤーにより、スラリー中の溶剤を蒸発させ、造粒
粉とすればよい。このとき、無機ポリシラザンは、造粒
のための成形用バインダーとして働くと同時に、焼結体
バインダー（焼結助剤）として、セラミックス粉体中に
均一に混合されたことになる。このようにして得られた
造粒粉をプレス成形することにより、所定の形状の成形
体を得ることができる。また、スラリー成形法によれ
ば、造粒粉を経ずに直接成形用かつ焼結用バインダーが
均一に混合された成形体を得ることができる。As an example, in order to apply the pressing method, the solvent in the slurry may be evaporated by a spray dryer to form granulated powder. At this time, the inorganic polysilazane acts as a molding binder for granulation and, at the same time, is uniformly mixed in the ceramic powder as a sintered binder (sintering aid). By pressing the granulated powder thus obtained, a compact having a predetermined shape can be obtained. Further, according to the slurry molding method, it is possible to obtain a molded body in which a binder for molding directly and uniformly for sintering is uniformly mixed without passing through granulated powder.
なお、本発明では、無機シラザン高重合体を溶剤に溶
解した溶液にセラミックス成形体（焼結体）を浸漬し
て、成形体（焼結体）中に無機シラザン高重合体を含浸
したセラミックス成形体を焼成することによって、セラ
ミックス成形体（焼結体）を緻密化することも可能であ
る。In the present invention, the ceramic molded body (sintered body) is immersed in a solution in which the inorganic silazane high polymer is dissolved in a solvent, and the ceramic molded body (sintered body) is impregnated with the inorganic silazane high polymer. By firing the body, the ceramic molded body (sintered body) can be densified.
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
などが使用できる。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, aromatic hydrocarbon solvents, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene, aliphatic ethers, alicyclic ethers. And the like. Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, halogenated hydrocarbons such as ethylidene chloride, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-dioxyethane, dioxane , Dimethyldioxane, tetrahydrofuran, ethers such as tetrahydropyran, pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane,
Hydrocarbons such as cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene.
得られたセラミックス成形体を焼成して無機シラザン
高重合体をセラミックス化し、セラミックス成形焼結体
を得ることができる。焼成条件は真空中、不活性ガス、
還元性ガス、炭化水素ガスのうちから選ばれる少なくと
も１種からなる雰囲気中で600〜2300℃の温度範囲内で
加熱焼結する。The obtained ceramic molded body is fired to turn the inorganic silazane high polymer into ceramics, and a ceramic molded sintered body can be obtained. The firing conditions are vacuum, inert gas,
Heat sintering is performed within a temperature range of 600 to 2300 ° C. in an atmosphere composed of at least one selected from a reducing gas and a hydrocarbon gas.
こうして得られる焼結体は、用いたセラミックス粒子
あるいはウィスカーの間をポリシラザンが加熱分解して
生成した非晶質または1000Å以下の極めて微細な粒子に
よってうめられた組織となる。The sintered body obtained in this manner has a structure formed by amorphous or extremely fine particles of 1000 ° or less, which are generated by heating and decomposing polysilazane between the used ceramic particles or whiskers.
こうして、本発明によれば、プレセラミックポリマー
としてポリシラザンを選択し、かつ側鎖に有機基を有し
ないポリシラザンを選択することによって、低温焼成で
機械的性質及び化学的性質に優れたセラミックス成形焼
結体が得られる。Thus, according to the present invention, by selecting polysilazane as a preceramic polymer and selecting polysilazane having no organic group in the side chain, ceramic forming and sintering excellent in mechanical properties and chemical properties at low temperature firing. The body is obtained.
本発明の無機シラザン高重合体は、前記の如き分子構
造的及び物性的特徴を有するもので、種々の分野に利用
することができる。次に、本発明の無機シラザン高重合
体の用途的及び製法的特徴を示す。The inorganic silazane high polymer of the present invention has the molecular structural and physical characteristics as described above, and can be used in various fields. Next, the application and production characteristics of the inorganic silazane high polymer of the present invention will be described.
無機シラザン高重合体は、有機溶媒に可溶であり、
焼成して窒化ケイ素あるいは窒化ケイ素含有セラミック
スに変換できるため、高性能のセラミックス成形体すな
わち、高温機械強度が高く、耐熱性、耐食性、耐酸化
性、耐熱衝撃性に優れた連続繊維、フィルム、被覆膜を
容易に得ることができる。また、セラミックス収率が高
いので、焼結用結合剤、含浸剤等としての利用も可能で
ある。The inorganic silazane high polymer is soluble in an organic solvent,
Since it can be converted to silicon nitride or silicon nitride-containing ceramics by firing, it has a high-performance ceramic molded body, that is, continuous fibers, films, and coatings with high mechanical strength at high temperatures and excellent heat resistance, corrosion resistance, oxidation resistance, and thermal shock resistance. A covering film can be easily obtained. Further, since the ceramic yield is high, it can be used as a binder for sintering, an impregnating agent, and the like.
無機シラザン高重合体は、その重合体中に分解を促
進する残留触媒等の不純物の混入がないため、安定性が
向上し、取扱いが容易になり、その上高温焼成後のセラ
ミックスの純度が向上する。Inorganic silazane high polymer does not contain impurities such as residual catalyst that promotes decomposition in the polymer, so stability is improved, handling is easy, and the purity of ceramics after high temperature firing is improved. I do.
無機シラザン高重合体は、原料無機シラザンに比べ
て架橋構造、分子量が増加するため、凝固性が向上し、
常温ですみやかに賦形化することが可能となる。Since the inorganic silazane high polymer has a crosslinked structure and a higher molecular weight than the raw material inorganic silazane, the solidification property is improved,
Immediate shaping can be performed at room temperature.
遷移金属等の触媒を用いないため、生成物と触媒と
の分離工程を必要としない。Since a catalyst such as a transition metal is not used, a step of separating the product from the catalyst is not required.
重合体中に触媒が残存しないため、安定性が向上
し、溶媒を除き、単離後も長期保存が可能である。Since no catalyst remains in the polymer, stability is improved, and long-term storage is possible even after isolation except for the solvent.
高価で危険な触媒を使用しないため、低コストで安
全である。Since no expensive and dangerous catalyst is used, it is low-cost and safe.
高分子量のため、高温焼成時の蒸発損失が小さいの
で、セラミックス収率が向上する。Due to the high molecular weight, the evaporation loss during high-temperature firing is small, so that the ceramic yield is improved.
不純物の混入がないため、高温焼成後のセラミック
スの純度が向上する。Since no impurities are mixed, the purity of the ceramic after high-temperature firing is improved.
無機シラザン高重合体を紡糸する場合、紡糸助剤を
添加せずに連続紡糸が可能となる。When spinning an inorganic silazane high polymer, continuous spinning becomes possible without adding a spinning aid.
以下、実施例により本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
参考例 １ 内容積500ml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280ml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（SiH2Cl2・2C5H5N）が生成した。
反応混合物を氷冷し、撹拌しながら、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30.0gを吹
き込んだ。Reference Example 1 A gas blow-in tube, a mechanical stirrer, and a dewar condenser were installed in a four-necked flask having an inner volume of 500 ml. After the inside of the reactor was replaced with deoxygenated dry nitrogen, 280 ml of degassed dry pyridine was placed in a four-necked flask, and cooled with ice. Then, when 51.6 g of dichlorosilane was added, a white solid adduct (SiH 2 Cl 2 .2C 5 H 5 N) was formed.
The reaction mixture was ice-cooled, and 30.0 g of purified ammonia was blown through a sodium hydroxide tube and an activated carbon tube while stirring.
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濾過して、濾
液520mlを得た。濾液5mlから溶媒を減圧留去すると樹脂
状固体無機シラザン0.98gが得られた。After completion of the reaction, the reaction mixture was centrifuged, washed with dry pyridine, and then filtered under a nitrogen atmosphere to obtain 520 ml of a filtrate. The solvent was distilled off from 5 ml of the filtrate under reduced pressure to obtain 0.98 g of a resinous solid inorganic silazane.
得られたポリマーの数平均分子量はGPCにより測定し
たところ、1020であった。また、このポリマーのIR（赤
外吸収）スペクトル（溶媒：乾燥ｏ−キシレン；無機シ
ラザンの濃度:9.8g/）を検討すると、波数（cm-1）33
50及び1175のNHに基づく吸収;2170（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
すことが確認された。またこのポリマーの1HNMR（プロ
トン核磁気共鳴）スペクトル（60MHz,溶媒CDCl3/基準物
質TMS）を検討すると、いずれも幅広い吸収を示してい
ることが確認された。即ちδ4.8及び4.4（br,SiH）;1.5
（br,NH）の吸収が確認された。The number average molecular weight of the obtained polymer was 1020 as measured by GPC. When the IR (infrared absorption) spectrum of this polymer (solvent: dry o-xylene; concentration of inorganic silazane: 9.8 g /) is examined, the wave number (cm -1 ) 33
Absorptions based on NH of 50 and 1175; absorptions based on SiH of 2170 (ε = 3.14); absorptions based on SiH and SiNSi of 1020-820 were confirmed. When the 1 H NMR (proton nuclear magnetic resonance) spectrum (60 MHz, solvent CDCl 3 / standard substance TMS) of this polymer was examined, it was confirmed that each of them showed a broad absorption. That is, δ 4.8 and 4.4 (br, SiH); 1.5
(Br, NH) absorption was confirmed.
参考例 ２ 参考例１と同一の装置を用いて反応を行った。即ち、
参考例１で示した四つ口フラスコに脱気した乾燥ジクロ
ロメタン260mlを入れ、これを氷冷した。次にジクロロ
シラン25.0gを加えた。この溶液を氷冷し、撹拌しなが
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22.3gを窒素との混合ガスとして吹き込ん
だ。反応中ガス流路に粉霧が生成したので、ガス流路を
時々たたいて閉塞を防いだ。Reference Example 2 A reaction was carried out using the same apparatus as in Reference Example 1. That is,
260 ml of degassed dry dichloromethane was put into the four-necked flask shown in Reference Example 1, and this was cooled with ice. Next, 25.0 g of dichlorosilane was added. The solution was cooled on ice, and while stirring, 22.3 g of purified ammonia was blown through a sodium hydroxide tube and an activated carbon tube as a mixed gas with nitrogen. During the reaction, fog was generated in the gas flow path, so that the gas flow path was occasionally tapped to prevent blockage.
反応混合物を参考例１と同様処理すると、粘性油状無
機シラザンが4.9g得られた。得られたポリマーの数平均
分子量はGPCにより測定したところ620であった。When the reaction mixture was treated in the same manner as in Reference Example 1, 4.9 g of a viscous oily inorganic silazane was obtained. The number average molecular weight of the obtained polymer was 620 as measured by GPC.
参考例３ 参考例１と同一の装置を用いて反応を行なった。すな
わち参考例１で示した四つ口フラスコに脱気した乾燥ベ
ンゼン300mlを入れ、これを水冷した。次にジクロロシ
ラン24.0gを加えた。この溶液を水冷し、撹拌しなが
ら、水酸化ナトリウム管および活性炭管を通して精製し
たアンモニア23.8gを窒素との混合ガスとして吹き込ん
だ。反応中ガス流路に粉霧が生成したので、ガス流路を
時々たたいて閉塞を防いた。Reference Example 3 A reaction was carried out using the same apparatus as in Reference Example 1. That is, 300 ml of degassed dry benzene was placed in the four-necked flask shown in Reference Example 1, and this was cooled with water. Next, 24.0 g of dichlorosilane was added. This solution was cooled with water, and while stirring, 23.8 g of purified ammonia was blown through a sodium hydroxide tube and an activated carbon tube as a mixed gas with nitrogen. During the reaction, fine particles were formed in the gas flow path, so that the gas flow path was sometimes beaten to prevent clogging.
反応混合物を参考例１と同様に処理すると粘性油状無
機シラザンが3.1g得られた。得られたポリマーの数平均
分子量はGPCにより測定したところ360であった。When the reaction mixture was treated in the same manner as in Reference Example 1, 3.1 g of a viscous oily inorganic silazane was obtained. The number average molecular weight of the obtained polymer was 360 as measured by GPC.
実施例１ 参考例１で得られた無機シラザンのピリジン溶液（無
機シラザンの濃度,5.24重量％）100mlを内容積300mlの
耐圧反応容器に入れ、窒素雰囲気、密閉系で150℃で３
時間撹拌しながら反応を行なった。この間大量の気体が
発生した。反応前後で圧力は1.0kg/cm2上昇した。室温
に冷却後、乾燥エチルベンゼン200mlを加え、圧力３〜5
mmHg,温度50〜70℃で溶媒を除いたところ、4.68gの白色
粉末が得られた。この粉末は、トルエン，テトラヒドロ
フラン，クロロホルムおよびその多の有機溶媒に可溶で
あった。Example 1 100 ml of the pyridine solution of inorganic silazane (concentration of inorganic silazane, 5.24% by weight) obtained in Reference Example 1 was placed in a pressure-resistant reaction vessel having an internal volume of 300 ml, and was placed under a nitrogen atmosphere in a closed system at 150 ° C. for 3 hours.
The reaction was performed with stirring for hours. During this time, a large amount of gas was generated. The pressure increased by 1.0 kg / cm 2 before and after the reaction. After cooling to room temperature, 200 ml of dry ethylbenzene was added, and the pressure was 3-5.
After removing the solvent at mmHg and a temperature of 50 to 70 ° C., 4.68 g of a white powder was obtained. This powder was soluble in toluene, tetrahydrofuran, chloroform and many other organic solvents.
前記重合体粉末の数平均分子量は、GPCにより測定し
たところ2470であった。また、そのIRスペクトル（溶
媒：エチルベンゼン）の分析の結果、波数（cm-1）3350
および1175のNHに基づく吸収;2170のSiHに基づく吸収;1
020〜820のSiHおよびSiNSiに基づく吸収を示すことが確
認された。さらに、前記重合体粉末の1HNMRスペクトル
（CDCl3,TMS）を分析したところ、いずれも幅広い吸収
を示している。すなわちδ4.8（br,SiH2），δ4.4（br,
SiH3），δ1.5（br,NH）の吸収が観測された。（SiH2）
／（SiH3）＝4.1であった。The number average molecular weight of the polymer powder was 2,470 as measured by GPC. As a result of analyzing the IR spectrum (solvent: ethylbenzene), the wave number (cm −1 ) of 3350
And 1175 based on NH; 2170 based on SiH; 1
It was confirmed to show absorption based on SiH and SiNSi of 020-820. Further, when the 1 H NMR spectrum (CDCl 3 , TMS) of the polymer powder was analyzed, each of them showed a broad absorption. That is, δ4.8 (br, SiH 2 ), δ4.4 (br,
SiH 3 ) and δ1.5 (br, NH) were observed. (SiH 2)
/ (SiH 3 ) = 4.1.
実施例２ 参考例１で得られた無機シラザンのピリジン溶液（無
機シラザンの濃度,6.18重量％）200mlを内容積300mlの
耐圧反応容器に入れ、窒素雰囲気、密閉系で120℃で３
時間撹拌をしながら反応を行なった。この間大量の気体
が発生したが、ガスクロマトグラフィー（GC）測定によ
り、この気体は水素であった。反応前後における圧力上
昇は2.0kg/cm2であった。室温に冷却後、乾燥ｏ−キシ
レン400mlを加え、圧力３〜5mmHg、温度50〜70℃で溶媒
を除いたところ、白色粉末が10.9g得られ、この粉末は
有機溶媒に可溶であった。Example 2 200 ml of the pyridine solution of inorganic silazane (concentration of inorganic silazane, 6.18% by weight) obtained in Reference Example 1 was placed in a pressure-resistant reaction vessel having an internal volume of 300 ml, and was placed under a nitrogen atmosphere in a closed system at 120 ° C. for 3 hours.
The reaction was carried out with stirring for hours. During this time, a large amount of gas was generated, and the gas was hydrogen as determined by gas chromatography (GC). The pressure increase before and after the reaction was 2.0 kg / cm 2 . After cooling to room temperature, 400 ml of dry o-xylene was added, the solvent was removed at a pressure of 3 to 5 mmHg and a temperature of 50 to 70 ° C., to obtain 10.9 g of a white powder, which was soluble in an organic solvent.
前記重合体粉末の数平均分子量は、GPCにより測定し
たところ1950であった。The number average molecular weight of the polymer powder was 1,950 as measured by GPC.
得られた改質無機シラザン高重合体の元素分析結果は
次の通りであった。（重量％） Si:62.7,N:25.7,O:3.52,C:4.4,H:5.00 実施例３ 実施例２で得られた無機シラザン高重合体を窒素中で
1400℃まで昇温速度３℃／分で加熱し、３時間焼成する
ことで茶かっ色粉末を79.6重量％の収率で得た。得られ
たセラミックスの粉末Ｘ線回折測定を行なったところ、
２θ＝20.゜にα−Si3N4の（101）回折線,2θ＝22.9゜
にα−Si3N4の（110）回折線,2θ＝26.4゜にα−Si3N4
の（200）回折線,2θ＝30.9゜にα−Si3N4の（201）回
折線,2θ＝31.7゜にα−Si3N4の（002）回折線,2θ＝3
4.5゜にα−Si3N4の（102）回折線,2θ＝35.2゜にα−S
i3N4の（210）回折線,2θ＝38.8゜にα−Si3N4の（21
1）回折線,2θ＝39.4゜にα−Si3N4の（112）回折線、
２θ＝40.1゜にα−Si3N4の（300）回折線,2θ＝41.8゜
にα−Si3N4の（202）回折線,2θ＝43.4゜にα−Si3N4
の（301）回折線,2θ＝46.9゜にα−Si3N4の）220）回
折線,2θ＝48.2゜にα−Si3N4の（212）回折線,2θ＝4
8.8゜にα−Si3N4の（310）回折線，さらに２θ＝23.3
゜にβ−Si3N4の（110）回折線,2θ＝26.9゜にβ−Si3N
4の（200）回折線,2θ＝33.6゜にβ−Si3N4の（101）回
折線,2θ＝36.0゜にβ−Si3N4の（210）回折線,2θ＝4
1.4゜にβ−Si3N4の（201）回折線,2θ＝49.9゜にβ−S
i3N4の（310）回折線,2θ＝28.4゜にSiの（111）回折
線,2θ＝47.3゜にSiの（220）回折線が認められ、結晶
質の窒化珪素であることが確認された。Elemental analysis results of the obtained modified inorganic silazane high polymer were as follows. (% By weight) Si: 62.7, N: 25.7, O: 3.52, C: 4.4, H: 5.00 Example 3 The inorganic silazane high polymer obtained in Example 2 was dissolved in nitrogen.
The mixture was heated to 1400 ° C. at a heating rate of 3 ° C./min and calcined for 3 hours to obtain a brownish powder in a yield of 79.6% by weight. When the powder X-ray diffraction measurement of the obtained ceramics was performed,
2 [Theta] = 20. ° α-Si 3 N 4 in (101) diffraction line, the 2 [Theta] = 22.9 ° α-Si 3 N 4 (110 ) diffraction line, 2 [Theta] = 26.4 ° α-Si 3 N 4
(200) diffraction line of α-Si 3 N 4 at 2θ = 30.9 °, (002) diffraction line of α-Si 3 N 4 at 2θ = 31.7 °, 2θ = 3
(102) diffraction line of α-Si 3 N 4 at 4.5 °, α-S at 2θ = 35.2 °
(210) diffraction line of i 3 N 4 , α-Si 3 N 4 (21
1) Diffraction line, (112) diffraction line of α-Si 3 N 4 at 2θ = 39.4 °,
2 [Theta] = 40.1 ° α-Si 3 N 4 in (300) diffraction line, the 2 [Theta] = 41.8 ° α-Si 3 N 4 (202 ) diffraction line, 2 [Theta] = 43.4 ° α-Si 3 N 4
(301) diffraction line of α-Si 3 N 4 at 2θ = 46.9 ゜) 220) diffraction line of α-Si 3 N 4 at 2θ = 48.2 ゜, 2θ = 4
(310) diffraction line of α-Si 3 N 4 at 8.8 °, and 2θ = 23.3
Of DEG β-Si 3 N 4 (110 ) diffraction line, 2 [Theta] = 26.9 ° β-Si 3 N
4 (200) diffraction line, β-Si 3 N 4 (101) diffraction line at 2θ = 33.6 °, 2θ = 36.0 ° β-Si 3 N 4 (210) diffraction line, 2θ = 4
(201) diffraction line of β-Si 3 N 4 at 1.4 °, β-S at 2θ = 49.9 °
(310) diffraction line of i 3 N 4 , (111) diffraction line of Si at 2θ = 28.4 °, (220) diffraction line of Si at 2θ = 47.3 °, confirming that it is crystalline silicon nitride Was done.
この結晶質窒化珪素の元素分析結果は（重量％） Si:63.8,N:28.7,O:2.17,C:0.36,H:0.11 であった。 The results of elemental analysis of this crystalline silicon nitride were (% by weight): Si: 63.8, N: 28.7, O: 2.17, C: 0.36, H: 0.11.
実施例４ 参考例１で得られた無機シラザンのα−ピコリン溶液
（無機シラザンの濃度,5.86重量％）120mlを内容積300m
lの耐圧反応容器に入れ、窒素雰囲気、密閉系で120℃で
３時間撹拌しながら反応を行なった。この間大量の気体
が発生した。実施例２と同様に溶媒を減圧留去したとこ
ろ、無機シラザン高重合体の白色粉末が6.22g得られ
た。この粉末は有機溶媒に可溶であり、その数平均分子
量はGPCにより測定したところ1850であった。Example 4 120 ml of the α-picoline solution of the inorganic silazane obtained in Reference Example 1 (concentration of inorganic silazane, 5.86% by weight) was placed in an internal volume of 300 m.
The reaction mixture was placed in a pressure-resistant reaction vessel (1) and stirred at 120 ° C. for 3 hours in a closed system under a nitrogen atmosphere. During this time, a large amount of gas was generated. When the solvent was distilled off under reduced pressure in the same manner as in Example 2, 6.22 g of a white powder of an inorganic silazane high polymer was obtained. This powder was soluble in an organic solvent, and its number average molecular weight was 1,850 as measured by GPC.
実施例５ 参考例２で得られた無機シラザンのピリジン溶液（無
機シラザンの濃度,7.25重量％）100mlを内容積300mlの
耐圧反応容器に入れ、窒素雰囲気、密閉系で120℃で５
時間撹拌しながら反応を行なった。この間大量の気体が
発生した。実施例２と同様に溶媒を減圧留去すると、無
機シラザン高重合体の白色粉末が6.43g得られた。この
粉末は有機溶媒に可溶であり、その数平均分子量はGPC
により測定したところ、2030であった。Example 5 100 ml of the pyridine solution of inorganic silazane (concentration of inorganic silazane, 7.25% by weight) obtained in Reference Example 2 was placed in a pressure-resistant reaction vessel having an internal volume of 300 ml, and placed in a nitrogen atmosphere at 120 ° C. in a closed system under a closed atmosphere.
The reaction was performed with stirring for hours. During this time, a large amount of gas was generated. The solvent was distilled off under reduced pressure in the same manner as in Example 2 to obtain 6.43 g of a white powder of a high inorganic silazane polymer. This powder is soluble in organic solvents and its number average molecular weight is GPC
Was 2030.
実施例６ 参考例３で得られた無機シラザンのピリジン溶液（無
機シラザンの濃度,10.3重量％）100mlを内容積300mlの
耐圧反応容器に入れ、窒素雰囲気、密閉系で120℃で８
時間撹拌しながら反内を行なった。この間大量の気体が
発生した。実施例２と同様に溶媒を減圧留去したとこ
ろ、無機シラザン高重合体の白色粉末が9.15g得られ
た。この粉末は有機溶媒に可溶であり、そのGPCによる
数平均分子量は1880であった。Example 6 100 ml of the pyridine solution of inorganic silazane (concentration of inorganic silazane, 10.3% by weight) obtained in Reference Example 3 was placed in a pressure-resistant reaction vessel having an internal volume of 300 ml, and placed in a nitrogen atmosphere and a closed system at 120 ° C.
The inside was performed while stirring for an hour. During this time, a large amount of gas was generated. When the solvent was distilled off under reduced pressure in the same manner as in Example 2, 9.15 g of a white powder of an inorganic silazane high polymer was obtained. This powder was soluble in an organic solvent, and its number average molecular weight by GPC was 1,880.
実施例７ 実施例２で得られた無機シラザン高重合体を乾燥トル
エンに溶解し、82重量％の無機シラザン高重合体を含む
トルエン溶液を得た。これをノズルより加熱雰囲気中に
吐出させ、巻き取ることで無色透明の無機シラザン高重
合体連続繊維が得られた。Example 7 The inorganic silazane high polymer obtained in Example 2 was dissolved in dry toluene to obtain a toluene solution containing 82% by weight of the inorganic silazane high polymer. This was discharged from a nozzle into a heated atmosphere and wound up to obtain a colorless and transparent inorganic silazane high polymer continuous fiber.
実施例８ 実施例１の方法で製造した無機シラザン高重合体粉末
（数平均分子量2470）にオルトキシレン及び充填剤とし
て炭化珪素（平均粒子径約10ミクロン）を添加し、無機
シラザン45重量％、オルトキシレン25重量％及び炭化珪
素30重量％の溶液を調製した。これをSS41基盤（70mm×
30mm×1mmt）の表面にスプレーにて塗布した。基盤に塗
布した後不活性ガス（窒素）雰囲気の乾燥炉内で200
℃、１時間加熱乾燥した。昇温速度は３℃／分とした。
その結果厚み約160μｍの被膜を得た。被膜の性能を表
−１に示す。Example 8 Ortho-xylene and silicon carbide (average particle diameter of about 10 microns) were added to the inorganic silazane high polymer powder (number average molecular weight 2470) produced by the method of Example 1, and 45% by weight of inorganic silazane was added. A solution of 25% by weight of ortho-xylene and 30% by weight of silicon carbide was prepared. This is SS41 base (70mm ×
30 mm x 1 mmt) was applied by spraying. After coating on the substrate, dry in an inert gas (nitrogen) atmosphere
C. and dried by heating for 1 hour. The heating rate was 3 ° C./min.
As a result, a film having a thickness of about 160 μm was obtained. Table 1 shows the performance of the coating.
検査方法は以下に示す通りである。 The inspection method is as follows.
イ）外観：肉眼観察でクラック、色調、その他塗膜の欠
点を調べる。A) Appearance: Cracks, color tone, and other defects of the coating film are examined by visual observation.
ロ）鉛筆硬度:JIS K5400に準ずる。B) Pencil hardness: according to JIS K5400.
ハ）密着性（基盤剥離試験）：塗膜上に鋼ナイフで1mm
四方の素材に達する切れ目を基盤目に100個作り、その
上にセロハンテープ（積水化学工業）をはりつけた後、
そのセロハンテープを上方90゜の方向に強くひきはがし
た時に残っているます目の数で評価する。C) Adhesion (substrate peeling test): 1 mm with a steel knife on the coating film
After making 100 cuts at the base of the material on each side, gluing cellophane tape (Sekisui Chemical) on it,
The cellophane tape is evaluated by the number of squares remaining when the cellophane tape is strongly peeled upward in the direction of 90 °.
実施例９ 無機シラザン高重合体25重量％、オルトキシレン15重
量％、炭化珪素60重量％、助剤0.5重量％の溶液を調製
し、SUS304基盤に刷毛塗りにより塗布し窒素ガス雰囲気
下で00℃、１時間焼成したこと以外は実施例の方法と同
様に処理したところ被膜として表−１に示す結果を得
た。Example 9 A solution containing 25% by weight of an inorganic silazane high polymer, 15% by weight of ortho-xylene, 60% by weight of silicon carbide, and 0.5% by weight of an auxiliary agent was prepared, applied to a SUS304 substrate by brushing, and heated at 00 ° C. under a nitrogen gas atmosphere. Except for baking for 1 hour, the coating was treated in the same manner as in the example, to obtain a coating as shown in Table 1.
実施例10 無機シラザン高重合体90重量％及びオルトキシレン10
重量％の溶液を調製し、SUS304上に浸漬により塗布し、
空気中400℃、１時間焼成したこと以外は実施例８の方
法と同様に処理したところ被膜として表−１に示す結果
を得た。Example 10 90% by weight of an inorganic silazane high polymer and ortho-xylene 10
Weight% solution, apply by dipping on SUS304,
Except for baking in air at 400 ° C. for 1 hour, the coating was treated in the same manner as in Example 8 to obtain a coating as shown in Table 1.
実施例11 無機ポリシラザンを用いるかわりに、実施例１の無機
シラザン高重合体を用いる他は、実施例１と全く同様な
手法でSi3N4焼結体を得た。本焼結体のかさ密度は2.75g
/cm3、抗折強度は18.2kg/mm2であり、実施例１に比べ高
密度高強度の焼結体が得られた。 Example 11 A Si 3 N 4 sintered body was obtained in exactly the same manner as in Example 1, except that the inorganic silazane high polymer of Example 1 was used instead of using the inorganic polysilazane. The bulk density of this sintered body is 2.75 g
/ cm 3 , the transverse rupture strength was 18.2 kg / mm 2 , and a sintered body with higher density and higher strength was obtained than in Example 1.
実施例12 無機ポリシラザンを用いるかわりに無機シラザン高重
合体を用いる他は、実施例２と全く同様な手法でSiC焼
結体を得た。本焼結体のかさ密度は2.75g/cm2、抗折強
度は16.4kg/mm2であり、実施例２の結果を上まわった。Example 12 A SiC sintered body was obtained in exactly the same manner as in Example 2 except that an inorganic silazane high polymer was used instead of using inorganic polysilazane. The bulk density of this sintered body was 2.75 g / cm 2 , and the transverse rupture strength was 16.4 kg / mm 2 , surpassing the results of Example 2.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０８Ｇ 77/62 Ｃ０８Ｇ 77/62 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical indication // C08G 77/62 C08G 77/62
Claims (4)
子中のSiH3基とSiH2基の比（SiH2基/SiH3基）が2.5〜8.
4であって、しかも元素比率がSi:50重量％〜70重量％、
N:20重量％〜34重量％、H:5重量％〜９重量％である無
機シラザン高重合体。(1) The number average molecular weight is from 200 to 500,000, and the ratio of SiH 3 groups to SiH 2 groups in one molecule (SiH 2 groups / SiH 3 groups) is 2.5 to 8.
4, and the element ratio is 50: 70% by weight of Si:
N: 20 wt% to 34 wt%, H: 5 wt% to 9 wt%, an inorganic silazane high polymer.
合物を含む溶媒中で加熱することを特徴とする請求項
（１）記載の無機シラザン高重合体の製造方法。2. The method for producing a high inorganic silazane polymer according to claim 1, wherein the inorganic silazane is heated in a basic solvent or a solvent containing a basic compound.
を必須成分としたコーティング剤。3. A coating agent comprising the inorganic silazane high polymer according to claim 1 as an essential component.
を必須成分とするバインダー。4. A binder comprising the inorganic silazane high polymer according to claim 1 as an essential component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63074918A JP2613787B2 (en) | 1987-08-13 | 1988-03-29 | Inorganic silazane high polymer, production method thereof and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20276587 | 1987-08-13 | ||
| JP62-202765 | 1987-08-13 | ||
| JP63074918A JP2613787B2 (en) | 1987-08-13 | 1988-03-29 | Inorganic silazane high polymer, production method thereof and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01138108A JPH01138108A (en) | 1989-05-31 |
| JP2613787B2 true JP2613787B2 (en) | 1997-05-28 |
Family
ID=26416080
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|---|---|---|---|
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| JP (1) | JP2613787B2 (en) |
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