JP3136412B2 - Resin molding having cured polysilazane film and method for producing the same - Google Patents
Resin molding having cured polysilazane film and method for producing the sameInfo
- Publication number
- JP3136412B2 JP3136412B2 JP02413273A JP41327390A JP3136412B2 JP 3136412 B2 JP3136412 B2 JP 3136412B2 JP 02413273 A JP02413273 A JP 02413273A JP 41327390 A JP41327390 A JP 41327390A JP 3136412 B2 JP3136412 B2 JP 3136412B2
- Authority
- JP
- Japan
- Prior art keywords
- inorganic polysilazane
- coating
- resin
- inorganic
- film
- 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.)
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Description
【０００１】[0001]
【技術分野】本発明は、無機ポリシラザン硬化被膜を表
面に有する樹脂成形体及びその製造方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a resin molded article having a cured inorganic polysilazane film on its surface and a method for producing the same.
【０００２】[0002]
【従来技術及びその問題点】樹脂成形体表面を改質する
ために、その樹脂表面に、α−アルミナや二酸化ケイ素
等の金属酸化物を含む被膜を形成することは知られてい
る（特開昭６１−２８１１３３号、特開昭６３−１１４
９５７号、特開昭６３−３０１２６７号、特開平２−２
０６６２４号等）。樹脂表面にこのような金属酸化物含
有被膜を形成することによって耐擦傷性、耐摩耗性等の
性状において改善された表面が得られるが、無機ガラス
表面等の無機質表面に比べると未だ十分なものとは言え
ない。2. Description of the Related Art It is known to form a film containing a metal oxide such as α-alumina or silicon dioxide on the surface of a resin in order to modify the surface of the resin molded product (Japanese Patent Application Laid-Open (JP-A) No. 2002-282686). JP-A-61-281133, JP-A-63-114
957, JP-A-63-301267, JP-A 2-2
No. 06624). By forming such a metal oxide-containing coating on the resin surface, a surface with improved properties such as scratch resistance and abrasion resistance can be obtained, but it is still sufficient compared to inorganic surfaces such as inorganic glass surfaces. It can not be said.
【０００３】また、樹脂成形体表面を改質するために、
イオンプレーティング等のＰＶＤ法により二酸化ケイ素
被膜を樹脂表面に形成する方法も知られているが、この
場合、二酸化ケイ素被膜の密着性が十分ではなく、剥離
やクラックが生じるという問題がある。In order to modify the surface of a resin molded product,
A method of forming a silicon dioxide film on a resin surface by a PVD method such as ion plating is also known, but in this case, there is a problem that the adhesion of the silicon dioxide film is not sufficient, and peeling or cracking occurs.
【０００４】[0004]
【発明の課題】本発明は、従来の樹脂表面改質技術に見
られる前記問題点を解決し、耐擦傷性、耐摩耗性及び耐
薬品性にすぐれた被膜を有する樹脂成形体及びその製造
方法を提供することをその課題とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems found in the conventional resin surface modification technology, and provides a resin molded article having a coating excellent in scratch resistance, abrasion resistance and chemical resistance, and a method for producing the same. Is to provide
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.
【０００６】即ち、本発明によれば、下記構造式（１） That is, according to the present invention, the following structural formula (1)
【化１】 で表される繰り返し単位を有し数平均分子量が９８０〜
１００，０００の無機ポリシラザンを１００〜２００℃
で熱処理又は電子線処理して得られるＳｉ−Ｎ−Ｏ結合
を有する無機ポリシラザン硬化被膜を表面の少なくとも
一部に有する樹脂成形体、特に該樹脂成形体の形状がフ
ィルムである樹脂成形体が提供される。Embedded image And having a number average molecular weight of 980 to 980.
100-200 ° C of 100,000 inorganic polysilazane
-N-O bond obtained by heat treatment or electron beam treatment
An inorganic polysilazane cured film having
The shape of the resin molding, particularly the shape of the resin molding
A resin molded article that is a film is provided.
【０００７】また、本発明によれば、樹脂成形体の表面
の少なくとも一部に下記構造式（１） Further, according to the present invention, the surface of the resin molded article is provided.
Has at least a part of the following structural formula (1)
【化２】 で表される繰り返し単位を有し数平均分子量が９８０〜
１００，０００の無機ポリシラザンの被膜を形成する工
程と、この無機ポリシラザン被膜を有する樹脂成形体を
１００〜２００℃で熱処理又は電子線処理する工程から
なるＳｉ−Ｎ−Ｏ結合を有する無機ポリシラザン硬化被
膜を有する樹脂成形体の製造方法が提供される。Embedded image And having a number average molecular weight of 980 to 980.
Process to form 100,000 inorganic polysilazane coating
And a resin molded article having this inorganic polysilazane coating.
From the step of heat treatment or electron beam treatment at 100-200 ° C
Cured inorganic polysilazane having Si-NO bond
A method for producing a resin molded article having a film is provided.
【０００８】さらに、本発明によれば、樹脂シートの表
面の少なくとも一部に下記構造式（１） Further, according to the present invention, the surface of the resin sheet
At least a part of the surface has the following structural formula (1)
【化３】 で表される繰り返し単位を有し数平均分子量が９８０〜
１００，０００の無機ポリシラザンの被膜を形成する工
程と、この無機ポリシラザン被膜を有する樹脂シートを
成形加工する工程と、この成形加工した成形体を１００
〜２００℃で熱処理又は電子線処理する工程からなるＳ
ｉ−Ｎ−Ｏ結合を有する無機ポリシラザン硬化被膜を有
する樹脂成形体の製造方法が提供される。なお、本明細
書で言う無機ポリシラザンの硬化被膜とは、無機ポリシ
ラザンの被膜を加熱処理又は電子線処理してセラミック
ス化させる際に、そのセラミック化の過程で生じる水素
及び/又は炭素を分子中に含有する耐熱性の無機ポリシ
ラザン硬化体からなる被膜を意味する。Embedded image And having a number average molecular weight of 980 to 980.
Process to form 100,000 inorganic polysilazane coating
And a resin sheet having this inorganic polysilazane coating.
Forming step, and forming the formed body by 100
S comprising a step of heat treatment or electron beam treatment at ~ 200 ° C
Inorganic polysilazane cured coating having i-N-O bond
The present invention provides a method for producing a molded resin article . Note that the cured coating of the inorganic polysilazane in the present specification, a coating of inorganic policy <br/> Razan heat treatment or electron beam treatment to the time of the ceramic of the hydrogen and / or generated in the course of its ceramization It means a coating made of a heat-resistant inorganic polysilazane cured product containing carbon in the molecule.
【０００９】本発明において用いられる無機ポリシラザ
ンとしては、従来公知の各種の無機ポリシラザンが使用
できるが、好ましくは以下のような無機ポリシラザンが
挙げられる。 （１）構造式[0009] As the inorganic Porishiraza <br/> emissions used in the present invention is conventionally known various inorganic polysilazane can be used, with preference given to inorganic polysilazane as follows. (1) Structural formula
【化４】 の繰り返し単位を有する数平均分子量が９８０〜５０，
０００の環状無機ポリシラザン、鎖状無機ポリシラザン
又はこれらの混合物（特開昭５９−２０７８１２号）。 （２）原料として上記の如き無機ポリシラザン又はＡ．
Ｓｔｏｃｋ，Ｂｅｒ，５４，ｐ７４０（１９２１）、
Ｗ．Ｍ．Ｓｃａｎｔｌｉｎ，ＩｎｏｒｇａｎｉｃＣｈｅ
ｍｉｓｔｒｙ，１１（１９７２）、Ａ．ＳｅｙＦｅｒｔ
ｈ，米国特許第４，３９７，３２８号明細書等により開
示された無機シラザン重合体をトリアルキルアミンの如
き第３級アミン類、立体障害性の基を有する第２級アミ
ン類、フォスフィン等の如き塩基性化合物を溶媒とする
か又はこれを非塩基性溶媒、例えば、炭化水素類に添加
し−７８℃〜３００℃で加熱し脱水素縮合反応を行わせ
ることにより得られる数平均分子量９８０〜１００，０
００の高重合体（特開平１−１３８１０８号）。Embedded image Having a repeating unit of the number average molecular weight of 980 to 50,
000 cyclic inorganic polysilazane, chain inorganic polysilazane or a mixture thereof (JP-A-59-207812). (2) Inorganic polysilazane as described above or A.I.
Stock, Ber, 54, p740 (1921),
W. M. Scantlin, InorganicChe
mystry, 11 (1972); SeeFert
h. The inorganic silazane polymers disclosed in US Pat. No. 4,397,328 and the like can be used to prepare tertiary amines such as trialkylamines, secondary amines having sterically hindered groups, phosphines, etc. Such a basic compound as a solvent or a non-basic solvent such as a hydrocarbon is added to a hydrocarbon and heated at −78 ° C. to 300 ° C. to carry out a dehydrocondensation reaction to obtain a number average molecular weight of 980 to 980 . 100,0
00 high polymer (JP-A-1-138108).
【００１０】（３）無機ポリシラザンの改質反応により
得られる重合体で架橋結合−ＮＨ−又は−ＮＨ−ＮＨ−
を有し、ケイ素原子に結合する窒素とケイ素との原子比
（Ｎ／Ｓｉ）が０．８以上で数平均分子量が９８０〜１
００，０００のもの。この改質無機ポリシラザンはアン
モニア又はヒドラジンを使用してポリシラザンの脱水素
縮合反応を行わせることにより製造することができる
（特開平１−１３８１０７号）。(3) A polymer obtained by a modification reaction of an inorganic polysilazane, which is a cross-linked -NH- or -NH-NH-
Having an atomic ratio (N / Si) of nitrogen to silicon bonded to a silicon atom of 0.8 or more and a number average molecular weight of 980 to 1
The thing of 00,000. This modified inorganic polysilazane can be produced by carrying out a dehydrocondensation reaction of polysilazane using ammonia or hydrazine (JP-A-1-138107).
【００１１】前記した各種のポリシラザンは、その種類
に応じて、常温で液状〜固体状を示す。本発明において
用いる無機ポリシラザンは、樹脂との密着性の点では、
ケイ素や窒素に直結する活性水素含有割合の高いものの
使用が好ましく、一般的には、ケイ素原子と窒素原子と
の合計原子数１００に対し、９０以上、好ましくは１０
０〜１５２の活性水素原子を有するものの使用が有利で
ある。The above-mentioned various polysilazanes exhibit a liquid to solid state at room temperature, depending on the type. Inorganic polysilazane used in the present invention, in terms of adhesion to the resin,
It is preferable to use those having a high content of active hydrogen directly linked to silicon or nitrogen, and generally 90 or more, preferably 10 or more, based on 100 in total of silicon atoms and nitrogen atoms.
The use of those having from 0 to 152 active hydrogen atoms is advantageous.
【００１２】本発明の無機ポリシラザンの硬化被膜を有
する樹脂成形体を製造するには、前記無機ポリシラザン
をコーティング材料として用い、これを樹脂成形体表面
にコーティングし、その樹脂表面に無機ポリシラザン被
膜を形成した後、これを加熱処理又は電子線処理する。
無機ポリシラザンが液状のものであれば、これを樹脂表
面にコーティングした後、空気や、不活性ガス（例えば
Ｎ2、アルゴン等）、還元性ガス（例えばアンモニア、
ヒドラジン等）または真空の雰囲気下において、常温か
らその樹脂の溶融点又は分解点の間の温度、通常、８０
〜２００℃の温度に一定時間保持する。これによって、
架橋化された固体状無機ポリシラザンからなる被膜が得
られる。また、ポリシラザンが固体状（粉末状）のもの
であれば、これを有機溶媒に溶解し、この溶液を樹脂表
面にコーティングし、使用した有機溶媒を蒸発除去して
固体状の無機ポリシラザン被膜とすることができる。In order to produce a resin molded article having a cured coating of inorganic polysilazane of the present invention, the above-mentioned inorganic polysilazane is used as a coating material, this is coated on the surface of the resin molded article, and an inorganic polysilazane coating is formed on the resin surface. After that, it is subjected to heat treatment or electron beam treatment.
If the inorganic polysilazane is in a liquid state, it is coated on a resin surface and then air, an inert gas (eg, N 2 , argon, etc.), a reducing gas (eg, ammonia,
Hydrazine) or a vacuum atmosphere, at a temperature between room temperature and the melting point or decomposition point of the resin, usually 80
Hold at a temperature of 200 ° C. for a certain time. by this,
A coating consisting of crosslinked solid inorganic polysilazane is obtained. If the polysilazane is solid (powder), it is dissolved in an organic solvent, this solution is coated on the resin surface, and the used organic solvent is removed by evaporation to form a solid inorganic polysilazane film. be able to.
【００１３】無機ポリシラザンを含むコーティング材料
には、有機アミンやカルボン酸無水物、イソシアネー
ト、チオール、カルボキシイミド、金属アルコキシド、
金属ハロゲン化物等の硬化剤を添加することができ、ま
た金属粉末やセラミックス粉末、例えば金属の窒化物
や、酸化物、炭化物等を適量添加することもできるし、
さらにチタン酸アルミニウムやシリコン樹脂を適量添加
することができる。[0013] Coating materials containing inorganic polysilazane include organic amines, carboxylic anhydrides, isocyanates, thiols, carboximides, metal alkoxides,
A curing agent such as a metal halide can be added, and a metal powder or a ceramic powder, for example, a metal nitride, an oxide, or a carbide can be added in an appropriate amount.
Further, an appropriate amount of aluminum titanate or silicon resin can be added.
【００１４】無機ポリシラザン被膜の加熱処理は、前記
した空気、不活性ガス、還元性ガスまたは真空の雰囲気
下において、１００℃以上の温度で行われる。この場
合、昇温速度は１００℃／分以下、好ましくは２０℃／
分以下である。加熱温度の上限は、その樹脂の溶融点又
は分解点である。加熱処理により無機ポリシラザン被膜
は硬化被膜に変換される。本発明で用いる無機ポリシラ
ザンの特性について述べると、このものは、一般的に
は、空気又は酸素雰囲気下で加熱処理すると、酸素の作
用により無機ポリシラザンの縮合又は分解が促進され、
温度１００〜３００℃程度の加熱では水素及び／又は炭
素を含む硬化体が生成され、約３００℃を超える加熱で
は水素や炭素を実質上含まないセラミックスが形成され
る。一方、不活性ガスや還元性雰囲気下での加熱におい
ては、１００〜５００℃程度までの加熱では、無機ポリ
シラザンの脱水素縮合が主として起り、水素及び／又は
炭素を含む硬化体が生成され、それ以上の温度では、無
機ポリシラザンの分解が主として起り、セラミックスが
形成される。The heat treatment of the inorganic polysilazane film is carried out at a temperature of 100 ° C. or more in the above-mentioned atmosphere of air, inert gas, reducing gas or vacuum. In this case, the heating rate is 100 ° C./min or less, preferably 20 ° C./min.
Minutes or less. The upper limit of the heating temperature is the melting point or decomposition point of the resin. The heat treatment converts the inorganic polysilazane coating into a cured coating. Regarding the characteristics of the inorganic polysilazane used in the present invention, generally, when heat treatment is performed in an air or oxygen atmosphere, the condensation or decomposition of the inorganic polysilazane is promoted by the action of oxygen,
Heating at a temperature of about 100 to 300 ° C. produces a cured product containing hydrogen and / or carbon, and heating above about 300 ° C. forms ceramics substantially free of hydrogen and carbon. On the other hand, in the heating under an inert gas or a reducing atmosphere, when heating to about 100 to 500 ° C., dehydrocondensation of inorganic polysilazane mainly occurs, and the cured product containing hydrogen and / or carbon is hardened. At higher temperatures, no
Degradation of the machine polysilazane occurs primarily ceramic is formed.
【００１５】樹脂成形品には、フィルム、シート、トレ
ー、容器、中空体、ブロック等の各種の形状のものが包
含される。また、その成形品を構成する樹脂としては、
その軟化点が１００℃以上、好ましくは１３０℃以上の
ものが用いられる。このような樹脂としては、例えば、
ポリカーボネート、ポリイミド、フェノール樹脂、ポリ
エーテルエーテルケトン、ポリブチレンテレフタレー
ト、ポリエーテルスルホン、ポリフェニレンエーテル、
ポリフェニレンサルファイド、エポキシ樹脂、ナイロ
ン、ポリプロピレン等が挙げられる。The resin molded product includes various shapes such as a film, a sheet, a tray, a container, a hollow body, and a block. In addition, as a resin constituting the molded product,
Those having a softening point of 100 ° C. or higher, preferably 130 ° C. or higher are used. As such a resin, for example,
Polycarbonate, polyimide, phenolic resin, polyetheretherketone, polybutyleneterephthalate, polyethersulfone, polyphenyleneether,
Examples include polyphenylene sulfide, epoxy resin, nylon, and polypropylene.
【００１６】無機ポリシラザンを電子線処理する場合、
その電子線発生装置としては、（株）アイ・エレクトロ
ンビーム ＥＬＥＣＴＯＲＯＣＵＲＴＡＩＮ ＴＹＰ
Ｅ：ＣＢ １７５／１５／１８０Ｌ等が用いられる。When the inorganic polysilazane is subjected to electron beam treatment,
As the electron beam generator, I-Electron Beam ELECTROCURTAIN TYP
E: CB 175/15 / 180L or the like is used.
【００１７】樹脂成形体表面に対する無機ポリシラザン
被膜の形成方法としては、従来公知の各種の塗布方法、
例えば、浸漬法やスプレー法等の方法が挙げられる。ま
た、本発明においては、あらかじめ形成した無機ポリシ
ラザンフィルムを樹脂成形体表面に熱圧着させる方法も
採用可能である。As a method for forming the inorganic polysilazane coating on the surface of the resin molded product, various conventionally known coating methods,
For example, a method such as an immersion method or a spray method can be used. Further, in the present invention, a method of thermocompression bonding an inorganic polysilazane film formed in advance to the surface of a resin molded product can also be adopted.
【００１８】本発明による無機ポリシラザンの硬化被膜
を有する樹脂成形体を得る方法としては、無機ポリシラ
ザンの被膜を有する樹脂シートを成形材料として用い、
これを所要形状に加工した後、熱処理や電子線処理する
方法や、無機ポリシラザン被膜を有する樹脂シートを加
熱処理や電線処理した後、所要形状に加工する方法等が
ある。被膜の加工性を考えると、無機ポリシラザン被膜
を有する樹脂シートを所要形状に加工した後、加熱処理
又は電子線処理する方法が好ましい。[0018] As a method of obtaining a resin molded article having a cured coating of the inorganic polysilazane according to the present invention, a resin sheet having an inorganic Porishira <br/> disilazane film as a molding material,
After processing this into a required shape, there is a method of performing a heat treatment or an electron beam treatment, or a method of subjecting a resin sheet having an inorganic polysilazane coating to a heat treatment or an electric wire treatment and then processing the resin sheet into a required shape. Considering the processability of the coating, it is preferable to process the resin sheet having the inorganic polysilazane coating into a required shape, and then perform a heat treatment or an electron beam treatment.
【００１９】[0019]
【発明の効果】本発明において、コーティング材料とし
て用いる無機ポリシラザンは、そのケイ素原子や窒素原
子に結合する水素原子が活性水素として作用することか
ら、樹脂との接着性に非常にすぐれたものである。ま
た、このポリシラザンを熱処理や電子線処理により硬化
させたものの樹脂に対する密着強度も非常に大きなもの
となり、耐久性にすぐれた被膜を与える。本発明で用い
る無機ポリシラザンは、その熱処理や電子線処理によ
り、脱水素縮合して架橋化されて硬質の硬化体となり、
最終的にはセラミックスとなる。従って、樹脂表面上の
被膜の性状は、その熱処理や電子線処理の条件によって
調節することができる。耐熱性、耐食性、耐摩耗性、耐
擦傷性にすぐれた硬化被膜とするには、水素や炭素含有
率ができるだけ小さな被膜、例えば、水素と炭素の合計
含有率が５重量％以下、好ましくは、０．２〜２重量％
の被膜とするのがよい。硬化被膜の厚さは、通常、０．
１〜１００μｍ、好ましくは０．５〜５０μｍである。According to the present invention, the inorganic polysilazane used as a coating material has a very good adhesiveness to a resin because a hydrogen atom bonded to a silicon atom or a nitrogen atom acts as active hydrogen. . Further, although the polysilazane is cured by heat treatment or electron beam treatment, the adhesion strength to the resin is also very large, and a film having excellent durability is provided. The inorganic polysilazane used in the present invention is dehydrogenatively condensed and crosslinked to form a hard cured product by heat treatment or electron beam treatment,
Eventually it will be ceramics. Therefore, the properties of the coating on the resin surface can be adjusted by the conditions of the heat treatment and the electron beam treatment. In order to form a cured film having excellent heat resistance, corrosion resistance, abrasion resistance, and scratch resistance, a film having as small a content of hydrogen and carbon as possible, for example, a total content of hydrogen and carbon of 5% by weight or less, preferably 0.2-2% by weight
It is good to make a film of. The thickness of the cured coating is usually 0.
It is 1 to 100 μm, preferably 0.5 to 50 μm.
【００２０】本発明で用いる無機ポリシラザンの硬化被
膜は、収縮が少なく、ワレ発生の極めて少ないもので、
かつ緻密なものであることから、ピンホールの発生の殆
んどないものである。The cured film of the inorganic polysilazane used in the present invention has a small shrinkage and an extremely small crack generation.
In addition, since it is dense, there is almost no occurrence of pinholes.
【００２１】[0021]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００２２】参考例１ 内容積１０ ｌの四つ口フラスコにガス吹込み管、メカ
ニカルスターラー、ジュ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５ ｌを入れ、これを氷
冷した。次に、ジクロロシラン５１６ｇを加えると白色
固体状のアダクト（ＳｉＨ2Ｃｌ2・２Ｃ5Ｈ 5 Ｎ）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５１
０ｇを吹込んだ。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、さらに窒素雰囲
気下で濾過して、濾液８．５ ｌを得た。得られた無機
ポリシラザンの数平均分子量はＧＰＣにより測定したと
ころ、９８０であった。Reference Example 1 A four-necked flask having an internal volume of 10 l was equipped with a gas injection tube, a mechanical stirrer, and a jug condenser. After the inside of the reactor was replaced with deoxygenated dry nitrogen, 5 l of degassed dry pyridine was placed in a four-necked flask and cooled with ice. Next, when 516 g of dichlorosilane was added, a white solid adduct (SiH 2 Cl 2 .2C 5 H 5 N) was formed. The reaction mixture was cooled on ice and, with stirring, purified ammonia 51 through a sodium hydroxide tube and an activated carbon tube.
0 g was blown. After completion of the reaction, the reaction mixture was centrifuged, washed with dry pyridine, and then filtered under a nitrogen atmosphere to obtain 8.5 l of a filtrate. The number average molecular weight of the obtained inorganic polysilazane was 980 as measured by GPC.
【００２３】参考例２ 参考例１で得られた無機ポリシラザンのピリジン溶液
（無機ポリシラザン濃度：６．２％）２００ｍｌを内容
積５００ｍｌの耐圧反応容器に入れ、窒素雰囲気、密閉
系で１２５℃で３時間撹拌しながら反応を行った。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測
定により、この気体は水素であることが確認された。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１１ｇ得られ、この粉末は有機溶媒に可
溶であった。この重合体粉末の数平均分子量は２２０
０、Ｓｉ／Ｎ比は１．２９であった。Reference Example 2 200 ml of the pyridine solution (inorganic polysilazane concentration: 6.2%) of the inorganic polysilazane obtained in Reference Example 1 was placed in a pressure-resistant reaction vessel having an internal volume of 500 ml, and was placed in a nitrogen atmosphere in a closed system at 125 ° C. for 3 hours. The reaction was performed with stirring for hours. During this period, a large amount of gas was generated, and gas chromatography confirmed that this gas was hydrogen. 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 11 g of a white powder, which was soluble in an organic solvent. The number average molecular weight of this polymer powder was 220
0 and the Si / N ratio was 1.29.
【００２４】参考例３ 参考例１で得られた無機ポリシラザンのピリジン溶液
（無機ポリシラザン濃度：６．２％）１００ｍｌを内容
積５００ｍｌのエバポレーターに入れ、乾燥ｏ−キシレ
ン３００ｍｌを加え、圧力３〜５ｍｍＨｇ、温度５０〜
７０℃で溶媒を除いたところ、６ｇの液状の無機ポリシ
ラザンが得られた。Reference Example 3 100 ml of the pyridine solution (inorganic polysilazane concentration: 6.2%) of the inorganic polysilazane obtained in Reference Example 1 was placed in an evaporator having an internal volume of 500 ml, and 300 ml of dry o -xylene was added thereto, and the pressure was 3 to 5 mmHg. , Temperature 50 ~
After removing the solvent at 70 ° C., 6 g of a liquid inorganic polysilazane was obtained.
【００２５】実施例１ 参考例２で得た無機シラザン高重合体の２０ｗｔ％ｏ−
キシレン溶液中に、厚さ５ｍｍのポリイミド樹脂基板を
浸漬した後、乾燥し、次いで２００℃で１時間大気中で
熱処理することにより、無色透明なＳｉ−Ｎ−Ｏ結合を
有する無機ポリシラザン硬化被膜（厚さ：約１μｍ）を
その基板表面に形成した。この被膜はピンホールやクラ
ックのない極めて緻密なものであった。この被膜の形成
された基板の硬度をマイクロビッカース硬度計（荷重：
１０ｇ）により測定した結果、７３ｋｇｆ／ｍｍ2であ
り、ポリイミド樹脂基板の硬度が３５ｋｇ／ｍｍ2であ
るのに比べて、表面硬度が著しく増大したことが確認さ
れた。また、前記のようにして得られた無機ポリシラザ
ン硬化被膜を有するポリイミド樹脂基板について、その
被膜密着性を、ＪＩＳ Ｄ−０２０２に準じたクロスカ
ットテープ試験法により調べたところ、１００／１００
の結果が得られ、すぐれた密着性を有することが確認さ
れた。さらに、その被膜を有する基板表面の鉛筆硬度
（荷重：１００ｇ）を調べたところ、９Ｈ以上であるこ
とが確認され、さらにまたその耐擦傷性を調べたとこ
ろ、表面には何らの異常もなく、すぐれた耐擦傷を有す
ることが確認された。なお、前記耐擦傷性は、スチール
ウールで基板の被膜面を１０回擦った後のその被膜面の
状態を目視により観察することで行った。Example 1 20 wt% o- of the inorganic silazane high polymer obtained in Reference Example 2
A 5 mm-thick polyimide resin substrate is immersed in a xylene solution, dried, and then heat-treated at 200 ° C. for 1 hour in the air to form a cured inorganic polysilazane film having a colorless and transparent Si—N—O bond ( (Thickness: about 1 μm) was formed on the substrate surface. This film was extremely dense without pinholes or cracks. The hardness of the substrate on which this coating was formed was measured using a micro Vickers hardness tester (load:
10 g), it was 73 kgf / mm 2 , and it was confirmed that the surface hardness was significantly increased as compared with the case where the hardness of the polyimide resin substrate was 35 kg / mm 2 . Further, with respect to the polyimide resin substrate having the cured inorganic polysilazane film obtained as described above, the film adhesion was examined by a cross-cut tape test method according to JIS D-0202. / 100
Was obtained, and it was confirmed that the composition had excellent adhesion. Furthermore, when the pencil hardness (load: 100 g) of the surface of the substrate having the coating was examined, it was confirmed that the hardness was 9H or more. Further, when the scratch resistance was examined, there was no abnormality on the surface. It was confirmed to have excellent scratch resistance. The scratch resistance was determined by visually observing the state of the coating surface after rubbing the coating surface of the substrate 10 times with steel wool.
【００２６】実施例２ 参考例３で得られた液状無機ポリシラザンを塗布液とし
て用い、スピンコーターにより、厚さ５ｍｍのポリカー
ボネート基板に塗布し、乾燥後、１３０℃で１時間、大
気中で熱処理し、Ｓｉ−Ｎ−Ｏ結合を有する無色透明な
無機ポリシラザン硬化被膜を形成した。この被膜の膜厚
は約０．５μｍであり、この被膜はピンホールやクラッ
クのない極めて緻密なものであった。このようにして得
られた無機ポリシラザン硬化被膜を有するポリカーボネ
ート基板について、その表面性状を調べたところ、次の
結果が得られた。 耐薬品性：２００回以上 密着性 ：１００／１００ 鉛筆硬度：７Ｈ 耐擦傷性：良好 なお、耐薬品性は、キシレン払拭試験により基板表面に
異常が生じるまで払拭した時のその払拭回数で示した。Example 2 The liquid inorganic polysilazane obtained in Reference Example 3 was used as a coating solution, applied to a 5 mm-thick polycarbonate substrate by a spin coater, dried, and then heat-treated at 130 ° C. for 1 hour in the air. , Transparent and colorless having a Si-NO bond
An inorganic polysilazane cured film was formed. The thickness of this coating was about 0.5 μm, and this coating was extremely dense without pinholes or cracks. The surface properties of the thus obtained polycarbonate substrate having an inorganic polysilazane cured film were examined, and the following results were obtained. Chemical resistance: 200 times or more Adhesion: 100/100 Pencil hardness: 7H Scratch resistance: good In addition, chemical resistance was indicated by the number of times of wiping until an abnormality occurred on the substrate surface in a xylene wiping test. .
【００２７】比較例１ 特開平２−２０６６２４号に記載の方法に従って、厚さ
５ｍｍのポリカーボネート基板上に、先ず樹脂被膜を形
成し、その上に二酸化ケイ素被膜を形成した。この場
合、樹脂被膜は、無水マレイン酸とＰ−アミノスチレン
との共重合体からなるもので、その厚さは約１μｍであ
る。このようにして得られた二酸化ケイ素被膜を有する
ポリカーボネート基板について、その表面性状を調べた
ところ、次の結果が得られた。 耐薬品性：８３回 密着性 ：１００／１００ 鉛筆硬度：６Ｈ 耐擦傷性：良好Comparative Example 1 According to the method described in JP-A-2-206624, a resin film was first formed on a polycarbonate substrate having a thickness of 5 mm, and a silicon dioxide film was formed thereon. In this case, the resin film is made of a copolymer of maleic anhydride and P-aminostyrene, and has a thickness of about 1 μm. When the surface properties of the thus obtained polycarbonate substrate having a silicon dioxide film were examined, the following results were obtained. Chemical resistance: 83 times Adhesion: 100/100 Pencil hardness: 6H Scratch resistance: good
───────────────────────────────────────────────────── フロントページの続き (72)発明者 磯田 武志 埼玉県入間郡大井町西鶴ケ岡１丁目３番 １号 東燃株式会社総合研究所内 (56)参考文献 特開 平１−221466（ＪＰ，Ａ) 特開 昭60−221470（ＪＰ，Ａ) 特開 昭54−126276（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 5/00 - 5/24 C08J 7/00 - 7/18 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Isoda 1-3-1 Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. Research Institute (56) References JP 1-2221466 (JP, A) JP-A-60-221470 (JP, A) JP-A-54-126276 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08J 5/00-5/24 C08J 7/00 -7/18
Claims (4)
１００，０００の無機ポリシラザンを１００〜２００℃
で熱処理又は電子線処理して得られるＳｉ−Ｎ−Ｏ結合
を有する無機ポリシラザン硬化被膜を表面の少なくとも
一部に有する樹脂成形体。 (1) The following structural formula (1) And having a number average molecular weight of 980 to 980.
100-200 ° C of 100,000 inorganic polysilazane
-N-O bond obtained by heat treatment or electron beam treatment
An inorganic polysilazane cured film having
Resin molded body partly.
請求項１に記載の樹脂成形体。 2. The resin molded article is a film.
The resin molded product according to claim 1.
記構造式（１） 【化２】 で表される繰り返し単位を有し数平均分子量が９８０〜
１００，０００の無機ポリシラザンの被膜を形成する工
程と、この無機ポリシラザン被膜を有する樹脂成形体を
１００〜２００℃で熱処理又は電子線処理する工程から
なるＳｉ−Ｎ−Ｏ結合を有する無機ポリシラザン硬化被
膜を有する樹脂成形体の製造方法。 3. A method in which at least a part of the surface of the resin molded body is
The structural formula (1) And having a number average molecular weight of 980 to 980.
Process to form 100,000 inorganic polysilazane coating
And a resin molded article having this inorganic polysilazane coating.
From the step of heat treatment or electron beam treatment at 100-200 ° C
Cured inorganic polysilazane having Si-NO bond
A method for producing a resin molded article having a film.
記構造式（１） 【化３】 で表される繰り返し単位を有し数平均分子量が９８０〜
１００，０００の無機ポ リシラザンの被膜を形成する工
程と、この無機ポリシラザン被膜を有する樹脂シートを
成形加工する工程と、この成形加工した成形体を１００
〜２００℃で熱処理又は電子線処理する工程からなるＳ
ｉ−Ｎ−Ｏ結合を有する無機ポリシラザン硬化被膜を有
する樹脂成形体の製造方法。 4. A method in which at least a part of the surface of the resin sheet is
The structural formula (1) And having a number average molecular weight of 980 to 980.
Engineering forming 100,000 inorganic port Rishirazan coating
And a resin sheet having this inorganic polysilazane coating.
Forming step, and forming the formed body by 100
S comprising a step of heat treatment or electron beam treatment at ~ 200 ° C
Inorganic polysilazane cured coating having i-N-O bond
Of manufacturing a molded resin article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02413273A JP3136412B2 (en) | 1990-12-21 | 1990-12-21 | Resin molding having cured polysilazane film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02413273A JP3136412B2 (en) | 1990-12-21 | 1990-12-21 | Resin molding having cured polysilazane film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08143689A JPH08143689A (en) | 1996-06-04 |
| JP3136412B2 true JP3136412B2 (en) | 2001-02-19 |
Family
ID=18521950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02413273A Expired - Fee Related JP3136412B2 (en) | 1990-12-21 | 1990-12-21 | Resin molding having cured polysilazane film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3136412B2 (en) |
Cited By (2)
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|---|---|---|---|---|
| JPH09157544A (en) * | 1995-12-05 | 1997-06-17 | Tonen Corp | Production of substrate provided with silica coating film and substrate provided with silica coating film produced thereby |
| JPH09183663A (en) * | 1995-10-30 | 1997-07-15 | Tonen Corp | Method of applying sio2 based ceramic on plastic film |
| US6383641B1 (en) | 1997-08-15 | 2002-05-07 | Asahi Glass Company Ltd. | Transparent coated molded product and method for producing the same |
| JP2002163838A (en) | 2000-09-14 | 2002-06-07 | Tdk Corp | Optical information medium |
| WO2003081296A1 (en) * | 2002-03-26 | 2003-10-02 | Tdk Corporation | Article with composite hardcoat layer and method for forming composite hardcoat layer |
| JP2007039694A (en) * | 2006-08-21 | 2007-02-15 | Clariant Internatl Ltd | Polycarbonate article coated with hard coating film and its manufacturing method |
| JP5734675B2 (en) * | 2011-01-17 | 2015-06-17 | 三井化学株式会社 | Laminated body and method for producing the same |
| WO2014003211A1 (en) * | 2012-06-25 | 2014-01-03 | Kolon Industries, Inc. | Transparent polyimide substrate and method of manufacturing the same |
| JP7230878B2 (en) | 2020-04-22 | 2023-03-01 | 信越化学工業株式会社 | Adhesive composition, coated substrate and cured product |
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1990
- 1990-12-21 JP JP02413273A patent/JP3136412B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014076509A (en) * | 2012-10-10 | 2014-05-01 | Dmg Mori Seiki Co Ltd | Machine tool |
| US9608608B2 (en) | 2014-05-28 | 2017-03-28 | Delta Electronics (Shanghai) Co., Ltd | Power module |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08143689A (en) | 1996-06-04 |
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