JPH05106191A - Heat-resistant sheet and its production - Google Patents
Heat-resistant sheet and its productionInfo
- Publication number
- JPH05106191A JPH05106191A JP29822891A JP29822891A JPH05106191A JP H05106191 A JPH05106191 A JP H05106191A JP 29822891 A JP29822891 A JP 29822891A JP 29822891 A JP29822891 A JP 29822891A JP H05106191 A JPH05106191 A JP H05106191A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyamide
- sheet
- heat
- resin
- microfibrillated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電気的性質、耐熱性、寸
法安定性に優れた耐熱シートで、特にプリント配線板用
として適した耐熱シートおよび製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant sheet having excellent electrical properties, heat resistance and dimensional stability, and particularly to a heat-resistant sheet suitable for printed wiring boards and a method for producing the same.
【０００２】[0002]
【従来の技術】一般にプリント配線板は、電気絶縁シー
トに耐熱性接着剤を介して、あるいは介さずに銅箔のよ
うな金属箔を積層した構成からなり、上記の金属箔に所
定の配線パターンを形成することにより得られる。これ
に用いられる絶縁性シートは耐熱性、寸法安定性などに
優れた特性が要求されるため、ポリイミドフィルムのよ
うな耐熱性樹脂フィルム、耐熱性合成繊維をバインダー
で結合させた乾式または湿式不織布、耐熱性合成パルプ
と耐熱性合成繊維の混抄またはガラスクロスやガラスペ
ーパーに耐熱性樹脂を含浸、硬化させたものが知られて
おり、これらは要求性能やコストに応じて選択され、使
用されている。2. Description of the Related Art Generally, a printed wiring board is constructed by laminating a metal foil such as a copper foil on an electric insulating sheet with or without a heat-resistant adhesive. It is obtained by forming. Since the insulating sheet used for this is required to have excellent properties such as heat resistance and dimensional stability, a heat resistant resin film such as a polyimide film, a dry or wet nonwoven fabric in which heat resistant synthetic fibers are bound with a binder, It is known that a mixture of heat-resistant synthetic pulp and heat-resistant synthetic fiber or glass cloth or glass paper impregnated with a heat-resistant resin and cured is selected and used according to the required performance or cost. ..
【０００３】[0003]
【本発明が解決しようとする課題】しかしながら、ポリ
イミドフィルムは耐熱性が良好であるものの、耐湿性、
寸法安定性が劣り、高価であるという欠点がある。However, although the polyimide film has good heat resistance,
It has the disadvantages of poor dimensional stability and high cost.
【０００４】また、乾式または湿式抄紙においては薄
く、かつ樹脂含浸工程に耐える強度の優れたシートを得
るにはバインダーが必要となる。このとき主体となる繊
維が耐熱性に優れていても、バインダーが耐熱性に劣る
という欠点があり、また樹脂含浸工程に支障をきたさな
い強度を得るためには、多量のバインダーを必要とし、
樹脂含量が低下するという欠点がある。またガラスクロ
スやガラスペーパーは樹脂含浸性に優れるものの、樹脂
硬化シ−トの寸法安定性が劣るという欠点がある。Further, in dry or wet papermaking, a binder is required to obtain a thin sheet having excellent strength to withstand the resin impregnation step. At this time, even if the main fiber has excellent heat resistance, there is a drawback that the binder is inferior in heat resistance, and in order to obtain strength that does not hinder the resin impregnation step, a large amount of binder is required,
There is a drawback that the resin content is reduced. Further, although glass cloth and glass paper are excellent in resin impregnation property, they have a drawback that the dimensional stability of the resin cured sheet is poor.
【０００５】耐熱性合成繊維としては芳香族ポリアミド
短繊維、特にパラ系のものは耐熱性、寸法安定性に優れ
ており、該繊維を主体としたシ−トが提案されている。
該繊維のバインダ−として、低配向ポリエステル短繊維
を用いるもの（特開昭６２−２７４６８９号公報、特開
昭６２−２６２６号公報）、熱可塑性ポリマーのミクロ
フィブリル化物とアラミッド系パルプ（アラミッド繊維
を摩砕してフィブリル化させた物またはフィブリッド）
を用いたもの（特開昭６３−３５９００号公報）、アラ
ミッド繊維状結合材（パルプ状芳香族ポリアミド）と熱
可塑性耐熱性ポリマーの繊維状結合材用いたもの（特開
昭６１−１７００８９号公報、特開昭６０−２６０６２
６号公報）が開示されている。芳香族ポリアミドに比
べ、ポリエステルは耐熱性、寸法安定性が劣り、熱可塑
性ポリマーも耐熱性、寸法安定性が劣り好ましくない。As the heat-resistant synthetic fibers, aromatic polyamide short fibers, especially para-type fibers, are excellent in heat resistance and dimensional stability, and sheets mainly composed of the fibers have been proposed.
As a binder for the fibers, low orientation polyester short fibers are used (Japanese Patent Laid-Open No. 62-274689 and Japanese Patent Laid-Open No. 62-2626), microfibrillated thermoplastic polymers and aramid-based pulp (aramid fibers (Milled and fibrillated or fibrid)
(Japanese Patent Laid-Open No. 63-35900), those using a fibrous binder of aramid fibrous binder (pulp-like aromatic polyamide) and thermoplastic heat-resistant polymer (Japanese Patent Laid-Open No. 61-170089). JP-A-60-26062
No. 6) is disclosed. Polyester is inferior in heat resistance and dimensional stability to aromatic polyamide, and thermoplastic polymer is also inferior in heat resistance and dimensional stability, which is not preferable.
【０００６】またパラ系芳香族ポリアミドの短繊維また
はそのフィブリル化物、あるいはそのいずれか一方と、
さらにメタ系芳香族ポリアミドのフィブリッドを用いた
もの（特開昭６０−２０７２１６号公報）が開示されて
いるが、パラ系芳香族ポリアミドに比べ、耐熱性、寸法
安定性に劣るメタ系芳香族ポリアミドが用いられており
好ましくない。In addition, short fibers of para-aromatic polyamide or fibrillated products thereof, or either one of them,
Further, there is disclosed one using a fibrid of a meta-aromatic polyamide (JP-A-60-207216), but a meta-aromatic polyamide having poor heat resistance and dimensional stability as compared with a para-aromatic polyamide. Is used, which is not preferable.
【０００７】さらに、従来の不織布を用いたものは、縦
方向、横方向の寸法安定性には優れるもの、厚み方向の
寸法安定性において、織布に劣るという欠点があった。
これは、繊維を２次元には配置できるが、厚み方向にも
配置することが、従来の方法では困難であったことに起
因する。Further, the conventional nonwoven fabrics have a drawback that they are excellent in dimensional stability in the longitudinal and transverse directions but inferior to woven fabrics in dimensional stability in the thickness direction.
This is because the fibers can be arranged two-dimensionally, but it is difficult to arrange them in the thickness direction by the conventional method.
【０００８】芳香族ポリアミド繊維のウェブを３次元的
に交絡した例としては、１９８５年Tappi Nonwoven Sym
posium 要項集に、エアレイ法により形成されたウェブ
を用い、交絡を行う方法が記載されている。このシート
は強度も大きく、繊維の耐熱性を活かし、耐炎化シート
としては優れた性能を有している。しかしながら、湿式
法に比べ、エアレイ法で得られれたウェブは、地合の点
で劣る。また、微細繊維の配合が困難で面質が劣る。As an example of three-dimensionally entangled webs of aromatic polyamide fibers, 1985 Tappi Nonwoven Sym
The posium essential point describes a method of interlacing using a web formed by the air laying method. This sheet also has high strength and takes advantage of the heat resistance of the fiber, and has excellent performance as a flameproof sheet. However, the web obtained by the air-laid method is inferior in terms of formation as compared with the wet method. Further, it is difficult to mix fine fibers and the surface quality is poor.
【０００９】本発明は上記従来の問題点を解決するもの
であり、耐熱性はもちろん、電気的特性、寸法安定性に
優れた耐熱シート、特にプリント配線板用に適したシ−
トを提供することを目的とする。The present invention solves the above-mentioned problems of the prior art, and is a sheet suitable not only for heat resistance but also for electrical characteristics and dimensional stability, especially for printed wiring boards.
The purpose is to provide
【００１０】[0010]
【課題を解決するための手段】本発明者らは前記の課題
を解決するため鋭意研究を行った。その結果、主鎖に芳
香族基を有する芳香族ポリアミド短繊維とさらに芳香族
ポリアミドのミクロフィブリル化物を使用することによ
り、坪量のふれや地合むらが少なく、均一な耐熱性シー
トが得られることが見いだされた。更に上記ミクロフィ
ブリル化物と併用し芳香族ポリアミドのパルプ状物を配
合することにより、同様の効果が有ることを見いだし
た。また、耐熱性樹脂が均一に含浸され、寸法安定性、
特に厚み方向の寸法安定性に優れた耐熱シートが得られ
ることが見いだされた。本発明は以上の知見により達成
されたものである。[Means for Solving the Problems] The inventors of the present invention have made extensive studies to solve the above problems. As a result, by using an aromatic polyamide short fiber having an aromatic group in the main chain and an aromatic polyamide microfibrillated product, a uniform heat resistant sheet is obtained with less fluctuation in basis weight and unevenness of the formation. It was found. Further, it was found that the same effect can be obtained by blending an aromatic polyamide pulp-like material in combination with the above microfibrillated product. In addition, the heat-resistant resin is uniformly impregnated to ensure dimensional stability,
In particular, it has been found that a heat-resistant sheet having excellent dimensional stability in the thickness direction can be obtained. The present invention has been achieved based on the above findings.
【００１１】すなわち、主鎖に芳香族基を有する芳香族
ポリアミド短繊維と繊維径０．７μm以下にフィブリル
化された芳香族ポリアミドのミクロフィブリル化物より
なる２成分、または該２成分にさらに繊維径が０．７μ
mより大きなパルプ状芳香族ポリアミドよりなる３成分
を含有し、これらの２成分、または３成分が３次元的に
交絡した耐熱シートである。また、耐熱性樹脂を含有す
る上記の耐熱シートである。That is, two components consisting of an aromatic polyamide short fiber having an aromatic group in the main chain and a microfibrillated product of an aromatic polyamide fibrillated to a fiber diameter of 0.7 μm or less, or a fiber diameter of the two components. Is 0.7μ
A heat-resistant sheet containing three components made of a pulp-like aromatic polyamide having a size larger than m, and these two components or three components being three-dimensionally entangled. Further, it is the above heat resistant sheet containing a heat resistant resin.
【００１２】また、主鎖に芳香族基を有する芳香族ポリ
アミド短繊維と繊維径０．７μm以下にフィブリル化さ
れた芳香族ポリアミドのミクロフィブリル化物よりなる
２成分、または該２成分にさらに繊維径が０．７μmよ
り大きなパルプ状芳香族ポリアミドよりなる３成分を含
有するスラリーを調整し、湿式抄造法により抄造したウ
ェブを単層あるいは複数層積層し、水流で交絡すること
を特徴とする耐熱シートの製造法である。さらには、水
流交絡前あるいは後に、耐熱性樹脂を含浸、乾燥し、水
流交絡後に硬化することを特徴とする耐熱シートの製造
方法である。Further, two components comprising aromatic polyamide short fibers having an aromatic group in the main chain and microfibrillated aromatic polyamide fibrillated to a fiber diameter of 0.7 μm or less, or a fiber diameter of the two components. Having a particle size of more than 0.7 μm, a slurry containing three components made of a pulp-like aromatic polyamide is prepared, and a web formed by a wet papermaking method is laminated in a single layer or a plurality of layers and entangled with a water stream. Is a manufacturing method. Furthermore, it is a method for producing a heat-resistant sheet, characterized by impregnating with a heat-resistant resin before or after hydroentanglement, drying, and curing after hydroentanglement.
【００１３】以下本発明の詳細な説明を行う。本発明で
用いる主鎖に芳香族基を持つ芳香族ポリアミドとは芳香
族ジカルボン酸またはその酸クロライドあるいは芳香族
ジカルボン酸およびその酸クロライドと、芳香族ジアミ
ンを主成分とするホモポリマーまたはコポリマーであ
る。芳香族ジカルボン酸および芳香族ジアミンは各々メ
タ体とパラ体をとり得る。得られたシートの寸法安定性
に優れる点から、パラ体が好ましく、具体例としてはポ
リーＰーフェニレンテレフタルアミド、またはポリーＰーフ
ェニレン・３，４′ジアミノジフェニルエーテル・テレ
フタルアミドがあげられる。The present invention will be described in detail below. The aromatic polyamide having an aromatic group in the main chain used in the present invention is an aromatic dicarboxylic acid or its acid chloride or an aromatic dicarboxylic acid and its acid chloride, and a homopolymer or a copolymer containing an aromatic diamine as a main component. .. The aromatic dicarboxylic acid and the aromatic diamine can take a meta form and a para form, respectively. The para-form is preferable from the viewpoint of excellent dimensional stability of the obtained sheet, and specific examples thereof include poly-P-phenylene terephthalamide or poly-P-phenylene.3,4'diaminodiphenyl ether.terephthalamide.
【００１４】本発明で用いる芳香族ポリアミド短繊維
の、繊度は１〜６デニール（以下ｄと略記）、繊維長は
５mm以上が好ましい。繊維長が５mmより短いと、交絡が
困難である。The aromatic polyamide short fibers used in the present invention preferably have a fineness of 1 to 6 denier (hereinafter abbreviated as d) and a fiber length of 5 mm or more. If the fiber length is shorter than 5 mm, the entanglement is difficult.
【００１５】本発明で用いる芳香族ポリアミドのミクロ
フィブリル化物は特開昭５６−１００８０１号公報に示
されているように、一般の製紙工程で用いられているリ
ファイナーによる処理とは異なり、均質化装置を用いて
ミクロフィブリル化したものである。すなわち、水に分
散させた芳香族ポリアミド繊維のスラリ−をその前後に
２００kgf／cm2以上の圧力差を設けたオリフィスを高速
で通過させ、直ちに減速することによりスラリ−粒子に
せん断力を加えると、芳香族ポリアミド繊維が繊維軸の
方向に縦分割されたミクロフィブリル状になる。この工
程を繰り返すことにより得られた物である。具体的な例
としては、パラ系芳香族ポリアミド繊維（ケブラ−繊
維、デュポン社製）をミクロフィブリル化したティアラ
４００（ダイセル社製）があげられる。The aromatic polyamide microfibrillated product used in the present invention, as disclosed in Japanese Patent Laid-Open No. 56-100801, is different from the treatment by a refiner used in a general papermaking process, and is a homogenizer. Is microfibrillated using. That is, when a slurry of aromatic polyamide fibers dispersed in water is passed through an orifice provided with a pressure difference of 200 kgf / cm 2 or more at a high speed before and after the slurry is rapidly decelerated, a shearing force is applied to the slurry particles. , Aromatic polyamide fibers are vertically divided into microfibrils in the fiber axis direction. It is a product obtained by repeating this process. As a specific example, there is a Tiara 400 (manufactured by Daicel), which is a microfibrillated para-aromatic polyamide fiber (Kevlar fiber, manufactured by DuPont).
【００１６】本発明で用いるパルプ状芳香族ポリアミド
とは、芳香族ポリアミドポリマーからなるパルプ状物で
あり、繊維フィブリル化物、フィブリッドが好ましい。
フィブリル化物とは、繊維を磨砕して発生させたフィブ
リルをいう。フィブリッドとは特公昭４０−９０４４号
公報に開示された方法で得られ、ポリマー溶液から高せ
ん断の元にポリマーの凝固剤に滴下し、凝固析出させた
繊維フィブリルや粒子を言う。The pulp-like aromatic polyamide used in the present invention is a pulp-like substance composed of an aromatic polyamide polymer, preferably a fiber fibrillated product or fibrid.
The fibrillated material means fibrils generated by grinding fibers. Fibrids refer to fiber fibrils and particles obtained by the method disclosed in Japanese Examined Patent Publication No. 40-9044, which are dropped from a polymer solution into a polymer coagulant under high shear to coagulate and precipitate.
【００１７】前記のミクロフィブリル化物は、繊維を摩
砕することまたはフィブリッドにすることではとうてい
得ることのできない微細な繊維径を有する。すなわち、
該ミクロフィブリル化物は繊維径が０．７μm以下と大
変微細になっているため、スラリー内でも、ミクロフィ
ブリル化物が主体繊維と絡むことで、フロック（繊維の
凝集）の形成を防止し、均一なスラリー調製が可能で、
抄造後のシートの坪量のふれや厚みのむらが少ない、地
合の良好なシートが得ることができる。また、繊維間の
絡みが大きいので、抄造後の湿紙強度が大きく、乾燥後
もシートのバインダーとしての効果が著しく、抄造後の
シートのハンドリングが容易である。The above-mentioned microfibrillated product has a fine fiber diameter which cannot be obtained by grinding or fibrating the fibers. That is,
Since the microfibrillated product has a very fine fiber diameter of 0.7 μm or less, even in the slurry, the microfibrillated product is entangled with the main fibers to prevent the formation of flocs (aggregation of fibers) and to make the fiber uniform. Slurry can be prepared,
It is possible to obtain a sheet having a good texture and having less fluctuation in the basis weight and unevenness in the thickness of the sheet after papermaking. Further, since the entanglement between the fibers is large, the strength of the wet paper after papermaking is large, the effect as a binder of the sheet is remarkable even after drying, and the handling of the sheet after papermaking is easy.
【００１８】抄造後のシートを３次元的に交絡すると、
繊維間の交絡が緻密で、強度の大きいシートを得ること
が可能であるだけでなく、ミクロフィブリル化物によ
り、交絡後のシート表面の平滑性が向上する。さらに、
短繊維間に充填され、シートが密になる。When the sheet after papermaking is three-dimensionally entangled,
Not only it is possible to obtain a sheet having a high degree of entanglement between fibers and high strength, but the microfibrillated product improves the smoothness of the sheet surface after entanglement. further,
Filled between the short fibers, the sheet becomes dense.
【００１９】一方、パルプ状物はミクロフィブリル化物
に比べ、繊維径が大きく、単独ではミクロフィブリル化
物程、強度の大きな抄造シ−トを形成することができな
いため、ハンドリングが困難で次の工程への移行が難し
い。むしろ、芳香族ポリアミドの短繊維とミクロフィブ
リル化物のスラリ−に混合することでミクロフィブリル
化物の歩留まりを向上させることができるという利点が
ある。On the other hand, the pulp-like material has a larger fiber diameter than the microfibrillated product, and cannot independently form a papermaking sheet having a higher strength than the microfibrillated product. Is difficult to transition. Rather, there is an advantage that the yield of the microfibrillated product can be improved by mixing it with the short fiber of the aromatic polyamide and the slurry of the microfibrillated product.
【００２０】また、芳香族ポリアミドは優れた耐熱性、
寸法安定性を持つが、これらの機能を阻害しない範囲で
あれば無機充填剤、無機繊維を混合しても良い。Further, aromatic polyamide has excellent heat resistance,
Inorganic fillers and inorganic fibers may be mixed as long as they are dimensionally stable but do not impair these functions.
【００２１】該シートは芳香族ポリアミド短繊維とミク
ロフィブリル化物とを均一に分散混合し、通常の抄紙機
でウェブを形成後、高圧柱状水流で繊維を３次元的に交
絡し、乾燥することにより得られる。必要ならばカレン
ダー等で加熱下あるいは非加熱下で加圧し、さらに緻密
で平滑なシートを得ることができる。The sheet is prepared by uniformly dispersing and mixing the aromatic polyamide short fibers and the microfibrillated product, forming a web by an ordinary paper machine, three-dimensionally interlacing the fibers with a high-pressure columnar water stream, and drying. can get. If necessary, it can be pressed with a calender or the like under heating or without heating to obtain a dense and smooth sheet.
【００２２】芳香族ポリアミドのミクロフィブリル化物
の量はシート重量に対し５％〜４０％で、さらに好まし
くは１０％〜４０％である。５％より少ないと抄造シー
ト強度が低下し、抄造シートのハンドリングが難しく、
交絡時の強度も弱く、樹脂含浸時にシートが切断してし
まう。４０％より多くなると、抄造時の濾水性が悪くな
り抄紙工程上好ましくない。The amount of the aromatic polyamide microfibrillated product is 5% to 40%, more preferably 10% to 40%, based on the weight of the sheet. If it is less than 5%, the strength of the paper sheet will be reduced, making it difficult to handle the paper sheet.
The strength at the time of entanglement is also weak, and the sheet is cut when impregnated with resin. When it is more than 40%, the drainage property at the time of papermaking is deteriorated, which is not preferable in the papermaking process.
【００２３】パルプ状芳香族ポリアミドは、芳香族ポリ
アミドのミクロフィブリル化物の歩留まりを向上させる
ために混合し、このパルプ状芳香族ポリアミドの量は、
シート重量に対し、３％〜３０％が好ましい。パルプ状
芳香族ポリアミドはミクロフィブリル化物に比べ、バイ
ンダーとしての機能が低く、単独で用いても効果は少な
いが、ミクロフィブリル化物と併用することで、バイン
ダーとしての機能だけでなく、抄造時、および交絡工程
でのミクロフィブリル化物のシート内での歩留まりを向
上させる効果もあった。このとき、パルプ状物とミクロ
フィブリル化物の合計量はシート重量の８％〜６０％
で、好ましくは１０％〜５０％である。８％より少ない
と抄造シート強度が低下し、抄造シートのハンドリング
が難しく、交絡時の強度も弱く、樹脂含浸時にシートが
切断してしまう。６０％より多いと濾水性が悪くなり好
ましくない。また、必要であれば、このパルプ状物を叩
解機で叩解し用いてもよい。The pulp-like aromatic polyamide is mixed in order to improve the yield of the microfibrillated product of the aromatic polyamide, and the amount of the pulp-like aromatic polyamide is
It is preferably 3% to 30% with respect to the weight of the sheet. Pulp-like aromatic polyamide has a low function as a binder as compared with a microfibrillated product, and is less effective when used alone, but when used in combination with a microfibrillated product, not only as a binder, but also during papermaking, and There was also an effect of improving the yield of the microfibrillated material in the sheet in the confounding step. At this time, the total amount of the pulp-like material and the microfibrillated material is 8% to 60% of the sheet weight.
And preferably 10% to 50%. If it is less than 8%, the strength of the papermaking sheet decreases, the handling of the papermaking sheet is difficult, the strength at the time of entanglement is weak, and the sheet is cut at the time of resin impregnation. If it is more than 60%, the drainage is poor, which is not preferable. If necessary, this pulp-like material may be beaten with a beater and used.
【００２４】次に、３次元交絡を強固にかつ適正に行う
条件を述べる。上記のシートを単層あるいは複数枚積層
し、５０〜２００メッシュ程度の支持体上に載せ、上方
から水流を打ち込み繊維の３次元交絡を行う。Next, the conditions for firmly and properly performing the three-dimensional entanglement will be described. A single layer or a plurality of the above-mentioned sheets are laminated and placed on a support of about 50 to 200 mesh, and a water stream is injected from above to perform three-dimensional entanglement of fibers.
【００２５】水流を打ち込み繊維を交絡させるためのノ
ズルの径は、交絡を強固に行い、地合を良好に保つため
に１０〜５００μｍの範囲が好ましい。ノズルの間隔は
１０〜１５００μｍが好ましい。The diameter of the nozzle for injecting the water stream to entangle the fibers is preferably in the range of 10 to 500 μm in order to perform the entanglement firmly and keep the texture well. The distance between the nozzles is preferably 10 to 1500 μm.
【００２６】これらのノズルはウェブ、シートの種類、
坪量、加工速度、水圧を考慮し、十分な交絡が得られる
範囲でノズルヘッドの数を変え用いることができる。ま
た、交絡回数も任意に選ぶことができる。These nozzles are used for web, sheet type,
In consideration of the basis weight, processing speed, and water pressure, the number of nozzle heads can be changed and used within a range where sufficient entanglement can be obtained. Also, the number of confounding can be arbitrarily selected.
【００２７】水圧は１０〜２５０kg／cm2の範囲で用い
ることができるが、芳香族ポリアミドは繊維の剛性が大
きく、通常より高い水圧で交絡を行うことが好ましい。
この場合、５０〜２５０kg／cm2が好ましい範囲であ
る。加工速度は１５〜２００m／分の範囲で用いること
が可能である。交絡の水圧が低いと十分な交絡が得られ
ない。また、水圧が必要以上に高いと地合が乱れたり、
シートが破損し好ましくない。The water pressure can be used in the range of 10 to 250 kg / cm 2 , but the aromatic polyamide has a large fiber rigidity, and it is preferable to perform the entanglement at a water pressure higher than usual.
In this case, 50 to 250 kg / cm 2 is a preferable range. The processing speed can be used in the range of 15 to 200 m / min. If the confounding water pressure is low, sufficient confounding cannot be obtained. Also, if the water pressure is higher than necessary, the formation will be disturbed,
The sheet is damaged, which is not preferable.
【００２８】水圧は加工初期から終盤にかけて順次圧力
を上げて行くことにより、面質を阻害することがなく、
強固な交絡が可能になる。また、ノズル径およびノズル
間隔、あるいはいずれか一方を順次小さくすることも可
能で、やはり不織布の面質が向上する点から好ましい。
また、ノズルのヘッダーを回転運動させること、左右に
振動させること、あるいはウェブの支持ワイヤーを左右
に振動させることで、さらに面質を改良することも可能
である。さらに、交絡後、ノズルとウェブの間に４０〜
１００メッシュの金網を挿入し、柱状水流を散水化しウ
ェブに噴射することでも面質改良を行うことが可能であ
る。さらに、交絡終了直前あるいは、直前と２列前の水
圧を下げることでも容易に面質の向上を図ることが可能
である。The water pressure does not hinder the surface quality by gradually increasing the pressure from the initial stage to the final stage of processing.
Strong confounding is possible. Further, it is possible to successively reduce the nozzle diameter and the nozzle interval, or either one, which is also preferable in that the surface quality of the nonwoven fabric is improved.
It is also possible to further improve the surface quality by rotating the header of the nozzle, vibrating it to the left or right, or vibrating the support wire of the web to the left or right. Further, after the entanglement, between the nozzle and the web, 40 ~
It is also possible to improve the surface quality by inserting a 100-mesh wire net and sprinkling the columnar water stream to spray it onto the web. Further, the surface quality can be easily improved by decreasing the water pressure immediately before the end of the confounding, or immediately before and two rows before.
【００２９】交絡方法は片面のみ、あるいは両面交絡を
行うことができる。また、交絡を行った後、さらにシー
トを積層し、交絡を行うことも可能である。As a method of entanglement, only one side or both sides can be entangled. It is also possible to further entangle by stacking sheets after the entanglement.
【００３０】このように３次元交絡処理中あるいは施し
た後、余分な水分を吸引あるいはウェットプレスなどの
方法で取り除いた後、エアードライヤー、エアースルー
ドライヤー、あるいはサクションドラムドライヤー等を
用い、乾燥を行うことができる。During or after the three-dimensional entanglement treatment as described above, excess water is removed by suction or a wet press, and then dried using an air dryer, an air through dryer, a suction drum dryer or the like. be able to.
【００３１】本発明に用いられ含浸されるべき耐熱性樹
脂としては、熱硬化性のポリエステルアミド樹脂、エポ
キシ樹脂、フェノール樹脂、ポリイミド樹脂等の熱硬化
性樹脂があげられ、これら単独もしくは２種類以上を混
合して用いる。また、必要に応じて無機充填剤を配合し
た物を使用することができる。Examples of the heat-resistant resin used in the present invention to be impregnated include thermosetting resins such as thermosetting polyesteramide resin, epoxy resin, phenol resin, and polyimide resin, which may be used alone or in combination of two or more. Are mixed and used. Moreover, the thing which mix | blended the inorganic filler as needed can be used.
【００３２】次にプリント配線板用シートを形成する方
法について述べる。抄造後乾燥し得られたシート、ある
いは交絡し得られたシートに、熱硬化性樹脂を含浸し、
溶媒を乾燥後、樹脂を硬化させればよい。樹脂溶液の含
浸は通常用いられる水平式あるいは垂直式の含浸機を用
いることができる。含浸後の乾燥も特別の手段を必要と
しない。乾燥時の含浸シ−トに粘着性があれば、適当な
工程で随意、離型シートを用いれば良い。含浸シートが
既に交絡されているならば、さらに、上記含浸シ−トを
複数枚重ねあわせ加熱加圧して一体化し、さらに硬化す
ることもできる。Next, a method for forming a printed wiring board sheet will be described. A sheet obtained by drying after papermaking, or a sheet obtained by entanglement is impregnated with a thermosetting resin,
After drying the solvent, the resin may be cured. For impregnation of the resin solution, a commonly used horizontal or vertical impregnation machine can be used. Drying after impregnation does not require any special means. If the impregnated sheet during drying has tackiness, a release sheet may be optionally used in an appropriate step. If the impregnated sheet has already been entangled, a plurality of the above-mentioned impregnated sheets can be superposed, heated and pressed to be integrated, and further cured.
【００３３】また、抄造乾燥シートであれば、樹脂含
浸、乾燥後、さらに積層し、樹脂含浸シート同士、ある
いは抄造乾燥シート、交絡シート等と交絡を行い、さら
に必要量の樹脂を含浸することは可能である。In the case of a paper-making dried sheet, after impregnating with a resin, drying and further laminating, the resin-impregnated sheets are entangled with each other, or with the paper-making dried sheet, the entangled sheet, etc., and further impregnated with a necessary amount of resin It is possible.
【００３４】本発明の耐熱シートに金属箔をさらに積層
するには、接着剤樹脂を介在させて積層できるが、接着
剤を用いることなく、シ−トが完全に硬化反応を終了す
る前に、金属箔を直接貼合わせた後、硬化させることも
できる。To further laminate the metal foil on the heat-resistant sheet of the present invention, it is possible to laminate with an adhesive resin interposed therebetween. However, without using an adhesive, before the sheet completely completes the curing reaction, The metal foil may be directly attached and then cured.
【００３５】また、芳香族ポリアミド繊維よりなる織布
や編布と積層し、一体化することも可能である。It is also possible to laminate and integrate with a woven or knitted fabric made of aromatic polyamide fiber.
【００３６】[0036]
【作用】本発明の耐熱シートは主鎖に芳香族基を持つ芳
香族ポリアミド短繊維に、芳香族ポリアミドのミクロフ
ィブル化物を用い、繊維が３次元交絡したシートであ
る。芳香族ポリアミドの特性を生かし、耐熱性樹脂を含
浸、硬化したシートは電気的特性、耐熱性、寸法安定
性、特に厚み方向の寸法安定性に優れたプリント配線板
として有効に作用する。The heat-resistant sheet of the present invention is a sheet in which microfibers of aromatic polyamide are used for aromatic polyamide short fibers having an aromatic group in the main chain, and the fibers are three-dimensionally entangled. A sheet impregnated with a heat-resistant resin and cured by taking advantage of the characteristics of aromatic polyamide effectively acts as a printed wiring board excellent in electrical characteristics, heat resistance, dimensional stability, and particularly dimensional stability in the thickness direction.
【００３７】[0037]
【実施例】以下に実施例をあげ本発明を具体的に説明す
るが、本発明は本実施例に限定されるものではない。実
施例において記載の部、％はすべて重量によるものであ
る。The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. All parts and percentages mentioned in the examples are by weight.
【００３８】なお、本実施例、比較例で用いた物性測定
法は次の通りである。抄造後のシートに関しては （１）坪量 （２）シートを抄造方向（縦）と抄造方向に対し直角方
向（横）の強度として、１５０mm、２０mmの試料片を作
製し、スパン１０cm、引張速度２０cm／分で、試料片が
破断するまでの最大荷重を測定した。 樹脂含浸、熱圧加工後は （１）寸法変化率（熱膨張係数） 樹脂含浸、熱圧成型した試料をＩＰＣ ＦＣ２４１法に
より１５０℃、３０分処理前後の寸法変化率を求めた。 （２）耐ハンダ性 ＪＩＳ Ｃ６４８１により膨れ、色の変化を観察した。The physical property measuring methods used in the examples and comparative examples are as follows. Regarding the sheet after paper making, (1) basis weight, (2) a sheet having 150 mm and 20 mm as strength in the papermaking direction (longitudinal) and the direction perpendicular to the papermaking direction (horizontal) was prepared, span 10 cm, pulling speed At 20 cm / min, the maximum load until breakage of the sample piece was measured. After resin impregnation and hot-pressing (1) Dimensional change rate (coefficient of thermal expansion) The resin-impregnated and hot-pressed sample was subjected to IPC FC241 method to determine the dimensional change rate before and after the treatment at 150 ° C for 30 minutes. (2) Solder resistance Swelling according to JIS C6481 and color change were observed.
【００３９】実施例１ テレフタル酸ジクロライド５０モル％、パラフェニレン
ジアミン５０モル％をヘキサメチルスルホルアミド（Ｈ
ＭＰＡ）とＮ−メチルピロリドン（ＮＭＰ）の混合溶媒
中て低温溶液重合させ、発生する酸は水酸化リチウムで
中和した。洗浄後、単離したポリーＰーフェニレンテレフ
タルアミドのポリマーを２０重量％硫酸に溶解し、９０
℃に加熱した後、紡糸する。このとき、溶液をノズルか
ら１cmの空気層を通して、低温凝固浴中に吐出し、繊維
を形成させた。このようにして得られた繊度２ｄのトウ
を、繊維長２０mmにカットし芳香族ポリアミド短繊維と
した。この短繊維８０部を０．５％濃度で予備分散し、
ポリーＰーフェニレンテレフタルアミドのミクロフィブリ
ル化物（ティアラ４００、ダイセル化学社製）２０部を
予め分散した水溶液中に加え、高分子ポリアクリルアミ
ド（粘剤）を加え、さらに撹拌し、水で希釈し、スラリ
ーを調整した。このスラリーを用い、円網抄紙機で坪量
５０ｇ／m2のシートを抄造、乾燥した。Example 1 50 mol% of terephthalic acid dichloride and 50 mol% of paraphenylenediamine were mixed with hexamethylsulforamide (H
Low temperature solution polymerization was carried out in a mixed solvent of MPA) and N-methylpyrrolidone (NMP), and the generated acid was neutralized with lithium hydroxide. After washing, the isolated polymer of poly-P-phenylene terephthalamide was dissolved in 20% by weight sulfuric acid,
After heating to ℃, spinning. At this time, the solution was discharged from a nozzle through an air layer of 1 cm into a low temperature coagulation bath to form fibers. The tow with a fineness of 2d thus obtained was cut into a fiber length of 20 mm to obtain aromatic polyamide short fibers. 80 parts of this short fiber is pre-dispersed at a concentration of 0.5%,
20 parts of a poly-P-phenylene terephthalamide microfibrillated product (Tiara 400, manufactured by Daicel Chemical Co., Ltd.) was added to a pre-dispersed aqueous solution, high-molecular polyacrylamide (sticky agent) was added, and the mixture was further stirred and diluted with water, The slurry was adjusted. Using this slurry, a sheet having a basis weight of 50 g / m 2 was made into paper by a cylinder paper machine and dried.
【００４０】抄造後のシートを強化ポリエステル製の１
００メッシュの支持体を上に配置し、下記の水流下、３
次元交絡を行った。ノズルヘッドを５ヘッド用いた。第
１ヘッドのノズルはノズル径１２０μm、ノズル間隔
１．２mm、２列で水圧１００kgf／cm2、第２ヘッドはノ
ズル径１２０μm、ノズル間隔１．２mm、２列で水圧１
３０kgf／cm2、第３ヘッドはノズル径１２０μm、ノズ
ル間隔０．６mm、２列で水圧１５０kgf／cm2、第４ヘッ
ドはノズル径１００μm、ノズル間隔０．６mm、１列で
水圧１４０kgf／cm2、第５ヘッドはノズル径１００μ
m、ノズル間隔０．６mm、１列で水圧１００kgf／cm2で
ある。交絡は、まずパルプの層を上に向け行った。次に
裏面にも同様の処理を行った。交絡の速度は１０ｍ／分
で行った。この交絡シートをサクションスルードライヤ
ーを用い、１３０℃で乾燥を行い、シートを得た。表１
に測定結果を示す。The sheet after papermaking is made of reinforced polyester 1
A 00 mesh support is placed on top and under the following water flow, 3
Dimensional confounding was performed. Five nozzle heads were used. The nozzle of the first head has a nozzle diameter of 120 μm, the nozzle interval is 1.2 mm, the water pressure is 100 kgf / cm 2 in two rows, and the second head has a nozzle diameter of 120 μm, the nozzle interval is 1.2 mm, and the water pressure is 1 in two rows.
30 kgf / cm 2 , No. 3 head, nozzle diameter 120 μm, nozzle spacing 0.6 mm, water pressure 150 kgf / cm 2 in 2 rows, No. 4 head, nozzle diameter 100 μm, nozzle spacing 0.6 mm, water pressure 140 kgf / cm 2 in 1 row , No. 5 head has a nozzle diameter of 100μ
m, nozzle spacing 0.6 mm, water pressure 100 kgf / cm 2 in one row. The entanglement was done with the pulp layer facing up first. Next, the same treatment was performed on the back surface. The entanglement speed was 10 m / min. This entangled sheet was dried at 130 ° C using a suction through dryer to obtain a sheet. Table 1
The measurement results are shown in.
【００４１】実施例２ 実施例１の短繊維７０部、ミクロフィブリル化物２０部
に、さらにパルプ状芳香族ポリアミド（ケブラーパル
プ、デュポン社製）１０部加えシートを製造した。以下
実施例１と同じ条件で交絡を行った。表１に結果を示
す。Example 2 70 parts of the short fibers of Example 1 and 20 parts of the microfibrillated product were further added with 10 parts of a pulp-like aromatic polyamide (Kevlar pulp, manufactured by DuPont) to prepare a sheet. The entanglement was performed under the same conditions as in Example 1 below. The results are shown in Table 1.
【００４２】実施例３ テレフタル酸クロライド５０モル％、パラフェニレンジ
アミン２５モル％、３，４’−ジアミノジフェニルエー
テル２５モル％をＮＭＰ中で低温溶液重合し、ポリパラ
フェニレン・３，４’−ジアミノペニルエーテルテレフ
タルアミドのポリマーを得た。発生する酸は水酸化カル
シウムで中和した。重合原液を１０重量％に希釈し、
１．５重量％塩化カルシウムを加え安定化させた溶液を
用い、可溶化助剤として５０重量％の塩化カルシウムを
含む水性凝固浴中に吐出し、繊維化した。さらに脱溶
剤、洗浄、乾燥し、５００℃で１０倍に延伸熱固定し
た。このようにして得られた繊度１．５ｄのトウを、繊
維長１５mmにカットし短繊維とした。 実施例１と同様
の方法で、シートを抄造し、交絡を行った。表１に結果
を示す。Example 3 50 mol% of terephthaloyl chloride, 25 mol% of paraphenylenediamine, and 25 mol% of 3,4'-diaminodiphenyl ether were subjected to low temperature solution polymerization in NMP to obtain polyparaphenylene-3,4'-diaminopenic acid. A polymer of luther terephthalamide was obtained. The acid generated was neutralized with calcium hydroxide. Dilute the polymerization stock solution to 10% by weight,
Using a solution in which 1.5% by weight of calcium chloride was added and stabilized, the solution was discharged into an aqueous coagulation bath containing 50% by weight of calcium chloride as a solubilizing agent to be fiberized. Further, the solvent was removed, washed, dried, and stretched and heat-fixed at 500 ° C. 10 times. The tow with a fineness of 1.5d thus obtained was cut into a short fiber having a fiber length of 15 mm. The sheet was made into paper and entangled in the same manner as in Example 1. The results are shown in Table 1.
【００４３】実施例４ 実施例３のトウを３mmにカットし、ナイアガラ式ビータ
ーで叩解し、パルプ状芳香族ポリアミドを製造した。こ
のパルプを実施例３の成分にさらに、混合し、実施例２
と同様の方法で、シートを抄造し、交絡を行った。表１
に結果を示す。Example 4 The tow of Example 3 was cut into 3 mm and beaten with a Niagara type beater to produce a pulp-like aromatic polyamide. This pulp was further mixed with the ingredients of Example 3 to give Example 2
The sheet was made into paper and entangled in the same manner as in (1). Table 1
The results are shown in.
【００４４】比較例１ 実施例２と同様の方法で抄造シートを製造した。ただ
し、交絡処理は行っていない。表１に結果を示す。Comparative Example 1 A papermaking sheet was produced in the same manner as in Example 2. However, no confounding process was performed. The results are shown in Table 1.
【００４５】[0045]
【表１】 [Table 1]
【００４６】以上の結果より、本発明のシートは強度的
に非常に優れたものであることが判る。また、同じ配合
でも、交絡がなされていないシートは強度的には劣った
ものとなる。From the above results, it can be seen that the sheet of the present invention is extremely excellent in strength. Further, even with the same composition, the sheet which is not entangled is inferior in strength.
【００４７】実施例５〜８ 実施例１〜４で得られたシートをビスマスレイイミド−
トリアジン樹脂（ＢＴレジン、三菱ガス化学社製）のメ
チルエチルケトン溶液（固形分濃度６０％）に含浸し、
過剰の樹脂をガラス製バーでしごいて樹脂付着を均一に
した。１４５℃で８分乾燥し、ついで該シートを４枚積
層し、１７５℃、２０kgf／cm2で１時間熱圧成型し、耐
熱シートを得た。表２に結果を示す。Examples 5 to 8 The sheets obtained in Examples 1 to 4 were bismuth rayimide-containing.
Impregnate a triazine resin (BT resin, manufactured by Mitsubishi Gas Chemical Co., Inc.) in a methyl ethyl ketone solution (solid content concentration 60%),
Excess resin was squeezed with a glass bar to even out the resin adhesion. After drying at 145 ° C. for 8 minutes, four sheets were laminated and thermocompression molded at 175 ° C. and 20 kgf / cm 2 for 1 hour to obtain a heat resistant sheet. The results are shown in Table 2.
【００４８】比較例２ 実施例１の抄造シートに樹脂含浸を行った。方法は実施
例５〜８の方法と同様に行った。表２に結果を示す。Comparative Example 2 The papermaking sheet of Example 1 was impregnated with resin. The method was the same as in Examples 5-8. The results are shown in Table 2.
【００４９】実施例９ 実施例１と同じ短繊維９０部、ミクロフィブリル化物１
０部を用い、シートを抄造した。エポキシ樹脂（エピコ
ート１００１、油化シェル社製）１００部、ジシアンア
ミド６部、ベンジルジメチルアミン０．４部、メチルエ
チルケトン６７部からなるエポキシ樹脂溶液を調液し、
さらにメチルエチルケトンで２０倍に希釈した溶液に含
浸し、１２０℃で１０分乾燥した。樹脂付着量はシート
重量に対し、２重量％であった。このシートを２層積層
し、実施例１と同じ方法で交絡を行った。ただし、水圧
は第１ヘッドから第５ヘッドまで順に１３０、１５０、
１８０、１６０、１００kgf／m2で行った。さらに、希
釈前の樹脂を含浸し、１２０℃で１０分乾燥し、ついで
４枚積層し、１７０℃、２０kgf／cm2で１時間熱圧成型
し、耐熱シートを得た。表２に結果を示す。Example 9 90 parts of the same short fibers as in Example 1, microfibrillated material 1
The sheet was made into paper using 0 part. An epoxy resin solution consisting of 100 parts of an epoxy resin (Epicoat 1001, manufactured by Yuka Shell Co., Ltd.), 6 parts of dicyanamide, 0.4 part of benzyldimethylamine and 67 parts of methyl ethyl ketone was prepared,
Further, it was impregnated with a solution diluted 20 times with methyl ethyl ketone and dried at 120 ° C. for 10 minutes. The resin adhesion amount was 2% by weight with respect to the sheet weight. Two layers of this sheet were laminated and entangled in the same manner as in Example 1. However, the water pressure is 130, 150 in order from the first head to the fifth head,
It was conducted at 180, 160 and 100 kgf / m 2 . Further, it was impregnated with the resin before dilution, dried at 120 ° C. for 10 minutes, then laminated four sheets, and thermocompression molded at 170 ° C. and 20 kgf / cm 2 for 1 hour to obtain a heat resistant sheet. The results are shown in Table 2.
【００５０】比較例３ 実施例１の短繊維５０部と実施例２のパルプ状芳香族ポ
リアミド５０部を用い、抄造シートを得ようと試みた。
このシート強度は非常に弱く、ハンドリングが困難であ
るばかりか、さらに樹脂を含浸し、熱圧成型しようと試
みたが、樹脂含浸シ−トがプレスにより破損し、耐熱シ
ートを得ることができなかった。Comparative Example 3 Using 50 parts of the short fibers of Example 1 and 50 parts of the pulp-like aromatic polyamide of Example 2, an attempt was made to obtain a paper sheet.
This sheet strength is very weak and difficult to handle, and an attempt was made to further impregnate a resin and thermocompression molding, but the resin-impregnated sheet was damaged by the press and a heat resistant sheet could not be obtained. It was
【００５１】比較例４ カードマシンを用い、芳香族ポリアミド短繊維のみのシ
ートをつくり、クロスラッパーで積層し、連続的に水流
交絡を行った。水圧は実施例１と同様である。このシー
トを透過光でかざし、観察したところ、斑模様が見られ
地合が悪いことがわかる。また、手でシートを垂直方向
に押すと、厚みむらとみれれる、ごつごつしたところが
感じられる。このシートに実施例５〜８と同様の方法で
樹脂含浸を行い、耐熱シートを得た。表２に結果を示
す。Comparative Example 4 Using a card machine, a sheet containing only aromatic polyamide short fibers was prepared, laminated with a cross wrapper, and continuously hydroentangled. The water pressure is the same as in Example 1. When this sheet was held with transmitted light and observed, a mottled pattern was observed and it was found that the texture was poor. Also, if you push the sheet vertically with your hands, you can feel the unevenness and unevenness. This sheet was impregnated with resin in the same manner as in Examples 5 to 8 to obtain a heat resistant sheet. The results are shown in Table 2.
【００５２】[0052]
【表２】 [Table 2]
【００５３】表２より、本発明の耐熱シートは縦、横の
みならず、厚み方向にも優れた寸法安定性を示すことが
判る。これに対し、交絡されていないシートは、厚み方
向の寸法安定性が劣り、乾式法により得られたものは、
シート全体の寸法安定性が劣る。From Table 2, it can be seen that the heat-resistant sheet of the present invention exhibits excellent dimensional stability not only in the vertical and horizontal directions but also in the thickness direction. On the other hand, the sheet which is not entangled has poor dimensional stability in the thickness direction, and the one obtained by the dry method is
The dimensional stability of the entire sheet is poor.
【００５４】[0054]
【発明の効果】本発明は芳香族ポリアミド短繊維と同じ
芳香族ポリアミドのミクロフィブリル化物よりなり、３
次元交絡されたシートである。またさらにパルプ状芳香
族ポリアミドを含有するシートである。このシートは大
きな強度を示し、ハンドリングが容易である。さらに、
耐熱性樹脂を含浸、硬化したシートはプリント配線回路
板の電気絶縁層に有用な耐熱シートである。すなわち、
耐熱性、寸法安定性、特に厚み方向の寸法安定性に優れ
ている。そのため微細回路設計の点で大変好ましい。The present invention comprises a microfibrillated product of the same aromatic polyamide as the aromatic polyamide short fibers.
It is a dimensionally entangled sheet. Further, it is a sheet further containing a pulp-like aromatic polyamide. This sheet shows great strength and is easy to handle. further,
A sheet impregnated with a heat resistant resin and cured is a heat resistant sheet useful as an electrical insulating layer of a printed wiring circuit board. That is,
It has excellent heat resistance and dimensional stability, especially in the thickness direction. Therefore, it is very preferable in terms of fine circuit design.
Claims (4)
ド短繊維と繊維径０．７μm以下にフィブリル化された
芳香族ポリアミドのミクロフィブリル化物よりなる２成
分、または該２成分にさらに繊維径が０．７μmより大
きなパルプ状芳香族ポリアミドよりなる３成分を含有
し、これらの２成分、または３成分が３次元的に交絡し
た耐熱シート。1. A two-component comprising an aromatic polyamide short fiber having an aromatic group in the main chain and a microfibrillated aromatic polyamide fibrillated to a fiber diameter of 0.7 μm or less, or a fiber diameter of the two components. Is a heat-resistant sheet containing three components made of a pulp-like aromatic polyamide having a size of more than 0.7 μm, and these two components or three components being three-dimensionally entangled.
熱シート。2. The heat-resistant sheet according to claim 1, which contains a heat-resistant resin.
ド短繊維と繊維径０．７μm以下にフィブリル化された
芳香族ポリアミドのミクロフィブリル化物よりなる２成
分、または該２成分にさらに繊維径が０．７μmより大
きなパルプ状芳香族ポリアミドよりなる３成分を含有す
るスラリーを調整し、湿式抄造法により抄造したウェブ
を単層あるいは複数層積層し、水流で交絡することを特
徴とする耐熱シートの製造法。3. A two-component comprising an aromatic polyamide short fiber having an aromatic group in the main chain and a microfibrillated aromatic polyamide fibrillated to a fiber diameter of 0.7 μm or less, or a fiber diameter of the two components. Having a particle size of more than 0.7 μm, a slurry containing three components made of a pulp-like aromatic polyamide is prepared, and a web formed by a wet papermaking method is laminated in a single layer or a plurality of layers and entangled with a water stream. Manufacturing method.
含浸、乾燥し、水流交絡後に硬化することを特徴とする
請求項３記載の耐熱シートの製造方法。4. The method for producing a heat-resistant sheet according to claim 3, wherein the heat-resistant resin is impregnated before or after hydroentanglement, dried, and cured after hydroentanglement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29822891A JP3026379B2 (en) | 1991-10-18 | 1991-10-18 | Heat-resistant sheet and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29822891A JP3026379B2 (en) | 1991-10-18 | 1991-10-18 | Heat-resistant sheet and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05106191A true JPH05106191A (en) | 1993-04-27 |
| JP3026379B2 JP3026379B2 (en) | 2000-03-27 |
Family
ID=17856893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29822891A Expired - Fee Related JP3026379B2 (en) | 1991-10-18 | 1991-10-18 | Heat-resistant sheet and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3026379B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10338809A (en) * | 1997-04-08 | 1998-12-22 | Sumitomo Chem Co Ltd | Composite film comprising low-permittivity resin and p-directing polyamide, prepreg thereof and use thereof |
| WO2002025010A1 (en) * | 2000-09-20 | 2002-03-28 | Shin-Kobe Electric Machinery Co., Ltd. | Nonwoven fabric for electrical insulation, prepreg, and laminate |
| JP2005264420A (en) * | 2004-02-19 | 2005-09-29 | Toray Ind Inc | Nano-fiber synthetic paper and method for producing the same |
| WO2005100688A1 (en) * | 2004-04-16 | 2005-10-27 | Dupont Teijin Advanced Papers, Ltd. | Aramid tissue material and electric/electronic component employing it |
| JP2008208514A (en) * | 1996-09-24 | 2008-09-11 | Kolon Ind Inc | Para-type wholly aromatic polyamide pulp |
-
1991
- 1991-10-18 JP JP29822891A patent/JP3026379B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008208514A (en) * | 1996-09-24 | 2008-09-11 | Kolon Ind Inc | Para-type wholly aromatic polyamide pulp |
| JPH10338809A (en) * | 1997-04-08 | 1998-12-22 | Sumitomo Chem Co Ltd | Composite film comprising low-permittivity resin and p-directing polyamide, prepreg thereof and use thereof |
| WO2002025010A1 (en) * | 2000-09-20 | 2002-03-28 | Shin-Kobe Electric Machinery Co., Ltd. | Nonwoven fabric for electrical insulation, prepreg, and laminate |
| JP2005264420A (en) * | 2004-02-19 | 2005-09-29 | Toray Ind Inc | Nano-fiber synthetic paper and method for producing the same |
| WO2005100688A1 (en) * | 2004-04-16 | 2005-10-27 | Dupont Teijin Advanced Papers, Ltd. | Aramid tissue material and electric/electronic component employing it |
| JP2005307360A (en) * | 2004-04-16 | 2005-11-04 | Du Pont Teijin Advanced Paper Kk | Aramid tissue material and electrical and electronic part using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3026379B2 (en) | 2000-03-27 |
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