JP3831103B2 - Method for producing polyparaphenylene terephthalamide short fiber - Google Patents
Method for producing polyparaphenylene terephthalamide short fiber Download PDFInfo
- Publication number
- JP3831103B2 JP3831103B2 JP36505997A JP36505997A JP3831103B2 JP 3831103 B2 JP3831103 B2 JP 3831103B2 JP 36505997 A JP36505997 A JP 36505997A JP 36505997 A JP36505997 A JP 36505997A JP 3831103 B2 JP3831103 B2 JP 3831103B2
- Authority
- JP
- Japan
- Prior art keywords
- polyparaphenylene terephthalamide
- ppta
- heat treatment
- producing
- short
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Description
【０００１】
【発明の属する技術分野】
本発明はイオン含有率が小さく、高ヤング率で、寸法安定性が良好で、かつ耐熱性および絶縁性に優れたポリパラフェニレンテレフタルアミド短繊維の製造方法およびその用途に関するものである。
【０００２】
【従来の技術】
従来から、ポリパラフェニレンテレフタルアミド（以下ＰＰＴＡと略称する）短繊維は、優れた強度、耐熱性および高ヤング率を有するため、産業用、特殊衣料用短繊維として用いられている。
【０００３】
ＰＰＴＡ繊維は紡糸時にポリマー溶解の溶媒として濃硫酸を用い液晶状態とした後、口金によるせん断を与えて結晶化度の高い糸に形成される。溶媒である濃硫酸は紡糸直後に水洗およびアルカリによる中和処理され、２００℃以上で乾燥・熱処理された後、フィラメントとして巻き取られることが知られている（米国特許第３，７６７，７５６号）。
【０００４】
このようにして得られた繊維を、カッターなどでアスペクト比５０〜５０００となるよう切断、あるいは機械的せん断を与えてフィブリル化するように加工することでＰＰＴＡ短繊維が得られる。
【０００５】
【発明が解決しようとする課題】
しかしながら、このようにして得られる短繊維は、中和によって形成された塩が繊維中に取り込まれており、通常０．５〜３重量％の塩を含んだ短繊維となってしまう。例えば中和の際に水酸化ナトリウムを用いた場合、塩を構成するイオンとしてはＮａ＋とＳＯ４２−が主なものでモル比はおよそ２：１である。
【０００６】
この塩は、多湿条件下で短繊維を使用した場合、水の介在でイオン化し、電気絶縁性を要求される場合、など通電の障害となることがある。
【０００７】
一方、ＰＰＴＡ短繊維から作った、紙、樹脂複合体、ゴム複合体あるいは織物は、そのポリマー構造から、電子・絶縁材料として用いた場合に絶縁・低誘電材料として良好な寸法安定性、加工性、高ヤング率、高温処理による低収縮性などの優れた特徴を発揮することが知られている。ところが、このような要因による通電が問題となる場合、例えばプリント配線板の材料として用いられた場合などではイオンを介したマイグレーションの要因となる可能性があり、用途展開が制限されることがあった。
【０００８】
本発明の目的は上記従来技術の欠点を解消し、ＰＰＴＡ短繊維本来の高耐熱性および高ヤング率を保持しながら、イオン含有率が小さく、特に電気・電子部品として有用な繊維の製造方法およびその用途を提供することにある。
【０００９】
【課題を解決するための手段】
本発明は上記課題を解決するため、次の手段をとるものである。
【００１０】
（１）ポリパラフェニレンテレフタルアミド硫酸溶液を紡出・中和し、水含有量を１５重量％以下となる履歴の無いように保ち、アスペクト比５０〜５０００となるよう切断、あるいはフィブリル化するよう機械加工して短繊維とし、次いで、脱イオン処理を行うことを特徴とする熱処理前のポリパラフェニレンテレフタルアミド短繊維の製造方法。
【００１１】
（２）アルカリイオン含有量が１．０重量％以下である上記（１）記載の熱処理前のポリパラフェニレンテレフタルアミド短繊維の製造方法。
【００１２】
（３）上記（１）〜（２）いずれか記載の製造法によって得られたポリパラフェニレンテレフタルアミド短繊維を１５０〜５００℃で熱処理することを特徴とするポリパラフェニレンテレフタルアミド短繊維の製造方法。
【００１３】
（４）熱処理することにより、結晶サイズを５０オングストローム以上にする上記（３）記載のポリパラフェニレンテレフタルアミド短繊維の製造方法。
【００１４】
（５）アルカリイオン含有量が０．２重量％以下である上記（３）〜（４）いずれか記載のポリパラフェニレンテレフタルアミド短繊維の製造方法。
【００１５】
（６）上記（１）〜（５）いずれか記載の方法で製造されたポリパラフェニレンテレフタルアミド短繊維を用いたことを特徴とする絶縁・低誘電材料。
【００１６】
（７）上記（１）〜（５）いずれか記載の方法で製造されたポリパラフェニレンテレフタルアミド短繊維を用いたことを特徴とする樹脂複合体。
【００１７】
（８）上記（１）〜（５）いずれか記載の方法で製造されたポリパラフェニレンテレフタルアミド短繊維を用いたことを特徴とするゴム複合体。
【００１８】
（９）上記（１）〜（５）いずれか記載の方法で製造されたポリパラフェニレンテレフタルアミド短繊維を用いたことを特徴とするプリント配線板用シート状構造物。
【００１９】
【発明の実施の形態】
本発明におけるポリパラフェニレンテレフタルアミド（ＰＰＴＡ）とは、テレフタル酸とパラフェニレンジアミンを重縮合して得られる重合体であるが、少量のジカルボン酸およびジアミンを共重合したものも使用でき、重合体または共重合体の分子量は通常２０，０００〜２５，０００が好ましい。
【００２０】
ＰＰＴＡ繊維は、ＰＰＴＡを濃硫酸に溶解し、その粘調な溶液を紡糸口金から押し出し、空気中または水中に紡出することによりフィラメント状にした後、水酸化ナトリウム水溶液で中和し、最終的には１２０〜５００℃の乾燥・熱処理をして得られる。乾燥・熱処理前のＰＰＴＡ繊維は結晶サイズ（１１０面）が５０オングストローム以下であり、乾燥・熱処理後では５０オングストロームを超えるのが普通である。
【００２１】
本発明の一つである、熱処理前のＰＰＴＡ短繊維は、短繊維の結晶サイズが５０オングストローム以下であり、かつアルカリイオン含有量が１．０重量％以下である必要があり、かつアルカリイオン量が１．０重量％以下である必要がある。結晶サイズ５０オングストロームを超えるとアルカリイオンを抽出することが困難となる。また、アルカリイオン含有量が１．０重量％を超えると本発明の目的である電気・電子分野への用途が制限される。そして、好ましくは結晶サイズが３５〜４５オングストロームであり、アルカリイオン含有量が０．５重量％以下である。
【００２２】
また、本発明の熱処理前のＰＰＴＡ短繊維の水含有量は１５〜１００重量％に保たれていることが好ましい。このような含水率にするには紡糸したＰＰＴＡ繊維を１００〜１５０℃で５〜２０秒間低温乾燥することが好ましい。乾燥温度が１００℃未満では水分の除去が難しく、１５０℃を超えると結晶化が進み、その後の脱イオンができなくなる傾向がある。このようにして得られた繊維を、カッターなどでアスペクト比５０〜５０００となるよう切断、あるいはフィブリル化するよう機械加工し、目的とするＰＰＴＡ短繊維が得られる。
【００２３】
本発明においては、このような物性を有する熱処理前のＰＰＴＡ短繊維を脱イオン処理する。脱イオン処理の条件は特に限定されないが、通常、水または温水で洗浄、あるいは抽出することが好ましい。そして、脱イオン処理されたＰＰＴＡ短繊維のアルカリイオン含有量は０．２重量％以下であることが好ましい。このようにして得られるＰＰＴＡ短繊維は、その後１５０〜５００℃の温度で熱処理することにより、結晶サイズを５０オングストローム以上にすることができる。
【００２４】
したがって、熱処理後のＰＰＴＡ短繊維は、結晶サイズが５０オングストローム以上であり、かつアルカリイオン含有量が０．２重量％以下である。
【００２５】
本発明のＰＰＴＡ短繊維の製造方法の代表例としては、ＰＰＴＡを濃硫酸に溶解して、１８〜２０重量％の粘調な溶液とし、これを紡糸口金から吐出して、わずかの間空気中に紡出後、水中へ紡糸する。この時、口金吐出時のせん断速度を２５，０００〜５０，０００ｓｅｃ−１にするのが好ましい。その後、紡糸浴中で凝固した繊維を水酸化ナトリウム水溶液で中和処理した後、１００〜１５０℃で、好ましくは５〜２０秒間乾燥する。このようにして得られた繊維を、カッターなどでアスペクト比５０〜５０００となるよう切断、あるいはフィブリル化するよう機械加工し、目的とするＰＰＴＡ短繊維が得られる。このようにして、本発明の熱処理前のＰＰＴＡ短繊維が得られる。その後、この熱処理前の短繊維を水で抽出し、脱イオン処理し、アルカリイオン含有量が０．２重量％以下となってから１５０〜５００℃の温度で熱処理を行い、熱処理後のＰＰＴＡ短繊維を得る。
【００２６】
本発明の方法で製造されたＰＰＴＡ短繊維は各種用途に有用である。まず、本発明の方法で製造されたＰＰＴＡ短繊維をバインダーと共に水中に分散させ、これを抄くことにより紙を得ることができる。あるいは本フィブリル化した構造を積極的に用いることで紙のバインダーとして用いることもできる。この紙はＰＰＴＡの優れた性質を有すると共に、アルカリイオン含有量が少ないため、絶縁性に優れ、電気・電子部品に最適である。
【００２７】
そのほか、本発明の方法で製造されたＰＰＴＡ短繊維は、その優れた性質を利用して、樹脂複合体、ゴム複合体、スパン糸、スパン糸を用いた織物、編み物、不織布などの布帛、さらにプリント配線板用シート状物などに有用である。
【００２８】
【実施例】
以下、実施例を示すが、実施例中の物性は次の測定法にしたがった。
【００２９】
（１）Ｎａ＋含有量
試料約０．５ｇを白金皿に採取し、硫酸に溶かしてガスバーナーおよび電気炉で灰化する。得られた灰化物を硫酸、硝酸およびふっ化水素酸で加熱分解し、希硝酸に溶かして定溶液とする。得られた定溶液中のＮａの測定を原子吸光分析法で行う。
【００３０】
（２）水含有量
試料約５ｇの重量を測定し、３００℃×２０分の熱処理を行い、標準状態で５分間放置した後、再度重量を測定する。ここで使う水分率は、［乾燥前重量−乾燥後重量］／［乾燥後重量］で得られるドライベース水分率である。
【００３１】
（３）結晶サイズ
試料を長さ４ｃｍ、重さ２０ｍｇに調製し、コロジオン溶液で固める。次に広角Ｘ線回折（ディフラクトメーター）法を用いデータを採取する。得られた２θ／θ強度データのうち、１１０方向の面の半値幅から、Ｓｃｈｅｒｒｅｒの式を用いて計算する。
【００３２】
実施例１
通常の方法で得られたＰＰＴＡ（分子量約２０，０００）１ｋｇを４ｋｇの濃硫酸に溶解し、直径０．１ｍｍのホールを１０００個有する口金からせん断速度３０，０００ｓｅｃ−１となるよう吐出し、４℃の水中に紡糸した後、１０％の水酸化ナトリウム水溶液で、１０℃×１５秒の条件で中和処理し、その後、１１０℃×１５秒間の低温乾燥をし、このようにして得られた繊維を、カッターでアスペクト比３００となるよう切断し、熱処理前のＰＰＴＡ短繊維を得た。
【００３３】
この熱処理前のＰＰＴＡ短繊維の性質を表１に示す。
【００３４】
このＰＰＴＡ短繊維を２０℃×１時間の条件で、水で抽出処理し、脱イオンを行い、その後４００℃×３０秒間熱処理を行った。この熱処理後のＰＰＴＡ短繊維の物性を表１に示す。
【００３５】
比較例１
中和処理後、低温乾燥を行わず、ただちに実施例１と同様の熱処理を行い、切断、その後、実施例と同じ抽出処理を行った。得られたＰＰＴＡ繊維の物性を表１に示す。
【００３６】
実施例２
実施例１および比較例１で得られたＰＰＴＡ繊維を用いて、公知の方法で紙を製造し、プリント配線板シートとして用いた。その結果、実施例１のものは優れた絶縁性と耐久性を示したが、比較例１のものは絶縁性に問題があった。
【００３７】
【表１】
【００３８】
【発明の効果】
本発明の熱処理前のＰＰＴＡ繊維は、脱イオン処理することにより、Ｎａ＋含有量をさらに減らすことができる。また、熱処理後のＰＰＴＡ繊維はＮａ＋含有量が少なく、各種用途に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention has a small ion content, a high Young's modulus, good dimensional stability, and a process for producing and use thereof in heat resistance and insulation properties superior polyparaphenylene terephthalamide short textiles.
[0002]
[Prior art]
Conventionally, polyparaphenylene terephthalamide (hereinafter abbreviated as PPTA) short fibers have been used as industrial and special clothing short fibers because they have excellent strength, heat resistance and high Young's modulus.
[0003]
PPTA fibers are formed into yarns having a high degree of crystallinity by applying concentrated sulfuric acid as a solvent for polymer dissolution during spinning to form a liquid crystal state, and then applying shear by a die. It is known that concentrated sulfuric acid as a solvent is washed with water and neutralized with alkali immediately after spinning, dried and heat-treated at 200 ° C. or higher, and then wound up as a filament (US Pat. No. 3,767,756). ).
[0004]
PPTA short fibers can be obtained by processing the fibers thus obtained so as to be fibrillated by cutting with a cutter or the like so as to have an aspect ratio of 50 to 5000 or by applying mechanical shear.
[0005]
[Problems to be solved by the invention]
However, in the short fibers obtained in this way, the salt formed by neutralization is incorporated into the fibers, and usually becomes short fibers containing 0.5 to 3% by weight of salt. For example, when sodium hydroxide is used in the neutralization, the ions constituting the salt are mainly Na + and SO 4 2− with a molar ratio of about 2: 1.
[0006]
When short fibers are used under humid conditions, this salt may be ionized in the presence of water, and may hinder energization, such as when electrical insulation is required.
[0007]
On the other hand, paper, resin composites, rubber composites or fabrics made from PPTA short fibers have good dimensional stability and workability as insulating / low dielectric materials when used as electronic / insulating materials due to their polymer structure. It is known to exhibit excellent characteristics such as high Young's modulus and low shrinkage due to high temperature treatment. However, when energization due to such factors becomes a problem, for example, when it is used as a material for a printed wiring board, it may become a factor of migration via ions, which may limit application development. It was.
[0008]
The object of the present invention is to eliminate the drawbacks of the prior art described above, and to maintain a high heat resistance and a high Young's modulus inherent in PPTA short fibers, while having a low ion content, and particularly a method for producing fibers useful as electrical / electronic components and The purpose is to provide its use.
[0009]
[Means for Solving the Problems]
In order to solve the above problems, the present invention takes the following means.
[0010]
( 1 ) Spin and neutralize polyparaphenylene terephthalamide sulfuric acid solution, keep the water content to 15% by weight or less, and cut or fibrillate to have an aspect ratio of 50-5000. A method for producing polyparaphenylene terephthalamide short fibers before heat treatment , characterized in that they are machined into short fibers and then deionized.
[0011]
(2) The method for producing polyparaphenylene terephthalamide short fibers before heat treatment according to the above (1 ), wherein the alkali ion content is 1.0% by weight or less.
[0012]
( 3 ) Production of polyparaphenylene terephthalamide short fibers obtained by heat-treating polyparaphenylene terephthalamide short fibers obtained by the production method according to any one of (1) to (2 ) above at 150 to 500 ° C. Method.
[0013]
(4) The method for producing a polyparaphenylene terephthalamide short fiber according to the above (3), wherein the crystal size is 50 angstroms or more by heat treatment.
[0014]
(5) The method for producing a polyparaphenylene terephthalamide short fiber according to any one of the above (3) to (4 ), wherein the alkali ion content is 0.2% by weight or less.
[0015]
( 6 ) An insulating / low-dielectric material using the polyparaphenylene terephthalamide short fiber produced by the method according to any one of (1) to (5 ) above.
[0016]
( 7 ) A resin composite comprising a polyparaphenylene terephthalamide short fiber produced by the method according to any one of (1) to (5 ) above.
[0017]
( 8 ) A rubber composite comprising the polyparaphenylene terephthalamide short fiber produced by the method according to any one of (1) to (5 ) above.
[0018]
( 9 ) A sheet-like structure for a printed wiring board using the polyparaphenylene terephthalamide short fibers produced by the method according to any one of (1) to (5 ) above.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The polyparaphenylene terephthalamide (PPTA) in the present invention is a polymer obtained by polycondensation of terephthalic acid and paraphenylene diamine, but a polymer obtained by copolymerizing a small amount of dicarboxylic acid and diamine can also be used. Or, the molecular weight of the copolymer is usually preferably 20,000 to 25,000.
[0020]
PPTA fibers can be prepared by dissolving the PPTA in concentrated sulfuric acid, extruding the viscous solution from the spinneret, after the filamentary by spinning in air or in water, neutralized with sodium hydroxide solution, finally Is obtained by drying and heat treatment at 120 to 500 ° C. The PPTA fiber before drying / heat treatment has a crystal size (110 face) of 50 angstroms or less, and usually exceeds 50 angstroms after drying / heat treatment.
[0021]
The PPTA short fiber before heat treatment, which is one of the present invention, needs to have a short fiber crystal size of 50 angstroms or less, an alkali ion content of 1.0% by weight or less, and an alkali ion content. Must be 1.0% by weight or less. When the crystal size exceeds 50 angstroms, it becomes difficult to extract alkali ions. On the other hand, if the alkali ion content exceeds 1.0% by weight , the application to the electric / electronic field, which is the object of the present invention, is limited. And preferably crystal | crystallization size is 35-45 angstrom, and alkali ion content is 0.5 weight% or less.
[0022]
Moreover, it is preferable that the water content of the PPTA short fiber before the heat treatment of the present invention is maintained at 15 to 100% by weight. In order to obtain such a moisture content, it is preferable to dry the spun PPTA fiber at 100 to 150 ° C. for 5 to 20 seconds at a low temperature. If the drying temperature is less than 100 ° C., it is difficult to remove moisture, and if it exceeds 150 ° C., crystallization proceeds and subsequent deionization tends to be impossible. The fiber thus obtained is cut or fibrillated with a cutter or the like so as to have an aspect ratio of 50 to 5000, and the intended PPTA short fiber is obtained.
[0023]
In the present invention, the deionization of PPTA short fibers before the heat treatment with such physical properties. The conditions for the deionization treatment are not particularly limited, but it is usually preferable to wash or extract with water or warm water. The alkali ion content of the deionized PPTA short fiber is preferably 0.2% by weight or less. The PPTA short fiber thus obtained can be heat treated at a temperature of 150 to 500 ° C. to make the crystal size 50 angstroms or more.
[0024]
Thus, PPTA short fibers after the heat treatment, the crystal size is less than 50 angstroms, and alkali ion content of more than 0.2 wt%.
[0025]
As a typical example of the method for producing the PPTA short fiber of the present invention, PPTA is dissolved in concentrated sulfuric acid to obtain a viscous solution of 18 to 20% by weight, and this is discharged from the spinneret, and in the air for a short time. Spin into water and spin into water. At this time, it is preferable to set the shear rate during discharge of the die to 25,000 to 50,000 sec −1 . Thereafter, the fiber solidified in the spinning bath is neutralized with an aqueous sodium hydroxide solution, and then dried at 100 to 150 ° C., preferably for 5 to 20 seconds. The fiber thus obtained is cut or fibrillated with a cutter or the like so as to have an aspect ratio of 50 to 5000, and the intended PPTA short fiber is obtained. Thus, the PPTA short fiber before heat treatment of the present invention is obtained. Thereafter, the short fibers before the heat treatment was extracted with water, and deionized, alkali ion content is subjected to heat treatment at a temperature of 150 to 500 ° C. from a 0.2 wt% or less, PPTA after heat treatment Get short fiber.
[0026]
The PPTA short fibers produced by the method of the present invention are useful for various applications. First, PPTA short fibers produced by the method of the present invention are dispersed in water together with a binder, and paper can be obtained by making the paper. Alternatively, it can be used as a paper binder by actively using the fibrillated structure. This paper has excellent properties of PPTA and has a low alkali ion content, so it has excellent insulation and is optimal for electrical and electronic parts.
[0027]
In addition, the PPTA short fibers produced by the method of the present invention can be used to make resin composites, rubber composites, spun yarns, fabrics using spun yarns, knitted fabrics, non-woven fabrics, and the like. Useful for printed wiring board sheets.
[0028]
【Example】
Hereinafter, although an Example is shown, the physical property in an Example followed the following measuring method.
[0029]
(1) Na + content About 0.5 g of a sample is collected in a platinum dish, dissolved in sulfuric acid, and incinerated with a gas burner and an electric furnace. The obtained ashed product is decomposed by heating with sulfuric acid, nitric acid and hydrofluoric acid, and dissolved in dilute nitric acid to obtain a constant solution. Measurement of Na in the obtained constant solution is performed by atomic absorption spectrometry.
[0030]
(2) Water content Approximately 5 g of the sample is weighed, heat-treated at 300 ° C. for 20 minutes, left in a standard state for 5 minutes, and then weighed again. The moisture content used here is the dry base moisture content obtained by [weight before drying−weight after drying] / [weight after drying].
[0031]
(3) Crystal size A sample is prepared to have a length of 4 cm and a weight of 20 mg, and is hardened with a collodion solution. Next, data is collected using a wide-angle X-ray diffraction (diffractometer) method. Of the obtained 2θ / θ intensity data, calculation is made from the half width of the surface in the 110 direction using the Scherrer equation.
[0032]
Example 1
1 kg of PPTA (molecular weight of about 20,000) obtained by a normal method is dissolved in 4 kg of concentrated sulfuric acid, and discharged from a die having 1000 holes with a diameter of 0.1 mm so as to have a shear rate of 30,000 sec-1. After spinning in water at 4 ° C, neutralization with 10% aqueous sodium hydroxide was performed at 10 ° C for 15 seconds, followed by low temperature drying at 110 ° C for 15 seconds. The cut fiber was cut with a cutter to an aspect ratio of 300 to obtain a short PPTA fiber before heat treatment.
[0033]
Table 1 shows the properties of the PPTA short fibers before the heat treatment.
[0034]
The PPTA short fibers were extracted with water under conditions of 20 ° C. × 1 hour, deionized, and then heat-treated at 400 ° C. × 30 seconds. Table 1 shows the physical properties of the PPTA short fibers after the heat treatment.
[0035]
Comparative Example 1
Immediately after the neutralization treatment, low-temperature drying was not performed, and the same heat treatment as in Example 1 was performed. The physical properties of the obtained PPTA fiber are shown in Table 1.
[0036]
Example 2
Using the PPTA fibers obtained in Example 1 and Comparative Example 1, paper was produced by a known method and used as a printed wiring board sheet. As a result, although the thing of Example 1 showed the outstanding insulation and durability, the thing of the comparative example 1 had a problem in insulation.
[0037]
[Table 1]
[0038]
【The invention's effect】
The PPTA fiber before heat treatment of the present invention can be further reduced in Na + content by deionization treatment. Moreover, the PPTA fiber after heat treatment has a small Na + content and is useful for various applications.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36505997A JP3831103B2 (en) | 1997-12-19 | 1997-12-19 | Method for producing polyparaphenylene terephthalamide short fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36505997A JP3831103B2 (en) | 1997-12-19 | 1997-12-19 | Method for producing polyparaphenylene terephthalamide short fiber |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006034075A Division JP2006176950A (en) | 2006-02-10 | 2006-02-10 | Polyparaphenylene terephthalamide (ppta) staple fiber and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11181622A JPH11181622A (en) | 1999-07-06 |
| JP3831103B2 true JP3831103B2 (en) | 2006-10-11 |
Family
ID=18483337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36505997A Expired - Lifetime JP3831103B2 (en) | 1997-12-19 | 1997-12-19 | Method for producing polyparaphenylene terephthalamide short fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3831103B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3676111B2 (en) * | 1998-06-03 | 2005-07-27 | 帝人テクノプロダクツ株式会社 | Aromatic polyamide fiber and paper using the same |
| KR100924908B1 (en) * | 2008-05-29 | 2009-11-03 | 주식회사 코오롱 | Aramide Fiber and Method for Manufacturing The Same |
-
1997
- 1997-12-19 JP JP36505997A patent/JP3831103B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11181622A (en) | 1999-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6592987B1 (en) | Wholly aromatic synthetic fiber produced by liquid-crystal spinning, process for producing the same, and use thereof | |
| WO2002072931A1 (en) | Method for producing fiber and film of silk and silk-like material | |
| PT1172466E (en) | Process for producing a meta-type wholly aromatic polyamide fiber | |
| JP4162685B2 (en) | Polyparaphenylene terephthalamide fiber composite and use thereof | |
| JPH0978349A (en) | Production of polybenzazole fiber | |
| JP3831103B2 (en) | Method for producing polyparaphenylene terephthalamide short fiber | |
| JPS5910894B2 (en) | Polyamide Hakumaku Knob Tree Textile Shitsuno | |
| JP3793341B2 (en) | Process for producing polyparaphenylene terephthalamide fiber composite | |
| EP0040833B1 (en) | Papery product | |
| JPH03104921A (en) | Production of fiber of polybenzothiazoles, polybenzoxazoles or polybenzimidazoles | |
| JP4773902B2 (en) | Nanofiber nonwoven fabric and method for producing the same | |
| JP3995532B2 (en) | Method for producing dense meta-type wholly aromatic polyamide fiber | |
| JP2001303365A (en) | Method for producing meta wholly aromatic polyamide yarn and yarn obtained by the method | |
| JP2006176950A (en) | Polyparaphenylene terephthalamide (ppta) staple fiber and its use | |
| KR20020047088A (en) | Wholly Aromatic Polyamide Fiber Paper and Laminated Sheet Therefrom | |
| JP2001248091A (en) | Highly heat resistant and highly flame retardant organic fiber paper and composite material using the same fiber paper | |
| JP2002317392A (en) | Method of producing poly-para-phenylene terephthalamide paper and method of producing printed circuit substrate therefrom | |
| JP2572426B2 (en) | Method for producing aromatic polyamide fiber paper | |
| JP3565614B2 (en) | Aromatic polyamide molding and production method | |
| JPS59624B2 (en) | Method for producing heat-resistant nonwoven fabrics and paper-like materials | |
| JPS591818B2 (en) | Thailand's history | |
| JP2008013872A (en) | Method for producing polymetaphenylene isophthalamide nanofiber nonwoven fabric | |
| JPS59622B2 (en) | Method for producing heat-resistant nonwoven fabrics and paper-like materials | |
| JP3929342B2 (en) | Method for producing dense meta-type wholly aromatic polyamide fiber | |
| JP2000026613A (en) | Composite pulp-like particle, composite paper and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040311 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20051201 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051213 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060210 |
|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20060130 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20060410 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20060412 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060410 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A132 Effective date: 20060613 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060711 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060713 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090721 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100721 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100721 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110721 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110721 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130721 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |