JPH01272899A - Polyphenylene sulfide fiber paper - Google Patents
Polyphenylene sulfide fiber paperInfo
- Publication number
- JPH01272899A JPH01272899A JP10068388A JP10068388A JPH01272899A JP H01272899 A JPH01272899 A JP H01272899A JP 10068388 A JP10068388 A JP 10068388A JP 10068388 A JP10068388 A JP 10068388A JP H01272899 A JPH01272899 A JP H01272899A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene sulfide
- paper
- fiber paper
- properties
- short fibers
- 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.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 37
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 23
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 23
- 238000010292 electrical insulation Methods 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 239000010754 BS 2869 Class F Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paper (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ポリフェニレンサルファイド短繊維からなる
紙に関し、特に、耐熱性、電気絶縁性に優れたポリフェ
ニレンサルファイド繊維紙に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to paper made of short polyphenylene sulfide fibers, and particularly to polyphenylene sulfide fiber paper having excellent heat resistance and electrical insulation properties.
（従来の技術）
最近、技術革新の高度化に伴って、祇に対して要求され
る性能が高くなり、従来の木材パルプに代わって、ビニ
ロン、ナイロン、ポリプロピレン、ポリアクリロニトリ
ル、ポリエステル、アラミド等の合成繊維が紙の原料と
して使用されるようになってきている。(Conventional technology) Recently, with the advancement of technological innovations, the performance required for wood pulp has increased, and instead of conventional wood pulp, vinylon, nylon, polypropylene, polyacrylonitrile, polyester, aramid, etc. Synthetic fibers are increasingly being used as raw materials for paper.
このうち、耐熱性、電気特性が要求される分野では、ポ
リエステル繊維紙、メタアラミド繊維紙などが使用され
ている。Among these, polyester fiber paper, meta-aramid fiber paper, etc. are used in fields where heat resistance and electrical properties are required.
（発明が解決しようとする課題）
しかしながら、ポリエステル繊維紙では、耐熱性が１２
０″Ｃと不満足であり、その上、難燃性、耐加水分解性
、極低温性及び吸湿、高温等の環境下での電気特性が不
足している。一方、かかる特性を必要とする用途が最近
増加しており、これに対処するために非常に高価な耐熱
性のポリイミドフィルムで電気絶縁用途に展開中である
が、このポリイミドもＦ種（１５５°Ｃ）の高温下で水
分がない場合は十分な耐熱性を示すが、１５５°Ｃ飽和
蒸気中では、１時間後には加水分解して、初期伸度の３
０％以下となる。ポリエステルは、３０分でこの値が５
％となり、大きな加水分解性を示すものである。(Problem to be solved by the invention) However, polyester fiber paper has a heat resistance of 12
0″C, and in addition, it lacks flame retardancy, hydrolysis resistance, cryogenic properties, moisture absorption, and electrical properties in high-temperature environments.On the other hand, applications that require such properties has been increasing recently, and in order to deal with this, extremely expensive heat-resistant polyimide films are being developed for electrical insulation purposes, but this polyimide also has no moisture at high temperatures of class F (155°C). However, in saturated steam at 155°C, it hydrolyzes after 1 hour, reducing the initial elongation to 3
It becomes 0% or less. For polyester, this value is 5 in 30 minutes.
%, indicating high hydrolyzability.
本発明の目的は、かかる従来技術の問題点である吸湿に
よる電気特性の低下を少な（し、高温加湿下での加水分
解のない、又力学特性も維持し、更に難燃性を有する安
価な、耐熱性で電気特性の良好なる信頼性の高い合成繊
維紙を提供することにある。The object of the present invention is to reduce the deterioration of electrical properties due to moisture absorption, which is a problem in the prior art, to avoid hydrolysis under high-temperature humidification, to maintain mechanical properties, and to provide an inexpensive flame-retardant material. The object of the present invention is to provide highly reliable synthetic fiber paper that is heat resistant and has good electrical properties.
（課題を解決するための手段）
本発明者らは、上記目的を達成すべく種々検討を重ねた
結果、ポリフェニレンサルファイド繊維からなる祇が上
記目的を達成するうえで適当であることを見出し、本発
明に到達した。(Means for Solving the Problems) As a result of various studies to achieve the above object, the present inventors found that a polyphenylene sulfide fiber is suitable for achieving the above object, and the present inventors The invention has been achieved.
即ち、本発明は、ポリフェニレンサルファイド短繊維か
らなることを特徴とするポリフェニレンサルファイド繊
維紙である。That is, the present invention is a polyphenylene sulfide fiber paper characterized by being made of polyphenylene sulfide short fibers.
本発明において用いられるポリフェニレンサルファイド
繊維は、公知の合成法、例えば極性有機溶剤中で無水硫
化ナトリウムと多ハロ置換の環状化合物とを反応させる
ことにより得られる、繰り返し単位の９０％以上が ＋
Ｑ−３−） で構成されたポリマーからなる繊維であ
る。The polyphenylene sulfide fiber used in the present invention is obtained by a known synthesis method, for example, by reacting anhydrous sodium sulfide with a polyhalo-substituted cyclic compound in a polar organic solvent, and 90% or more of the repeating units are +
Q-3-) It is a fiber made of a polymer composed of Q-3-).
また、本発明で使用されるポリフェニレンサルファイド
短繊維は、単糸繊度が０．１〜１５ｄｅ、好ましくは２
〜８ｄｅ、繊維長が２〜２５閤、好ましくは５〜１５ｍ
ｍであることが望ましい。Further, the polyphenylene sulfide short fibers used in the present invention have a single yarn fineness of 0.1 to 15 de, preferably 2.
~8de, fiber length 2-25m, preferably 5-15m
It is desirable that it is m.
本発明のポリフェニレンサルファイド繊維紙を抄紙する
に際しては、酢酸ビニル系バインダ又はメタアラミド系
のパルプ状物などをポリフェニレンサルファイド繊維紙
の特性を余りそこなわない程度添加し、バインダとして
使用できる。また、ポリフェニレンサルファイド短繊維
の少なくとも一部を未延伸糸にして、抄紙後熱プレス（
カレンダー）して、バインダとして使用することもでき
る。When making the polyphenylene sulfide fiber paper of the present invention, a vinyl acetate binder or a meta-aramid pulp material can be added as a binder to an extent that does not significantly impair the properties of the polyphenylene sulfide fiber paper. In addition, at least a part of the polyphenylene sulfide short fibers is made into undrawn yarn, and after paper making, heat press (
calendar) and can also be used as a binder.
本発明のポリフェニレンサルファイド繊維紙は、通常、
湿式抄紙法によって製造されるが、乾式抄紙法、スパン
ボンド法等によって製造されることもできる。尚、湿式
抄紙法による場合は、スラリー中の繊維濃度は０．０１
〜１％が用いられるが特にこれに限定されるものではな
い。また、ポリフェニレンサルファイド短繊維は、分散
性、濾水性が非常に良いため、分散剤を使わなくても十
分均一な紙を効率良く安価に抄紙することができる。The polyphenylene sulfide fiber paper of the present invention usually has
Although it is manufactured by a wet papermaking method, it can also be manufactured by a dry papermaking method, a spunbond method, etc. In addition, when using the wet papermaking method, the fiber concentration in the slurry is 0.01
~1% is used, but is not particularly limited to this. In addition, since polyphenylene sulfide short fibers have very good dispersibility and drainage properties, it is possible to make sufficiently uniform paper efficiently and inexpensively without using a dispersant.
（実施例）
以下、実施例により本発明を更に詳細に説明する。尚、
ＵＬ規格での耐熱温度指数としての機械特性と電気特性
、ｔａｎδ及びオリゴマー抽出量を次の方法により測定
した。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. still,
Mechanical properties and electrical properties as heat resistance temperature index according to UL standard, tan δ and oligomer extraction amount were measured by the following method.
（１）ＵＬ規格（ＵＬ−７４６Ｂ）における耐熱温度指
数としての機械特性（引張伸度、強度）及び電気特性の
絶縁破壊電圧
ポリフェニレンサルファイド繊維紙を高温エージングし
たときの各特性の半減期をエージング温度の関数として
アレニウスの式でプロットして求めた。(1) The half-life of each property when aging polyphenylene sulfide fiber paper at high temperature is the aging temperature It was determined by plotting using the Arrhenius equation as a function of .
（２）ｔａｎδ ＪＩＳ Ｃ５１０２に準じて測定した。(2) tanδ Measured according to JIS C5102.
（３）オリゴマー抽出量 キシレンにて１５日間リフラックスして測定した。(3) Oligomer extraction amount The measurement was performed after refluxing in xylene for 15 days.
実施例１
３２０’Ｃ，シャーレイト１０００／ｓｅｃでのメルト
ビスコシティ−（ＭＶ）が１１００ポイズであるポリフ
ェニレンサルファイドを３２０°Ｃで溶融紡糸し、紡糸
速度６００ｍ／分で紡糸して未延伸糸を得た。この未延
伸糸は単糸繊度６ｄｅ、伸度３２０％、強度１゜０ｇ／
ｄｅであった。この未延伸糸を１００ ’Ｃのホットロ
ーラで３．５倍に延伸し、次いで１２０°Ｃ及び２２０
°Ｃ（７）ホットローラで定長２段セットを行って、全
繊度１７１ ｄ ｅ ／１００ ｆｉｌｓの延伸糸を得
た。この延伸糸をカセにして切断し、単糸繊度１．７ｄ
ｅ 、強度５．３ｇ／ｄｅ、伸度２８％の短繊維を得た
。Example 1 Polyphenylene sulfide having a melt viscocity (MV) of 1100 poise at 320°C and a shear rate of 1000/sec was melt-spun at 320°C and spun at a spinning speed of 600 m/min to obtain an undrawn yarn. Obtained. This undrawn yarn has a single yarn fineness of 6de, an elongation of 320%, and a strength of 1゜0g/
It was de. This undrawn yarn was stretched 3.5 times with a hot roller at 100'C, then 120°C and 220°C.
Two stages of constant length setting were performed using a hot roller at 7°C to obtain a drawn yarn with a total fineness of 171 d e /100 fils. This drawn yarn was cut into a skein, and the single yarn fineness was 1.7 d.
Short fibers with a strength of 5.3 g/de and an elongation of 28% were obtained.
この短繊維を、繊維濃度が０．５％となるように水中へ
分散させ、これに、繊維重量に対して１０重量％の酢酸
ビニル系バインダを添加した。The short fibers were dispersed in water to a fiber concentration of 0.5%, and a vinyl acetate binder was added thereto in an amount of 10% by weight based on the weight of the fibers.
この分散液を円網抄紙機へ送り、通常の方法で目付６５
ｇ ／ ｒｄの紙を得た。この紙を２５０°Ｃのカレ
ンダーにかけ、熱プレスし、得られた紙の耐熱温度指数
としての機械特性、電気特性、ｔａｎδ及びオリゴマー
抽出量は第１表に示す通りであった。This dispersion was sent to a circular mesh paper machine, and the fabric weight was 65 by the usual method.
g/rd paper was obtained. This paper was calendered at 250°C and hot pressed, and the mechanical properties, electrical properties, tan δ, and oligomer extraction amount as heat resistance temperature index of the paper obtained were as shown in Table 1.
実施例２
実施例１で得た未延伸糸を５Ｍ長に切断したもの２０％
、実施例１で得た延伸糸を５胴長に切断したちの８０％
とを混合して、繊維濃度が０．４％となるように水中へ
分散させた。Example 2 20% of the undrawn yarn obtained in Example 1 cut into 5M length
, 80% of the drawn yarn obtained in Example 1 was cut into 5 body lengths.
were mixed and dispersed in water so that the fiber concentration was 0.4%.
この分散液を円網抄紙機へ送り、通常の方法で抄紙後、
２６０°Ｃのホットカレンダーに連続して送り、目付８
０ｇ／ｒｒｉの紙を得た。This dispersion is sent to a cylinder paper machine, and after paper is made in the usual manner,
Continuously sent to a hot calender at 260°C, with a basis weight of 8.
A paper of 0 g/rri was obtained.
得られた紙の特性を実施例１と同様に測定し、第１表に
示した。The properties of the obtained paper were measured in the same manner as in Example 1 and are shown in Table 1.
比較例１
実施例１において、ポリフェニレンサルファイド繊維の
代わりにポリエチレンテレフタレート短繊維（単糸繊度
１．５ ｄａ、強度４．５ｇ／ｄｅ、伸度２５％）を用
い、他の条件は実施例１と同じにして抄紙を行った。Comparative Example 1 In Example 1, polyethylene terephthalate short fibers (single fineness 1.5 da, strength 4.5 g/de, elongation 25%) were used instead of polyphenylene sulfide fibers, and the other conditions were the same as in Example 1. Paper was made in the same manner.
得られた紙を２３０°Ｃのカレンダーにかけ６５ｇ／ボ
のプレス紙と、し、実施例１と同様に各特性を測定し、
第１表に示した。The obtained paper was calendered at 230°C to make 65g/bo press paper, and each property was measured in the same manner as in Example 1.
It is shown in Table 1.
比較例２
実施例１において、ポリフェニレンサルファイド繊維の
代わりにメタアラミド短繊維（単糸繊度２ｄｅ、強度５
．２ｇ／ｄｅ、伸度２６％）を用い、他の条件は実施例
１と同じにして抄紙、ホットプレスを行った。Comparative Example 2 In Example 1, meta-aramid short fibers (single yarn fineness 2 de, strength 5
．． 2g/de, elongation 26%), and other conditions were the same as in Example 1, and paper making and hot pressing were performed.
得られた紙の特性を第１表に示す。The properties of the obtained paper are shown in Table 1.
第 １ 表
以上の結果から明らかなように、本発明のポリフェニレ
ンサルファイド繊維紙は、従来のポリエステル繊維紙に
対しては、ＵＬ耐熱の機械特性における温度指数が１６
０〜１６５°Ｃとポリエステルの１１０〜１２０°Ｃに
対して高く、又電気特性の耐熱指数も１８０°Ｃとポリ
エステルの１２５°Ｃに対して大である。ｔａｎδも非
常に低く、吸湿率も０．０５％と極端に低いし、誘電率
も３．０〜３．１とポリエステルの３．３より低い。ま
た、オリゴマー抽出量も０．９％又は１．１％と、ポリ
エステルの２．５％よりもはるかに少ない。As is clear from the results in Table 1, the polyphenylene sulfide fiber paper of the present invention has a temperature index of 16 in terms of mechanical properties of UL heat resistance compared to conventional polyester fiber paper.
The temperature is 0 to 165°C, which is higher than the 110 to 120°C of polyester, and the heat resistance index of electrical properties is 180°C, which is higher than the 125°C of polyester. The tan δ is also very low, the moisture absorption rate is extremely low at 0.05%, and the dielectric constant is 3.0 to 3.1, which is lower than polyester's 3.3. Furthermore, the amount of oligomer extracted is 0.9% or 1.1%, which is much lower than the 2.5% of polyester.
比較例２のメタアラミド繊維紙は、ＵＬ耐熱の機械特性
、電気特性では、１９０〜２１０°Ｃと本発明のものよ
りも良好な温度指数を示しているが、ｔａｎδが０．０
１９と１０倍以上大であり、その誘電率も５．３と２倍
近くも大きく、オリゴマー抽出量、吸水率も非常に大で
ある。また、難燃性としても、ＬＯＩが本発明のものは
、３２〜３５と、ポリエステルの２０、メタアラミドの
２６より大で、自己消火性が優れている。The meta-aramid fiber paper of Comparative Example 2 has a temperature index of 190 to 210°C, which is better than that of the present invention, in terms of UL heat-resistant mechanical properties and electrical properties, but tan δ is 0.0.
19, which is more than 10 times larger, and its dielectric constant is 5.3, which is nearly twice as large.The amount of oligomer extracted and the water absorption rate are also very large. In terms of flame retardancy, the LOI of the present invention is 32 to 35, which is higher than 20 for polyester and 26 for meta-aramid, and has excellent self-extinguishing properties.
（本発明の効果）
本発明のポリフェニレンサルファイド繊維紙は、Ｆ種に
十分合格する機械的特性、電気的特性の耐熱温度指数を
有し、しかも非常に小さいｔａｎδを各周波数で有して
いると共に、誘電率も小さく、吸湿性が極めて少な（、
オリゴマー量も非常に少なく、更に自己消火性を有する
難燃性を有しており、高温、高温雰囲気下で使用するの
に好適である。(Effects of the present invention) The polyphenylene sulfide fiber paper of the present invention has a heat resistance temperature index of mechanical properties and electrical properties that satisfactorily pass Class F, and also has a very small tan δ at each frequency. , has a low dielectric constant and extremely low hygroscopicity (,
The amount of oligomers is very small, and it also has flame retardant properties with self-extinguishing properties, making it suitable for use at high temperatures and in high-temperature atmospheres.
Claims (2)
特徴とするポリフェニレンサルファイド繊維紙。1. A polyphenylene sulfide fiber paper characterized by being made of polyphenylene sulfide short fibers.
３以下である第１項記載のポリフェニレンサルファイド
繊維紙。Dielectric loss tangent (tanδ) at 2.1KHz is 0.00
3 or less, the polyphenylene sulfide fiber paper according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10068388A JPH01272899A (en) | 1988-04-22 | 1988-04-22 | Polyphenylene sulfide fiber paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10068388A JPH01272899A (en) | 1988-04-22 | 1988-04-22 | Polyphenylene sulfide fiber paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01272899A true JPH01272899A (en) | 1989-10-31 |
Family
ID=14280544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10068388A Pending JPH01272899A (en) | 1988-04-22 | 1988-04-22 | Polyphenylene sulfide fiber paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01272899A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949082A (en) * | 2010-08-31 | 2011-01-19 | 天津工业大学 | Method for preparing polyphenylene sulfide fiber insulation paper |
| WO2012033085A1 (en) * | 2010-09-07 | 2012-03-15 | 東レ株式会社 | Nonwoven fabric comprising polyphenylene sulfide fibers |
| CN103174054A (en) * | 2011-12-23 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Mixed paper containing polyphenylene sulfide fiber and preparation method thereof |
-
1988
- 1988-04-22 JP JP10068388A patent/JPH01272899A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949082A (en) * | 2010-08-31 | 2011-01-19 | 天津工业大学 | Method for preparing polyphenylene sulfide fiber insulation paper |
| WO2012033085A1 (en) * | 2010-09-07 | 2012-03-15 | 東レ株式会社 | Nonwoven fabric comprising polyphenylene sulfide fibers |
| US8900413B2 (en) | 2010-09-07 | 2014-12-02 | Toray Industries, Inc. | Nonwoven fabric comprising polyphenylene sulfide fiber |
| CN103174054A (en) * | 2011-12-23 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Mixed paper containing polyphenylene sulfide fiber and preparation method thereof |
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