JPH01314724A - Copolyimide yarn - Google Patents

Copolyimide yarn

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Publication number
JPH01314724A
JPH01314724A JP14008088A JP14008088A JPH01314724A JP H01314724 A JPH01314724 A JP H01314724A JP 14008088 A JP14008088 A JP 14008088A JP 14008088 A JP14008088 A JP 14008088A JP H01314724 A JPH01314724 A JP H01314724A
Authority
JP
Japan
Prior art keywords
component
fiber
acid anhydride
yarn
copolyimide
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
Application number
JP14008088A
Other languages
Japanese (ja)
Inventor
Takuma Kanda
神田 拓馬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP14008088A priority Critical patent/JPH01314724A/en
Publication of JPH01314724A publication Critical patent/JPH01314724A/en
Pending legal-status Critical Current

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  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Artificial Filaments (AREA)

Abstract

PURPOSE:To obtain the subject yarn suitable for electric insulating material, fire proofing wear, filter or interior material of vehicles, etc., having excellent continuity of heat resistance, nonflammability and dimensional stability at high temperature, containing diaminodiphenylether is diamine component and specific component of acid anhydride component. CONSTITUTION:The aimed fiber is composed of 4,4'-diaminodiphenylether as diamine component and acid anhydride component of (A) pyromellitic dianhydride and (B) 3,3', 4,4'-benzophenone tetracarboxylic dianhydride and/or 3,3', 4,4'-biphenyltetracarboxylic dianhydride and fraction of the component A in the acid anhydride is 85-35mol%. To obtain said fiber, at first above monomers are reacted to form polyamic acid solution, then spun to fiber by wet or dry spinning method and at last converted to polyimide by cyclization with heat or chemical means.

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は耐熱性のすぐれたコポリイミド繊維に関するも
のでおる。ざらに詳しくは著しくすぐれた耐熱寿命と適
度の高温寸法安定性を兼ね備えた]ポリイミド繊維に関
する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a copolyimide fiber with excellent heat resistance. More specifically, the present invention relates to a polyimide fiber which has both extremely excellent heat resistance life and moderate high temperature dimensional stability.

[従来の技術] 全芳香族ポリイミドは有機ポリマの中で最高級の耐熱性
を有しており、その特徴を生かしていくつかの成型品が
すでに実用化されている。その代表的なポリマであるポ
リ(4,4°−オキシジフェニレンピロメリットイミド
〉はフィルム(商品名Kapton)が著名でおるか、
かつて繊維としても検討された(特公昭42−2936
号公報)。
[Prior Art] Fully aromatic polyimide has the highest heat resistance among organic polymers, and several molded products have already been put into practical use by taking advantage of this characteristic. Poly(4,4°-oxydiphenylenepyromellitimide), which is a typical polymer, is famous for its film (trade name: Kapton).
It was once considered as a fiber (Special Publication No. 42-2936
Publication No.).

この繊維は難燃性および熱寸法安定性は極めてすぐれて
いるけれども、通常の熱環化法でつくった繊維の場合、
比較的高い温度に長時間暴露した後の引張特性の保持性
、Vなわち、耐熱寿命はかなり劣ることがわかった。
Although this fiber has extremely high flame retardancy and thermal dimensional stability, in the case of fibers made by the usual thermal cyclization method,
It was found that the retention of tensile properties, V, or heat resistance life after long-term exposure to relatively high temperatures was quite poor.

[発明が解決しようとする課題] したがって、すぐれた耐熱寿命、高温寸法安定性および
難燃性を兼ね備えた繊維が特に望まれるのである。
[Problems to be Solved by the Invention] Therefore, fibers that have excellent heat-resistant life, high-temperature dimensional stability, and flame retardancy are particularly desired.

本発明者は上記ポリ(4,4°−オキシジフェニレンピ
ロメリットイミド>S維の耐熱寿命がなぜ悪いかについ
て考察した結果、この繊維が高度に結晶性であり、耐熱
試験処理時におこる熱結晶化の進行に伴う物性低下、す
なわち、いわゆる結晶化劣化がその理由で必ろうと推測
した。したがって、伯のモノマを共重合して結晶性をあ
る程度低下させることが耐熱寿命の向上に有効であろう
と考え、この方向で鋭意検討した結果、特定の酸無水物
成分を特定の割合で共重合させれば上記の目標を達成し
うろことを見出し本発明に到達した。。
As a result of considering why the heat resistance life of the poly(4,4°-oxydiphenylene pyromellitimide>S fiber) is poor, the present inventor found that this fiber is highly crystalline and that thermal crystallization occurs during heat resistance test treatment. We speculated that the reason for this must be a decrease in physical properties as the chemical reaction progresses, that is, so-called crystallization deterioration.Therefore, copolymerization of the monomers with a certain degree of crystallinity to reduce the crystallinity to some extent would be effective in improving the heat-resistant life. As a result of intensive study in this direction, we discovered that the above goal could be achieved by copolymerizing specific acid anhydride components in a specific ratio, and thus arrived at the present invention.

[課題を解決するための手段] すなわち、本発明は、ジアミン成分が4,4°−ジアミ
ノジフェニルエーテル、酸無水物成分が無水ピロメリッ
ト酸(A>と3,3°、4,4°−ベンゾフェノンテト
ラカルボン酸二無水物および/または3,3″、4,4
°−ビフェニルテトラカルボン酸二無水物からなり、酸
無水物成分中のAの比率が85〜35モル%であること
を特徴とするコポリイミド繊維である。
[Means for Solving the Problems] That is, in the present invention, the diamine component is 4,4°-diaminodiphenyl ether, and the acid anhydride component is pyromellitic anhydride (A> and 3,3°, 4,4°-benzophenone). Tetracarboxylic dianhydride and/or 3,3″, 4,4
It is a copolyimide fiber made of °-biphenyltetracarboxylic dianhydride and characterized in that the ratio of A in the acid anhydride component is 85 to 35 mol%.

以下、本発明をさらに詳細に説明する。The present invention will be explained in more detail below.

本発明のコポリイミド繊維を構成するジアミン成分は、
4,4゛−ジアミノジフェニルエーテルである。また、
酸無水物成分のひとつとして必ず無水ピロメリット酸(
PMDA)を用いる。他の酸無水物成分は3,3°、4
,4°−ベンゾフェノンテトラカルボン酸二無水物(B
丁DA>および/または3,3゛、 、!l、 4’−
ビフェニルテトラカルボン酸二無水物(BPDA)であ
る。酸無水物成分中のPMDAの比率が85モル%を越
えると、通常の熱環化法で繊維をつくった場合、結晶性
が高すぎるためか熱寸法安定性はずぐれているけれども
耐熱寿命は低下する。また、酸無水物成分中のPMDA
の比率が35モル%未渦の場合、ポリマは非品性または
極めて低結晶性のために熱寸法安定性か著しく悪くなる
。 本発明のコポリイミド繊維を得るには、まず、アミ
ド系溶媒中で上記のモノマを重合させてポリアミド酸溶
液をつくり、ついで湿式あるいは乾式法で紡糸し、最後
に熱あるいは化学的手段を用いて環化してポリイミドに
変換させる。
The diamine component constituting the copolyimide fiber of the present invention is
4,4'-diaminodiphenyl ether. Also,
One of the acid anhydride components is always pyromellitic anhydride (
PMDA) is used. Other acid anhydride components are 3, 3°, 4
, 4°-benzophenonetetracarboxylic dianhydride (B
Ding DA> and/or 3,3゛, ,! l, 4'-
It is biphenyltetracarboxylic dianhydride (BPDA). When the ratio of PMDA in the acid anhydride component exceeds 85 mol%, when fibers are made by the usual thermal cyclization method, the thermal dimensional stability is poor, perhaps because the crystallinity is too high, but the heat resistance life is reduced. do. In addition, PMDA in the acid anhydride component
When the ratio of 35 mol % is unvortexed, the polymer has significantly poor thermal dimensional stability due to poor quality or extremely low crystallinity. To obtain the copolyimide fiber of the present invention, first, the above-mentioned monomers are polymerized in an amide solvent to create a polyamic acid solution, then spun by a wet or dry method, and finally by thermal or chemical means. It is cyclized and converted into polyimide.

アミド系溶媒としてはN−メチルピロリドン(NMP)
、N、N−ジメチルホルムアミド、N、N−ジメチルア
セトアミドなどがあり、重合は公知の低温溶液重合法を
適用する。
N-methylpyrrolidone (NMP) as an amide solvent
, N,N-dimethylformamide, N,N-dimethylacetamide, etc., and a known low-temperature solution polymerization method is used for polymerization.

湿式紡糸では通常、水系凝固浴を用いる。この場合、紡
糸原液としては重合で得たポリアミド酸溶液そのもので
もよいが、本発明者らが先に特開昭59−163416
号公報で提案した方法、すなわち、アミド酸単位の一部
を化学的にイミド化させた部分環化ポリアミド酸溶液を
用いる方が透明性のよい、ボイドの少ない凝固糸条を与
えるのでより好ましい。
Wet spinning typically uses an aqueous coagulation bath. In this case, the spinning stock solution may be the polyamic acid solution itself obtained by polymerization, but the present inventors have previously proposed
It is more preferable to use the method proposed in the publication, that is, to use a partially cyclized polyamic acid solution in which a part of the amic acid units are chemically imidized, because it provides a coagulated yarn with good transparency and fewer voids.

凝固糸状はついで熱的あるいは化学的手段で環化させ、
目的のコポリイミド繊維を得ることができる。
The coagulated filament is then cyclized by thermal or chemical means,
The desired copolyimide fiber can be obtained.

環化手段としては通常、熱環化の方が経済性の点でより
好ましい。環化させたコポリイミド繊維は最終的に高温
で熱延伸または熱処理して力学特性の向上を図るが、こ
の熱延伸または熱処理を4oo’c以上の高温で実施す
るとポリマの熱結晶化が過度に進んで耐熱寿命の低下を
きたす。したがって、熱延伸または熱処理温度は400
″C以下が好ましい。
As the cyclization method, thermal cyclization is usually more preferable from the economic point of view. The cyclized copolyimide fiber is finally hot-stretched or heat-treated at high temperatures to improve its mechanical properties, but if this hot-stretching or heat treatment is carried out at a high temperature of 4 o'clock or higher, the thermal crystallization of the polymer will be excessive. This progresses and causes a decrease in heat resistance life. Therefore, the hot stretching or heat treatment temperature is 400
"C or less is preferable.

本発明のコポリイミド繊維は極めてすぐれた耐熱寿命を
有しており、難燃性、高温時の寸法安定性も高い。また
、実用的な力学特性をもっており、さらに、耐薬品性、
耐放射線性能もすぐれている。
The copolyimide fiber of the present invention has an extremely excellent heat-resistant life, and also has high flame retardancy and dimensional stability at high temperatures. It also has practical mechanical properties, as well as chemical resistance and
It also has excellent radiation resistance.

本発明の]ポリイミド繊維の形態は、ステープル、フィ
ラメント、パルプのいずれてもよく、また、それらから
なる織物、編物、不織布および紙、あるいは、さらに、
伯の繊維との混紡、交織物も含まれる。
The polyimide fiber of the present invention may be in the form of staple, filament, or pulp, and may also be woven, knitted, nonwoven, or paper made of these, or
It also includes blended fabrics with Haku fibers and mixed fabrics.

[実施例] 以下の実施例および比較例によって本発明をさらに詳細
に説明する。
[Example] The present invention will be explained in further detail by the following Examples and Comparative Examples.

例中の、ポリアミド酸の固有粘度(7inh)はボリア
0.59/溶媒100m!!の割合になるよう、ポリマ
溶液をNMPで希釈し、25°Cで測定した。
In the example, the intrinsic viscosity (7 inh) of the polyamic acid is boria 0.59/solvent 100 m! ! The polymer solution was diluted with NMP to give a ratio of .

また、引張特性は東洋ボールドウィン(株)製テンシロ
ンを用い、試長100mのヤーンについて引張速度50
m/minの条件で測定した。
In addition, the tensile properties were measured using Tensilon manufactured by Toyo Baldwin Co., Ltd., and the tensile speed was 50 for a yarn with a sample length of 100 m.
The measurement was performed under the conditions of m/min.

実施例1 本実施例はジアミン成分が4,4“−ジアミノジフェニ
ルエーテル(DA) 、l無水物成分がPMDA60モ
ル%、BTDA40モル%からなるコポリイミド繊維の
製造例とその特性を示す。
Example 1 This example shows the production of a copolyimide fiber whose diamine component is 4,4''-diaminodiphenyl ether (DA) and whose anhydride components are 60 mol% PMDA and 40 mol% BTDA, and its properties.

NMP中、DAとPMDAおよびBTDAを上記比率で
反応させて得た7inh2.56のポリアミド酸溶液に
アミド酸単位の0.25当量の無水酢酸およびピリジン
を添加し、ポリマ濃度12%、溶液粘度1080ポイズ
(25°C)の部分環化ポリマ溶液を得た。
In NMP, 0.25 equivalents of amic acid units of acetic anhydride and pyridine were added to a 7 inch h2.56 polyamic acid solution obtained by reacting DA with PMDA and BTDA at the above ratio to obtain a polymer concentration of 12% and a solution viscosity of 1080. A partially cyclized polymer solution of poise (25°C) was obtained.

この溶液を0.08mΦ、20ホールの口金を用いてN
MP/水(容積比25/75 )からなる25°Cの凝
固浴中に湿式紡糸しく紡糸速度10m/min ) 、
ついで水中で1.4倍に延伸した後、ガラスボビンに巻
取った。80’Cのエアオーブン中30分加熱して乾燥
後、同オーブン中で約20分かけて280’Cに昇温し
、同温度に30分加熱して熱環化を進めた。
This solution was mixed with N using a 0.08 mΦ, 20-hole cap.
Wet spinning in a 25°C coagulation bath consisting of MP/water (volume ratio 25/75) at a spinning speed of 10 m/min),
The film was then stretched to 1.4 times in water and then wound onto a glass bobbin. After drying by heating in an air oven at 80'C for 30 minutes, the temperature was raised to 280'C over about 20 minutes in the same oven, and thermal cyclization was proceeded by heating at the same temperature for 30 minutes.

この熱環化系を350°Cの熱板を用い1.3倍に延伸
した糸の糸質は繊度73デニール、強度3゜22び/d
、伸度19.4%、弾性率529/dであり、空気中2
90’Cに112時間処理後の糸質は強度3.19g/
d (保持率99%)、伸度17.7%(保持率91%
)と耐熱寿命は著しくすぐれていた。また、この延伸糸
の450°C15分処理後の収縮率は1.4%と高温寸
法安定性も極めて高かった。
This thermocyclized yarn was stretched 1.3 times using a hot plate at 350°C, and the yarn quality was 73 denier and strength 3°22/d.
, elongation 19.4%, elastic modulus 529/d, and 2 in air.
After being heated to 90'C for 112 hours, the fiber strength was 3.19g/
d (retention rate 99%), elongation 17.7% (retention rate 91%)
) and the heat resistance life was significantly superior. In addition, the shrinkage rate of this drawn yarn after treatment at 450° C. for 15 minutes was 1.4%, indicating extremely high high-temperature dimensional stability.

上記の熱環化系を420’Cの熱板を用い2.8倍に延
伸した糸は繊度35デニール、強度7.179/d、伸
度11.5%、弾性率92σ/dであり、空気中、29
0’Cに112時間処理後の強度保持率は70%、伸度
保持率78%であった。
The yarn obtained by drawing the above thermocyclized system 2.8 times using a hot plate at 420'C has a fineness of 35 denier, a strength of 7.179/d, an elongation of 11.5%, and an elastic modulus of 92σ/d. in the air, 29
After treatment at 0'C for 112 hours, the strength retention rate was 70% and the elongation retention rate was 78%.

比較例1 本比較例はDAとPMDAからなるホモポリイミド繊維
の製造例とその特性を示す。
Comparative Example 1 This comparative example shows a production example of homopolyimide fibers made of DA and PMDA and its characteristics.

NMP中、DAとPMDAを反応させて得たη1nh3
.81のポリアミド酸溶液から、実施例1の処方でポリ
マ濃度7.0%、部分環化度25%、溶液粘度570ポ
イズ(25°C〉の部分環化ポリマ溶液を得た。
η1nh3 obtained by reacting DA and PMDA in NMP
.. A partially cyclized polymer solution having a polymer concentration of 7.0%, a degree of partial cyclization of 25%, and a solution viscosity of 570 poise (at 25° C.) was obtained from the polyamic acid solution of No. 81 using the recipe of Example 1.

この溶液を実施例1と全く同じ装置および処方を用いて
湿式紡糸後、熱環化した。
This solution was wet-spun using exactly the same equipment and recipe as in Example 1, and then thermally cyclized.

この熱環化系を430°Cの熱板を用い、1.5倍に延
伸した糸の糸質は繊度38デニール、強度4.19s/
d、伸度6.71%、弾性率76SJ/dであり、また
、空気中、290°C1112時間処理後の強度1.7
7y/d (保持率42%)、伸度2.74%(保持率
41%〉でおった。 なお、熱板温度3’50℃、倍率
1.2倍の延伸糸は繊度47デニール、強度2.999
/d、伸度9゜10%、弾性率51/dであり、空気中
、290′C1112時間処理後の強度保持率58%、
伸度保持率50%と耐熱寿命はわずかに向上するだけで
あった。
This thermocyclized system was stretched 1.5 times using a hot plate at 430°C, and the yarn quality was 38 denier and strength 4.19 s/
d, elongation 6.71%, elastic modulus 76 SJ/d, and strength 1.7 after treatment in air at 290°C for 1112 hours.
7y/d (retention rate 42%), elongation 2.74% (retention rate 41%).The drawn yarn with a hot plate temperature of 3'50°C and a magnification of 1.2x has a fineness of 47 denier and a strength of 2.999
/d, elongation 9°10%, elastic modulus 51/d, strength retention rate 58% after treatment in air for 290'C1112 hours,
The elongation retention rate was 50% and the heat resistance life was only slightly improved.

比較例2 本比較例はDAとBTDAからなるホモポリイミド繊維
の製造例とその特性を示す。
Comparative Example 2 This comparative example shows a production example of homopolyimide fibers made of DA and BTDA and its characteristics.

NMP中、DAとBTDAを反応させて得たη1nh1
,42のポリアミド酸溶液から、実施例1の処方でポリ
マ濃度16%、部分環化度30%のポリマ溶液を得た。
η1nh1 obtained by reacting DA and BTDA in NMP
, 42, a polymer solution having a polymer concentration of 16% and a degree of partial cyclization of 30% was obtained using the formulation of Example 1.

この溶液を実施例の処方に準じて湿式紡糸し、ついで熱
環化した。
This solution was wet-spun according to the recipe in the example, and then thermally cyclized.

この熱環化糸を360′Cの熱板を用い2,5倍に延伸
した糸は繊度35デニール、強度3.47y/d、伸度
31.2%、弾性率479/dでおり、空気中、290
°C1112時間処理後の強度保持率95%、伸度保持
率103%と耐熱寿命は著しくすぐれているれれども、
非晶性ポリマであるために熱寸法安定性は悪く、350
’C110分処理後の収縮率は44%と極めて高く、ま
た、4oo’c以上では糸同志が融着した。
This thermally cyclized yarn was drawn 2.5 times using a hot plate at 360'C and had a fineness of 35 denier, a strength of 3.47 y/d, an elongation of 31.2%, and an elastic modulus of 479/d. Medium, 290
Although the heat resistance life is extremely excellent, with a strength retention rate of 95% and an elongation retention rate of 103% after treatment at 1112 hours at °C,
Since it is an amorphous polymer, its thermal dimensional stability is poor, and 350
The shrinkage rate after treatment for 'C110 minutes was extremely high at 44%, and the yarns fused together at 4oo'C or more.

実施例2 本実施例はジアミン成分がDA、酸無水物成分がPMD
A80モル%、BTDA20モル%からなるコポリイミ
ド繊維の製造例と糸特性を示す。
Example 2 In this example, the diamine component is DA and the acid anhydride component is PMD.
A manufacturing example and yarn properties of a copolyimide fiber consisting of 80 mol% A and 20 mol% BTDA are shown.

NMP中、上記比率でモノマを反応させη1nh2.3
0のポリアミド酸をつくり、ついで実施例1の処方でポ
リマ濃度9.7%、部分環化度25%、溶液粘度600
ポイズ(25°C)の部分環化ポリマ溶液を得た。
The monomers were reacted at the above ratio in NMP and η1nh2.3
0 polyamic acid was prepared, and then using the recipe of Example 1, the polymer concentration was 9.7%, the degree of partial cyclization was 25%, and the solution viscosity was 600.
A partially cyclized polymer solution of poise (25°C) was obtained.

この溶液を実施例1の処方に準じて湿式紡糸しついで熱
環化した。
This solution was wet-spun according to the recipe of Example 1 and then thermally cyclized.

この熱環化糸を350’Cの熱板を用い1.3倍に延伸
して得た糸の糸質は繊度65デニール、強度3.55g
/d、伸度15.3%、弾性率589/dており、空気
中、290’C1112時間処理後の強度保持率80%
、伸度保持率80%であった。また、450’Cに5分
放置した後の収縮率は5.4%であった。9 [発明の効果] 本発明のコポリイミド繊維は、前述のように耐熱寿命、
難燃性、高温寸法安定性がとくにすぐれ、また、実用的
な力学特性を有しているので、たとえば電気絶縁材料、
防炎服、フィルター、車輌内装材など各種産業資材用途
に広く展開できる。
This thermocyclized yarn was stretched 1.3 times using a hot plate at 350'C, and the yarn quality was 65 denier and 3.55 g in strength.
/d, elongation 15.3%, elastic modulus 589/d, strength retention rate 80% after treatment in air for 290'C1112 hours.
, the elongation retention rate was 80%. Further, the shrinkage rate after being left at 450'C for 5 minutes was 5.4%. 9 [Effects of the Invention] As mentioned above, the copolyimide fiber of the present invention has a long heat-resistant life,
It has particularly excellent flame retardancy and high-temperature dimensional stability, as well as practical mechanical properties, so it can be used as an electrical insulating material, for example.
It can be widely used in various industrial materials such as flame-retardant clothing, filters, and vehicle interior materials.

Claims (1)

【特許請求の範囲】[Claims] (1)ジアミン成分が4,4′−ジアミノジフェニルエ
ーテル、酸無水物成分が無水ピロメリット酸(A)と3
,3′,4、4′−ベンゾフェノンテトラカルボン酸二
無水物および/または3,3′,4,4′−ビフェニル
テトラカルボン酸二無水物からなり、酸無水物成分中の
Aの比率が85〜35モル%であることを特徴とするコ
ポリイミド繊維。
(1) The diamine component is 4,4'-diaminodiphenyl ether, and the acid anhydride component is pyromellitic anhydride (A) and 3
,3',4,4'-benzophenonetetracarboxylic dianhydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride, and the ratio of A in the acid anhydride component is 85 A copolyimide fiber characterized in that it has a content of ~35 mol%.
JP14008088A 1988-06-07 1988-06-07 Copolyimide yarn Pending JPH01314724A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14008088A JPH01314724A (en) 1988-06-07 1988-06-07 Copolyimide yarn

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14008088A JPH01314724A (en) 1988-06-07 1988-06-07 Copolyimide yarn

Publications (1)

Publication Number Publication Date
JPH01314724A true JPH01314724A (en) 1989-12-19

Family

ID=15260497

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14008088A Pending JPH01314724A (en) 1988-06-07 1988-06-07 Copolyimide yarn

Country Status (1)

Country Link
JP (1) JPH01314724A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013159867A (en) * 2012-02-02 2013-08-19 Kuraray Co Ltd Polyimide fiber

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013159867A (en) * 2012-02-02 2013-08-19 Kuraray Co Ltd Polyimide fiber

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