JPH03199424A - Polyether copolymer fiber - Google Patents
Polyether copolymer fiberInfo
- Publication number
- JPH03199424A JPH03199424A JP33809589A JP33809589A JPH03199424A JP H03199424 A JPH03199424 A JP H03199424A JP 33809589 A JP33809589 A JP 33809589A JP 33809589 A JP33809589 A JP 33809589A JP H03199424 A JPH03199424 A JP H03199424A
- Authority
- JP
- Japan
- Prior art keywords
- polyether copolymer
- temperature
- melt
- spinning
- fiber
- 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
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 68
- 229920000570 polyether Polymers 0.000 title claims abstract description 68
- 239000000835 fiber Substances 0.000 title claims abstract description 56
- 238000002074 melt spinning Methods 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 30
- 229920001577 copolymer Polymers 0.000 abstract description 17
- 230000007935 neutral effect Effects 0.000 abstract description 11
- 239000002798 polar solvent Substances 0.000 abstract description 11
- 150000001339 alkali metal compounds Chemical class 0.000 abstract description 10
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 238000009987 spinning Methods 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 229920005594 polymer fiber Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 2
- LLJNTLUXOZPFQB-UHFFFAOYSA-N [4-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=CC(F)=CC=2)C=C1 LLJNTLUXOZPFQB-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- NCNWTBAWLAFYDR-UHFFFAOYSA-N 1,6-dimethylpiperidin-2-one Chemical compound CC1CCCC(=O)N1C NCNWTBAWLAFYDR-UHFFFAOYSA-N 0.000 description 1
- IVUYGANTXQVDDG-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrolidin-2-one Chemical compound CC(C)CN1CCCC1=O IVUYGANTXQVDDG-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 1
- IVVVGBHWWAJRAY-UHFFFAOYSA-N 1-ethyl-3-methylpyrrolidin-2-one Chemical compound CCN1CCC(C)C1=O IVVVGBHWWAJRAY-UHFFFAOYSA-N 0.000 description 1
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical compound CCN1CCCCC1=O VUQMOERHEHTWPE-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- GVDQKJQFVPXADH-UHFFFAOYSA-N 1-propan-2-ylpiperidin-2-one Chemical compound CC(C)N1CCCCC1=O GVDQKJQFVPXADH-UHFFFAOYSA-N 0.000 description 1
- GHELJWBGTIKZQW-UHFFFAOYSA-N 1-propan-2-ylpyrrolidin-2-one Chemical compound CC(C)N1CCCC1=O GHELJWBGTIKZQW-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- GRUHREVRSOOQJG-UHFFFAOYSA-N 2,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C(Cl)=C1 GRUHREVRSOOQJG-UHFFFAOYSA-N 0.000 description 1
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 description 1
- DRYYJQYUHPRVBN-UHFFFAOYSA-N 3-ethyl-1-methylpiperidin-2-one Chemical compound CCC1CCCN(C)C1=O DRYYJQYUHPRVBN-UHFFFAOYSA-N 0.000 description 1
- QQGNLKJAIVSNCO-UHFFFAOYSA-N N-butylformamide Chemical compound CCCCNC=O QQGNLKJAIVSNCO-UHFFFAOYSA-N 0.000 description 1
- MYLHDKKILSIAGC-UHFFFAOYSA-N [2-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1C(=O)C1=CC=C(F)C=C1 MYLHDKKILSIAGC-UHFFFAOYSA-N 0.000 description 1
- RYFRLXAJUKKJKD-UHFFFAOYSA-N [4-(4-chlorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=CC(Cl)=CC=2)C=C1 RYFRLXAJUKKJKD-UHFFFAOYSA-N 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 1
- IFTIBNDWGNYRLS-UHFFFAOYSA-N n,n-dipropylacetamide Chemical compound CCCN(C(C)=O)CCC IFTIBNDWGNYRLS-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ポリエーテル系共重合体繊維に関し、更に詳
しく言うと、耐熱性、機械的強度等に優れ、例えば、複
合材料の素材、織編物材料などとして好適に使用するこ
とができるポリエーテル系共重合体繊維に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyether copolymer fiber, and more specifically, it has excellent heat resistance, mechanical strength, etc., and is suitable for use as a material for composite materials, textiles, etc. The present invention relates to polyether copolymer fibers that can be suitably used as knitted fabric materials.
近年、耐熱性、機械的強度に優れた種々のエンジニアリ
ング樹脂が開発され、これらよりなる繊維が広い分野で
用いられているが、種々の面で十分に満足しておらず、
新しい素材からなる繊維の開発が望まれている。In recent years, various engineering resins with excellent heat resistance and mechanical strength have been developed, and fibers made of these resins are used in a wide range of fields, but they are not fully satisfied in various aspects.
The development of fibers made from new materials is desired.
例えば、エンジニアリング樹脂のひとつとしてポリエー
テルケトン系共重合体が知られており、その利用面での
いくつかの提案がなされている（例えば、特開昭５９−
１９１３２２号公報を参照）。For example, polyetherketone-based copolymers are known as one of the engineering resins, and several proposals have been made for their use (for example, JP-A-59-1999-1).
(See Publication No. 191322).
しかしながら、これらの従来の樹脂は、ガラス転移温度
（Ｔ９）が低く、高耐熱性が要求される分野においては
通用し難かったり、機械的強度等の機械的特性（例えば
、引張強度、結節強度、ヤング率など）が、なお不十分
であるなどの欠点を有している。また、樹脂によっては
、ゲルが発生し易く、繊維に加工する際に支障をきたす
などの問題点もある。However, these conventional resins have a low glass transition temperature (T9) and are difficult to be used in fields that require high heat resistance. Young's modulus) is still insufficient. Furthermore, depending on the resin, gels tend to form, which poses problems when processed into fibers.
〔発明が解決しようとする課題］ 本発明は前記の事情を鑑みてなされたものである。[Problem to be solved by the invention] The present invention has been made in view of the above circumstances.
本発明の目的は、前記問題点を解決し、ガラス転移温度
が十分に高く、耐熱性に優れるとともに、機械的強度等
の機械的性質に優れ、しかも、繊維への加工性（紡糸及
び延伸加工等）にも優れるなどの利点を有する新規なポ
リマー繊維であるポリエーテル系共重合体繊維を提供す
ることにある。The purpose of the present invention is to solve the above-mentioned problems, have a sufficiently high glass transition temperature, excellent heat resistance, excellent mechanical properties such as mechanical strength, and processability into fibers (spinning and drawing processing). An object of the present invention is to provide a polyether copolymer fiber, which is a new polymer fiber having advantages such as excellent properties such as polyether copolymer fiber.
〔課題を解決するための手段〕
本発明者らは、前記目的を達成するために鋭意研究を重
ねた結果、ガラス転移温度が十分に高く、耐熱性に優れ
、しかも機械的強度等の機械的性質に優れた特定のポリ
エーテル系共重合体を原料樹脂として用い、これを特定
の条件で溶融紡糸してなる繊維、特に該溶融紡糸後、特
定の延伸倍率に延伸してなる繊維が、前記目的を満足す
る優れたポリマー繊維であることを見出し、これらの知
見に基づいて本発明を完成するに至った。[Means for Solving the Problems] As a result of extensive research to achieve the above object, the present inventors have found that the glass transition temperature is sufficiently high, the heat resistance is excellent, and the mechanical properties such as mechanical strength are excellent. Fibers obtained by melt-spinning a specific polyether copolymer with excellent properties as a raw material resin under specific conditions, especially fibers obtained by stretching to a specific draw ratio after melt-spinning, are as follows. The present inventors have discovered that this is an excellent polymer fiber that satisfies the purpose, and have completed the present invention based on these findings.
すなわち、本発明は、 次の一般式ＣＩ）Ｎ
で表される繰り返し単位からなり、前記式〔Ｉ〕で表さ
れる繰り返し単位の含有量と前記式（ＩＩ）で表される
繰り返し単位の含有量との合計に対する数式（Ｉ）で表
される繰り返し単位の含有量の割合（モル比（（Ｉ〕／
（１）＋ ［：ＩＩ））））が０．１−０．５である
とともに、４００℃における熔融粘度が５００ボイズ以
上であるポリエーテル系共重合体を、その融点よりも１
０ないし７０℃高い温度において熔融紡糸してなること
を特徴とするポリエーテル系共重合体繊維よりなるもの
である。That is, the present invention consists of a repeating unit represented by the following general formula CI)N, and the content of the repeating unit represented by the above formula [I] and the content of the repeating unit represented by the above formula (II) The ratio of the content of the repeating unit represented by formula (I) to the total amount (molar ratio ((I)/
(1) + [:II)))) is 0.1-0.5 and the melt viscosity at 400°C is 500 voids or more.
It is made of a polyether copolymer fiber characterized by being melt-spun at a temperature 0 to 70°C higher.
以下に、本発明について詳細に説明する。The present invention will be explained in detail below.
−ポリエーテル系共重合体−
本発明の樹脂Ｍｉ戊物の配合成分として使用する前記ポ
リエーテル系共重合体において重要な点のひとつは、前
記一般式〔Ｉ〕で表される繰り返し単位と前記式ＣＩＩ
）で表される繰り返し単位からなり、かつ、これらの繰
り返し単位の割合が、前記したように特定の範囲にある
点である。-Polyether copolymer- One of the important points in the polyether copolymer used as a compounding component of the resin Mi body of the present invention is that the repeating unit represented by the general formula [I] and the Formula CII
), and the ratio of these repeating units is within a specific range as described above.
ここで、もし、前記一般式（Ｉ）で表される繰り返し単
位の割合〔すなわち、モル比（〔Ｉ〕／（（１）＋ ［
ＩＩ））））が０．１未満であると、ポリマーの融点が
高すぎて、溶融粘度が高くなり、底形性（溶融紡糸性）
が低下する。また、該ポリマーに各種の添加成分を配合
して樹脂組成物の繊維となす場合に、添加成分との溶融
混合が困難となって、均一な樹脂組成物やその繊維の製
造が困難となることがある。また、前記一般式〔Ｉ〕で
表される繰り返し単位の割合が０．５を超えると、結晶
性の度合いが十分でなくなり、耐熱性が低下するほか、
機械的強度や耐溶剤性、耐薬品性の低下を招くことにな
る。Here, if the proportion of repeating units represented by the general formula (I) [i.e., molar ratio ([I]/((1)+[
II)))) is less than 0.1, the melting point of the polymer is too high, the melt viscosity becomes high, and the bottom shape property (melt spinnability)
decreases. In addition, when blending various additive components with the polymer to make fibers of a resin composition, it becomes difficult to melt and mix the additive components, making it difficult to manufacture a uniform resin composition and its fibers. There is. Further, if the proportion of the repeating unit represented by the general formula [I] exceeds 0.5, the degree of crystallinity will not be sufficient, and the heat resistance will decrease.
This results in a decrease in mechanical strength, solvent resistance, and chemical resistance.
なお、前記ポリエーテル系共重合体は、本発明の目的を
阻害しない範囲内の割合で、他の繰り返し単位を含有し
ていてもよい。Note that the polyether copolymer may contain other repeating units in a proportion that does not impede the object of the present invention.
本発明においては、前記各種のポリエーテル系共重合体
は、１種単独で使用してもよいし１．所望に応じて、２
種以上を混合物あるいは組成物などとして併用してもよ
い。In the present invention, the various polyether copolymers may be used alone or 1. 2 as desired
More than one species may be used in combination as a mixture or composition.
ポリエーテル系共重合体の製造方法−
前記ポリエーテル系共重合体は、その製造方法としては
特に制限はなく、種々の方法に従って製造することがで
きる。Method for producing polyether copolymer The method for producing the polyether copolymer is not particularly limited, and can be produced according to various methods.
本発明に好適なポリエーテル系共重合体の製造方法とし
て、例えば、以下に示す方法などを挙げることができる
。Examples of methods for producing polyether copolymers suitable for the present invention include the following methods.
すなわち、ジハロゲノベンゾニトリルと１４ビス（４−
ハロヘンジイル）ベンゼンとの合計量に対してモル比で
０．１〜０．５に相当する量のジハロゲノベンゾニトリ
ルと、前記合計量とほぼ等モル量の４．４′−ビフェノ
ール（すなわち、４゜４′−ジヒドロキシビフェニル）
とを、アルカリ金属化合物及び中性極性溶媒の存在下に
反応させた後、得られた反応生成物と前記合計量に対し
てモル比で０．９〜０．５に相当する量の１，４−ビス
（４−へロベンゾイル）ベンゼンとの共重合反応を行う
ことにより製造する。That is, dihalogenobenzonitrile and 14bis(4-
dihalogenobenzonitrile in an amount corresponding to a molar ratio of 0.1 to 0.5 with respect to the total amount of dihalogenobenzonitrile and 4.4'-biphenol (i.e., 4.4'-biphenol (i.e.,゜4'-dihydroxybiphenyl)
and 1, in an amount corresponding to a molar ratio of 0.9 to 0.5 with respect to the total amount, and the resulting reaction product in the presence of an alkali metal compound and a neutral polar solvent. It is produced by performing a copolymerization reaction with 4-bis(4-herobenzoyl)benzene.
使用に供される前記ジハロゲノベンゾニトリルとしては
、２．３−ジハロゲノベンゾニトリル、２．４−ジハロ
ゲノベンゾニトリル、２，５−ジハロゲノベンゾニトリ
ル、２，６−ジハロゲノベンゾニトリル、３．４−ジハ
ロゲノベンゾニトリル、３．５−ジハロゲノベンゾニト
リルあるいはこれらの２種以上の混合物を挙げることが
できるが、通常は、例えば、次式
（ただし、式中、Ｘはハロゲン原子であり、式中の２つ
のＸは、互いに同一であってもよく、相違していてもよ
い。）
で表される２、６−ジハロゲノベンゾニトリルや、次式
（ただし、式中、Ｘは前記と同じ意味である。）で表さ
れる２、４−ジハロゲノベンゾニトリルなどが好適に使
用される。The dihalogenobenzonitrile used includes 2,3-dihalogenobenzonitrile, 2,4-dihalogenobenzonitrile, 2,5-dihalogenobenzonitrile, 2,6-dihalogenobenzonitrile, 3 .4-dihalogenobenzonitrile, 3.5-dihalogenobenzonitrile, or a mixture of two or more of these can be mentioned, but usually, for example, the following formula (wherein, X is a halogen atom) , the two X's in the formula may be the same or different.) 2,6-dihalogenobenzonitrile represented by 2,4-dihalogenobenzonitrile, which has the same meaning as ), is preferably used.
これらの中でも、好ましいのは２，６−ジクロロベンゾ
ニトリル、２．６−ジフルオロベンゾニトリル、２，４
−ジクロロベンゾニトリル、２゜４−ジフルオロベンゾ
ニトリルであり、特に好ましいのは２，６−ジクロロベ
ンゾニトリルである。Among these, preferred are 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and 2,4-dichlorobenzonitrile.
-dichlorobenzonitrile, 2°4-difluorobenzonitrile, and 2,6-dichlorobenzonitrile is particularly preferred.
なお、これらは、１種単独で使用してもよいし、必要に
応じて、２種以上を併用してもよい。In addition, these may be used individually by 1 type, and may use 2 or more types together as needed.
前記ジハロゲノベンゾニトリルは、次式テ表すれる４、
４′−ビフェノールとをアルカリ金属化合物及び中性極
性溶媒の存在下で反応させる。The dihalogenobenzonitrile is represented by the following formula 4,
4'-biphenol is reacted in the presence of an alkali metal compound and a neutral polar solvent.
使用に供される前記アルカリ金属化合物は、前記４．４
′−ビフェノールをアルカリ金属塩にすることのできる
ものであればよく、特に制限はないが、好ましいのはア
ルカリ金属炭酸塩、アルカリ金属炭酸水素塩である。The alkali metal compound to be used is as described in 4.4 above.
Any substance that can convert '-biphenol into an alkali metal salt is acceptable, and there are no particular limitations, but alkali metal carbonates and alkali metal hydrogen carbonates are preferred.
前記アルカリ金属炭酸塩としては、例えば炭酸リチウム
、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭
酸セシウムなどが挙げられる。Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
これらの中でも、好ましいのは炭酸ナトリウム、炭酸カ
リウムである。Among these, preferred are sodium carbonate and potassium carbonate.
前記アルカリ金属炭酸水素塩としては、例えば炭酸水素
リチウム、炭酸水素ナトリウム、炭酸水素カリウム、炭
酸水素ルビジウム、炭酸水素セシウムなどが挙げられる
。Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
これらの中でも、好ましいのは炭酸水素ナトリウム、炭
酸水素カリウムである。Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.
上記各種のアルカリ金属化合物の中でも、炭酸ナトリウ
ム、炭酸カリウムが特に好適に使用される。Among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate are particularly preferably used.
なお、これらは、１種単独で使用してもよいし、必要に
応じて２種以上を併用してもよい。In addition, these may be used individually by 1 type, and may use 2 or more types together as needed.
前記中性極性溶媒としては、例えばＮ、 Ｎ−ジメチル
ホルムアミド、Ｎ、Ｎ−ジュチルホルムアξド、Ｎ、Ｎ
−ジメチルアセトアミド、Ｎ、 Ｎジエチルアセトア
ミド、Ｎ、Ｎ−ジプロピルアセトアミド、Ｎ、Ｎ−ジメ
チル安息香酸アミド、Ｎメチル−２−ピロリドン（ＮＭ
Ｐ）、Ｎ−エチル−２−ピロリドン、Ｎ−イソプロピル
−２−ピロリドン、Ｎ−イソブチル−２−ピロリドン、
Ｎ−ｎ−プロピル−２−ピロリドン、Ｎ−ｎ−ブチル−
２−ピロリドン、Ｎ−シクロへキシル−２−ピロリドン
、Ｎ−メチル−３−メチル−２−ピロリドン、Ｎ−エチ
ル−３−メチル−２−ピロリドン、Ｎ−メチル−３，４
，５−）リフチル−２ピロリドン、Ｎ−メチル−２−ピ
ペリドン、Ｎ−エチル−２−ピペリドン、Ｎ−イソプロ
ピル−２−ピペリドン、Ｎ−メチル−６−メチル−２−
ピペリドン、Ｎ−メチル−３−エチルピペリドン、ジメ
チルスルホキシド、ジエチルスルホキシド、１−メチル
−１−オキソスルホラン、１−エチル−１−オキソスル
ホラン、１−フェニル−１−オキソスルホラン、Ｎ、Ｎ
’ −ジメチルイミダゾリジノン（ＤＭＩ）、ジフェニ
ルスルホンなどが挙げられる。Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-butylformamide, N,N-dimethylformamide, and N,N-dimethylformamide.
-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone (NM
P), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone,
N-n-propyl-2-pyrrolidone, N-n-butyl-
2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4
,5-)rifthyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-
Piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N,N
'-dimethylimidazolidinone (DMI), diphenyl sulfone, and the like.
好ましいのはＮＭＰ、ＤＭＩ、スルホラン、ジフェニル
スルホン及びジメチルスルホキシドであり、特に好まし
いのはＮＭＰである。Preferred are NMP, DMI, sulfolane, diphenylsulfone and dimethylsulfoxide, particularly preferred is NMP.
なお、これらの溶媒は、１種単独で使用してもよいし、
必要に応じて、２種以上を併用してもよい。また、必要
に応して、例えば、芳香族炭化水素溶媒等の他の溶媒と
の混合溶媒として使用することができる。例えば、トル
エン等の水と共沸しやすい芳香族炭化水素を前記中性極
性溶媒と併用することにより、重合反応の際、縮合等に
よって生成する水を反応系から有効に除去することがで
きる。Note that these solvents may be used alone, or
If necessary, two or more types may be used in combination. Further, if necessary, it can be used as a mixed solvent with other solvents such as aromatic hydrocarbon solvents. For example, by using an aromatic hydrocarbon that easily azeotropes with water, such as toluene, in combination with the above-mentioned neutral polar solvent, water generated by condensation or the like during the polymerization reaction can be effectively removed from the reaction system.
前記ジハロゲノベンゾニトリルの使用割合は、ジハロゲ
ノベンゾニトリルと１．４−ビス（４−ハロベンゾイル
）ベンゼンとの合計量に対するモル比で、前記ジハロゲ
ノベンゾニトリルが、通常、０、１〜０．５の割合であ
り、前記アルカリ金属化合物の使用割合は、使用する４
、４′−ビフェノールの水酸基１個につき、通常１．０
３〜２．５０当量、好ましくは１．０５〜１．２５当量
とするのが適当である。The proportion of the dihalogenobenzonitrile used is a molar ratio to the total amount of dihalogenobenzonitrile and 1,4-bis(4-halobenzoyl)benzene, and the proportion of the dihalogenobenzonitrile is usually 0, 1 to 0. The ratio of the alkali metal compound used is 4.
, usually 1.0 per hydroxyl group of 4'-biphenol
A suitable amount is 3 to 2.50 equivalents, preferably 1.05 to 1.25 equivalents.
前記中性極性溶媒の使用量については、特に制限はない
が、通常、前記ジハロゲノベンゾニトリルと前記４．４
′−ビフェノールと前記アルカリ金属化合物との合計１
００重量部当たり、２００〜２，０００重量部の範囲で
選ばれる。There is no particular restriction on the amount of the neutral polar solvent used, but usually the dihalogenobenzonitrile and the 4.4
'-Biphenol and the alkali metal compound total 1
The amount is selected in the range of 200 to 2,000 parts by weight per 00 parts by weight.
前記アルカリ金属化合物及び前記中性極性溶媒の存在下
での前記ジハロゲノベンゾニトリルと前記４．４′−ビ
フェノールとの反応を行って得られる反応生成物と前記
１．４−ビス（４−ハロベンゾイル）ベンゼンを反応さ
せる。使用に供される前記１．４−ビス（４−ハロベン
ゾイル）ベンゼンは、次式
中の２つのＹは、互いに同一であってもよく、相違して
いてもよい。）
で表される化合物であり、これらの中でも１． ４ビス
（４−クロロベンゾイル）ベンゼン、１゜４−ビス（４
−フルオロベンゾイル）ベンゼン、１−（４−クロロベ
ンゾイル）−４−（４−フルオロベンゾイル）ベンゼン
が好ましく、特に、ｌ。The reaction product obtained by reacting the dihalogenobenzonitrile with the 4,4'-biphenol in the presence of the alkali metal compound and the neutral polar solvent and the 1,4-bis(4-halo benzoyl) benzene. In the 1,4-bis(4-halobenzoyl)benzene used, the two Y's in the following formula may be the same or different. ), and among these, 1. 4-bis(4-chlorobenzoyl)benzene, 1°4-bis(4
-fluorobenzoyl)benzene, 1-(4-chlorobenzoyl)-4-(4-fluorobenzoyl)benzene is preferred, especially l.
４−ビス（４−クロロベンゾイル）ベンゼン及びビス（
４−フルオロベンゾイル）ベンゼンが好ましい。4-bis(4-chlorobenzoyl)benzene and bis(
4-fluorobenzoyl)benzene is preferred.
なお、これらは、１種単独で使用してもよいし、必要に
応じて、２種以上を併用してもよい。In addition, these may be used individually by 1 type, and may use 2 or more types together as needed.
前記１．４−ビス（４−ハロベンゾイル）ベンゼンは、
１，４−ビス（４−ハロベンゾイル）ベンゼンとジハロ
ゲノベンゾニトリルとの合計量の、前記４．４′−ビフ
ェノールの使用量に対するモル比が、通常、０．９８〜
１．０２、好ましくは１．００〜１．０１になるような
割合で使用する。The 1,4-bis(4-halobenzoyl)benzene is
The molar ratio of the total amount of 1,4-bis(4-halobenzoyl)benzene and dihalogenobenzonitrile to the amount of 4,4'-biphenol used is usually from 0.98 to
It is used at a ratio of 1.02, preferably 1.00 to 1.01.
ポリエーテル系共重合体を得るには、例えば、前記中性
極性溶媒中に、前記ジハロゲノベンゾニトリルと、前記
４．４′−ビフェノールと、前記アルカリ金属化合物と
を、同時に添加して、前記ジハロゲノベンゾニトリルと
前記４．４′−ビフェノールの反応を行わせた後、更に
前記１．４ビス（４−ハロベンゾイル）ベンゼンを添加
し、通常は１５０〜３８０℃１好ましくは１８０〜３３
０℃の範囲の温度において一連の反応を行わせる。To obtain a polyether copolymer, for example, the dihalogenobenzonitrile, the 4,4'-biphenol, and the alkali metal compound are simultaneously added to the neutral polar solvent, and the alkali metal compound is added to the neutral polar solvent. After the dihalogenobenzonitrile and the 4,4'-biphenol are reacted, the 1,4bis(4-halobenzoyl)benzene is further added, and the temperature is usually 150 to 380°C, preferably 180 to 33°C.
A series of reactions are carried out at temperatures in the range of 0°C.
反応温度が１５０″Ｃ未満では、反応速度が遅すぎて実
用的ではないし、３８０″Ｃを超えると、副反応を招く
ことがある。If the reaction temperature is less than 150''C, the reaction rate is too slow to be practical, and if it exceeds 380''C, side reactions may occur.
また、この一連の反応の反応時間は、通常、０゜１〜１
０時間であり、好ましくは１〜５時間である。In addition, the reaction time of this series of reactions is usually 0°1 to 1
0 hours, preferably 1 to 5 hours.
反応の終了後、得られるポリエーテル系共重合体を含有
する中性極性溶媒溶液から、公知の方法に従って、ポリ
エーテル系共重合体を分離、精製することにより、ポリ
エーテル系共重合体を得ることができる。After completion of the reaction, the polyether copolymer is separated and purified from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method to obtain a polyether copolymer. be able to.
このようにして、ポリエーテル系共重合体を簡単な工程
で効率良く製造することができる。In this way, a polyether copolymer can be efficiently produced in a simple process.
しかも、前記ポリエーテル系共重合体含有の中性極性溶
媒溶液から、嵩密度の大きいポリエーテル系共重合体の
粉末を得ることができる。Moreover, a polyether copolymer powder having a large bulk density can be obtained from the polyether copolymer-containing neutral polar solvent solution.
以上のようにして得られたポリエーテル系共重合体は、
耐熱性、機械的強度等の特性に優れており、本発明のポ
リエーテル系共重合体繊維の素材として使用される。The polyether copolymer obtained as above is
It has excellent properties such as heat resistance and mechanical strength, and is used as a material for the polyether copolymer fiber of the present invention.
−ポリエーテル系共重合体繊維−
本発明のポリエーテル系共重合体繊維（以下、これを共
重合体繊維又は繊維と称すことがある。-Polyether copolymer fiber- The polyether copolymer fiber of the present invention (hereinafter, this may be referred to as copolymer fiber or fiber).
）は、前記ポリエーテル系共重合体（以下、これを共重
合体又は樹脂と称すことがある。）を、その融点（以下
、この融点を℃単位でＴ、で表すことがある。）より１
０〜７０℃高い温度、すなわち（Ｔ、＋１０）”Ｃ〜（
Ｔ、＋７０）°ｃの範囲内の温度（溶融紡糸温度）で溶
融紡糸することにより製造される。) is the polyether copolymer (hereinafter sometimes referred to as a copolymer or resin) based on its melting point (hereinafter, this melting point may be expressed as T in degrees Celsius). 1
0~70℃ higher temperature, i.e. (T, +10)''C~(
T, +70)° C. (melt spinning temperature).
ここで、前記溶融紡糸温度が（Ｔ、＋１０）”Ｃ未満で
あると、紡糸が困難となったり、紡糸における成形加工
性が低下する。一方、（Ｔ、＋７０）℃を超えると、紡
糸におけるポリマーの流動性が高くなり過ぎて繊維への
加工が困難となったり、あるいは紡糸原料の分解等の不
都合を招くことがある。Here, if the melt spinning temperature is less than (T, +10)"C, spinning becomes difficult or moldability during spinning decreases. On the other hand, if it exceeds (T, +70)"C, spinning becomes difficult. The fluidity of the polymer may become too high, making it difficult to process it into fibers, or causing problems such as decomposition of the spinning raw material.
なお、溶融紡糸温度とは、紡糸に際して樹脂（ポリエー
テル系共重合体）を溶融させるための紡糸装置本体の加
熱温度のことであり、紡出糸が紡出する紡糸口金の温度
は、この溶融紡糸温度とは別途に定めることができる。Note that the melt spinning temperature refers to the heating temperature of the main body of the spinning device to melt the resin (polyether copolymer) during spinning, and the temperature of the spinneret from which the spun yarn is spun is determined by It can be determined separately from the spinning temperature.
この紡糸口金の温度は、必ずしも前記の（Ｔ、＋１０）
’Ｃ〜（Ｔ。The temperature of this spinneret is not necessarily the above (T, +10)
'C~(T.
＋７０）’Ｃの範囲内としなくてもよく、適宜選定すれ
ばよいのであるが、通常は、溶融紡糸温度よりも５〜２
０℃程度低めに設定するのが望ましい。It does not have to be within the range of +70)'C and can be selected as appropriate, but usually the
It is desirable to set the temperature to about 0 degrees Celsius.
なお、前記ポリエーテル系共重合体は、通常、１種単独
で溶融紡糸に供されるが、必要に応じて、２種以上を混
合物や組成物などとして併用して溶融紡糸を行ってもよ
い。Note that the polyether copolymers are usually subjected to melt spinning alone, but if necessary, two or more types may be used in combination as a mixture or composition for melt spinning. .
また、前記ポリエーテル系共重合体は、所望に応して、
本発明の目的に支障のない範囲内で、他の樹脂や添加成
分を適宜含有させて溶融紡糸に供することもできる。Further, the polyether copolymer may optionally contain:
Other resins and additive components may be suitably contained within the range that does not impede the purpose of the present invention, and the composition may be subjected to melt spinning.
前記溶融紡糸に使用する紡糸装置としては、前記溶融紡
糸温度を十分に達成できる適当な加熱機構を有するもの
であれば市販のものなど各種のものが使用可能であり、
適宜目的に合わせて設定使用すればよい。例えば、５０
０℃位まで昇温可能な溶融押出装置などを充当すればよ
い。As the spinning device used for the melt spinning, various types such as commercially available devices can be used as long as they have an appropriate heating mechanism that can sufficiently achieve the melt spinning temperature.
You can use the settings as appropriate depending on the purpose. For example, 50
A melt extrusion device or the like capable of raising the temperature to about 0° C. may be used.
紡糸口金の種類としては、特に制限はなく、この分野で
常用されている単一孔のノズル、多孔型の口金（単糸用
のものやフィラー状繊維用のものを含む、）など各種の
ものを、目的に応じて適宜採用すればよい。There are no particular restrictions on the type of spinneret, and various spinnerets commonly used in this field, such as single-hole nozzles and multi-hole spinnerets (including those for single yarns and those for filler fibers), may be used. may be adopted as appropriate depending on the purpose.
紡出糸の冷却、巻き取り方法としても、特に制限はなく
、公知の技術等の各種の技法によって行うことができ、
その手法や条件は目的に応じて適宜選定すればよい。There are no particular restrictions on the cooling and winding method of the spun yarn, and various techniques such as known techniques can be used.
The method and conditions may be appropriately selected depending on the purpose.
例えば、紡糸繊維の単糸デニールが１． ０００ｄｅ以
上の繊維を紡糸する場合には、紡糸口金の直下に冷却用
の液浴を用いて固化させて、トルクワイングー等により
巻き取る方式が好適に採用することができるし、１，０
ＯＯｄｅ以下の繊維の場合には、空気中で冷却固化する
方式が好適に採用されるであろう。For example, the single yarn denier of spun fiber is 1. When spinning fibers with a diameter of 1,000 de
In the case of fibers with OOde or less, a method of cooling and solidifying in air may be suitably employed.
なお、この冷却速度を適宜制御するために、所望に応じ
て、紡糸口金の直後に加熱筒等の加熱装置を設け、これ
に紡出糸を通過させる方法を好適に採用することができ
る。In order to appropriately control this cooling rate, it is possible to suitably adopt a method in which a heating device such as a heating tube is provided immediately after the spinneret and the spun yarn is passed through the heating device, if desired.
本発明のポリエーテル系共重合体繊維は、上記の溶融紡
糸後、延伸処理等の後処理を施してもよいし、使用目的
によっては、特に施さないでもよいし、いずれでもよい
が、−Ｃ的には、少なくとも延伸処理を施すことが好ま
しい。The polyether copolymer fiber of the present invention may be subjected to post-treatment such as stretching treatment after the above-mentioned melt spinning, or depending on the purpose of use, it may not be subjected to any post-treatment, or any treatment may be performed, but -C Specifically, it is preferable to perform at least a stretching process.
適当な延伸処理を施すことにより、得られる繊維の機械
的強度等の機械的性質などをより一層向上させることが
できるからである。This is because by applying an appropriate stretching treatment, the mechanical properties such as mechanical strength of the resulting fiber can be further improved.
この延伸処理は、通常、使用する樹脂（ポリエーテル系
共重合体）のガラス転移温度（Ｔ、）よりも１０〜６０
℃高い温度で行うことが望ましい。This stretching process is usually performed by 10 to 60 degrees higher than the glass transition temperature (T) of the resin (polyether copolymer) used.
It is desirable to carry out the test at a temperature higher than 10°C.
ここで、延伸温度が（Ｔ９＋１０）”Ｃより低いと、延
伸性が低下し、一方、（Ｔ、＋６０）’Ｃより高いと、
毛羽やラップが発生し、安定した延伸ができないことが
ある。Here, if the stretching temperature is lower than (T9+10)'C, the stretchability will decrease, while if it is higher than (T, +60)'C,
Fuzz and wrap may occur, making stable stretching impossible.
この延伸は、延伸倍率が、通常、１．５以上、好ましく
は２〜１０となるように行うことが望ましい。It is desirable that this stretching is carried out so that the stretching ratio is usually 1.5 or more, preferably 2 to 10.
この延伸倍率が、１．５未満では、十分な延伸効果が得
られず、特に引張強度等の機械的性質の向上が不十分と
なる。If the stretching ratio is less than 1.5, a sufficient stretching effect will not be obtained, and in particular, mechanical properties such as tensile strength will not be sufficiently improved.
なお、一般に、この延伸後、延伸された繊維に適宜加熱
処理を施すことが望ましい。In general, after this stretching, it is desirable to subject the stretched fibers to an appropriate heat treatment.
この加熱処理は、通常、樹脂（ポリエーテル系共重合体
）の結晶化温度より高く、かつ融点よりも低い温度範囲
内の温度で、必要に応じ緊張下又は無緊張下で行うこと
ができる。This heat treatment is usually carried out at a temperature within a temperature range higher than the crystallization temperature of the resin (polyether copolymer) and lower than the melting point, and can be carried out under tension or without tension as required.
このように延伸後の繊維に加熱処理を施すことにより、
繊維の強度を更に向上させることができる。By applying heat treatment to the fibers after stretching in this way,
The strength of the fiber can be further improved.
なお、前記延伸処理及び加熱処理は、前記溶融紡糸と組
み合わせて連続的操作によって行うことができる。Note that the stretching treatment and heat treatment can be performed in combination with the melt spinning in a continuous operation.
このようにして本発明のポリエーテル系共重合体繊維を
得ることができる。In this way, the polyether copolymer fiber of the present invention can be obtained.
これらのポリエーテル系共重合体繊維は、耐熱性に優れ
るとともに、引張強度等の機械的強度等の機械的性質に
優れるほか、耐溶剤性や耐薬品性にも優れるという利点
を有しており、例えば、複合材料の素材、織編物材料等
をはしめとする各種のポリマー繊維の利用分野に好適に
利用することができる。These polyether copolymer fibers have the advantage of not only having excellent heat resistance but also mechanical properties such as tensile strength and other mechanical strength, as well as excellent solvent resistance and chemical resistance. For example, it can be suitably used in fields where various polymer fibers are used as binding materials for composite materials, woven and knitted materials, and the like.
次に、本発明の実施例及び比較例を示し、本発明につい
て更に具体的に説明するが、本発明はこれらの実施例に
限定されるものではない。Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention, but the present invention is not limited to these examples.
実施例１
■ポリエーテル系共重合体の製造例
トルエンを満たしたディーンスタルクトラップ、撹拌装
置及びアルゴンガス吹込管を備えた内容積５１の反応器
に、２．６−シクロロヘンゾニトリル３８．７０ｇ（０
，２２５モル）、４．４’−ビフェノール１３９．６６
ｇ（０，７５モル）、炭酸カリウム１２４３９ ｇ （
０，９モル）及びＮ−メチル−２−ピロリドン】、５１
を入れ、アルゴンガスを吹込みながら、１時間かけて室
温より１９５℃まで昇温した。Example 1 ■Production example of polyether copolymer 38.70 g of 2,6-cyclohenzonitrile was placed in a reactor with an internal volume of 51 mm and equipped with a Dean-Starck trap filled with toluene, a stirring device, and an argon gas blowing tube. (0
, 225 mol), 4,4'-biphenol 139.66
g (0.75 mol), potassium carbonate 12439 g (
0.9 mol) and N-methyl-2-pyrrolidone], 51
was added, and the temperature was raised from room temperature to 195° C. over 1 hour while blowing argon gas.
昇温後、少量のトルエンを加えて生成する水を共沸によ
り除去した。After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy.
次いで、温度１９５℃にて３０分間反応を行った後、１
，４−ビス（４−フルオロベンゾイル）ベンゼン１６９
．２ｇ（０，５２５モル）をＮ−メチル−２−ピロリド
ン１．５１に？容解した）各法を加えて、更に１時間反
応を行った。Next, after carrying out a reaction at a temperature of 195°C for 30 minutes, 1
,4-bis(4-fluorobenzoyl)benzene 169
．． 2g (0,525 mol) to 1.51 N-methyl-2-pyrrolidone? Each method (dissolved) was added and the reaction was further carried out for 1 hour.
反応終了後、生成物をブレンダーで粉砕し、アセトン、
メタノール、水、アセトンの順に洗浄を行ってから、乾
燥させて、白色粉末状の共重合体３０４．０ｇ（収率９
８％）を得た。After the reaction is complete, the product is ground in a blender and mixed with acetone,
After washing with methanol, water, and acetone in this order, the product was dried to obtain 304.0 g of a white powdery copolymer (yield: 9).
8%).
この得られた共重合体の構造は次の繰り返し単位（１）
Ｎ
とからなり、繰り返し単位（１）と繰り返し単位（ｎ）
の割合がモル比で０．３０：０．７０であるポリエーテ
ル系共重合体であった。The structure of the obtained copolymer consists of the following repeating unit (1) N and repeating unit (1) and repeating unit (n).
The polyether copolymer had a molar ratio of 0.30:0.70.
また、この共重合体の特性について測定したところ、温
度４００℃における溶融粘度（ゼロ剪断粘度）は１３，
０００ボイズであり、ガラス転移温度は１９０℃、結晶
融点は３８４℃１熱分解開始温度５６４℃（空気中、５
％重量減）であり、高い耐熱性を示した。In addition, when the properties of this copolymer were measured, the melt viscosity (zero shear viscosity) at a temperature of 400°C was 13,
000 voids, glass transition temperature is 190°C, crystal melting point is 384°C, thermal decomposition onset temperature is 564°C (in air, 5
% weight loss) and showed high heat resistance.
■ポリエーテル系共重合体繊維の製造側上記の■で製造
したポリエーテル系共重合体を４００℃に加熱して溶融
し、これを内径１．０ ｍｍ、長さ１．０ ＩｍＤのノ
ズルを用いてノズル温度３９０″Ｃの条件下に紡糸した
。その後、直ちに紡出糸を３００℃に保持した長さ３０
０１の加熱筒を通過させてから空冷し、速度１２０ｍ／
ｗｉｎで巻き取って３５デニールの未延伸糸（未延伸ポ
リエーテル系共重合体繊維）を得た。■Manufacturing side of polyether copolymer fiber The polyether copolymer manufactured in step (1) above was heated to 400°C to melt it, and then passed through a nozzle with an inner diameter of 1.0 mm and a length of 1.0 ImD. The spun yarn was then spun at a nozzle temperature of 390''C. Immediately after that, the spun yarn was kept at 300℃ and spun to a length of 30"C.
After passing through a heating cylinder of 01, it is air cooled and the speed is 120m/
The fibers were wound up with a 35-denier undrawn yarn (undrawn polyether copolymer fiber).
次に、この未延伸糸を、延伸温度２００″Ｃの条件で、
延伸ローラにより延伸倍率が２となるように延伸し、更
に熱板ヒーターにより熱処理温度２４０℃の条件で熱処
理を行ってポリエーテル系共重合体繊維（延伸糸）を得
た。Next, this undrawn yarn was drawn at a drawing temperature of 200″C.
It was stretched with a stretching roller to a stretching ratio of 2, and then heat treated with a hot plate heater at a heat treatment temperature of 240°C to obtain a polyether copolymer fiber (drawn yarn).
この延伸ポリエーテル系共重合体繊維について、引張強
度、伸度、結節強度及びヤング率を測定した。The tensile strength, elongation, knot strength, and Young's modulus of this drawn polyether copolymer fiber were measured.
結果を第１表に示す。The results are shown in Table 1.
なお、これらの物性の測定は、いずれも、ＪＴＳ−Ｌ−
１０１３−８１に準拠して行った。Note that all measurements of these physical properties are based on JTS-L-
1013-81.
実施例２
延伸倍率を３とした以外は実施例１の■と同様にしてポ
リエーテル系共重合体繊維（延伸糸）を製造し、前記各
物性を測定した。Example 2 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 1, except that the stretching ratio was 3, and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
実施例３
延伸倍率を４とし、かつ延伸温度を２１０ ’Ｃとした
以外は実施例１の■と同様にしてポリエーテル系共重合
体繊維（延伸糸）を製造し、前記各物性を測定した。Example 3 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 1 except that the draw ratio was 4 and the drawing temperature was 210'C, and the above physical properties were measured. .
結果を第１表に示す。The results are shown in Table 1.
実施例４
実施例１の■で製造したポリエーテル系共重合体を４０
０℃に加熱して溶融し、これを内径０．４５ｍｍ、長さ
１３５＋ｍ、孔数６０の紡糸口金を用いて紡糸した。な
お、紡糸口金の温度は、３９０″Ｃに設定しておいた。Example 4 40% of the polyether copolymer produced in Example 1
It was heated to 0° C. to melt it, and this was spun using a spinneret with an inner diameter of 0.45 mm, a length of 135+ m, and a number of holes of 60. Note that the temperature of the spinneret was set at 390''C.
この紡出糸を、紡糸口金の出口に設けである温度３００
℃に保持した長さ３００℃１ｍの加熱筒を連続的に通過
させ、空冷してから給油して、速度１５０ｍ／ｓｉｎで
巻き取って８００デニール／６０フイラメントの未延伸
糸（未延伸ポリエーテル系共重合体線Ｉりを得た。This spun yarn was placed at the outlet of the spinneret at a temperature of 300°C.
The undrawn yarn of 800 denier/60 filament (undrawn polyether yarn) was passed through a heating cylinder of 1 m length at 300°C kept at 300°C, cooled in air, refueled, and wound at a speed of 150 m/sin. A copolymer wire was obtained.
次〜に、この未延伸糸を、延伸温度２００ ’Ｃの条件
で、延伸ローラにより延伸倍率が２となるように延伸し
、更に熱板ヒーターにより熱処理温度２４０℃の条件で
熱処理を行って延伸糸（延伸ポリエーテル系共重合体繊
維）を得た。Next, this undrawn yarn is stretched with a stretching roller at a stretching temperature of 200'C to a stretching ratio of 2, and further heat-treated with a hot plate heater at a heat treatment temperature of 240'C, and then stretched. A thread (drawn polyether copolymer fiber) was obtained.
このポリエーテル系共重合体繊維（延伸糸）について、
実施例１の■の測定方法と同様にして、前記各物性を測
定した。Regarding this polyether copolymer fiber (drawn yarn),
The above-mentioned physical properties were measured in the same manner as in the measurement method (2) of Example 1.
結果を第１表に示す。The results are shown in Table 1.
実施例５
延伸倍率を３とした以外は実施例４と同様にしてポリエ
ーテル系共重合体繊維（延伸糸）を製造し、前記各物性
を測定した。Example 5 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 4 except that the stretching ratio was 3, and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
実施例６
延伸倍率を４とし、かつ延伸温度を２１０”Ｃとした以
外は実施例４と同様にしてポリエーテル系共重合体繊維
（延伸糸）を製造し、前記各物性を測定した。Example 6 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 4 except that the stretching ratio was 4 and the stretching temperature was 210''C, and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
実施例７
■ポリエーテル系共重合体の製造例
２．６−シクロロベンゾニトリルと１，４−ビス（４−
フルオロベンゾイル）ベンゼンの仕込み割合（モル比）
を３ニアに代えて４：６とした以外は実施例１の■と同
様にして共重合体を製造した。Example 7 ■Production example of polyether copolymer 2.6-cyclobenzonitrile and 1,4-bis(4-
fluorobenzoyl)benzene charging ratio (molar ratio)
A copolymer was produced in the same manner as in Example 1, except that the ratio was changed to 4:6 instead of 3-near.
この共重合体は、実施例１の■に示した繰り返し単位（
１）と繰り返し単位（Ｉｔ）からなり、該繰り返し単位
ＣＩ）と繰り返し単位（ＩＩ）の割合がモル比で０．４
：０．６であるポリエーテル系共重合体であった。This copolymer contained the repeating units (
1) and a repeating unit (It), and the ratio of the repeating unit CI) to the repeating unit (II) is 0.4 in molar ratio.
:0.6.
また、この共重合体の特性について測定したところ、こ
の共重合体は、温度４００ ”Ｃにおける溶融粘度（ゼ
ロ剪断粘度）が１４，０００ポイズであり、ガラス転移
温度が１９３”Ｃ２結晶融点が３５２℃１熱分解開始温
度が５７０″Ｃ（空気中、５％重量減）であり、高い耐
熱性を示した。Further, when the properties of this copolymer were measured, it was found that the copolymer had a melt viscosity (zero shear viscosity) of 14,000 poise at a temperature of 400"C, a glass transition temperature of 193" and a C2 crystal melting point of 352. The starting temperature of thermal decomposition at 1 °C was 570''C (5% weight loss in air), indicating high heat resistance.
■ポリエーテル系共重合体繊維の製造側実施例１の■で
得たポリエーテル系共重合体に代えて上記の■で得られ
たポリエーテル系共重合体を用い、かつ、延伸温度を２
１０℃１熱処理温度を２５０℃とした以外は実施例１の
■と同様にして延伸倍率が２の延伸糸であるポリエーテ
ル系共重合体繊維を得た。■ Production side of polyether copolymer fiber The polyether copolymer obtained in step (1) above was used in place of the polyether copolymer obtained in step (2) of Example 1, and the stretching temperature was set to 2.
A polyether copolymer fiber having a drawing ratio of 2 was obtained in the same manner as in Example 1, except that the heat treatment temperature at 10°C was changed to 250°C.
このポリエーテル系共重合体繊維（延伸糸）について実
施例１の■と同様の測定法により前記各物性を測定した
。The above-mentioned physical properties of this polyether copolymer fiber (drawn yarn) were measured using the same measuring method as in Example 1 (2).
結果を第１表に示す。The results are shown in Table 1.
実施例８
延伸倍率を３とした以外は実施例７の■と同様にしてポ
リエーテル系共重合体繊維（延伸糸）を製造し、前記各
物性を測定した。Example 8 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 7 (2) except that the stretching ratio was 3, and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
実施例９
延伸倍率を４とし、かつ、延伸温度を２２０℃とした以
外は実施例７の■と同様にしてポリエーテル系共重合体
繊維（延伸糸）を製造し、前記各物性を測定した。Example 9 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 7, except that the stretching ratio was 4 and the stretching temperature was 220°C, and the above-mentioned physical properties were measured. .
結果を第１表に示す。The results are shown in Table 1.
実施例１０
実施例１の■で得た共重合体に代えて実施例７の■で得
た共重合体を用い、かつ、延伸温度を２１０、熱処理温
度を２５０℃とした以外は、実施例４と同様にして延伸
倍率が２の延伸糸（延伸ポリエーテル系共重合体繊維）
を製造し、前記各物性を測定した。Example 10 Example except that the copolymer obtained in Example 7 (■) was used in place of the copolymer obtained in Example 1 (■), and the stretching temperature was 210°C and the heat treatment temperature was 250°C. Drawn yarn (drawn polyether copolymer fiber) with a draw ratio of 2 in the same manner as in 4.
was manufactured, and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
実施例１１
延伸倍率を３とし、かつ、延伸温度を２２０℃とした以
外は実施例１０と同様にしてポリエーテル系共重合体繊
維（延伸糸）を製造し、前記各物性を測定した。Example 11 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 10 except that the stretching ratio was 3 and the stretching temperature was 220° C., and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
実施例１２
延伸倍率を４とし、延伸温度を２２０℃とした以外は実
施例１０と同様にしてポリエーテル系共重合体繊維（延
伸糸）を製造し、前記各物性を測定した。Example 12 A polyether copolymer fiber (drawn yarn) was produced in the same manner as in Example 10 except that the stretching ratio was 4 and the stretching temperature was 220° C., and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
比較例１
実施例１の■で得た共重合体に代えて市販のポリエーテ
ルエーテルケトン（ＩＣ１社製：Ｖｉｃｔｒｅｘ Ｐ
ＥＥＫ４５０Ｇ）を用い、第１表に示す条件を採用した
以外は、実施例１の■と同様にして延伸倍率が２の延伸
糸を得た。Comparative Example 1 Commercially available polyether ether ketone (manufactured by IC1: Victrex P) was used in place of the copolymer obtained in Example 1
A drawn yarn with a draw ratio of 2 was obtained in the same manner as in Example 1 (2) except that EEK450G) was used and the conditions shown in Table 1 were adopted.
この延伸糸について実施例１の■と同様の測定法により
、前記各物性を測定した。The above-mentioned physical properties of this drawn yarn were measured by the same measuring method as in Example 1 (2).
結果を第１表に示す。The results are shown in Table 1.
比較例２及び３
延伸倍率をそれぞれ３及び４とした以外は比較例１と同
様にして延伸糸を製造し、前記各物性を測定した。Comparative Examples 2 and 3 Drawn yarns were produced in the same manner as in Comparative Example 1 except that the draw ratios were 3 and 4, respectively, and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
例４と同様にして延伸系を製造し、前記各物性を測定し
た。A stretching system was produced in the same manner as in Example 4, and the above-mentioned physical properties were measured.
結果を第１表に示す。The results are shown in Table 1.
比較例４
実施例１の■で得た共重合体に代えて市販のポリエーテ
ルエーテルケトン（ＩＣ１社製：Ｖｉｃｔｒｅｘ Ｐ
ＥＥＫ４５０Ｇ）を用い、第１表に示す条件を採用した
以外は、実施例４と同様にして延伸倍率が２の延伸糸を
得た。Comparative Example 4 Commercially available polyether ether ketone (manufactured by IC1: Victrex P) was used in place of the copolymer obtained in Example 1.
A drawn yarn with a draw ratio of 2 was obtained in the same manner as in Example 4, except that EEK450G) was used and the conditions shown in Table 1 were adopted.
この延伸糸について実施例１の■と同様の測定法により
、前記各物性を測定した。The above-mentioned physical properties of this drawn yarn were measured by the same measuring method as in Example 1 (2).
結果を第１表に示す。The results are shown in Table 1.
比較例５及び６
延伸倍率をそれぞれ３及び４とした以外は比較〔発明の
効果〕
本発明によると、特定のポリエーテル系共重合体を特定
の条件で紡糸して繊維となしており、特にその紡糸後、
特定の延伸倍率で延伸して繊維となしているので、耐熱
性に優れるとともに、例えば、従来のポリエーテルエー
テルケトン等の従来のエンジニアリング樹脂からなる繊
維と比較しても著しく機械的強度等の機械的特性に優れ
るなどの利点を有する新規なポリマー繊維を提供するこ
とができる。Comparative Examples 5 and 6 Comparison except that the draw ratio was 3 and 4, respectively [Effect of the invention] According to the present invention, a specific polyether copolymer is spun under specific conditions to form a fiber, and in particular After spinning,
Since the fibers are drawn at a specific stretching ratio, they not only have excellent heat resistance but also have remarkable mechanical strength compared to fibers made of conventional engineering resins such as conventional polyetheretherketone. It is possible to provide a novel polymer fiber having advantages such as excellent physical properties.
Claims (1)
〕で表される繰り返し単位の含有量との合計に対する該
式〔 I 〕で表される繰り返し単位の含有量の割合（モ
ル比｛〔 I 〕／〔 I 〕＋〔II〕）｝）が０．１〜０．
５であるとともに、４００℃における溶融粘度が５００
ポイズ以上であるポリエーテル系共重合体を、その融点
よりも１０ないし７０℃高い温度において溶融紡糸して
なることを特徴とするポリエーテル系共重合体繊維。 ２、請求項１に記載のポリエーテル系共重合体を、その
融点よりも１０ないし７０℃高い温度において溶融紡糸
した後、そのガラス転移温度よりも１０ないし６０℃高
い温度において、延伸倍率１．５以上に延伸してなるこ
とを特徴とするポリエーテル系共重合体繊維。[Claims] 1. The following general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼The repeating unit represented by [I] and the following formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] The content of the repeating unit represented by the above formula [I] and the above formula [II]
] The ratio of the content of the repeating unit represented by the formula [I] to the total content of the repeating unit represented by the formula [I] (molar ratio {[I]/[I]+[II])}) is 0 .1~0.
5, and the melt viscosity at 400°C is 500
A polyether copolymer fiber, characterized in that it is obtained by melt-spinning a polyether copolymer having a polyether polyurethane polyamide (Poise) or higher at a temperature 10 to 70° C. higher than its melting point. 2. After melt-spinning the polyether copolymer according to claim 1 at a temperature 10 to 70°C higher than its melting point, at a temperature 10 to 60°C higher than its glass transition temperature, a stretching ratio of 1. A polyether copolymer fiber characterized by being stretched to a length of 5 or more.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33809589A JPH03199424A (en) | 1989-12-28 | 1989-12-28 | Polyether copolymer fiber |
| US07/612,609 US5149581A (en) | 1989-11-21 | 1990-11-13 | Polyether copolymers, resin compositions containing them, and molded articles formed from them |
| EP19900121831 EP0429964A3 (en) | 1989-11-21 | 1990-11-14 | Polyether copolymers, a method of producing them, resin compositions containing them, and molded articles formed from them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33809589A JPH03199424A (en) | 1989-12-28 | 1989-12-28 | Polyether copolymer fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03199424A true JPH03199424A (en) | 1991-08-30 |
Family
ID=18314860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33809589A Pending JPH03199424A (en) | 1989-11-21 | 1989-12-28 | Polyether copolymer fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03199424A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6506327B2 (en) | 1997-11-05 | 2003-01-14 | Pedex & Co. Gmbh | Process of making monofilaments |
| US6871373B2 (en) | 1998-09-14 | 2005-03-29 | Braun Gmbh | Bristle for a toothbrush, particularly for an electric toothbrush, and method for its manufacture |
| WO2023100943A1 (en) * | 2021-12-01 | 2023-06-08 | 旭化成株式会社 | Resin fiber sheet, prepreg and method for producing prepreg |
-
1989
- 1989-12-28 JP JP33809589A patent/JPH03199424A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6506327B2 (en) | 1997-11-05 | 2003-01-14 | Pedex & Co. Gmbh | Process of making monofilaments |
| US6871373B2 (en) | 1998-09-14 | 2005-03-29 | Braun Gmbh | Bristle for a toothbrush, particularly for an electric toothbrush, and method for its manufacture |
| WO2023100943A1 (en) * | 2021-12-01 | 2023-06-08 | 旭化成株式会社 | Resin fiber sheet, prepreg and method for producing prepreg |
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