JP2019026990A - Production method of polyvinyl alcohol-based fiber - Google Patents
Production method of polyvinyl alcohol-based fiber Download PDFInfo
- Publication number
- JP2019026990A JP2019026990A JP2017150934A JP2017150934A JP2019026990A JP 2019026990 A JP2019026990 A JP 2019026990A JP 2017150934 A JP2017150934 A JP 2017150934A JP 2017150934 A JP2017150934 A JP 2017150934A JP 2019026990 A JP2019026990 A JP 2019026990A
- Authority
- JP
- Japan
- Prior art keywords
- spinning
- coagulation bath
- pva
- polyvinyl alcohol
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 78
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 71
- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000009987 spinning Methods 0.000 claims abstract description 85
- 230000015271 coagulation Effects 0.000 claims abstract description 38
- 238000005345 coagulation Methods 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 230000001112 coagulating effect Effects 0.000 claims abstract description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 36
- 229910003002 lithium salt Inorganic materials 0.000 claims description 29
- 159000000002 lithium salts Chemical class 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 13
- 239000011550 stock solution Substances 0.000 claims description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 5
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- -1 LiCF 3 SO 3 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000010586 diagram Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000009878 intermolecular interaction Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
【課題】高弾性率のＰＶＡ繊維の製造方法を提供する。【解決手段】濃度（重量％）が、０．１〜５重量％の範囲にあるリチウム塩及びポリマーの濃度（重量％）が、５〜３０重量％の範囲で重合度が少なくとも１０００のポリビニルアルコール系ポリマーを含む紡糸原液を、凝固することによって得られる紡糸原糸を、全延伸倍率が８倍以上となるように、凝固浴液中及び凝固浴液から引き上げられた後、巻き取られるまでに加熱延伸することによるポリビニルアルコール系繊維の製造方法。【選択図】なしPROBLEM TO BE SOLVED: To provide a method for producing a PVA fiber having a high elastic modulus. SOLUTION: Polyvinyl alcohol having a concentration (% by weight) in the range of 0.1 to 5% by weight and a polymer having a concentration (% by weight) in the range of 5 to 30% by weight and having a degree of polymerization of at least 1000. The spinning raw yarn obtained by coagulating the spinning raw liquid containing the system polymer is pulled up in the coagulation bath liquid and from the coagulation bath liquid so that the total draw ratio becomes 8 times or more, and then is wound up. A method for producing a polyvinyl alcohol-based fiber by heating and stretching. [Selection diagram] None
Description
本発明は、高弾性率化されたポリビニルアルコール系繊維の製造方法に関する。 The present invention relates to a method for producing a highly elastic polyvinyl alcohol fiber.
ポリピニルアルコール（ＰＶＡ）の繊維は安価で強度に優れることが知られており、産業界でも多くの用途に使用されている。ＰＶＡ系繊維は、水を溶媒とした湿式紡糸法、及び乾式紡糸法、有機溶媒を用いたゲル紡糸法などにより製造されている。特許文献１は、湿式紡糸法による高強度のＰＶＡ繊維の製造方法を開示している。 Polypinyl alcohol (PVA) fibers are known to be inexpensive and excellent in strength, and are used in many applications in industry. PVA fibers are produced by a wet spinning method using water as a solvent, a dry spinning method, a gel spinning method using an organic solvent, and the like. Patent document 1 is disclosing the manufacturing method of the high intensity | strength PVA fiber by a wet spinning method.
ＰＶＡ繊維は、カーボン繊維（ＣＦ）を上回る高い強度を示すと共にＣＦよりも低比重である。コストパフォーマンスも考慮すると、ＣＦの一部用途では、代替が可能になると期待できる。しかし、ＰＶＡ繊維は弾性率が低いという大きな不利がある。 PVA fibers exhibit higher strength than carbon fibers (CF) and have a lower specific gravity than CF. Considering cost performance, it can be expected that substitution will be possible in some CF applications. However, PVA fibers have a major disadvantage of low elastic modulus.
ＰＶＡは紡糸が比較的困難である。現在でも湿式紡糸により高強度のＰＶＡ繊維が製造されているが、紡糸困難であり欠陥の多い繊維であるために、弾性率は低い。本発明者の見積もりによれば、高強度のＰＶＡ繊維とされている繊維の弾性率は理論値のわずか２５％程度にとどまる。このように、ＰＶＡ繊維は、高弾性率化の要求が存在し、本来は高弾性率化の潜在力がありながら、それが実現されないままとなっていた。 PVA is relatively difficult to spin. Even now, high-strength PVA fibers are produced by wet spinning, but the elastic modulus is low because the fibers are difficult to spin and have many defects. According to the estimate of the present inventor, the elastic modulus of the fiber made of high-strength PVA fiber is only about 25% of the theoretical value. As described above, there is a demand for increasing the elastic modulus of the PVA fiber. Originally, although there is a potential for increasing the elastic modulus, it has not been realized.
したがって、本発明の目的は、高弾性率のＰＶＡ繊維を提供することにある。 Accordingly, an object of the present invention is to provide a high modulus PVA fiber.
本発明者は、ＰＶＡ繊維の高弾性率化について鋭意探索研究してきたところ、驚くべきことに、ＰＶＡの紡糸において、リチウム塩を混合するという簡便な手段によって、得られるＰＶＡ繊維が著しく高弾性率化されることを見いだして、本発明に到達した。 The present inventor has eagerly searched for an increase in the elastic modulus of the PVA fiber. Surprisingly, in the spinning of the PVA, the obtained PVA fiber has an extremely high elastic modulus by a simple means of mixing a lithium salt. As a result, the present invention has been reached.
したがって、本発明は次の（１）以下を含む。
（１）
リチウム塩及び重合度が少なくとも１０００のポリビニルアルコール系ポリマーを含む紡糸原液を、凝固することによって得られる紡糸原糸を、延伸することによってポリビニルアルコール系繊維を、製造する方法。
（２）
リチウム塩が、ＬｉＢｒ、ＬｉＦ、ＬｉＣｌ、ＬｉＩ、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＣ2Ｆ5ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、及びＬｉＮ（Ｃ2Ｆ5ＳＯ2）2からなる群から選択されたリチウム塩である、（１）に記載の製造方法。
（３）
紡糸原液に含有されるリチウム塩の濃度（重量％）が、紡糸原液に含有されるポリビニルアルコール系ポリマーの濃度（重量％）に対して、１／１００〜１／１０の範囲の比率の濃度である、（１）〜（２）のいずれかに記載の製造方法。
（４）
紡糸原液に含有されるポリビニルアルコール系ポリマーの濃度（重量％）が、５〜３０重量％の範囲にある、（１）〜（３）のいずれかに記載の製造方法。
（５）
紡糸原液に含有されるリチウム塩の濃度（重量％）が、０．１〜５重量％の範囲にある、（１）〜（４）のいずれかに記載の製造方法。
（６）
ポリビニルアルコール系ポリマーの重合度が、１２００〜６０００の範囲にある、（１）〜（５）のいずれかに記載の製造方法。
（７）
紡糸原液が水溶液である、（１）〜（６）のいずれかに記載の製造方法。
（８）
凝固が、紡糸原液を凝固浴液中へ吐出することによって行われる、（１）〜（７）のいずれかに記載の製造方法。
（９）
凝固浴液が、水溶液である、（８）に記載の製造方法。
（１０）
紡糸原糸が、凝固浴液中で行われる延伸がなされた紡糸原糸である、（８）〜（９）のいずれかに記載の製造方法。
（１１）
紡糸原糸が、凝固浴から引き上げられた後に、巻き取られるまでに行われる延伸がなされた紡糸原糸である、（８）〜（１０）のいずれかに記載の製造方法。
（１２）
紡糸原糸が、凝固浴中へ吐出された後に巻き取られるまでに行われた延伸（紡糸延伸）がなされた紡糸原糸であり、
さらに、紡糸原糸の延伸として、紡糸され乾燥された後に行われる延伸（加熱延伸）がなされ、
これらの紡糸延伸と加熱延伸をあわせた全延伸倍率が８倍以上となるように延伸されている、（８）〜（１１）のいずれかに記載の製造方法。
Accordingly, the present invention includes the following (1) and below.
(1)
A method for producing a polyvinyl alcohol fiber by drawing a spinning yarn obtained by coagulating a spinning stock solution containing a lithium salt and a polyvinyl alcohol polymer having a polymerization degree of at least 1000.
(2)
Lithium salts are LiBr, LiF, LiCl, LiI, LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiC 2 F 5 SO 3 , LiN (CF 3 SO 2 ) 2 , and LiN (C 2 is F 5 SO 2) lithium salt selected from the group consisting of 2, the production method according to (1).
(3)
The concentration (wt%) of the lithium salt contained in the spinning dope is at a concentration in the range of 1/100 to 1/10 with respect to the concentration (wt%) of the polyvinyl alcohol polymer contained in the spinning dope. The manufacturing method according to any one of (1) to (2).
(4)
The production method according to any one of (1) to (3), wherein the concentration (% by weight) of the polyvinyl alcohol-based polymer contained in the spinning dope is in the range of 5 to 30% by weight.
(5)
The production method according to any one of (1) to (4), wherein the concentration (wt%) of the lithium salt contained in the spinning dope is in the range of 0.1 to 5 wt%.
(6)
The production method according to any one of (1) to (5), wherein the polymerization degree of the polyvinyl alcohol-based polymer is in the range of 1200 to 6000.
(7)
The production method according to any one of (1) to (6), wherein the spinning dope is an aqueous solution.
(8)
The production method according to any one of (1) to (7), wherein the coagulation is performed by discharging the spinning stock solution into a coagulation bath solution.
(9)
The production method according to (8), wherein the coagulation bath liquid is an aqueous solution.
(10)
The production method according to any one of (8) to (9), wherein the spinning yarn is a spinning yarn that has been stretched in a coagulation bath.
(11)
The production method according to any one of (8) to (10), wherein the spinning base yarn is a spinning base yarn that has been stretched before being wound up after being pulled up from the coagulation bath.
(12)
The spinning yarn is subjected to stretching (spinning stretching) performed until the spinning yarn is discharged after being discharged into the coagulation bath and wound up.
Furthermore, as stretching of the spinning yarn, stretching (heat stretching) performed after spinning and drying is performed,
The production method according to any one of (8) to (11), wherein the drawing is performed so that a total drawing ratio of the spinning drawing and the heat drawing is 8 times or more.
本発明は、高弾性率のＰＶＡ繊維を提供する。本発明によれば、紡糸工程におけるリチウム塩の添加という簡便な手段により、高弾性率のＰＶＡ繊維を提供できる。本発明によるＰＶＡ繊維は、高い強度と低い比重という従来のＰＶＡ繊維の特性に加えて、高い弾性率を備えているので、軽くて強くしなやかな繊維であり、これまで高価な炭素繊維でなければ実現できなかった性能を優れた経済性を伴って実現できる、いわばスーパー繊維を提供するものである。 The present invention provides a high modulus PVA fiber. According to the present invention, a high elastic modulus PVA fiber can be provided by a simple means of adding a lithium salt in the spinning process. The PVA fiber according to the present invention has a high elastic modulus in addition to the properties of the conventional PVA fiber such as high strength and low specific gravity. The present invention provides a super fiber that can realize performance that could not be realized with excellent economic efficiency.
具体的な実施の形態をあげて、以下に本発明を詳細に説明する。本発明は、以下にあげる具体的な実施他の形態に限定されるものではない。 The present invention will be described in detail below by giving specific embodiments. The present invention is not limited to the following specific embodiments and other embodiments.
［ＰＶＡ系繊維の製造］
本発明のＰＶＡ系高弾性率繊維の製造は、リチウム塩及び重合度が少なくとも１０００のポリビニルアルコール系ポリマー（ＰＶＡ系ポリマー）を含む紡糸原液を、凝固することによって得られる紡糸原糸を、延伸することによって行われる。
[Production of PVA fiber]
In the production of the PVA-based high elastic modulus fiber of the present invention, a spinning yarn obtained by coagulating a spinning stock solution containing a lithium salt and a polyvinyl alcohol polymer (PVA polymer) having a polymerization degree of at least 1000 is drawn. Is done by.
［紡糸原液］
本発明に使用される紡糸原液は、リチウム塩及びポリビニルアルコール系ポリマー（ＰＶＡ系ポリマー）を含む。紡糸原液は、好ましくはこれらを溶解した水溶液である。紡糸原液は、例えば、ＰＶＡ系ポリマーを公知の手段によって加熱攪拌して溶解した後に、リチウム塩水溶液を添加して、加熱混合することによって、調製することができる。あるいは、公知の手段を用いて、例えばＰＶＡ系ポリマー水溶液中へリチウム塩の固体を投入して加熱混合して、紡糸原液を得てもよい。
[Spinning stock solution]
The spinning dope used in the present invention contains a lithium salt and a polyvinyl alcohol polymer (PVA polymer). The spinning dope is preferably an aqueous solution in which these are dissolved. The spinning dope can be prepared, for example, by dissolving a PVA polymer by heating and stirring by a known means, adding an aqueous lithium salt solution, and mixing by heating. Alternatively, using a known means, for example, a lithium salt solid may be put into a PVA polymer aqueous solution and heated and mixed to obtain a spinning dope.
［ＰＶＡ系ポリマー］
ＰＶＡ系ポリマーは、重合度が少なくとも１０００であり、好ましくは重合度が、１２００〜６０００の範囲、さらに好ましくは１２００〜４０００の範囲、さらに好ましくは１２００〜３０００の範囲にある。ＰＶＡ系ポリマーのけん化度は、例えば９０モル％以上とすることができ、ＰＶＡ繊維の耐熱性、耐水性の観点より、９９モル％以上であると好ましい。ＰＶＡ系ポリマーは、他のビニル基を有するモノマー、例えば酢酸ビニル、エチレン、ポリエチレングリコールなどの若干の共重合成分を含んでいても良い。
[PVA polymer]
The PVA polymer has a degree of polymerization of at least 1000, preferably a degree of polymerization in the range of 1200 to 6000, more preferably in the range of 1200 to 4000, and still more preferably in the range of 1200 to 3000. The degree of saponification of the PVA polymer can be, for example, 90 mol% or more, and is preferably 99 mol% or more from the viewpoint of heat resistance and water resistance of the PVA fiber. The PVA polymer may contain some copolymer components such as other vinyl group-containing monomers such as vinyl acetate, ethylene, and polyethylene glycol.
ＰＶＡ系ポリマーを水溶液中に加熱溶解するとき、ＰＶＡ系ポリマーに不純物として残留する酢酸ナトリウムはＰＶＡ系ポリマーの部分的な熱分解に伴う着色を生じたり、得られた繊維の物性を損なったりするために、これらを抑制することを目的として、ＰＶＡ系ポリマーをあらかじめ純水で水洗し、酢酸ナトリウムを除去しておくことが望ましい。この際、重合度が１０００程度の比較的分子量の低いＰＶＡの水洗には、１５℃程度の冷水を用いたり、水とメタノールの混合物を用いたりして、ＰＶＡの溶解性を低下させて回収率を上げることも有効である。 When a PVA polymer is dissolved in an aqueous solution by heating, sodium acetate remaining as an impurity in the PVA polymer may cause coloring due to partial thermal decomposition of the PVA polymer or damage the physical properties of the obtained fiber. For the purpose of suppressing these, it is desirable to wash the PVA polymer with pure water in advance to remove sodium acetate. At this time, the PVA having a polymerization degree of about 1000 having a relatively low molecular weight is washed with cold water of about 15 ° C. or a mixture of water and methanol to reduce the PVA solubility and recover the recovery rate. It is also effective to raise
［ＰＶＡ系ポリマーの濃度］
紡糸原液中に含有されるＰＶＡ系ポリマーの濃度は、例えば２〜５０重量％の範囲とすることができる。紡糸原液のポリマー濃度は、ポリマーの溶解性及び紡糸時の曳糸性を十分なものとし、さらに、紡糸時のゲル化性能及び紡糸後の延伸性を優れたものとするために５〜３０重量％とすることが好ましい。
[Concentration of PVA polymer]
The concentration of the PVA polymer contained in the spinning dope can be, for example, in the range of 2 to 50% by weight. The polymer concentration of the stock solution for spinning is 5 to 30% by weight in order to ensure sufficient solubility of the polymer and spinnability at the time of spinning, and excellent gelling performance at spinning and stretchability after spinning. % Is preferable.
［リチウム塩］
リチウム塩として、ＬｉＢｒ、ＬｉＦ、ＬｉＣｌ、ＬｉＩ、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＣ2Ｆ5ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、及びＬｉＮ（Ｃ2Ｆ5ＳＯ2）2からなる群から選択されたリチウム塩を使用することができ、好ましくはＬｉＢｒ、ＬｉＦ、ＬｉＣｌ、ＬｉＩ、又はＬｉＣｌＯ4を使用することができ、特に好ましくはＬｉＢｒ（臭化リチウム）を使用することができる。
[Lithium salt]
Lithium salts include LiBr, LiF, LiCl, LiI, LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiC 2 F 5 SO 3 , LiN (CF 3 SO 2 ) 2 , and LiN (C 2 A lithium salt selected from the group consisting of F 5 SO 2 ) 2 can be used, preferably LiBr, LiF, LiCl, LiI or LiClO 4 can be used, particularly preferably LiBr (lithium bromide). ) Can be used.
［リチウム塩の濃度］
紡糸原液に含有されるリチウム塩の濃度（重量％）は、紡糸原液に含有されるポリビニルアルコール系ポリマーの濃度（重量％）に対して、１／１００〜１／１０の範囲の比率の濃度、好ましくは１／５０〜１／２０の範囲の比率の濃度とすることができる。リチウム塩の濃度（重量％）は、上記範囲において、例えば０．１〜５重量％の範囲、好ましくは０．３〜１．０重量％の範囲とすることができる。
[Concentration of lithium salt]
The concentration (wt%) of the lithium salt contained in the spinning dope is a concentration in a ratio in the range of 1/100 to 1/10 with respect to the concentration (wt%) of the polyvinyl alcohol polymer contained in the spinning dope, The concentration may preferably be a ratio in the range of 1/50 to 1/20. The concentration (% by weight) of the lithium salt in the above range can be, for example, in the range of 0.1 to 5% by weight, preferably in the range of 0.3 to 1.0% by weight.
［紡糸原液の吐出と凝固］
紡糸原液は、溶液状態を維持するために、例えば７０℃以上、好ましくは８０℃以上に加熱しておき、これを凝固させて紡糸を行う。好適な実施の態様において、凝固は、紡糸原液を、凝固浴の液中へ吐出することによって行う。吐出は、公知の装置及び器具を使用して行うことができる。例えば直径０．０１〜０．５ｍｍの孔を備えた押出機先端部から吐出することができる。吐出量や孔の個数は適宜選択することができ、例えば吐出量１〜５０ｃｃ／ｍｉｎで、例えば５０〜１０００個の孔を備えた押出機先端部から吐出することができる。
[Discharge and coagulation of spinning dope]
In order to maintain the solution state, the spinning dope is heated to, for example, 70 ° C. or higher, preferably 80 ° C. or higher, and solidified to perform spinning. In a preferred embodiment, the coagulation is performed by discharging the spinning dope into the liquid of the coagulation bath. Discharging can be performed using a known apparatus and instrument. For example, it can discharge from the front-end | tip part of an extruder provided with the hole of diameter 0.01-0.5mm. The discharge amount and the number of holes can be selected as appropriate. For example, the discharge amount can be 1 to 50 cc / min, and the discharge can be made from, for example, the tip of the extruder having 50 to 1000 holes.
［凝固浴］
凝固浴の液（凝固浴液）として、好ましくは水溶液が使用される。水溶液へは紡糸原液の凝固体から、リチウム塩が溶解除去されてゆくことが期待されるために、好ましい。凝固浴液としては、ＰＶＡ水溶液に対して脱水能のある無機塩類水溶液が好適に使用でき、特に高濃度水溶液、なかでも飽和水溶液が好適に使用できる。このような無機塩類としては、硫酸ナトリウム（芒硝）、硫酸アンモニウム、炭酸ナトリウムなど脱水能を有する塩類、好ましくは硫酸ナトリウムをあげることができる。特に好ましい凝固浴液として、硫酸ナトリウム飽和水溶液を使用することができる。紡糸原液がその中に吐出される凝固浴液の温度は、例えば３０〜６０℃、好ましくは３５〜４５℃とすることができる。凝固浴液中に吐出された紡糸原液は、凝固して、その後の処理に供される。
[Coagulation bath]
As the coagulation bath liquid (coagulation bath liquid), an aqueous solution is preferably used. The aqueous solution is preferable because the lithium salt is expected to be dissolved and removed from the solidified body of the spinning dope. As the coagulation bath liquid, an inorganic salt aqueous solution having a dehydrating ability with respect to the PVA aqueous solution can be preferably used, and a high concentration aqueous solution, in particular, a saturated aqueous solution can be preferably used. Examples of such inorganic salts include salts having a dehydrating ability such as sodium sulfate (sodium sulfate), ammonium sulfate and sodium carbonate, preferably sodium sulfate. As a particularly preferred coagulation bath liquid, a saturated aqueous solution of sodium sulfate can be used. The temperature of the coagulation bath liquid into which the spinning dope is discharged can be, for example, 30 to 60 ° C., preferably 35 to 45 ° C. The spinning dope discharged into the coagulation bath liquid coagulates and is subjected to subsequent processing.
好適な実施の態様において、凝固浴が、複数の温度の凝固浴液を通過させることによって行われていてもよい。すなわち、吐出された紡糸原液が、上記例えば３０〜６０℃好ましくは３５〜４５℃の温度の凝固浴液中を通過した後に（すなわち低温凝固浴液を通過し後に）、例えば７０〜９５℃好ましくは８０〜９０℃の温度の凝固浴液を通過させて（すなわち高温凝固浴液を通過させて）、凝固浴の処理を行ってもよい。好適な実施の態様において、この高温凝固浴液の通過の間に、延伸する処理を行うことができる。凝固浴液中で行われる延伸は、例えば１．５〜１０倍の延伸とすることができる。 In a preferred embodiment, the coagulation bath may be performed by passing a coagulation bath solution at a plurality of temperatures. That is, after the discharged spinning solution has passed through the coagulation bath liquid at a temperature of, for example, 30 to 60 ° C., preferably 35 to 45 ° C. (that is, after passing through the low-temperature coagulation bath liquid), for example, 70 to 95 ° C. is preferable. May be subjected to coagulation bath treatment by passing a coagulation bath solution at a temperature of 80 to 90 ° C. (that is, passing a high temperature coagulation bath solution). In a preferred embodiment, a stretching process can be performed during the passage of the hot coagulation bath liquid. The stretching performed in the coagulation bath liquid can be, for example, 1.5 to 10 times stretching.
紡糸原液の凝固体は、凝固溶液から引き上げられた後に、公知の手段により、原糸として巻き取られる。巻き取り時に、さらに延伸がなされる。好適な実施の態様において、凝固浴液から引き上げられた後に、所望により洗浄を行ってもよい。洗浄としては、例えば水による洗浄（水洗）が好ましい。水洗の水の温度は、例えば５〜４０℃、あるいは例えば室温の水によって行うことができる。 The solidified body of the spinning stock solution is pulled up from the coagulating solution and then wound up as a raw yarn by a known means. Further stretching is performed during winding. In a preferred embodiment, after being pulled out from the coagulation bath liquid, washing may be performed as desired. As washing, for example, washing with water (water washing) is preferable. The temperature of the water for washing can be 5 to 40 ° C., for example, or room temperature water.
［紡糸延伸］
紡糸原液が、凝固浴液中へ吐出されてから、原糸として巻き取られるまでに、所望により数段階の延伸を受ける。これらの延伸の全てをまとめて、紡糸延伸と称する。紡糸延伸による全延伸倍率は、例えば３倍以上、好ましくは８倍以上とすることができる。
[Spinning drawing]
The spinning stock solution is subjected to several stages of stretching as desired from when it is discharged into the coagulation bath solution until it is wound up as a raw yarn. All of these stretching operations are collectively referred to as spinning stretching. The total draw ratio by spin-drawing can be, for example, 3 times or more, preferably 8 times or more.
［マルチフィラメント］
巻き取られる紡糸原糸は、押し出された１本の原糸（モノフィラメント）とすることもできるが、好ましくは複数のモノフィラメントのまとまりを少しねじって１本に形成されたマルチフィラメントとすることができる。例えば５０〜１０００個の孔を備えた押出機先端部から吐出されて形成されたマルチフィラメントのまとまりから、これらを少しねじって１本に形成されたマルチフィラメントとすることができる。
[Multifilament]
The spinning yarn to be wound can be a single extruded yarn (monofilament), but preferably a plurality of monofilaments can be twisted a little to form a multifilament formed into one. . For example, from a set of multifilaments formed by discharging from the tip of an extruder having 50 to 1000 holes, these can be twisted slightly to form a multifilament formed into one.
［加熱延伸」
上記巻き取られた紡糸原糸は、十分に乾燥した後に、加熱延伸（乾熱延伸）によって延伸される。加熱延伸における延伸倍率は、例えば２．５倍以上、好ましくは２．７倍以上とすることができる。加熱延伸のための加熱の温度は、例えば１５０〜２００℃の範囲とすることができる。
[Heating stretching]
The wound spinning yarn is sufficiently dried and then stretched by heat stretching (dry heat stretching). The draw ratio in the heat drawing can be, for example, 2.5 times or more, preferably 2.7 times or more. The heating temperature for heat stretching can be set in the range of 150 to 200 ° C., for example.
好適な実施の態様において、紡糸延伸と加熱延伸をあわせた延伸倍率を、例えば３倍以上、好ましくは８倍以上、さらに好ましくは９倍以上とすることができる。好適な実施の態様において、紡糸延伸と加熱延伸をあわせた延伸倍率を、例えば３倍〜６０倍、８倍〜５０倍、９倍〜４５倍の範囲とすることができる。 In a preferred embodiment, the draw ratio of the combined spinning drawing and heat drawing can be, for example, 3 times or more, preferably 8 times or more, and more preferably 9 times or more. In a preferred embodiment, the draw ratio obtained by combining the spinning draw and the heat draw can be, for example, in the range of 3 to 60 times, 8 to 50 times, and 9 to 45 times.
［ＰＶＡ系高弾性率繊維］
上記の製造方法によって得られたＰＶＡ系繊維は、これまでのＰＶＡ系繊維と同様の強度を示すと同時に、これまでのＰＶＡ系繊維では実現できなかった高弾性率を示すものとなっている。好適な実施の態様において、ヤング率の値として、従来のＰＶＡ系繊維と対比して、例えば１．０５倍以上、好ましくは１．１倍以上、さらに好ましくは１．２倍以上、さらに好ましくは１．３倍以上の値を示し、本発明者の検討によれば、その比率の上限として、例えば４．０倍以下あるいは３．０倍以下の値とすることができる。あるいは、ヤング率の値として、マルチフィラメントをほどいた単繊維の形態であっても高い弾性率を発揮することができるが、マルチフィラメントの形態である場合が、高弾性率化された点で、特に好ましい。
[PVA-based high modulus fiber]
The PVA fiber obtained by the above production method exhibits the same strength as that of the conventional PVA fiber, and at the same time exhibits a high elastic modulus that cannot be achieved with the conventional PVA fiber. In a preferred embodiment, the value of Young's modulus is, for example, 1.05 times or more, preferably 1.1 times or more, more preferably 1.2 times or more, more preferably, as compared with conventional PVA fibers. A value of 1.3 times or more is shown, and according to the study of the present inventor, the upper limit of the ratio can be set to, for example, 4.0 times or less or 3.0 times or less. Alternatively, as a value of Young's modulus, a high elastic modulus can be exhibited even in the form of a single fiber in which a multifilament is unwound, but in the case of a multifilament form, in terms of a high elastic modulus, Particularly preferred.
紡糸原液へのリチウム塩の添加という簡便な工程によって、このように優れた高弾性率化が達成できた理由は不明であるが、本発明者は、リチウム塩の添加によってＰＶＡにおいて水素結合による分子間相互作用が大幅に低下しているという実験結果を得たことから、リチウム塩によるＰＶＡ系繊維の高弾性率化は、水素結合による分子間相互作用を弱めて、紡糸時の分子配向性を改善することによって生じているのではないかと考えている。 The reason why such an excellent elastic modulus can be achieved by a simple process of adding a lithium salt to a spinning dope is unclear, but the present inventor believes that molecules added by hydrogen bonding in PVA by adding a lithium salt. From the experimental result that the intermolecular interaction is greatly reduced, the increase in the elastic modulus of the PVA fiber by lithium salt weakens the intermolecular interaction caused by hydrogen bonding and improves the molecular orientation during spinning. I think that it may be caused by improvement.
以下に実施例をあげて、本発明を詳細に説明する。本発明は、以下に例示する実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to the examples illustrated below.
［実施例１］
［ＬｉＢｒを用いた原液による紡糸：ＰＶＡ ｗｉｔｈ ＬｉＢｒ］
重合度１７００、ケン化度９９．５ｍｏｌ％のＰＶＡ（日本酢ビ・ポバール社製、製品名ＶＨ）を蒸留水に加え、約９０℃の温度でポリマーが完全に溶解するまでホットスターラーで撹拌・溶解させた。これとは別に蒸留水に臭化リチウムを加えてよく撹拌して完全に溶解し、臭化リチウム水溶液を作製した。上記調製したＰＶＡ水溶液に対して、臭化リチウム水溶液を添加して加熱混合して、紡糸原液を得た。臭化リチウム水溶液は、紡糸原液の臭化リチウム濃度が最終的に０．５重量％となるように添加した。紡糸原液中のＰＶＡ濃度は最終的に約１５重量％となるようにした。
[Example 1]
[Spinning with stock solution using LiBr: PVA with LiBr]
Add PVA having a polymerization degree of 1700 and a saponification degree of 99.5 mol% (product name: VH, manufactured by Nippon Vinegar Pover Co., Ltd.) to distilled water and stirring with a hot stirrer until the polymer is completely dissolved at a temperature of about 90 ° C Dissolved. Separately, lithium bromide was added to distilled water and stirred well to dissolve completely to prepare an aqueous solution of lithium bromide. An aqueous lithium bromide solution was added to the PVA aqueous solution prepared above and mixed by heating to obtain a spinning dope. The lithium bromide aqueous solution was added so that the concentration of lithium bromide in the spinning stock solution was finally 0.5% by weight. The PVA concentration in the spinning dope was finally about 15% by weight.
紡糸原液を、吐出量１５ｃｃ／ｍｉｎにて２５０個の孔（各直径０．１ｍｍ）のある押出機先端部から、凝固浴（４０℃、４２０〜４３０ｇ／Ｌ硫酸ナトリウム飽和水溶液）中に吐出して、凝固させ、これを巻き取った。巻き取りながら、さらに８５〜９０℃の凝固浴中を通過させて、約１．５倍に延伸して、凝固浴中から引き上げた。凝固中から引き上げた後に水（３０℃）で洗浄して、巻き取った。ここまでの延伸倍率はあわせて約３．４倍であった。この２５０本のまとまりを少しねじってマルチフィラメントとした。これを乾燥後に、１７０℃で約２．８倍に加熱延伸した。この加熱延伸と、紡糸延伸とをあわせて、約９．６倍の延伸となっていた。得られたマルチフィラメントの一部をほどいて、単繊維を得た。得られた繊維密度は約１．３ｇ／ｃｍ3であった。 The spinning dope is discharged into a coagulation bath (40 ° C, 420 to 430 g / L sodium sulfate saturated aqueous solution) from the tip of the extruder having 250 holes (each diameter 0.1 mm) at a discharge rate of 15 cc / min. And solidified and wound up. While winding, it was further passed through a coagulation bath at 85 to 90 ° C., stretched about 1.5 times, and pulled up from the coagulation bath. After being raised from the solidification, it was washed with water (30 ° C.) and wound up. The draw ratio so far was about 3.4 times. The 250 bundles were twisted slightly to obtain multifilaments. After drying, the film was stretched by heating at 170 ° C. about 2.8 times. The combined heat stretching and spinning stretching resulted in a stretching of about 9.6 times. A part of the obtained multifilament was unwound to obtain a single fiber. The fiber density obtained was about 1.3 g / cm 3 .
［比較例１］
［ＬｉＢｒを用いない原液による紡糸：ＰＶＡ］
臭化リチウム水溶液を添加しないＰＶＡ水溶液を紡糸原液として用いたこと以外は実施例１と同様に紡糸、延伸を行った。得られたマルチフィラメントの一部をほどいて、単繊維を得た。
[Comparative Example 1]
[Spinning with stock solution without LiBr: PVA]
Spinning and drawing were performed in the same manner as in Example 1 except that a PVA aqueous solution to which no lithium bromide aqueous solution was added was used as the spinning stock solution. A part of the obtained multifilament was unwound to obtain a single fiber.
［評価］
実施例１及び比較例１において得られた単繊維及びマルチフィラメントについて、その特性を測定した結果を、表１にまとめて示す。
[Evaluation]
The results of measuring the properties of the single fibers and multifilaments obtained in Example 1 and Comparative Example 1 are summarized in Table 1.
上記の結果から、ＰＶＡの紡糸原液にリチウム塩を添加することによって、強度を維持しながら、高いヤング率を有する繊維が得られること、すなわちＰＶＡ繊維の高弾性率化が実現できることがわかった。 From the above results, it was found that by adding a lithium salt to the PVA spinning dope, fibers having a high Young's modulus can be obtained while maintaining strength, that is, a higher elastic modulus of the PVA fibers can be realized.
［動的粘弾性の温度依存性試験］
試験用の試料として、臭化リチウム含有ＰＶＡ試料（試料１）（ＰＶＡ／ＬｉＢｒ）とＰＶＡ試料（試料２）（ｐｕｒｅ ＰＶＡ）を用意した。臭化リチウム含有ＰＶＡ試料（試料１）として、上記実施例１の紡糸原液を使用して、室温で乾燥させることにより溶液キャストフィルムを作成した。装置はＵＢＭ社製、強制振動型動的固体粘弾性測定装置ＤＶＥ−Ｖ４を用いて、動的引張弾性率の温度依存性を測定した。測定周波数は１０Ｈｚ、昇温速度は２℃／分である。ＰＶＡ試料（試料２）として、上記比較例１の紡糸原液を使用して、同様にキャストフィルムを作成した。これらの試料に対して、次の条件で動的粘弾性の温度依存性を測定した。この結果を図１にまとめて示す。
[Temperature dependence test of dynamic viscoelasticity]
As a test sample, a lithium bromide-containing PVA sample (sample 1) (PVA / LiBr) and a PVA sample (sample 2) (pure PVA) were prepared. As a lithium bromide-containing PVA sample (sample 1), a solution cast film was prepared by drying at room temperature using the spinning dope of Example 1 above. The apparatus measured the temperature dependence of a dynamic tensile elasticity modulus using the forced vibration type dynamic solid viscoelasticity measuring apparatus DVE-V4 made from UBM. The measurement frequency is 10 Hz, and the heating rate is 2 ° C./min. As a PVA sample (sample 2), a cast film was similarly prepared using the spinning solution of Comparative Example 1 described above. For these samples, the temperature dependence of dynamic viscoelasticity was measured under the following conditions. The results are summarized in FIG.
図１に示される結果から、リチウム塩の添加によって、ＰＶＡにおいて水素結合による分子間相互作用が大幅に低下していることがわかった。この結果から、本発明者は、リチウム塩によるＰＶＡの高弾性率化は、水素結合による分子間相互作用を弱めて、紡糸時の分子配向性を改善することによって生じているのではないかと考えている。 From the results shown in FIG. 1, it was found that the intermolecular interaction due to hydrogen bonding in PVA is greatly reduced by the addition of lithium salt. From this result, the present inventor believes that the increase in the elastic modulus of PVA by the lithium salt is caused by weakening the intermolecular interaction due to hydrogen bonding and improving the molecular orientation during spinning. ing.
本発明は、高弾性率のＰＶＡ繊維を提供する。本発明は産業上有用な発明である。 The present invention provides a high modulus PVA fiber. The present invention is industrially useful.
Claims (12)
さらに、紡糸原糸の延伸として、紡糸され乾燥された後に行われる延伸（加熱延伸）がなされ、
これらの紡糸延伸と加熱延伸をあわせた全延伸倍率が８倍以上となるように延伸されている、請求項８〜１１のいずれかに記載の製造方法。 The spinning yarn is subjected to drawing (spinning drawing) performed until the spinning yarn is discharged after being discharged into the coagulation bath liquid and wound up.
Furthermore, as stretching of the spinning yarn, stretching (heat stretching) performed after spinning and drying is performed,
The production method according to any one of claims 8 to 11, wherein the drawing is performed so that a total drawing ratio of the spinning drawing and the heating drawing is 8 times or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017150934A JP7058854B2 (en) | 2017-08-03 | 2017-08-03 | Method for manufacturing polyvinyl alcohol fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017150934A JP7058854B2 (en) | 2017-08-03 | 2017-08-03 | Method for manufacturing polyvinyl alcohol fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019026990A true JP2019026990A (en) | 2019-02-21 |
| JP7058854B2 JP7058854B2 (en) | 2022-04-25 |
Family
ID=65477757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017150934A Active JP7058854B2 (en) | 2017-08-03 | 2017-08-03 | Method for manufacturing polyvinyl alcohol fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7058854B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020204104A (en) * | 2019-06-17 | 2020-12-24 | 株式会社クラレ | Polyvinyl alcohol fiber and method for producing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63120107A (en) * | 1986-11-05 | 1988-05-24 | Toray Ind Inc | High-strength and high-elastic modulus polyvinyl alcohol based fiber having excellent hot water resistance and production thereof |
| JPH04108109A (en) * | 1990-08-27 | 1992-04-09 | Kuraray Co Ltd | Polyvinyl alcohol fiber and its manufacturing method |
| JPH0428804B2 (en) * | 1984-11-02 | 1992-05-15 | Toray Industries | |
| JPH0657523A (en) * | 1992-08-12 | 1994-03-01 | Kuraray Co Ltd | Production of polyvinyl alcoholic fiber excellent in quality |
| JP2996407B2 (en) * | 1990-01-22 | 1999-12-27 | 株式会社クラレ | Fiber and production method thereof |
| JP2006002304A (en) * | 2004-06-21 | 2006-01-05 | Kuraray Co Ltd | Polyvinyl alcohol fiber |
-
2017
- 2017-08-03 JP JP2017150934A patent/JP7058854B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0428804B2 (en) * | 1984-11-02 | 1992-05-15 | Toray Industries | |
| JPS63120107A (en) * | 1986-11-05 | 1988-05-24 | Toray Ind Inc | High-strength and high-elastic modulus polyvinyl alcohol based fiber having excellent hot water resistance and production thereof |
| JP2996407B2 (en) * | 1990-01-22 | 1999-12-27 | 株式会社クラレ | Fiber and production method thereof |
| JPH04108109A (en) * | 1990-08-27 | 1992-04-09 | Kuraray Co Ltd | Polyvinyl alcohol fiber and its manufacturing method |
| JPH0657523A (en) * | 1992-08-12 | 1994-03-01 | Kuraray Co Ltd | Production of polyvinyl alcoholic fiber excellent in quality |
| JP2006002304A (en) * | 2004-06-21 | 2006-01-05 | Kuraray Co Ltd | Polyvinyl alcohol fiber |
Non-Patent Citations (1)
| Title |
|---|
| 藤田貴彦ら: "塩化リチウムがポリビニルアルコール繊維の構造と力学物性に与える影響", 繊維学会予稿集, vol. 1995, JPN6021005930, 23 June 1995 (1995-06-23), JP, pages 241, ISSN: 0004449627 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020204104A (en) * | 2019-06-17 | 2020-12-24 | 株式会社クラレ | Polyvinyl alcohol fiber and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7058854B2 (en) | 2022-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106591992B (en) | A kind of modified gelatin fiber | |
| JP2569352B2 (en) | High strength water-soluble polyvinyl alcohol fiber and method for producing the same | |
| TW202200860A (en) | Method for producing polyamide 4 fiber by using a wet spinning method without carrying out a procedure for removing residual components | |
| JPH0611927B2 (en) | High-strength, high-modulus polyvinyl alcohol fiber and method for producing the same | |
| JP7058854B2 (en) | Method for manufacturing polyvinyl alcohol fiber | |
| JP4172888B2 (en) | Monofilament and method for producing the same | |
| JPS5818444B2 (en) | Microporous acrylic fiber with improved water absorption | |
| JPH01104815A (en) | Polyvinyl alcohol fiber and production thereof | |
| JPS6021905A (en) | Acrylic fiber having high strength and elastic modulus and its manufacture | |
| US4658004A (en) | Polyacrylonitrile fiber with high strength and high modulus of elasticity | |
| JPS63120107A (en) | High-strength and high-elastic modulus polyvinyl alcohol based fiber having excellent hot water resistance and production thereof | |
| JPS61108713A (en) | Polyvinyl alcohol fiber having good fiber properties and its production | |
| CN103172959B (en) | Composite raw material, carbon fiber material and forming method thereof | |
| JPH10273821A (en) | Water absorbing acrylic fiber | |
| US2645556A (en) | Production of artificial filaments | |
| JPH076087B2 (en) | High strength and high modulus PVA fiber and method for producing the same | |
| JPH0233314A (en) | High strength polyvinyl alcohol fiber and its manufacturing method | |
| JP2888496B2 (en) | Method for producing high modulus polyvinyl alcohol fiber | |
| JP7556148B2 (en) | Monofilament and its manufacturing method | |
| US3073670A (en) | Process for the wet-spinning of acrylonitrile polymers | |
| JP2865736B2 (en) | Manufacturing method of high strength polyvinyl alcohol fiber | |
| JPS60199912A (en) | Spinning of cellulose solution | |
| JP2905545B2 (en) | High strength and high modulus polyvinyl alcohol fiber with excellent hot water resistance | |
| JP3023918B2 (en) | Polyvinyl alcohol-based synthetic fiber with excellent heat resistance | |
| JPH06235117A (en) | Production of high strength polyvinyl alcohol fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170825 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171011 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20200406 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200417 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20200407 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20200611 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210204 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210224 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210423 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20210524 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20210524 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20211013 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220112 |
|
| C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20220112 |
|
| C11 | Written invitation by the commissioner to file amendments |
Free format text: JAPANESE INTERMEDIATE CODE: C11 Effective date: 20220126 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20220228 |
|
| C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20220302 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220316 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220406 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7058854 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |