JPH02133620A - Production of high-strength polyamide yarn - Google Patents
Production of high-strength polyamide yarnInfo
- Publication number
- JPH02133620A JPH02133620A JP28257188A JP28257188A JPH02133620A JP H02133620 A JPH02133620 A JP H02133620A JP 28257188 A JP28257188 A JP 28257188A JP 28257188 A JP28257188 A JP 28257188A JP H02133620 A JPH02133620 A JP H02133620A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- methyl
- yarn
- solvent
- ethyl
- 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
- 239000004952 Polyamide Substances 0.000 title claims abstract description 19
- 229920002647 polyamide Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000009987 spinning Methods 0.000 claims abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 239000011550 stock solution Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- -1 oxygen free radical Chemical group 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001891 gel spinning Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高強力ポリアミド繊維の製造法に関し、得られ
る繊維はタイヤコードなどの産業資材分野において幅広
く使用される。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing high-strength polyamide fibers, and the resulting fibers are widely used in the field of industrial materials such as tire cords.
（従来の技術）
一般に高分子からなる繊維の極限構造とは、分子鎖が折
り畳まれて形成されるラメラが繊維軸に垂直に整列した
構造か、もしくは伸びきり鎖結晶から成る構造などが考
えられるが、繊維の高強力化極限構造を実現させるため
には、特に後方が必要である。この伸びきり鎖構造を発
現させる方法としては、■剛直な分子鎖を用いて配向結
晶化時に伸びきり鎖を発現させる液晶紡糸法、■屈曲性
分子鎖を用いて固化後の変形過程で伸びきり３１″１構
造に近づける高圧押しだし法等がある。しかし、これら
の方法では、得られる強度、弾性率は殆どの場合理論値
より低くなっている。又、これらの従来法は生成速度や
生産速度が低く、改善ずべき余地が多分にあり、技（ネ
ｊ的あるいは経済的な面に多くの問題がある。さらに、
スミス、ベニングスらにより重合物溶液を紡糸し、重合
物分子量の増加に関連する延伸比増加を利用したゲル紡
糸、熱延伸により、超高分子量ポリマーの高弾性率繊維
が得られているが、ポリエチレンについての事例が多く
、分子内に水素結合を有するポリマーについての事例は
なく、熱延伸時の延伸ｍ率を大きくすることができず高
強力化は見込めない。又、Ｄ。(Prior art) In general, the ultimate structure of fibers made of polymers is considered to be a structure in which lamellae formed by folding molecular chains are aligned perpendicular to the fiber axis, or a structure consisting of fully extended chain crystals. However, in order to realize the ultimate structure with high fiber strength, the rear part is especially necessary. Methods for developing this fully extended chain structure include: (1) liquid crystal spinning method in which rigid molecular chains are used to develop fully extended chains during oriented crystallization, and (2) flexible molecular chains are used to create fully extended chains in the deformation process after solidification. There are high-pressure extrusion methods that can approach a 31"1 structure. However, with these methods, the strength and modulus of elasticity obtained are in most cases lower than the theoretical values. Also, these conventional methods have low production speed and is low, there is a lot of room for improvement, and there are many problems in technical (negotiable) and economic aspects.Furthermore,
Smith, Bennings et al. have obtained high elastic modulus fibers of ultra-high molecular weight polymers by spinning a polymer solution and using gel spinning and hot stretching that utilize the increase in the stretching ratio associated with the increase in the molecular weight of the polymer, but polyethylene There are many cases of polymers having hydrogen bonds in the molecule, and there are no cases of polymers having hydrogen bonds in the molecule, and it is not possible to increase the stretching m ratio during hot stretching, so high strength cannot be expected. Also, D.
Ａｃ１ｃｒｎｏ等は、ナ・イロン６に少量の塩化リチウ
ムを）、卜加し、分子間力・を弱めた状態で溶融紡糸し
、これを延伸熱処理することにより高弾性率繊維を得て
いるが、延伸倍率は高々５倍であった。Ac1crno et al. obtain high elastic modulus fibers by adding a small amount of lithium chloride to Nylon 6, melt-spinning with weakened intermolecular forces, and subjecting this to drawing heat treatment. The stretching ratio was at most 5 times.
（Ｊ、ｌ’ｏｌｙｍ、Ｓｃｉ、、Ｉ’ｏｌｙｍ、Ｐｈｙ
ｓ、Ｉｉｄ、 １７．１９０３ （１９７９））（発明
が解決しようとする問題点）
前述したように、従来より知られた方法で得られる繊維
は、高弾性率を得るには充分であるが、高強力繊維を得
られず、繊維自体の物性にも問題があり、さらにそれ以
外でも技術的、経済的に多くの問題がある。本発明は、
かかる従来技術の問題点を解消した高強力ポリアミド繊
維の製造法を提供するものである。(J, l'olym, Sci,, I'olym, Phy
s, Iid, 17.1903 (1979)) (Problems to be Solved by the Invention) As mentioned above, fibers obtained by conventionally known methods are sufficient to obtain a high modulus of elasticity; High strength fibers cannot be obtained, there are problems with the physical properties of the fibers themselves, and there are many other technical and economical problems. The present invention
The present invention provides a method for producing high-strength polyamide fibers that solves the problems of the prior art.
（問題点を解決するための手段）
本発明者は、ポリアミド重合体より伸びきり鎖結晶から
なる繊維を得るため、高延伸倍率を取れる条件について
鋭意研究を重ねた結果、ついに本発明に到達した。(Means for Solving the Problems) The present inventor has finally arrived at the present invention as a result of extensive research into conditions that allow for a high stretching ratio in order to obtain fibers made of extended chain crystals from polyamide polymers. .
本発明は、ポリアミド重合体と弐（１）で示される化合
物の一種又は二種以上の混合物とを、ポリアミド重合体
が可溶な溶媒に溶解した原液より溶液紡糸法で紡出した
繊維を、式（１）で示される化合物の一種又は二種以上
の混合物を残存させたまま溶媒を除去した後、加熱延伸
することを特徴とする高強力ポリアミド繊維の製造法
式（］）中、Ｒはメチル、エチルの中から選ばれる一種
又は二種混合の置換基、Ｒ５は水素、メチル、エチルの
中から選ばれる一種又は二種以上混合装置１０基、Ｒ２
はメチル、エチル、酸素フリーラジカルから選ばれる置
換基である。The present invention provides fibers spun using a solution spinning method from a stock solution in which a polyamide polymer and one or a mixture of two or more of the compounds represented by (1) are dissolved in a solvent in which the polyamide polymer is soluble. A method for producing a high-strength polyamide fiber, which is characterized in that the solvent is removed while leaving one or a mixture of two or more compounds represented by formula (1), and then the fiber is heated and stretched.In the formula (]), R is methyl. , one or a mixture of two substituents selected from ethyl, R5 is hydrogen, methyl, 10 mixing devices of two or more selected from ethyl, R2
is a substituent selected from methyl, ethyl, and oxygen free radicals.
すなわち、本発明ではポリアミド重合体を弐（１）で示
される化合物と共に溶液紡糸することにより、該化合物
をポリアミド重合体のアミド基に作用さけ、水素結合を
減少さセ、分子間の凝集力を小さくし、分子鎖の引き揃
えをスムーズに行なおうどするものである。さらに水素
結合弛緩剤として用いる式（１）で示される化合物が無
機物と異なり有機物であるため、無機物が析出した場合
のように高次の欠陥にならないと思われる。That is, in the present invention, by solution-spinning a polyamide polymer together with the compound represented by (2) (1), the compound is prevented from acting on the amide groups of the polyamide polymer, reducing hydrogen bonds and increasing the cohesive force between molecules. The purpose is to make it smaller and to smoothly align the molecular chains. Furthermore, since the compound represented by formula (1) used as a hydrogen bond relaxant is an organic substance, unlike an inorganic substance, it is thought that higher-order defects will not occur as would occur if an inorganic substance were precipitated.
本発明で使用されるポリアミド重合体はナイロン６、ナ
イｌコン１１、ナイロン１２、ナイロン６６、ナイロン
６１０、ナイロン６１２、ナイロン１１６等のポリアミ
ド又はこれら二種以上を組み合わせてなるコポリアミド
が挙げられる。なお、重合度と強力の間には相関がある
事は公知の事実であり、本発明においても高重合度ポリ
マーが望ましく、具体的な重合度としては、９５，５％
硫酸相対粘度換算でナイロン６６の場合、相対粘度が５
〜６０、ナイロン６の場合、相対粘度が１０〜８０が好
ましい。Examples of the polyamide polymer used in the present invention include polyamides such as nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612, and nylon 116, or copolyamides formed by combining two or more of these. It is a well-known fact that there is a correlation between the degree of polymerization and strength, and in the present invention, a polymer with a high degree of polymerization is desirable, and the specific degree of polymerization is 95.5%.
In the case of nylon 66, the relative viscosity is 5 in terms of sulfuric acid relative viscosity.
-60, and in the case of nylon 6, the relative viscosity is preferably 10-80.
本発明では溶液紡糸により繊維化するため、）容融紡糸
のように高重合度化が安定紡糸困難な原因につながるこ
とはない。In the present invention, since the fibers are formed by solution spinning, increasing the degree of polymerization does not lead to difficulty in stable spinning unlike in melt spinning.
本発明に用いられる式（１）で示される化合物はＮ−Ｒ
Ｒの窒素によりアミド基の水素と水素結合を持ちアミド
−アミドの間の水素結合を減少さ−１！分子間凝集力を
小さくする効果がある。The compound represented by formula (1) used in the present invention is N-R
The nitrogen of R forms a hydrogen bond with the hydrogen of the amide group, reducing the hydrogen bond between amide and amide -1! It has the effect of reducing intermolecular cohesion.
本発明において用いられる式（１）で示される化合物の
Ｒ，Ｒ，に示される置換基は、Ｒはメチル、エチル基か
ら選ばれるものである。ここでＲの位置にエチル基より
大きなプロピル、イソブ！］ピル基等をつけると、立体
的な障害が起こりアミドアミＦ間の水素結合の減少に寄
与しなくなる。In the substituents R, R, of the compound represented by formula (1) used in the present invention, R is selected from methyl and ethyl groups. Here, in the R position, propyl, which is larger than the ethyl group, isobut! ] If a pyl group or the like is attached, steric hindrance occurs and it no longer contributes to the reduction of hydrogen bonds between amide amines F.
方、Ｒの位置にメチル基より小さな水素が一つ付くと、
窒素と水素により、又二つ水素が付くと水素と水素、窒
素と水素により式（りで示される化合物を橋にして二つ
のアミド基の連結が起こり、分子間凝集力の低下が起こ
らず、延伸がされにくい。On the other hand, if one hydrogen smaller than a methyl group is attached to the R position,
By nitrogen and hydrogen, or by hydrogen and hydrogen when two hydrogens are attached, or by nitrogen and hydrogen, the two amide groups are linked by using the compound represented by the formula (ri) as a bridge, and the intermolecular cohesive force does not decrease, Hard to stretch.
本発明における、式（１）で示される化合物は、例えば
、２．２．６．６−チトラメヂルー４−ジメチルアミノ
ピペリジン−Ｎ−酸素フリーラジカル、Ｎメチル−２，
２，６，６−テトラメチル−４−ジメチルアミノピペリ
ジン、Ｎ−メチル−２，６〜ジメチル２．６−ダニチル
−４−ジエチルアミノビベリジン等である。In the present invention, the compound represented by formula (1) is, for example, 2.2.6.6-titramedy-4-dimethylaminopiperidine-N-oxygen free radical, N-methyl-2,
These include 2,6,6-tetramethyl-4-dimethylaminopiperidine, N-methyl-2,6-dimethyl2,6-danityl-4-diethylaminobiveridine, and the like.
本発明において用いられる溶媒としてはポリアミド重合
物が可溶なものであれば良く、単一あるいは混合系の低
分子化合物が用いられる。溶Ｍ温度は本発明で用いられ
る重合物の分解温度より高くてはならない。なお、高温
で溶解を行う場合には、溶媒中に活性な水素などを有し
ていると、重合物の分解等が起こり好ましくない。具体
的な例としては、ピリジン、Ｎ−メチル−２−ピロリド
ン、１．３−＝−ジメチル−２−イミダゾリジノン、ジ
メチルアセトアミｒ等が挙げられ、分子内にアミド結合
を有するものが好ましい溶解性を示す。The solvent used in the present invention may be any solvent as long as it can dissolve the polyamide polymer, and a single or mixed low-molecular compound may be used. The melt M temperature must not be higher than the decomposition temperature of the polymer used in the present invention. In addition, when dissolving at a high temperature, if the solvent contains active hydrogen or the like, decomposition of the polymer may occur, which is not preferable. Specific examples include pyridine, N-methyl-2-pyrrolidone, 1.3-=-dimethyl-2-imidazolidinone, dimethylacetamide, etc., and those having an amide bond in the molecule are preferred. Shows solubility.
本発明において用いる式（１）で示される化合物の添加
には任意であるが、通常はアミド基故に対して０．１〜
ＩＯ倍の量を添加する。これよりも少ないと水素結合減
少による分子間凝集力減少への効果が小さく、一方これ
よりも多いと塩析効果によりポリマ〜の溶解性を低下さ
せることにもなる。Although the addition of the compound represented by formula (1) used in the present invention is optional, it is usually 0.1 to
Add IO times the amount. If the amount is less than this, the effect of reducing intermolecular cohesive force due to the reduction of hydrogen bonds will be small, while if it is more than this, the solubility of the polymer will be reduced due to the salting out effect.
なお、加熱延伸後、式（１）で示される化合物はそのま
ま繊維中に残存させても良いし、水、メタツル等により
抽出して除去しても良い。Note that after heating and stretching, the compound represented by formula (1) may remain in the fiber as it is, or may be removed by extraction with water, metal chloride, or the like.
本発明において、溶液紡糸法とは、重合物を溶媒に熔解
した後、原液を紡［］より押しだし、アクリロニトリル
、銅アンモニアレーヨン等のように湿式紡糸と呼ばれる
、凝固浴中で溶媒を抽出する事により繊維化する方法、
あるいは、一般にゲル紡糸と呼ばれる、原液を押出した
後、冷却し繊維化する方法などいずれでも構わない。In the present invention, the solution spinning method refers to a process in which a polymer is dissolved in a solvent, the stock solution is pushed out through a spinning process, and the solvent is extracted in a coagulation bath, which is called wet spinning, such as with acrylonitrile, cuprammonium rayon, etc. A method of making fibers by
Alternatively, any method may be used, such as a method generally called gel spinning, in which a stock solution is extruded and then cooled to form fibers.
溶液紡糸により得られる繊維は繊維内に溶媒を含んでお
り加熱延伸前に取り除く必要がある。Fibers obtained by solution spinning contain a solvent within the fibers, which must be removed before heating and stretching.
本発明で用いる式（１）で示される化合物がほとんどの
有機溶剤、水に溶解するため、溶媒はできるだけ減圧下
で気化させるのが好ましい。もらろん抽出により溶媒を
除去しても良いが、その時は、系中の溶媒とは親和性が
あるが、式（１）で示される化合物とは親和性の小さい
溶剤を探せば良い。Since the compound represented by formula (1) used in the present invention is soluble in most organic solvents and water, it is preferable to vaporize the solvent under reduced pressure as much as possible. The solvent may be removed by Moraron extraction, but in that case, a solvent that has an affinity with the solvent in the system but has a low affinity with the compound represented by formula (1) may be found.
本発明において、加熱延伸には、通常の合成繊維の延伸
と同じようにホットプレー ト、スリットヒーター等を
使用して行えば良く、延伸の段数は、本発明で使用する
重合体の種類により異なるが、−段あるいは多段のいず
れでも良い。又、延伸温度は室温から式（１）で示され
る化合物を含むポリアミドの融点までの間で任意である
が、通常１００°Ｃから２００°Ｃの間で行われる。In the present invention, heating and stretching can be carried out using a hot plate, slit heater, etc. in the same way as in the stretching of ordinary synthetic fibers, and the number of stages of stretching varies depending on the type of polymer used in the present invention. However, it may be either -stage or multi-stage. Further, the stretching temperature is arbitrary between room temperature and the melting point of the polyamide containing the compound represented by formula (1), but it is usually carried out between 100°C and 200°C.
（実施例）
以下に実施例でもって本発明を具体的に説明する。但し
、本発明は実施例に限定されるものではない。(Example) The present invention will be specifically described below with reference to Examples. However, the present invention is not limited to the examples.
実施例１
窒素ガス導入管、コンデンサー及び攪拌翼を取り付けた
５ ００ ｍｆｌセパラブルフラスコ中に、相対粘度３
０．０ （９５，５％硫酸 １ｇ／＋Ｒ２２５°Ｃ）の
ナイロン６６ポリマー１０ｇ、式（１）で示される化合
物（Ｒ，Ｒ＋ はメチル、Ｒ２は酸素フリーラジカル）
１．７．６ｇ及びＮ−メチル−２−ピロリドン１００ｇ
を取り、Ｎ２ガスを用いて３回置換した。Example 1 In a 500 mfl separable flask equipped with a nitrogen gas inlet tube, condenser and stirring blade, a sample with a relative viscosity of 3
0.0 (1 g of 95.5% sulfuric acid/+R225°C) 10 g of nylon 66 polymer, compound represented by formula (1) (R, R+ are methyl, R2 is oxygen free radical)
1.7.6g and 100g N-methyl-2-pyrrolidone
was removed and replaced with N2 gas three times.
セパラブルフラスコをオイルバスに入れ、Ｎ２気流下に
て攪拌しながら１５０°Ｃに昇１１■し、更に攪拌を９
０分間続け、ナイロン６６ポリマーを完溶させたのち、
減圧にすることにより脱泡を行なった。この原液を内温
を１５０’Ｃに保った押出し機に移し、直径０．５＋ｎ
ｍのオリフィスより０．３ ｇ／分で吐出させ、３ｃｍ
の空気層を通過させた後、巻速度１０ｍ／分で巻きとっ
た。Place the separable flask in an oil bath, raise the temperature to 150°C for 11 seconds while stirring under a N2 stream, and continue stirring for 9 seconds.
After continuing for 0 minutes to completely dissolve the nylon 66 polymer,
Defoaming was performed by reducing the pressure. Transfer this stock solution to an extruder kept at an internal temperature of 150'C, and
Discharge at 0.3 g/min from an orifice of 3 cm.
After passing through a layer of air, it was wound at a winding speed of 10 m/min.
巻きとった糸を、ボビンごと減圧（１＋ｎｍｎｍ１ｌ下
、４５゛Ｃで乾燥し、含有しているＮ−、メチル−２ピ
ロリドンを除去し、式（１）で示される化合物を残存さ
せたナイロン６６フイラメント含得た。The wound yarn was dried with the bobbin at 45°C under reduced pressure (1+ nm nm 1 liter) to remove the N-, methyl-2-pyrrolidone contained therein, leaving the compound represented by formula (1) as a nylon 66 filament. Contained.
得られたフィラメン１−を接触式ヒーターを使用し、１
６０°Ｃで延伸したところ、延伸倍率が１３．５倍とな
り、１６０°Ｃで１２．５倍に延伸した糸の室温での物
性は引張り強度が１２．８ ｇ／ｄ、初期弾性゛ドが５
９．５ ｇ／ｄであった。Using a contact heater, the obtained filament 1-
When stretched at 60°C, the stretching ratio was 13.5 times, and the physical properties at room temperature of the yarn stretched 12.5 times at 160°C were that the tensile strength was 12.8 g/d, and the initial elasticity was 12.8 g/d. 5
It was 9.5 g/d.
実施例２
式（１）で示される化合物（Ｒはメチル、Ｒ５はメチル
、Ｒ２はメチル）を用いた以外は、実施例１古全く同様
な操作を行ない、ナイロン６６フィラメントを得た。糸
の室温での物性は引張り強度が１２．０ ｇ／ｄ、初期
弾性率が６０．３８／ｄ −（？あった。Example 2 A nylon 66 filament was obtained in exactly the same manner as in Example 1 except that the compound represented by formula (1) (R is methyl, R5 is methyl, R2 is methyl) was used. The physical properties of the yarn at room temperature were a tensile strength of 12.0 g/d and an initial elastic modulus of 60.38/d -(?).
実施例３〜５
式（１）で示される化合物（Ｒはメチル、Ｒ３はメチル
、［７２は、酸素フリーラジカル）の添加量を変えた以
外は実施例１と全く同様の１９作を行ない、フィラメン
トを得た。ただし延伸温度、延伸倍率は化合物の添加量
？、こより、表１に示すように変更した。その糸の室温
での物性を表１に示す。Examples 3 to 5 Nineteen operations were carried out in exactly the same manner as in Example 1, except that the amount of the compound represented by formula (1) (R is methyl, R3 is methyl, [72 is oxygen free radical) was added, I got the filament. However, is the stretching temperature and stretching ratio the amount of compound added? , the changes were made as shown in Table 1. Table 1 shows the physical properties of the yarn at room temperature.
表 １
比較例
実施例１と同様な操作を行ない、ただし、加熱延伸を行
なう前に、メタノールにより糸を洗浄し、式（＋）で示
される化合物を抽出し、減圧乾燥した後に加熱延伸を行
なった。しかし２００ ’Ｃ以下の温度ではほとんど延
伸されず、２１０°Ｃで４．５倍に延伸した。この糸の
室温での物性は引張り強度が３．８ ｇ／ｄ 、初ルＩ
弾性率が２０．３ ｇ／ｄであった。Table 1 Comparative Example The same operation as in Example 1 was performed, except that before heating and stretching, the yarn was washed with methanol, the compound represented by formula (+) was extracted, and the yarn was dried under reduced pressure before heating and stretching. Ta. However, it was hardly stretched at temperatures below 200'C, and was stretched 4.5 times at 210C. The physical properties of this yarn at room temperature are tensile strength of 3.8 g/d,
The elastic modulus was 20.3 g/d.
（発明の効果）
本発明により高延伸倍率を達成でき、その結果充分に分
子鎖の引き揃えを行なうことが可能になり、高強力ポリ
アミド繊維が製造できる。(Effects of the Invention) According to the present invention, a high draw ratio can be achieved, and as a result, molecular chains can be sufficiently aligned, and a high-strength polyamide fiber can be produced.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
は二種以上の混合物とを、ポリアミド重合体が可溶な溶
媒に溶解した原液より溶液紡糸法で紡出した繊維を、式
（１）で示される化合物の一種又は二種以上の混合物を
残存させたまま溶媒を除去した後、加熱延伸することを
特徴とする高強力ポリアミド繊維の製造法 ▲数式、化学式、表等があります▼式（１） 式（１）中、Ｒはメチル、エチルの中から選ばれる一種
又は二種混合の置換基、Ｒ＿１は水素、メチル、エチル
の中から選ばれる一種又は二種以上混合の置換基、Ｒ＿
２はメチル、エチル、酸素フリーラジカルから選ばれる
置換基。[Scope of Claims] A fiber spun by a solution spinning method from a stock solution in which a polyamide polymer and one or a mixture of two or more compounds represented by formula (1) are dissolved in a solvent in which the polyamide polymer is soluble. A method for producing a high-strength polyamide fiber, which comprises removing the solvent while leaving one or a mixture of two or more compounds represented by formula (1), and then heating and stretching ▲Mathematical formula, chemical formula, table ▼Formula (1) In formula (1), R is one or a mixture of two substituents selected from methyl and ethyl, and R_1 is one or more substituents selected from hydrogen, methyl, and ethyl. Mixed substituents, R_
2 is a substituent selected from methyl, ethyl, and oxygen free radicals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28257188A JPH02133620A (en) | 1988-11-10 | 1988-11-10 | Production of high-strength polyamide yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28257188A JPH02133620A (en) | 1988-11-10 | 1988-11-10 | Production of high-strength polyamide yarn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02133620A true JPH02133620A (en) | 1990-05-22 |
Family
ID=17654220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28257188A Pending JPH02133620A (en) | 1988-11-10 | 1988-11-10 | Production of high-strength polyamide yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02133620A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03130432A (en) * | 1989-07-10 | 1991-06-04 | E I Du Pont De Nemours & Co | Improvement of multifilament apparel nylon yarn |
| US10358420B2 (en) | 2016-07-07 | 2019-07-23 | Evonik Degussa Gmbh | Process for preparing an N-methyl-substituted triacetonamine compound |
-
1988
- 1988-11-10 JP JP28257188A patent/JPH02133620A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03130432A (en) * | 1989-07-10 | 1991-06-04 | E I Du Pont De Nemours & Co | Improvement of multifilament apparel nylon yarn |
| US10358420B2 (en) | 2016-07-07 | 2019-07-23 | Evonik Degussa Gmbh | Process for preparing an N-methyl-substituted triacetonamine compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6385107A (en) | Production of filament high in modulus and tensile strength | |
| WO1994012702A1 (en) | Method for rapid spinning of a polybenzazole fiber | |
| JP3072442B2 (en) | Method for producing cellulosic article | |
| JPS636649B2 (en) | ||
| JP4118721B2 (en) | Method for producing polyketone fiber | |
| JPH02133620A (en) | Production of high-strength polyamide yarn | |
| JP4588032B2 (en) | Improved process of wet spinning for salt-containing aramid polymers | |
| JPS63120107A (en) | High-strength and high-elastic modulus polyvinyl alcohol based fiber having excellent hot water resistance and production thereof | |
| WO1997044510A1 (en) | Aromatic polyamide bristle | |
| JPS61108711A (en) | Production of polyvinyl alcohol fiber of high strength and high elastic modulus | |
| JPS6197415A (en) | Polyacrylonitrile fiber having high strength and modulus | |
| CN106589352B (en) | A kind of preparation method of the PPTA with fluorescent effect | |
| US4035465A (en) | Drawing polyoxadiazoles filaments | |
| JP2007154328A (en) | Method for producing aromatic copolyamide fiber | |
| JP2763786B2 (en) | High elastic modulus polyamide linear body and method for producing the same | |
| JPS6285013A (en) | High-tenacity and high-modulus pva fiber and production thereof | |
| JPH0874122A (en) | Production of meta-aromatic polyamide fiber | |
| JPS6335820A (en) | Production of polyacrylonitrile fiber having high tenacity | |
| JPH0617310A (en) | Preparation of fiber from meta-aramide | |
| JPH06235117A (en) | Production of high strength polyvinyl alcohol fiber | |
| JPH01314725A (en) | Filament formed from melt composed of at least one kind of aromatic polymer and production thereof | |
| JPH02216211A (en) | Production of improved poly-p-phenylene terephthalamide fiber | |
| JPH01132822A (en) | Production of high-tenacity polyamide fiber | |
| JPH03185025A (en) | Aromatic polyether sulfone fiber and production thereof | |
| JPH02127512A (en) | Pyrazine ring-containing aromatic polyamide yarn |