JP3276475B2 - Manufacturing method of high strength elastic yarn - Google Patents

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、ポリウレタンウレア弾
性糸の製造方法に関し、更に詳しくは、２，４’−ジフ
ェニルメタンジイソシアネート（以下２，４’−ＭＤＩ
と表す）を含有するジフェニルメタンジイソシアネート
（以下ＭＤＩと表す）を必須成分とし、ポリマー溶液の
安定性に優れ、高破断強度を発現し、且つ加工した際に
編斑を生じない弾性糸を提供することのできる製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane urea elastic yarn, and more particularly, to 2,4'-diphenylmethane diisocyanate (hereinafter referred to as 2,4'-MDI).
The present invention is to provide an elastic yarn which contains diphenylmethane diisocyanate (hereinafter, referred to as MDI) containing as an essential component, has excellent stability of a polymer solution, exhibits high breaking strength, and does not cause knitting when processed. The present invention relates to a manufacturing method that can be performed.

【０００２】[0002]

【従来の技術】一般にポリウレタンウレア弾性体は、末
端基に水酸基を有するポリエステル、ポリエーテルの如
きポリマージオールと過剰モル量の有機ジイソシアネー
トとを反応させ、両末端にイソシアネート基を有するポ
リウレタン中間重合体を製造し、該中間重合体のイソシ
アネート基と容易に反応し得る活性水素を有するジアミ
ノ化合物等を不活性な有機溶剤中で反応させて、セグメ
ント化ポリウレタンウレアを製造した後、成形、溶剤を
除去することにより得られる。2. Description of the Related Art Generally, a polyurethane urea elastomer is obtained by reacting a polymer diol such as polyester or polyether having a hydroxyl group at an end group with an excess molar amount of an organic diisocyanate to form a polyurethane intermediate polymer having isocyanate groups at both ends. Manufactured and reacted in an inert organic solvent, such as a diamino compound having an active hydrogen capable of easily reacting with the isocyanate group of the intermediate polymer, to produce a segmented polyurethaneurea, followed by molding and removing the solvent. It can be obtained by:

【０００３】ポリウレタンウレア弾性糸は、その弾性的
性質から水着、ファンデーション、インナーウエア、サ
ポートタイプパンスト等に、ナイロン、ポリエステル等
と混用して用いられる。製品加工の際に糸切れの起きな
い加工性能の優れた弾性糸を得るためには、１．７５ｇ
／Ｄ以上の高い破断強度を発現するセグメント化ポリウ
レタンウレアを紡糸する必要がある。破断強度を向上さ
せる方法としては、例えば紡糸速度を上げて、紡糸筒内
の張力を上げる方法があるが、分子鎖の配向によって破
断伸度が低下する欠点があった。これを解決する方法と
して、ポリマーの重合度を上げる方法があるが、ポリマ
ーの重合度を上げすぎると、高破断強度の弾性糸を得る
ことができる反面、原液の粘性が上がり破断伸度が低下
する。またポリマーの凝集が進むためと思われるが、経
時的にポリマー溶液粘度が上昇して不安定になり、一定
品質の糸を紡糸するのが困難となり、このような糸で加
工した際には編斑を生じやすくなる。このため、ポリマ
ーの重合度を上げることには限界があり、期待する効果
は得られない。[0003] Due to its elastic properties, polyurethane urea elastic yarns are used in swimwear, foundations, innerwear, support type pantyhose, etc., mixed with nylon, polyester and the like. In order to obtain an elastic yarn having excellent processing performance without causing yarn breakage during product processing, 1.75 g is required.
It is necessary to spin a segmented polyurethane urea exhibiting a high breaking strength of at least / D. As a method for improving the breaking strength, for example, there is a method in which the spinning speed is increased to increase the tension in the spinning cylinder. However, there is a disadvantage that the elongation at break is reduced by the orientation of the molecular chains. As a method of solving this, there is a method of increasing the degree of polymerization of the polymer, but if the degree of polymerization of the polymer is too high, an elastic yarn having high breaking strength can be obtained, but the viscosity of the stock solution increases and the breaking elongation decreases. I do. This is probably due to polymer aggregation, but the viscosity of the polymer solution increases with time and becomes unstable, making it difficult to spin yarn of a certain quality. Spots are likely to occur. For this reason, there is a limit in increasing the degree of polymerization of the polymer, and the expected effect cannot be obtained.

【０００４】また特公平４−７４４５７によれば、イソ
シアネート末端を有する中間重合体と活性水素を有する
多官能性及び１官能性アミノ化合物とを以下の式を満足
する量比、すなわち１．５≦（Ｂ＋Ｃ−Ａ）／Ｃ≦５．
０（但し、式中Ａ：中間重合体中のイソシアネート基の
当量、Ｂ：多官能性アミノ化合物の当量、Ｃ：１官能性
アミノ化合物の当量）で反応させて得られた重合体を紡
糸巻取り後、熱処理する事により高分子量化させて優れ
た弾性的性質を発現する弾性糸を得ている。しかしなが
らこの方法では、紡糸巻取り後の熱処理という後工程が
増え、操業上の不利を有するばかりか、本発明で掲げる
物理的性質を満足するには至っていない。According to Japanese Patent Publication No. 74457/94, a ratio of an intermediate polymer having an isocyanate terminal to a polyfunctional and monofunctional amino compound having active hydrogen satisfying the following formula, that is, 1.5 ≦ (B + CA) / C ≦ 5.
0 (where A: equivalent of isocyanate groups in the intermediate polymer, B: equivalent of polyfunctional amino compound, C: equivalent of functional amino compound), and spin-winding the polymer obtained. After the removal, heat treatment is performed to increase the molecular weight to obtain an elastic yarn exhibiting excellent elastic properties. However, in this method, the number of post-processes, ie, heat treatment after spinning and winding, is increased, resulting in disadvantages in operation and not satisfying the physical properties described in the present invention.

【０００５】[0005]

【発明が解決しようとする課題】本発明の目的は、ポリ
マー溶液の安定性に優れ、高い破断強度を発現し、加工
時の編斑を生じないポリウレタンウレア弾性糸を提供す
ることにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyurethaneurea elastic yarn which is excellent in stability of a polymer solution, exhibits high breaking strength, and does not cause unevenness during processing.

【０００６】[0006]

【課題を解決するための手段】本発明者等は、上記欠点
を解決し、破断強度の高い優れた弾性糸を得るべく鋭意
研究の結果、ポリマー溶液、特にハードセグメントの流
動性が破断強度及び糸の均一性に影響を及ぼすことを発
見し、本発明に到達した。すなわち、本発明は分子量６
００〜５０００である実質的に線状のポリマージオール
と、２，４’−ＭＤＩの分率が１．８０〜１３．０重量
％であるＭＤＩをジオールに対し過剰モル反応させて、
末端イソシアネート基を有する中間重合体を得た後、該
中間重合体のイソシアネート基と当量あるいは過剰量の
アミノ化合物とを反応させて得られる重合体を紡糸し、
高破断強度を有する弾性糸を提供することのできる製造
方法である。DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned drawbacks and obtain an excellent elastic yarn having a high breaking strength. The inventors have found that this affects the uniformity of the yarn and arrived at the present invention. That is, the present invention provides a molecular weight of 6
A substantially linear polymer diol of from 0.00 to 5000 and an MDI having a fraction of 2,4′-MDI of 1.80 to 13.0% by weight in an excess molar reaction with respect to the diol;
After obtaining an intermediate polymer having a terminal isocyanate group, spinning a polymer obtained by reacting an isocyanate group of the intermediate polymer with an equivalent or excess amount of an amino compound,
This is a production method capable of providing an elastic yarn having high breaking strength.

【０００７】本発明におけるポリウレタンウレア弾性体
は、ポリマージオールと、２，４’−ＭＤＩを所定量含
有するＭＤＩとを、不活性な有機溶剤中で反応させて、
両末端が実質的にイソシアネート基である中間重合体を
製造し、該中間重合体に多官能性アミノ化合物及び１官
能性アミノ化合物とを反応させて得られるポリウレタン
ウレア重合体である。The polyurethaneurea elastic body of the present invention is obtained by reacting a polymer diol with MDI containing a predetermined amount of 2,4′-MDI in an inert organic solvent,
A polyurethane urea polymer obtained by producing an intermediate polymer having both isocyanate groups at both ends and reacting the intermediate polymer with a polyfunctional amino compound and a monofunctional amino compound.

【０００８】用いられるポリマージオールとしては、数
平均分子量６００〜５０００好ましくは１０００〜３０
００の実質的に線状のポリマージオールであり、例えば
ポリオキシエチレングリコール、ポリオキシプロピレン
グリコール、ポリオキシテトラメチレングリコール、ポ
リオキシペンタメチレングリコール、ポリオキシプロピ
レンテトラメチレングリコール等のポリエーテルジオー
ル、アジピン酸、セバチン酸、マレイン酸、イタコン
酸、アゼライン酸、マロン酸等の二塩基酸の１種または
２種以上とエチレングリコール、プロピレングリコー
ル、１，３−プロパンジオール、２，２−ジメチル−
１，３−プロパンジオール、１，４−ブタンジオール、
２，３−ブタンジオール、ヘキサメチレングリコール、
ジエチレングリコール、１，１０−デカンジオール、
１，３−シクロヘキサンジメタノール等のグリコールの
１種または２種以上とから得られたポリエステルジオー
ル、ポリ−ε−カプロラクトン、ポリバレロラクトン等
のポリラクトンジオール、またポリエステルアミドジオ
ール、ポリチオエーテルジオール、ポリカーボネートジ
オール、或いはそれらの混合物を挙げることができる。The polymer diol to be used has a number average molecular weight of 600 to 5000, preferably 1000 to 30.
00 is a substantially linear polymer diol, for example, polyether diols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, polyoxypropylene tetramethylene glycol, and adipic acid , One or more dibasic acids such as sebacic acid, maleic acid, itaconic acid, azelaic acid, malonic acid and ethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-
1,3-propanediol, 1,4-butanediol,
2,3-butanediol, hexamethylene glycol,
Diethylene glycol, 1,10-decanediol,
Polyester diols obtained from one or more glycols such as 1,3-cyclohexanedimethanol, poly-ε-caprolactone, polylactone diols such as polyvalerolactone, polyesteramide diols, polythioether diols, polycarbonates Diols or mixtures thereof can be mentioned.

【０００９】本発明で使用する有機ジイソシアネート
は、２，４’−ＭＤＩを１．８０〜１３．０重量％、ポ
リマー溶液の安定性を考慮すると好ましくは下限が３．
００重量％、弾性糸に成形したときの耐熱性を考慮する
と好ましくは上限が１０．０重量％、すなわち好ましく
は３．００〜１０．０重量％含有するＭＤＩであり、残
りが４，４’−ＭＤＩである。２，４’−ＭＤＩ分率の
制御は、市販されている４，４’−ＭＤＩに２，４’−
ＭＤＩを多く含有する液状ＭＤＩを所定量加えることで
容易に行える。ＭＤＩ中の２，４’−ＭＤＩ分率の測定
は、１，２−ジクロロエタンにＭＤＩを溶解させて、ガ
スクロマトグラフィによって行うことができる。なお本
発明で述べる２，４’−ＭＤＩ分率とは次式で表される
値を言う。すなわち２，４’−ＭＤＩ分率（％）＝２，
４’−ＭＤＩ重量／（２，４’−ＭＤＩ重量＋４，４’
−ＭＤＩ重量）×１００である。また本発明で用いられ
るポリマージオールのモル量と有機ジイソシアネートの
モル量の比は、１：１．３〜１：２．０であるが特に限
定されるものではない。The organic diisocyanate used in the present invention is preferably 1.80 to 13.0% by weight of 2,4′-MDI, and the lower limit is preferably 3.80 in consideration of the stability of the polymer solution.
Considering the heat resistance when formed into an elastic yarn, the upper limit is preferably 10.0% by weight, that is, MDI containing preferably 3.0 to 10.0% by weight, and the remainder is 4,4 ′. -MDI. The control of the 2,4'-MDI fraction is based on commercially available 4,4'-MDI and 2,4'-MDI.
It can be easily performed by adding a predetermined amount of liquid MDI containing a large amount of MDI. The 2,4′-MDI fraction in MDI can be measured by dissolving MDI in 1,2-dichloroethane and performing gas chromatography. The 2,4′-MDI fraction described in the present invention refers to a value represented by the following equation. That is, 2,4′-MDI fraction (%) = 2
4'-MDI weight / (2,4'-MDI weight + 4,4 '
−MDI weight) × 100. The ratio of the molar amount of the polymer diol to the molar amount of the organic diisocyanate used in the present invention is from 1: 1.3 to 1: 2.0, but is not particularly limited.

【００１０】また多官能性アミノ化合物としては、エチ
レンジアミン、プロピレンジアミン、ヘキサメチレンジ
アミン、トリメチレンジアミン、ヘキサメチレンジアミ
ン、ヒドラジン、カルボジヒドラジド、アジピン酸ジヒ
ドラジド，Ｎ，Ｎ−ビス（γ−アミノプロピル）−Ｎ，
Ｎ−ジメチルエチレンジアミンなどの２官能性脂肪族ジ
アミン、芳香族ジアミノウレア化合物、或いはそれらの
混合物を例示することができる。The polyfunctional amino compounds include ethylenediamine, propylenediamine, hexamethylenediamine, trimethylenediamine, hexamethylenediamine, hydrazine, carbodihydrazide, adipic dihydrazide, N, N-bis (γ-aminopropyl)- N,
Examples thereof include bifunctional aliphatic diamines such as N-dimethylethylenediamine, aromatic diaminourea compounds, and mixtures thereof.

【００１１】同時に使用する１官能性アミノ化合物とし
ては、ジメチルアミン、エチルメチルアミン、ジエチル
アミン、メチルプロピルアミン、イソプロピルメチルア
ミン、ジイソプロピルアミン、ブチルメチルアミン、イ
ソブチルメチルアミン、イソペンチルメチルアミン等を
挙げることができる。本発明で用いられる不活性有機溶
剤としては、上記の諸原料を溶解し、且つ生成するポリ
ウレタンウレア重合体を溶解または分散し得る溶剤、例
えばジメチルホルムアミド、ジメチルアセトアミド、ジ
メチルスルホキシドなどの溶剤が挙げられる。Examples of the monofunctional amino compound used simultaneously include dimethylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine and the like. Can be. As the inert organic solvent used in the present invention, a solvent capable of dissolving the above-mentioned various raw materials and dissolving or dispersing the produced polyurethaneurea polymer, such as dimethylformamide, dimethylacetamide, and a solvent such as dimethylsulfoxide. .

【００１２】中間重合体とアミノ化合物との反応は、通
常多官能性アミノ化合物と１官能性アミノ化合物とを含
む不活性溶剤溶液を、中間重合体の不活性有機溶剤溶液
に導入してポリウレタンウレア重合体が製造される。こ
こで中間重合体中のイソシアネート基とイソシアネート
基に対して１．０〜１．５倍のアミノ基を有する多官能
性アミノ化合物と１官能性アミノ化合物とが反応させら
れる。この時のポリマー溶液の濃度は２０〜４５重量％
が好ましく、ポリマー溶液の粘度が３０℃測定で２００
０〜７０００ｐｏｉｓｅ（Ｂ型粘度計）であるように、
多官能性アミノ化合物と１官能性アミノ化合物との添加
量比を調節し、ポリマーの重合度を決定する。４５重量
％を超えるポリマー溶液の濃度では、ポリマー溶液中の
ハードセグメントが凝集することにより、一定の粘度を
保持することが困難となり、原液の安定性が低下する。
２０重量％未満では紡糸時に蒸発させる溶剤の量が多い
ため、一定の熱量下では、溶剤の蒸発潜熱に使われる熱
量分が多く、糸の物性発現に使われる熱量分が少なくな
り破断強度が低下する。ポリマー溶液の粘度が７０００
ｐｏｉｓｅを超えると紡糸時の圧力が高くなりすぎ、紡
糸筒での紡出が困難となり、２０００ｐｏｉｓｅ未満で
は、紡糸時の紡糸筒内の糸条の揺れが大きくなり、糸斑
が大きくなるので好ましくない。従って、ポリマー溶液
の濃度を２０〜４５重量％、粘度を２０００〜７０００
ｐｏｉｓｅの範囲に調整することが、均一な糸条物を得
るために好ましい。The reaction between the intermediate polymer and the amino compound is usually carried out by introducing an inert solvent solution containing a polyfunctional amino compound and a monofunctional amino compound into an inert organic solvent solution of the intermediate polymer. A polymer is produced. Here, the isocyanate group in the intermediate polymer and the polyfunctional amino compound having an amino group 1.0 to 1.5 times the isocyanate group and the monofunctional amino compound are reacted. At this time, the concentration of the polymer solution is 20 to 45% by weight.
Is preferable, and the viscosity of the polymer solution is 200
0-7000 poise (B-type viscometer)
The degree of polymerization of the polymer is determined by adjusting the ratio of the polyfunctional amino compound to the monofunctional amino compound. If the concentration of the polymer solution exceeds 45% by weight, it becomes difficult to maintain a constant viscosity due to aggregation of the hard segments in the polymer solution, and the stability of the stock solution is reduced.
If the amount is less than 20% by weight, the amount of solvent to be evaporated during spinning is large. Therefore, under a certain amount of heat, a large amount of heat is used for latent heat of evaporation of the solvent, and a small amount of heat is used for developing physical properties of the yarn, resulting in a decrease in breaking strength. I do. The viscosity of the polymer solution is 7000
If it exceeds poise, the pressure during spinning becomes too high and spinning with a spinning cylinder becomes difficult. If it is less than 2,000 poise, the yarn in the spinning cylinder at the time of spinning becomes unsteady, and the yarn spots become unfavorably large. Therefore, the concentration of the polymer solution is 20 to 45% by weight and the viscosity is 2000 to 7000.
Adjustment within the poise range is preferable for obtaining a uniform yarn.

【００１３】ポリマー溶液の安定性については、ポリウ
レタンウレアの重合直後のポリマー溶液粘度と、一週間
後のポリマー溶液粘度を測定することで評価できる。常
温で放置した時の一週間後のポリマー溶液粘度が重合直
後の粘度と比べほぼ同程度（差が２００ｐｏｉｓｅ未満
（Ｂ型粘度計））なら安定である。得られたポリマー溶
液は通常、常法により、乾式紡糸し、ボビンに巻取る。The stability of the polymer solution can be evaluated by measuring the viscosity of the polymer solution immediately after polymerization of the polyurethane urea and the viscosity of the polymer solution one week later. If the viscosity of the polymer solution one week after standing at room temperature is almost the same as the viscosity immediately after the polymerization (the difference is less than 200 poise (B-type viscometer)), it is stable. The obtained polymer solution is usually dry-spun and wound up on a bobbin by a conventional method.

【００１４】本発明のポリウレタンウレア重合体の溶液
には所望により、通常使用されているガス黄変防止剤、
紫外線吸収剤等の安定剤、硫酸バリウム、珪酸マグネシ
ウム、珪酸カルシウム、酸化亜鉛等の無機微粒子、ステ
アリン酸マグネシウム、ポリテトラフルオロエチレン、
オルガノポリシロキサン等の粘着防止剤、その他配向剤
等を適宜配合しても良い。また紡糸後、公知の油剤、滑
剤等を付与することができる。The solution of the polyurethaneurea polymer of the present invention may optionally contain a commonly used gas yellowing inhibitor,
Stabilizers such as ultraviolet absorbers, inorganic fine particles such as barium sulfate, magnesium silicate, calcium silicate, zinc oxide, magnesium stearate, polytetrafluoroethylene,
An anti-tackiness agent such as an organopolysiloxane and other alignment agents may be appropriately compounded. After spinning, known oils, lubricants and the like can be applied.

【００１５】原料として用いられるＭＤＩ中の２，４’
−ＭＤＩ分率が１．８０〜１３．０重量％で破断強度が
高くなる理由は、おそらく、イソシアネート基が２，
４’位に位置していることによりその立体障害のため、
ハードセグメント内の分子間水素結合、或いは分子内水
素結合が乱され、分子間の凝集が起こりにくくなった結
果、ポリマー溶液がハードセグメントの均一な分散相と
なり、そのため紡糸時にハードセグメントが糸中に均一
に分散でき、巨大なハードセグメントの凝集体などが糸
中に存在せず、糸の欠陥構造が非常に少なくなる為と考
えられる。ＭＤＩ中の２，４’−ＭＤＩ分率が、１．８
０重量％未満では、ポリマー溶液中のハードセグメント
の高次構造が不均一なため紡糸後の糸にそのまま不均一
な斑が残り、加工時の編斑を引き起こし、通常の破断強
度の糸しか得ることが出来ず、更に、ポリマー溶液の安
定性を考慮するとポリマー溶液の高濃度化は困難であ
る。１３．０重量％を超える２，４’−ＭＤＩ分率では
２，４’−ＭＤＩがハードセグメント部を乱すため、耐
熱性が低下するので好ましくない。従ってＭＤＩ中の
２，４’−ＭＤＩ分率は１．８０〜１３．０重量％、好
ましくは３．００〜１０．０重量％が良く、ポリマー溶
液の安定性が高く、耐熱性を維持した、編斑の起きな
い、高破断強度の弾性糸が得られる。2,4 'in MDI used as a raw material
The reason why the breaking strength is high when the MDI fraction is 1.80 to 13.0% by weight is probably that isocyanate groups are 2,2.
Due to its steric hindrance by being located at the 4 'position,
The intermolecular hydrogen bond or intramolecular hydrogen bond in the hard segment was disturbed, and the intermolecular aggregation became difficult to occur. As a result, the polymer solution became a uniform dispersed phase of the hard segment, and thus the hard segment was incorporated into the yarn during spinning. This is presumably because the particles could be uniformly dispersed, and no large hard segment aggregates were present in the yarn, and the defect structure of the yarn was extremely reduced. 2,4′-MDI fraction in MDI is 1.8
If the amount is less than 0% by weight, the higher order structure of the hard segments in the polymer solution is uneven, so that uneven spots remain on the spun yarn as it is, causing knitting spots during processing and obtaining only a yarn having a normal breaking strength. In addition, it is difficult to increase the concentration of the polymer solution in consideration of the stability of the polymer solution. When the 2,4′-MDI fraction exceeds 13.0% by weight, the 2,4′-MDI disturbs the hard segment portion, so that heat resistance is undesirably reduced. Therefore, the 2,4′-MDI fraction in MDI is preferably 1.80 to 13.0% by weight, preferably 3.00 to 10.0% by weight, and the stability of the polymer solution was high and the heat resistance was maintained. Thus, an elastic yarn having high breaking strength and no knitting unevenness can be obtained.

【００１６】糸の耐熱性については、１８０℃にコント
ロールした金属円筒の壁面に５０％伸長下で糸を押しつ
けて切断するまでの時間（以下耐熱切断秒数と表す）で
評価できる。熱セット時の糸の耐熱性を考慮すると耐熱
切断秒数は１３０秒以上が望ましい。加工時の編斑の評
価については、ドラフト率３．０で弾性糸を走らせたと
きの応力（以下走行応力と表す）をチャートに記録した
際の応力変動で評価することが出来る。走行応力変動
と、編斑は相関があり、走行応力変動が小さいときは編
斑も少なく、走行応力変動が大きいときは編斑が多い。The heat resistance of the yarn can be evaluated by the time required to cut the yarn by pressing it under 50% elongation against the wall surface of a metal cylinder controlled at 180 ° C. (hereinafter referred to as heat-resistant cutting seconds). Considering the heat resistance of the yarn during heat setting, the heat-resistant cutting time is preferably 130 seconds or more. Regarding the evaluation of knitting unevenness during processing, the stress (hereinafter, referred to as running stress) when the elastic yarn runs at a draft rate of 3.0 can be evaluated based on the stress fluctuation when recording the chart. There is a correlation between the running stress variation and the knitting unevenness. When the running stress variation is small, the knitting unevenness is small, and when the running stress variation is large, the knitting unevenness is large.

【００１７】[0017]

【実施例】本発明の具体例を以下の実施例により説明す
る。なお実施例中における原料ＭＤＩ中の２，４’−Ｍ
ＤＩ分率、糸の特性値、走行応力変動、耐熱切断秒数は
それぞれ下記の方法にて行った。 （１）原料ＭＤＩ中の２，４’−ＭＤＩ分率 （ａ）サンプル調製 ２，４’−ＭＤＩを所定量含むＭＤＩを８０℃の温水浴
で１時間融解、撹拌した後、２０ｍｌサンプル瓶に０．
５０ｇ秤量し、１，２−ジクロロエタンを１０．００ｇ
加え、撹拌、溶解させ、これを分析試料とした。EXAMPLES Specific examples of the present invention will be described with reference to the following examples. Note that 2,4′-M in the raw material MDI in the examples was used.
The DI fraction, the characteristic value of the yarn, the fluctuation of running stress, and the number of heat-resistant cutting seconds were respectively measured by the following methods. (1) 2,4′-MDI fraction in raw material MDI (a) Sample preparation MDI containing a predetermined amount of 2,4′-MDI was melted and stirred in a warm water bath at 80 ° C. for 1 hour, and then placed in a 20 ml sample bottle. 0.
50 g is weighed, and 10.00 g of 1,2-dichloroethane is weighed.
In addition, the mixture was stirred and dissolved to obtain an analysis sample.

【００１８】（ｂ）ガスクロマトグラフィによる２，
４’−ＭＤＩ分率の定量 測定機器：ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ ＨＰ５８
９０ カラム：Ｕｌｔｒａ−１（Ｃｒｏｓｓｌｉｎｋｅｄ Ｍ
ｅｔｈｙｌＳｉｌｉｃｏｎｅ Ｇｕｍ） ＩＮＪ：３００℃ ＦＩＤ：３００℃ カラム：２００℃（０ｍｉｎ）−５℃／ｍｉｎ−２７５
℃（０ｍｉｎ） キャリア：Ｈｅ サンプル量：１μｌ 定量方法：異性体の相対面積比で２，４’−ＭＤＩ分率
を求めた。 （２）糸の特性値 （ａ）測定条件 測定機器：引張り試験機（株）東洋ボールドウィンＵＴ
Ｍ−ＩＩＩ−１００ 条件：初期長５０ｍｍ、伸長速度５００ｍｍ／ｍｉｎ 上記条件で伸長したときの破断強度（ｇ／Ｄ）、破断伸
度（％）で評価した。 （３）走行応力変動 １．５ｍ間隔で送り用ローラー、巻き取り用ローラーを
設置し、ローラー間中央部に応力測定器（ＥＩＫＯ Ｓ
ＯＫＫＩ タイプ３０００）を置き、送り速度４３ｍ／
ｍｉｎ、巻き取り速度９８ｍ／ｍｉｎで弾性糸を走ら
せ、そのときの応力変動をチャートに記録した。以下の
判定で評価した。(B) 2, by gas chromatography
Quantification of 4'-MDI fraction Measuring instrument: HEWLETT PACKARD HP58
90 column: Ultra-1 (Crosslinked M)
(ethylsilicon Gum) INJ: 300 ° C FID: 300 ° C Column: 200 ° C (0 min) -5 ° C / min-275
° C (0 min) Carrier: He Sample amount: 1 μl Quantitative method: 2,4′-MDI fraction was determined by the relative area ratio of isomers. (2) Yarn characteristic value (a) Measurement conditions Measuring equipment: Tensile tester Co., Ltd. Toyo Baldwin UT
M-III-100 Conditions: Initial length 50 mm, elongation speed 500 mm / min Evaluated by breaking strength (g / D) and elongation at break (%) when stretched under the above conditions. (3) Fluctuation in running stress A feed roller and a take-up roller are installed at 1.5 m intervals, and a stress measuring device (EIKO S
OKKI type 3000) and feed speed 43m /
The elastic yarn was run at a take-up speed of 98 m / min at a winding speed of min. Evaluation was made by the following judgment.

【００１９】判定：ほとんど変動がない ◎ 若干変動が認められる○ 大きな変動がある × （４）耐熱切断秒数 １８０℃にコントロールした金属円筒の壁面に、５０％
伸長下で糸を押しつけて切断するまでの時間を求めた。Judgment: Little change ◎ Slight change observed ○ Large change × (4) Heat-resistant cutting seconds 50% on the wall surface of the metal cylinder controlled at 180 ° C
The time until the yarn was pressed and cut under elongation was determined.

【００２０】[0020]

【実施例１】日本ポリウレタン（株）の固体状ＭＤＩ
（商品名ミリオネートＭＴ、２，４’−ＭＤＩ分率１．
２重量％）に武田バーディシェ工業（株）の液状ＭＤＩ
（商品名ルプラネートＭＩ、２，４’−ＭＤＩ分率５０
重量％）を所定量加え、２，４’−ＭＤＩ分率を１．８
０重量％に調節したＭＤＩ ２１７．４７重量部と、数
平均分子量１８００のポリオキシテトラメチレングリコ
ール１０００重量部とを８０℃で３時間反応させた。反
応終了後、Ｎ，Ｎ−ジメチルアセトアミド１８２６．２
１重量部を加え、中間重合体溶液とした。Example 1 Solid MDI of Nippon Polyurethane Co., Ltd.
(Millionate MT, trade name, 2,4′-MDI fraction 1.
2% by weight) Liquid MDI of Takeda Birdish Industry Co., Ltd.
(Product name: Lepranate MI, 2,4'-MDI fraction 50
% By weight) and a 2,4′-MDI fraction of 1.8 was added.
217.47 parts by weight of MDI adjusted to 0% by weight and 1000 parts by weight of polyoxytetramethylene glycol having a number average molecular weight of 1800 were reacted at 80 ° C. for 3 hours. After completion of the reaction, N, N-dimethylacetamide 1826.2
One part by weight was added to obtain an intermediate polymer solution.

【００２１】該中間重合体溶液に、エチレンジアミン１
７．２２重量部、ジエチルアミン２．８７重量部及び
Ｎ，Ｎ−ジメチルアセトアミド１００７．１５重量部か
らなる混合液を導入し、混合、反応させ、３０重量％の
ポリマー溶液を得た。該ポリマー溶液の粘度は、３０℃
測定で３５００ｐｏｉｓｅ（Ｂ型粘度計）となった。得
られたポリマー溶液の常温で放置したときの一週間後の
粘度は、重合直後の粘度と同程度で安定であった。[0021] Ethylenediamine 1 is added to the intermediate polymer solution.
A mixed solution consisting of 7.22 parts by weight, 2.87 parts by weight of diethylamine and 1007.15 parts by weight of N, N-dimethylacetamide was introduced, mixed and reacted to obtain a 30% by weight polymer solution. The viscosity of the polymer solution is 30 ° C.
The measured value was 3500 poise (B-type viscometer). The viscosity of the obtained polymer solution after one week when allowed to stand at room temperature was as stable as the viscosity immediately after the polymerization.

【００２２】該ポリマー溶液を常法により乾式紡糸し、
２０Ｄ／２フィラメントの弾性糸を得た。該弾性糸の特
性値は、破断強度１．９０ｇ／Ｄ、破断伸度６３０％、
走行応力変動判定○、耐熱切断秒数３００秒であった。The polymer solution is dry-spun by a conventional method,
An elastic yarn of 20D / 2 filament was obtained. The characteristic values of the elastic yarn are: breaking strength 1.90 g / D, breaking elongation 630%,
Judgment of running stress fluctuation 、, heat-resistant cutting seconds was 300 seconds.

【００２３】[0023]

【実施例２】原料ＭＤＩ中の２，４’−ＭＤＩ分率を
３．００重量％に調整し、実施例１と同様の方法で３４
００ｐｏｉｓｅの３０重量％のポリマー溶液を製造し
た。得られたポリマー溶液の常温で放置したときの一週
間後の粘度は、重合直後の粘度と同程度で安定であり、
このポリマー溶液を用いて２０Ｄ／２フィラメントの弾
性糸を得た。該弾性糸の特性値は、破断強度２．０２ｇ
／Ｄ、破断伸度６２９％、走行応力変動判定◎、耐熱切
断秒数２８２秒であった。EXAMPLE 2 The 2,4′-MDI fraction in the raw material MDI was adjusted to 3.00% by weight, and 34% was obtained in the same manner as in Example 1.
A 30% by weight polymer solution of 00 poise was prepared. The viscosity of the obtained polymer solution after one week when left at room temperature is as stable as the viscosity immediately after polymerization,
Using this polymer solution, an elastic yarn of 20D / 2 filaments was obtained. The characteristic value of the elastic yarn is 2.02 g of breaking strength.
/ D, elongation at break 629%, fluctuation in running stress ◎, heat-resistant cutting seconds 282 seconds.

【００２４】[0024]

【実施例３】原料ＭＤＩ中の２，４’−ＭＤＩ分率を
５．００重量％に調整し、実施例１と同様の方法で３３
００ｐｏｉｓｅの３０重量％のポリマー溶液を製造し
た。得られたポリマー溶液の常温で放置したときの一週
間後の粘度は、重合直後の粘度と同程度で安定であり、
このポリマー溶液を用いて２０Ｄ／２フィラメントの弾
性糸を得た。該弾性糸の特性値は、破断強度２．１０ｇ
／Ｄ、破断伸度６２５％、走行応力変動判定◎、耐熱切
断秒数２６０秒であった。Example 3 The 2,4′-MDI fraction in the raw material MDI was adjusted to 5.00% by weight, and 33% was obtained in the same manner as in Example 1.
A 30% by weight polymer solution of 00 poise was prepared. The viscosity of the obtained polymer solution after one week when left at room temperature is as stable as the viscosity immediately after polymerization,
Using this polymer solution, an elastic yarn of 20D / 2 filaments was obtained. The characteristic value of the elastic yarn has a breaking strength of 2.10 g.
/ D, elongation at break of 625%, fluctuation in running stress ◎, heat-resistant cutting time was 260 seconds.

【００２５】[0025]

【実施例４】原料ＭＤＩ中の２，４’−ＭＤＩ分率を
７．００重量％に調整し、実施例１と同様の方法で３２
００ｐｏｉｓｅの３０重量％のポリマー溶液を製造し
た。得られたポリマー溶液の常温で放置したときの一週
間後の粘度は、重合直後の粘度と同程度で安定であり、
このポリマー溶液を用いて２０Ｄ／２フィラメントの弾
性糸を得た。該弾性糸の特性値は、破断強度２．３１ｇ
／Ｄ、破断伸度６２０％、走行応力変動判定◎、耐熱切
断秒数２２３秒であった。Example 4 The 2,4′-MDI fraction in the raw material MDI was adjusted to 7.00% by weight, and 32% was obtained in the same manner as in Example 1.
A 30% by weight polymer solution of 00 poise was prepared. The viscosity of the obtained polymer solution after one week when left at room temperature is as stable as the viscosity immediately after polymerization,
Using this polymer solution, an elastic yarn of 20D / 2 filaments was obtained. The characteristic value of the elastic yarn is a breaking strength of 2.31 g.
/ D, elongation at break 620%, fluctuation in running stress evaluation ◎, heat-resistant cutting seconds 223 seconds.

【００２６】[0026]

【実施例５】原料ＭＤＩ中の２，４’−ＭＤＩ分率を１
０．０重量％に調整し、実施例１と同様の方法で３００
０ｐｏｉｓｅの３０重量％のポリマー溶液を製造した。
得られたポリマー溶液の常温で放置したときの一週間後
の粘度は、重合直後の粘度と同程度で安定であり、この
ポリマー溶液を用いて２０Ｄ／２フィラメントの弾性糸
を得た。該弾性糸の特性値は、破断強度２．４０ｇ／
Ｄ、破断伸度６２２％、走行応力変動判定◎、耐熱切断
秒数１７９秒であった。Example 5 The 2,4′-MDI fraction in the raw material MDI was 1
It was adjusted to 0.0% by weight and 300
A 30% by weight polymer solution of 0 poise was prepared.
The viscosity of the obtained polymer solution after one week when allowed to stand at room temperature was as stable as the viscosity immediately after polymerization, and an elastic yarn of 20D / 2 filaments was obtained using this polymer solution. The characteristic value of the elastic yarn is a breaking strength of 2.40 g /
D, elongation at break was 622%, fluctuation in running stress was evaluated A, and heat-resistant cutting time was 179 seconds.

【００２７】[0027]

【実施例６】原料ＭＤＩ中の２，４’−ＭＤＩ分率を１
３．０重量％に調整し、実施例１と同様の方法で３００
０ｐｏｉｓｅの３０重量％のポリマー溶液を製造した。
得られたポリマー溶液の常温で放置したときの一週間後
の粘度は、重合直後の粘度と同程度で安定であり、この
ポリマー溶液を用いて２０Ｄ／２フィラメントの弾性糸
を得た。該弾性糸の特性値は、破断強度２．５０ｇ／
Ｄ、破断伸度６２３％、走行応力変動判定◎、耐熱切断
秒数１３５秒であった。Example 6 The 2,4′-MDI fraction in the raw material MDI was 1
Adjusted to 3.0% by weight, and adjusted to 300% by the same method as in Example 1.
A 30% by weight polymer solution of 0 poise was prepared.
The viscosity of the obtained polymer solution after one week when allowed to stand at room temperature was as stable as the viscosity immediately after polymerization, and an elastic yarn of 20D / 2 filaments was obtained using this polymer solution. The characteristic value of the elastic yarn is a breaking strength of 2.50 g /
D, elongation at break was 623%, running stress fluctuation judgment was ◎, and heat-resistant cutting time was 135 seconds.

【００２８】[0028]

【実施例７】原料ＭＤＩ中の２，４’−ＭＤＩ分率を
５．００重量％に調整し、実施例１と同様の方法で中間
重合体溶液を合成し、該中間重合体溶液に、エチレンジ
アミン１７．２２重量部、ジエチルアミン２．８７重量
部及びＮ，Ｎ−ジメチルアセトアミド４７２．１２重量
部からなる混合液を導入し、混合、反応させ、３５重量
％ポリマー溶液を得た。該ポリマー溶液の粘度は、３０
℃測定で５５００ｐｏｉｓｅ（Ｂ型粘度計）となり、常
温で放置したときの一週間後の粘度は、重合直後の粘度
と同程度で安定であり、このポリマー溶液を用いて２０
Ｄ／２フィラメントの弾性糸を得た。該弾性糸の特性値
は、破断強度２．００ｇ／Ｄ、破断伸度６６０％、走行
応力変動判定◎、耐熱切断秒数２５０秒であった。Example 7 The 2,4′-MDI fraction in the raw material MDI was adjusted to 5.00% by weight, and an intermediate polymer solution was synthesized in the same manner as in Example 1. A mixed solution consisting of 17.22 parts by weight of ethylenediamine, 2.87 parts by weight of diethylamine and 472.12 parts by weight of N, N-dimethylacetamide was introduced, mixed and reacted to obtain a 35% by weight polymer solution. The viscosity of the polymer solution is 30
5500 poise (B-type viscometer) as measured in ° C., and the viscosity after one week when left at room temperature is as stable as the viscosity immediately after polymerization.
An elastic yarn of D / 2 filament was obtained. The characteristic values of the elastic yarn were a breaking strength of 2.00 g / D, a breaking elongation of 660%, a running stress fluctuation judgment ◎, and a heat-resistant cutting time of 250 seconds.

【００２９】[0029]

【比較例１】原料ＭＤＩ中の２，４’−ＭＤＩ分率を
１．２０重量％のままで、実施例１と同様の方法で３５
００ｐｏｉｓｅの３０重量％ポリマー溶液を製造した。
得られたポリマー溶液の常温で放置したときの一週間後
の粘度は、重合直後の粘度と同程度で安定であり、この
ポリマー溶液を用いて２０Ｄ／２フィラメントの弾性糸
を得た。該弾性糸の特性値は、破断強度１．７０ｇ／
Ｄ、破断伸度６３０％、走行応力変動判定×、耐熱切断
秒数３２０秒であった。Comparative Example 1 The same method as in Example 1 was repeated except that the 2,4′-MDI fraction in the raw material MDI was 1.20% by weight.
A 30% by weight polymer solution of 00 poise was prepared.
The viscosity of the obtained polymer solution after one week when allowed to stand at room temperature was as stable as the viscosity immediately after polymerization, and an elastic yarn of 20D / 2 filaments was obtained using this polymer solution. The characteristic value of the elastic yarn is a breaking strength of 1.70 g /
D, elongation at break: 630%, judgment of running stress fluctuation x, heat-resistant cutting seconds: 320 seconds.

【００３０】[0030]

【比較例２】原料ＭＤＩ中の２，４’−ＭＤＩ分率を１
５．０重量％に調整し、実施例１と同様の方法で２８５
０ｐｏｉｓｅの３０重量％ポリマー溶液を製造した。得
られたポリマー溶液の常温で放置したときの一週間後の
粘度は、重合直後の粘度と同程度で安定であり、このポ
リマー溶液を用いて２０Ｄ／２フィラメントの弾性糸を
得た。該弾性糸の特性値は、破断強度２．５５ｇ／Ｄ、
破断伸度６２０％、走行応力変動判定◎、耐熱切断秒数
１２１秒であった。Comparative Example 2 The 2,4′-MDI fraction in the starting MDI was 1
It was adjusted to 5.0% by weight, and 285 was prepared in the same manner as in Example 1.
A 30% by weight polymer solution of 0 poise was prepared. The viscosity of the obtained polymer solution after one week when allowed to stand at room temperature was as stable as the viscosity immediately after polymerization, and an elastic yarn of 20D / 2 filaments was obtained using this polymer solution. The characteristic value of the elastic yarn is a breaking strength of 2.55 g / D,
The breaking elongation was 620%, the running stress variation was evaluated as ◎, and the heat-resistant cutting time was 121 seconds.

【００３１】[0031]

【比較例３】原料ＭＤＩ中の２，４’−ＭＤＩ分率を
１．２０重量％のままで、実施例７と同様の方法でポリ
マー溶液を製造し、３５重量％のポリマー溶液を得た。
該ポリマー溶液の粘度は、３０℃測定で６６００ｐｏｉ
ｓｅ（Ｂ型粘度計）となり、常温で１週間放置するとゲ
ル化し、紡糸は出来なかった。Comparative Example 3 A polymer solution was produced in the same manner as in Example 7 except that the 2,4′-MDI fraction in the raw material MDI was kept at 1.20% by weight to obtain a polymer solution of 35% by weight. .
The viscosity of the polymer solution was 6600 poi measured at 30 ° C.
It became se (B-type viscometer), and when left at normal temperature for 1 week, it gelled and spinning was not possible.

【００３２】実施例１〜実施例７、比較例１、比較例２
で得られた弾性糸の物理的性質を表１、表２、図１、図
２に示す。Examples 1 to 7, Comparative Example 1, Comparative Example 2
Tables 1 and 2 and FIGS. 1 and 2 show the physical properties of the elastic yarn obtained in the above.

【００３３】[0033]

【表１】 [Table 1]

【００３４】[0034]

【表２】 [Table 2]

【００３５】[0035]

【発明の効果】本発明では、原料ＭＤＩ中の２，４’−
ＭＤＩ分率を１．８０〜１３．０重量％に制御すること
によってポリマー溶液の安定性が向上し、また、破断伸
度と耐熱性のバランスのとれた、高破断強度、編斑の生
じない優れた物理的性質を有する弾性糸を得ることがで
きる。According to the present invention, 2,4'-
By controlling the MDI fraction to 1.80 to 13.0% by weight, the stability of the polymer solution is improved, and the high elongation at break balanced with the elongation at break and the heat resistance is achieved, and no knitting occurs. An elastic yarn having excellent physical properties can be obtained.

【図面の簡単な説明】[Brief description of the drawings]

【図１】原料ＭＤＩ中の２，４’−ＭＤＩ分率に対する
破断強度である。FIG. 1 shows the breaking strength versus the 2,4′-MDI fraction in the raw material MDI.

【図２】原料ＭＤＩ中の２，４’−ＭＤＩ分率に対する
耐熱切断秒数である。FIG. 2 shows heat-resistant cutting seconds with respect to a 2,4′-MDI fraction in a raw material MDI.

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−41714（ＪＰ，Ａ) 特開 平４−153313（ＪＰ，Ａ) 特開 昭56−67327（ＪＰ，Ａ) 特開 平７−70278（ＪＰ，Ａ) 特公 平４−74457（ＪＰ，Ｂ２) 特公 昭42−23971（ＪＰ，Ｂ１) 特公 昭49−6127（ＪＰ，Ｂ１) 特公 昭47−35317（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.⁷，ＤＢ名) D01F 6/70 C08G 18/76 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-41714 (JP, A) JP-A-4-153313 (JP, A) JP-A-56-67327 (JP, A) JP-A-7- 70278 (JP, A) JP 4-74457 (JP, B2) JP 42-23971 (JP, B1) JP 49-6127 (JP, B1) JP 47-31717 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) D01F 6/70 C08G 18/76

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 ２，４’−ジフェニルメタンジイソシア
ネートの分率が１．８０〜１３．０重量％であるジフェ
ニルメタンジイソシアネートを用いることを特徴とする
ポリウレタンウレア弾性糸の製造方法。1. A method for producing a polyurethaneurea elastic yarn, comprising using diphenylmethane diisocyanate having a fraction of 2,4′-diphenylmethane diisocyanate of 1.80 to 13.0% by weight. 【請求項２】 ２，４’−ジフェニルメタンジイソシア
ネートの分率が３．００〜１０．０重量％である請求項
１記載のポリウレタンウレア弾性糸の製造方法。2. The method according to claim 1, wherein the fraction of 2,4′-diphenylmethane diisocyanate is from 3.0 to 10.0% by weight.