JP2014095162A - Polyurethane elastic fiber and fiber product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane elastic fiber having less thread breakage during a spinning process, and excellent in dyeability, washing fastness and heat-setting property.SOLUTION: A polyurethane elastic fiber contains a polyurethane polymer (A component), a compound represented by a specific chemical formula having a tertiary nitrogen group at a terminal group and having a molecular weight of 300 or more and less than 2000 (B component) and a specific phenolic antioxidant (C component), and has contents of the B component and the C component of 0.01 to 8 mass% and 0.01 to 5 mass% respectively based on the A component and a pts.wt. ratio of the C component to the B component, C/B of 0.03 to 30.

Description

  The present invention relates to a polyurethane elastic fiber having little yarn breakage during spinning and excellent in dyeing fastness, heat setting property and metal friction property.

Polyurethane elastic fibers are rich in elasticity and are widely used in textile products such as foundations, underwear, body suits, legs, pantyhose, swimwear, jeans, sportswear and hygiene materials because of their excellent physical and chemical properties. ing.
Polyurethane elastic fibers are generally used after being knitted or woven with other fiber materials such as nylon fibers. In particular, it is often used in combination with nylon fibers, and the fabric is usually dyed with an acid dye, acid medium dye and metal-containing dye, which are anionic dyes used as nylon dyes.

  However, since textile products containing polyurethane elastic fibers have low dyeing fastness of polyurethane elastic fibers, when washing, if the dye comes out of the polyurethane fibers in the bathtub and fades or is rubbed with other fabrics, Is contaminated with dyes. Polyurethane elastic fibers have a different affinity for dyes than nylon. Nylon fibers are dyed well, but polyurethane elastic fibers may only be dyed thinly. In the knitted fabric of nylon and polyurethane elastic fibers, the same color mismatch There is a problem of deterioration in aesthetics.

In other words, polyurethane elastic fibers do not have sufficient dyeability and dyeing fastness during washing. Conventionally, examination of processing conditions during dyeing, development of dyes, modification of polyurethane polymer itself, blending of additives into polyurethane Various studies such as these have been made, but it is still not sufficient, and further improvement is desired for the dyeing performance of polyurethane elastic fibers.
Furthermore, polyurethane elastic fibers are inferior in elasticity and therefore have poor dimensional stability when made into fabrics, so the fabric curls after the fabric is cut and burdens the operator when sewing the fabric into the product. There is a problem of poor setability, such as wearing or shrinking the size of clothing during wearing. Although it can be set at a high temperature, polyurethane is prone to thermal degradation. Furthermore, another problem with polyurethane elastic fibers is that they are inherently sticky, so that yarn breakage tends to occur during the knitting process of the fabric due to metal friction with the knitting needles and guides.

  Many things have been studied in the past to solve the above-mentioned problems. For example, a polyurethane compound in which a tertiary amino group is built in a polyurethane molecular chain has been proposed (see Patent Documents 1 to 3 below). However, in this method, the elastic properties and heat resistance of the polyurethane elastic fiber are greatly reduced.

  Improvement has also been proposed using a polyurethane reaction product of a tertiary amino compound having a hydroxyl group at both ends and a diisocyanate compound (see Patent Documents 4 and 5 below). However, this method is not sufficient in improving the heat setting property. Furthermore, attempts have been made to simultaneously improve the heat setting properties and dyeability of polyurethane elastic fibers (see Patent Documents 6 and 7 below). This method is also not effective enough.

  In addition, there is an attempt to improve the dyeability of polyurethane by incorporating an inorganic compound hydrotalcite into polyurethane (see Patent Documents 8 and 9 below). However, hydrotalcite tends to solidify itself during storage, and may cause frequent yarn breakage during spinning of the polyurethane elastic fiber, which may make stable production of the polyurethane elastic fiber difficult. Furthermore, although the dyeability of polyurethane elastic fibers has been improved by using these hydrotalcites, it has not yet reached a satisfactory level of performance.

  There is also a proposal for improving the dyeing fastness of polyurethane urea elastic fibers by containing a specific maleimide structure compound (see Patent Document 10 below). However, in this method, in the production of the maleimide structure compound, the reaction of the diamine to the maleic anhydride skeleton is complicated, causing a crosslinking reaction or an incomplete reaction. Further, since the structure does not have a urethane bond or a urea bond, the affinity with the polyurethane polymer is not sufficient, and there is a problem that filter clogging and thread breakage frequently occur in the spinning process.

In addition, a method for producing a fiber by adding a specific low-molecular diamino compound to a polyurethane solution has been proposed (see Patent Document 11 below). However, the polyurethane elastic fiber spun by adding and mixing this diamino compound to the polyurethane polymer has a small effect on the dyeing performance improvement.
That is, many proposals have been made for the above-mentioned problem, but a satisfactory result has not yet been obtained.

Japanese Examined Patent Publication No. 47-51645 Japanese Patent Publication No. 48-25432 Japanese Examined Patent Publication No. 61-7212 JP 50-117847 A JP 2000-313802 A JP-A-11-200168 JP 2001-40587 A JP 2000-119510 A JP 2007-303025 A Japanese Patent Publication No. 3-6177 Japanese Patent Laid-Open No. 5-155842

  An object of the present invention is to provide a polyurethane elastic fiber which has few yarn breakage during the spinning process and is excellent in dyeability, fastness to washing and heat setting property. Another object is to provide a polyurethane elastic fiber excellent in metal friction.

  As a result of intensive studies, the present inventors have shown that a specific compound having a tertiary nitrogen group as a terminal group and a specific phenolic antioxidant are contained in the polyurethane polymer, whereby heat resistance and heat setting properties are improved. It was found for the first time that dyeability and spinning performance can be improved at the same time. Furthermore, it discovered that metal friction property was improved by containing an effective amount of a specific inorganic compound. That is, the present invention provides the following inventions.

（但し、式中、Ｒ^１〜Ｒ^４は炭素原子数が１〜５のアルキル基またはヒドロキシアルキレン基であるか、Ｒ^１とＲ^２およびＲ^３とＲ^４がそれぞれ結合し、それらが結合した窒素原子と共に複素環基を形成しており、Ｒ^５はジイソシアナート残基であり、Ｒ^６およびＲ^７は炭素原子数が１〜５の直鎖又は分岐したアルキル基、エチレンオキシ繰り返し単位が１〜５の基またはプロピレンオキシ繰り返し単位が１〜５の基であり、ＸおよびＹはウレタン結合及び又はウレア結合であり、ｎは１〜６の整数である。）
（Ｉ）：１，３，５−トリス（４−ｔ−ブチル−３−ヒドロキシ−２、６−ジメチルベンジル）イソシアヌレート、ビス［３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオン酸］（２，４，８，１０−テロラオキサスピロ［５，５］ウンデカン−３，９−ジイル）ビス（２，２−ジメチル−２，１−エタンジイル）、ビス（３‐ｔ‐ブチル‐４‐ヒドロキシ‐５‐メチルベンゼンプロパン酸）エチレンビス（オキシエチレン）、片ヒンダードのヒドロキシフェニル基を少なくとも１個有する分子量が約３００以上である片ヒンダードフェノール化合物、ｐ―クレゾールとジビニルベンゼンの重合体、ｐ―クレゾールとジシクロペンタジエンの重合体、ｐ−クロロメチルスチレンとｐ−クレゾールの重合体
［２］Ｍｇ、Ａｌ、Ｚｎ、Ｃａ、ＴｉおよびＳｉの群から選ばれた１種以上の金属の酸化物、炭酸化物または水酸化物から構成された無機化合物（Ｄ成分）をさらに含有し、Ｄ成分の含有量がＡ成分に対して０．０１〜８質量％であり、Ｂ成分、Ｃ成分およびＤ成分の合計がＡ成分に対して０．５〜１５質量％であることを特徴とする上記［１］に記載のポリウレタン弾性繊維。
［３］上記［１］または［２］に記載のポリウレタン弾性繊維と、ポリアミド繊維、ポリエステル繊維、ポリアクリル繊維、天然繊維およびセルロース誘導体繊維からなる群から選ばれた繊維とからなる繊維製品。
［４］インナー、アウター、レッグ、スポーツウェア、ジーンズ、水着および衛生材からなる群から選ばれた上記［３］に記載の繊維製品。 [1] A polyurethane polymer (component A), a compound (component B) having a tertiary nitrogen group at the end group and a molecular weight of 300 or more and less than 2000 represented by the following formula (1) and the following group (I) Phenolic antioxidant (component C), the content of component B and component C is 0.01 to 8% by mass and 0.01 to 5% by mass with respect to component A, respectively. A polyurethane elastic fiber having a weight part ratio C / B of components of 0.03 to 30.

(However, in the formula, R ^{1 to} R ⁴ are an alkyl group or a hydroxyalkylene group having 1 to 5 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ are bonded to each other, and they are bonded. A heterocyclic group is formed together with the nitrogen atom, R ⁵ is a diisocyanate residue, R ⁶ and R ⁷ are linear or branched alkyl groups having 1 to 5 carbon atoms, ethyleneoxy repeating units 1 to 5 groups or propyleneoxy repeating units are 1 to 5 groups, X and Y are urethane bonds and / or urea bonds, and n is an integer of 1 to 6.)
(I): 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis [3- (3-t-butyl-4-hydroxy-5-methyl) Phenyl) propionic acid] (2,4,8,10-terolaoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl), bis (3-t -Butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene), a hindered phenolic compound having at least one hindered hydroxyphenyl group and a molecular weight of about 300 or more, p-cresol and divinyl Benzene polymer, p-cresol and dicyclopentadiene polymer, p-chloromethylstyrene and p-cresol polymer [2] Mg, It further contains an inorganic compound (component D) composed of an oxide, carbonate or hydroxide of one or more metals selected from the group consisting of Al, Zn, Ca, Ti and Si, and the content of component D Is 0.01 to 8% by mass with respect to the A component, and the total of the B component, C component and D component is 0.5 to 15% by mass with respect to the A component [1] The polyurethane elastic fiber according to 1.
[3] A fiber product comprising the polyurethane elastic fiber according to the above [1] or [2] and a fiber selected from the group consisting of polyamide fiber, polyester fiber, polyacryl fiber, natural fiber and cellulose derivative fiber.
[4] The textile product according to the above [3], which is selected from the group consisting of an inner, an outer, a leg, sportswear, jeans, a swimsuit, and a sanitary material.

Since the B component used in the present invention has a urethane bond or a urea bond in its structure, it has good affinity with the polyurethane polymer to be added. In the case of a compound having a molecular weight of less than 300, the fastness to dyeing at the time of washing is not sufficient, and when the molecular weight is 2000 or more, the stretch recovery property, which is a physical characteristic of polyurethane elastic fibers, is lowered.
In addition, the component B has a tertiary nitrogen group at the terminal and is relatively compared to the case where a urethane polymer having a tertiary nitrogen-containing compound in the main chain or side chain of a conventional polymer is used. Since it has a low molecular weight, it can be present in a non-crystalline portion in the polyurethane polymer, and since it easily binds to a dye that has infiltrated into the polymer at the time of dyeing, the dyeability is also good.

  However, the component B promotes an alphanate bond reaction and / or a burette bond reaction in the polyurethane polymer when the spinning stock solution containing this compound stays in the dead space in the piping in the spinning process, and the yarn is spun during spinning. May cause cuts. This undesirable side reaction during the residence is greatly suppressed by using the C component in combination with the B component, and the long-term spinning stability is greatly improved.

  Moreover, the polyurethane elastic fiber containing this B component has a tendency that the metal friction with respect to the knitting needle is lowered and yarn breakage tends to occur during the knitting process. However, by using the D component in combination with the B component and the C component, the metal friction property is improved, and the polyurethane elastic fiber of the present invention is excellent in heat resistance, heat setting property, dyeing fastness and metal friction property, There are few yarn breaks during spinning and knitting.

2 is an NMR chart of a reaction product of diethylaminopropylamine and 4,4′-diphenylmethane diisocyanate. 2 is an NMR chart of a reaction product of diethylaminoisopropanol and 4,4′-diphenylmethane diisocyanate. It is the schematic of the metal-friction evaluation apparatus of a test yarn. It is an example of a metal friction property evaluation test result.

  The diamino compound as the component B used in the present invention includes a diisocyanate compound, a compound having an amino group that reacts with an isocyanate group in the diisocyanate compound or a hydroxyl group and a tertiary amino group at the same time in the molecular structure. Can be obtained by substantially equivalent reaction with an isocyanate group.

  Preferable examples of the diisocyanate compound include known aliphatic, alicyclic or aromatic organic diisocyanates having two isocyanate groups in the molecule. Specifically, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate and the like are exemplified, and preferably 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate. is there. Moreover, you may use the compound which has the blocked isocyanate group converted into a free isocyanate group as organic diisocyanate.

  Examples of compounds having a tertiary amino group and simultaneously having an amino group that reacts with an isocyanate group in one molecular structure include dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, N, N-diisopropylaminoethylamine, Dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethoxypropylamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl4-pipecoline, N-aminopropylpiperidine, N-aminopropyl- Examples are amines such as 2-pipecoline, N-aminopropylmorpholine, 4-aminomethyl-1-butylpiperidine.

Examples of the compound having a tertiary amino group and a hydroxyl group that reacts with an isocyanate group simultaneously in one molecular structure include diethylaminopropyl alcohol, diethylaminoisopropyl alcohol, dimethylaminoethyl alcohol, dipropylaminoethyl alcohol, Examples include alcohols such as dimethylaminoethoxypropyl alcohol.
Preferred are diethylaminopropylamine and dibutylaminopropylamine, which are diamine compounds having a tertiary amino group and simultaneously having an amino group that reacts with an isocyanate group in one molecular structure.

  The reaction between the diisocyanate compound and the diamino compound having a tertiary amino group is carried out so that the amino group or hydroxyl group of the diisocyanate compound is substantially equivalent or excessive with respect to the isocyanate group of the diisocyanate compound. It is preferable. The reaction can be carried out in the presence of a solvent or in the absence of a solvent with a large excess of diamino compound, but in order to avoid side reactions of isocyanate groups, in the presence of a solvent and under anhydrous conditions at low temperature. It is preferable to carry out with stirring.

Preferred solvents include solvents inert to isocyanate groups, such as toluene, xylene, THF, dimethylacetamide (DMAc), dimethylformamide, dimethylsulfoxide, and the like.
In the production of polyurethane fibers, DMAc is usually used as a preferred solvent, so if a diamino compound is produced using a DMAc solvent, it can be mixed directly into the spinning dope without isolating the diamino compound. It is preferable to use DMAc as the solvent.

  The present invention is characterized in that the diamino compound is contained in an amount of 0.01 to 8% by mass based on the polyurethane polymer. If it is this range, an effect can be expressed, without exerting a bad influence on a fiber. If the amount is less than 0.01% by mass, the above-described effects are insufficient. If the amount exceeds 8% by mass, the physical properties of the polyurethane elastic fiber are adversely affected. Preferably it is 0.5-6 mass%, More preferably, it is 1-5 mass%.

  Spinnability in the production of polyurethane elastic fibers is important, and without this, stable production cannot be achieved. When the diamino compound used in the present invention stays in the stock solution transport pipe for a long time after being mixed with polyurethane, it undergoes a gelation side reaction to the polyurethane polymer in the dead space or the high temperature residence part in the spinneret at the top of the spinning cylinder. Facilitate.

  Further, when the polyurethane elastic fiber is produced, the temperature in the spinning cylinder is raised to a high temperature of 200 ° C. or higher for a short time to dry the DMAc solvent. At that time, the thermal decomposition of the diamino compound itself and the resulting thread breakage problem in the spinning process.

  In order to solve this problem, it is effective to add the following phenolic antioxidant having a specific structure. That is, when the above diamino compound is used, it is necessary to use it together with the following phenolic antioxidant. Examples of the phenolic antioxidant used in the present invention include 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis [3- (3-t-butyl). -4-hydroxy-5-methylphenyl) propionic acid] (2,4,8,10-terolaoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1- Ethanediyl), bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene), one hindered having a molecular weight of at least about 300 having at least one hydroxyphenyl group in one hindered Phenolic compounds, polymers of p-cresol and divinylbenzene, polymers of p-cresol and dicyclopentadiene, p-chloromethylstyrene Like the p- cresol polymer.

  The one-hindered phenol compound is preferably a compound containing at least two one-hindered hydroxyphenyl groups and having a skeleton selected from bisesters and alkylidenes. Further, the alkyl group present at the ring position adjacent to the hydroxyl group in the hydroxyphenyl group is preferably a tertiary butyl group, and more preferably the equivalent of the hydroxyl group is 600 or less.

  Examples of the one-hindered phenol compound include ethylene-1,2-bis (3,3-bis [3-t-butyl-4-hydroxy] having a structure in which a hydroxyphenyl group of one hindered is covalently bonded to a bisester skeleton. Phenyl] butyrate), and 1,1-bis (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane having a structure in which a hindered hydroxyphenyl group is covalently bonded to an alkylidene skeleton, 1,1,3- Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butaneethylene-1,2-bis (3,3-bis [3-tert-butyl-4-hydroxyphenyl] butyrate), 1,1- Bis (2-methyl-5-tert-butyl-4hydroxyphenyl) butane and 1,1,3-tris (2-methyl-5-tert-butyl-4-hydride) Kishifeniru) butane and the like can be mentioned.

Preferred hindered phenol compounds include 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis [3- (3-t-butyl-4-hydroxy- 5-methylphenyl) propionic acid] (2,4,8,10-terolaoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl), bis ( 3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylenebis (oxyethylene), a polymer of P-cresol and divinylbenzene, and a polymer of P-cresol and dicyclopentadiene.
These phenolic antioxidants are preferably used in an amount of 0.01 to 5% by weight, more preferably 0.2 to 3% by weight, based on the polyurethane polymer. If it is less than 0.01% by mass, the heat resistance in the spinning process becomes insufficient, and if it exceeds 5% by mass, scum is generated in the knitting needles and guides during fabric knitting, which is not preferable.

  In the present invention, the ratio C / B of the C component, that is, the phenolic antioxidant to the B component, that is, the diamino compound, is preferably in the range of 0.03 to 30. Furthermore, it is preferably 0.1-20. If this ratio is less than 0.03, the heat resistance of the yarn is lowered, which is not preferable. On the contrary, if it exceeds 10, the dyeability is lowered, which is not preferable.

  Since the diamino compound used in the present invention is a relatively low molecular weight compound, this also means that good dyeability can be obtained. On the other hand, the metal friction against the knitting needle is reduced, and yarn breakage and fabric during the knitting process are reduced. There is a tendency to deteriorate. This problem is solved by adding an inorganic compound composed of an oxide, carbonate or hydroxide made of one or more metals selected from Mg, Al, Zn, Ca, Ti and Si. The Furthermore, when these inorganic compounds are added, yarn breakage in the spinning process is improved.

  Specific examples of the inorganic compound include huntite, zinc oxide, magnesium oxide, aluminum oxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, solid solution of magnesium oxide and zinc oxide, and aluminum dissolved in zinc oxide crystals. Zinc oxide solid solution, complex oxide of zinc and aluminum, mineral mixture of titanium oxide, huntite and hydromagnesite, metal solid solution containing titanium oxide and ZnO, hydroxide complex salt of Si and Zn, and metal composite oxidation containing ZnO Thing etc. are mentioned. Among these, preferred inorganic compounds are hydrotalcite, titanium oxide and huntite. These inorganic compounds are preferably used in an amount of 0.01 to 8% by mass, more preferably 0.2 to 6% by mass, based on the polyurethane polymer. Less than 0.01% by mass is not preferable because the metal frictional improvement is insufficient and yarn breakage is liable to occur during the knitting process. On the other hand, if it exceeds 8% by mass, clogging of the spinning dope solution is likely to occur during the spinning process, and yarn breakage tends to occur during spinning, which is not preferable because production is not stable.

  Moreover, in this invention, it is preferable that the total amount of the said diamino compound, a phenolic antioxidant, and an inorganic compound is 0.5-15 mass% of a polyurethane polymer, More preferably, it is 1.0-10 mass%. is there. If the amount is less than 0.5% by mass, the effect of the present invention is poor. On the other hand, if the amount exceeds 20% by mass, not only will long-term stable production of yarn such as yarn breakage or filter clogging be hindered, but the cost will increase. The general advantage is lost

The polyurethane polymer used in the present invention is obtained by a known method in which an active hydrogen-containing compound is reacted with a prepolymer obtained by reacting a polymer diol and diisocyanate.
Examples of the polymer diol include polyester diol, polycarbonate diol, and polyether diol. Polyether diols are preferable, and polyalkylene ether diols in which one or two or more linear or branched alkylene groups having 2 to 10 carbon atoms are ether-bonded are particularly preferable.

  The polyalkylene ether diol is preferably a single or copolymerized polyalkylene ether diol. The number average molecular weight (Mn) of the polyalkylene ether diol used in the present invention is preferably 500 to 6000, more preferably 1000 to 3000. When Mn is smaller than 500, the elastic recovery property is lowered, and when it is larger than 6000, the spinnability is deteriorated.

  In the copolymerized polyalkylene ether diol, an alkylene group is ether-bonded in a block shape or a random shape. Compared to PTMG (polytetramethylene ether glycol), a single-polymerized polyalkylene ether diol widely used as a raw material for polyurethane elastic fibers, a copolymer polyalkylene ether diol composed of two or more types of alkylene groups. In the case of a polyurethane elastic fiber using a polyurethane, since the diol component occupying 65 wt% to 85 wt% of the polyurethane component is amorphous, the dye easily penetrates into the polyurethane polymer, and the diamino compound and the dye are contained in the polyurethane elastic fiber. Because of efficient binding, a vivid color with better dyeability and hue can be obtained.

  In addition, the advantage of using a copolymerized diol is that the elastic function is further improved, so that this polyurethane elastic fiber has excellent elastic function, namely high elongation at break, small stress fluctuation with respect to strain at elongation and Has low hysteresis loss of stress etc. Therefore, pantyhose and outerwear using the same have an excellent elastic function, are excellent in wearing feeling, and have good aesthetic properties. Among the copolymerized polyalkylene ether diols, a copolymerized polyalkylene ether diol containing a butylene group, that is, a tetramethylene ether unit, is preferable from the viewpoint of water resistance, light resistance, abrasion resistance, elastic function, and the like of the obtained polyurethane elastic fiber. Furthermore, a combination of a butylene group, that is, a tetramethylene ether unit and a 2,2-dimethylpropylene group, that is, a neopentylene ether unit, or a combination of a tetramethylene ether unit and a 2-methylbutylene group is preferable.

  The alkylene ether unit other than the tetramethylene group is preferably contained in an amount of 4 mol% to 85 mol%. If the alkylene ether unit is less than 4 mol%, the effect of improving the elastic function of the polyurethane elastic fiber is small, and if it exceeds 85 mol%, the strength or elongation of the elastic fiber is greatly reduced.

  As said diisocyanate, the well-known aliphatic, alicyclic, or aromatic organic diisocyanate which has two isocyanate groups in a molecule | numerator is mentioned. Specifically, 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4 An organic diisocyanate such as 4,4'-dicyclohexylmethane diisocyanate is exemplified, and 4,4'-diphenylmethane diisocyanate is preferable. Moreover, you may use the compound which has the blocked isocyanate group converted into a free isocyanate group as organic diisocyanate.

  As the active hydrogen-containing compound that reacts with an isocyanate group, a conventional chain extender in polyurethane, that is, a low-molecular compound having a molecular weight of 500 or less and containing at least two hydrogen atoms that can react with isocyanate can be used. Specific examples thereof include diamines such as ethylenediamine, propylenediamine, tolylenediamine, m-xylylenediamine, 1,3-diaminocyclohexane, isophoronediamine, hydrazine, 4,4'-diaminodiphenylmethane, dihydrazide, piperazine, and the like. Examples thereof include diamine compounds disclosed in JP-A No. 5-155842, diols such as ethylene glycol, propylene glycol, and 1,4-butanediol, preferably ethylenediamine, 1,2-propylenediamine, and JP-A Examples thereof include diamine compounds disclosed in JP-A-5-155581. These compounds may be used alone or in admixture of two or more. Moreover, you may use together with the compound containing one active hydrogen which can react with isocyanate depending on the case.

  As a method for producing polyurethane using diisocyanate, polymer diol, and active hydrogen-containing compound, a known urethanization technique can be employed. The stoichiometric ratio of various compounds used in the present invention is such that the sum of the hydroxyl groups of the polymer diol and the active hydrogens of the active hydrogen-containing compound is 1.00 or more and 1.07 equivalents relative to the isocyanate group of the diisocyanate compound. Less than is preferable.

The polyurethane polymer thus obtained is further added to known organic or inorganic compound heat stabilizers, antioxidants, UV inhibitors, yellowing inhibitors, heat discoloration inhibitors and anti-resistance agents useful for polyurethane polymers. A sterilizing chlorine agent for pools may be added.
The specific viscosity (ηsp / c) of the polyurethane polymer constituting the polyurethane elastic fiber of the present invention is preferably 1.1 to 3.5 dl / g. By setting it as this range, it becomes an elastic fiber excellent in elastic recovery property. Here, the specific viscosity (ηsp / c) is a value calculated by (η / η ₀ −1) / C in a N, N′-dimethylacetamide solvent (where C is a polymer 0.5 g / The solution viscosity is 99.5 g (0.5 wt%) of DMAC, η is the number of seconds dropped in a dilute solution by an Ostwald viscometer, and η ₀ is the number of seconds dropped by only the DMAC by the viscometer.

The polyurethane polymer thus obtained is formed into a slender flat fiber shape by a fiber or an extrusion method through a spinning tube spinneret by a conventionally known dry spinning method, melt spinning method, etc., and then wound around a tube. Taken, a polyurethane elastic fiber is obtained. A polyurethane elastic fiber obtained by dry spinning is preferable.
At this time, a known oil agent for polyurethane elastic fibers may be further adhered as an oil agent from the outside using an oiling device during spinning. The oil component used here is, in addition to ether-modified silicone, polyester-modified silicone, polyether-modified silicone, polyamino-modified silicone, polyorganosiloxane, mineral oil, talc, silica, colloidal alumina and other mineral fine particles, magnesium stearate Also, various fatty acid metal salt powders such as calcium stearate, higher aliphatic carboxylic acids, higher aliphatic alcohols, waxes that are solid at room temperature such as paraffin polyethylene, and the like may be used in combination.

  The polyurethane elastic fiber of the present invention may contain various stabilizers, pigments and the like as necessary as long as the effects of the present invention are not impaired. For example, as a light-proofing agent, an antioxidant, etc., benzotriazoles such as “Tinuvin” manufactured by Ciba Geigy, benzophenone drugs, phosphorus-based drugs such as “Sumilyzer” P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amines Chemicals, inorganic pigments such as titanium oxide and carbon black, fluorine resin powders or silicone resin powders, metal soaps such as magnesium stearate, disinfectants containing silver, zinc and their compounds, deodorants In addition, a lubricant such as silicone and mineral oil, various antistatic agents such as barium sulfate, cerium oxide, betaine, and phosphoric acid are added, and it may be present by reacting with a polymer. In order to further enhance the durability to light and various nitric oxides in particular, a nitric oxide scavenger, for example, HN-150 manufactured by Nippon Finechem Co., Ltd., a thermal oxidation stabilizer, a light stabilizer, for example, Sumitomo Chemical It is preferable to contain a light stabilizer such as “SUMISOB” 300 # 622 manufactured by Kogyo Co., Ltd.

  The polyurethane elastic fiber thus obtained may be used as a bare thread as it is in practice, and other fibers such as polyamide fiber, wool, cotton, recycled fiber, polyester fiber, cellulose fiber, etc. It can also be coated with a conventionally known fiber and used as a coated elastic fiber. In particular, it is preferably used in combination with a fiber material selected from the group consisting of nylon, ester, acrylic, natural fiber and cellulose derivative.

  The polyurethane elastic fiber of the present invention can be used for foundations, socks, mouth rubbers, corsets, surgical bandages, braids, woven fabrics and knitted swimsuits. In particular, it is preferably used for textile products selected from the group consisting of inner, outer, legs, sportswear, jeans, swimwear and sanitary materials.

  When the polyurethane elastic fiber of the present invention is dyed, the same method as the dyeing method of ordinary synthetic fiber and natural fiber may be used. That is, dyeing methods such as a dip dyeing method, a pad steam method, a pad thermofix method, a textile printing method, and a spray method can be applied. As the dyeing machine, ordinary dyeing machines such as a liquid dyeing machine, a Wins dyeing machine, and an airflow dyeing machine can be used.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Various evaluations were performed by the following methods.
(1) JNM JX GX 400 type manufactured by JEOL Ltd. was used as the NMR apparatus, and ¹ H-SGNON was used as the nuclear magnetic resonance spectrometer. Accumulation was 100 times, the solvent was dated DMSO (20 mg / 0.8 ml), the measurement temperature was 50 ° C., and the pulse was 45 °.

(2) Evaluation of spinning stability A spinning stock solution containing various additives produced according to the method described in the following examples was spun for 20 hours by the method described in the examples, and the number of yarn breaks (times / hour). ) Was measured. The smaller the number of times, the more stable the productivity.

(3) Dry heat set rate measuring method The dry heat set rate was calculated | required with the following measurement and numerical formula. Tensile box is passed through a tenter box adjusted to 190 ± 1 ° C, and stretched for 30 seconds. And immediately take out the elastic yarn, twist it with a length of Ld0 or less, relax sufficiently, and leave it at room temperature for 18 hours. Again, when the elastic yarn was in a non-tensioned and linear state, and the length at that time was Ld1, the set rate was defined by the following formula.
Dry heat setting rate (%) = [(Ld1−Ld0) / Ld0] × 100

(4) Evaluation of dyeability of polyurethane elastic fiber A two-weight recot knitted fabric was used for dyeing evaluation. That is, a 33 dt / 10f nylon fiber is used for the front heel, a 44 dt polyurethane elastic fiber of this example or comparative example is used for the middle heel and the back heel, the front heel structure is 10/23, and the middle heel structure is 10/01. Then, a two-weight ricott knitted fabric having a back heel structure of 12/10 was knitted. The blending ratio of polyurethane elastic fibers in this fabric was 35%, and was put into a continuous scouring machine in the expanded state. At this time, use a continuous scouring machine with four liquid tanks, change the temperature at which the fabrics pass sequentially, such as 20 ° C, 50 ° C, 70 ° C, 90 ° C, and in each liquid tank 2 g / L of a scouring agent (score roll FC-250 manufactured by Kao Corporation) was added. The cloth which passed through the continuous scouring machine was dehydrated with a mangle after passing through a washing bath, and pre-set at 190 ° C. for 45 seconds with a pin tenter.

Next, it was put into a liquid flow dyeing machine, and 2g / L of a scouring agent (score roll FC-250 manufactured by Kao Co., Ltd.) 2g / L was added in the liquid for scouring, and scouring was performed in an acidic bath at 70 ° C for 20 minutes. . After draining, rinsing and re-watering, a black acidic dye adjusted to pH 4 was added and dyed at 95 ° C. for 60 minutes.
After rinsing, fix processing (natural tannin S 6% owf, tartar stone L 3% owf, 80 ° C./40 minutes treatment), the fabric is removed from the dyeing machine, processed with a soft resin, and further 170 ° C. with a pin tenter. Finished the set.

The dyeability when dyed black was determined according to the following criteria.
Grade 5 dark black,
4th grade black,
3rd class light black,
2nd grade gray,
Grade 1 light gray

(5) Evaluation of fastness to washing of fabric Evaluation was performed by JIS L0844 discoloration.
The detergent used at that time was detergent product name “Attack” 2 g / L manufactured by Kao Corporation, each was washed for 30 minutes under the condition of a washing liquid temperature of 80 ° C., rinsed with running water for 30 minutes, dehydrated, and room temperature (20 ° C., 65% RH), the change in hue after drying for 24 hours was measured.
Hue change (Class Δ) = class before washing the fabric-class after washing the fabric The higher the series before washing and the smaller the Δ class value, the less the color change and the better the dyeability and fastness. It can be said that there is.

(6) Metal friction evaluation of polyurethane elastic fiber (metal friction evaluation test)
FIG. 3 shows a metal friction evaluation apparatus. The obtained test yarn 1 (44 dt / 4 filament) was left in an atmosphere of 25 ° C. and 65% RH for 20 days, and then applied to the apparatus shown in FIG. 3, and a draw rate of 2 at a feeding speed of 100 m / min and a winding speed of 200 m / min. The running stress of the test yarn 7 and its stress fluctuation were measured before and after passing through the knitting needle 4. An example of the measurement result is shown in FIG. The friction coefficient μd is given by the following formula (6).
μd = ln (T1 / T2) /2.6376 (6)
However, T1 and T2 are respectively the center value (g) of the running stress after passing the knitting needle and the center value (g) of the running stress before passing the knitting needle in the illustration of FIG.

Example 1
[Synthesis of diamino compounds used in the present invention]
To a solution of 52.5 parts of diethylaminopropylamine dissolved in 200 parts of DMAc (dimethylacetamide), a solution of 50.0 parts of 4,4'-diphenylmethane diisocyanate dissolved in 300 parts of DMAc was gradually added dropwise. The dropping was carried out with stirring while cooling so as to keep the temperature at 10 ° C to 20 ° C. After completion of the dropwise addition, stirring was further continued for 1 hour.

  A part of the obtained reaction solution was taken and dropped into water, and the white precipitate was filtered, sufficiently washed with water, and dried under reduced pressure at 80 ° C. The measurement result of NMR is shown in FIG. This precipitate was confirmed to be a compound having a tertiary nitrogen group at the end group having a target molecular weight of 510. Similarly, a synthesis reaction was carried out using diethylaminoisopropanol instead of diethylaminopropylamine. The NMR measurement result of the obtained precipitate is shown in FIG. This was confirmed to be a compound having a tertiary nitrogen group at the target terminal group having a molecular weight of 381.

  Various diamino compounds were synthesized in the same manner as described above using various amines listed in Table 1 and various diisocyanates instead of diethylaminopropylamine. A compound having a nitrogen group was obtained.

(Example 2)
[Polymerization polymerization and production of polyurethane elastic fiber]
400 g of polytetramethylene ether diol having a number average molecular weight of 1800, which is a single polymerization diol, and 91.7 g of 4,4′-diphenylmethane diisocyanate are reacted under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours, A polyurethane prepolymer capped with an isocyanate was obtained. After cooling this to room temperature, 720 g of dried dimethylacetamide (DMAc) was added and dissolved to prepare a polyurethane prepolymer solution. On the other hand, 8.111 g of ethylenediamine and 1.37 g of diethylamine were dissolved in 390 g of dimethylacetamide and added to the prepolymer solution at room temperature to obtain a polyurethane solution having a viscosity of 3700 poise (30 ° C.).

  Next, a solution in which the phenolic antioxidants listed in Table 2 are uniformly dispersed by stirring in a DMAc solution of various diamino compounds listed in Table 1 becomes mass% described in Table 2 with respect to the polyurethane polymer solids. In addition to the polyurethane polymer solution thus obtained, stirring was performed to obtain a uniform stock solution for spinning.

After defoaming the spinning dope obtained in this way, it was pushed out from the pores of 16 spinnerets (each of which has 4 pores) into the lower part of the spinning tube at about 230 ° C. with hot air. DMAc (dimethylacetamide) solvent was evaporated. The dried yarn is false twisted, passed through a godet roller, oiled with dimethyl silicone as a main component is applied on an oiling roller, wound around a paper tube at a speed of 850 m / min, and a 44 dt / 4 filament polyurethane elastic Fiber was obtained.
Various evaluation results of the obtained polyurethane elastic fiber are shown in Table 2.

(Comparative Examples 1-6)
No addition of the diamino compound of the present invention, no addition of the phenolic antioxidant of the present invention, addition of a prior art compound, addition of a compound other than the phenolic antioxidant of the present invention, outside the proper range of C / B of the present invention In the same manner as in Example 2, polyurethane elastic fibers were spun and evaluated. Various evaluation results of the obtained polyurethane elastic fibers are shown in Table 2 as comparative examples.

(Example 3)
To the polyurethane polymer, a DMAc solution of a diamino compound synthesized from the raw materials shown in Table 1, a phenol-based antioxidant and an inorganic compound are added in parts by weight as shown in Table 3, and a liquid uniformly dispersed by stirring is carried out. In addition to the polyurethane solution obtained in Example 2, a uniform spinning stock solution was obtained. Spinning was performed in the same manner as in Example 2 to obtain a 44 dt / 4 filament polyurethane elastic fiber, and various evaluation results of this polyurethane elastic fiber are shown in Table 3.

(Examples 4 and 5)
With respect to an example in which no inorganic compound was added, polyurethane elastic fibers were spun in the same manner as in Example 3 and evaluated. Various evaluation results of the obtained polyurethane elastic fiber are shown in Table 3.
(Comparative Example 7)
For an example containing an inorganic compound but not containing a diamino compound, polyurethane elastic fibers were spun in the same manner as in Example 3 and evaluated. Various evaluation results of the obtained polyurethane elastic fiber are shown in Table 3.

  The polyurethane elastic fiber of the present invention has excellent dyeability, fastness during washing, heat setting property and anti-metal (knitting needle) friction property, and is used as an inner, outer, leg, sportswear, jeans, swimwear and sanitary material. Useful.

DESCRIPTION OF SYMBOLS 1 Test yarn 2 Feeding roller 3 Tension meter 4 Knitting needle 5 Winding part 6 Winding roller 7 Test yarn running yarn 8 Angle formed by the yarn applied to the knitting needle = 29 °

Claims (4)

A polyurethane polymer (component A), a compound having a tertiary nitrogen group at the end group (1), a molecular weight of 300 or more and less than 2000 (component B), and a phenolic group selected from the following group (I) It consists of an antioxidant (C component), and the content of the B component and the C component is 0.01 to 8% by mass and 0.01 to 5% by mass with respect to the A component, respectively, and the weight of the C component with respect to the B component A polyurethane elastic fiber having a part ratio C / B of 0.03 to 30.

(However, in the formula, R ^{1 to} R ⁴ are an alkyl group or a hydroxyalkylene group having 1 to 5 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ are bonded to each other, and they are bonded. A heterocyclic group is formed together with the nitrogen atom, R ⁵ is a diisocyanate residue, R ⁶ and R ⁷ are linear or branched alkyl groups having 1 to 5 carbon atoms, ethyleneoxy repeating units 1 to 5 groups or propyleneoxy repeating units are 1 to 5 groups, X and Y are urethane bonds and / or urea bonds, and n is an integer of 1 to 6.)
(I): 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis [3- (3-t-butyl-4-hydroxy-5-methyl) Phenyl) propionic acid] (2,4,8,10-terolaoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl), bis (3-t -Butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene), a hindered phenolic compound having at least one hindered hydroxyphenyl group and a molecular weight of about 300 or more, p-cresol and divinyl Benzene polymer, p-cresol and dicyclopentadiene polymer, p-chloromethylstyrene and p-cresol polymer   It further contains an inorganic compound (D component) composed of one or more metal oxides, carbonates or hydroxides selected from the group consisting of Mg, Al, Zn, Ca, Ti and Si. Content is 0.01-8 mass% with respect to A component, and the sum total of B component, C component, and D component is 0.5-15 mass% with respect to A component, 2. The polyurethane elastic fiber according to 1.   A fiber product comprising the polyurethane elastic fiber according to claim 1 or 2 and a fiber selected from the group consisting of polyamide fiber, polyester fiber, polyacrylic fiber, natural fiber and cellulose derivative fiber.   The textile product according to claim 3, selected from the group consisting of an inner, an outer, a leg, sportswear, jeans, a swimsuit and a sanitary material.

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