JP2014091891A - Polyurethane elastic fiber and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane elastic fiber superior in heat setting properties, dye-affinity, color fastness and spinning productivity.SOLUTION: This invention provides a polyurethane elastic fiber, wherein as a polyurethane polymer, the polyurethane polymer of a specific structure whose number average molecular weight is 2000-100000 and whose end group is a tertiary nitrogen group is contained in the amount of 0.01-30 wt.% relative to the other polyurethane polymers.

Description

  The present invention relates to a polyurethane elastic fiber. More specifically, the present invention relates to a polyurethane elastic fiber excellent in heat resistance, dyeability, heat setting property, and dyeing fastness in washing and dry cleaning, and a method for producing the same.

  Polyurethane elastic fibers are rich in elasticity and are widely used in textile products such as foundations, underwear, body suits, pantyhose, swimwear, sportswear and hygiene materials because of their excellent physical properties. In general, polyurethane elastic fibers are used after being knitted or woven with other fiber materials such as nylon and ester. However, the following problems have been pointed out regarding polyurethane elastic fibers.

  (1) Polyurethane elastic fibers are highly stretchable, so they have low moldability (heat setability) and poor dimensional stability when made into fabrics. Curls and places a heavy burden on the sewing manufacturer. Furthermore, when the consumer repeats wearing and washing, there is a problem that the dimensions of the clothing gradually shrink.

(2) In general, polyurethane does not have a dyeing seat having a strong binding force with a dye in its structure, so that it is difficult to dye, and furthermore, fastness to dyeing during washing and dry cleaning is poor. For this reason, polyurethane elastic fibers are dyed only thinly with respect to acid dyes, but nylon fibers have the same color mismatch due to being dyed well, and there is a problem that the commercial value of fabric products with nylon materials is lowered. Furthermore, even after the polyurethane elastic fiber is once dyed, the binding force with the dye in the polyurethane polymer is weak, so the dye can easily fall out of the fiber and fade, or contaminate other products during washing. There's a problem. Furthermore, in recent years, the use of polyurethane elastic fibers has expanded, and in combination with ester materials, polyurethane elastic fibers have become widely used in outer clothing such as denim and suits, and dyeing fastness during dry cleaning washing is also large. It has become a problem.
(3) When the polyurethane elastic fiber contains a tertiary nitrogen group, the heat resistance is lowered, and yarn breakage occurs due to hot air in a spinning tower of dry spinning, and long-term stable production is difficult.

Various attempts have been made to improve these problems.
For example, there is an attempt to improve the setting property by blending polyvinyl pyrrolidone (see Patent Document 1 below). However, although the set rate immediately after heat setting is good, there is a problem that the fabric dimensions gradually shrink as it is worn for a long period of time, and the dyeing fastness after dry cleaning is not sufficient.

  Regarding the improvement in dyeing fastness during dry cleaning of polyurethane elastic fibers and fabrics made from other materials, it is difficult to improve the dyeing fastness of polyurethane elastic fibers themselves. (For example, see Patent Document 2 below). However, in this method, there are subtle condition changes and seasonal changes in the dyeing bath for each processing batch, and color blurring occurs every time the finish is finished, and color matching becomes a problem.

  In order to improve the polyurethane elastic fiber itself, there is an attempt to add a tannin compound to the polyurethane elastic fiber (see Patent Document 3 below). However, since the tannin compound itself is slightly brown, when used in a light-colored product, the hue becomes dull and the use of dyeing in a light-colored system is limited.

  It has been proposed to improve the dyeing fastness of polyurethane urea elastic fibers by containing a specific maleimide structure compound (see Patent Document 4 below). However, in this method, in the production process of the maleimide structure compound, the reaction of the diamine to the maleic anhydride skeleton is complicated and the reaction is often incomplete. In this case, the clogging of the filter or the yarn breakage occurs in the spinning process. .

  Attempts have been made to improve the dyeability of polyurethane by incorporating tertiary nitrogen groups into the main chain of the urethane polymer or adding compounds with tertiary nitrogen groups in the side chains of polyacrylic acid to the polymer polymer. (See Patent Documents 5 to 8 below). However, when a compound having a tertiary nitrogen group is built in the main chain of the urethane polymer, the crystal structure in the polyurethane structure is disturbed, so the heat resistance of the fiber is reduced by the heat flow and the physical properties of the elastic fiber. The elastic recoverability is reduced.

  Further, when the main chain is built-in, the movement of the tertiary nitrogen group as a dyeing seat is restricted in the polyurethane polymer, so that the reaction with the dye is not sufficient. Furthermore, the heat resistance and light embrittlement resistance of the urethane polymer are also lowered. In addition, for polymers such as acrylate esters having a tertiary group in the side chain, since the compatibility with polyurethane is not good, stable spinning for a long period of time is difficult, and scum is generated during knitting processing. The dyeability was not sufficient.

JP-A-11-200168 JP 2003-201683 A JP 2001-140167 A Japanese Patent Publication No. 3-6177 Japanese Examined Patent Publication No. 47-51645 Japanese Examined Patent Publication No. 47-48895 Japanese Patent Publication No.46-2904 Japanese Examined Patent Publication No. 61-7212

As described above, it has already been known that a tertiary nitrogen group-containing compound is effective in improving the dyeability of polyurethane elastic fibers. However, the tertiary nitrogen group is mainly used in the main chain and side chain of the polymer. If present in the above, it will adversely affect the performance of the polyurethane elastic fiber, or the following problems related to the performance improvement of the polyurethane elastic fiber: (i) to improve the heat setting property and stabilize the size, (ii) to improve the dyeability Not able to be satisfied at the same time with improved and vivid color development, (iii) improving dye fastness during washing and dry cleaning, and (iv) ensuring stable spinning productivity without reducing heat resistance It was.
The object of the present invention is to achieve the above-mentioned problems (i) to (iv) at the same time.

As a result of intensive investigations for solving the above problems, the present inventors have made a tertiary nitrogen compound having a specific structure present in the terminal group of the polymer as a terminal terminator, thereby enabling the elastic recovery characteristics and heat resistance of the polyurethane elastic fiber. It has been found that polyurethane elastic fibers satisfying the above (i) to (iv) can be obtained at the same time without adversely affecting the properties and light resistance.
That is, the present invention provides the following inventions.

（Ｒ^１およびＲ^２は、同一または異なる炭素原子数が１〜１０の直鎖又は分岐したアルキル基またはヒドロキシアルキル基であるか、もしくはＲ^１とＲ^２が結合し、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^３は炭素原子数が１〜８の直鎖又は分岐したアルキレン基、繰り返し単位が１〜５のエチレンオキシ基または繰り返し単位が１〜５のプロピレンオキシ基であり、Ｒ^４はジイソシアネート残基であり、Ｘはウレタン結合またはウレア結合であり、Ｒ^５およびＲ^６は同一又は異なるジイソシアネート残基であり、Ｐはジオール残基であり、Ｑはジアミン残基であり、ＵＴはウレタン結合であり、ＵＡはウレア結合であり、ｋ、ｍおよびｎはそれぞれ正の数であってｍとｎのどちらかは０でも良い。）
［２］第三級窒素基を有する単活性水素化合物を１０モル％以上含有する末端停止剤を用いて製造されたポリウレタン重合体を紡糸することを特徴とする前記［１］に記載のポリウレタン弾性繊維の製造方法。
［３］単活性水素化合物がアミノ基または水酸基を有する前記［２］に記載のポリウレタン弾性繊維の製造方法。 [1] As a polyurethane polymer, a polyurethane polymer in which the terminal group having a number average molecular weight of 2000 to 100,000 represented by the following formula (1) is a tertiary nitrogen group is 0.01 to 30% by weight of other polyurethane polymers. % Polyurethane elastic fiber characterized by containing.

(R ¹ and R ² are the same or different carbon atoms is a linear or branched alkyl or hydroxyalkyl group having 1 to 10, or R ¹ and R ² are bonded, the nitrogen atom to which they are attached And R ³ is a linear or branched alkylene group having 1 to 8 carbon atoms, an ethyleneoxy group having 1 to 5 repeating units, or a propyleneoxy group having 1 to 5 repeating units. R ⁴ is a diisocyanate residue, X is a urethane bond or urea bond, R ⁵ and R ⁶ are the same or different diisocyanate residues, P is a diol residue, and Q is a diamine residue UT is a urethane bond, UA is a urea bond, k, m, and n are positive numbers, and either m or n may be 0.)
[2] Polyurethane elasticity as described in [1] above, wherein a polyurethane polymer produced using a terminal terminator containing 10 mol% or more of a monoactive hydrogen compound having a tertiary nitrogen group is spun. A method for producing fibers.
[3] The method for producing a polyurethane elastic fiber according to [2], wherein the monoactive hydrogen compound has an amino group or a hydroxyl group.

Compared to the case of having a tertiary nitrogen group in the main chain or side chain of the urethane polymer, if the tertiary nitrogen group is at the terminal, the steric hindrance to the tertiary nitrogen group has a relatively high degree of freedom. Tertiary nitrogen groups are likely to be present in the amorphous part of the polyurethane. As a result, there is a high probability of reactivity between the tertiary nitrogen group that is the dyeing seat and the dye that has entered the amorphous part of the polyurethane. It becomes easy to make. Accordingly, the dyeability and fastness are improved. In addition, since the tertiary nitrogen group is present at the terminal group, the elastic recovery property of the polymer, which is the physical property of the elastic fiber, is not adversely affected. As a result, those having a tertiary amine at the end group have good setting properties and do not impair elastic recovery.
Accordingly, the polyurethane elastic fiber of the present invention containing a specific amount of a polyurethane polymer having a tertiary nitrogen group at the end is composed of (i) spinning stability, (ii) heat resistance, (iii) dyeability with a dye, (iii) washing and Dye fastness after dry cleaning (iv) Polyurethane elastic fiber with excellent heat setting.

The polyurethane elastic fiber of the present invention is characterized in that an effective amount of a polyurethane polymer in which the terminal group having a number average molecular weight of 2000 to 100000 represented by the above formula (1) is a tertiary nitrogen group is contained in the polyurethane. is there. The effective amount is 0.01 to 30% by weight, preferably 0.1 to 10% by weight, more preferably 1 to 8% by weight, based on the total polyurethane polymer. If it is less than 0.01% by weight, the above effect of the present invention cannot be exhibited. On the other hand, if it exceeds 30% by weight, the elastic recovery after the yarn is stretched is not preferable.
If the number average molecular weight is less than 2000, the fastness to dyeing by dry cleaning is not sufficient, and if it is greater than 100,000, the dyeability is not sufficiently exhibited. Preferably it is 3000 to 80000, and still more preferably 4000 to 70000.

  In order to obtain the polyurethane elastic fiber of the present invention, a tertiary nitrogen-containing compound may be used as a part of the terminal terminator during the production of the raw material polyurethane polymer, and the number average molecular weight represented by the above formula (1) is A polyurethane polymer having 2000 to 100000 terminal groups that are tertiary nitrogen groups may be newly produced, and an effective amount thereof may be added to the raw polyurethane polymer for polyurethane elastic fibers.

The polyurethane elastic fiber of the present invention can be produced by using a tertiary nitrogen-containing compound having a monoactive hydrogen group that reacts with an isocyanate group as a part of a terminal stopper when producing a raw material polyurethane polymer. . As an advantage of this method, there is a rational method in which a polyurethane polymer corresponding to the above formula (1) can be prepared in a separate batch and the process can be simplified without the need for addition as an additive.
As another method, when emphasizing the physical properties (elastic recovery properties) of the original polyurethane polymer, after the polyurethane polymer corresponding to the above formula (1) is produced in a separate batch, the raw material polyurethane weight is added as an additive. An effective amount may be added to the coalescence.

  The polyurethane polymer represented by the above formula (1) having a tertiary nitrogen group at the terminal used in the present invention includes a polyol, a diisocyanate, a compound having a bifunctional active hydrogen group that reacts with an isocyanate group, and a third polymer. It is a reaction product of a monoactive hydrogen compound having a secondary nitrogen group, and the number average molecular weight is in the range of 2000 to 100,000.

  Examples of the polyol used in the present invention include polyester diol, polycarbonate diol, and polyether diol. Preferred is a polyether diol, and more preferred is a polyalkylene ether diol in which one or two or more linear or branched alkylene groups having 2 to 10 carbon atoms are ether-bonded.

  As the polyalkylene ether diol, one or two or more linear or branched alkylene groups having 2 to 10 carbon atoms are ether-bonded, and a single or copolymer poly having a number average molecular weight of 300 to 6000 is used. Alkylene ether diols are preferred. The copolymerized polyalkylene ether diol is a copolymerized polyalkylene ether diol having a number average molecular weight of 300 to 6000, in which 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 polyurethane elastic fiber using styrene, it is a copolymer and the diol component occupying 65 wt% to 85 wt% of the polyurethane component is amorphous, so that the dye can easily penetrate into the polyurethane polymer and exists in the polyurethane elastic fiber. Since the diaminodiurea compound used in the present invention and the dye are efficiently bonded, vivid color development with a better 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. The number average molecular weight (Mn) of the polyalkylene ether diol used in the present invention is 300 to 6000, preferably 1000 to 4000. When Mn is smaller than 300, the elastic recovery property is lowered, and when it is larger than 6000, the spinnability is deteriorated.

  Preferable examples of the diisocyanate compound used in the present invention 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 Organic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and trimethylhexamethylene diisocyanate are 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 bifunctional active hydrogen-containing compound that reacts with the isocyanate group used in the present invention, a conventional chain extender in polyurethane, that is, a low molecular compound having a molecular weight of 500 or less 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. For these chain extenders, a triamine compound capable of forming a crosslinked structure, such as diethylenetriamine, can be used to the extent that the effect is not lost.

  Examples of the monoactive hydrogen compound having a tertiary nitrogen group that reacts with an isocyanate group that can be used as a terminal terminator during the polyurethane polymerization used in the present invention include the following compounds. Dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, N, N-diisopropylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethoxypropylamine, diethanolaminopropylamine, N-aminoethylpiperidine N-aminoethyl 4-pipercoline, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropylmorpholine, 4-aminomethyl-1-butylpiperidine, dimethylaminoethoxypropylamine, N-aminoethylpiperidine, N-aminoethyl 4-pipecholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropi Morpholine, amine compounds such as 4-aminomethyl-1-butyl piperidine is exemplified. Examples of alcohol compounds having a tertiary nitrogen group and simultaneously having a hydroxyl group that reacts with an isocyanate group in one molecular structure include diethylaminopropyl alcohol, diethylaminoisopropyl alcohol, dimethylaminoethyl alcohol, dipropylaminoethyl alcohol, Examples include dimethylaminoethoxypropyl alcohol. A monoactive hydrogen group that reacts with an isocyanate group quickly completes the reaction, so that there is less cross-linking of side reactions, so that a compound having an active amino group is more elastic and elastic than a compound having an active hydroxyl group. More preferable from the viewpoint of heat resistance.

In addition to the above monoactive hydrogen compound, it may be used in combination with another monoactive hydrogen-containing compound that reacts with the following isocyanate groups used in the polymerization reaction of polyurethane. If the fiber is spun, the polyurethane elastic fiber of the present invention is obtained. The following can be mention | raise | lifted as an example of those compounds.
Monoalcohols such as methanol, ethanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol, 3-methyl-1-butanol, isopropylamine, n-butylamine, t- Examples thereof include monoalkylamines such as butylamine and 2-ethylhexylamine, and dialkylamines such as diethylamine, dimethylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, di-2-ethylhexylamine and diisopropylamine. These can be used alone or in combination. Monoalkylamines or dialkylamines which are monofunctional amines are preferred over monoalcohols.

  When the monoactive hydrogen compound having a tertiary nitrogen group and the monoactive hydrogen-containing compound are mixed and used as a terminal terminator, the monoactive hydrogen compound having a tertiary nitrogen group is a monoactive hydrogen-containing compound. It is necessary to be 10 mol% or more based on the total molar amount with the monoactive hydrogen compound having the tertiary nitrogen group. If it is less than 10 mol%, the effect of the present invention cannot be obtained sufficiently. Preferably it is 20 mol% or more, More preferably, it is 50 mol% or more.

  If an example of the manufacturing method of the raw material urethane polymer in this invention is given, excess diisocyanate will react previously with a polyol, the prepolymer of a terminal isocyanate group will be obtained, and the obtained prepolymer will be bifunctional. An active hydrogen-containing compound, a monoactive hydrogen compound having a tertiary nitrogen group, and a monoactive hydrogen-containing compound are reacted.

  In this production method, in addition to the prepolymer to be produced, polyol and unreacted diisocyanate also exist, so a small amount of low molecular weight reacted with a monoactive hydrogen compound having tertiary nitrogen groups at both ends of the diisocyanate. A compound is formed at the same time. Therefore, the isocyanate group equivalent of the diisocyanate to the polyol at the time of prepolymer production is preferably 1.1 to 2.0 times equivalent, more preferably 1.3 to 1.8 times the hydroxyl equivalent of the polyol. Is equivalent.

The reaction of the bifunctional active hydrogen-containing compound, the monoactive hydrogen compound having a tertiary group, and the monoactive hydrogen-containing compound with respect to the terminal isocyanate group of the prepolymer is effective to react the active group of these compounds with respect to the terminal isocyanate group. Can be obtained by a substantially equivalent reaction. Although this reaction can be performed in the presence of a solvent or in the absence of a solvent, it is preferably performed in the presence of a solvent with stirring.
Preferable solvents include amide solvents which are inert to isocyanate groups such as dimethylacetamide (hereinafter abbreviated as DMAc) and dimesylformamide.

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 (0.5 wt%) of DMAC is 99.5 g, η is the number of seconds dropped in a dilute solution by an Ostwald viscometer, and η ₀ is the number of seconds dropped only by DMAc by the viscometer).

  The polyurethane polymer thus obtained is further added to known organic or inorganic compound heat stabilizers, antioxidants, UV inhibitors, yellowing inhibitors, thermal discoloration inhibitors and hydrogels useful for polyurethane polymers. You may add the stabilizer of the polyurethane with respect to the chlorine agent for disinfection of pool water, such as a talcite, a huntite, and a zinc oxide. The polyurethaneurea elastic fiber of the present invention may contain various stabilizers, pigments and the like as required as long as the effects of the present invention are not impaired.

  For example, phenolic antioxidants include 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,9-bis [2- [3- [3- Tert-butyl-4-hydroxy-5methylphenyl] propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane, triethylene glycol-bis (3-t -Butyl-4-hydroxy-5-methylphenyl) propionate, a hindered phenol compound having a molecular weight of at least about 300 having at least one hindered hydroxyphenyl group, a polymer of p-cresol and divinylbenzene, p- Polymer of cresol and dicyclopentadiene, polymer of p-chloromethylstyrene and p-cresol It is raised. Benzotriazole and benzophenone drugs such as “Tinubin” manufactured by Ciba Geigy, Inc. Phosphorus drugs such as “Sumilyzer” P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amine drugs, inorganic such as titanium oxide and carbon black Pigment, fluororesin powder or silicone resin powder, metal soap such as magnesium stearate, bactericides, deodorizers including silver, zinc and these compounds, lubricants 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 polymer composition thus obtained can be formed into a fiber by a conventionally known dry spinning method.
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 obtained in this way may be used as a bare thread as it is in practice, and other fibers such as polyamide fiber, wool, cotton, regenerated fiber, polyester fiber and the like are conventionally known. It can also be used as a coated elastic fiber by coating with a 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.

  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.

  The polyurethane elastic fiber of the present invention can also be used for tights, pantyhose, foundation, socks, mouth rubber, corset, surgical bandage, string, woven fabric and knitted swimsuit. In particular, it is preferably used for applications selected from the group consisting of inner, outer, legs, sports wear, jeans, swimwear and sanitary materials.

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) Evaluation of spinning stability A spinning stock solution produced according to the method described in the following examples was spun for 24 hours by the method described in the examples, and the number of yarn breaks (times / hour) was measured. It can be said that the lower the number of yarns, the more stable the productivity.

(2) Number of seconds for thermal cutting The test yarn having an initial length of 14 cm is stretched to 50% to 21 cm and pressed against a cylindrical heating body filled with silicon oil having a diameter of 6 cm and having a surface temperature controlled at 185 ° C. 1 cm), and measure the number of seconds from the start of contact until cutting. If the number of seconds is long, the heat resistance is high, and if the heat resistance is low, a fabric pinhole defect due to yarn cutting is likely to occur in the heat setter process during fabric processing.

(3) Heat set rate measuring method The heat set rate was calculated | required with the following measurements and numerical formula. After stretching and fixing the elastic yarn of length Ld0 in a non-tensioned and straight state to 2.0 times the length, it passes through a tenter box adjusted to 185 ± 1 ° C. as it is, and the tenter box passage time is 30 Second, immediately take out the elastic yarn, let it twist at a length of Ld0 or less, relax sufficiently, and leave it at room temperature for 16 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.
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.

Then, it was put into a liquid flow dyeing machine, and a scouring agent (score roll FC-250 manufactured by Kao Co., Ltd.) 2 g / L was put in the liquid for scouring, followed by scouring 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) Fastness to washing dyeing of fabric Evaluation was made by JIS L0844 discoloration.
The detergent used at that time is a detergent brand name “Attack” 2 g / L manufactured by Kao Corporation. After washing for 30 minutes each under the condition of a washing liquid temperature of 80 ° C., rinsing with running water for 30 minutes, dehydration, and room temperature (20 ° C. , 65% RH), and 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) Dye fastness after dry cleaning treatment of dough Evaluation was performed according to JIS L-0860.
When the polyurethane elastic fiber of the present invention is subjected to a dry cleaning test of a disperse dye dyeing product, the liquid contamination is preferably third or higher. When the liquid contamination evaluation in this dry cleaning test is less than the third grade, the dry cleaning fastness of the fiber material obtained by dyeing the mixed fabric of polyurethane elastic fiber and disperse dyeable fiber with the disperse dye is obtained. It may not be possible.

[1] Preparation of bare polyurethane elastic fiber knitted fabric for evaluation test 1.2 g of bare polyurethane elastic fiber knitted fabric knitted with polyurethane elastic fiber using a circular knitting machine (CR-C type, Koike Machinery Co., Ltd.) Weigh and fasten 4.8 g of bare knitted fabric made of polyester fiber and the surface together, put it in a stainless steel container, I. Disperse Blue 167 (benzeneazo disperse dye) 5% owf, bath ratio 1:50, pH 5.0, dyed at 130 ° C. for 30 minutes. The dyed polyurethane elastic fiber and the polyester fiber are subjected to a reduction washing treatment at 80 ° C. for 20 minutes at a hydrosulfite of 1.6 g / l and a caustic soda of 1.6 g / l and a bath ratio of 1:50. The resulting polyurethane elastic fiber bare knitted fabric is washed with water and air-dried for evaluation.

[2] Preparation of polyurethane elastic fiber / polyester fiber mixed fabric for evaluation test Polyester fiber 55 decitex / 24 filament made of polyurethane elastic fiber and polyethylene terephthalate is knitted in a normal manner so that the mixture ratio of polyurethane elastic fiber is 20%. A 6-course satin net knitted fabric was obtained under the conditions. This mixed fabric was made into C.I. I. Disperse Blue 167 (benzeneazo disperse dye) is dyed at 130 ° C. for 30 minutes at 5% owf, bath ratio 1:50, pH 5.0. Subsequently, this dyed fabric is subjected to a reduction washing treatment at 80 ° C. for 20 minutes at 1.6 g / l hydrosulfite and 1.6 g / l caustic soda at a bath ratio of 1:50. The obtained dyed / knitted fabric of polyurethane elastic fiber and polyester fiber is washed with water and air-dried, and used for evaluation.

[3] Contamination of dry cleaning liquid A dry cleaning test is performed according to JIS L-0860, and 8 ml of the dry cleaning liquid and the dirt liquid after the dry cleaning test are collected in a porcelain container (20 m / m × 40 m / m × 10 m / m). The degree of color fading was determined by comparing the degree of liquid contamination with the gray scale for contamination.

Example 1
(Production of urethane polymer whose terminal is a tertiary nitrogen group)
400 g of polytetramethylene ether diol having a number average molecular weight of 1800 and 91.7 g of 4,4′-diphenylmethane diisocyanate were reacted under stirring in a dry nitrogen atmosphere at 80 ° C. for 3 hours. In this case, the charged value of polyol and diisocyanate (abbreviated as N value) = (isocyanate equivalent of diisocyanate) / (hydroxyl equivalent of polyol) is 1.65. In this way, a urethane prepolymer having an isocyanate group at the end was obtained. The urethane prepolymer was cooled to room temperature and dissolved in 500 g of DMAc, and 37.6 g of diethylaminopropylamine was dissolved in 300 g of DMAc while cooling and maintaining vigorously stirring at a temperature of 20 ° C. to 30 ° C. The solution was added dropwise. After completion of the dropwise addition, stirring was further continued for 2 hours.
A part of this solution was taken, and from the measurement results of IR, NMR and GPC, it was confirmed that it was a polyurethane polymer represented by the target formula (1) having a number average molecular weight of 5800. In the same manner, polyurethane polymers represented by various formulas (1) were prepared using various raw materials described in Table 1.

(Example 2)
(Manufacture of stock solution for spinning)
A terminal polymerization reaction was conducted by reacting 400 g of polytetramethylene ether diol having a number average molecular weight of 1800, which is a single polymerization diol, with 91.7 g of 4,4′-diphenylmethane diisocyanate under a dry nitrogen atmosphere at 80 ° C. for 3 hours with stirring. An isocyanate-capped urethane prepolymer was obtained. After cooling this to room temperature, 720 g of dimethylacetamide was added and dissolved to prepare a urethane prepolymer solution. Meanwhile, 8.11 g of ethylenediamine and 1.37 g of diethylamine were dissolved in 390 g of dimethylacetamide, and this was added to the prepolymer solution at room temperature to obtain a polyurethane solution having a viscosity of 3500 poise (30 ° C.).

  Next, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate was added to the DMAc solution of the polyurethane polymer represented by the various formulas (1) shown in Table 1. The solution which was added and uniformly dissolved and dispersed by high-speed stirring was added to the polyurethane solution and stirred to obtain a uniform stock solution for spinning. In addition, the amount of the isocyanurate was 1% by weight, and the amount of the polyurethane polymer represented by the formula (1) was the weight% described in Table 2 with respect to the polyurethane polymer.

(Manufacture of polyurethane elastic fiber)
After defoaming the above spinning stock solution, the DMAc (dimethylacetamide) solvent was evaporated by extruding into hot air at about 230 ° C. through the pores of 16 spinnerets (each of which has 4 pores). I let you. The dried yarn is false twisted, passed through a godet roller, oiled with dimethyl silicon as a main component on an oiling roller, wound onto a paper tube at a speed of 700 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 1-4)
The polyurethane polymer represented by the formula (1) was not added (Comparative Example 1), and the conventional additives shown in Table 2 were added instead of the polyurethane polymer represented by the formula (1) (Comparison Except for Examples 2 to 4), polyurethane elastic fibers were produced in the same manner as in Example 2 and evaluated. Various evaluation results of the obtained polyurethane elastic fiber are shown in Table 2.

(Example 3)
(Polyurethane polymerization is carried out using a tertiary nitrogen group-containing monoactive hydrogen compound as a part of the terminal terminator, and simultaneously adding and mixing the polyurethane polymer whose terminal group is a tertiary nitrogen group in the polyurethane polymer. Preparation of spinning dope and production of polyurethane elastic fiber)
Urethane whose end is capped with isocyanate by reacting 400 g of polytetramethylene ether diol having a number average molecular weight of 1800 with 91.7 g of 4,4′-diphenylmethane diisocyanate in a dry nitrogen atmosphere at 80 ° C. for 3 hours with stirring. A prepolymer was obtained. After cooling this to room temperature, 720 g of dimethylacetamide was added and dissolved to prepare a urethane prepolymer solution. On the other hand, 8.111 g of ethylenediamine, 1.98 g of diethylaminopropylamine and 0.26 g of diethylamine were dissolved in 390 g of dimethylacetamide, and this was added to the prepolymer solution at room temperature to give a polyurethane solution having a viscosity of 2950 poise (30 ° C.). Got. A part of this solution was taken, and from the measurement results of IR, NMR and GPC, the polyurethane polymer represented by the formula (1) having a number average molecular weight of 67,000 was contained in an amount of 27% by weight relative to other polyurethane polymers. It was confirmed that A DMAc solution of 1% by mass of 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate based on the polyurethane polymer is added to the polyurethane polymer solution and stirred. As a result, a uniform stock solution for spinning was obtained.
A polyurethane elastic fiber was obtained in the same manner as in Example 2 by using the obtained stock solution for spinning. Various evaluation results of the obtained polyurethane elastic fiber are shown in Table 3. In Table 3, the result of Comparative Example 1 is also shown as an example using only diethylamine as a terminal stopper.

  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.

Claims (3)

As a polyurethane polymer, 0.01-30 weight% of other polyurethane polymers contain the polyurethane polymer whose terminal group shown by the following (1) formula whose number average molecular weight is 2000-100000 is a tertiary nitrogen group. Polyurethane elastic fiber characterized by the above.

(R ¹ and R ² are the same or different carbon atoms is a linear or branched alkyl or hydroxyalkyl group having 1 to 10, or R ¹ and R ² are bonded, the nitrogen atom to which they are attached And R ³ is a linear or branched alkylene group having 1 to 8 carbon atoms, an ethyleneoxy group having 1 to 5 repeating units, or a propyleneoxy group having 1 to 5 repeating units. R ⁴ is a diisocyanate residue, X is a urethane bond or urea bond, R ⁵ and R ⁶ are the same or different diisocyanate residues, P is a diol residue, and Q is a diamine residue UT is a urethane bond, UA is a urea bond, k, m, and n are positive numbers, and either m or n may be 0.)   2. The method for producing a polyurethane elastic fiber according to claim 1, wherein a polyurethane polymer produced using a terminal stopper containing 10 mol% or more of a monoactive hydrogen compound having a tertiary nitrogen group is spun. .   The method for producing a polyurethane elastic fiber according to claim 2, wherein the monoactive hydrogen compound has an amino group or a hydroxyl group.