JP6425409B2 - Polyurethane elastic fiber and method for producing the same - Google Patents

Description

  In the present invention, by using a metal soap comprising 12-hydroxystearate metal salt and metal stearate, stable production during spinning, filament cohesion, release from paper tube, friction against metal, etc. And a method of manufacturing the same. Further, the present invention relates to a polyurethane elastic fiber having the above-mentioned properties further improved by using the above-mentioned metal soap in combination with a polyether-modified silicone and / or a polycarboxylic acid-based copolymer compound, and a method for producing the same.

  More specifically, the present invention improves the high-speed spinning stability of fine yarn and the friction characteristics of the fiber surface, and the residual tension of the yarn wound on a paper tube is small, and the winding shape is good, and warping, weaving, knitting The present invention relates to a polyurethane elastic fiber which has good metal abrasion resistance in the process, less thread breakage and less variation in friction stress, and as a result, can obtain a good fabric surface quality of commercial value. In addition, a viscosity stabilized metal soap composition comprising a metal soap comprising 12-hydroxystearate metal salt, a metal stearate comprising a metal salt and an amide solvent and the like used to obtain such polyurethane elastic fiber, and a composition thereof Manufacturing method of polyurethane elastic fiber using a metal.

  Polyurethane elastic fibers obtained from 4,4'-diphenylmethane diisocyanate, polyhydroxy polymers and polyfunctional active hydrogen-containing compounds have a high degree of rubber elasticity, excellent mechanical properties such as tensile stress, recoverability, and heat It is widely used in products such as disposable diapers, foundations, legs, sportswear, medical textile materials and the like because it also has excellent properties with regard to its behavioral behavior. However, the polyurethane elastic fiber itself is strongly sticky and has a flexible rubber thread-like property, so that the release failure of the yarn wound from the paper tube from the inner layer portion, and further, the wrinkles of the warper. Also, the metal friction with the knitting needles of the knitting machine is poor, and the range of friction fluctuation is large, so the processing characteristics are inferior, and the finished fabric is likely to have an uneven surface quality. Therefore, there is a problem that the commercial value of the fabric decreases.

Furthermore, in recent years, technological development of polyurethane elastic fibers that stably spin thin yarns of 5 to 20 dtex per single yarn at a high speed of 1000 m / min or more is advanced due to demand for thinning of fabrics and production cost reduction. ing.
In addition, when the solid content concentration is 10% or more, the dispersion consisting of a metal salt of stearic acid and an amide solvent has a high viscosity even immediately after the dispersion, and the fluidity of the dispersion decreases during storage, and the viscosity is There is also a problem of poor viscosity stability such as rising.

  Magnesium stearate has been widely used as an internal additive for polyurethane elastic fibers and as a component in silicone oils as a post-treatment agent for the surface of fibers in order to improve the friction properties of polyurethane elastic yarns. Applicants have disclosed polyurethane elastic fibers (see Patent Document 1 below) containing a fatty acid metal salt and a polycarboxylic acid-based copolymer compound, a polyurethane polymer, an amide-based solvent, a fatty acid metal salt, and a polycarboxylic acid-based copolymer compound. The proposal of the polyurethane composition (refer the following patent document 2) containing was performed.

However, with regard to the proposal of the above polyurethane elastic fiber, the improvement effect of the yarn shrinkage and friction property at the time of high-speed spinning of fine yarn of 1000 m / min or more is not yet at a sufficiently satisfactory level. When the concentration of the fatty acid metal salt is increased, the fatty acid metal salt tends to aggregate and the viscosity tends to increase, and the viscosity increases with time during storage in the storage tank, which causes the fatty acid metal salt to pass through the piping. There has been a problem that transport of the composition to the spinning process becomes difficult.
The polyurethane elastic fiber using the fatty acid metal salt composition with such increased viscosity is released from the yarn in the inner layer of the paper with time by pseudo adhesion while being wound and stored in a paper tube. It becomes difficult, and there is a problem that the inner layer yarn can not be used and is discarded.

  In addition, as a means for improving the frictional properties of polyurethane elastic fibers, it has been proposed to add a combination of metal soap and silicone and modified silicone to a polyurethane polymer solution before spinning (see Patent Documents 3 and 4 below). However, in this case, metal salts of stearic acid and silicone used as metal soaps do not have sufficient affinity for polyurethane polymers and amide solvents, so metal salts of stearic acid which are finely dispersed once are in the polymer stock solution. Flocculation and separation occur with time, causing fine threads during high-speed spinning of fine threads, or silicone transfer to the fiber surface during solvent drying in the spinning cylinder, which makes the threads and threads slippery, paper There was a problem that the shape of the tube thread winding was deformed, and yarn warping occurred during warping.

  Furthermore, the applicant has proposed a polyurethane elastic fiber suitable for pantyhose obtained by adding polyether-modified silicone alone into a polyurethane polymer (see Patent Document 5 below). However, as described in paragraph [0020] of Patent Document 5, in the case of multifilament elastic fiber, ether-modified silicone added internally is likely to move to the surface of single yarn and cause single yarn peeling, for example, two In the elastic fiber to which the multifilaments are bonded, the single yarn may be separated during the covering process to be separated into two filaments, which may cause yarn breakage in the covering process.

That is, although conventionally used magnesium stearate and silicones have the advantage of improving the friction characteristics of polyurethane elastic fibers, on the other hand, since they have low affinity with polyurethane polymers and amide solvents, various types of agents are used. There was a problem.
In addition, with regard to the combination of a metal salt of stearic acid and a polycarboxylic acid-based copolymer compound, there has been a problem that yarn thinning occurs at the time of high-speed spinning of fine yarn.

JP, 2012-207332, A JP 2012-193259 A Japanese Patent Application Publication No. 2007-100248 Japanese Patent Application Publication No. 2007-100251 Unexamined-Japanese-Patent No. 2004-332126

  An object of the present invention is to provide a polyurethane elastic fiber which can be stably spun for a long time when spinning a fine yarn at a high speed, has excellent friction characteristics, and is excellent in improving the quality of a fabric. Another object of the present invention is a metal soap composition containing a metal salt of stearic acid for use in the production of such polyurethane elastic fiber, which has a low viscosity even at high concentration, during storage in a storage tank An object of the present invention is to provide a metal soap composition in which the increase in viscosity with time is suppressed and the piping can be easily transported to the spinning process.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the polyurethane elastic fiber and the metal soap composition used for its manufacture, in order to solve the said subject, the present inventors are a polyurethane polymer, its amide system solvent, and any of a stearic-acid metal salt. When the metal salt of 12-hydroxystearate having good affinity is also used in combination, the aggregation of the metal salt of stearate in the spinning stock solution can be remarkably improved, and further, it is possible to further modify the ether modified silicone and / or polycarboxylic acid. By using the copolymer compound in combination, further improvement was observed, and it was found that the production of high speed spinning of fine yarn can be stabilized for a long time. That is, the present invention is as follows.

(1) relative to the polyurethane polymer 100 parts by weight, a metal soap consisting of 12-hydroxystearic acid metal salt and stearic acid metal salt has chromatic 0.001 parts by weight, and 12-hydroxystearic acid metal salt A polyurethane elastic fiber characterized in that the weight ratio of the metal salt to the metal salt of stearic acid (metal salt of 12-hydroxystearic acid / metal salt of stearic acid) is 50/50 to 10/90 .
(2) The polyurethane elastic fiber according to (1) above, wherein the metal constituting the metal soap is selected from the group consisting of magnesium, calcium, aluminum, zinc and barium.
(3) The polyurethane elastic fiber according to (1) or (2) above, having 0.0001 to 2 parts by weight of polyether-modified silicone per 100 parts by weight of the polyurethane polymer.
(4) relative to the polyurethane polymer 100 parts by weight, the polycarboxylic acid-based copolymer compound Propelled by one 0.0001 parts by weight, and said polycarboxylic acid-based copolymer compound, and a polyoxyalkylene derivative The polyurethane elastic fiber according to any one of the above (1) to (3), which is a compound copolymerized with an unsaturated carboxylic acid compound and having a polycarboxylic acid group in the main chain and a polyoxyalkylene group in the graft chain. .
(5) The method for producing a polyurethane elastic fiber according to any one of the above (1) to (4) , which is spun by a dry spinning method.

  The polyurethane elastic fiber having a metal soap consisting of a metal salt of 12-hydroxystearate and a metal salt of a stearate according to the present invention has a high speed of fine thread because the aggregation of the metal soap in the process and in the spinning nozzle is suppressed. During spinning, long-term stable spinning can be performed, and the obtained polyurethane elastic fiber is also capable of smoothly releasing the yarn from the inner layer of the paper in the step of producing the fabric, having excellent metal friction characteristics, and further having a filament As bonding between the two is also good, there is less yarn shrinkage at the time of processing due to filament breakage of multifilaments, and the finished fabric has a good quality and a high commercial value. In addition, the metal soap composition of the present invention used for producing polyurethane elastic fibers has a low viscosity even at high concentrations, and also has a low viscosity increase with time and is excellent in stability of viscosity.

It is the schematic of the metal friction evaluation apparatus of the test thread | yarn in this invention. It is a figure which shows an example of the measurement result in cohesion evaluation. It is a figure which shows an example of the measurement result in metal friction evaluation.

The present invention will be described in detail below.
The polyurethane elastic fiber of the present invention is characterized by having 0.001 to 5 parts by weight of a metal soap consisting of a metal salt of 12-hydroxystearic acid and a metal salt of stearic acid per 100 parts by weight of the polyurethane polymer. .
Since magnesium stearate, which is conventionally used frequently in polyurethane elastic fibers, has low stearyl group polarity, it has low affinity with polyurethane polymers and their amide solvents.
On the other hand, the 12-hydroxy stearin metal salt used in the present invention is characterized in that the polarity of the stearyl group is improved by the hydroxyl group present in its chemical structure and at the same time it has a low polarity group derived from stearyl residue. . That is, due to the presence of a hydroxyl group, the 12-hydroxystearyl metal salt has good affinity to both the polyurethane polymer and the amide solvent, and further, because it has a hydroxyl group on the side chain of the stearyl group, this is a steric hindrance. It is believed that the effect is to suppress aggregation of the metal stearate. That is, the metal salt of 12-hydroxystearate used in the present invention has an affinity to any of polyurethane, amide solvents and metal stearate, so stearic acid in an amide solution of a polyurethane polymer can be used. It is thought that it plays a role as a dispersing agent which also suppresses the aggregation of metal salts.

  The blending amount of metal soap consisting of 12-hydroxystearin metal salt and metal stearate is 0.001 to 5 parts by weight with respect to 100 parts by weight of polyurethane polymer, and less than 0.001 part by weight improves friction The effect can not be fully realized. If it exceeds 5 parts by weight, the effect is saturated and it is not economical and scum is likely to occur. The preferred compounding amount of the metal soap is 0.005 to 3 parts by weight.

The weight ratio of metal 12-hydroxystearate to metal stearate constituting the metal soap used in the present invention (metal 12-hydroxystearate / stearate metal salt) is 98/2 to 2/98. Is preferred.
The viscosity stability of the metal soap composition in an amide based solvent is reduced whether the ratio by weight of 12-hydroxystearate metal salt to metal stearate is less than 2/98 or greater than 98/2. Further, since 12-hydroxystearic acid metal salt is more expensive than metallic stearate, it is economically advantageous to use 12-hydroxystearic acid metal salt in a lower blending ratio. The preferred parts by weight ratio of metal 12-hydroxystearate to metal stearate is 70/30 to 2/98. More preferably, it is 50/50 to 5/95.

  The metal constituting the metal soap composed of 12-hydroxystearate metal salt and metal stearate is preferably selected from the group consisting of magnesium, calcium, aluminum, zinc and barium. More preferably, they are magnesium, calcium, aluminum and zinc. Particularly preferred are magnesium and calcium salts.

The polyurethane elastic fiber of the present invention preferably contains 0.0001 to 2 parts by weight of the polyether-modified silicone with respect to 100 parts by weight of the polyurethane polymer.
The polyether-modified silicone which can be used in the present invention is a side-chain polyether-modified silicone and / or a both-end-type polyether-modified silicone, and among these, one or more kinds of them may be used. The preferable HLB characteristic value of polyether modified silicone is 0-17. More preferable HLB characteristic values are 0 to 15, and particularly preferable HLB values are 0 to 8. Polyether modified silicone has a combination of a polar group derived from a polyether group and a less polar group derived from a silicone group. The polyether-modified silicone is in common with the metal salt of 12-hydroxystearate in that it is a substance having both polar and nonpolar groups in the molecule, and the polyether-modified silicone and the metal salt of 12-hydroxystearate mutually It is thought that, when used in combination, they have a synergistic effect on the role of the dispersant with respect to the metal stearate.

  Specific examples of the polyether-modified silicone used in the present invention include Shin-Etsu Chemical Co., Ltd. trade names X-22-4952, X-22-2427, X-22-6266, KF-6123, and KF-. 351A, KF-352A, KF-353, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6020, KF- 6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X22-2516 and the like. Among these, they can be used alone or in combination. Preferred compounds are X-22-4952, X-22-2427, X-22-6123, KF-945, KF-6020, KF-6015, X-22-2516. A particularly preferred compound is X-22-4952.

The viscosity at 25 ° C. of the polyether-modified silicone that can be used in the present invention is 1000 mm ² / s or less, preferably 600 mm ² / s or less, and more preferably 300 mm ² / s or less. A high viscosity material having a viscosity of more than 1000 mm ² / s is preferably a low viscosity material because there is a problem that bubbles do not easily disappear when vacuum degassing the spinning stock solution.
The blending amount of the polyether modified silicone is preferably 0.0001 to 2 parts by weight, and more preferably 0.0002 to 1 parts by weight with respect to 100 parts by weight of the polyurethane polymer. If the amount is less than 0.0001 parts by weight, the above-mentioned effect obtained by the present invention is insufficient, and if it exceeds 2 parts by weight, the fiber becomes slippery, and the winding shape of the thread wound around the paper tube is easily deformed Become.

The polyurethane elastic fiber of the present invention preferably has 0.0001 to 2 parts by weight of a polycarboxylic acid-based copolymer compound based on 100 parts by weight of the polyurethane polymer.
The polycarboxylic acid-based copolymer compound used in the present invention preferably has both a polyether group and a carboxylic acid group in its structure, and the hydrophilic polyether group is 12-hydroxystearic acid. Good affinity with metal salts and amide solvents. In addition, the carboxylic acid group has an affinity for the carbonyl group of the metal soap used in the present invention, and the polycarboxylic acid type copolymer compound is also an amide type with respect to metal stearate and metal 12-hydroxystearate. It is believed that the dispersant effect is exhibited in the solvent. Furthermore, when vacuum degassing in the case of using the above-mentioned ether-modified silicone, there is a problem that air bubbles are hard to disappear, but it was found that the improvement can be greatly achieved by using a polycarboxylic acid copolymer together.

Examples of such polycarboxylic acid-based copolymer compounds include copolymer compounds of a polyoxyalkylene derivative and an unsaturated carboxylic acid compound, and compounds having a polycarboxylic acid group in the main chain and a polyoxyalkylene group in the graft chain Be
The above-mentioned polycarboxylic acid-based copolymer compounds are described in detail in Japanese Patent Application Laid-Open No. 2012-193259 filed by the present applicant. As a specific example of a preferable polycarboxylic acid type copolymer compound, the trade name Maria Lim AKM-0531 made by NOF Corporation, AFB-0561, AFB-1521, AAB-0851, AEM-3511, AWS-0851 etc. can give. Further preferred compounds are AKM-0531 and AAB-0851.
The preferable blending amount of the polycarboxylic acid-based copolymer compound is 0.0001 to 2 parts by weight, more preferably 0.0002 to 1 parts by weight to 100 parts by weight of the polyurethane polymer based on 100 parts by weight of the polyurethane polymer. It is a department. If the amount is less than 0.0001 parts by weight, the effect is small, and if it is more than 2 parts by weight, the effect does not change and it is not economical.

  The metal salt of 12-hydroxystearic acid and the metal salt of stearic acid constituting the metal soap can be dispersed in an amide-based solvent and added separately or simultaneously to the polymer stock solution before spinning at an appropriate stage. The 12-hydroxystearic acid metal salt and the stearic acid metal salt are integrated and mixed and dispersed in an amide solvent, or dispersed separately in an amide solvent, and then uniformly mixed, and then processed in the polymer stock solution before spinning Can be added at an appropriate stage of It is better to lower the viscosity of the dispersion, stabilize the viscosity over time, and obtain particles with a narrow particle size distribution if the metal salt of 12-hydroxystearate and the metal salt of stearic acid are uniformly mixed in advance and then dispersed and micronized. preferable. It is considered that this is because the metal salt of 12-hydroxystearate and the metal salt of stearate interact with each other in the dispersion step. At this time, the polyether-modified silicone and the polycarboxylic acid-based copolymer compound used in the present invention may also be mixed with the metal soap after being co-dispersed or separately added and dispersed. The metal salt of 12-hydroxystearic acid and metal salt of stearic acid and polyether modified silicone and / or polycarboxylic acid copolymer may be added before or after polymerization of polyurethane polymer, but usually polyurethane prepolymer Is reacted with the chain extender and then added to the polyurethane polymer.

Next, an amide-based solvent, metal soap consisting of a metal salt of 12-hydroxystearate and a metal salt of stearic acid, polyether-modified silicone, and a copolymer of polycarboxylic acid, which are used to produce the polyurethane elastic fiber of the present invention The metal soap composition containing
When the metal soap is uniformly dispersed in an amide solvent by using a metal soap consisting of a metal salt of 12-hydroxystearate and a metal salt of stearic acid in combination with a polyether modified silicone and a polycarboxylic acid copolymer, a dispersion solution Production of dispersion solution with less change in viscosity and time-lapse change during storage, enabling filter flow stability in the process of polyurethane elastic fiber production and further spinning stabilization of high-speed spinning of fine yarn It turned out to do.

  The amide solvent used in the present invention is preferably at least one amide solvent selected from the group consisting of dimethylacetamide and dimethylformamide, and the amount of the amide solvent is 100 to 100 parts by weight of the metal soap. The amount is preferably 1000 parts by weight, more preferably 150 to 800 parts by weight.

  Various known pulverizing methods can be used for the above-mentioned dispersion and micronization, and among them, a wet pulverizing method of pulverizing after being mixed or dissolved in a solvent is preferable. As a grinder used for wet grinding, various wet grinders, such as a vertical bead mill, a horizontal bead mill, a sand grinder, a colloid mill, a ball mill, etc., can be used. When the 12-hydroxystearate metal salt and the stearic acid metal salt are integrally made into fine particles, since the affinity to the amide solvent is improved, it is possible to disperse even using a homomixer or a line mixer. Is also possible, in this case the temperature which can be used for dispersion is 10-110.degree. Specifically, in the case of a mixture of magnesium 12-hydroxystearate and magnesium stearate, it is dispersed at a high speed using a homomixer or line mixer in a state of being uniformly dissolved in an amide solvent at about 90 ° C. Gradually cooling to room temperature while dispersing at high speed, or at high speed, has the advantage of maintaining particulate morphology. The obtained dispersion has low viscosity and little change in viscosity with time, and stable transport to the spinning process is easy, and it is uniformly added to the polyurethane polymer before spinning using a static mixer etc. It can be mixed. On the other hand, when magnesium stearate alone is subjected to the same treatment, when it is cooled to room temperature, the magnesium stearate rapidly precipitates, so that the particles become large and the shape of the fine particles can not be maintained. The advantage of dispersing using a homomixer or line mixer is that the particle size is not too fine and the distribution is narrower than when dispersed using a bead mill, so the problem of viscosity increase over time due to reaggregation due to fine particles It can be avoided.

  When the metal soap composition is a single use of a metal salt of stearic acid, thickening at about 15% by weight, or aging at 50 ° C., there is a problem that the fluidity is greatly reduced in several days. On the other hand, the concentration of the metal soap composition of the metal soap of 12-hydroxystearate and metal stearate according to the present invention is as high as the solid concentration of about 40% by weight in the dimethylacetamide solution. It is fluid and can be maintained at 50 ° C. for long periods of time.

In the present invention, the preferred particle size of the metal salt of 12-hydroxystearate and metal salt of stearic acid is measured in an amide solvent, for example, in dimethylacetamide, and the average particle size is larger than 1 μm and smaller than 20 μm.
Small particles with an average particle size of 1 μm or less tend to reaggregate and become large particles, and are likely to be clogged with a filter or a spinneret. Large particles of 20 μm or more tend to cause clogging of the filter in the process and yarn squeezing during high-speed spinning of fine yarns. A further preferable average particle size is 2 to 10 μm.

  The polyurethane constituting the polyurethane elastic fiber of the present invention has hydroxyl groups at both ends, and a molecular weight of 600 to 4000, substantially on-line polymers, such as polyester diols and polyethers consisting of homo or copolymer Diol, polyester amide diol, polycarbonate ester diol, polyacrylic diol, polythioester diol, polythioether diol, polyhydrocarbon diol or a mixture thereof or a copolymer thereof, an organic diisocyanate and a polyfunctional active hydrogen atom A chain extender having, for example, a polyol, a polyamine, a hydroxylamine, a hydrazine, a polyhydrazide, a polysemicarbazide, water, a mixture thereof, or the like as a main component. Further details are described in paragraphs [0043] to [0049] of JP 2012-207332A.

The polyurethane elastic fiber of the present invention includes other metal soaps such as palmitic acid, myristic acid, eicosanoic acid, docosanoic acid, lauric acid, araquinic acid, behenic acid, octanoic acid, fatty acids such as tall oil fatty acid, abietic acid, neo Resin acids such as abietic acid, d-pimaric acid, iso-d-pimaric acid, podocarp acid, agarten dicarboxylic acid, benzoic acid, cinnamic acid, p-oxycinnamic acid, diterpenic acid or organic acids such as naphthenic acid It is also possible to use a metal salt in combination.
Furthermore, other commonly used compounds such as ultraviolet light absorbers, antioxidants, light stabilizers, gas resistant stabilizers, coloring agents, matting agents, fillers and the like may be used in combination.

  The polyurethane elastic fiber of the present invention can be produced by a conventionally known melt spinning method, wet spinning method or dry spinning method. The preferred production method is a dry spinning method, which uses a polyurethane spinning solution prepared by dissolving a polyurethane polymer in a solvent capable of dissolving a polyurethane polymer such as dimethylacetamide and dimethylformamide, and stably thins threads for a long time by high speed spinning. The dry spinning method that can be produced is preferred. The preferred polymer solids concentration of the polyurethane spinning solution in dry spinning is 20 to 50% by weight, and if the concentration is less than 20% by weight, there is a risk that the desolvation may be incomplete in the spinner during high speed spinning, If the concentration is more than 10%, the polyurethane spinning solution is unstable and easily causes a viscosity increase and a gelation phenomenon, which may cause yarn breakage during spinning. A more preferred concentration is 30 to 40% by weight.

  The preferred single yarn dtex of the polyurethane elastic fiber of the present invention is 5 to 20 dtex, and the further preferred single yarn dtex is 8 to 15. In the case of a thin yarn of less than 5 dtex, the frictional resistance between the high temperature air stream for solvent drying and the yarn increases in spinning at the time of spinning, yarn thinning occurs, and stable high-speed production becomes difficult. In addition, in the case of a thick fiber having a single yarn size larger than 20 dtex, the drying of the solvent from the inside of the fiber is delayed, so the spinning speed needs to be greatly reduced, which causes a problem of an increase in production cost.

  The preferable total number of filaments of the polyurethane elastic fiber of the present invention is mono and multifilament elastic fibers consisting of 1 to 100 filaments, and the particularly preferable total number of filaments is 1 to 80 filaments. In the case of multifilaments, several multifilaments are temporarily twisted and bonded in the spinning cylinder using a rotating ring or a rotating air flow in the spinning process, so that the filaments are bonded together even if they are multifilaments, It looks like an elastic fiber and is wound up.

  The metal salt of 12-hydroxystearate in the present invention has high affinity to polyurethane polymers and amide solvents, and the migration to the fiber surface is relatively eased during solvent volatilization in the fiber formation process in the spinning tower. After being spun, it is wound into a paper tube and gradually transferred to the surface of the fiber, which contributes to the improvement of the friction resistance of the guide and the knitting needle during metal processing. In the spinning tower, since the precipitation is suppressed and the influence of lowering the cohesion of the filaments is small, it is presumed that cohesion becomes strong.

  On the other hand, since metal stearates have low affinity to solvents and polymers, they are deposited on the fiber surface before being dried in the spinning tower, which is considered to inhibit the coalescence of single yarns in the spinning tower. Be However, if the 12-hydroxystearic acid metal salt is used in combination, precipitation of the stearic acid metal salt on the yarn surface can be suppressed. The bondability of the multifilament single yarn of polyurethane elastic fiber is stronger bondability as compared with the case of using only stearic acid metal salt, and the single yarn by the friction resistance of the guide, in the fabric processing process There is also little thread breakage due to cracking.

  On the other hand, the advantage of using metal stearates is that deposition on the fiber surface begins relatively quickly during the spinning process and tends to migrate to the fiber surface before the yarn is wound up. Therefore, since the fiber reduces the frictional resistance of the yarn against the metal godet roll or traverse guide that contacts before being wound into the paper tube, the residual tension of the yarn wound on the paper tube on the package is low and the tension fluctuation is There are also few. That is, as an advantage of using a metal salt of 12-hydroxystearate and a metal salt of stearate together, the stability to friction with a guide or metal until the yarn is wound up from the inside of the spinning tower to the paper tube is metal stearate. Is effective, and 12-hydroxystearate metal salt is effective for the cohesion between the winding form of the paper tube and the single yarn, and the two are effective in complementing each other. The metal soap consisting of 12-hydroxystearate metal salt and metal stearate may be mixed with the polymer stock solution before spinning, or it may be used by solvent-drying the yarn from the nozzle in the spinning cylinder. It may be attached to the fiber surface as a component composition in silicone oil used before winding into a tube.

  That is, when winding the yarn obtained after spinning, the ratio of polyalkyl siloxane having a kinematic viscosity of 5 to 50 centistokes at 25 ° C. and mineral oil having a kinematic viscosity of 30 to 70 centistokes at 25 ° C. is 100 0.1 to 10 parts by weight of an oil component having a weight ratio of 0:50 to 50, and 0.1 to 10 parts by weight of metal soap consisting of a metal salt of 12-hydroxystearate and a metal salt of stearate with respect to 100 parts by weight of the oil component; It is a manufacturing method of polyurethane elastic fiber which adheres a textiles processing agent containing 0.001-5 weight sections of polymers, and 0.00001-5 weight sections of polyether denaturation silicone to yarn.

In this case, the metal soap used in the present invention has a good affinity to the polyurethane polymer and is uniformly dispersed on the fiber surface. As a result, a polyurethane elastic fiber having a good frictional property and a small change in friction stress is obtained. Be That is, the polyurethane elastic fiber of the present invention is an embodiment in which the metal soap of the present invention is added to the polyurethane polymer before spinning and is present inside the polyurethane elastic fiber after spinning, a portion of the metal soap is aged from the inside of the fiber It includes an embodiment in which the resin is transferred to the surface of the fiber and an embodiment in which a metal soap is attached as a post-treatment agent before being wound as a component of the silicone oil agent into a paper tube. When the fiber treatment agent used in the present invention is micronized in a silicone oil, the metal salt of 12-hydroxystearate and the metal salt of stearate can be dispersed individually or in combination using the various dispersing groups described above. It is preferable to mix both in advance and uniformly dissolve and atomize while optionally raising the temperature, as a warrior treatment agent having a narrow particle size distribution of metal soap can be obtained.
In the polyurethane elastic fiber of the present invention, the thread wound shape wound around a paper tube is good without losing its shape. Since the polyurethane elastic fiber of the present invention has good processing characteristics, the quality of the obtained fabric is uniform and the commercial value is also high.

Hereinafter, the present invention will be described in detail by way of examples and comparative examples. However, the present invention is not limited to only these examples. The various measurement methods described in the examples were performed using the methods described below.
(1) <Method of measuring viscosity>
It measured under atmosphere of 25 ° C using Toki Sangyo Co., Ltd. make TVE-20H type E viscosity meter.

(2) <Method of measuring average particle size of metal soap>
Using a solution of metal soap uniformly dispersed in the form of slurry in dimethylacetamide solvent beforehand, drop several drops of sample solution with a Beckman Coulter LS13-320 particle size distribution analyzer using dimethylacetamide solvent After adjusting to the proper measurable concentration of this device, the average particle size was determined from the measurement value on the basis of the volumetric statistic value.

(3) <Method of spinning polyurethane elastic fiber>
After degassing the stock solution for polyurethane elastic fiber under reduced pressure, using a 400 mesh wire mesh filter as a spinneret filter, in a hot air 210 from the pores of a spinning nozzle (the nozzle has 4 or 2 pores) The solvent was evaporated by pumping to ° C. The dried yarn is false-twisted in the process of passing it to a ring false twister, passes through a godet roller, and adheres to the polyurethane elastic fiber 5% by weight of an oiling agent component consisting mainly of polyalkylsiloxane and mineral oil on an oiling roller. Then, 500 g of polyurethane elastic fibers of 22 dtex / 2 filaments and 44 dtex / 4 filaments (single yarn fineness 11 dtex) were wound on a paper tube at a speed of 1020 m / min. The strength and elongation physical properties of the produced yarn and the residual solvent were within the range of suitability as a polyurethane elastic fiber. Various evaluations were performed using this elastic fiber.

(4) <Method of measuring physical properties of strength and elongation>
The elastic fiber of 22 dtex / 2 filaments was measured using a tensile tester ORIENTEC Co., Ltd. UTM-III-100 type. The sample was set in a tensile tester at a grip interval of 50 mm, and measured under conditions of a tensile speed of 500 mm / min, a temperature of 20 ° C., and a humidity of 65% RH.

(5) <Method for evaluating spinning stability and discharge pressure increase rate>
The number of yarn breaks which occurred during 24 hours of spinning at 22 dtex / 2 filament spinning was evaluated. In addition, when a 400 mesh wire mesh filter was used as a filter medium, an increase in discharge pressure (kgf / cm ² ) after 24 hours was determined as a discharge pressure increase rate.

(6) <Method for evaluating winding form of yarn on paper tube>
500 g of polyurethane elastic fiber of 22 dtex / 2 filaments (single yarn fineness 11 dtex) was wound on a paper tube at a speed of 1020 m / min. The state of the winding form of the yarn wound around the paper tube was comprehensively evaluated by visual judgment of five persons in accordance with the following evaluation criteria.
○: The winding form of the yarn on the paper tube is in order and beautiful.
Δ: The winding shape of the yarn on the paper tube is starting to break up a little.
X: The winding form of the yarn on the paper tube is broken so much that it is not beautiful.

(7) <Method of evaluating release of polyurethane elastic fiber from paper tube>
After leaving the paper tube at 45 ° C. and 65% RH for 30 days, place the paper tube on a textured roller and rotate the roller at a roller surface speed of 40 m / min. Send out. The fed elastic fiber is wound on a satin roller of the same diameter installed at a distance of 50 cm. The surface velocity on the take-up roller is gradually reduced by 80 m / min, elastic fiber is caught in the paper tube and reverse-wound in the paper tube on the delivery roller, and the speed Sm / s when elastic fiber is cut and not sent out Measure the minutes. The smaller the value of Sm / min, the better the separation of the elastic yarn from the paper tube, and it is judged that the releasability is good.
However, if the yarn separation is too good, on the other hand, the outer layer of the elastic fiber wound on the paper tube tends to fall off when transporting the polyurethane elastic fiber wound on the paper tube, which causes a handling problem, There is a proper range. In this measurement, S (hereinafter referred to as SO) of elastic fibers of preferable outer layer of paper tube is SO = 45 to 55 m / min, S (hereinafter referred to as SI) of elastic fibers of inner layer of paper is SI = 50 to 65 m / Min. It is judged whether SI and SO fall within this range. If any of SI and SO is out of this range, if the value is small, it is easy to drop the yarn during transportation or warping process, and conversely, if the value is large, reverse winding to the paper tube or yarn breakage often occur. Yes, it becomes a problem.

(8) <Method for evaluating bonding of polyurethane elastic fiber>
A tensile tester, Orientec Co., Ltd. UTM-III-100 was used. The temperature was measured by the following method under the conditions of a temperature of 20 ° C. and a humidity of 65% RH. The filament of 22 dtex / 2 filaments is manually torn apart into two single yarns. After each filament is set to tear the crotch separately on the upper and lower chucks, the stress measurement is initiated in the same manner as the tenacity measurement.
When measurement is made so as to tear a single yarn, the portion where the bonding is strong shows high stress, and the portion where the bonding is weak shows a low value. The polyurethane elastic fiber having a small fluctuation range and a large average stress value can be judged to be strong and good in the cohesiveness of the filaments.
An example of a measurement result is shown in FIG. As shown in FIG. 2, the average value and fluctuation range of stress are determined from the measurement chart. If the average value stress (a) is large and the fluctuation range (b) is small with the measurement start as a baseline, it can be judged that the polyurethane elastic fiber has a strong cohesiveness of the filaments and is good. In FIG. 2, (1) is an example in which the cohesion is good, and (2) is an example in which the cohesion is poor.

(9) <Metal friction evaluation method>
The elastic fiber of 44 dtex / 4 filament was evaluated using the apparatus of FIG. 1 after being left for 30 days in an atmosphere of 25 ° C. and 65% RH. In FIG. 1, 1 is a test yarn, 2 is a delivery roller, 3 is a tension meter, 4 is a knitting needle, 5 is a winding portion, 6 is a winding roller, 7 is a test yarn running thread, and 8 is a thread applied to the knitting needle Is 29 ° at the angle that The test yarn was run at a feed rate of 100 m / min and a take-up speed of 200 m / min and a draw ratio of 2 times, and the running stress of the yarn of the test thread before and after passing through the knitting needles and its stress variation were measured. FIG. 3 shows an example of the measurement result, and T1 and T2 are 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, respectively. The coefficient of friction μd is given by the following equation (1).
μd = Ln (T1 / T2) /2.6376 Formula (1)
The smaller the friction coefficient μd, the smaller the friction and the better.

(10) <Warning and knitting methods of fabric preparation>
Attach 588 elastic fibers of 44 dtex / 4 filament to the elastic yarn warper manufactured by River Co., and carry out elastic fiber feeding speed 150 m / min, beam winding speed 300 m / min, elastic fiber per beam 16 beams of 14.7 kg by weight were warped. The polyurethane elastic fibers thus warped were used as test yarns for the back, nylon 66 processed yarns 44 dtex / 34 filaments as the front, warped with a draft rate of 80%, and knitted under the half fabric knitting conditions of the following conditions.
<Organization condition>
Knitting machine: 36 gauge / inch KARL MAYER Tricot knitting machine Organization: Front 10/23, back 12/10
Runner length: Front 120 cm / 480 course
Back 77.6 cm / 480 course Aircraft course: 100 course / inch 20 anti-knitted in the condition of 15 kg / 1 anti in this knitting process.

(11) <Determination method of fabric quality>
The obtained warp knitting machine was refined at 90 ° C. for 1 minute, and treated as a heat treatment condition at a temperature of 190 ° C. for 60 seconds, using a tenter finisher as a preset. Then, it was stained at 100 ° C. for 60 minutes using a jet flow dyeing machine. As a final set, a tenter finishing machine was used, and heat treatment conditions were performed at 180 ° C. for 45 seconds to obtain a dyed reverse of a warp knitted fabric. The fabric quality of the warp knitted fabric obtained by interlacing the test yarn and the nylon yarn was comprehensively evaluated by visual judgment of five persons according to the following evaluation criteria.
◎: There is almost no striation and it is very beautiful.
○: The melancholy muscle is inconspicuous and beautiful.
Δ: Trans-muscular line slightly visible.
X: There are many threads and not beautiful.

[Reference Example 1] (Production of polyurethane polymer solution and stock solution for spinning (A))
166.6 parts by weight of polytetramethylene glycol having an average molecular weight of 2000 and 31.2 parts by weight of 4,4'-diphenylmethane diisocyanate are reacted with stirring in a nitrogen gas stream at 95 ° C for 80 minutes, leaving isocyanate groups at both ends The obtained prepolymer was obtained. Then, after cooling to room temperature, 270 parts by weight of dimethylacetamide was added and dissolved to obtain a prepolymer solution.
On the other hand, 2.34 parts by weight of ethylene diamine and 0.37 parts by weight of diethylamine are dissolved in 157 parts by weight of dimethylacetamide and added to the prepolymer solution at room temperature to obtain a polyurethane polymer solution with a viscosity of 2050 poise (30 ° C.) I got In the viscous polymer solution thus obtained, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3 in terms of polymer solids of polyurethane polymer. 1.5% by weight of 5-triazine-2,4,6- (1H, 3H, 5H) -trione (trade name CYANOX 1790), 2- (2'-hydroxy-3'-t-butyl-5'-methyl 0.5 wt% of phenyl) -5-chloro-benzotriazole was added to prepare a spinning solution (A).

[Reference Example 2] (Production of 15% by weight metal soap dispersion: bead mill dispersion method)
A solution of magnesium stearate (26.25 Kg) and magnesium 12-hydroxystearate (11.25 Kg) in dimethyl acetamide solvent (212.5 Kg) was stirred and mixed for 10 minutes to form a 15 wt% solution. This solution was treated for a circulation time equivalent to 2 passes using a wet bead mill (Ashizawa Finetech Co., Ltd., trade name Star mill LME-20 type) containing zirconia beads of 0.5 mm to prepare a dispersion. did. As a result of measuring this dispersion with a particle size distribution analyzer, the average particle size was 1.3 μm.

[Reference Example 3] (Production of 35% by weight metal soap dispersion: Homomixer dispersion method)
245.0 g of magnesium stearate, 105.0 g of magnesium 12-hydroxystearate, and 650.0 g of dimethylacetamide are added to a 2 L dispersion beaker set with a homomixer (TKROBO MICS, manufactured by Tokushu Kika Kogyo Co., Ltd.) Of 35% by weight of metal soap in dimethylacetamide. Further, 30.0 g of Shin-Etsu Chemical Co., Ltd. trade name X-22-4952 and 10.0 g of NOF Corporation trade name Maririm AKM-0531 were added. This solution was heated up from room temperature to 90 ° C. while stirring at high speed with a homomixer, and then slowly cooled to room temperature while stirring to prepare a dispersion. As a result of measuring this dispersion with a particle size distribution analyzer, the average particle size was 1.8 μm. The viscosity of the dispersion immediately after production was 90 mPa · s. The viscosity after standing for 10 days at 50 ° C. was 100 mPa · s, it was fluid, and the change in viscosity was also small and stable. The particle size distribution showed a narrow distribution with fewer particles being smaller than that obtained by dispersing the same composition using a wet bead mill.

[Examples 1 to 6, Reference Example 4 and Comparative Examples 1 and 2]
In the same manner as in Reference Example 2, the dispersion composition described in Table 1 was made into a dispersion solution containing 15% by weight of metal soap, and depending on the composition, simultaneously, modified silicone and / or polycarboxylic acid was used. The copolymer compound was added in a predetermined amount as shown in Table 1 and wet bead milled to prepare a dispersion. The measured viscosity of the obtained dispersion immediately after preparation and the viscosity after standing at 50 ° C. for 10 days are shown in Table 1.
Next, each dispersion obtained was added to the stock solution for spinning (A) prepared in Reference Example 1, and mixed uniformly to prepare each stock solution for spinning. However, the addition amount was adjusted so as to be the composition shown in Table 1 with respect to 100 parts by weight of the polyurethane polymer.
The polyurethane elastic fiber was manufactured according to the above-mentioned <spinning method of polyurethane elastic fiber> using each obtained spinning solution, and various evaluations were performed using the obtained yarn. The results are shown in Table 2.

[Examples 8 to 10 and Comparative Examples 3 and 4]
22 dtex / 2 filaments and 44 dtex / 4 filaments polyurethane elastic fibers are produced according to the above-mentioned <Method of spinning polyurethane elastic fibers> using the stock solution for spinning (A) prepared in Reference Example 1, and each is a paper tube Prior to winding, 5 parts by weight of each fiber treatment agent composition shown in Table 3 was uniformly attached by a nozzle oiling device to 100 parts by weight of polyurethane elastic fiber, and 500 g of each polyurethane elastic fiber was wound up. The results of various evaluations using the obtained yarn are shown in Table 4.

  The polyurethane elastic fiber according to the present invention can be stably spun for a long time even in the production of fine yarn, has few yarn breakages in the processing step, and has good metal friction characteristics. Therefore, the fabric produced using this polyurethane elastic fiber is uniform in surface quality and excellent in commercial value.

1 Test yarn 2 Delivery roller 3 Tension meter 4 Knitting needle 5 Take-up section 6 Winding roller 7 Test yarn running yarn 8 Angle formed by yarn applied to knitting needle = 29 °

Claims (5)

To the polyurethane polymer 100 parts by weight, a metal soap consisting of 12-hydroxystearic acid metal salt and stearic acid metal salt has chromatic 0.001 parts by weight, and 12-hydroxystearic acid metal salt and stearic acid A polyurethane elastic fiber characterized in that a weight ratio of metal salt (metal 12-hydroxystearate / metal stearate) is 50/50 to 10/90 . The metal constituting the metallic soap is magnesium, calcium, aluminum, selected from the group consisting of zinc and barium, polyurethane elastic fiber according to claim 1. The polyurethane elastic fiber according to claim 1 or 2 , wherein the polyether modified silicone is contained in an amount of 0.0001 to 2 parts by weight with respect to 100 parts by weight of the polyurethane polymer. To the polyurethane polymer 100 parts by weight, the polycarboxylic acid-based copolymer compound Propelled by one 0.0001 parts by weight, and said polycarboxylic acid-based copolymer compound, polyoxyalkylene derivatives and unsaturated carboxylic The polyurethane elastic fiber according to any one of claims 1 to 3 , which is a compound copolymerized with an acid compound and having a polycarboxylic acid group in its main chain and a polyoxyalkylene group in its graft chain . The method for producing a polyurethane elastic fiber according to any one of claims 1 to 4 , characterized in that it is spun by a dry spinning method.

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