JP2015206151A - Polyurethane elastic fiber and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane elastic fiber that has excellent production stability at high speed spinning, and also has a metal friction property with excellent unwindability from a package and excellent fiber processability.SOLUTION: A polyurethane elastic fiber comprises, based on polyurethane polymer of 100 pts. wt., 0.001-3 pts. wt. of fatty acid metal salt having 10-30 carbon atoms, 0.00001-5 pts. wt. of polycarboxylic acid copolymerization compound, and 0.00001-5 pts. wt. of polyether-modified silicone.

Description

  The present invention relates to a polyurethane elastic fiber. More specifically, the present invention is excellent in spinning production stability obtained by dry spinning using a spinning stock solution and a fiber treatment agent in which aggregation of fatty acid metal salts is suppressed, and has good unwinding from the package. The present invention relates to a polyurethane elastic fiber having a metal friction property with good workability.

  Polyurethane elastic fibers have high elongation and excellent elastic properties. However, since polyurethane polymer is a flexible and sticky material, yarn breakage due to frictional resistance at the guide and rollers in the spinning process, and yarn breakage and friction fluctuations due to knitting needles and guides in the fabric processing process. If the dough is made easy to receive, the quality of the dough tends to deteriorate.

  In order to improve these, a fatty acid metal salt is added to the spinning stock solution of the polyurethane elastic fiber, or a fiber treatment agent containing the fatty acid metal salt is adhered when winding the fiber during spinning. Furthermore, in recent years, the trend of polyurethane elastic fiber manufacturing technology is toward further fineness (5 to 20 dtex) and cost reduction, and for this reason, high-speed winding spinning has been developed. However, when a partially agglomerated fatty acid metal salt is mixed in the spinning dope, yarn breakage frequently occurs in the spinning process, resulting in a significant reduction in productivity. Therefore, many filters are installed in the piping through which the spinning solution passes to remove aggregates. In addition, a metal laminated filter having a pore size (cut of a particle size of 20 μm to 50 μm) is also incorporated in the spinning nozzle immediately before spinning to eliminate aggregates.

  If the fatty acid metal salt is poorly dispersed, the filter must be frequently replaced due to clogging. When the fatty acid metal salt is simply mixed in the spinning dope, the fatty acid metal salt is not stably dispersed in the spinning dope, and aggregates are likely to be generated during the process. Due to a decrease in the content of the fatty acid metal salt and uneven distribution on the fiber surface, the package shape of the package also deteriorates. Furthermore, in the processing process from fiber to fabric, unwinding failure from the package and smoothness of the fiber deteriorate.

  Further, in order to improve the fabric processability of the polyurethane elastic fiber, a fatty acid metal salt is blended together with silicone oil and mineral oil in the fiber surface treating agent component in the take-up winding. However, fatty acid metal salts tend to aggregate even in oil components. For this reason, clogging of the processing agent-provided oil nozzle and accumulation due to aggregation of fatty acid metal salts occur on the oil roller, causing adhesion spots on the fiber surface, thread breakage, and further to the fabric. During the processing, fatty acid metal salt scum is generated on the guide, roller, knitting needle, etc., and there is a problem that the smoothness of the fiber and the friction against metal are greatly reduced.

  Many attempts have been made to solve the technical problem of stabilizing the dispersion of fatty acid metal salts used in polyurethane elastic fibers. For example, in Patent Documents 1 and 2 below, a specific organic phosphoric acid-containing compound is used as a dispersant for a fatty acid metal salt for a spinning dope, and in Patent Document 3 below, a specific nitrogen-containing compound is used. However, Patent Documents 4 and 5 below disclose that silicone oil, a fatty acid metal salt, and a modified silicone compound are used in combination. The present applicant also discloses a polyurethane elastic fiber containing a fatty acid metal salt and a polycarboxylic acid-based copolymer compound in the following Patent Document 6, and a polyurethane polymer, an amide solvent, a fatty acid metal salt, and a polycarboxylic acid system in the following Patent Document 7: A polyurethane composition containing a copolymer compound was proposed. However, with regard to these proposals, the effect of improving the yarn cracking and frictional properties at the time of spinning at a high speed of 1000 m / min or more is not yet sufficiently satisfactory, and the fatty acid metal salt concentration in the solvent is increased. In addition, the viscosity of the dispersion increases, and further, the viscosity increases with time even during storage in the storage tank, which makes it difficult to transport the fatty acid metal salt composition to the spinning process through the pipe. there were.

  Patent Documents 8 to 10 listed below disclose the use of silicone, amino-modified silicone, fatty acid metal salt and organic carboxylic acid as a fiber treatment agent. However, these fiber treatment agents also have low dispersion stability, and problems have arisen due to aggregation of fatty acid metal salts of the fiber treatment agent, particularly in summer. Further, in the step of attaching the fiber treatment agent to the fiber, it is necessary to keep the oil viscosity constant in order to uniformly apply a certain amount of oil to the fiber. Therefore, since the temperature of the fiber treatment agent bath is set to around 50 ° C., there is a problem that the aggregation of the fatty acid metal salt in the treatment agent bath is more likely to proceed.

  As described above, many attempts have been made to improve the smoothness and friction of polyurethane elastic fibers of fatty acid metal salts, but there are still various problems in polyurethane elastic fibers when using a spinning solution or a fiber treatment agent. It has not yet been fully resolved.

Special table 2003-527476 gazette Japanese Patent No. 4397028 JP 2006-219768 A JP 2009-287126 A JP 2007-1000025 A JP 2012-207332 A JP 2012-193259 A Japanese Patent Laid-Open No. 11-12951 JP 2002-371467 A JP 2009-179889 A

  The problem to be solved by the present invention is to provide a polyurethane elastic fiber obtained by using a spinning dope and / or a fiber treating agent in which aggregation of fatty acid metal salts is suppressed. That is, it is to provide a polyurethane elastic fiber that is excellent in production stability during high-speed spinning, and has a metal friction property that is excellent in unwinding from the package and fiber processability.

  In general, fatty acid metal salts are poor in affinity with amide solvents for dissolving polyurethane polymers and silicone oil as a fiber treatment agent. Therefore, before mixing, fine particles with an average particle size of solid fine particles of 1 μm or less are used. However, in the amide solvent or silicone oil, the aggregation progresses to form aggregate particles of several tens of μm, and the filters present at various places are blocked during the process. Even in fatty acid metal salts that have been mechanically dispersed in a silicone oil with a mill or the like and then finely divided into particles of 1 μm or less, aggregation proceeds with time, so that the temperature is 30 ° C. or less during mechanical dispersion and storage. Preferably, when the temperature is not lower than 20 ° C., aggregates of fatty acid metal salts are formed, which causes clogging of the treatment agent nozzle and causes problems in the dough processing step when adhering to the fibers. That is, finding a suitable dispersant for a fatty acid metal salt in a liquid of an amide solvent or silicone oil is a point for solving the above problem.

As a result of earnestly examining and repeating experiments from such a viewpoint, the present inventors have used a specific polycarboxylic acid copolymer compound and a specific polyether-modified silicone in combination with a fatty acid metal salt in both amide solvents and silicone oils. As a result, it was found that the dispersibility of the fatty acid metal salt was remarkably improved, and the present invention was completed.
That is, the present invention is as follows.

[1] 0.001 to 3 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms, 0.00001 to 5 parts by weight of a polycarboxylic acid copolymer compound and a polyether with respect to 100 parts by weight of a polyurethane polymer A polyurethane elastic fiber comprising 0.00001 to 5 parts by weight of modified silicone.
[2] The above 1 characterized in that the fatty acid constituting the fatty acid metal salt is selected from the group consisting of stearic acid and palmitic acid, and the constituent metal is selected from the group consisting of magnesium, calcium, aluminum and zinc. The polyurethane elastic fiber according to Item.
[3] The polycarboxylic acid copolymer compound is a copolymer compound of a polyoxyalkylene derivative and an unsaturated carboxylic acid compound, and has a polycarboxylic acid group in its main chain and a polyoxyalkylene group in its graft chain. 3. The polyurethane elastic fiber as described in 1 or 2 above, wherein
[4] The polyurethane elastic fiber as described in any one of 1 to 3 above, wherein the polyether-modified silicone is a side-chain polyether-modified silicone and / or a both-end polyether-modified silicone.
[5] The polyurethane as described in any one of 1 to 4 above, wherein the polyether-modified silicone has an HLB characteristic value of 0 to 16 and a viscosity at 25 ° C. of 1000 mm ² / s or less. Elastic fiber.
[6] 100 parts by weight of a polyurethane polymer, 0.001 to 3 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms and 1000001 parts by weight of a polycarboxylic acid copolymer compound with respect to 100 parts by weight of the polyurethane polymer 5 steps by weight and polyether modified silicone 0.00001-5 parts by weight dissolved and mixed in an amide solvent to prepare a spinning dope, spinning the obtained spinning dope by a dry spinning method, and obtained The method for producing a polyurethane elastic fiber according to any one of 1 to 5 above, which comprises a step of winding a yarn.
[7] A step of preparing a spinning stock solution by dissolving and mixing a polyurethane polymer in an amide solvent, a step of spinning the obtained spinning stock solution by a dry spinning method, and a kinematic viscosity at 25 ° C. of 5 to 50 centistokes An oil component having a ratio (polyalkylsiloxane / mineral oil) of 100/0 to 50/50 of a polyalkylsiloxane and a mineral oil having a kinematic viscosity at 25 ° C. of 30 to 70 centistokes, and 100 parts by weight of the oil component And 0.1 to 10 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms, 0.001 to 5 parts by weight of a polycarboxylic acid copolymer, and 0.00001 to 5 parts by weight of a polyether-modified silicone. The polyurethane bullet according to any one of 1 to 5 above, comprising a step of adhering a fiber treating agent to a spun yarn and a step of winding the yarn after adhesion. Method for producing a fiber.

  The polyurethane elastic fiber of the present invention has a fatty acid metal salt, a specific polycarboxylic acid copolymer compound and a specific polyether-modified silicone, the fatty acid metal salt is stably dispersed, and there is little yarn breakage during spinning, It is a polyurethane elastic fiber with excellent fabric processing stability. In the polyurethane elastic fiber of the present invention, the well-dispersed fatty acid metal salt is contained in the fiber or attached to the fiber surface at one or both of the stages before and after the spinning process. And a package with a good ridge shape can be obtained. In the polyurethane elastic fiber of the present invention, since the fatty acid metal salt is uniformly dispersed in the fiber and on the surface of the yarn, the function of the fatty acid metal salt is effectively exhibited. As a result, the surface quality of the fabric surface is good. We guess that we can obtain a fabric with high commercial value.

It is the schematic of the metal-friction evaluation apparatus of the test yarn in this invention. It is an example of the chart which measured the cohesiveness of the test yarn in this invention. It is an example of the chart which measured the metal friction property of the test thread | yarn in this invention.

  The polyurethane elastic fiber of the present invention comprises 0.001 to 3 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms and 0.00001 to 5 parts by weight of a polycarboxylic acid copolymer compound with respect to 100 parts by weight of the polyurethane polymer. And a polyurethane elastic fiber containing 0.00001 to 5 parts by weight of a polyether-modified silicone.

  The fatty acid constituting the fatty acid metal salt having 10 to 30 carbon atoms used in the present invention is preferably stearic acid or palmitic acid, and the constituent metal is preferably selected from magnesium, calcium, aluminum and zinc. Specific examples of preferable fatty acid metal salts include magnesium stearate, magnesium palmitate, calcium stearate, and calcium palmitate. The fatty acid metal salt is attached to or contained in the polyurethane elastic fiber in an amount of 0.001 to 3 parts by weight, preferably 0.005 to 2 parts by weight, based on 100 parts by weight of the polyurethane polymer. If it is less than 0.001 part by weight, it is not effective, and if it exceeds 3 parts by weight, the effect is not changed and it is not economical. On the other hand, the elastic function such as the high elongation property of the fiber is lowered, or the frictional property between the fibers is Lowering causes thread slipping, resulting in poor package winding shape.

  The polycarboxylic acid copolymer compound used in the present invention is preferably a copolymer compound of a polyoxyalkylene derivative and an unsaturated carboxylic acid compound, a polycarboxylic acid group in its main chain, and its graft chain. A copolymer compound having a polyoxyalkylene group.

  Fatty acid metal salts have poor affinity with polyurethane polymer solvents and silicone fluids. In the polycarboxylic acid copolymer used in the present invention, the carbonyl group in the main chain faces the fatty acid metal salt side, and the polyoxyalkylene group in one graft chain has an affinity for the solvent or oil agent. Therefore, it is estimated that the dispersion stability in a solvent or an oil agent is improved. In order to exert such an effect, the blending amount of the polycarboxylic acid copolymer is preferably 0.00001 to 5 parts by weight, more preferably 0.00002 to 2 parts by weight with respect to 100 parts by weight of the polyurethane polymer. Part.

  The polycarboxylic acid-based copolymer compound used in the present invention is described in detail in JP 2012-193259 A by the present applicant. Specific examples of the polycarboxylic acid-based copolymer include NOM Corporation's product names Mariarim AKM-0531, AFB-0561, AFB-1521, AAB-0851, AEM3511, AWS-0551, and the like. Preferred compounds are AKM-0531, AAB-0851. These polycarboxylic acid copolymer compounds can be used alone or in combination.

  The polyether-modified silicone used in the present invention is preferably a side chain-type polyether-modified silicone and / or a both-end-type polyether-modified silicone, and these can be used alone or in combination of several kinds. The polyether modified silicone preferably has an HLB characteristic value of 0 to 16, more preferably an HLB characteristic value of 0 to 14, and particularly preferably an HLB characteristic value of 0 to 8.

Since the polyether-modified silicone has a lipophilic silicone group and a part of the polyether group, this has an affinity for the polyoxyalkylene group in the graft chain of the polycarboxylic acid copolymer, By using both in combination, it is considered that the function of one dispersant is synergistically exhibited with respect to the fatty acid metal salt. The viscosity of the polyether-modified silicone used in the present invention at 25 ° C. is preferably 1000 mm ² / s or less, more preferably 600 mm ² / s or less, particularly preferably 300 mm ² / s or less. A product having a viscosity higher than 1000 mm ² / s is preferably a low-viscosity product because there is a problem that bubbles are difficult to disappear when the spinning dope is degassed by vacuum.
Insufficient defoaming of the spinning dope will cause yarn cracking during spinning. However, it has also been found that the problem of poor defoaming when a high viscosity polyether-modified silicone is used can be greatly improved by the combined use of the polycarboxylic acid copolymer of the present invention.

  Specific examples of the polyether-modified silicone used in the present invention include trade names X-22-4952, X-22-4272, X-22-6266, KF-6123, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 351A, KF-352A, KF-353, KF-354L, KF-355A, KF615A, 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, and these can be used alone or in combination of several kinds thereof. Among these, preferred compounds are X-22-4952, X-22-2479, X-22-6123, KF-640, KF-945, KF-6020, KF-6015 and X-22-2516, especially Preferred compounds are X-22-4952 and X-22-4272.

  The blending amount of the polyether-modified silicone is preferably 0.00001 to 5 parts by weight, more preferably 0.0001 to 2 parts by weight, particularly preferably 0.0002 to 1 part by weight based on 100 parts by weight of the polyurethane polymer. It is. If the amount is less than 0.00001 part by weight, the effect is not achieved. If the amount exceeds 5 parts by weight, the elastic function such as the high elongation property of the fiber is lowered, and the frictional property between the fibers is lowered to cause yarn slippage. Occurs, and the winding shape of the package becomes worse.

  The polyurethane elastic fiber of the present invention is produced by blending a fatty acid metal salt, a polycarboxylic acid copolymer compound, and a polyether-modified silicone in a solvent that dissolves the polyurethane polymer, and is produced through a spinning process. Examples thereof include dimethylacetamide, dimethylformamide, and dimethylsulfoxide, and amide solvents such as dimethylacetamide and dimethylformamide are preferable.

The solid content concentration of the polyurethane polymer in the spinning dope is preferably 20% by weight or more and 50% by weight or less. Outside this range, yarn breakage tends to occur during high-speed spinning of fine yarn.
As a method for preparing a spinning dope comprising a fatty acid metal salt, a polycarboxylic acid copolymer compound and a polyether-modified silicone, (1) after mixing these three components uniformly in a solvent and adding them to a polyurethane polymer (2) A method in which a fatty acid metal salt is uniformly mixed and dispersed in a solvent in advance and added to a polyurethane polymer solution, and then a polycarboxylic acid copolymer and a polyether-modified silicone are mixed, (3) An example is a method in which a polyurethane polymer solution and a polycarboxylic acid copolymer are mixed and then mixed with a liquid in which a fatty acid metal salt and a polyether-modified silicone are uniformly dispersed in a solvent.

  Preferably, the fatty acid metal salt is previously uniformly treated with a polycarboxylic acid copolymer compound and a polyether-modified silicone, and then added to and mixed with the polyurethane polymer solution. Thereby, aggregation of the fatty acid metal salt in the solvent is further suppressed, and a spinning stock solution in which the dispersion state of the fatty acid metal salt is preferably maintained can be obtained.

As a method of pulverizing a polycarboxylic acid copolymer and a polyether-modified silicone mixed with a fatty acid metal salt, micronization and fine dispersion can be simultaneously performed using a ball mill, a bead mill or the like. More preferred is a wet bead mill from the viewpoint of uniform fine dispersion. As a method other than the wet bead mill, a high speed stirring homomixer or a line homomixer can be used.
In the case of using a wet bead mill or the like, a fatty acid metal salt having an average particle size of 50 to 100 μm can be used. However, in the case of using a homomixer, the fatty acid metal salt having an average particle size of 20 to 60 μm in a state before mixing with a solvent. Is preferably used.

  In the present invention, a fatty acid metal salt is uniformly and stably dispersed in a solvent and a polyurethane polymer by using a specific polycarboxylic acid copolymer and a specific polyether-modified silicone in combination, and the average particle size by volume distribution is determined. Can be obtained in a dispersion of 20 μm or less, more preferably 15 μm or less, and even more preferably 0.1 to 10 μm.

As spinning methods for spinning polyurethane elastic fibers, generally, a melt spinning method, a wet spinning method, and a dry spinning method are known. In the present invention, the spinning method is preferably a dry spinning method capable of stably producing fine yarns during high-speed spinning.
When the polyurethane elastic fiber of the present invention is spun and wound into a package, a polyalkylsiloxane having a kinematic viscosity at 25 ° C. of 5 to 50 centistokes and a mineral oil having a kinematic viscosity at 25 ° C. of 30 to 70 centistokes The yarn with a fiber treating agent comprising an oil component, a fatty acid metal salt, a polycarboxylic acid copolymer and a polyether-modified silicone, wherein the ratio of polyalkylsiloxane / mineral oil is 100/0 to 50/50 Can do.

  More specifically, when the polyurethane elastic fiber of the present invention is spun and wound into a package, a polyalkylsiloxane having a kinematic viscosity at 25 ° C. of 5 to 50 centistokes and a kinematic viscosity at 25 ° C. of 30 to 70 centistokes are used. An oil component having a ratio of 100/0 to 50/50 with a certain mineral oil, 0.1 to 10 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms based on 100 parts by weight of the oil component, polycarboxylic acid The yarn can be treated with a fiber treatment agent containing 0.001 to 5 parts by weight of a copolymer and 0.00001 to 5 parts by weight of a polyether-modified silicone. Other fiber treatment agents include modified silicone, phosphate compounds, mineral particles such as talc, silica, colloidal alumina, higher aliphatic alcohols, paraffin, polyethylene, solid wax at room temperature, colorants, rosin, pigments, Carbon black or the like may be further added as long as the effects of the present invention are not impaired.

The fiber treatment agent comprising these mixed compositions can be uniformly dispersed by a known method using a ball mill device, a bead mill device, or a homomixer device. It is preferable to uniformly disperse with a wet bead mill.
The amount of the fiber treatment agent attached to the polyurethane elastic fiber is preferably 0.5 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the polyurethane elastic fiber to which no treatment agent is applied. It is.

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

  The polyalkylene ether diol is a single or common polyalkylene ether diol in which one or two or more linear or branched alkylene groups having 2 to 10 carbon atoms are ether-bonded and the number average molecular weight is 500 to 6000. Polymerized polyalkylene ether diol. The copolymerized polyalkylene ether diol is a copolymerized polyalkylene ether diol in which an alkylene group is ether-bonded in a block shape or a random shape, and the number average molecular weight is 500 to 6000. 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. Is used, the diol component occupying 65 wt% to 85 wt% of the polyurethane component is amorphous, and the polyurethane polymer is more tacky, so that the effects of the present invention are more easily exhibited.

  An advantage of using a copolymerized diol is that the elastic function is further improved. When the copolymerized diol is used, the resulting polyurethane elastic fiber has an excellent elastic function, that is, a high breaking elongation, a small stress fluctuation with respect to the strain at the time of elongation, a small hysteresis loss of the stress at the time of elongation, and the like. Therefore, pantyhose and outerwear using polyurethane elastic fibers using copolymerized diols have excellent elastic functions, are excellent in wearing feeling, and are good textile products. 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.

  Examples of the diisocyanate used in the polyurethane polymer of the present invention include known aliphatic, alicyclic or aromatic organic diisocyanates having two isocyanate groups in the molecule, and these may be used alone or in combination. May be. 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 diisocyanate such as 4,4'-dicyclohexylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate is preferable. Further, as the organic diisocyanate, a compound having a blocked isocyanate group that is converted into a free isocyanate group may be used.

  The active hydrogen-containing compound that reacts with the isocyanate group used in the polyurethane polymer of the present invention is a conventional chain extender in the polyurethane polymer, that is, a molecular weight of 500 or less containing at least two hydrogen atoms that can react with isocyanate. Low molecular weight compounds can be used. Specific examples 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-5-155841, diols such as ethylene glycol, propylene glycol, and 1,4-butanediol, preferably ethylenediamine, 1,2-propylenediamine, and JP-A-5-155841. And the diamine compounds disclosed in Japanese Patent Publication. These compounds may be used alone or in admixture of two or more. Moreover, you may use together with the compound containing one active hydrogen which can react with isocyanate depending on the case.

  As a method for producing polyurethane using diisocyanate, polymer diol, and active hydrogen-containing compound, a known urethanization technique can be employed. The stoichiometric ratio of various compounds used in the present invention is such that the sum of the hydroxyl groups of the polymer diol and the active hydrogens of the active hydrogen-containing compound is 1.00 or more and 1.1 equivalents relative to the isocyanate group of the diisocyanate compound. It is preferable that it is less than.

The specific viscosity (ηsp / c) of the polyurethane polymer 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 an N, N′-dimethylacetamide solvent. Here, C is a solution viscosity (0.5 wt%) of polymer 0.5 g / DMAC 99.5 g, η is the number of seconds dropped in a dilute solution by an Ostwald viscometer, and η ₀ is a viscometer as above. This is the number of seconds that only the DMAC falls.

  Polyurethane polymers obtained in this way are heat stabilizers, antioxidants, UV inhibitors, yellowing inhibitors, thermal discoloration inhibitors, anti-pooling agents for known organic or inorganic compounds useful for polyurethane polymers. Bactericidal chlorine agents, colorants, rosin, pigments, carbon black, etc. may be further added.

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

Hereinafter, the present invention will be described in detail by examples and comparative examples. However, the present invention is not limited only to these examples. Various measurement methods described in Examples were performed using the methods described below.
(1) <Measurement method of viscosity>
It was measured under an atmosphere of 25 ° C. using a TVE-20H type E viscometer manufactured by Toki Sangyo Co., Ltd.
(2) <Measurement method of average particle diameter of fatty acid metal salt>
Using a solution of a fatty acid metal salt uniformly dispersed in a slurry form in advance in a dimethylacetamide solvent, a few drops of a sample solution are dropped with a LS13-320 type particle size distribution analyzer manufactured by Beckman Coulter Co., Ltd. using a dimethylacetamide solvent. Then, after adjusting to an appropriate measurable concentration of this apparatus, the average particle diameter was obtained from the measured value on the basis of the volume statistics value.

(3) <Polyurethane elastic fiber spinning method>
After defoaming the spinning stock solution for polyurethane elastic fiber under reduced pressure, using a 400-mesh wire mesh filter as the spinner filter, the hot nozzle 210 (from the spinneret has 4 or 2 pores) into the hot air 210 The solvent was evaporated by pushing out to ° C. The dried yarn is falsely twisted in the process of passing through a ring false twister, and the oil component mainly composed of polyalkylsiloxane and mineral oil is attached to the polyurethane elastic fiber by 5% by weight on the oiling roller via the Godet roller. Then, 500 g of polyurethane elastic fibers of 22 dtex / 2 filament and 44 dtex / 4 filament (single yarn fineness 11 dtex) were wound around a paper tube at a speed of 1020 m / min. The strength properties and residual solvent of the produced yarn were within the range suitable for polyurethane elastic fiber. Various evaluations were performed using this elastic fiber.

(4) <Method for measuring properties of high elongation>
The 22 decitex / 2 filament elastic fiber was measured using a UTM-III-100 model manufactured by Tenritech Co., Ltd. The sample was gripped in a tensile tester and set at an interval of 50 mm, and measurement was performed under the conditions of a tensile speed of 500 mm / min, a temperature of 20 ° C., and a humidity of 65 wt%.
(5) <Method for evaluating spinning stability and rate of increase in discharge pressure>
The evaluation was based on the number of yarn breaks that occurred during spinning for 24 hours at the time of 22 dtex / 2 filament spinning. Further, the discharge pressure increase (kgf / cm ² ) after 24 hours when a 400 mesh wire mesh filter was used as the filter medium was determined as the discharge pressure increase rate.

(6) <Evaluation method of winding form on paper tube>
At a speed of 1020 m / min, 500 g of polyurethane elastic fiber of 22 dtex / 2 filament (single yarn fineness 11 dtex) was wound around a paper tube. The state of the winding form of the yarn wound around the paper tube was comprehensively evaluated by visual judgment of five persons according to the following evaluation criteria, relatively between samples.
○: The winding form of the thread on the paper tube is in order and beautiful.
(Triangle | delta): The winding form of the thread | yarn on a paper tube has begun to collapse a little.
X: The winding form of the thread on the paper tube is greatly broken and not beautiful.

(7) <Method for evaluating release of polyurethane elastic fiber from paper tube>
After leaving 44 decitex / 4 filament polyurethane elastic fiber in an atmosphere of 45 ° C. and 65% RH for 30 days, place the paper tube on a satin roller and rotate the roller at a roller surface speed of 40 m / min. Send it out. The sent elastic fiber is wound up on a satin roller of the same diameter installed at a distance of 50 cm. The surface speed on the winding roller is gradually decreased from 80 m / min, and the elastic fiber is entangled with the paper tube on the feeding roller and wound backward, and the elastic fiber is cut and not sent out. Measure minutes. The smaller the value of Sm / min, the better the yarn separation of the elastic yarn from the paper tube, and this is judged to have good release properties.
However, if the thread separation is too good, when the polyurethane elastic fiber wound around the paper tube is transported, the yarn in the outer layer of the paper tube of the elastic fiber wound around the paper tube is likely to fall off, resulting in a handling problem. So there is an appropriate range. In this measurement, S (hereinafter referred to as SO) of the preferable elastic fiber of the outer layer of paper tube is SO = 45 to 55 m / min, and S (hereinafter referred to as SI) of the elastic fiber of the inner layer of paper tube is SI = 50 to 65 m. / Min. Judgment is made based on whether SI and SO are within this range. If the value of either SI or SO is outside this range, if the value is small, the yarn is likely to fall off during transportation or the warping process. Conversely, if the value is large, reverse winding or thread breakage around the paper tube may occur frequently. There is a problem.

(8) <Evaluation method for adhesion of polyurethane elastic fiber>
A tensile tester UTM-III-100 manufactured by Orientec Co., Ltd. was used. Measurement was performed by the following method under conditions of a temperature of 20 ° C. and a humidity of 65 wt%. The filament of 22 dtex / 2 filament is torn by hand and divided into two single yarns. After each of the single yarns is set on the upper and lower chucks so as to tear the crotch separately, stress measurement is started under the same conditions as the high elongation measurement. When the two single yarns are pulled apart and the stress is measured, the strongly bonded portion shows high stress, and the weakly bonded portion shows a low value.
FIG. 2 shows an example of the measurement result. As shown in FIG. 2, the average value and fluctuation range of the stress are obtained from the measurement chart. If the average stress (a) is large and the fluctuation range (b) is small with the measurement start as the baseline, it can be determined that the polyurethane elastic fiber has a good filament bonding property. In FIG. 2, (1) is an example with good bonding properties, and (2) is an example with poor bonding properties.

(9) <Metal friction evaluation method>
The 44 dtex / 4 filament elastic fiber was allowed to stand for 30 days in an atmosphere of 25 ° C. and 65% RH, and then evaluated using the apparatus shown in FIG. 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 traveling yarn shape, and 8 is a yarn shape applied to the knitting needle. Is an angle of 29 °. The test yarn was run at a draw rate of 2 times at a feed rate of 100 m / min and a take-up rate of 200 m / min, and the running stress of the yarn of the test yarn before and after passing the knitting needle and its stress fluctuation were measured. FIG. 3 shows an example of measurement results, where T1 and T2 are the central value (g) of running stress after passing through the knitting needle and the central value (g) of running stress before passing through the knitting needle, respectively. The friction coefficient μd is given by the following formula (1).
μd = Ln (T1 / T2) /2.6376 (1)
The smaller the value of the friction coefficient μd, the smaller the friction and the better.

(10) <Warning and knitting method for fabric creation>
588 elastic fibers of 44 decitex / 4 filament were attached to a warp machine for elastic yarn manufactured by River, and warped at an elastic fiber feeding speed of 150 m / min and a beam winding speed of 300 m / min. Weighed 14.7 kg with 16 beams. The warped polyurethane elastic fiber was used as the test yarn for the back, the nylon 66 processed yarn 44 dtex / 34 filament was used as the front, warped at a draft rate of 80%, and knitted under the half fabric knitting conditions of the following conditions.
<Knitting conditions>
Knitting machine: 36 gauge / inch Tricot knitting machine manufactured by KARL MAYER Organization: Front 10/23, Back 12/10
Runner length: Front 120cm / 480 course
Back 77.6 cm / 480 course On-machine course: 100 courses / inch In this knitting process, 20 knitted fabrics were knitted under the condition of 15 kg / 1 counterweight.

(11) <Evaluation method for 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. Subsequently, it dye | stained on the conditions for 100 degreeC x 60 minutes using the liquid-flow dyeing machine. As a final set, a tenter finisher was used and the heat treatment was performed at 180 ° C. for 45 seconds to obtain a warp knitted fabric. The fabric quality of the warp knitted fabric obtained by knitting the test yarn and the nylon yarn was comprehensively evaluated by visual judgment of five persons according to the following evaluation criteria, relatively between samples.
A: There are few meridians and it is very beautiful.
○: The meridians are inconspicuous and beautiful.
(Triangle | delta): A warp is slightly visually observed.
X: There are many meridians and it is not beautiful.

[Reference Example 1] (Production of polyurethane polymer solution and spinning stock solution (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 were reacted in a nitrogen gas stream at 95 ° C. with stirring for 80 minutes, so that both ends had residual isocyanate groups. A prepolymer was obtained. Next, 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 ethylenediamine and 0.37 parts by weight of diethylamine were dissolved in 157 parts by weight of dimethylacetamide, and this was added to the prepolymer solution at room temperature to give a polyurethane polymer solution having a viscosity of 2050 poise (30 ° C.). Got. To the viscous polymer solution thus obtained, 1,3,5-tris (4-tertiarybutyl-3-hydroxy-2,6-dimethylbenzyl) -1,3 in terms of polyurethane polymer solids. , 5-triazine-2,4,6- (1H, 3H, 5H) -trione (trade name CYANOX1790), 1.5% by weight, 2- (2′-hydroxy-3′-tert-butyl-5′-) A stock solution for spinning (A) was prepared by adding 0.5% by weight of methylphenyl) -5-chloro-benzotriazole.

[Reference Example 2] <Preparation of fatty acid metal salt dispersion 1>
1. 37.5 kg of magnesium stearate and 0.5 kg of polycarboxylic acid copolymer (trade name Marialim AKM-053 manufactured by NOF Corporation) and polyether-modified silicone (X-22-4952 manufactured by Shin-Etsu Chemical Co., Ltd.) 0 Kg was added to a dimethylacetamide solvent (212.5 Kg) and stirred for 20 minutes to adjust the concentration of magnesium stearate in the dimethylacetamide solvent to 15% by weight. Using a wet bead mill (trade name Star Mill LME-20, manufactured by Ashizawa Finetech Co., Ltd.) containing 0.5 mm zirconia beads, this dispersion solution is treated with a mill circulation time equivalent to 1.5 passes. A dispersion was made. As a result of measuring the obtained dispersion with a particle size distribution meter, the average particle size was 1.5 μm.
The viscosity at 25 ° C. immediately after preparation of this dispersion was 980 mm ² / s. The viscosity at 25 ° C. after 10 days at 50 ° C. was 1010 mm ² / s, and the viscosity was stable.

[Reference Example 3] <Production of fatty acid metal salt dispersion 2>
In the same manner as in Reference Example 2, the same treatment was carried out with the composition of magnesium stearate, polyether-modified silicone and dimethylacetamide solvent except that the polycarboxylic acid copolymer was removed from the composition of Reference Example 2, and a fatty acid metal salt A dispersion was prepared. The average particle diameter of the dispersion excluding the polycarboxylic acid copolymer was 1.5 μm.
The viscosity at 25 ° C. immediately after the preparation of this dispersion was 2990 mm ² / s. The viscosity at 25 ° C. after 10 days at 50 ° C. was 4880 mm ² / s and was thickened.

[Reference Example 4] <Preparation of fatty acid metal salt dispersion 3>
(3) In the same manner as in Reference Example 2, the same treatment was carried out with the composition of magnesium stearate, polycarboxylic acid copolymer and dimethylacetamide solvent excluding the polyether-modified silicone from the composition of Reference Example 2. A fatty acid metal salt dispersion was prepared. The average particle size of the obtained dispersion was 1.3 μm. The viscosity at 25 ° C. immediately after preparation of this dispersion was 1890 mm ² / s. The viscosity at 25 ° C. after 10 days of standing at 50 ° C. was 2170 mm ² / s and was slightly thickened.

[Examples 1 to 5 and Comparative Examples 1 and 2]
Dispersions prepared in the same manner as in Reference Examples 2 to 4 so as to have the compositions of Examples 1 to 5 and Comparative Examples 1 and 2 shown in Table 1 were used as the spinning dope (A) prepared in Reference Example 1. Each spinning dope was prepared by mixing uniformly. However, the addition amount was adjusted so as to have the composition shown in Table 1 with respect to 100 parts by weight of the polyurethane polymer.
Next, using the obtained spinning dope, polyurethane elastic fibers were produced according to the above <Method of spinning polyurethane elastic fibers>, and the results of various evaluations using the obtained yarns are shown in Table 2.

[Examples 6 and 7 and Comparative Examples 3 to 5]
Using the spinning dope (A) prepared in Reference Example 1, polyurethane elastic fibers of 22 dtex / 2 filaments and 44 dtex / 4 filaments were produced according to the above <Method of spinning polyurethane elastic fibers>. However, as the oil agent to be attached before winding on the paper tube, each fiber treatment agent composition shown in Table 3 is used, and 5 parts by weight of the fiber treatment agent is uniformly attached to 100 parts by weight of the polyurethane elastic fiber with a nozzle oiling device. After that, 500 g of each polyurethane elastic fiber of each example and comparative example 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 period of time in the production of fine yarn, has little yarn breakage in the processing step, and has good metal friction characteristics. Therefore, the fabric made using the polyurethane elastic fiber has a uniform surface quality and an excellent commercial value.

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

Claims (7)

  0.001 to 3 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms, 0.00001 to 5 parts by weight of a polycarboxylic acid copolymer compound and polyether-modified silicone with respect to 100 parts by weight of a polyurethane polymer. A polyurethane elastic fiber comprising 0.00001 to 5 parts by weight.   The fatty acid constituting the fatty acid metal salt is selected from the group consisting of stearic acid and palmitic acid, and the constituent metal is selected from the group consisting of magnesium, calcium, aluminum and zinc. Polyurethane elastic fiber.   The polycarboxylic acid copolymer compound is a copolymer compound of a polyoxyalkylene derivative and an unsaturated carboxylic acid compound, and has a polycarboxylic acid group in its main chain and a polyoxyalkylene group in its graft chain. The polyurethane elastic fiber according to claim 1 or 2, wherein   The polyurethane elastic fiber according to any one of claims 1 to 3, wherein the polyether-modified silicone is a side-chain polyether-modified silicone and / or a both-end polyether-modified silicone. The polyurethane elastic fiber according to any one of claims 1 to 4, wherein the polyether-modified silicone has an HLB characteristic value of 0 to 16 and a viscosity at 25 ° C of 1000 mm ² / s or less.   100 parts by weight of a polyurethane polymer, 0.001 to 3 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms, and 0.00001 to 5 parts by weight of a polycarboxylic acid copolymer compound with respect to 100 parts by weight of the polyurethane polymer Part and polyether-modified silicone 0.00001-5 parts by weight in an amide solvent and mixed to prepare a spinning dope, spinning the resulting spinning dope by a dry spinning method, and the obtained yarn The method for producing a polyurethane elastic fiber according to any one of claims 1 to 5, further comprising a step of winding the fiber.   A step of preparing a spinning dope by dissolving and mixing a polyurethane polymer in an amide solvent, a step of spinning the obtained spinning dope by a dry spinning method, a polyalkylsiloxane having a kinematic viscosity at 25 ° C. of 5 to 50 centistokes And an oil component having a kinematic viscosity at 25 ° C. of 30 to 70 centistokes (polyalkylsiloxane / mineral oil) of 100/0 to 50/50, and 100 parts by weight of the oil component Fiber treatment comprising 0.1 to 10 parts by weight of a fatty acid metal salt having 10 to 30 carbon atoms, 0.001 to 5 parts by weight of a polycarboxylic acid copolymer and 0.00001 to 5 parts by weight of a polyether-modified silicone The polyurethane elastic fiber according to any one of claims 1 to 5, comprising a step of adhering the agent to the spun yarn and a step of winding the yarn after the adhesion. Manufacturing method.

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