JP5821097B2 - Polyurethane elastic fiber and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane elastic fiber and a method for producing the same. More specifically, the present invention relates to a polyurethane elastic fiber excellent in stretchability and function expression rate per unit compound by spinning a spinning stock solution containing polyurethane into a fiber and coating the surface of the fiber with a functional compound, and a method for producing the same. .

  Polyurethanes produced from polymer diols, diisocyanates and low molecular weight polyfunctional active hydrogen compounds are used for fibers, elastomers, foams, synthetic leather, paints, etc. because of their excellent mechanical properties and molding processability. It is used for. Among polyurethanes, polyurethane elastic fibers are used for elastic clothing such as legwear, innerwear, and sportswear, sanitary applications such as disposable diapers and sanitary napkins, hygiene applications, medical applications, and industrial materials. Widely used in Such polyurethane elastic fibers are required to exhibit a function by adding a minimum amount of a functional agent from the viewpoints of spinnability stabilization and production cost reduction.

  For example, a method disclosed in Patent Document 1 is known as an attempt to obtain a polyurethane elastic fiber excellent in functions such as wearability, detachability, fit property, moisture absorption and desorption. However, in this method, in order to correct the effect upward, it is necessary to increase the amount of polyacrylic acid and / or polyacrylamide to be added to the spinning dope. Lowering and cost increase are likely to occur.

  As methods for treating fibers with a functional agent by graft polymerization, methods disclosed in Patent Documents 2 and 3 are known. However, when these methods are applied to a polyurethane elastic fiber, the function expression rate is excellent in either method, but the stretch performance peculiar to the polyurethane elastic fiber due to a decrease in strength and elongation tends to be impaired. The cause of the loss of stretchability is estimated as follows. In the method disclosed in Patent Document 2, regardless of the type of fiber and the urethane group concentration of polyurethane, a solution having a certain concentration of vinyl monomer as a functional agent is brought into contact with the fiber for graft polymerization. For this reason, it is considered that the fiber surface is liable to be loosened in the process, the surface structure is disturbed, and the thickness of the coating polymer cannot be controlled, the strength and elongation are lowered, and the stretch performance is impaired. Moreover, in the method disclosed in Patent Document 3, the double bond is introduced into the polyurethane, so that the reactivity with the functional agent is higher than that of the polyurethane having no double bond, and the functional agent is efficiently used as a fiber. Although it is contained in it, it is expected that the crystal structure in the polyurethane elastic fiber will change due to the influence of having a double bond, and as a result, both the strength and elongation will decrease and the stretch performance will be impaired. It is done. For these reasons, the methods disclosed in Patent Documents 2 and 3 cannot exhibit the stretch performance unique to polyurethane elastic fibers, and the application to clothing materials is limited.

JP 2002-249930 A Japanese Patent Application Laid-Open No. 2004-292956 JP 2000-192329 A

  The present invention provides a polyurethane elastic fiber that improves the disadvantages of the prior art and has an excellent function expression rate per unit compound of the functional compound while maintaining the strength and elongation important for the stretchability of the polyurethane elastic fiber. The task is to do.

The present invention employs any of the following means in order to solve the above-described problems.
(1) A polyurethane elastic fiber containing polyurethane starting from a polymer diol and a diisocyanate, wherein the urethane group concentration of the polyurethane is 0.2 mol / kg or more and 3.5 mol / kg or less with respect to 1 kg of the polyurethane, and the fiber surface Has a film polymer obtained by polymerizing a vinyl monomer represented by the following general formula (1), and the average thickness of the film polymer is 1 nanometer or more and 5 micrometers or less. Polyurethane elastic fiber. The average thickness of the coating polymer is preferably 121 nm or more and 2246 nm or less.

(In the formula, R, R ′, and R ″ each independently represent a hydrogen atom or an arbitrary substituent.)
(2) The polyurethane elastic fiber according to (1) above, wherein the content of the coating polymer in the polyurethane elastic fiber obtained from the weight ratio conversion is 0.1% or more and 40% or less.
(3) The polyurethane elastic fiber according to (1) or (2), wherein the film polymer has in its molecule at least one of a carboxyl group, a phosphorylcholine group, and a benzotriazole structure.
(4) The vinyl monomer is (meth) acrylic acid or a compound represented by the following general formula (2) or (3): The polyurethane elastic fiber as described.

(5) The polyurethane elastic fiber according to any one of (1) to (4), wherein the film polymer is directly bonded to the polyurethane by graft polymerization.
(6) A fiber having a urethane group concentration of 0.2 mol / kg or more and 3.5 mol / kg or less with respect to 1 kg of polyurethane by spinning a spinning stock solution containing polyurethane starting from a polymer diol and diisocyanate from a die. Then, a vinyl monomer represented by the following general formula (1) or an oligomer composed of the vinyl monomer is polymerized or a polymer composed of the vinyl monomer is fixed to the surface of the fiber, and the average thickness is 1 nanometer. A method for producing a polyurethane elastic fiber, comprising forming a film polymer having a thickness of 5 micrometers or less. The average thickness of the coating polymer is preferably 121 nm or more and 2246 nm or less.

(In the formula, R, R ′, and R ″ each independently represent a hydrogen atom or an arbitrary substituent.)
(7) At the time of forming the coating polymer, the fibers are added to a solution in which the vinyl monomer or an oligomer composed of the vinyl monomer or a polymer composed of the vinyl monomer has a concentration of 0.1% by weight to 40% by weight. The method for producing a polyurethane elastic fiber according to the above (6), wherein the method comprises contacting the polymer to polymerize the vinyl monomer or the oligomer composed of the vinyl monomer or to fix the polymer composed of the vinyl monomer.
(8) The above-mentioned (6) or (7), wherein the polyurethane elastic fiber is polymerized so that the content of the coating polymer obtained from the weight ratio conversion is 0.1% or more and 40% or less. A method for producing the polyurethane elastic fiber according to 1.
(9) The polyurethane elasticity according to any one of (6) to (8), wherein the film polymer has in its molecule at least one of a carboxyl group, a phosphorylcholine group, and a benzotriazole structure. A method for producing fibers.
(10) The vinyl monomer is (meth) acrylic acid or a compound represented by the following general formula (2) or (3): The manufacturing method of the polyurethane elastic fiber of description.

(11) The method for producing a polyurethane elastic fiber according to any one of (6) to (10), wherein the film polymer is directly bonded to the polyurethane by graft polymerization.
(12) The method for producing a polyurethane elastic fiber according to any one of (6) to (11) above, wherein the spinning method is dry.

  According to the present invention, the surface of an elastic fiber containing polyurethane whose main constituent components are polymer diol and diisocyanate is obtained by polymerizing the vinyl monomer represented by the general formula (1), and has a thickness average of 1 nanometer or more and 5 Since it is coated with a coating polymer (functional compound) in the range of micrometer or less, it becomes a polyurethane elastic fiber excellent in stretchability and function expression rate per unit compound. As a result, the polyurethane elastic fiber and the woven or knitted fabric such as clothes using the polyurethane elastic fiber are excellent in lightness, durability, texture and appearance quality.

  The present invention will be described in further detail below.

  First, the polyurethane used in the present invention will be described.

  The polyurethane used in the present invention may be any as long as it uses a polymer diol and diisocyanate as starting materials, and is not particularly limited. Also. The synthesis method is not particularly limited. That is, for example, it may be a polyurethane urea composed of a polymer diol, diisocyanate and a low molecular weight diamine, or may be a polyurethane urethane composed of a polymer diol, diisocyanate and a low molecular weight diol. Furthermore, polyurethane urea using a compound having a hydroxyl group and an amino group in the molecule as a chain extender may be used. It is also preferable to use trifunctional or higher polyfunctional glycol or isocyanate or the like as long as the effects of the present invention are not hindered.

  The polymer diol is preferably a polyether-based, polyester-based diol, polycarbonate diol or the like. In particular, a polyether diol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.

  Examples of the polyether diol include polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (THF) and 3-methyltetrahydrofuran copolymer. A modified PTMG (hereinafter abbreviated as 3M-PTMG), a modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, a polyol having side chains on both sides as disclosed in Japanese Patent No. 2615131, THF Random copolymers in which ethylene oxide and / or propylene oxide are randomly arranged are preferably used. These polyether diols may be used alone or in combination of two or more.

  Further, from the viewpoint of obtaining abrasion resistance and light resistance, polyester diols such as butylene adipate, polycaprolactone diol, polyester polyol having a side chain disclosed in JP-A No. 61-26612, and the like, The polycarbonate diol etc. which are indicated by 2-289516 gazette etc. are used preferably.

  These polymer diols may be used alone or in combination of two or more.

  The molecular weight of the polymer diol is preferably a number average molecular weight of 1000 or more and 8000 or less, and more preferably 1800 or more and 6000 or less, from the viewpoint of obtaining elongation, strength, heat resistance, and the like when formed into a yarn. By using a polyol having a molecular weight within this range, an elastic fiber excellent in elongation, strength, elastic recovery force, and heat resistance can be easily obtained.

  Next, as diisocyanates, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are particularly suitable for heat resistance and strength. Suitable for synthesizing high polyurethane. Further, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate) (hereinafter referred to as H12MDI), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexa Hydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively particularly in suppressing yellowing of polyurethane elastic fibers. And these diisocyanates may be used independently and may use 2 or more types together.

  Next, it is preferable to use at least one of a low molecular weight diamine and a low molecular weight diol as the chain extender used in synthesizing polyurethane from the polymer diol and diisocyanate as described above. In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine.

  Preferred low molecular weight diamines include, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p, p ′. -Methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl) phosphine oxide and the like. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred is ethylenediamine. By using ethylenediamine, a yarn excellent in elongation, elastic recovery, and heat resistance can be easily obtained. You may add the triamine compound which can form a crosslinked structure in these chain extenders, for example, diethylenetriamine, etc. to such an extent that an effect is not lost.

  Typical low molecular weight diols include ethylene glycol, 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol, and the like. is there. It is preferable that 1 type (s) or 2 or more types are used among these. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, the diol-extended polyurethane has higher heat resistance, and a yarn having higher strength can be obtained.

  Moreover, it is preferable that the molecular weight of the polyurethane used for this invention is the range of 30000 or more and 150,000 or less as a number average molecular weight from a viewpoint of obtaining fiber with durability and high intensity | strength. The molecular weight is measured by GPC and converted by polystyrene.

  Furthermore, it is also preferable that one or more end blockers are used in the polyurethane. As end-capping agents, monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, Monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.

  Moreover, the urethane group density | concentration of the polyurethane which comprises the polyurethane elastic fiber in this invention is 0.2 mol / kg or more and 3.5 mol / kg or less with respect to 1 kg of polyurethane. A urethane group concentration of less than 0.2 mol / kg is not preferable because it causes a decrease in elongation and a significant decrease in strength. On the other hand, a urethane group concentration exceeding 3.5 mol / kg is not preferable because it causes a decrease in strength and a significant decrease in elongation. From the viewpoint of achieving both good elongation and strength better, it is preferably 0.4 mol / kg or more and 1.0 mol / kg or less.

  In the present invention, the surface of the polyurethane elastic fiber containing polyurethane having the basic structure as described above is expressed by the formula (1) that expresses functions such as deodorizing property, antifouling property, hygroscopic property, and biocompatibility. The vinyl monomer or oligomer comprising the vinyl monomer is polymerized, or the polymer comprising the vinyl monomer is fixed, and a coating polymer having a thickness average in the range of 1 nanometer to 5 micrometers is provided. It is possible to improve the function expression rate per weight of the polymer composed of the vinyl monomer represented by the formula (1) while maintaining.

  In the present invention, the vinyl monomer constituting the film polymer may be any one as long as it has a structure satisfying the formula (1), and is not particularly limited. However, the structure of the vinyl monomer of the formula (1) that is particularly preferably used for imparting an aging deodorizing function to the polyurethane elastic fiber includes the following general formulas (4) and (5). It is done.

In the formula, R1 and R2 each independently represent H or a saturated hydrocarbon / unsaturated hydrocarbon having 1 to 10 carbon atoms. R3 represents carboxylic acid, sulfonic acid, (phosphorous) phosphoric acid, or any one of the following R6, R7, R8, and R9. R4 is H, OH, CN, saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 50 carbon atoms, aldehyde, carboxylic acid, sulfonic acid, (sub-) phosphoric acid, halogen, the following R6, R7, R8, One of R9, R10, R11, and R12 is shown.

In the formula, R13 and R14 each independently represent a saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 20 carbon atoms. X represents H, OH, saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 20 carbon atoms, carboxylic acid, sulfonic acid, (sub) phosphoric acid, or halogen.

  Examples of vinyl monomers containing structural units represented by formulas (4) and (5) include (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylic acid, 10-undecenoic acid, 1-phenylethenylphosphonic acid 1-vinyl phosphite, 4-vinylbenzoic acid, arachidonic acid, allyl sulfonic acid, itaconic acid, eleostearic acid, oleic acid, crotonic acid, cinnamic acid, diallyl acetic acid, sodium styrene sulfonate, styrene phosphonic acid, Sorbic acid, parinaric acid, bis-methacryloxyethyl phosphate, vinyl sulfonic acid, alkyl vinylphosphonate, vinyl pivalate, phthalic acid, fumaric acid, maleic acid, maleic anhydride, linoleic acid, linolenic acid, vinyl phosphate, Examples include 2- (methacryloyloxy) ethyl phosphate.Among these, (meth) acrylic acid is particularly preferable.

  Further, examples of the structure of the vinyl monomer of the formula (1) that is particularly preferably used for imparting the antifouling function to the polyurethane elastic fiber include the following general formulas (13) and (14).

In the formula, R1 and R2 each independently represent H or a saturated hydrocarbon / unsaturated hydrocarbon having 1 to 10 carbon atoms. R5 represents H, CN, C1-C50 saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon, aldehyde, halogen, or any of the following R15, R16, R17, R18, R19, R20.

In the formula, R22 and R23 each independently represent a saturated hydrocarbon / unsaturated hydrocarbon / oxy hydrocarbon having 1 to 50 carbon atoms, a halogenated hydrocarbon having 1 to 20 carbon atoms, a silicon hydride having 2 to 200 silicon atoms / One of alkyl silicon / oxyalkyl silicon is shown. n represents a natural number from 1 to 20. Y represents H, CN, a saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 50 carbon atoms, an aldehyde, a halogen, or a 3 to 10-membered heterocyclic ring.

  Examples of vinyl monomers containing structural units represented by formulas (13) and (14) include 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic. Ethoxyethyl acid, octyl (meth) acrylate, glycidyl (meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic Propyl acid, hexyl (meth) acrylate, methyl (meth) acrylate, methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acryloylmorpholine, (meth ) Acrylonitrile, 3-phenyl-1-morpholino-2-propyl Pen-1-one, oxiranylmethyl 4-vinylbenzoate, 4-methylstyrene, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, 2- (meth) acrylic acid 2- ( Trimethylsilyloxy) ethyl, 2,2,2-trifluoroethyl (meth) acrylate, 3- (1,1,3,3,3-pentamethylpropanedisiloxane-1-yl) propyl (meth) acrylate (Meth) acrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl, (meth) acrylic acid 3- [tris (trimethylsilyloxy) Silyl] propyl, allyl p-toluenesulfonate, acrolein, ethylene, vinyl chloride, vinyl chloroacetate, allyl acetate, vinyl acetate, vinyl dichloroacetate, styrene, triacetate Carboxymethyl (vinyl) silane, vinyl trifluoroacetate, butadiene, vinyl fluoride, propylene, methane sulfonic acid allyl and the like.

  Furthermore, examples of the structure of the vinyl monomer of the formula (1) that is particularly preferably used for imparting a biocompatible function to the polyurethane elastic fiber include the following general formula (21).

In the formula, R1 and R2 each independently represent H or a saturated hydrocarbon / unsaturated hydrocarbon having 1 to 10 carbon atoms. R21 represents OH, a 3- to 10-membered heterocyclic ring, or any one of the following R24 and R25.

In the formula, R26 and R27 each independently represents one of saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 10 carbon atoms. n represents a natural number from 1 to 20. Z represents any of H, OH, amine, ammonium salt, and phosphorylcholine.

  Examples of the vinyl monomer containing the structural unit represented by the formula (21) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methacryloyloxyethyl phosphorylcholine, hydroxyethyl (meta) ) Acrylamide, N- (2-hydroxypropyl) methacrylamide, N-vinyl-2-pyrrolidone, vinyl alcohol, and the like.

  In particular, a compound of the general formula (3) shown below is preferable.

  And as a structure of the vinyl monomer of the formula (1) that is particularly preferably used for imparting a hygroscopic function to the polyurethane elastic fiber, the following general formulas (24) and (25) are exemplified.

In the formula, R1 and R2 each independently represent H or a saturated / unsaturated hydrocarbon having 1 to 10 carbon atoms. R28 represents OH, carboxylic acid, sulfonic acid, (phosphorous) phosphoric acid, or any of the following R30, R31, R32, R33, R34, R35, and R36. R29 is H, OH, CN, saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 50 carbon atoms, aldehyde, carboxylic acid, sulfonic acid, (sub) phosphoric acid, halogen, the following R30, R31, R32, One of R33, R34, R35 and R36 is shown.

  In the formula, R37 and R38 each independently represent a saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 20 carbon atoms or a halogenated hydrocarbon having 1 to 20 carbon atoms. W is H, OH, saturated hydrocarbon / unsaturated hydrocarbon / oxyhydrocarbon having 1 to 50 carbon atoms, aldehyde, carboxylic acid, sulfonic acid, (phosphite), halogen, amine, ammonium salt, phosphorylcholine, 3 One of 10-membered heterocycles is shown.

  Examples of vinyl monomers containing structural units represented by formulas (24) and (25) include (meth) acrylic acid 2-dimethylaminoethyl, (meth) acrylic acid 2-trimethylammonioethyl chloride, (meth) Ethoxydiethylene glycol acrylate, ethoxytriethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, N-phenyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) Acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide methyl chloride quaternary salt, N- [3- (dimethylamino) propyl] acrylamide, (meth) acrylamide methyl Propanesulfonic acid, (meth) acrylic acid, 10-undecenoic acid, 1-phenylethenylphosphonic acid, 1-vinyl phosphite, 4-vinylbenzoic acid, arachidonic acid, allyl sulfonic acid, itaconic acid, eleostearic acid , Oleic acid, crotonic acid, cinnamic acid, diallylacetic acid, sodium styrene sulfonate, styrene phosphonic acid, sorbic acid, parinaric acid, bis-methacryloxyethyl phosphate, vinyl sulfonic acid, alkyl vinyl phosphonate, vinyl pivalate, phthalate Acid, fumaric acid, maleic acid, maleic anhydride, linoleic acid, linolenic acid, vinyl phosphate, 2- (methacryloyloxy) ethyl phosphate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl, 2-methacryloyloxyethylphos Rirukorin, hydroxyethyl (meth) acrylamide, N- (2-hydroxypropyl) methacrylamide, N- vinyl-2-pyrrolidone, and vinyl alcohol.

  Furthermore, antibacterial properties, light resistance and the like can be given as functions other than those described above, and these functions are also expressed in the same manner as described above from the vinyl monomer represented by the formula (1) or the vinyl monomers expressing the functions. By polymerizing the oligomer or the polymer consisting of the vinyl monomer, and providing a film polymer having a thickness average in the range of 1 nanometer or more and 5 micrometers or less, while maintaining the stretch property, the formula (1) It is possible to improve the function expression rate per weight of the polymer composed of the represented vinyl monomer.

  The vinyl monomer structure represented by the formula (1) used for imparting light resistance to the polyurethane elastic fiber is preferably a compound represented by the following general formula (2).

  The structure of the vinyl monomer represented by the formula (1) used for imparting antibacterial properties to the polyurethane elastic fiber is preferably a compound represented by the following general formula (33).

  In the formula, R1 and R2 each independently represent H or a saturated hydrocarbon / unsaturated hydrocarbon having 1 to 10 carbon atoms. R39 represents either an ammonium salt or a phosphonium salt.

  Examples of the vinyl monomer containing the structural unit represented by the formula (33) include (meth) acrylic acid 2-trimethylammonioethyl chloride, (meth) acrylaminopropyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, tributyl- 4-vinyl benzyl phosphonium chloride etc. are mentioned.

  The average thickness of the coating polymer obtained by polymerizing the functional agent having the structure of the formula (1) as described above is 1 nanometer or more and 5 micrometers or less. When the thickness of the coating polymer is less than 1 nanometer on average, the concentration of the functional agent exposed on the surface of the polyurethane elastic fiber is low, which is not preferable because the effect of the functional agent is not sufficient. On the other hand, if the thickness of the coating polymer exceeds 5 micrometers on average, the polyurethane elastic fiber becomes bulky and the texture is impaired when it is made into a fabric, which is not preferable. From the viewpoint of achieving a good balance between good function expression and texture, an average range of 5 nanometers to 2 micrometers is preferable.

  The average thickness of the coating polymer can be observed using a transmission electron microscope (TEM) at a magnification of 100000 times. As an observation method, a single yarn of a fiber structure is observed by an OsO4 dyeing ultrathin section method. The thickness of the OsO4 dark dye layer observed on the fiber surface is measured at any four or more points, and the average value thereof is taken as the average thickness of the coating polymer in the present invention.

  In the present invention, the content in the polyurethane elastic fiber of the coating polymer obtained by polymerizing the functional agent having the structure of the formula (1) is preferably in the range of 0.1% by weight to 40% by weight. . If the content of the coating polymer is 0.1% by weight or more, the functional agent is exposed to the surface of the polyurethane elastic fiber at a sufficient concentration, and the effect of the functional agent can be efficiently expressed. . Preferably it is 0.3 weight% or more. On the other hand, if the content of the coating polymer is 40% by weight or less, the strength and elongation depending on the polyurethane are more reliably maintained, the stretch property is excellent, and the texture is excellent even when the fabric is used. Cheap. Preferably it is 20 weight% or less. From the viewpoint of achieving both a better texture and maintaining stretchability, a range of 0.3 wt% or more and 20 wt% or less is preferable.

  In addition, the content rate of a film polymer can be calculated | required from each molecular weight obtained by performing GPC measurement about the whole polyurethane elastic fiber and the film polymer isolated by hydrolyzing this polyurethane elastic fiber.

  From the viewpoint of reducing the chargeability of the polyurethane elastic fiber, it is also preferable that the coating polymer forms a salt or complex with the metal. The metal is not particularly limited as long as it forms a salt or complex. For example, alkali metal, alkaline earth metal, iron, cobalt, nickel, copper, zinc, manganese, aluminum, silver, zirconium, and the like can be given. Also, the method for synthesizing the salt or complex with the film polymer is not particularly limited. For example, a metal salt or complex may be formed using an aqueous solution containing a metal-containing compound in polyurethane elastic fibers.

  The polyurethane elastic fiber of the present invention may contain various stabilizers, pigments and the like. For example, hindered phenolic agents such as BHT and “Sumilyzer” (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., various types of “Chinubin” (registered trademark) manufactured by Ciba Geigy Co., Ltd. Benzotriazoles, benzophenone drugs, phosphorus-based drugs such as “Sumilyzer” (registered trademark) P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amine drugs, various pigments such as iron oxide and titanium oxide, hydrotal Site compounds, minerals such as huntite, hydromagnesite, tourmaline, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide, calcium carbonate, carbon black, metal soap such as fluorine or silicone resin powder, magnesium stearate, In addition, sterilization including silver, zinc, and these compounds , Deodorants, also silicone, lubricants such mineral oil, cerium oxide, it is also preferred to include various kinds of antistatic agents such as betaine and phosphoric acid, and also that they are reacted with polymers preferred. In order to further enhance the durability to light and various nitric oxides in particular, for example, nitric oxide supplements such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., “Sumilyzer” manufactured by Sumitomo Chemical Co., Ltd. (registered) It is also preferred to use a thermal oxidation stabilizer such as trade mark GA-80 and a light stabilizer such as “SUMISOB” (registered trademark) 300 # 622 manufactured by Sumitomo Chemical Co., Ltd. Further, when these various stabilizers and pigments are blended, for the purpose of improving the dispersibility in the yarn and stabilizing the spinning, for example, organic substances such as fatty acids, fatty acid esters, polyol organic substances, It is also preferable to use inorganic chemicals surface-treated with a silane coupling agent, a titanate coupling agent, or a mixture thereof.

  Next, the manufacturing method of the polyurethane elastic fiber of this invention is demonstrated in detail.

  In the present invention, a polymer diol and a diisocyanate are used as starting materials, a spinning stock solution containing polyurethane obtained therefrom is spun from a die into a fiber, and then the vinyl represented by the formula (1) is formed on the surface of the fiber. A monomer or an oligomer composed of the vinyl monomer is polymerized, or a polymer composed of the vinyl monomer represented by the formula (1) is fixed to form a film polymer. The polymer to be fixed means a polymer in a broad sense and includes oligomers.

  The method for producing the polyurethane solution and the method for producing the polyurethane as the solute of the solution may be either a melt polymerization method or a solution polymerization method, or may be another method. However, the solution polymerization method is more preferable. In the case of the solution polymerization method, there is little generation of foreign substances such as gel in the polyurethane, it is easy to spin, and it is easy to obtain polyurethane elastic fibers with low fineness. Of course, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.

  The polyurethane particularly suitable for the present invention includes PTMG having a molecular weight of 1800 to 6000 as a polymer diol, MDI as a diisocyanate, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine as a chain extender. And those synthesized using at least one of them.

  Polyurethane can be obtained, for example, by synthesizing using the above-mentioned raw materials in DMAc, DMF, DMSO, NMP or the like or a solvent containing these as main components. For example, each raw material is charged in such a solvent, dissolved, heated to an appropriate temperature and reacted to form polyurethane, a so-called one-shot method, or polymer diol and diisocyanate are first melt-reacted and then reacted. A particularly preferable method is a method in which a product is dissolved in a solvent and reacted with the above-described chain extender to form polyurethane.

  When a diol is used as the chain extender, it is preferable to adjust the melting point on the high temperature side of the polyurethane to a range of 200 ° C. or higher and 260 ° C. or lower from the viewpoint of obtaining a product having excellent heat resistance. Exemplary methods can be achieved by controlling the type and ratio of polymer diol, MDI, diol. When the molecular weight of the polymer diol is low, a polyurethane having a high melting point at a high temperature can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the diol is low, the proportion of the polymer diol is relatively By reducing the amount of the polyurethane, a polyurethane having a high temperature melting point can be obtained.

  In the case where the molecular weight of the polymer diol is 1800 or more, in order to increase the melting point on the high temperature side to 200 ° C. or more, the polymerization is advanced at a ratio of (number of moles of MDI) / (number of moles of polymer diol) = 1.5 or more. Is preferred.

  In the synthesis of such polyurethane, it is also preferable to use one or a mixture of two or more catalysts such as amine catalysts and organometallic catalysts.

  Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ′ , N ′, N′-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N′-dimethylpiperazine, N-methyl-N′-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N, N-dimethylamido Noethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethyl Examples include aminohexanol and triethanolamine.

  Examples of organometallic catalysts include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.

  The concentration of polyurethane in the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.

  Depending on the spinning conditions, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethyl are used to control the viscosity suitable for spinning of polyurethane solutions. One or two end capping agents such as monoamines such as amine, isopentylmethylamine, dibutylamine and diamylamine, monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate It is also preferable to use a mixture of two or more species.

  The basic fiber in the present invention can be obtained by, for example, dry-spinning, wet-spinning, or melt-spinning and winding up the spinning stock solution configured as described above. Of these, dry spinning is preferred from the viewpoint of stable spinning at all finenesses from fine to thick.

  The fineness, the cross-sectional shape, etc. of the polyurethane elastic fiber of the present invention and any fiber to be mixed are not particularly limited. For example, the cross-sectional shape of the yarn may be circular or flat.

  Also, the dry spinning method is not particularly limited, and spinning may be performed by appropriately selecting a spinning condition or the like suitable for desired characteristics and spinning equipment.

  For example, the permanent set rate and stress relaxation of the polyurethane elastic fiber of the present invention are particularly easily influenced by the speed ratio of the godet roller and the winder, and therefore, it is preferably determined as appropriate according to the intended use of the yarn. That is, from the viewpoint of obtaining a polyurethane elastic fiber having a desired permanent set rate and stress relaxation, it is preferable that the speed ratio between the godet roller and the winder is 1.10 to 1.65. The spinning speed is preferably 250 m / min or more from the viewpoint of improving the strength of the obtained polyurethane elastic fiber.

  In the present invention, after the polyurethane solution is spun from the die into fibers as described above, for example, the vinyl monomer represented by the above formula (1) or the oligomer composed of the vinyl monomer is formed on the surface of the fiber. Is polymerized, or a film polymer is formed by fixing a polymer composed of a vinyl monomer represented by the formula (1).

  When a film polymer is provided on the fiber surface by polymerization, any method such as a graft polymerization method of vinyl monomers or oligomers composed of vinyl monomers onto fiber molecules can be employed.

  On the other hand, as a resin fixing method to the fiber surface, a method of fixing the polymer layer composed of the vinyl monomer represented by the formula (1) to the fiber surface with a binder resin, or a fiber in a solution containing the polymer composed of the vinyl monomer. And a method of covering the fiber surface with the polymer. The binder resin is not particularly limited, and any of them can be applied. Resins such as acrylate resin, urethane resin, polyester resin, silicone resin, melamine resin, polypropylene resin, or a prepolymer thereof can be applied.

  However, graft polymerization is preferable because the coating polymer can be directly bonded to the polyurethane constituting the fiber, and the coating polymer can be prevented from falling off from the fiber surface during post-processing of the fiber.

  Various methods can be applied as a graft polymerization method to vinyl molecules of vinyl monomers or oligomers composed of vinyl monomers. One example will be described below.

  The vinyl monomer represented by the above formula (1) for forming a film polymer or an oligomer composed of the vinyl monomer, generally known graft polymerization known as AIBN as an azo initiator, BPO as an organic peroxide initiator, and the like. After immersing the fiber to be treated in an aqueous mixture containing an initiator and a surfactant, the desired amount of applied liquid is adjusted by a nip or the like. As a method for applying the aqueous mixed solution, in addition to the nip method, a pad vacuum method, a spray method, a centrifugal dehydration method, a coating method, or the like can be used. In addition, the to-be-processed fiber may already comprise the cloth, The application | coating method of the said aqueous mixture liquid can be suitably selected and used according to the form of an to-be-processed fiber or a cloth, the amount of application liquids, etc.

  Next, graft polymerization is performed by heating the fiber to be treated to which the above mixed solution is applied. A normal heating mechanism can be applied as the heating means, but from the viewpoint of graft polymerization efficiency and the like, heating using microwaves or microwave steam is preferred. The treatment temperature varies somewhat depending on the type of vinyl monomer or oligomer composed of vinyl monomer or initiator, but a temperature condition of usually 50 to 200 ° C., more preferably 80 to 180 ° C. can be employed.

  The treated fiber that has been grafted by heat treatment is subjected to dry heat treatment after washing with hot water using an open leaver or the like to remove residual matter. The weight after the dry heat treatment is measured, and the graft ratio can be determined from the weight increase rate.

  In addition to the graft polymerization method described above, a graft polymerization method using radiation or plasma can also be used as a method not using a polymerization initiator. Examples of the radiation include alpha rays, beta rays, gamma rays, proton rays, neutron rays, electron rays, X rays, ultraviolet rays, and the like. Preferably, electron rays, gamma rays, and ultraviolet rays can be employed.

  As a method of graft polymerization by irradiating with an electron beam, for example, a film polymer is formed by irradiating a fiber to be treated with an electron beam in advance and then immersing it in a solution containing a vinyl monomer or an oligomer composed of a vinyl monomer. A pre-irradiation polymerization method or a simultaneous irradiation polymerization method in which a fiber to be treated is immersed in a solution containing a vinyl monomer or an oligomer composed of a vinyl monomer and then irradiated with an electron beam to form a coating polymer can be employed.

  In the present invention, in order to make the thickness average of the coating polymer 1 nanometer or more and 5 micrometers or less, for example, the urethane group concentration of polyurethane is 0.2 mol / kg or more and 3.5 mol / kg with respect to 1 kg of polyurethane. A certain fiber is brought into contact with a vinyl monomer represented by the formula (1) or a solution having a concentration of an oligomer composed of the vinyl monomer of 0.1% by weight to 40% by weight, and the vinyl monomer or the oligomer composed of the vinyl monomer. Is preferably polymerized on the fiber surface. By carrying out like this, the polyurethane elastic fiber by which the average thickness of the coating polymer was controlled by 1 nanometer or more and 5 micrometers or less can be obtained easily. As long as the urethane group concentration and the solution concentration of the vinyl monomer represented by the formula (1) or the oligomer of the vinyl monomer are within the above range, the method for forming the coating polymer may be any of the methods described above, preferably The method using a polymerization initiator, electron beam, gamma ray, or ultraviolet ray can be employed.

  The polymerization is preferably performed such that the content of the coating polymer obtained from the weight ratio conversion is 0.1% or more and 40% or less. As a method for polymerizing to the above content range, polymerization is performed at a solution concentration in which the concentration of the vinyl monomer represented by the formula (1) or the oligomer composed of the vinyl monomer is 0.1 wt% or more and 40 wt% or less. It is preferable to perform polymerization at a reaction temperature in the range of 80 ° C. or higher and 180 ° C. or lower.

  The present invention will be described in more detail with reference to examples.

[Fiber spinnability]
Spinning was carried out continuously for 24 hours, and the number of yarn breaks at that time was judged. The smaller the number of times, the better the spinnability.

[Film thickness of coating polymer]
The thickness of the coating polymer on the surface of the polyurethane elastic fiber was observed at a magnification of 100,000 using a transmission electron microscope (TEM). In addition, the single yarn of the fiber structure was observed by an OsO4 dyeing ultrathin section method, and the film thickness was defined as the thickness of the OsO4 dark dye layer observed on the fiber surface. The measurement was n = 4, and an average value of the n data was obtained. In addition, when the boundary between the deeply dyed layer and the lightly dyed layer was not observed and the layer had a uniform density, it was determined that the film thickness was “none”.

[Concentration of urethane groups in polyurethane]
The urethane group concentration in the polyurethane was determined based on the following formula. The number of moles of the polymer diol contained in the polyurethane elastic fiber was calculated from the calibration curve using the known polymer diol concentration-containing polyurethane elastic fiber after obtaining the oxymethylene peak intensity of the polymer diol by 13C-NMR method.

[Functional expression rate]
As an index indicating the degree of expression of the function per weight of the polymer composed of the vinyl monomer represented by the formula (1) contained in the polyurethane elastic fiber, aging deodorant property, antifouling property, biocompatibility, moisture absorption The respective function expression rates F1, F2, F3, F4, F5, and F6 of the property, antibacterial property, and light resistance were evaluated as follows.

[Aging deodorant F1]
The aging odor and deodorization test is based on the deodorant processed fiber product certification standard (established by the Product Evaluation Department of the Textile Evaluation Technology Council of Japan, the establishment date is September 1, 2002), and the equipment test (detection tube) Method or GC method).

(Test method)
1. Samples were prepared to a predetermined size.
2. A sample, an odor component, and a dilution gas were placed in a container, and the residual gas concentration (ppm) after 2 hours was measured with a component-compatible detector tube (manufactured by Gastec) or gas chromatography. The gas filling amount was 3 L, and the dilution gas was dry air or nitrogen gas.
3. The same evaluation was performed without using a sample, and a blank test was performed.
4). All the evaluations were performed according to Table 1, and the reduction rate of the residual gas concentration was calculated according to Equation 2 for the detector tube method and Equation 3 for the GC method.

In addition, the measurement was set to n = 3, and the average value of these n pieces of data was used as the reduction rate.
5. In the above device test, the Japan Fiber Evaluation Technology Council recognizes that each odor component has a deodorizing effect when the reduction rate is 70% or more. Moreover, it is defined as having an aging odor deodorizing property when the decrease rate with respect to the odor components ammonia, acetic acid, isovaleric acid and nonenal is 70% or more, 80% or more, 85% or more, 75% or more, respectively. Has been. Therefore, in the examples and comparative examples, the aging odor deodorizing property is an index indicating the degree of function per weight of the polymer composed of the vinyl monomer represented by the formula (1) contained in the polyurethane elastic fiber. The function expression rate F1 (%) for was expressed as follows.

However, it was set to 0 when even one odor component was not deodorant.
[Anti-fouling F2]
The antifouling test was conducted as follows.
1. A 10 cm × 10 cm sample was prepared.
2. Place the sample on a 10 cm × 10 cm glass plate, drop 0.05 cc of heavy oil B onto the center of the test piece, place a 1 mm thick 5 cm × 5 cm glass plate on the glass plate, and place it on the glass plate. A 200 g load was applied and left for 1 minute.
3. The load and the glass plate were removed, and the sample was transferred onto a filter paper and covered with a tissue paper, and the stain was wiped off by rolling on the paper, and left to stand for 24 hours in a horizontal state to be naturally dried.
4). The sample after contamination was dissolved in an automatic inversion swirl electric washing machine with 25 L of a weak alkaline synthetic detergent specified in JIS K337 (established in 1972, revised in 1994) to a concentration of 0.1% by volume. The bath ratio was 1:50 at a temperature of 40 ± 2 ° C., washed under strong conditions for 5 minutes, then drained and washed with water for 5 minutes.
5. The sample after washing was taken out without squeezing it, and lightly pressed with filter paper to drain the water, and then naturally dried in a horizontal state.
6). Contamination of the dried sample was graded from grade 1 to grade 5 according to the gray scale for contamination according to JIS L 0805 (established in 1965, revised in 2005). It shows that antifouling property is good as it goes from 1st grade to 5th grade.

  In addition, the measurement was set to n = 3, and the average value of these n pieces of grade data was defined as a function expression rate F2 regarding antifouling properties.

[Biocompatibility F3]
The biocompatibility in the present invention means a property that is not recognized or hardly recognized as a foreign substance in blood, and means that the higher this property is, the more difficult it is to form a thrombus in blood. The biocompatibility evaluation method is as follows.
1. Ketamine (Ketalar (registered trademark), Sankyo Co., Ltd.) 0.8 mL / kg and Xylazine (Seractal (registered trademark), Bayer Co., Ltd.) 0.8 mL / kg were each intramuscularly administered to rats and anesthetized and placed in the dorsal position After fixation, the right carotid artery and left jugular vein are removed.
2. A sample cut to a length of 3 cm and a width of 1.5 mm was inserted into a 5 cm long polyethylene tube (PE240: inner diameter 1.67 mm), and a polyethylene tube (PE160: inner diameter 1.. 14 mm), two polyethylene tubes (PE90: inner diameter 0.86 mm, length 13 cm) were connected.
3. After the connected polyethylene tube was filled with physiological saline, one end of the polyethylene tube (PE90) was inserted into the left jugular vein and the other end was inserted into the right carotid artery.
4. After circulating blood in the polyethylene tube for 20 minutes, the sample in the central polyethylene tube was taken out and the wet weight was measured.
5. The value obtained by subtracting the weight of the sample measured in advance from the obtained wet weight was defined as the thrombus wet weight.
6). The value of the thrombus wet weight when using a fabric composed of a polyurethane elastic fiber (E1 described in Example 1) that does not contain a polymer composed of the vinyl monomer represented by the formula (1) is Y0, The thrombus formation inhibition rate was calculated from the following equation, where Y1 was the value of the thrombus wet weight when the fabric composed of the polyurethane elastic fiber finally obtained in the comparative example was used. A higher thrombus formation inhibition rate indicates better biocompatibility.

  In addition, the measurement was set to n = 3 and the average value of those n data was shown as the function expression rate F3 (%) regarding biocompatibility.

[Hygroscopic F4]
The hygroscopicity test is as follows.
1. A sample of 1 g was prepared, and its dry weight (W0) was measured.
2. The sample was left in a constant temperature and humidity chamber (PR-2G manufactured by Tabai) conditioned at 20 ° C. and 65% RH for 24 hours, and the weight (W20) of the sample in an equilibrium state was measured to absorb moisture. The rate was determined by the following formula. The higher the moisture absorption rate, the better the hygroscopicity. Moreover, this moisture absorption was shown as the function expression rate F4 (%) regarding a hygroscopic property.

  In addition, the measurement was set to n = 3 and the average value of those n data was described.

[Antimicrobial F5]
The antibacterial test was carried out in accordance with the antibacterial test procedure (JIS L1902: 2008, bacterial solution absorption method) designated by the Council for Textile Products New Function Evaluation. Antibacterial activity was evaluated by the bacteriostatic activity value according to the following formula. The higher the bacteriostatic activity value, the better the antibacterial property. In addition, Staphylococcus aureus (ATCC 6538P) was used as a test microbe.

However, test establishment condition: satisfy Log (B) -Log (A)> 1.5 A: average number of bacteria recovered immediately after inoculation of raw product B: fungus cultured and recovered for 18 hours of raw product Average value C: Average value of the number of bacteria collected and cultured for 18 hours for processed products (samples subjected to antibacterial treatment) Using samples after washing 10 times prepared to a constant weight, all measurements were performed at n = 3 The average of these n values is shown. The bacteriostatic activity value was defined as a function expression rate F5 regarding antibacterial properties.

[Light resistance F6]
Light resistance was evaluated based on durability by UV exposure treatment. The method is as follows.
1. The polyurethane elastic fiber was fixed in a 100% stretched state.
2. Using a carbon arc type fade meter manufactured by Suga Test Instruments Co., Ltd., UV exposure was performed at 63 ° C. and 60% RH.
3. 2. The polyurethane elastic fiber was left free at room temperature for 24 hours, and the breaking strength (Z1) was measured by the method described below in [Strength and elongation of polyurethane elastic fiber]. did. The ratio (retention rate) of the breaking strength (Z1) after the treatment to the breaking strength (Z0) of the untreated yarn was defined as light resistance. These are defined by:

  In addition, the frequency | count of measurement was set to n = 3, and those average values were made into the function expression rate F6 (%) regarding light resistance.

[Strength and elongation of polyurethane elastic fiber]
The strength and elongation were measured by subjecting the sample yarn to a tensile test using an Instron 4502 type tensile tester. The number of measurements was measured at n = 3, and the average value thereof was adopted. These are defined by:

  That is, a 5 cm (L1) sample was stretched at a tensile speed of 50 cm / min until the sample yarn was cut. The stress at break was (G1), and the length of the sample yarn at break was (L2). Hereinafter, the characteristic is given by the following equation.

In the following, Examples 1-4, 6, 9, 11, 14 and 19 are reference examples.
[Example 1]
A DMAc solution (35% by weight) of a polyurethaneurea polymer (urethane group concentration = 0.7 mol / kg) composed of PTMG, MDI, ethylenediamine having a molecular weight of 2900 and diethylamine as an end-capping agent was prepared by a conventional method. did. Next, as an antioxidant, a polyurethane solution ("Megachlor" (registered trademark) 2462 manufactured by DuPont) produced by a reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), 2: 1 (weight ratio) was mixed with a condensation polymer of p-cresol and divinylbenzene (“METACROL” (registered trademark) 2390, manufactured by DuPont), and an antioxidant DMAc solution (concentration 35% by weight). The other additive solution B1 (35% by weight) was prepared.

  A1 and B1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution D1. This was dry-spun at a spinning speed of 600 m / min, with a speed ratio of 1.2 between the godet roller and the winder, wound up, 20 dtex, 2 fil multifilament polyurethane elastic fiber E1 (urethane group concentration = 0.7 mol / kg) Of 500 g was obtained.

  Further, AIBN as an initiator, methacrylic acid (corresponding to Formula 4) as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M1 (methacrylic acid 0.3 wt%) did.

  Graft polymerization was performed using E1 and M1 under the conditions of 80 ° C. for 2 hours to obtain a polyurethane elastic fiber G1 having a polymer component (f1) made of methacrylic acid of 0.50% by weight. Furthermore, using only G1, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G1 and the function expression rate in the fabric.

[Example 2]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and methacrylic acid as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M2 (2.0% by weight of methacrylic acid). Graft polymerization was performed using E1 and M2 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G2 having f1 of 31.30% by weight.

  Furthermore, using only G2, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G2, and the function expression rate in the fabric.

[Example 3]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2,2,2-trifluoroethyl methacrylate (corresponding to Formula 13) as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to prepare a reaction solution M3 ( (2,2,2-trifluoroethyl methacrylate 0.1% by weight).

  Polyurethane elasticity in which the graft polymerization treatment using E1 and M3 is carried out at 80 ° C. for 2 hours, and the polymer component (f2) composed of 2,2,2-trifluoroethyl methacrylate is 0.08% by weight Fiber G3 was obtained. Furthermore, using only G3, knitting with a 320-needle one-necked cylinder knitting machine, steam setting at 120 ° C. for 1 minute was performed, and a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm was obtained. It was.

  Table 2 shows the composition and various characteristics of G3 and the function expression rate in the fabric.

[Example 4]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2,2,2-trifluoroethyl methacrylate as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to prepare a reaction solution M4 (methacrylic acid 2,2, 2-trifluoroethyl 0.4 wt%).

  Graft polymerization was performed using E1 and M4 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber G4 having f2 of 0.30% by weight. Furthermore, using only G4, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G4 and the function expression rate in the fabric.

[Example 5]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2,2,2-trifluoroethyl methacrylate as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to prepare a reaction solution M5 (methacrylic acid 2,2, 2-trifluoroethyl 10.0 wt%).

  A graft polymerization treatment was performed using E1 and M5 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber G5 having an f2 of 29.70% by weight. Furthermore, using only G5, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G5 and the function expression rate in the fabric.

[Example 6]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-methacryloyloxyethyl phosphorylcholine (corresponding to Formula 3) as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol 5 to 1 (weight ratio) to prepare a reaction solution M6 (2-methacryloyloxyethyl). Phosphorylcholine (4.0 wt%).

  Graft polymerization was performed using E1 and M6 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber G6 having a polymer component (f3) composed of 2-methacryloyloxyethyl phosphorylcholine of 1.20% by weight. . Furthermore, using only G6, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G6 and the function expression rate in the fabric.

[Example 7]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-methacryloyloxyethyl phosphorylcholine as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to prepare a reaction solution M7 (2-methacryloyloxyethyl phosphorylcholine 30.0% by weight). ).

  Graft polymerization was performed using E1 and M7 under the conditions of 80 ° C. for 2 hours to obtain polyurethane elastic fiber G7 having f3 of 16.80% by weight. Furthermore, using only G7, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a tubular knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G7 and the function expression rate in the fabric.

[Example 8]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-methacryloyloxyethyl phosphorylcholine as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M8 (2-methacryloyloxyethyl phosphorylcholine 35.0% by weight). ).

  Graft polymerization was performed using E1 and M8 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G8 having f3 of 45.02% by weight. Furthermore, using only G8, knitting on a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G8 and the function expression rate in the fabric.

[Example 9]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-hydroxyethyl methacrylate (corresponding to Formulas 21 and 24) as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to prepare a reaction solution M9 (methacrylic acid 2 -0.2% by weight of hydroxyethyl).

  The graft polymerization treatment was carried out using E1 and M9 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber G9 having a polymer component (f4) composed of 2-hydroxyethyl methacrylate of 0.19% by weight. . Furthermore, using only G9, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

Table 2 shows the composition and various characteristics of G9 and the function expression rate in the fabric.
[Example 10]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-hydroxyethyl methacrylate as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M10 (3.0% by weight of 2-hydroxyethyl methacrylate). ).

  Graft polymerization was performed using E1 and M10 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber G10 having f4 of 8.00% by weight. Furthermore, using only G10, knitting with a 320-needle one-necked knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a tubular knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of G10 and the function expression rate in the fabric.

[Example 11]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-hydroxyethyl methacrylate as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M11 (20.0% by weight of 2-hydroxyethyl methacrylate). ).

  Graft polymerization was performed using E1 and M11 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G11 having f4 of 28.10% by weight. Furthermore, using only G11, knitting with a 320-needle one-neck knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a tubular knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various properties of G11 and the function expression rate in the fabric.

[Example 12]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, a solution polymerization reaction was carried out by a conventional method using M2 described in Example 2, and the obtained polymer was extracted with hexane and dried to obtain polymethacrylic acid as f1. This was dissolved in a mixed solvent of 5: 1 (weight ratio) of water and isopropanol, and AIBN was added thereto to obtain a reaction solution M12 (polymethacrylic acid 0.3 wt%).

  M12 was impregnated with E1, and polymethacrylic acid was fixed on the surface of E1 at 80 ° C. for 2 hours, to obtain a polyurethane elastic fiber G12 having f1 fixed to 0.50% by weight. Furthermore, using only G12, knitting with a 320-needle one-necked cylinder knitting machine, steam setting at 120 ° C. for 1 minute was performed, and a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm was obtained. It was.

  Table 2 shows the composition and various characteristics of G12 and the function expression rate in the fabric.

[Example 13]
A DMAc solution (35% by weight) of a polyurethane urethane polymer (urethane group concentration = 1.4 mol / kg) comprising PTMG, MDI, ethylene glycol having a molecular weight of 1800 and butanol as an end-capping agent was prepared by a conventional method, and polymer solution A5 It was.

  A5 and B1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution D9. This was dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, wound up, 20 gtex, 200 g of monofilament polyurethane elastic fiber E4 (urethane group concentration = 1.4 mol / kg) A thread was obtained.

  Using E4 and M1 described in Example 1, graft polymerization was performed at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G13 having f1 of 0.50% by weight. Further, using only G13, knitting was performed with a 320-needle one-necked cylinder knitting machine, and steam setting was performed at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. This was used as a fabric for evaluation.

  Table 2 shows the composition and various characteristics of G13 and the function expression rate in the fabric.

[Example 14]
Using E4 described in Example 13 and M4 described in Example 4, graft polymerization was performed at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G14 having f2 of 0.30% by weight. Furthermore, using only G14, knitting was performed with a 320-needle one-necked cylinder knitting machine, and steam setting was performed at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. This was used as a fabric for evaluation.

  Table 2 shows the composition and various characteristics of G14 and the function expression rate in the fabric.

[Example 15]
Graft polymerization was carried out using E4 described in Example 13 and M7 described in Example 7 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G15 having f3 of 16.80% by weight. Furthermore, using only G15, knitting was performed with a 320-needle one-necked cylinder knitting machine and steam setting was performed at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. This was used as a fabric for evaluation.

  Table 2 shows the composition and various characteristics of G15 and the function expression rate in the fabric.

[Example 16]
Graft polymerization was carried out using E4 described in Example 13 and M10 described in Example 10 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G16 having f4 of 8.00% by weight. Furthermore, using only G16, knitting was performed with a 320-needle one-necked knitting machine, and steam setting was performed at 120 ° C. for 1 minute to obtain a tubular knitted fabric having a diameter of about 7 cm and a length of 50 cm. This was used as a fabric for evaluation.

  Table 2 shows the composition and various characteristics of G16 and the function expression rate in the fabric.

[Example 17]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Furthermore, AIBN as an initiator, and “RUVA-93” (6- (2H-benzotriazol-2-yl) -4-methacryloyloxyethyl) -2- [3 ′-(2H) manufactured by Otsuka Chemical Co., Ltd. as a vinyl monomer. -Benzotriazol-2-yl) -2'-hydroxy-5'-methylphenyl] methylphenol (corresponding to Formula 2) is dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio). M17 (RUVA-93 0.5 wt%).

  Graft polymerization was performed using E1 and M17 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber G17 containing 0.50% by weight of the polymer component (f5) composed of RUVA-93. Furthermore, using only G17, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 3 shows the composition and various characteristics of G17 and the function expression rate in the fabric.

[Example 18]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and vinylbenzyltrimethylammonium chloride (corresponding to Formula 33) as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M18 (vinylbenzyltrimethylammonium chloride 0). 0.5% by weight).

  Graft polymerization was performed using E1 and M18 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G18 having a polymer component (f6) composed of vinylbenzyltrimethylammonium chloride of 0.50% by weight. Furthermore, using only G18, knitting on a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 3 shows the composition and various characteristics of G18 and the function expression rate in the fabric.

[Example 19]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 3- (methacryloyloxy) propyltris (trimethylsiloxy) silane (formula 13) as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to prepare a reaction solution M19 ( 3- (methacryloyloxy) propyltris (trimethylsiloxy) silane 0.5 wt%.

  The graft polymerization treatment was carried out using E1 and M19 at 80 ° C. for 2 hours, and the polymer component (f7) composed of 3- (methacryloyloxy) propyltris (trimethylsiloxy) silane was 0.50% by weight. A polyurethane elastic fiber G19 was obtained. Furthermore, using only G19, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 3 shows the composition and various characteristics of G19 and the function expression rate in the fabric.

[Example 20]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as the initiator, styrene (corresponding to Formula 13) as the vinyl monomer, and maleic anhydride (corresponding to Formula 4) are dissolved in a mixed solvent of water and isopropanol 5 to 1 (weight ratio) to prepare a reaction solution M20 ( Styrene 0.5% by weight, maleic anhydride 0.47% by weight).

  Graft polymerization was performed using E1 and M20 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber G20 having a polymer component (f8) composed of styrene and maleic anhydride of 0.50% by weight. Furthermore, using only G20, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 3 shows the composition and various characteristics of G20 and the function expression rate in the fabric.

[Comparative Example 1]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

Further, a mixed solvent of 5: 1 (weight ratio) of water and isopropanol was prepared, impregnated with E1, and treated at 80 ° C. for 2 hours, and the treated polyurethane elastic yarn was designated as E11. E11
Knitted with a 320-needle one-neck knitting machine and steam set at 120 ° C. for 1 minute to obtain a tubular knitted fabric having a diameter of about 7 cm and a length of 50 cm. This was used as a fabric for evaluation. .

  Tables 2 and 3 show the composition and various characteristics of E11 and the function expression rate in the fabric.

[Comparative Example 2]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-methacryloyloxyethyl phosphorylcholine as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M13 (2-methacryloyloxyethyl phosphorylcholine 0.03% by weight). ).

  Graft polymerization treatment was carried out using E1 and M13 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber H1 having f3 of 0.01% by weight. Furthermore, using only H1, knitting on a 320-needle one-necked cylinder knitting machine, steam setting was performed at 120 ° C. for 1 minute, and a tubular knitted fabric having a diameter of about 7 cm and a length of 50 cm was obtained. It was.

  Table 2 shows the composition and various characteristics of H1, and the function expression rate in the fabric.

[Comparative Example 3]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and methacrylic acid as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol 5 to 1 (weight ratio) to obtain a reaction solution M14 (0.03% by weight of methacrylic acid).

  Graft polymerization was performed using E1 and M14 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber H2 having f1 of 0.05% by weight. Furthermore, using only H2, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of H2, and the function expression rate in the fabric.

[Comparative Example 4]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2,2,2-trifluoroethyl methacrylate as a vinyl monomer are dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to prepare a reaction solution M15 (methacrylic acid 2,2, 2-trifluoroethyl).

  Graft polymerization was performed using E1 and R15 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber H3 having f2 of 48.20% by weight. Furthermore, using only H3, knitting with a 320-needle one-neck knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a tubular knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of H3 and the function expression rate in the fabric.

[Comparative Example 5]
A polyurethane elastic fiber E1 described in Example 1 was prepared.

  Further, AIBN as an initiator and 2-hydroxyethyl methacrylate as a vinyl monomer were dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio) to obtain a reaction solution M16 (2-hydroxyethyl methacrylate 50.0% by weight). ).

  Graft polymerization was performed using E1 and M16 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber H4 having f4 of 45.10% by weight. Furthermore, using only H4, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of H4 and the function expression rate in the fabric.

[Comparative Example 6]
A solution polymerization reaction was carried out by a conventional method using M2 described in Example 2, and the resulting polymer was extracted with hexane and dried to obtain f1 polymethacrylic acid. Using this, a DMAc dispersion solution P1 containing 35% by weight of f1 was prepared.

  D1 and P1 described in Example 1 were uniformly mixed at 99.5 wt% and 0.5 wt%, respectively, to obtain a polyurethane spinning solution D2. This was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.2 between the godet roller and the winder, wound up, 20 dtex, 2 fil multifilament polyurethane elastic fiber H5 (urethane group concentration = 0.7 mol / kg) 200 g of wound yarn was obtained. Furthermore, using only H5, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of H5 and the function expression rate in the fabric.

[Comparative Example 7]
A solution polymerization reaction was carried out by a conventional method using M5 described in Example 5, and the resulting polymer was extracted with hexane and dried to obtain poly (2,2,2-trifluoromethacrylate) which is f2. Ethyl was obtained. Using this, a DMAc dispersion solution P2 containing 35% by weight of f2 was prepared.

  D1 and P2 described in Example 1 were uniformly mixed at 81.6 wt% and 18.4 wt%, respectively, to obtain a polyurethane spinning solution D3. This was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.2 between the godet roller and the winder, wound up, 20 dtex, 2 fil multifilament polyurethane elastic fiber H6 (urethane group concentration = 0.7 mol / kg) Of 500 g was obtained. Furthermore, using only H6, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of H6 and the function expression rate in the fabric.

[Comparative Example 8]
The solution polymerization reaction was carried out in a conventional manner using M8 described in Example 8, and the resulting polymer was extracted with hexane and dried to obtain poly (2-methacryloyloxyethyl phosphorylcholine) as f3. It was. Using this, a DMAc dispersion solution P3 containing 35% by weight of f3 was prepared.

  D1 and P3 described in Example 1 were uniformly mixed at 64.6% by weight and 35.4% by weight, respectively, to obtain a polyurethane spinning solution D4. Attempts were made to dry-spin this, but because there were too many polymer components in the spinning solution, yarn breakage occurred frequently, and spinning was impossible and yarn could not be obtained.

[Comparative Example 9]
A solution polymerization reaction was carried out by a conventional method using M11 described in Example 11, and the resulting polymer was extracted with hexane and dried to obtain polyhydroxy 2-hydroxyethyl methacrylate f4. Using this, a DMAc dispersion solution P4 containing 35% by weight of f4 was prepared.

  D1 and P4 described in Example 1 were uniformly mixed at 70.5 wt% and 29.5 wt%, respectively, to obtain a polyurethane spinning solution D5. Attempts were made to dry-spin this, but because there were too many polymer components in the spinning solution, yarn breakage occurred frequently, and spinning was impossible and yarn could not be obtained.

[Comparative Example 10]
A polyurethane urethane polymer (urethane group concentration = 0.7 mol / kg) composed of PBD (manufactured by Nippon Soda Co., Ltd.), HPBD (manufactured by Nippon Soda Co., Ltd.), MDI and 1,4-butanediol described in Patent Document 3. Obtained. Further, a dioxane solution (12% by weight) of this polyurethane urethane polymer was prepared, and a methanol solution (30% by weight) of 2-methacryloyloxyethyl phosphorylcholine was added to the polyurethane urethane polymer: 2-methacryloyloxyethyl phosphorylcholine = 2.5. : 1 (weight ratio). AIBN was added to this mixed solution, graft polymerization was carried out at 80 ° C. for 2 hours, and the resulting polymer was extracted with methanol and hexane and then dried, so that f3 was 16.80%. A polyurethane polymer was obtained.

  A DMAc solution (35% by weight) of the grafted polyurethane polymer was prepared by a conventional method to obtain a polymer solution A2.

  A2 and B1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution D6. This was dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder and wound up. While spinning for 24 hours, the yarn was broken 35 times, but 20 dtex, monofilament polyurethane elastic fiber H9 ( A 50 g wound body with a urethane group concentration of 0.7 mol / kg was obtained. Furthermore, using only H9, knitting with a 320-needle one-necked cylinder knitting machine, and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. A fabric was obtained.

  Table 2 shows the composition and various characteristics of H9 and the function expression rate in the fabric.

[Comparative Example 11]
A DMAc solution (35% by weight) of polyurethane urea polymer (urethane group concentration = 0.1 mol / kg) composed of PTMG having a molecular weight of 2900, MDI, ethylenediamine and diethylamine as an end-capping agent was prepared by a conventional method. did.

  A3 and B1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution D7. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.2 between the godet roller and the winder and wound up. While spinning for 24 hours, the yarn was broken 23 times, but 20 dtex, 2fil multifilament polyurethane elasticity A 50 g wound body of fiber E2 was obtained.

  Using E2 and M1 described in Example 1, a graft polymerization treatment was performed at 80 ° C. for 2 hours, and polyurethane elastic fiber H7 having an f1 of 0.51% by weight (urethane group concentration = 0.1 mol / kg) ) Furthermore, using only H7, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of H7 and the function expression rate in the fabric.

[Comparative Example 12]
A DMAc solution (35% by weight) of a polyurethaneurea polymer (urethane group concentration = 3.8 mol / kg) composed of PTMG, MDI, ethylenediamine having a molecular weight of 2900, and diethylamine as an end-capping agent was prepared by a conventional method. did.

  A4 and B1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution D8. This was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.2 between the godet roller and the winder, wound up, and broken 27 times during 24 hours of spinning, but 20dtex, 2fil multifilament polyurethane elasticity A 40 g wound body of fiber E3 (urethane group concentration = 3.8 mol / kg) was obtained.

  Using E3 and M1 described in Example 1, graft polymerization was carried out at 80 ° C. for 2 hours to obtain polyurethane elastic fiber H8 having f1 of 0.49% by weight. Furthermore, using only H8, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 2 shows the composition and various characteristics of H8 and the function expression rate in the fabric.

[Comparative Example 13]
A solution polymerization reaction was carried out by a conventional method using M17 described in Example 17, and the obtained polymer was extracted with hexane and dried to obtain a polymer component consisting of f5. Using this, a DMAc dispersion solution P5 containing 35% by weight of f5 was prepared.

  D1 and P5 described in Example 1 were uniformly mixed at 99.5 wt% and 0.50 wt%, respectively, to obtain a polyurethane spinning solution D10. When this was dry-spun in the same manner as in Example 1, the yarn was broken three times during the spinning for 24 hours, but 300 g of 20 dtex, 2 fil multi-filament polyurethane elastic fiber H10 (urethane group concentration = 0.7 mol / kg). A wound body was obtained.

  Furthermore, using only H10, knitting with a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 3 shows the composition and various characteristics of H10 and the function expression rate in the fabric.

[Comparative Example 14]
A solution polymerization reaction was carried out using M18 described in Example 18 by a conventional method, and the polymer obtained was extracted with hexane and dried to obtain a polymer component consisting of f6. Using this, a DMAc dispersion solution P6 containing 35% by weight of f6 was prepared.

  D1 and P6 described in Example 1 were uniformly mixed at 99.5% by weight and 0.50% by weight, respectively, to obtain a polyurethane spinning solution D11. When this was dry-spun in the same manner as in Example 1, the yarn was broken 21 times during the spinning for 24 hours, but 150 g of 20 dtex, 2 fil multi-filament polyurethane elastic fiber H11 (urethane group concentration = 0.7 mol / kg). A wound body was obtained.

  Furthermore, using only H11, knitting on a 320-needle one-necked cylinder knitting machine and performing steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 3 shows the composition and various characteristics of H11 and the function expression rate in the fabric.

[Comparative Example 15]
A solution polymerization reaction was carried out using M19 described in Example 19 by a conventional method, and the polymer obtained was extracted with hexane and then dried to obtain a polymer component consisting of f7. Using this, a DMAc dispersion solution P7 containing 35% by weight of f7 was prepared.

  D1 and P7 described in Example 1 were uniformly mixed at 99.5% by weight and 0.50% by weight, respectively, to obtain a polyurethane spinning solution D12. When this was dry-spun in the same manner as in Example 1, the yarn was broken eight times during the spinning for 24 hours, but 250 g of 20 dtex, 2 fil multifilament polyurethane elastic fiber H12 (urethane group concentration = 0.7 mol / kg). A wound body was obtained.

  Furthermore, using only H12, knitting with a 320-needle one-necked cylinder knitting machine and steam setting at 120 ° C. for 1 minute to obtain a cylindrical knitted fabric having a diameter of about 7 cm and a length of 50 cm. It was.

  Table 3 shows the composition and various characteristics of H12 and the function expression rate in the fabric.

[Comparative Example 16]
A solution polymerization reaction was carried out using M20 described in Example 20 by a conventional method, and the polymer obtained was extracted with hexane and then dried to obtain a polymer component consisting of f8. Using this, a DMAc dispersion solution P8 containing 35% by weight of f8 was prepared.

  D1 and P8 described in Example 1 were uniformly mixed at 99.5% by weight and 0.50% by weight, respectively, to obtain a polyurethane spinning solution D13. In the same manner as in Example 1, dry spinning was attempted. However, yarn breakage occurred frequently, and spinning was impossible and a yarn could not be obtained.

  The polyurethane elastic fiber of the present invention has an excellent function expression rate per unit compound of a functional molecule in addition to stretchability. Because it has an excellent function expression rate, it is possible to functionalize the fiber with a low concentration of functional agent, which makes it excellent in lightness, durability, texture and appearance quality without impairing the stretchability of polyurethane elastic fiber It becomes.

  In addition, according to the present invention, since the polyurethane elastic fiber has these excellent characteristics, it is possible to obtain an excellent stretch fabric by combining it with various fibers as well as using it alone. Suitable for string processing. Specific applications that can be used include socks, stockings, circular knitting, tricots, swimwear, ski pants, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, various textile products such as gloves, fastening materials, Further examples include fastening materials for preventing sanitary items such as paper diapers, waterproofing materials, imitation baits, artificial flowers, electrical insulation materials, wiping cloths, copy cleaners, and gaskets.

Claims (12)

A polyurethane elastic fiber containing polyurethane starting from a polymer diol and a diisocyanate, wherein the urethane group concentration of the polyurethane is 0.2 mol / kg or more and 3.5 mol / kg or less with respect to 1 kg of polyurethane, A polyurethane having a coating polymer obtained by polymerizing a vinyl monomer represented by the general formula (1), and having an average thickness of 121 nanometers or more and 2246 nanometers or less. Elastic fiber.

(In the formula, R, R ′, and R ″ each independently represent a hydrogen atom or an arbitrary substituent.) 2. The polyurethane elastic fiber according to claim 1, wherein the content of the coating polymer in the polyurethane elastic fiber determined from the weight ratio is 0.1% or more and 40% or less. 3. The polyurethane elastic fiber according to claim 1, wherein the film polymer has at least one of a carboxyl group, a phosphorylcholine group, and a benzotriazole structure in a molecule. The polyurethane elastic fiber according to any one of claims 1 to 3, wherein the vinyl monomer is (meth) acrylic acid or a compound represented by the following general formula (2) or (3).

The polyurethane elastic fiber according to any one of claims 1 to 4, wherein the coating polymer is directly bonded to the polyurethane by graft polymerization. A spinning stock solution containing a polyurethane starting from a polymer diol and a diisocyanate was spun from a die to obtain a fiber having a urethane group concentration of 0.2 to 3.5 mol / kg of polyurethane relative to 1 kg of polyurethane. Thereafter, a vinyl monomer represented by the following general formula (1) or an oligomer made of the vinyl monomer is polymerized or a polymer made of the vinyl monomer is fixed to the surface of the fiber, and the average thickness is 121 nanometers or more and 2246 nanometers. A method for producing a polyurethane elastic fiber, comprising forming a film polymer having a diameter of less than a meter .

(In the formula, R, R ′, and R ″ each independently represent a hydrogen atom or an arbitrary substituent.) At the time of forming the coating polymer, the fiber is brought into contact with a solution in which the concentration of the vinyl monomer or the oligomer composed of the vinyl monomer or the concentration of the polymer composed of the vinyl monomer is 0.1 wt% or more and 40 wt% or less. The method for producing a polyurethane elastic fiber according to claim 6, wherein the vinyl monomer or an oligomer made of the vinyl monomer is polymerized or a polymer made of the vinyl monomer is fixed. The polyurethane elastic fiber according to claim 6 or 7, wherein the polyurethane elastic fiber is polymerized so that the content of the coating polymer obtained from weight ratio conversion is 0.1% or more and 40% or less. Production method. The method for producing a polyurethane elastic fiber according to any one of claims 6 to 8, wherein the film polymer has in its molecule at least one of a carboxyl group, a phosphorylcholine group, and a benzotriazole structure. The polyurethane elastic fiber according to any one of claims 6 to 9, wherein the vinyl monomer is (meth) acrylic acid or a compound represented by the following general formula (2) or (3). Production method.

The method for producing a polyurethane elastic fiber according to any one of claims 6 to 10, wherein the film polymer is directly bonded to the polyurethane by graft polymerization. The method for producing a polyurethane elastic fiber according to any one of claims 6 to 11, wherein the spinning method is dry.