JP5636616B2 - Stretch fabric - Google Patents

Description

  The present invention relates to stretch fiber products. More specifically, a stretch fiber product having excellent stretch properties, deodorizing properties and appearance quality obtained by pulverizing polyurethane after spinning into polyurethane elastic short fibers and coating the fiber surface with an anionic vinyl monomer. About.

  In recent years, awareness of health and hygiene has increased in daily life. Good stretchability for clothing items (clothing fabrics, knitted fabrics, fiber structures, etc.) and materials (automobile materials, packaging materials, etc.) Products and technologies that have added functions such as deodorizing and antibacterial properties to daily odors in addition to the buffer and buffer properties are also attracting attention.

  In general, life odors include aging odors and excretion odors, and according to the evaluation standard of “deodorization processing” published by the Fiber Evaluation Technology Council, odors of aging are ammonia, acetic acid. In addition, the function of removing all components of isovaleric acid and nonenal is essential, and the function of removing all components of ammonia, acetic acid, methyl mercaptan, hydrogen sulfide and indole is essential for the elimination of excretion odor. It is said that. Therefore, there is a demand for a textile product that has both a deodorizing effect and stretchability for each of these odors, and that exhibits performance with the minimum necessary functional agents from the standpoint of process stabilization during manufacturing and reduction in manufacturing costs. ing.

  Stretch fabrics that combine modified cellulosic fibers, polyester fibers, and polyurethane elastic fibers are known to have excellent aging odor and deodorant properties as an attempt to impart stretch and deodorant properties to textile products. (Patent Document 1). However, in the technique described in this document, in order to obtain a stretch fiber product having aging deodorant properties, it is essential to combine specific fibers with polyurethane elastic fibers at a specific ratio.

  Further, in order to impart excrement deodorant properties and antibacterial properties, there is provided a fiber structure in which a polymer film containing inorganic fine particles is formed on the fiber surface and an antibacterial agent and a photocatalyst are contained on the surface or inside of the film. It has been proposed (Patent Document 2). However, the technique described in this document is a technique belonging to a post-processing technique for imparting excrement deodorant property and antibacterial property to a fabric using a single inelastic fiber such as polyester fiber. Therefore, when the same structure is applied to a fiber structure containing polyurethane elastic fibers, the stretchability and appearance quality depending on the polyurethane elastic fibers are often impaired due to the influence of the added inorganic particles and antibacterial agents.

  Moreover, the technique which mixes the polyurethane short fiber which adhered the hydrophilic processing agent to the cellulose paper product used for goods packaging, and provides stretch property is proposed (patent document 3). However, there is no description of deodorant and antibacterial properties in this document, and the hydrophilic treatment agent described in this document improves the water dispersibility of polyurethane short fibers and is expected to have a deodorant effect and an antibacterial effect. It is not possible.

JP 2009-191415 A JP 2008-155671 A JP 2004-19069 A

  The present invention provides a stretch fiber product that improves the disadvantages of the prior art and maintains the strength and elongation important for the stretchability of polyurethane elastic fibers, and has an excellent deodorizing function and appearance quality. Let that be the issue.

The present invention employs any of the following means in order to solve the above-described problems.
(1) Containing urethane elastic short fibers 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, and the elastic short fibers have a fiber length in the range of 1 mm or more and 100 mm or less. A stretch fiber product comprising a coating polymer obtained by polymerizing at least one kind of anionic vinyl monomer on the fiber surface.
(2) The stretch fiber according to (1) above, wherein the content of the coating polymer in the elastic short fiber obtained from the weight ratio conversion is 0.1% to 40% by weight. Product.
(3) The stretch fiber product according to (1) or (2) above, wherein the average thickness of the coating polymer is 1 nanometer or more and 5 micrometers or less.
(4) The stretch fiber product according to any one of (1) to (3), wherein the content of the elastic short fibers in the stretch fiber product is 1% by weight or more and 50% by weight or less.
(5) The stretch fiber product according to any one of (1) to (4), wherein the film polymer is directly bonded to the polyurethane by graft polymerization.
(6) The stretch fiber product according to any one of (1) to (5), wherein the film polymer forms a salt or a complex with a metal ion.
The stretch fiber product is a stretch fabric, and the content of the coating polymer in the elastic short fiber obtained from the weight ratio conversion is 0.1% by weight to 2.6% by weight, and the elasticity The short fiber content is preferably 1% by weight or more and 20% by weight or less.

  The stretch fiber product of the present invention is excellent not only in stretch properties and appearance quality, but also in antibacterial properties and deodorizing properties (especially deodorizing properties against aging odor and excretion odor).

  Details of the present invention will be described below.

  First, the elastic short fibers of polyurethane used in the present invention will be described.

The elastic short fiber is obtained by shortening an elastic fiber containing polyurethane. The polyurethane constituting the elastic fiber may be any as long as it uses a polymer diol and a diisocyanate as starting materials. It 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, polyolefin-based 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 elastic short 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 polyurethane elastic fiber containing polyurethane having the basic structure as described above is shortened to a fiber length in the range of 1 mm to 100 mm, and antibacterial and deodorant functions are exhibited on the fiber surface. Maintaining excellent stretch and appearance quality as a textile product by polymerizing an anionic vinyl monomer or an oligomer made of the anionic vinyl monomer, or providing a film polymer to which the polymer made of the anionic vinyl monomer is fixed. However, excellent antibacterial and deodorizing functions can be exhibited. That is, by providing the film polymer on the surface of the polyurethane fiber having a specific urethane group concentration, it can be a fiber that can exhibit antibacterial and deodorizing functions while maintaining stretch properties based on polyurethane, At the same time, by making the polyurethane elastic fibers short fibers as described above, the surface area per mass of the fiber product can be increased, thereby exhibiting excellent antibacterial and deodorant properties as a fiber product. In addition, the stretchability and appearance quality can be kept good.

  In addition, when the fiber length is less than 1 mm, it is difficult to produce by mechanical shredding, and the stretch property is lowered when a stretch fiber product is obtained. When the fiber length exceeds 100 mm, the appearance of the polyurethane elastic fiber tends to be exposed when it is made into a stretch fiber product, resulting in poor appearance quality. In order to further improve stretchability and appearance quality, the thickness is more preferably 3 to 70 mm, and further preferably 5 to 50 mm.

  The anionic vinyl monomer in the present invention is a vinyl monomer having one or more functional anion active groups that dissociate while forming anions in an aqueous solution, and is a vinyl monomer having a pH of less than 7 in an aqueous solution. is there.

  In the present invention, the anionic vinyl monomer constituting the film polymer may be any and is not particularly limited. One molecule of the anionic vinyl monomer preferably contains at least one or more of a carboxyl group, a sulfo group, a sulfonyl group, a phosphoric acid group, a phosphorous acid group and a phenolic hydroxyl group as an anionic group. Anionic vinyl monomers particularly preferably used for imparting antibacterial properties, age-related odor and deodorizing properties to elastic fibers include (meth) acrylamidomethylpropanesulfonic acid, (meth) acrylic acid, ( (Meth) acrylic acid sodium, 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 phospho Acid, sorbic acid, parinaric acid, bis-methacryloxyethyl phosphate, vinyl sulfonic acid, alkyl vinylphosphonate, vinyl pivalate, phthalic acid, fumaric acid, maleic acid, linoleic acid, linolenic acid, vinyl phosphate, phosphoric acid 2- (methacryloyloxy) ethyl and the like can be mentioned.

  The thickness of the coating polymer obtained by polymerizing the above anionic vinyl monomers is preferably 1 nanometer or more and 5 micrometers or less on average. When the thickness of the coating polymer is 1 nanometer or more on average, the functional agent is exposed at a more sufficient concentration on the surface of the elastic short fiber, and the effect of the functional agent can be efficiently expressed. Preferably it is 5 nanometers or more on average. On the other hand, if the average thickness of the coating polymer is 5 micrometers or less, the strength and elongation depending on polyurethane are more reliably maintained, the stretch property is excellent, and the texture is excellent even when the fiber product is used. It is easy to become. The average is preferably 2 micrometers or less. From the viewpoint of achieving both better effect of the functional agent and maintaining the texture and stretchability, an average range of 5 nanometers to 2 micrometers is more 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 of the film polymer obtained by polymerizing the anionic vinyl monomer in the elastic elastic fiber of polyurethane is preferably in the range of 0.1 wt% to 40 wt%. If the content of the coating polymer is 0.1% by weight or more, the functional agent is exposed at a sufficient concentration on the surface of the elastic short fiber, and the effect of the functional agent can be efficiently expressed. it can. Preferably it is 0.3 weight% or more. On the other hand, when the content of the coating polymer is 40% by weight or less, the strength and elongation depending on polyurethane are more reliably maintained, the stretch property is excellent, and the texture is excellent even when the fiber product is used. It is easy to become. 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.

  Further, from the viewpoint of reducing the chargeability of the polyurethane elastic short fibers, it is also preferable that the film 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 elastic short fibers.

  Although the stretch fiber product of the present invention may be composed of only the elastic short fibers of polyurethane as described above, it is preferable to mix other fibers as described below. The range of the content of polyurethane elastic fibers in the stretch fiber product is preferably 1% by weight or more and 50% by weight or less. From the viewpoint of achieving a good balance between good antibacterial and deodorizing properties and texture, a range of 5% by weight to 20% by weight is more preferable.

  Arbitrary fibers can be used as the other fibers to be mixed, and are not particularly limited. That is, examples of synthetic fibers include polyester fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyacrylonitrile fibers, and fluorine fibers. It is done. Examples of the polyester fiber include a polyester fiber containing an aromatic component and an aliphatic polyester fiber. Examples of polyester fibers containing an aromatic component include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, or those and third components such as isophthalic acid, isophthalic acid sulfonate, adipic acid, and polyethylene glycol. can do. Examples of the aliphatic polyester fiber include poly-L lactic acid, poly-D lactic acid and poly-D, homopolymer composed of L-lactic acid, and polylactic acid-glycolic acid copolymer.

  Non-synthetic fibers include regenerated cellulose fibers such as viscose rayon and copper-ammonia rayon polynosic, refined cellulose fibers such as tencel, semi-synthetic fibers such as acetate and diacetate, natural materials such as cotton, hemp, silk, and wool. Examples thereof include regenerated fibers such as fibers, chitin / chitosan fibers, and collagen fibers.

  These other fibers can be used alone or in admixture of two or more with the above-mentioned polyurethane elastic short fibers. In addition, about another fiber, you may mix a short fiber, a long fiber, or these.

  In the present invention, there are no particular limitations on the fineness, cross-sectional shape, etc., of the elastic fibers of polyurethane and other fibers used in combination. For example, the cross-sectional shape of the yarn may be circular or flat.

  Further, the elastic short fibers of polyurethane used in the present invention and any other fibers mixed therewith contain various stabilizers, pigments and the like as long as they do not impair the effects of the present invention. It may be. 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.

  The stretch fiber product referred to in the present invention refers to fabrics such as woven fabrics, knitted fabrics, nonwoven fabrics, felts, and paper.

  Next, the manufacturing method of the stretch fiber product of this invention is demonstrated in detail.

  First, polyurethane short elastic fibers used in the stretch fiber product of the present invention are manufactured. A polymer diol and diisocyanate are used as starting materials, and a spinning stock solution containing polyurethane obtained therefrom is spun from a die into fibers. Thereafter, the fiber is chopped into short fibers having a fiber length of 1 mm to 100 mm, and an anionic vinyl monomer or an oligomer made of the anionic vinyl monomer is polymerized on the surface of the fiber, or the anion A polymer composed of a conductive vinyl monomer 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 a spinning stock solution containing polyurethane and the method for producing polyurethane as a solute in the spinning stock 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 make the melting point on the high temperature side 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 spinning dope 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 spinning dope to a viscosity suitable for spinning. 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.

  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, as a method for shortening the polyurethane elastic fiber to make the fiber length in the range of 1 mm to 100 mm, a method of mechanically chopping the spun fiber by a known method is preferable. Although the shredding method is not particularly limited, a general method of shredding with a blade or heat after spinning can be employed.

  In the present invention, in providing a film polymer obtained by polymerizing at least one or more types of anionic vinyl monomers on the surface of polyurethane elastic short fibers, the polyurethane solution is spun from the die as described above to obtain fibers. Later, the fibers are chopped into short fibers having a fiber length of 1 mm to 100 mm, and an anionic vinyl monomer or an oligomer made of the vinyl monomer is polymerized on the surface of the fiber, or a polymer made of the anionic vinyl monomer. It is preferable to form a film polymer by fixing. Note that the order of the step of forming the coating polymer and the step of chopping the fibers to shorten them may be reversed.

  When a film polymer is provided on the fiber surface by polymerization, any method such as graft polymerization of an anionic vinyl monomer or an oligomer composed of an anionic vinyl monomer onto a fiber molecule can be employed.

  On the other hand, the resin fixing method to the fiber surface includes a method in which a polymer layer made of an anionic vinyl monomer is fixed to the fiber surface with a binder resin, or a fiber is immersed in a solution containing the polymer made of the anionic vinyl monomer. Examples thereof include 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 of an anionic vinyl monomer or an oligomer composed of an anionic vinyl monomer onto a fiber molecule. One example will be described below.

  An anionic vinyl monomer that forms a film polymer or an oligomer composed of the anionic vinyl monomer, a commonly known graft polymerization initiator known as AIBN as an azo initiator, BPO as an organic peroxide initiator, and an interface After immersing the fiber to be treated in an aqueous mixed solution containing an activator, a 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 fiber to be treated is irradiated with an electron beam in advance and then immersed in a solution containing an anionic vinyl monomer or an oligomer made of an anionic vinyl monomer. A pre-irradiation polymerization method for forming a polymer, or simultaneously forming a coating polymer by irradiating an electron beam after immersing the treated fiber in a solution containing an anionic vinyl monomer or an oligomer made of an anionic vinyl monomer An irradiation polymerization method 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 solution having an anionic vinyl monomer or an oligomer composed of the anionic vinyl monomer in a concentration of 0.1% by weight to 40% by weight, and the anionic vinyl monomer or the oligomer composed of the anionic 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. If the urethane group concentration and the solution concentration of the anionic vinyl monomer or the oligomer composed of the anionic vinyl monomer are within the above range, the method for forming the coating polymer may be any of the methods described above, preferably a polymerization initiator. , Electron beam, gamma ray, and ultraviolet ray methods can be used.

  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, it is preferable to polymerize at a solution concentration in which the concentration of the anionic vinyl monomer or the oligomer composed of the anionic vinyl monomer is 0.1 wt% or more and 40 wt% or less, Furthermore, it is preferable to polymerize at a reaction temperature in the range of 80 ° C. or higher and 180 ° C. or lower.

  The stretch fiber product of the present invention is obtained by producing a blend or a fabric from the above-mentioned polyurethane elastic short fibers and any other fibers according to a conventional method, and is any of a woven fabric, a knitted fabric, a non-woven fabric or a felt. May be. For example, a nylon yarn may be covered with a spun yarn obtained by twisting polyurethane elastic short fibers to obtain a fabric as a covering elastic fiber, or a spinning obtained by twisting polyurethane elastic short fibers to a polyester yarn. The yarn may be woven or knitted with bare yarn (bare) as an interwoven fabric. Furthermore, in the case of a woven fabric, it may be woven only with the above-mentioned spun yarn made of polyurethane elastic short fibers and other fibers, or fibers other than these may be interwoven.

  Weaving organization includes plain weaving, oblique weaving, satin weaving, etc., changing plain weaving, changing weaving weaving, changing satin weaving, etc., weaving weaving, imitation weaving, satin weaving, etc. Double weave such as double weave, weft double weave, double weave weave, bag weave, double velvet such as double velvet, multi-layer structure such as belt weave, vertical pile weave such as velvet, towel, seal, velor In addition, bevel piles such as bevel, velvet, velvet, cole heaven and the like, and entangled structures such as cocoons, cocoons and crests are preferred.

  Weaving is preferably carried out with a loom (such as a fly shuttle loom) or a non-weaving loom (such as a rapier loom, a gripper loom, a water jet loom, an air jet loom).

  Also, in the case of a knitted fabric, the yarn may be knitted only with the spun yarn composed of the polyurethane elastic short fibers and other fibers, or fibers other than these may be knitted. The type of the knitted fabric may be a weft (weft) knitted fabric or a warp (warp) knitted fabric. The weaving structure is preferably a flat knitting, rubber knitting, double-sided knitting, pearl knitting, tuck knitting, floating knitting, one-sided knitting, lace knitting, or splicing. Atlas knitting, double cord knitting, half tricot knitting, back hair knitting, jacquard knitting and the like are preferable. The number of layers may be a single layer or a multilayer of two or more layers.

  The knitting is preferably performed by a flat knitting machine such as a circular knitting machine, a flat knitting machine, or a cotton knitting machine, a tricot knitting machine, a Raschel knitting machine, a Milanese knitting machine, or the like.

  Furthermore, the stretch fiber product of the present invention is particularly suitable as socks and underwear such as tights, stockings, pantyhose and socks.

  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.

[Deodorization]
The deodorization test conforms to the deodorant processed fiber product certification standard (the enactor is the fiber evaluation technology council product certification department, the establishment date is September 1, 2002), equipment test (detection tube method or GC The deodorant property of odor components was evaluated by the 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. In addition, when the reduction rate of ammonia, acetic acid, indole, methyl mercaptan, and hydrogen sulfide is 70% or more, 80% or more, 70% or more, 70% or more, 70% or more, respectively, excretion odor deodorization It is defined as having sex. About age-related odor deodorant and excretion odor deodorant, when all the odor component reduction rates defined in each were satisfied (indicated by ○), even one odor component was not deodorized The case was rejected (display x).

[Antimicrobial]
Conforms to the manual for quantitative antibacterial testing of textile products established by the Council for Evaluation of New Functionality of Textile Products. The test method is as follows.
1. The sterilized neutral broth at 1/20 concentration was uniformly inoculated with 0.4 g of the following test bacteria 1 ± 0.3 × 10 ⁵ cells / ml and cultured at 37 ° C. for 18 hours.
2. After completion of the culture, the test bacteria are washed out, and a pouch plate agar medium is prepared with the solution, followed by culturing at 37 ° C. for 24 to 48 hours and measuring the number of viable bacteria. For unprocessed products (samples not subjected to antibacterial treatment), the test bacteria are washed out immediately after inoculation, and a pouched plate agar medium is prepared with the solution, followed by culturing at 37 ° C. for 24-48 hours. The number of viable bacteria was measured.
3. Antibacterial properties are 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.

  The fabric after washing 10 times was used as a sample, all measurements were performed at n = 3, and the average of these n values was expressed. In addition, according to the antibacterial and deodorant processed fiber product certification standard established by the Japan Fiber Evaluation Technology Council, the antibacterial effect is recognized when the bacteriostatic activity value is 2.2 or more. In the case where the bacteriostatic activity value was 2.2 or more, it was regarded as acceptable (displayed ○), and all other cases were regarded as rejected (displayed ×).

[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.

[Dough stretchability]
Stretch fabric stipulated in JIS L1096-1998 6.14.1 with fabric elongation S1 (%) at a temperature of 23 ° C. and humidity 65 RH% and fabric elongation S2 (%) at a temperature of 43 ° C. and humidity 65 RH% The elasticity was measured by the stretch B method (constant load method).

  The determination of fabric stretchability is a pass (indication ○) when both S1 and S2 are 20% or more, and a failure (indication ×) when at least one of S1 and S2 is less than 20%. did.

[Appearance quality]
After making it into a fabric fabric, it was preset and subjected to a dry heat treatment to produce a stretch fabric. About the obtained stretch fabric (a fabric with a width of 1.8 m and a length of about 20 m), the appearance of the fabric was visually inspected, the polyurethane structure was enlarged and observed, and the determination was made according to the following criteria. The determination was performed by five people, and the mode value (the determination that appeared most frequently) was used. When the determination was divided into two, two, and one, the determination was “◯”.
A: There are no wavy or streak-like defects, and the structure is homogeneous.
○: There are partial undulations and streak-like defects, and no more than one place per 20 m.
X: There are wavy and streak-like defects, and there are one or more places per 20 m.

[Other fiber raw material ingredients]
The following were used for lyocell raw cotton and PET raw cotton which are other fiber raw cotton components described in the present invention.

Lyocell raw cotton: Lyocell raw lyocell raw cotton (1.5 denier)
PET raw cotton: Invista polyester fiber raw cotton (1.5 denier)
[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 are uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution, and this is dry-spun at a spinning speed of 600 m / min. , 20 dtex, 2 fil multifilament polyurethane elastic fiber C1 (500 g wound yarn).

  Further, AIBN as an initiator and sodium methacrylate as an anionic 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 R1 (sodium methacrylate 0.5% by weight).

  Graft polymerization treatment was performed using C1 and R1 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber D1 having a polymer component (f1) composed of sodium methacrylate of 2.30% by weight.

  D1 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn and steam set at 120 ° C. for 1 minute to obtain a stretch fabric E1, which was used as an evaluation fabric. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E1.

[Example 2] (This example is a reference example.)
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, AIBN as an initiator and sodium styrenesulfonate as an anionic 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 R2 (sodium styrenesulfonate 13.0% by weight). .

  Graft polymerization treatment was performed using C1 and R2 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber D2 having a polymer component (f2) composed of sodium styrenesulfonate of 30.5% by weight.

  D2 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute to obtain a stretch fabric E2, which was used as an evaluation fabric. did.

  Tables 2 and 3 show the composition and various characteristics of D2 and the results of functional evaluation of fabric E2.

[Example 3]
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D1 is cut into polyurethane short fibers with a fiber length of 3 mm, and 20% by weight and 80% by weight of lyocell raw cotton (fiber length 50 mm) are mixed uniformly, using a ring weaving spinning machine manufactured by Toyota Industries Corporation. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E3 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E3.

[Example 4]
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D4 is cut into polyurethane short fibers with a fiber length of 90 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively, and a ring weaving spinning machine manufactured by Toyota Industries Corporation is used. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E4 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E4.

[Example 5]
A DMAc solution (35% by weight) of a polyurethane urea polymer (urethane group concentration = 2.4 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.

  A2 and B1 described in Example 1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution. This was a speed ratio of 1.4 between the godet roller and the winder, and a spinning speed of 500 m / min. The yarn was dry-spun and wound up to obtain 20 dtex, 2 fil multifilament polyurethane elastic fiber C2 (350 g wound yarn).

  Using C2 and R1 described in Example 1, graft polymerization was performed at 80 ° C. for 2 hours to obtain polyurethane elastic fiber D3 having f1 of 2.30% by weight.

  D3 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38-inch diameter, 24-gauge, 114 feeder) was prepared from the prepared blended yarn and steam set at 120 ° C. for 1 minute to obtain a stretch fabric E5. did.

  Tables 2 and 3 show the composition and various characteristics of D3 and the functional evaluation results of fabric E5.

[Example 6] (This example is a reference example.)
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, AIBN as an initiator and sodium methacrylate as an anionic 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 R3 (sodium methacrylate 15.0% by weight).

  A graft polymerization reaction was carried out by a conventional method using C1 and R3 to obtain a polyurethane elastic fiber D4 having f1 of 31.1% by weight.

  D4 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E6 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D4 and the functional evaluation results of the fabric E6.

[Example 7]
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, AIBN as an initiator and sodium methacrylate as an anionic 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 R4 (sodium methacrylate 0.1% by weight).

  A graft polymerization reaction was carried out using C1 and R4 by a conventional method to obtain a polyurethane elastic fiber D5 having f1 of 0.05% by weight.

  D5 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E7 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D5 and the functional evaluation results of the fabric E7.

[Example 8] (This example is a reference example.)
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, AIBN as an initiator and sodium methacrylate as an anionic 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 R5 (sodium methacrylate 25.5% by weight).

  A graft polymerization reaction was carried out by a conventional method using C1 and R5 to obtain a polyurethane elastic fiber D6 having f1 of 35.5% by weight.

  D6 is chopped into polyurethane short fibers with a fiber length of 50 mm, and 20% by weight and 80% by weight of lyocell raw cotton (fiber length 50 mm) are mixed uniformly, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E8 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D6 and the results of functional evaluation of the fabric E8.

[Example 9]
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, AIBN as an initiator and sodium methacrylate as an anionic 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 R6 (0.25 wt% sodium methacrylate).

  A graft polymerization reaction was carried out by a conventional method using C1 and R6 to obtain a polyurethane elastic fiber D7 having f1 of 0.5% by weight.

  D7 is chopped into polyurethane short fibers with a fiber length of 50 mm, and this is mixed with 20% by weight and 80% by weight of lyocell raw cotton (fiber length 50 mm), respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E9 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D7, and the function evaluation results of fabric E9.

[Example 10] (This example is a reference example.)
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, AIBN as an initiator and sodium methacrylate as an anionic 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 R7 (sodium methacrylate 31.0% by weight).

  A graft polymerization reaction was carried out by a conventional method using C1 and R7 to obtain a polyurethane elastic fiber D8 having f1 of 45.1% by weight.

  D8 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E10 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D8, and the results of functional evaluation of the fabric E10.

[Example 11] (This example is a reference example.)
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D1 is cut into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 0.3% by weight and 99.7% by weight, respectively. Using a spinning machine, a blend yarn of 30th English cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E11 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E11.

[Example 12] (This example is a reference example.)
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D1 is cut into polyurethane short fibers with a fiber length of 50 mm, and 60% by weight and 40% by weight of lyocell raw cotton (fiber length 50 mm) are mixed uniformly, using a ring weaving spinning machine manufactured by Toyota Industries Corporation. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E12 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E12.

[Example 13]
A DMAc solution (35% by weight) of a polyurethane urethane polymer (urethane group concentration = 2.4 mol / kg) composed of PTMG, MDI, and ethylene glycol having a molecular weight of 1800 was prepared by a conventional method to obtain a polymer solution A3.

  A3 and B1 described in Example 1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution, which was a speed ratio of 1.4 between a godet roller and a winder and a spinning speed of 500 m / min. The yarn was dry-spun and wound up to obtain 20 dtex, monofilament polyurethane elastic fiber C3 (350 g wound yarn).

  Using C3 and R1 described in Example 1, graft polymerization was performed at 80 ° C. for 2 hours to obtain polyurethane elastic fiber D9 having f1 of 2.30% by weight.

  D9 is chopped into polyurethane short fibers with a fiber length of 50 mm, and 20% by weight and 80% by weight of lyocell raw cotton (fiber length 50 mm) are mixed uniformly, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn and steam set at 120 ° C. for 1 minute to obtain a stretch fabric E13. This was used as an evaluation fabric. did.

Tables 2 and 3 show the composition and various characteristics of D9 and the results of functional evaluation of the fabric E13.
[Example 14]
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, a solution polymerization reaction was carried out by a conventional method using R7 described in Example 10, and the obtained polymer was extracted with hexane and then dried to obtain a polymer component (f1) composed of sodium methacrylate. A polysodium methacrylate was obtained. This was dissolved in a mixed solvent of water and isopropanol in a ratio of 5 to 1 (weight ratio), and AIBN was added thereto to obtain a reaction solution R8 (polysodium methacrylate 1.5% by weight).

  R8 was impregnated with C1, and polymethacrylic acid was fixed to the surface of C1 at 80 ° C. for 2 hours to obtain polyurethane elastic fiber D10 having 2.6% by weight of f1.

  D10 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E14 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D10 and the functional evaluation results of the fabric E14.

[Example 15]
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  Further, AIBN as an initiator and methacrylic acid as an anionic 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 R9 (methacrylic acid 0.5% by weight).

  Graft polymerization treatment was performed using C1 and R9 at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber D11 having a polymer component (f3) made of methacrylic acid of 2.30% by weight.

  D11 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E15 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D11 and the results of functional evaluation of the fabric E15.

[Example 16]
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D1 is cut into polyurethane short fibers with a fiber length of 50 mm, and 5% by weight and 95% by weight of lyocell raw cotton (fiber length 50 mm) are mixed uniformly, using a ring weaving spinning machine manufactured by Toyota Industries Corporation. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute to obtain a stretch fabric E16, which was used as an evaluation fabric. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E16.

Example 17 (This example is a reference example.)
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D1 is cut into polyurethane short fibers with a fiber length of 50 mm, and 45% by weight and 55% by weight of lyocell raw cotton (fiber length 50 mm) are mixed uniformly, and a ring weaving spinning machine manufactured by Toyota Industries Corporation is used. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric E17 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E17.

[Example 18]
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D1 is cut into polyurethane short fibers with a fiber length of 50 mm, and this is mixed with PET raw cotton (fiber length 50 mm) at 20% by weight and 80% by weight, respectively, using a ring weaving spinning machine manufactured by Toyota Industries Corporation. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn and steam set at 120 ° C. for 1 minute to obtain a stretch fabric E18. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric E18.

[Comparative Example 1]
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.

  A4 and B1 described in Example 1 are uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution, which is a speed ratio of 1.4 between a godet roller and a winder and a spinning speed of 500 m / min. The yarn was dry-spun and wound up to obtain 20 dtex, 2 fil multifilament polyurethane elastic fiber C4 (100 g wound yarn).

  Using C4 and R1 described in Example 1, graft polymerization was performed at 80 ° C. for 2 hours to obtain a polyurethane elastic fiber D12 having f1 of 2.40% by weight.

  D12 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn and steam set at 120 ° C. for 1 minute to obtain a stretch fabric H1. This was used as a fabric for evaluation. did.

  Tables 2 and 3 show the composition and various characteristics of D12 and the results of functional evaluation of the fabric H1.

[Comparative Example 2]
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 a terminal blocking agent (urethane group concentration = 3.8 mol / kg) was prepared by a conventional method. did.

  A5 and B1 described in Example 1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution, which was a spinning speed of 500 m / min with a speed ratio of 1.4 between the godet roller and the winder. The yarn was dry-spun and wound up to obtain 20 dtex, 2 fil multifilament polyurethane elastic fiber C5 (110 g wound yarn).

  Using C5 and R1 described in Example 1, graft polymerization was performed at 80 ° C. for 2 hours to obtain polyurethane elastic fiber D13 having f1 of 2.60% by weight.

  D13 is shredded into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively. Used to produce a blend yarn of 30th English style cotton count. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric H2 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D13 and the functional evaluation results of the fabric H2.

[Comparative Example 3]
A polyurethane elastic fiber C1 described in Example 1 was prepared.

  C1 is cut into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively, and a ring weaving spinning machine manufactured by Toyota Industries Corporation is used. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric H3 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of C1, and the function evaluation results of the fabric H3.

[Comparative Example 4]
A polyurethane elastic fiber D1 described in Example 1 was prepared.

  D1 is cut into a polyurethane short fiber having a fiber length of 140 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively, and a ring weaving spinning machine manufactured by Toyota Industries Corporation is used. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn and steam set at 120 ° C. for 1 minute to obtain a stretch fabric H4. This was used as an evaluation fabric. did.

  Tables 2 and 3 show the composition and various characteristics of D1, and the function evaluation results of the fabric H4.

[Comparative Example 5]
A stretch fabric H3 described in Comparative Example 3 was prepared. Further, H3 was immersed in the following treatment liquid in which the weight ratio of the polymerizable monomer / inorganic fine particles as the coating polymer component was adjusted to 1 / 0.4, and squeezed with mangles so that the squeezing rate was 80%. It is treated in a saturated steam atmosphere at 106 ° C for 3 minutes, washed at 60 ° C for 1 minute in an aqueous solution containing 1 g / L of a nonionic surfactant and 1 g / L of sodium carbonate, washed with hot water and then at 130 ° C. Dried.
Polymerizable monomer (coating polymer component): polyethylene glycol dimethacrylate 20 g / L
(Molecular weight of polyalkylene oxide segment 1000)
Inorganic fine particles: Silicon oxide (Snowtex: particle size 40-50 nm, manufactured by Nissan Chemical Co., Ltd.) 8 g / L
Ammonium persulfate 2g / L
Next, it is immersed in a treatment solution comprising the following components, squeezed with a mangle so that the squeezing rate is 80%, dried at 130 ° C. for 2 minutes, and then finished with a pin tenter at 170 ° C. for 1 minute, and stretch fabric H5 is obtained. Since it was obtained, this was used as a fabric for evaluation.
Photocatalyst: Titanium oxide (STS-21: particle size 20 nm, manufactured by Ishihara Sangyo Co., Ltd.) 10 g / L
Aliphatic polycarboxylate (SZ-2B-ZC, manufactured by Nagase ChemteX Corporation) 20 g / L
Porous material (Silicia # 550: specific surface area 500 m ² / g, particle size 2.7 μm, manufactured by Fuji Silysia) 10 g / L
Copper sulfate 4g / L
Antibacterial agent: 2-pyridylthiol-1-oxide zinc 5 g / L
Acrylic resin (T-23M, manufactured by Kyoeisha) 15g / L
Tables 2 and 3 show the composition and various characteristics of C1, and the function evaluation results of the fabric H5.

[Comparative Example 6]
A DMAc solution (35% by weight) of a polyurethaneurea polymer (urethane group concentration = 0.887 mol / kg) composed of PTMG having a molecular weight of 1800, MDI, ethylenediamine and diethylamine as a terminal blocking agent was prepared by a conventional method. did.

  A6 and B1 described in Example 1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a polyurethane spinning solution, which was a spinning speed of 500 m / min with a speed ratio of 1.4 between the godet roller and the winder. The yarn was dry-spun and wound up to obtain a 20 dtex, 2 fil multifilament polyurethane elastic fiber C6 (350 g wound yarn).

  Polypropylene glycol having a molecular weight of 400 was added to C6 as a film polymer component in an amount of 2.30% by weight to obtain a polyurethane elastic fiber D14.

  D14 is cut into polyurethane short fibers with a fiber length of 50 mm, and lyocell raw cotton (fiber length 50 mm) is uniformly mixed with 20% by weight and 80% by weight, respectively, and a ring weaving machine manufactured by Toyota Industries Corporation is used. Thus, a blend yarn of 30th English style cotton count was prepared. A bare tengu circular knitted fabric (38 inch pot diameter, 24 gauge, 114 feeder) was prepared from the prepared blended yarn, steam set at 120 ° C. for 1 minute, and a stretch fabric H6 was obtained. did.

  Tables 2 and 3 show the composition and various characteristics of D14 and the results of functional evaluation of the fabric H6.

In Table 2, Examples 2, 6, 8, 10-12 and 17 are reference examples.

In Table 3, Examples 2, 6, 8, 10-12, and 17 are reference examples.

  The stretch fiber product of the present invention is excellent in stretchability and appearance quality, and also excellent in antibacterial properties and deodorizing properties (especially deodorizing properties against aging odor and excretion odor). Therefore, various textile products such as socks, stockings, circular knitting, tricots, swimsuits, ski pants, work clothes, smoke fire suits, golf pants, wet suits, bras, girdles and gloves, fastening materials, and sanitary items such as paper diapers It can be suitably used for fastening materials for preventing leakage, fastening materials for waterproofing materials, imitation bait, artificial flowers, electrical insulation materials, wiping cloths, packaging materials, copy cleaners, gaskets and the like.

Claims (4)

Containing urethane elastic short fibers whose urethane group concentration is 0.2 mol / kg or more and 3.5 mol / kg or less with respect to 1 kg of polyurethane, the elastic short fibers are within a range of fiber lengths of 1 mm or more and 100 mm or less, and have a coating polymer in which at least one or more anionic vinyl monomer is formed by polymerizing the surface of the fiber content of the coating polymer in the elastic short fiber obtained from the weight ratio in terms of the, 0.1% A stretch fabric having a weight of 2.6% by weight or less and a content of the elastic short fibers of 1% by weight or more and 20% by weight or less . The stretch fabric according to claim 1, wherein the average thickness of the coating polymer is 1 nanometer or more and 5 micrometers or less. The stretch fabric according to claim 1 or 2 , wherein the film polymer is directly bonded to the polyurethane by graft polymerization. The stretch fabric according to any one of claims 1 to 3 , wherein the coating polymer forms a salt or a complex with a metal ion.