JP4941410B2 - Polyurethane elastic yarn and stretchable fabric using the same - Google Patents

Description

  The present invention relates to a polyurethane elastic yarn excellent in dyeing fastness and a stretchable fabric using the same.

  Elastic fibers are widely used for stretch clothing and industrial materials such as leg wear, inner wear, and sports wear due to their excellent stretch properties. In particular, polyurethane elastic yarns are used in various applications and materials, and recently combined with not only synthetic fibers such as nylon and polyester yarns, but also natural fibers such as cotton and wool, semi-synthetic fibers, etc. Widely used. These stretchable products are required to have good dyeing fastness according to the intended use as well as being dyed.

  Conventional elastic products are dyed according to various materials and have good fastness to dyeing, but polyurethane elastic yarns themselves are generally not colored because they cannot be dyed firmly. . This is because the polyurethane polymer does not have sufficient functional groups for adsorbing the dye, and further, there is a problem in chemical structure that the degree of crystallinity is low and the absorbed dye cannot be held firmly. It is. Therefore, in a polyurethane-based elastic yarn-mixed fabric, in order to obtain practically sufficient dyeing fastness, it is a common practice to repeatedly wash the dye contaminated with the polyurethane-based elastic yarn. Repeated cleaning of a once contaminated dye not only consumes a large amount of water and energy, but also has a problem that the color reproducibility for each dyeing lot is deteriorated.

  On the other hand, if the polyurethane elastic yarn is not dyed, it will be dyed in the same color as the fiber material to be combined because the polyurethane elastic yarn inside will appear outside when the fabric is stretched and the aesthetics and deep color will be lost. In particular, there is a strong demand for use in dark dyed fabrics such as black. Furthermore, as a method of changing the color of the textile product, it is required to dye other materials combined with the polyurethane elastic yarn into different colors.

On the other hand, as a conventional technique for dyeing elastic fibers, an original yarn technique for spinning by adding a pigment to a polyurethane spinning solution is known. (For example, see Patent Document 1)
However, the polyurethane elastic yarn containing the pigment as described above has excellent fastness, but the number of colors is limited and the cost is very high, so that it can be used only for limited applications.

  As another conventional technique, for example, a dyeing technique for introducing an amine additive into a polyurethane elastic yarn and adsorbing an acid dye or a metal-containing dye is known. However, when the amount of functional groups is small, a sufficient color density cannot be obtained. Conversely, when the amount of functional groups of amines is increased, the dye adsorption characteristics with other fibers such as nylon to be mixed differ. When dyed with a combination dye of the primary colors, etc., there is a disadvantage that color difference phenomenon occurs and color matching is difficult.

As another conventional technique, a dyeing technique using a disperse dye is known. Disperse dyes are well absorbed by polyurethane-based elastic yarns, but they have a low dye adsorbing power, and a dye fastness that is practically durable cannot be obtained in a medium-deep color having a high dye concentration. Rather, a technique for obtaining disperse dye resistance of polyurethane-based elastic yarn is known. (For example, see Patent Document 2)
As another conventional technique, for example, a fiber structure using a cationic dye dyeable polyether / polyester block copolymer elastic fiber is known. Polyether / polyester block copolymer elastic fibers are rarely used because they have low yarn elongation and poor heat resistance compared to polyurethane elastic fibers. (For example, see Patent Document 3)
Japanese Patent Publication No. 60-44406 Japanese Patent No. 3326005 Japanese Patent Publication No. 7-68657

  An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a polyurethane-based elastic yarn having a strong cationic dye dyeability and a fabric having excellent aesthetics obtained by the mixture thereof.

  The polyurethane elastic yarn of the present invention employs the following means in order to achieve the above object.

  That is, the main constituents of the raw material are polymer diol and diisocyanate, containing a polymer of a compound having an anionic functional group (terminal group), and having a dyeing property of L * ≦ 20 when dyed with a black cationic dye. This is a polyurethane-based elastic yarn characterized by the following. (However, L * represents a color density value according to the CIE 1976 L * a * b * color system.)

  Since the polyurethane-based elastic yarn of the present invention has a strong cationic dye dyeability, clothes using this elastic yarn are excellent in fit, wearing feeling, etc., while being resistant to discoloration, appearance quality, It also has excellent dyeability. In the combination with other cationic dyeable fibers, the same color can be obtained and the deep color is more excellent. In combination with acid dye-dyeable fibers, there is no staining of acid dyes, so not only excellent dyeing fastness is obtained, but also by dyeing in different colors using both acid dyes and cationic dyes, You can get a product with a different color.

  The raw material polymer of the present invention is not particularly limited as long as it is a polyurethane whose main components are a polymer diol and a diisocyanate. Also, the synthesis method is not particularly limited.

  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 composed of a polymer diol, diisocyanate and a low molecular weight diol. Moreover, the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule | numerator as a chain extender may be used. In addition, it is also preferable to use trifunctional or higher polyfunctional glycols, isocyanates and the like as long as the effects of the present invention are not hindered.

  Here, typical structural units constituting the polyurethane used in the present invention will be described.

  As the polymer diol of the structural unit constituting the polyurethane, polyether diol, polyester diol, polycarbonate diol and the like are preferable. In particular, a polyether diol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.

  The polyether-based diol preferably contains a copolymerized diol compound containing a unit represented by the following general formula (I).

(Where a and c are integers of 1 to 3, b is an integer of 0 to 3, R1 and R2 are H or an alkyl group of 1 to 3 carbon atoms)
Specific examples of the polyether diol include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF). Modified PTMG, which is a copolymer of 3-methyl-THF, modified PTMG, which is a copolymer of THF and 2,3-dimethyl-THF, modified PTMG which is a copolymer of THF and neopentyl glycol, THF and ethylene Examples thereof include random copolymers in which oxides and / or propylene oxide are irregularly arranged. One kind of these polyether diols may be used, or two or more kinds may be mixed or copolymerized. Among these, PTMG or modified PTMG is preferable.

  Further, from the viewpoint of enhancing the wear resistance and light resistance of the polyurethane-based elastic yarn, polycondensation is performed with polybutylene adipate, polycaprolactone diol, a mixture of 3-methyl-1,5-pentanediol and polypropylene polyol, adipic acid, and the like. A dicarboxylic acid ester unit derived from a diol component and a polyester-based diol having a side chain and a dicarboxylic acid component consisting of 3,8-dimethyldecanedioic acid and / or 3,7-dimethyldecanedioic acid. The contained polycarbonate diol is preferably used.

  Moreover, such polymer diol may be used independently, and may be used by mixing or copolymerizing 2 or more types.

  The molecular weight of the polymer diol used in the present invention is preferably 1000 to 8000 in terms of number average molecular weight, in order to obtain desired levels of elongation, strength, elastic recovery, heat resistance and the like when converted into an elastic yarn. 6000 is more preferable. By using a polymer diol having a molecular weight within this range, a polyurethane excellent in elongation, strength, elastic recovery and heat resistance can be obtained.

  Next, as the diisocyanate of the structural unit constituting the polyurethane, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc. However, it is particularly suitable for synthesizing polyurethane having high heat resistance and high strength. Further, as alicyclic diisocyanates, for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydroxylylene diisocyanate, hexa Hydrotolylene diisocyanate, octahydro-1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively particularly in suppressing yellowing of polyurethane-based elastic yarns. 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 of the structural unit constituting the polyurethane. In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine.

The low molecular weight diamine and the low molecular weight of the low molecular weight diol are preferably 30 to 300, and 40 to 200 are more preferable from the viewpoint of obtaining a high melting point polyurethane. 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, Examples thereof include 2-methylpentamethylenediamine and bis (4-aminophenyl) phosphine oxide. It is also preferred that one or more of these are used. Particularly preferred is ethylenediamine. By using ethylenediamine, it is possible to obtain a yarn excellent in elongation, elastic recovery, and heat resistance. A triamine compound capable of forming a crosslinked structure such as diethylenetriamine may be added to these chain extenders to such an extent that the effects of the present invention are 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. It is mentioned as a thing. It is also preferred that one or more of these are used. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. When these are used, the diol-extended polyurethane-based elastic yarn has a high heat resistance and a high strength yarn can be obtained.

  In addition, the molecular weight of the polyurethane elastic yarn of the present invention is preferably in the range of 40000 to 150,000 as a number average molecular weight from the viewpoint of obtaining a fiber having durability and high strength. The molecular weight is measured by GPC (gel permeation chromatography) and is a value converted by polystyrene.

  And, particularly preferred as the polyurethane constituting the elastic yarn of the present invention, including the process passability, there is no practical problem, and from the viewpoint of obtaining an excellent heat resistance, it consists of a polymer diol and diisocyanate, In addition, the melting point on the high temperature side is in the range of 150 ° C. or higher and 300 ° C. or lower. Here, the melting point on the high temperature side corresponds to the melting point of so-called hard segment crystals of polyurethane or polyurethane urea as measured by DSC.

  That is, PTMG having a molecular weight of 1000 to 8000 as a polymer diol, MDI as a diisocyanate, ethylene glycol, 1,3-propanediol, 1,4-butanediol, ethylenediamine, 1,2-propanediamine as a chain extender A polyurethane produced by using at least one selected from the group consisting of 1,3-propanediamine and having a melting point on the high temperature side in the range from 150 ° C. to 300 ° C. Yarn is particularly preferable because it has a high elongation and, as described above, has no practical problems including process passability and is excellent in heat resistance.

  The polyurethane elastic yarn of the present invention contains a polymer of a compound having an anionic functional group. For this reason, it becomes possible to couple | bond a polyurethane-type elastic thread and a cationic dye by an ionic bond, and can exhibit the effect of this invention. On the other hand, when the polyurethane elastic yarn does not contain a polymer of a compound having an anionic functional group, it is difficult to dye the cationic dye.

  The polymer of the compound having an anionic functional group used in the present invention is not particularly limited as long as it is a compound obtained by polymerizing a compound having an anionic functional group as a constituent monomer. A copolymer having both of the constituent monomers may be used. In the case of a copolymer, there is no particular limitation on the molar ratio of other constituent monomers and monomers having an anionic functional group.

  Examples of the anionic functional group herein include sulfonic acid groups, nitro groups, carboxyl groups, phosphoric acid groups, and those whose ends are blocked with a metal salt as a counter cation. By introducing sulfonic acid groups and their salts into the polymer structure, it is possible to approximate the adsorption behavior of the dye species with cationic dye-dyeable polyester fibers and acrylic fibers that are used in combination with fabrics. , Dyeability can be enhanced. Among them, the anionic functional group is preferably a sulfonic acid group having high reactivity with the cationic dye. By containing a polymer of a compound having a sulfonic acid group in the polyurethane elastic yarn, the elastic yarn is likely to exhibit a lower L * when dyed with a black cationic dye.

  In addition, it is preferable to introduce a polyester fiber or acrylic fiber dyed with a cationic dye by copolymerizing a monomer containing a sulfonic acid group and a salt thereof in a certain ratio in the polymer structure. For polyurethane-based elastic yarns, in order to reduce costs and stabilize the viscosity of the spinning dope, and to obtain good spinnability, a polymer having an anionic functional group that is compatible with the starting solution is prepared separately. It is desirable to introduce in a uniform mixture with polyurethane.

  There are no particular restrictions on the polymerization method of the polymer of the compound having an anionic functional group, and examples thereof include addition polymerization, condensation polymerization including formaldehyde crosslinking, and the like, for example, protecting an important sulfonic acid group expressing the anionic property of the polymer. Therefore, it is also preferable that the starting monomer is appropriately selected from a precursor such as sulfonate and sulfoamide, polymerized as a starting material, and then ion-exchanged with an acid to be derived into a sulfonic acid group. Further, from the viewpoint of stabilizing the viscosity of the raw material spinning solution of the polyurethane-based elastic yarn, obtaining good spinnability, and obtaining a yarn having high chemical resistance, the polymer of the compound having a sulfonic acid group has a sulfonic acid group. It is preferably a random or alternating copolymer of a compound having a sulfonyl group and a compound having a sulfonyl group, and more preferably a molecular weight of 2,000 to 500,000 from the viewpoint of increasing the spinning speed.

  The amount of the polymer of the compound having an anionic functional group in the polyurethane-based elastic yarn of the present invention is not limited as long as the amount of the functional group that can sufficiently obtain the dye coloring is included. It is preferably 1% by weight or more and 50% by weight or less. The amount of the functional group that can sufficiently obtain the dye color is preferably 10 mmol / kg to 200 mmol / kg, more preferably 20 mmol / kg to 100 mmol / kg in the polyurethane elastic yarn. If the amount is too small, a sufficient amount of dye cannot be adsorbed. If the amount is excessive, dye coloration can be obtained, but the spinnability of polyurethane-based elastic yarn is deteriorated and the elasticity is lowered.

  Furthermore, the polymer of the compound having an anionic functional group used in the present invention speeds up the dispersion and dissolution in the polyurethane, makes the properties of the polyurethane-based elastic yarn the target property, and further provides an appropriate transparency. In view of the fact that the content of the polymer of the compound having an anionic functional group does not decrease and the yarn is not discolored even when subjected to heat or the like in the spinning process. A liquid in which the viscosity of a 20 wt% solution of N, N′-dimethylacetamide (hereinafter abbreviated as DMAc) or N, N′-dimethylformamide (hereinafter abbreviated as DMF) at 10 ° C. is 10 cP or more and 10,000 P or less. The polymer itself is preferably uncolored or less colored.

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

  In the present invention, various stabilizers and pigments may be contained in the polyurethane elastic yarn or polyurethane solution. For example, hindered phenols such as 2,6-di-t-butyl-p-cresol (BHT) and “Sumizer GA-80” (product name) manufactured by Sumitomo Chemical Co. Drugs, various benzotriazole and benzophenone drugs such as “Chinubin” (product name) manufactured by Ciba Geigy, phosphorus-based drugs such as “Sumilyzer P-16” (product name) manufactured by Sumitomo Chemical Co., Ltd., and various hindered amines Chemicals, various pigments such as iron oxide and titanium oxide, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide and carbon black, fluorine or silicone resin powder, metal soap such as magnesium stearate, silver and zinc And bactericides, deodorants, silicone, mineral oil and other lubricants, barium sulfate, oxidation Helium, it is also preferred to include various kinds of antistatic agents such as betaine and phosphoric acid and also the reaction of these with polyurethane preferred. In order to further enhance the durability to light and various types of nitric oxide, it is also preferable to use a nitric oxide scavenger such as HN-150 manufactured by Nippon Hydrazine Co., Ltd.

  Further, from the viewpoint of easily increasing the spinning speed in the dry spinning process, fine particles of metal oxide such as titanium dioxide and zinc oxide may be added. In addition, from the viewpoint of improving heat resistance and functionality, inorganic materials and inorganic porous materials (such as bamboo charcoal, charcoal, carbon black, porous mud, clay, diatomaceous earth, coconut shell activated carbon, coal-based activated carbon, zeolite, pearlite, etc.) , And may be added within a range that does not impair the effects of the present invention.

  Next, the method for producing the polyurethane elastic yarn of the present invention will be described in detail.

  In the present invention, it is preferable to prepare a polyurethane solution first. The method for producing a polyurethane solution and polyurethane as a solute in the solution may be either a melt polymerization method or a solution polymerization method, or may be another method. Of these, the solution polymerization method is preferably used. In the case of the solution polymerization method, since the generation of foreign matters such as gel is small in the polyurethane, it is easy to spin and it is easy to produce a polyurethane-based elastic yarn having a low fineness. Further, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.

  As a polyurethane particularly suitable for the present invention, PTMG having a molecular weight of 1000 to 8000 is used as a polymer diol, MDI is used as a diisocyanate, ethylene glycol, 1,3-propanediol, 1,4 is used as a chain extender. -Synthesized using at least one of butanediol, ethylenediamine, 1,2-propanediamine and 1,3-propanediamine and having a melting point on the high temperature side in the range of 150 ° C to 300 ° C. Can be mentioned.

  Such polyurethane can be obtained, for example, by synthesis using DMAc, DMF, dimethyl sulfoxide, N-methylpyrrolidone or the like or a solvent containing these as a main component, using the above raw materials. For example, each raw material is charged in such a solvent, dissolved, heated to an appropriate temperature and reacted to form polyurethane, the so-called one-shot method, or polymer diol and diisocyanate are first melt reacted and then dissolved in the solvent. And the method of making it react with the above-mentioned chain extender to make a polyurethane etc. can be employ | adopted as a particularly suitable method.

  When a low molecular weight diol is used as a chain extender, typical methods for setting the melting point on the high temperature side of polyurethane within the range of 150 ° C. or more and 300 ° C. or less include the types and ratios of polymer diol, MDI, and low molecular weight diol. Control. For example, when the molecular weight of the polymer diol is low, a polyurethane having a high melting point on the high temperature side can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the low molecular weight diol is low, a polyurethane having a high melting point on the high temperature side can be obtained by relatively reducing the proportion of the polymer diol. When the molecular weight of the polymer diol is 1800 or more, in order to make the melting point on the high temperature side 150 ° 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.

  In the present invention, it is preferable to add a polymer of a compound having an anionic functional group to such a polyurethane solution to obtain a polyurethane spinning solution. The method for adding the polymer having a compound having an anionic functional group to the polyurethane solution is not particularly limited. As typical methods, various means such as a method using a static mixer, a method using stirring, a method using a homomixer, a method using a biaxial extruder, and the like can be adopted. Here, the polymer of the compound having an anionic functional group to be added is preferably added as a solution from the viewpoint of uniform addition to the polyurethane solution.

  The addition of a polymer having a compound having an anionic functional group to a polyurethane solution may cause a phenomenon that the solution viscosity of the mixed solution after the addition becomes higher than expected compared to the solution viscosity of the polyurethane before the addition. However, from the viewpoint of preventing this phenomenon, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine One or two end-capping agents such as monoamines such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate It is also preferred to be used in the above mixed.

  When the polymer having a compound having an anionic functional group is added to the polyurethane solution, for example, a drug such as a light-resistant agent or an antioxidant or a pigment may be added at the same time.

  Then, the polyurethane elastic yarn of the present invention is obtained by spinning the polyurethane spinning solution.

  The fineness, the number of filaments, the cross-sectional shape, etc. of the polyurethane elastic yarn of the present invention are not particularly limited. For example, the yarn may be a monofilament composed of a single yarn or a multifilament composed of a plurality of yarns. The cross-sectional shape of the yarn may be circular or flat.

  The spinning method of the polyurethane elastic yarn is not particularly limited, but a dry spinning method is preferably used.

  The strength and elongation characteristics of the polyurethane-based elastic yarn of the present invention are particularly susceptible to the speed ratio between 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-based elastic yarn having desired strength and elongation characteristics, the speed ratio of the godet roller and the winder is preferably wound in the range of 1.15 to 1.65.

  Further, since the strength of the polyurethane elastic yarn can be improved by increasing the spinning speed, it is preferable to take a spinning speed of 450 m / min or more in order to obtain a practically suitable strength level. Furthermore, considering industrial productivity, about 450 to 1000 m / min is preferable.

  The polyurethane elastic yarn of the present invention constitutes a stretchable fabric by being mixed with other fibers, for example, but the form of the stretchable fabric is not limited at all, and the blending rate, the material fibers to be combined, and the mixed use The method may be appropriately selected and made into a fabric by a known production means. The polyurethane elastic yarn may be used as a bare yarn as it is, or one or more kinds of conventionally known fibers such as polyamide fibers, polyester fibers and synthetic fibers such as acrylic fibers, and natural fibers such as cotton and wool. You may use what was coat | covered freely combining.

  In addition, as a fiber combined with a polyurethane elastic yarn in constituting a fabric, it is represented by polyamide fiber such as nylon, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and copolymer polyester fiber mainly composed of these. Polyester synthetic fiber, acrylic synthetic fiber, polypropylene synthetic fiber, semi-synthetic fiber typified by acetate fiber, natural fiber typified by cotton, hemp or wool, or a mixture of two or more types is preferably used Is done.

  The polyurethane elastic yarn of the present invention can be dyed with a cationic dye and has a property that it is difficult to dye with an acid dye. In the case of a fabric combined with fibers known as cationic dyeable fibers, such as acrylic synthetic fibers, wool, and cationic dyeable polyester fibers, the polyurethane elastic yarn of the present invention can be similarly dyed with cationic dyes. Therefore, the same hue can be dyed in one dyeing step. In addition, when combined with fibers known as acid dyeable fibers, such as polyamide fibers, silk, wool, etc., the polyurethane elastic yarn of the present invention does not adsorb acid dyes. The phenomenon is suppressed, and excellent dyeing fastness can be expected. Furthermore, it is also possible to dye the polyurethane elastic yarn of the present invention using a cationic dye with a hue different from the dye hue of the acid dye-dyeable fiber.

  The dyeing method is not particularly limited, and may be a continuous dyeing method performed at a low bath ratio, or a batch such as a liquid dyeing machine, a wins dyeing machine, a jigger dyeing machine, a beam dyeing machine, or a cheese dyeing machine. It can also be processed using a dyeing machine of the formula. Moreover, you may print a fine pattern on a fabric using a well-known printing technique.

  In order to dye the polyurethane elastic yarn of the present invention, a normal dyeing method using a cationic dye can be used. That is, the dyeing temperature is 80 to 135 ° C, preferably 100 to 130 ° C. A leveling agent, a pH adjuster, a softener in the bath, etc. may be used. For example, in combination with a cationic dye dyeable polyester fiber, 2 to 3 g / kg of bow glass is used to prevent strength reduction. It is preferable to add about L. After dyeing, a washing step using a surfactant may be added. Dye type and chemical structure used for dyeing are not limited at all, but in the case of medium to light color, it is desirable to use a dispersive cationic dye from the viewpoint of leveling, and in the case of dark colors such as black and navy Is preferably a raw cationic dye having excellent hue build-up properties.

  The polyurethane-based elastic yarn of the present invention exhibits a dyeing property of L * ≦ 20 when dyed with a black cationic dye with the above configuration. Cationic dyes are classified into raw cationic dyes excellent in color density and dispersed cationic dyes excellent in handling in the process, and the black cationic dye used for dyeing property evaluation in the present invention is a commercially available raw cationic dye. For example, the dye “Eisenkachiron” (registered trademark) Black CD-BLH, Black SH 200%, Black MH, Black KBH, Black NH 200%, Black AWH Liquid, Black BH Liquid manufactured by Hodogaya Chemical Co., Ltd., Dye Star Co., Ltd. dye "Astrazon" (registered trademark) Black FDL Liquid, SW200%, Black SW Liquid, "Daiacryl" (registered trademark) Black ESL-N, Black NSL-N 200%, Black CSL-N 200%, Black VS-N, Black SWR-N Liquid, manufactured by Nippon Kayaku Co., Ltd. Kayakuriru "(registered trademark) Black NP200, black NL, and the like. The evaluation of the dyeing property of the black cationic dye was carried out using any dye selected from these at a dye bath adjusted to pH 4.5 using 5.0% owf based on the weight of the fabric, at 110 ° C. for 60 minutes. Dyeing is performed. In actual fabric dyeing, commercially available cationic dyes other than those described above can be used as appropriate, and a dispersed cationic dye may be used, or a mixture of a plurality of dyes may be used.

  The invention is explained in more detail by means of examples.

  A method for measuring the dyeing property of the polyurethane elastic yarn in the present invention will be described.

[Creation of evaluation knitted fabric]
Polyurethane elastic yarns were knitted in a 50% stretched state using a 29 gauge one-necked cylinder knitting machine (with a polyurethane elastic yarn rotary feed device) to produce a tubular knitted fabric made of 100% polyurethane elastic yarns. The front and rear ears of the sample were knitted with a small amount of nylon filament (78 decitex 24 filament) manufactured by Toray Industries, Inc., which is not dyed with a cationic dye, so as not to fray. Next, dry heat heat setting was performed at 190 ° C. for 60 seconds in a state where the produced tubular knitted fabric was not stretched. Subsequently, this cylinder knitted fabric was scoured with 0.1% by weight of a scouring agent (“Sun Mall” (registered trademark) WX24 manufactured by Nikka Chemical) under conditions of a bath ratio of 1:20, 80 ° C. and 20 minutes. The raw oil was removed.

[Dyeing property of black cationic dye]
The sample after scouring is placed in a stainless steel dyeing pot with a capacity of 300 cc, and a black cationic dye (Dyster Co., Ltd. dye “Astrazone” (registered trademark) Black FDL is used under a bath ratio of 1:20, 110 ° C., 60 minutes). Liquid) was dyed with 5% owf using a Tecsum Giken mini color dyeing machine. To the dye bath, 0.025 wt% acetic acid and 0.025 wt% sodium acetate were added to control the pH at around 4.5. The dyed tubular knitted fabric was washed with water, squeezed with a centrifugal dehydrator, and then dried in an unstretched state at 160 ° C. for 60 seconds to obtain an evaluation tubular knitted fabric. This cylindrical knitted fabric is folded into a flat shape, and the color is measured using a spectrocolorimeter (Konica Minolta Co., Ltd., model CM-3600d) in a two-ply state, and the CIE 1976 L * a * b * color system The L * value was measured, and the average value of three measurements was taken as the measurement result. A lower L * value indicates a deeper color and a deeper dyeing. A case where the L * value was 16 or less was evaluated as ◎ (dense dyeing property), a case where it was 20 or less was judged as ◯ (good dyeing property), and a case where it was larger than 20 was judged as x (dyeing property poor).

[Washing fastness]
Evaluation was made according to JIS L-0848 A-2 method. The discoloration of the test piece was judged using a gray scale for discoloration.

[Fabric appearance grade]
Polyurethane elastic yarns are knitted using a 29 gauge one-necked cylinder knitting machine (with a polyurethane elastic yarn rotary feed device), and cationic dyeable copolyester fibers (56 dtex 24 filaments) manufactured by Toray Industries, Inc. A bare sheet fabric made of polyurethane elastic yarn (50% stretch knitted) was produced. Next, dry heat heat setting was performed at 190 ° C. for 60 seconds in a state where the produced knitted fabric was not stretched. Subsequently, this cylinder knitted fabric was scoured with 0.1% by weight of a scouring agent (“Sun Mall” (registered trademark) WX24 manufactured by Nikka Chemical) under conditions of a bath ratio of 1:20, 80 ° C. and 20 minutes. The raw oil was removed. Subsequently, the scoured sample is put into a stainless steel dyeing pot having a capacity of 300 CC, and a black dye (a dye “Astrazone” (registered trademark) manufactured by Dystar Co., Ltd.) is used under a bath ratio of 1:20, 110 ° C. for 60 minutes. Black FDL liquid) was dyed with 5% owf using a Tecsum Giken mini color dyeing machine. To the dye bath, 0.025 wt% acetic acid and 0.025 wt% sodium acetate were added to control the pH at around 4.5. The dyed knitted fabric was washed with water, squeezed with a centrifugal dehydrator, and then dried at 160 ° C. for 60 seconds without being stretched to obtain a cylindrical knitted fabric for dyeability evaluation. The color of the polyurethane elastic yarn visible when the dyed tubular knitted fabric was pulled was determined. When the hue is close to that of the cationic dyeable copolyester fiber, ◎ (no eye peeling), ○ (close to an acceptable eye peeling) when near, and × (with eye peeling) when the hue is different .

[Polymer content of an anionic functional group-containing compound and determination method of anionic functional group content in polyurethane-based elastic yarn]
First, the polymer of the compound having an anionic functional group in the yarn sample and the polyurethane in the yarn sample were separated by a reprecipitation method. First, 50 ml of DMAc was added to 1 g of the yarn sample (A) to completely dissolve the yarn, and then 100 ml of ethanol was slowly added to precipitate and separate a polymer of a compound having an anionic functional group, followed by evaporation to dryness. On the other hand, the polyurethane solution from which the precipitate was removed was also evaporated to dryness, and the polyurethane in the yarn sample was isolated from DMAc. This reprecipitation was repeated three times. The polymer of the compound having an anionic functional group isolated from the precipitate side is (B), and the polyurethane isolated from the solution side is (C).

Next, the anionic functional group concentration in (B) was determined. Specifically, for (B), the structure of the anionic functional group is determined by ¹ H-NMR or the like, and a suitable detection method is selected (for example, when the anionic functional group is sulfonic acid, (Neutralization titration method using sodium oxide) The anionic functional group concentration in (B) was quantified, and the anionic functional group concentration (α) mmol / kilogram was determined.

And the polymer content of the compound which has an anionic functional group in a thread | yarn sample was calculated | required. Specifically, first, a polymer (B) of a compound having an anionic functional group with a predetermined weight is contained in polyurethane (C), a uniform mixture is prepared, and a calibration curve is created from IR spectrum analysis measurement. did. When the anionic functional group species is sulfonic acid, the procedure is as follows: in the total weight of (B) and (C), (B) weight is 0 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, to prepare a sample which is 20% by weight, [nu in their six each IR spectrum (CO) 1700cm ^-1 ~1800cm ^-1 and ν (SO) 630~670cm peak area ratio of ^-1 (X) Asked. For the IR spectrum measurement, FT-IR manufactured by PerkinElmer was used, and a cast film made of DMAc was used as the measurement sample. And the analytical curve of the polymer content rate (weight%) of the compound which has an anionic functional group with respect to peak area ratio (X) was created, and the inclination ((beta)) and intercept ((gamma)) were obtained. Thereafter, in order to determine the polymer content of the compound having an anionic functional group in the target yarn sample (A), the yarn sample (A) was washed again with n-hexane and then cast film as described above. And an IR spectrum was measured. In the obtained spectrum, the peak area ratio (Xs) between ν (CO) 1700 cm ^{−1 to} 1800 cm ⁻¹ and ν (SO) 630 to 670 cm ⁻¹ was determined.

Polymer content (% by weight) of compound having anionic functional group in yarn sample = (Xs−γ) / β
Anionic functional group amount (mmol / kg) in yarn sample = ((Xs−γ) / β) × α
[Example 1]
A DMAc solution (35% by weight) of a polyurethane polymer (a1) comprising PTMG, MDI and ethylene glycol having a molecular weight of 2900 was polymerized by a conventional method to obtain a polymer solution A1. Next, as a polymer of a compound having an anionic functional group, formaldehyde having a molar ratio of phenolsulfonic acid and 4,4′-dihydroxydiphenylsulfone represented by the following chemical formula (II) of 20 to 80 (containing molar concentration of 20%) The DMAc solution was prepared using the condensation polymer (b1). For its preparation, a horizontal mill WILLY A. Using DYNO-MIL KDL manufactured by BACHOFE, filled with 85% zirconia beads and uniformly finely dispersed under the condition of a flow rate of 50 g / min, a DMAc solution B1 of a polymer of a compound having an anionic functional group (35% by weight) ).

Polymer solution A1 and polymer solution B1 of a compound having an anionic functional group were uniformly mixed at 97 wt% and 3 wt%, respectively, to obtain spinning solution C1. The spinning solution C1 was dry-spun at a spinning speed of 540 m / min at a speed ratio of 1.4 between the godet roller and the winder, and wound up. The polymer content of the compound having 20 dtex, monofilament and anionic functional group was 3 A polyurethane elastic yarn (200 g wound body) having a weight% was produced. The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. The calculated amount of anionic functional group (calculated functional group amount compared with the yarn weight calculated from the functional group amount and content of the compound (raw material) having an anionic functional group) is 24 mmol / kg from the molar amount of the sulfonic acid group. The amount of anionic functional group determined from the obtained polyurethane elastic yarn was 23 mmol / kg. As a result of evaluating the dyeing property of the black elastic dye of this polyurethane elastic yarn, it showed very good dyeing property, and the washing fastness was a good grade 4 color change. Furthermore, as a result of evaluating the appearance quality, it was determined that the hue was close to that of the cationic dyeable copolyester fiber and there was no eye-catching, and the appearance quality was excellent.

[Example 2]
A DMAc solution (35% by weight) of polyurethane urea polymer (a2) composed of PTMG having a molecular weight of 1800, MDI, ethylenediamine, and diethylamine as a terminal blocking agent was polymerized by a conventional method to obtain a polymer solution A2. Next, the DMAc solution A2 and the copolymer solution B1 of the compound having an anionic functional group prepared in Example 1 were uniformly mixed at 98.5% by weight and 1.5% by weight, respectively. C2. This spinning solution C2 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, 20 decitex, 2-filament multifilament, and a compound having an anionic functional group. A polyurethane-based elastic yarn (200 g wound yarn) having a polymer content of 1.5% by weight was produced.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. The calculated amount of the anionic functional group was 12 mmol / kg from the molar amount of the sulfonic acid group. The amount of anionic functional group determined from the obtained polyurethane elastic yarn was 10 mmol / kilogram. As a result of evaluating the dyeing property of the black cationic dye of this polyurethane-based elastic yarn, it showed good dyeing property, and the washing fastness was a good color change color grade 4-5. Furthermore, as a result of evaluating the appearance quality, it was judged to be acceptable eye-opening close to the hue with the cationic dyeable copolyester fiber, and the appearance quality was excellent.

[Example 3]
A DMAc solution was prepared using a compound (b2) represented by the chemical formula (III) as a polymer of a compound having an anionic functional group. For its preparation, a horizontal mill WILLY A. Using DYNO-MIL KDL manufactured by BACHOFEN, filled with 85% zirconia beads and uniformly finely dispersed under the condition of a flow rate of 50 g / min, a DMAc solution B2 (35% by weight) of a polymer of a compound having an anionic functional group ).

  The DMAc solution A2 prepared in the same manner as in Example 2 and the polymer solution B2 of the compound having an anionic functional group were uniformly mixed at 97.0 wt% and 3.0 wt%, respectively, to prepare a spinning solution. did. This spinning solution was dry-spun at a spinning speed of 600 m / min with a speed ratio of godet roller and winder of 1.20, wound up, 20 decitex, 2-filament multifilament, and co-polymerization of compounds having anionic functional group A polyurethane-based elastic yarn (200 g wound yarn) having a combined content of 3.0% by weight was produced.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. The calculated amount of the anionic functional group was 150 mmol / kg from the molar amount of the sulfonic acid group. The amount of the anionic functional group determined from the obtained polyurethane elastic yarn was 135 mmol / kg. As a result of evaluating the dyeing property of the black elastic dye of this polyurethane elastic yarn, it showed very good dyeing property, and the washing fastness was a good grade 4 color change. Furthermore, as a result of evaluating the appearance quality, it was determined that the hue was close to that of the cationic dyeable copolyester fiber and there was no eye-catching, and the appearance quality was excellent.

[Example 4]
As a polymer of a compound having an anionic functional group, the DMAc solution was prepared using (b3) represented by the following chemical formula (IV). A polyurethane-based elastic yarn (200 g wound yarn), which is a 20 dtex, 2-filament multifilament, was prepared in the same manner as in Example 3 except that the polymer of the compound having an anionic functional group was b3.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. The calculated amount of the anionic functional group was 172 mmol / kg from the molar amount of the sulfonic acid group. The amount of anionic functional group determined from the obtained polyurethane elastic yarn was 156 mmol / kg. As a result of evaluating the dyeing property of the black elastic dye of this polyurethane elastic yarn, it showed very good dyeing property, and the washing fastness was a good grade 4 color change. Furthermore, as a result of evaluating the appearance quality, it was determined that the hue was close to that of the cationic dyeable copolyester fiber and there was no eye-catching, and the appearance quality was excellent.

[Example 5]
As a polymer of a compound having an anionic functional group, a DMAc solution was prepared using a compound (b5) represented by the following chemical formula (V). A polyurethane-based elastic yarn (200 g wound yarn), which is a 20 dtex, 2-filament multifilament, was prepared in the same manner as in Example 3 except that the polymer of the compound having an anionic functional group was changed to b5.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. The calculated amount of the anionic functional group was 51 mmol / kg from the molar amount of sodium sulfonate. The amount of anionic functional group determined from the obtained polyurethane elastic yarn was 45 mmol / kg. As a result of evaluating the dyeing property of the black elastic dye of this polyurethane elastic yarn, it showed very good dyeing property, and the washing fastness was a good grade 4 color change. Furthermore, as a result of evaluating the appearance quality, it was determined that the hue was close to that of the cationic dyeable copolyester fiber and there was no eye-catching, and the appearance quality was excellent.

[Example 6]
A polyurethane-based elastic yarn (200 g winding) that is a 20-dtex, 2-filament multifilament in the same manner as in Example 5 except that the content of the functional group b5 is reduced as a polymer of a compound having an anionic functional group. Thread body).

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. The calculated amount of the anionic functional group was 26 mmol / kg from the molar amount of sodium sulfonate. The amount of anionic functional group determined from the obtained polyurethane elastic yarn was 25 mmol / kg. As a result of evaluating the dyeing property of the black cationic dye of this polyurethane-based elastic yarn, it showed good dyeing property, and the washing fastness was a good color change color grade 4-5. Furthermore, as a result of evaluating the appearance quality, it was judged to be acceptable eye-opening close to the hue with the cationic dyeable copolyester fiber, and the appearance quality was excellent.

[Comparative Example 1]
Using a spinning solution using 100% of the polymer solution A1 prepared in Example 1, the speed ratio of the godet roller and the winder was 1.40, and the yarn was dry-spun at a spinning speed of 540 m / min, wound up, 20 dtex, monofilament A polyurethane-based elastic yarn was prepared.

  There was no anionic functional group, and this polyurethane elastic yarn did not show any black cationic dye dyeability. Furthermore, as a result of evaluating the appearance quality by the cloth, it was judged that there was a peeling of the eyes, and the appearance quality was inferior.

[Comparative Example 2]
Using a spinning solution using 100% of the polymer solution A2 prepared in Example 2, the speed ratio of the godet roller and the winder was 1.20, and the yarn was dry-spun at a spinning speed of 600 m / min. Polyurethane-based elastic yarns that are multifilaments of filaments were prepared.

  There was no anionic functional group, and this polyurethane elastic yarn did not show any black cationic dye dyeability. Furthermore, as a result of evaluating the appearance quality by the cloth, it was judged that there was a peeling of the eyes, and the appearance quality was inferior.

[Comparative Example 3]
As a copolymer of the compound solution A2 prepared in Example 2 as a base polymer and a compound having a sulfonic acid group, a commercially available synthetic dye fixing agent for nylon (“HIFIX” (registered trademark) GM manufactured by Aussie Co., Ltd.) The DMAc solution was prepared using b4). Each was uniformly mixed at 97% by weight and 3% by weight to obtain a spinning solution C3. This spinning solution C3 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, wound up, and 20 dtex, 2-filament multifilament, a compound having an anionic functional group A polyurethane-based elastic yarn (200 g wound yarn) having a polymer content of 3% by weight was produced.

  The calculated amount of the anionic functional group is unknown, but the amount of the anionic functional group determined from the obtained polyurethane elastic yarn was 10 mmol / kilogram. This polyurethane elastic yarn showed almost no dyeing property of black cationic dye. Furthermore, as a result of evaluating the appearance quality by the cloth, it was judged that there was a peeling of the eyes, and the appearance quality was inferior.

[Comparative Example 4]
Using the polymer solution A2 prepared in Example 2 as a base polymer and b5 used in Examples 5 and 6 as a copolymer of a compound having an anionic functional group, a DMAc solution thereof was prepared. They were uniformly mixed at 99% by weight and 1% by weight, respectively, to obtain a spinning solution C4. This spinning solution C4 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, and 20 dtex, two-filament multifilament, and a compound having an anionic functional group. A polyurethane-based elastic yarn (200 g wound yarn) having a polymer content of 1% by weight was produced.

  The calculated amount of the anionic functional group was 17 mmol / kg from the molar amount of sodium sulfonate. The amount of anionic functional group determined from the obtained polyurethane elastic yarn was 15 mmol / kg. This polyurethane elastic yarn did not exhibit sufficient black cationic dyeing properties. Furthermore, as a result of evaluating the appearance quality by the cloth, it was judged that there was a peeling of the eyes, and the appearance quality was inferior.

  Since the polyurethane-based elastic yarn of the present invention has a strong cationic dye dyeability without losing its elongation recovery property, clothes using this elastic yarn are resistant to discoloration, appearance quality, dyeing, etc. It is excellent in performance, fit and wearing feeling. Because of these excellent properties, the polyurethane elastic yarn of the present invention can be used alone or in combination with various fibers to obtain an excellent stretch fabric. Suitable for processing.

  In combination with a cationic dye-dyeable fiber, the same color can be obtained and the deep color is more excellent. In combination with acid dye-dyeable fibers, there is no staining of acid dyes, so not only excellent dyeing fastness is obtained, but also by dyeing in different colors using both acid dyes and cationic dyes, You can get a product with a different color. Specific applications that can be used include socks, stockings, circular knitting, tricots, swimsuits, ski trousers, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, gloves, and other textile products. Examples include leakage prevention fastening materials for sanitary products such as paper diapers, waterproofing material fastening materials, fake baits, artificial flowers, electrical insulation materials, wiping cloths, copy cleaners, and gaskets.

Claims (4)

The main constituents of the raw material are a polymer diol and a diisocyanate, containing a polymer of a compound having an anionic functional group, and exhibiting a dyeing property of L * ≦ 20 when dyed with a black cationic dye Polyurethane elastic yarn. (However, L * represents a color density value according to the CIE 1976 L * a * b * color system.) 2. The polyurethane elastic yarn according to claim 1, wherein the content of the anionic functional group is 10 mmol / kg or more and 200 mmol / kg or less in the polyurethane elastic yarn. The polyurethane elastic yarn according to claim 1, wherein the anionic functional group is a sulfonic acid group. A stretchable fabric comprising the polyurethane-based elastic yarn according to any one of claims 1 to 3 and other fibers.