JP4352406B2 - Method for producing polyurethane elastic yarn - Google Patents

Description

The present invention relates to a method for producing a polyurethane elastic yarn having improved moisture retention, moisture absorption / release properties, antistatic properties and light resistance.

  Polyurethane 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.

  Among these uses, stockings and innerwear are in direct contact with the skin when worn, and therefore it is required to impart moisture absorption / release properties to polyurethane elastic fibers in order to improve wearing comfort. Therefore, as a technique for enhancing the moisture absorption / release properties of the polyurethane elastic fiber, a method of copolymerizing polyethylene glycol in polyurethane and a method of adding polyvinylpyrroliton to polyurethane have been proposed (respectively, Patent Document 1, Patent Reference 2).

  However, in the case of stretchable clothing using these moisture-absorbing / releasing polyurethane fibers, discomfort such as stuffiness and stickiness is reduced even when worn in contact with the skin, but it prevents drying of the skin surface due to cooling in winter and summer. However, it is still insufficient in terms of so-called skin care which gives a moisturizing effect, and further improvement has been desired.

  Also, sericin is attached to the surface by attaching sericin aqueous solution to stocking products made of nylon yarn and polyurethane elastic yarn, synthetic fiber such as nylon yarn 100% tricot, etc. A fiber product imparted with skin care performance by imparting properties and moisture retention has been proposed (see Patent Document 3 and Patent Document 4).

  However, in this case, even when a sticking agent is used in combination with the aqueous sericin solution, the sericin is only stuck to the surface of the fiber product. There is a drawback that the functionality gradually decreases.

  As described above, the conventional technology for imparting moisture absorption / release properties, antistatic properties, and moisture retention to a textile product containing polyurethane elastic yarns makes it difficult to maintain the imparting function for a long period of time, and a functionally imparted polyurethane that is practically satisfactory. It has been difficult to produce elastic yarns.

  In addition, nylon fibers and polyester fibers that are mixed with polyurethane elastic fibers when manufacturing stretch fabrics have been improved to add functionality such as moisture absorption and desorption and antistatic properties. In addition to elastic properties, polyurethane elastic fibers have also been required to have functions such as moisture retention, moisture absorption / release properties, and antistatic properties.

JP 2000-144532 A JP 2002-249929 A Japanese Patent No. 2998022 Japanese Patent No. 2588445

An object of the present invention is to solve the above-described problems of the prior art and to provide a method for producing a polyurethane elastic yarn having moisture retention, moisture absorption / release properties, antistatic properties, and light resistance.

In order to achieve the above object, a method for producing a polyurethane yarn of the present invention is characterized by a method for producing an elastic yarn comprising a silk protein, which is composed of a polyurethane polymerized with polymer diol and diisocyanate as main components. Is.

Specifically, Polyurethane elastic yarn, a solution of polyurethane which is polymerized in the main constituent polymer diol and diisocyanate, a spinning solution was prepared by adding sericin dispersion, then, it is prepared by solution spinning However, the present invention is characterized in that the sericin dispersion is a dimethylacetamide dispersion containing sericin and a compound having a dimethylacetamide-soluble hydrophilic group.

The polyurethane elastic yarn according to the present invention has light resistance, moisture absorption / release properties, antistatic properties, and moisture retention properties in addition to excellent elastic properties and elongation properties. It is suitable as an elastic yarn used for clothing. A stretch fabric or clothing using this elastic yarn has excellent wear comfort as well as detachability and fit. Furthermore, these characteristics are less likely to deteriorate even after repeated wearing and washing, and the function can be maintained over a long period of time.

The present invention is described in further detail below.
First, the polyurethane used in the present invention will be described.

  The polyurethane used in the present invention may be any polyurethane as long as it is polymerized from a raw material composition whose main constituents are polymer diol and diisocyanate, and is not particularly limited. Also, the synthesis method is not particularly limited.

  That is, for example, polyurethane urea polymerized from polymer diol, diisocyanate and diamine may be used, and polyurethane polymerized from polymer diol, diisocyanate and diol may be used. 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 sufficient. In addition, trifunctional or higher polyfunctional glycol or isocyanate may be used as long as the effect of the present invention is not hindered.

  Here, typical constituent components of the polymerization raw material constituting the polyurethane used in the present invention will be described.

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

  Examples of polyether glycols include polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF), and 3-methyl-THF. Modified PTMG (hereinafter abbreviated as 3M-PTMG), which is a copolymer of PTFE, and modified PTMG, which is a copolymer of THF and 2,3-dimethyl-THF, such as a copolymer of THF and neopentyl glycol. Polymer diols having chains on both sides, random copolymers in which THF and ethylene oxide and / or propylene oxide are randomly arranged are preferred. These polyether glycols may be used alone or in combination of two or more.

  Further, from the viewpoint of enhancing the abrasion resistance and light resistance of polyurethane yarn, it is obtained by polycondensing a mixture of butylene adipate, polycaprolactone diol, 3-methyl-1,5-pentanediol and polypropylene polyol with adipic acid or the like. Dicarboxylic acid ester units derived from a dicarboxylic acid component consisting of a polyester glycol such as polyester polymer diol having a side chain and 3,8-dimethyldecanedioic acid and 3,7-dimethyldecanedioic acid and a diol component A polycarbonate diol containing bismuth is preferably used.

  These polymer diols may be used alone, or may be used by mixing or copolymerizing two or more thereof.

  The molecular weight of the polymer diol used in the present invention is preferably 1000 to 8000, more preferably 1800 to 6000 in terms of number average molecular weight in order to obtain the desired level of elongation, strength, heat resistance and the like when formed into yarn. By using a polymer diol having a molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery force, and heat resistance can be obtained.

  Next, as a diisocyanate as a polymerization raw material constituting component of polyurethane, aromatics such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc. Group diisocyanates are particularly suitable for synthesizing polyurethanes with high heat resistance and strength. 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 when suppressing yellowing of polyurethane yarns. And these diisocyanates may be used independently and may use 2 or more types together.

  Next, as a chain extender of a polymerization raw material constituent component constituting polyurethane, a low molecular weight diamine and a low molecular weight diol are preferable, and one or two or more of them may be used. 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 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 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. One or two or more of these may be used. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, a diol-extended polyurethane has a high heat resistance and a high strength yarn can be obtained.

In the present invention , the molecular weight of the polyurethane constituting the polyurethane elastic yarn is preferably in the range of 40,000 to 150,000 as the number average molecular weight from the viewpoint of obtaining fibers having high durability and strength. The number average molecular weight is a value measured by GPC and converted by polystyrene.

In the present invention , particularly preferred as the polyurethane constituting the elastic yarn is a polymer diol and a diisocyanate from the viewpoint of obtaining a product having no practical problems including process passability and excellent in high heat resistance. It becomes a main component and has a melting point on the high temperature side in the range of 200 ° C to 300 ° C. Here, the melting point on the high temperature side refers to the value of second run when measuring polyurethane or polyurethane yarn by DSC, and corresponds to the melting point of the so-called hard segment of polyurethane.

  Specifically, PTMG having a molecular weight in the range of 1800 to 6000 is used as the polymer diol, MDI is used as the diisocyanate, and ethylene glycol, 1,3 propanediol and 1,4 butanediol are used as the low molecular weight diol. An elastic yarn made of polyurethane synthesized using at least one kind and having a melting point on the high temperature side in the range of 200 ° C. to 300 ° C. is particularly high in elongation, and further as described above. In addition, there are no practical problems including process passability and high heat resistance is preferable.

  In addition, as a method for setting the melting point on the high temperature side of the polyurethane yarn to 200 ° C. to 300 ° C., a method of selecting an optimum value of the ratio of diisocyanate, polymer diol, and low molecular weight diol by a prior test is preferable. The constitution of the polyurethane used in the present invention is preferably such.

In the present invention , the polyurethane elastic yarn contains silk protein such as sericin. That is, it is a polyurethane elastic yarn produced by containing silk protein in the spinning dope, and thereby functions such as high moisture retention and moisture absorption / release properties are exhibited.

  Examples of the silk protein used in the present invention include sericin and fibroin derived from cocoons. Sericin is a protein component covering the surface of the silk thread constituting the cocoon, and can be obtained by extraction from a treatment liquid obtained by scouring silk thread (raw silk) collected from the cocoon. For example, it can be obtained by scouring silk thread collected from cocoons by a normal method such as high-temperature treatment in alkaline water using soap or alkali salt, and recovering sericin contained in the treatment liquid by extraction or the like. it can. The silk protein such as sericin preferably has a number average molecular weight of about 10,000 to 300,000.

  When the molecular weight of natural silk protein collected from silk thread (raw silk) is too large, it can be hydrolyzed by the following method to obtain a desired molecular weight level.

  For example, natural sericin is treated with hydrochloric acid at 50 ° C. for about 1 to 2 hours to make the molecular weight about 10,000 to 300,000, neutralized with caustic soda, and the filtrate passed through an activated carbon layer and an ultrafiltration membrane is used. be able to. The component concentration of the filtrate obtained by this method is about 0.2%, but it may be further concentrated.

  Similarly, silk fibroin can also be used at a molecular weight of 10,000 to 300,000 by lowering the molecular weight by hydrolysis. In order for silk protein to exert a horny moisturizing effect and a skin barrier effect, it is preferable that the molecular weight is not too large. Furthermore, in order not to disturb the properties of the produced polyurethane yarn, the molecular weight is 10,000 to 100,000. More preferably.

  Moreover, when using sericin as silk protein, it is preferable that the average particle diameter is 1-20 micrometers.

In the present invention , the content of the silk protein contained in the polyurethane elastic yarn is required to some extent from the viewpoint of imparting the function by the silk protein, and is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more. In particular, 1% by weight is preferred. Further, from the viewpoint of obtaining good spinnability, well-balanced mechanical properties and elastic properties, it is preferably not too much, specifically, preferably 20% by weight or less, more preferably 10% by weight or less, especially 5% by weight. % Or less is preferable. In addition, it is preferable to test these contents beforehand according to a use, and to determine an optimal value suitably.

  This silk protein is preferably added to the fiber by adding it to a polyurethane solution to be used for solution spinning. For example, when sericin is used, a sericin dispersion is added to the polyurethane solution to prepare a spinning solution. To prepare.

  In order to speed up the dispersion of sericin in the polyurethane solution, without disturbing the properties and color tone of the polyurethane yarn produced, and to prevent the sericin in the fiber from being altered or dissipated by the heat in the spinning process, The viscosity of the sericin dispersion to be added at 20 ° C. is preferably 100 centipoise or more and 1000 poise or less.

The sericin dispersion sericin the Ri dispersion der dispersed in dimethylacetamide (DMAc), further, Ru dispersion der in combination adding a compound having a DMAc soluble hydrophilic groups. The compound having a DMAc-soluble hydrophilic group is not particularly limited as long as the solubility in DMAc at room temperature is 5% or more. For example, polyvinyl alcohol, its copolymer, polyvinylpyrrolidone, its copolymer Coalescence etc. can be used.

  As a copolymer of polyvinyl alcohol, for example, a hydroxyl group of polyvinyl alcohol is esterified, or vinyl alcohol is mixed with ethylene, methacrylate, vinyl sulfonate, styrene sulfonic acid, sodium ethylene sulfonate, propylene sulfonic acid. What copolymerized sodium etc. are preferable. More specifically, vinyl alcohol-vinyl acetate-vinyl sulfonate copolymer, vinyl alcohol-vinyl acetate-vinyl phosphate copolymer, vinyl alcohol-vinyl acetate-ethylene copolymer, vinyl alcohol-vinyl acetate-methacrylic. Acid esters and the like are preferable.

  The number average molecular weight of these polyvinyl alcohols and / or copolymers thereof is preferably in the range of 1,000 to 1,000,000.

  Examples of the copolymer of polyvinyl pyrrolidone include N-isopropenyl 2-pyrrolidone, N-vinyl 4-methyl 2-pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl enantolactam, and N-vinyl valero. Lactam, N-butenyl-2,4-di (1-butenyl) -2-pyrrolidone vinyl acetate, dimethylaminoethyl methacrylate, ethylene, styrene, acrylic acid, maleic acid, styrene sulfonic acid, ethyl sulfonic acid, methacrylic acid, malee Those obtained by using sodium acid, sodium styrenesulfonate, methacrylic acid ester, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylic acid, diallyldimethylammonium chloride and the like are preferable. These copolymers may be block copolymers or random copolymers.

  A polyurethane elastic yarn containing sericin is produced by adding a sericin dispersion to a polyurethane solution polymerized with polymer diol and diisocyanate as main components to prepare a spinning stock solution, and then solution spinning. Can do.

  The method for producing polyurethane 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. This is because 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 a low-definition polyurethane yarn. Further, when preparing a spinning dope for solution polymerization, there is an advantage that the polymer solution obtained by the solution polymerization method can be used as it is as a polyurethane solution.

  For example, using PTMG having a molecular weight of 1800-6000 as the polyol, using MDI as the diisocyanate, and using at least one of ethylene glycol, 1,3 propanediol and 1,4 butanediol as the diol, In the case of synthesis, these polymerization raw materials can be produced, for example, by synthesis in dimethylacetamide (hereinafter referred to as DMAc), DMF, DMSO, NMP or the like or an organic solvent containing these as main components. For example, each raw material is charged and dissolved in such a solvent, and heated to an appropriate temperature to be reacted to form a polyurethane, a so-called one-shot method, or a polyol and a diisocyanate are first melt-reacted, and then the reaction product A method of dissolving polyurethane in a solvent and reacting with the above-mentioned diol to form polyurethane can be employed.

  When a diol is used as the chain extender, a typical method for adjusting the melting point on the high temperature side of the polyurethane to a range of 200 ° C. or higher and 260 ° C. or lower is a method of controlling the types and ratios of polyol, MDI and diol. is there. For example, when the molecular weight of the polyol 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 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 polyol.

  When the molecular weight of the polyol is 1800 or more, it is preferable to proceed the polymerization at a ratio of (number of moles of MDI) / (number of moles of polyol) = 1.5 or more in order to make the melting point on the high temperature side 200 ° C. or more. .

  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 the polyurethane solution obtained by polymerization by such a method is usually preferably in the range of 30% by weight to 80% by weight.

A sericin dispersion is added to the polyurethane solution thus produced to prepare a spinning dope. The sericin dispersion, as described above, sericin, and Ru dimethylacetamide dispersion der containing a compound having a dimethylacetamide soluble hydrophilic groups. Addition as such a dispersion is effective to achieve uniform mixing into the polyurethane solution.

  Any method can be adopted as a method of adding the sericin dispersion to the polyurethane solution. 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.

  In addition, in order to suppress the viscosity increase of the polyurethane solution by adding sericin dispersion and to optimize the solution viscosity of the spinning stock solution, and to stabilize the polyurethane solution and spinning stock solution, the polyurethane solution before the addition of sericin dispersion is added. It is also preferable to use one or more end-blocking agents in the spinning stock solution during or after addition of the sericin dispersion. This end-capping agent includes monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine , Ethanol, propanol, butanol, isopropanol, allyl alcohol, monools such as cyclopentanol, and monoisocyanates such as phenyl isocyanate.

  Further, the polyurethane solution and the spinning dope may contain various stabilizers, pigments and the like. For example, hindered phenolic agents such as 2,6-di-t-butyl-p-cresol (BHT) and “Sumilyzer GA-80” manufactured by Sumitomo Chemical Co., Ltd., manufactured by Ciba Geigy Co., Ltd. Examples include benzotriazoles such as “tinuvin”, benzophenone drugs, phosphorus drugs such as “Sumilyzer P-16” manufactured by Sumitomo Chemical Co., Ltd., and various hindered amine drugs. In addition, 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 these Bactericides including compounds and the like, deodorants, lubricants such as silicone and mineral oil, various antistatic agents such as barium sulfate, cerium oxide, betaine, and phosphates may be included. Moreover, these may be made to react with a polymer and contain. In order to further improve the durability to light and various types of nitric oxide, for example, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., “Sumilyzer GA-80” manufactured by Sumitomo Chemical Co., Ltd. It is preferable to use a light stabilizer such as “Sumisorb 300 # 622” manufactured by Sumitomo Chemical Co., Ltd.

  The spinning dope prepared by the above method is solution-spun to produce a polyurethane yarn. Examples of the spinning method include dry spinning and wet spinning. Among them, dry spinning is preferable. This dry spinning method is not particularly limited, and any method can be applied.

  Since the setting property and stress relaxation property of the polyurethane yarn are particularly susceptible to the speed ratio between the godet roller and the winder, the speed ratio may be appropriately determined according to the intended use of the yarn. Further, in order to obtain a polyurethane yarn having generally required setability and stress relaxation characteristics, the speed ratio between the godet roller and the winder (= winder speed / godet roller speed) is generally A range of 1.15 to 1.65 is preferred.

  And when obtaining the polyurethane yarn which has especially a high set property and a low stress relaxation characteristic, the range of the said speed ratio is more preferably 1.15 to 1.4, and further preferably 1.15 to 1.35. . On the other hand, when obtaining a polyurethane yarn having low setting properties and high stress relaxation properties, the speed ratio is more preferably in the range of 1.25 to 1.65, and still more preferably in the range of 1.35 to 1.65.

  In order to improve the strength of the polyurethane elastic yarn, it is preferable to increase the spinning speed. Therefore, taking a spinning speed of 450 m / min or more is preferable in order to obtain a practically suitable strength level. Further, considering the point of industrial production, about 450 to 1000 m / min is preferable.

  The polyurethane yarn produced by the method of the present invention is not particularly limited, such as fineness, number of single yarns, cross-sectional shape. For example, the yarn may be a monofilament composed of one single yarn or a multifilament composed of a plurality of single yarns. The cross-sectional shape of the yarn may be circular or flat.

The invention is explained in more detail by means of examples.
A method for measuring the setting property, stress relaxation, strength, elongation, light resistance, moisture absorption / release property of polyurethane elastic yarn, and antistatic property and moisture retention property of stretch fabric using polyurethane yarn will be described.

[Setting properties, stress relaxation, strength, elongation of polyurethane yarn]
The setability, stress relaxation, strength, and elongation were measured by subjecting the polyurethane yarn to a tensile test using an “Instron” 4502 type tensile tester.

  The operation of stretching and recovering a sample having a test length of 5 cm (L1) by 300% at a tensile speed of 50 cm / min was repeated five times. At this time, the stress at the time of 300% elongation for the fifth time was defined as (G1). Next, the length of the sample was maintained for 30 seconds with 300% elongation. The stress after holding for 30 seconds was defined as (G2). Next, the length of the sample when the elongation of the sample was recovered and the stress became zero was defined as (L2). Furthermore, it extended until the sample cut | disconnected the 6th time. The stress at the time of rupture was defined as (G3), and the sample length at the time of rupture was defined as (L3). Hereinafter, the above characteristics are calculated by the following formula.

Strength = (G3)
Stress relaxation = 100 × ((G1) − (G2)) / (G1)
Set property = 100 × ((L2) − (L1)) / (L1)
Elongation = 100 × ((L3) − (L1)) / (L1)

[Moisture absorption and desorption of polyurethane yarn]
The moisture absorption / release coefficient ΔMR was measured by the following method as an index indicating moisture absorption / release properties.
The moisture absorption and desorption coefficient ΔMR is a constant temperature in an atmosphere of 20 ° C. × 65% RH or 30 ° C. × 90% RH using an approximately 1 g knitted fabric obtained by knitting yarn in a cylindrical shape as a sample. The weight after being left in a humidity chamber for 24 hours was measured, and from these weight values, the moisture absorption rate (MR1) under the condition of 20 ° C. × 65% RH and the moisture absorption rate under the condition of 30 ° C. × 90% RH (MR2) was determined by the following equation.

MR1 (%) = [(weight after moisture absorption at 20 ° C. × 65% RH−weight when completely dried) / weight when completely dried] × 100
MR2 (%) = [(30 ° C. × 90% RH weight after moisture absorption−weight at the time of absolute drying) / weight at the time of absolute drying] × 100
Moisture absorption and desorption coefficient ΔMR (%) = MR2−MR1

  The moisture absorption and desorption coefficient ΔMR when the sample is a thread is a driving force to obtain comfort by releasing moisture in the clothes to the outside when wearing the clothes, and performs light to medium work or light to medium exercise. This is the difference in moisture absorption between the temperature in clothes represented by 30 ° C. × 90% RH and the outside air temperature humidity represented by 20 ° C. × 65% RH. The larger the ΔMR, the higher the hygroscopicity and the better the comfort when worn.

[Light resistance of polyurethane yarn]
Ultraviolet rays were irradiated for 15 hours using a sunshine weather meter manufactured by Suga. Using a polyurethane elastic yarn not irradiated with ultraviolet light and an irradiated polyurethane elastic yarn as a sample, an "Instron" 4502 type tensile tester was used to stretch a 5 cm long sample at a tensile rate of 50 cm / min until it broke, The breaking strength of was measured. The strength retention was calculated from the following formula and compared.
Strength retention (%) = (Strength of polyurethane elastic yarn after irradiation / Strength of untreated polyurethane elastic yarn) × 100

[Antistatic property of stretch fabric]
A stretch fabric was used as a sample, and the frictional voltage was measured by the following method as an index indicating antistatic properties.
Using a rotary static tester manufactured by Koa Shokai Co., Ltd., the target fabric is cotton gold width No. 3, temperature and humidity is 20 ° C. × 30% RH, rotation speed is 400 rpm, and the charged voltage (friction band voltage after 1 minute rotation) ) Was measured.

[Moisture retention of stretch fabric]
A cylindrical supporter was made from stretch fabric, and 10 test subjects were worn almost always on the skin surface, and the wearing test was repeated for 15 days to clean the skin surface with soap for 20 minutes or more per day. The skin surface moisture content before and after the implementation was measured. The average value of the retention rate of the moisture content on the skin surface was calculated to evaluate the moisture retention. In addition, the phase difference each layer moisture meter ASA-M1 by Asahi Biomed Co., Ltd. was used for the moisture content measurement of the skin surface.
Skin surface moisture retention (%) = (Skin surface moisture after 15 days of wear / Skin surface moisture before wearing) × 100

[Example 1]
A polymer solution A1 was prepared by polymerizing a DMAc solution (35% by weight) of a polyurethane polymerization raw material consisting of PTMG, MDI and ethylene glycol having a molecular weight of 2900 by a conventional method.

  Moreover, the sericin powder (number average molecular weight 50,000) by Takada Seiren Co., Ltd. was used as sericin, and the DMAc dispersion liquid was adjusted. For the adjustment, polyvinyl alcohol (number average molecular weight 500,000, “GOHSENOL” (registered trademark) manufactured by Nippon Synthetic Chemical Co., Ltd.) is also added and a horizontal mill (DYNO-MIL KDL manufactured by WILLY A. BACHOFEN) is used. Used, filled with 85% zirconia beads, pulverized to an average particle size of 1.2 μm under the condition of a flow rate of 50 g / min, and uniformly finely dispersed to obtain sericin dispersion B1. This sericin dispersion contained 20% by weight of sericin and 0.5% by weight of polyvinyl alcohol.

  Furthermore, as an antioxidant, polyurethane ("Metacral" (registered trademark) 2462 manufactured by DuPont) produced by reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), p -Using a 2 to 1 (weight ratio) mixture of cresol and a condensation polymer of divinylbenzene ("Megachlor" (registered trademark) 2390, manufactured by DuPont), this DMAc solution (35% by weight) The other additive solution C1 (35% by weight) was prepared.

  Polymer solution A1, sericin dispersion B1, and other additive solution C1 were uniformly mixed at a ratio of 93% by weight, 5% by weight, and 2% by weight, respectively, to obtain spinning solution D1. This spinning solution D1 was dry-spun at a speed ratio of 1.4 between the godet roller and the winder at a spinning speed of 540 m / min, wound, 20 dtex, monofilament polyurethane elastic yarn (200 g wound body) Was made. The content of sericin in the obtained polyurethane elastic yarn was 3% by weight.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, light resistance, and moisture absorption / release (ΔMR) of the obtained polyurethane elastic yarn. Breaking strength, breaking elongation, setability, which is an index of recoverability, and stress relaxation are the same as when sericin is not blended (Comparative Example 1 described later), and light resistance is approximately 1.1 times that of Comparative Example 1, ΔMR was 2.5 times or more.

  Furthermore, a stretch fabric was produced by the following method, and the antistatic property and moisture retention of the fabric were evaluated.

  First, the obtained polyurethane elastic yarn was covered. A cationic dyeable polyester 168dtex-48fil was used as the covering yarn, and it was processed using a covering machine under the conditions of twist number = 450 t / m and draft = 3.0 to prepare a weft covering yarn. Similarly, a cation dyeable polyester 168dtex-48fil is used as a covering yarn, and it is processed using a covering machine under conditions of a twist number of 700 T / M and a draft = 3.5, and a covering yarn for warp yarn. Was made.

  Next, warping and weaving were performed. 5100 warp yarns (1100 rough winding warp) were glued and warped, and woven with a 2/1 twill structure using a rapier loom. Next, dyeing was performed. The raw machine obtained by weaving is scoured according to conventional methods, intermediate set (185 ° C), weight loss, dyeing (cationic dye, 120 ° C), drying, finishing agent treatment, finishing set (180 ° C, cloth speed 20m / min) The set zone 24m) was sequentially performed.

  Table 1 shows the antistatic property and moisture retention of the obtained stretch fabric. The antistatic property was increased to about 5 times that of the sericin-free formulation (Comparative Example 1) and the moisturizing property was increased to about 1.3 times.

[Example 2]
Polymer solution A1, sericin dispersion B1 and other additive solution C1 prepared in Example 1 were uniformly mixed at a ratio of 81% by weight, 17% by weight and 2% by weight, respectively, to obtain spinning solution D2.

  Using this spinning solution D2, dry spinning was carried out in the same manner as in Example 1 to prepare 20 dtex, monofilament polyurethane elastic yarn (200 g wound yarn). The content of sericin in the obtained polyurethane elastic yarn was 10% by weight.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, light resistance, and moisture absorption / release (ΔMR) of the obtained polyurethane elastic yarn. Compared to the case where sericin was not blended (Comparative Example 1 described later), the setability and stress relaxation, which are indicators of recoverability, increased. In addition, light resistance increased about 1.3 times and ΔMR increased about 7 times.

  Furthermore, a stretch woven fabric was produced in the same manner as in Example 1 using this elastic yarn. The antistatic property and moisturizing property are as shown in Table 1. The antistatic property was increased by about 8 times that of Comparative Example 1, and the moisturizing property was increased by about 1.5 times.

[Example 3]
A polymer solution A2 was prepared by polymerizing a DMAc solution (35 wt%) of a polyurethane urea polymerization raw material composed of PTMG, MDI, ethylenediamine, and diethylamine (endblocker) having a molecular weight of 1800 by a conventional method.

  Next, the DMAc solution A2, the sericin dispersion B1 prepared in Example 1, and the other additive solution C1 prepared in Example 1 were uniformly distributed at a ratio of 93% by weight, 5% by weight, and 2% by weight, respectively. To prepare a spinning solution D3. The spinning solution D3 was dry-spun at a spinning speed of 600 m / min with a speed ratio between the godet roller and the winder of 1.20, wound up, and 20 dtex, 2 fil of polyurethane polyurethane yarn (500 g wound body) was wound. Produced. The content of sericin in the obtained polyurethane elastic yarn was 3% by weight.

  The obtained polyurethane elastic yarn has the breaking elongation, breaking strength, setability, stress relaxation, light resistance, moisture absorption / desorption (ΔMR), and is shown in Table 1. Breaking strength, breaking elongation, setability, which is an index of recovery, and stress relaxation are the same as when sericin is not blended (Comparative Example 2 described later), light resistance is about 1.2 times that of Comparative Example 2, ΔMR Was more than three times.

  Furthermore, a stretch woven fabric was produced in the same manner as in Example 1 using this elastic yarn. The antistatic property and moisturizing property are as shown in Table 1. The antistatic property was 7 times that of Comparative Example 2, and the moisturizing property was increased to about 1.3 times.

[Example 4]
Polymer solution A2 prepared in Example 3 and sericin dispersion B1 prepared in Example 1 and other additive solution C1 were uniformly mixed at a ratio of 81% by weight, 17% by weight, and 2% by weight, respectively. A spinning solution D4 was obtained.

  Using this spinning solution D4, dry spinning was carried out in the same manner as in Example 3 to prepare a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound yarn). The content of sericin in the obtained polyurethane elastic yarn was 10% by weight.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, light resistance, and moisture absorption / release (ΔMR) of the obtained polyurethane elastic yarn. Compared to the case where sericin was not blended (Comparative Example 2), the setability and the stress relaxation, which are indicators of recoverability, increased. Light resistance was increased about 1.3 times that of Comparative Example 2, and ΔMR was increased about 10 times.

  Furthermore, a stretch woven fabric was produced in the same manner as in Example 1 using this elastic yarn. The antistatic property and moisturizing property are as shown in Table 1. The antistatic property was increased about 9 times that of Comparative Example 2, and the moisturizing property was increased about 1.6 times.

[Comparative Example 1]
Polymer solution A1 prepared in Example 1 and other additive solution additive solution C1 were uniformly mixed at a ratio of 98% by weight and 2% by weight, respectively, to obtain spinning solution E1. The spinning solution E1 was dry-spun at a spinning speed of 540 m / min at a speed ratio between the godet roller and the winder of 1.40, and wound to produce a 18 dtex, monofilament polyurethane elastic yarn. Furthermore, a stretch woven fabric was produced in the same manner as in Example 1 using this elastic yarn.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, light resistance, and ΔMR of the obtained polyurethane elastic yarn, and Table 1 shows the antistatic property and moisture retention of the stretch fabric. The light resistance, ΔMR, antistatic property, and moisture retention were inferior compared to the case containing sericin (Examples 1 to 4).

[Comparative Example 2]
Polymer solution A2 prepared in Example 3, and other additive solution additive solution C1 prepared in Example 1, respectively, 98 wt%, uniformly mixed in a proportion of 2 wt%, thereby making spinning solution E2. This spinning solution E2 was dry-spun at a spinning speed of 600 m / min with a speed ratio between the godet roller and the winder of 1.20, and wound to produce a 20 dtex, 2 fil polyurethane elastic yarn (500 g wound body). did. Furthermore, a stretch woven fabric was produced in the same manner as in Example 1 using this elastic yarn.

  Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, light resistance, and ΔMR of the obtained polyurethane elastic yarn, and Table 1 shows the antistatic property and moisture retention of the stretch fabric. The light resistance, ΔMR, antistatic property, and moisture retention were inferior compared to the case containing sericin (Examples 1 to 4).

The polyurethane elastic yarn according to the present invention can be used alone or in combination with other fibers to obtain an excellent stretch fabric, and is suitable as an elastic yarn used in knitting, weaving, and string processing. .

  Specific applications that can be used include socks, stockings, circular knitting, tricots, swimwear, ski trousers, work clothes, smoke fire clothes, clothes, golf pants, wet suits, bras, girdles, gloves and socks. Examples of the fastening material include a leakage prevention fastening material for sanitary products such as paper diapers, a fastening material for waterproofing material, imitation bait, artificial flower, an electrical insulating material, a wiping cloth, a copy cleaner, and a gasket.

Claims (1)

To a solution of polyurethane to polymer diol and a diisocyanate was polymerized in the main component, a spinning solution was prepared by adding sericin dispersion, then Lupolen polyurethane elastic yarn to produce polyurethane elastic yarn by solution spinning a manufacturing method, sericin dispersion, sericin, and features and to Lupo polyurethane manufacturing process of the elastic yarn that dimethylacetamide dispersion containing a compound having a dimethylacetamide soluble hydrophilic groups.