JP4834858B2 - Polyurethane yarn and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane yarn and a method for producing the same. More specifically, the present invention relates to a polyurethane yarn having particularly excellent characteristics such as improvement of spinnability by improving the slipperiness of the base in spinning and improvement of hot melt adhesiveness in gather wrapping, and a method for producing the same.

  Various proposals have heretofore been made for polyurethane yarns that are laminated between non-woven fabrics as so-called rubber parts such as waists and legs of paper diapers.

  For example, various inorganic metal compounds may be added to the polyurethane yarn in order to reduce the manufacturing process of the disposable diaper, that is, the friction property with the guide for changing the yarn path in the process until the polyurethane yarn is laminated. . However, when the inorganic metal compound is added in this way, the spinneret becomes clogged during the production of the polyurethane yarn, and the spinnability tends to deteriorate.

  In addition, as described in Patent Document 1, when adding polyethylene oxide and / or its derivative to a polyurethane solution and spinning, there is a problem of spinnability deterioration due to clogging of the spinneret as well, which solves this problem. Therefore, a method of adding silicone oil, modified silicone, and metal soap has been attempted (Patent Document 2). However, this technique is not compatible with the hot melt adhesive used to laminate the polyurethane yarn between the added silicone oil or modified silicone and the laminated nonwoven fabric. In terms of sex, no satisfactory one is obtained.

In order to improve the hot melt adhesion of the polyurethane yarn, (a) a homo- or copolymerized polyalkylene ether diol having a number average molecular weight of 300 to 2000 and a melting point of 20 ° C. or less, (b) an OH group at the terminal A higher alcohol having 8 to 25 carbon atoms, (c) a mineral oil having a kinematic viscosity at 25 ° C. of 5 to 50 centistokes, and (d) a dimethyl silicone having a kinematic viscosity at 25 ° C. of 5 to 50 centistokes. There has been an attempt to attach a treating agent to a polyurethane yarn at a specific ratio (Patent Document 3). However, even with this method, the hot melt adhesiveness of the polyurethane yarn is not sufficiently satisfactory because dimethyl silicone is not a small amount and inhibits the hot melt adhesiveness.
Japanese Patent Laid-Open No. 2002-212834 JP 2007-100408 A JP 2005-344215 A

  It is an object of the present invention to prevent the clogging of the spinneret and the yarn breakage during spinning, and to produce excellent hot melt adhesiveness when used in gathers for paper diapers and the like. It is to provide a method.

  The polyurethane yarn of the present invention has the following means for solving the above-mentioned problems. That is, it is a polyurethane yarn characterized by containing a nonionic surfactant and silicone oil.

  Moreover, in order to solve the said subject, the manufacturing method of the polyurethane thread | yarn of this invention has the following solution means. That is, in the production of a polyurethane yarn whose main constituent components are a polymer diol and a diisocyanate, a method of producing a polyurethane yarn is characterized in that a nonionic surfactant and a silicone oil are contained for spinning.

  According to the present invention, since the polyurethane yarn contains a nonionic surfactant and silicone oil, it has excellent spinnability at the time of production, contributes to the improvement of productivity, and hot melt when used for gathering paper diapers. Excellent adhesiveness.

  The present invention is described in further detail below.

  The polyurethane yarn of the present invention is characterized by containing a nonionic surfactant and silicone oil. First, the polyurethane constituting the yarn will be described.

  The polyurethane used in the present invention may be any, and is not particularly limited. Also, the synthesis method is not particularly limited. That is, for example, it may be a polyurethane urea composed of a polymer diol, a diisocyanate and a diamine, or may be a polyurethane composed of a polymer diol, a diisocyanate and a 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 a polyfunctional polymer diol or isocyanate having a trifunctional or higher functionality within a range not impeding the effects of the present invention.

  Here, typical structural units constituting the polyurethane yarn of the present invention will be described.

  The polymer diol used in the present invention is preferably a polyether diol, a polyester diol, a polycarbonate diol, or the like. And it is preferable to use a polyether diol from the viewpoint of imparting flexibility and elongation to the polyurethane yarn.

  Examples of the polyether diol include polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), modified PTMG (which is a copolymer of THF and 3-MeTHF ( Hereinafter, abbreviated as 3M-PTMG), modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, polymer diol having side chains on both sides disclosed in Japanese Patent Publication No. 2615131, etc. are preferably used. Is done. These polyether diols may be used alone or in combination of two or more.

  Further, from the viewpoint of obtaining abrasion resistance and light resistance as a polyurethane yarn, polyester-based diols such as butylene adipate, polycaprolactone diol, polyester polyol having a side chain disclosed in JP-A No. 61-26612 and the like, Polycarbonate diol disclosed in JP-B-2-289516 and the like is preferably used.

  These polymer diols may be used alone or in combination of two or more. The polymer diol used in the present invention preferably has a number average molecular weight of 1,000 or more and 8,000 or less, preferably 1800 or more and 6000 or less from the viewpoint of excellent elongation, strength, elastic recovery, heat resistance and the like when formed into a yarn. Is more preferable.

  Next, as the diisocyanate used in the present invention, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, modified products of these diisocyanates (carbodiimide modified products, urethane modified products, uretdione modified products, etc.) And a mixture of two or more of these.

  Specific examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4, 4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4, 4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate and the like are preferable.

  Specific examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, Bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like are preferable.

Specific examples of the alicyclic diisocyanate include dicyclohexylmethane-4,4′-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxyl. , 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, methylenebis (cyclohexyl isocyanate) (hereinafter referred to as H ₁₂ MDI), methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1 , 4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalene diisocyanate, etc. are preferred. .

  Specific examples of the araliphatic diisocyanate include m-xylylene diisocyanate, p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate and the like.

Among these, aromatic diisocyanates are preferable and MDI is particularly preferable from the viewpoint of improving the strength of the final product and obtaining excellent heat resistance and strength in various applications.
Moreover, aliphatic diisocyanate is preferable from the viewpoint of suppressing yellowing of the polyurethane yarn.
And these diisocyanates may be used independently and 2 or more types may be used together.

Next, it is preferable that at least one of the low molecular weight diamine and the low molecular weight diol is used as the chain extender in the present invention. In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine.
Examples of the low molecular weight diamine include 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 are preferable. It is also preferred that one or more of these are used.

  From the viewpoint of obtaining a polyurethane yarn excellent in elongation, elastic recovery and heat resistance, ethylenediamine is particularly preferable. Furthermore, it is also preferable to add a triamine compound capable of forming a crosslinked structure to these chain extenders, such as diethylenetriamine, to the extent that the effect is not lost.

  As the low molecular weight diol, for example, ethylene glycol, 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol and the like are preferable. It is also preferred that one or more of these are used.

  As the diol-extended polyurethane, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are particularly preferable from the viewpoint of obtaining a polyurethane yarn having high heat resistance and high strength.

  Moreover, in this invention, it is preferable that the number average molecular weights of a polyurethane thread | yarn exist in the range of 40000 or more and 150,000 or less from a viewpoint of obtaining a thing with durability and high intensity | strength. The molecular weight in the present invention is measured by GPC and converted by polystyrene.

  And, the polyurethane yarn of the present invention has a practical problem, including process passability, and from the viewpoint of obtaining a product having excellent heat setting properties, and is composed of diol and diisocyanate, and has a melting point on the high temperature side of the polyurethane yarn. Is preferably in the range of 200 ° C. or more and 260 ° C. or less. The melting point on the high temperature side in the present invention refers to the value of second run when the yarn is measured by DSC, and corresponds to the melting point of the so-called hard segment of polyurethane.

  Furthermore, the polyurethane yarn of the present invention has a high molecular weight as a polymer diol of 1800 or more and 6000 or less from the viewpoint of obtaining a high degree of elongation, no practical problems including processability, and excellent heat setting properties. PTMG in the range, MDI as diisocyanate, ethylene glycol as diol, at least one selected from the group consisting of 1,3 propanediol and 1,4 butanediol is used, and the melting point on the high temperature side Is more preferably in the range of 200 ° C. or higher and 260 ° C. or lower. In addition, from the viewpoint of setting the melting point on the high temperature side of the polyurethane yarn to 200 ° C. or more and 260 ° C. or less, it is preferable to perform a test in advance and select the ratio of diisocyanate, polymer diol, and diol.

  In the present invention, the non-ionic surfactant and silicone oil are contained in the polyurethane yarn having the basic structure as described above.

The nonionic surfactant used in the present invention is preferably an ether type surfactant, and more preferably an end-modified derivative of an ethylene oxide polymer, an end-modified derivative of a propylene oxide polymer, and an end of a copolymer of ethylene oxide and propylene oxide. Preferably, at least one of the modified derivatives is used. By containing at least one of a terminal-modified derivative of an ethylene oxide polymer, a terminal-modified derivative of a propylene oxide polymer, and a terminal-modified derivative of a copolymer of ethylene oxide and propylene oxide, hot melt is improved while improving spinnability. In the present invention, the terminal modified derivative of an ethylene oxide polymer, the terminal modified derivative of a propylene oxide polymer, and the terminal modified derivative of a copolymer of ethylene oxide and propylene oxide can be used in the present invention. A polymer obtained by linking ethylene oxide or propylene oxide molecules or ethylene oxide / propylene oxide copolymer molecules to about 10,000 to several hundred thousand is preferable.

  Further, as a terminal-modified derivative of an ethylene oxide polymer, a terminal-modified derivative of a polymer of propylene oxide, and a terminal-modified derivative of a copolymer of ethylene oxide and propylene oxide, for example, those obtained by ring-opening polymerization of ethylene oxide or propylene oxide, Also preferred are those obtained by lowering the molecular weight by decomposing the polymer once polymerized to a high molecular weight. More specifically, it is a product obtained by reacting a terminal hydroxyl group of polyethylene glycol or polypropylene glycol as a primary alcohol, and at least one selected from the group consisting of an ester group, an amine group, an acetal group, and the like. In addition, a polyethylene glycol derivative or a polypropylene glycol derivative containing a functional group is preferable. Of these, particularly preferred are polyethylene glycol or an ether of polypropylene glycol and alkyl.

  In the present invention, a terminal-modified derivative of an ethylene oxide polymer, a terminal-modified derivative of a propylene oxide polymer, and a terminal-modified derivative of a copolymer of ethylene oxide and propylene oxide are used in an appropriate catalyst species, suspending agent, solvent in the polymerization process. In some cases, the carbon skeleton structure of the molecule may be changed by selecting, but it may be linear or branched.

  In the present invention, the number average molecular weight of the terminal modified derivative of the ethylene oxide polymer, the terminal modified derivative of the propylene oxide polymer, and the terminal modified derivative of the copolymer of ethylene oxide and propylene oxide is in the range of 100 or more and 10,000 or less. preferable. The number average molecular weight here can be determined by measurement by GPC, and is a polystyrene equivalent value.

  On the other hand, the silicone oil used in the present invention is represented by polydimethylsiloxane. Polydimethylsiloxane includes 1) polydimethylsiloxane composed of dimethylsiloxane units, 2) polydialkylsiloxanes composed of dimethylsiloxane units and dialkylsiloxane units containing an alkyl group having 2 to 4 carbon atoms, and 3) dimethylsiloxane units; Polysiloxanes composed of methylphenylsiloxane units are included.

The silicone oil preferably has a viscosity at 25 ° C. of 10 × 10 ⁻⁶ to 10 × 10 ⁻¹ m ² / S. The silicone oil viscosity is a viscosity value at 25 ° C. measured by a method described in JIS-K2283 (petroleum product kinematic viscosity test method).

  In the present invention, it is also preferable to use one or more terminal blocking agents. 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, the polyurethane may contain various stabilizers, pigments and the like. For example, hindered phenolic agents such as BHT and Sumitomo Chemical Co., Ltd. “Sumilyzer GA-80”, and various benzotriazole and benzophenone agents such as “Tinubin” manufactured by Ciba Geigy Co., Ltd. , Sumitomo Chemical Co., Ltd. "Sumilyzer P-16" and other phosphorous agents, various hindered amine agents, 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 powders, metal soaps such as magnesium stearate, bactericides, deodorizers including silver, zinc and their compounds, lubricants such as silicone and mineral oil, barium sulfate, oxidation It is also preferable that various antistatic agents such as cerium, betaine and phosphate are included. Properly, It is also preferred that they are reacted with the polymer. In order to further enhance the durability to light and various nitric oxides, for example, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., for example, “Sumilyzer GA manufactured by Sumitomo Chemical Co., Ltd.” It is also preferable to use a thermal oxidation stabilizer such as -80 ", for example, a light stabilizer such as" Sumisorb 300 # 622 "manufactured by Sumitomo Chemical Co., Ltd.

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

  In the present invention, when a polyurethane yarn whose main constituent components are a polymer diol and a diisocyanate is produced, spinning is performed with a nonionic surfactant and a silicone oil. The nonionic surfactant and the silicone oil may be added together in the polymerization stage of the polyurethane, but it is preferable to prepare a polyurethane solution in advance and then add it.

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

  Particularly suitable polyurethanes for the present invention include PTMG having a molecular weight of 1800 to 6000 as a polymer diol, MDI as a diisocyanate, ethylene glycol, diol, 1,3 propanediol and 1,4 butanediol as a diol. And those having a melting point on the high temperature side of 200 ° C. or higher and 260 ° C. or lower.

  Such a polyurethane is preferably synthesized by using the above raw materials in, for example, DMAc, DMF, DMSO, NMP, or a solvent containing these as a main component. For example, each raw material is charged in such a solvent, dissolved, heated to an appropriate temperature and reacted to obtain polyurethane, a so-called one-shot method, or a polymer diol and diisocyanate are first melted and reacted. A method in which a product is dissolved in a solvent and reacted with the diol to obtain polyurethane is preferred.

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. to 260 ° C. is achieved by controlling the types and ratios of the polymer diol, MDI, and diol. obtain. When the molecular weight of the polymer diol is low, a polyurethane having a high melting point at a high temperature can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the diol is low, the proportion of the polymer diol is relatively By reducing the amount of the polyurethane, a polyurethane having a high temperature melting point can be obtained.
In the case where the molecular weight of the polymer diol is 1800 or more, in order to make the melting point on the high temperature side 200 ° C. or more, the polymerization is advanced at a ratio of (number of moles of MDI) / (number of moles of polymer diol) = 1.5 or more. Is preferred.

  In the synthesis of such polyurethane, it is also preferable to use one or a mixture of two or more catalysts such as amine catalysts and organometallic catalysts. Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ′ , N ′, N′-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N′-dimethylpiperazine, N-methyl-N′-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N, N-dimethylamido Noethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethyl Aminohexanol, triethanolamine and the like are preferable. Further, as the organometallic catalyst, tin octoate, dibutyltin dilaurate, lead dibutyl octoate and the like are preferable.

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

  In the present invention, a nonionic surfactant, particularly a terminal-modified derivative of an ethylene oxide polymer, a terminal-modified derivative of a propylene oxide polymer, and a terminal-modified derivative of a copolymer of ethylene oxide and propylene oxide are added to such a polyurethane solution. It is preferable to add at least one kind and silicone oil.

  As a method for adding the nonionic surfactant and the silicone oil to the polyurethane solution, any method can be adopted. 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 nonionic surfactant and the silicone oil to be added are preferably added as a solution from the viewpoint of uniform addition to the polyurethane solution.

  Note that the addition of a nonionic surfactant to the polyurethane solution may cause a phenomenon in which 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. From the viewpoint of preventing, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine and other monoamines, ethanol, One or more end-capping agents such as monools such as propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate are used in combination. And it is also preferred.

  When the nonionic surfactant and the silicone oil are added to the polyurethane solution, for example, the agents such as the light-proofing agent and the antioxidant and the pigment may be added at the same time.

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

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

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

  For example, the setting properties (permanent strain rate) and stress relaxation characteristics of the polyurethane elastic yarn of the present invention are particularly affected by the speed ratio between the godet roller and the winder, and therefore are appropriately determined according to the intended use of the yarn. Is preferred. That is, from the viewpoint of obtaining a polyurethane elastic yarn having desired setting properties and stress relaxation, the speed ratio of the godet roller and the winder is preferably wound in a range of 1.15 to 1.65. When obtaining a polyurethane elastic yarn having particularly low setting properties and low stress relaxation, the speed ratio between the godet roller and the winder is more preferably in the range of 1.15 to 1.40, and preferably 1.15 to 1. A range of .35 or less is more preferable. On the other hand, when obtaining a polyurethane elastic yarn having high setability and high stress relaxation, it is preferable that the speed ratio of the godet roller and the winder is wound in the range of 1.25 to 1.65. The range of 1.65 or less is more preferable.

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

  First, evaluation of spinnability and hot melt adhesion, terminal-modified derivative of ethylene oxide polymer, terminal-modified derivative of propylene oxide polymer, and terminal-modified derivative of copolymer of ethylene oxide and propylene oxide, A quantitative method will be described.

[Evaluation of spinnability]
The continuous spinning time was displayed.

[Evaluation of hot melt adhesion]
A hot melt adhesive is attached to one elastic fiber of 940 dtex stretched twice, 0.1 g / m, both sides are sandwiched between polypropylene non-woven fabrics, and pressed from above with a roller. This is cut into a length of 30 cm (L1), and the length (L2) of the elastic fiber after standing for 48 hours in an atmosphere of 40 ° C. and 80% RH is measured. The hot-melt adhesiveness retention was calculated by the following formula. The higher the value, the better the hot melt adhesion. In addition, a measurement is performed about 30 elastic fibers and it evaluates with the average value of those 30 hot-melt-adhesion retention.
Hot-melt adhesiveness retention (%) = 100 × (L2) / (L1)
[Contents of a terminal-modified derivative of an ethylene oxide polymer, a terminal-modified derivative of a propylene oxide polymer, and a terminal-modified derivative of a copolymer of ethylene oxide and propylene oxide]
The calculation method of the content of the terminal modified derivative of the ethylene oxide polymer in the sample yarn is shown below. The n number is 1, and the same measurement is performed for a terminal-modified derivative of a propylene oxide polymer and a terminal-modified derivative of a copolymer of ethylene oxide and propylene oxide.

  First, 50 ml of DMAc was added to 1 g of sample yarn (A), and after completely dissolving the sample yarn, 100 ml of ethanol was slowly added to precipitate the end-modified derivative of the ethylene oxide polymer, and the remaining polyurethane solution was evaporated to dryness. The polyurethane (B) in the yarn had been isolated.

Next, a calibration curve was prepared from an IR spectrum of a mixture of polyurethane (B) having a predetermined weight ratio and an end-modified derivative of an ethylene oxide polymer. The procedure is to prepare samples of ethylene oxide polymer having a terminal modified derivative content of 0% by weight, 1% by weight, 3% by weight, 6% by weight, 10% by weight, 20% by weight, and 40% by weight. The peak area ratio (X) between characteristic absorption ν (CO) 1700 cm ^{−1 to} 1800 cm ⁻¹ and ν (—O—) YYYcm ⁻¹ was determined. For the IR spectrum measurement, FT-IR manufactured by PerkinElmer was used, and a sample film of DMAc was used as the measurement sample. A calibration curve of the content (% by weight) of the terminal modified derivative of the ethylene oxide polymer with respect to the peak area ratio (X) was prepared, and the slope (α) was obtained.
Finally, after the yarn sample (A) was washed with n-hexane, an IR spectrum was measured under the same conditions. In the obtained spectrum, the peak area ratio (Xs) between ν (CO) 1700 cm ^{−1 to} 1800 cm ⁻¹ and ν (—O—) YYYcm ⁻¹ was determined.

The content was calculated by the following formula.
Derivative content (% by weight) = (α) × (Xs)
[Content of silicone oil]
The calculation method of the content of silicone oil in the sample yarn is shown below. The n number is 1.

First, 1 g of the sample yarn is washed with n-hexane, immersed in 20 ml of tetrachloroethylene for 24 hours, and then the polyurethane yarn is filtered to obtain a measurement sample solution. Next, the absorbance at 1260 cm ⁻¹ of a tetrachloroethylene solution containing 0% by weight, 1% by weight, 3% by weight, and 6% by weight of silicone oil was measured in advance to prepare a calibration curve. For the absorbance measurement, FT-IR manufactured by PerkinElmer was used. The absorbance (A) of the measurement sample solution was measured under the same conditions. The content was calculated by the following formula.
Silicone oil content (wt%) = 0.1088A-0.024
[Example 1]
A polyurethane urea DMAc solution (35% by weight) composed of PTMG having a molecular weight of 1800, MDI, ethylenediamine and diethylamine as a terminal blocking agent was polymerized to obtain a solution A1. Next, a DMAc solution (35% by weight) of polyoxyethylene cetyl ether (number average molecular weight 600) manufactured by Riken Vitamin Co., Ltd. was prepared. This was designated as B1. Further, polyurethanes produced by the reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate) described in US Pat. No. 3,555,115 and those described in US Pat. No. 3,553,290 are described. A DMAc solution (35% by weight) of a 2 to 1 weight ratio mixture of the condensation polymer of p-cresol and divinylbenzene was prepared as an antioxidant solution C1. Furthermore, D1 is a silicone oil made of unmodified polydimethylsiloxane and having a viscosity at 25 ° C. of 20 × 10 ⁻⁶ m ² / S.

  A1, B1, C1, and D1 were uniformly mixed at 95% by weight, 1% by weight, 2% by weight, and 2% by weight to obtain a solution P1. By spinning this at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder, 3000 g of polyurethane yarn having a content of 940 decitex, 50 filaments and polyoxyethylene cetyl ether of 1% by weight A wound body was obtained.

  Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. Spinnability was far superior to Comparative Example 1 in which B1 was not blended. Hot melt adhesiveness increased 1.18 times compared to Comparative Example 1 containing no B1.

[Example 2]
A DMAc solution (35% by weight) of polyoxyethylene cetyl ether (number average molecular weight 1200) (manufactured by Riken Vitamin Co., Ltd.) was prepared. This was designated as B2. In addition, titanium oxide was manufactured by Ishihara Sangyo Co., Ltd. '(Registered trademark) PF-711 was designated as E1.

  A1, B2, C1, D1, and E1 were uniformly mixed at 94.5 wt%, 1 wt%, 2 wt%, 2 wt%, and 0.5 wt% to obtain Solution P2. By spinning this at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder, 3000 g of polyurethane yarn having a content of 940 decitex, 50 filaments and polyoxyethylene cetyl ether of 1% by weight A wound body was obtained.

  Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. The spinnability was far superior to that of Comparative Example 1 containing no B2. Hot melt adhesiveness increased 1.17 times compared to Comparative Example 1 containing no B2.

[Example 3]
A DMAc dispersion (35% by weight) of polyoxypropylene 2-ethylhexyl ether (number average molecular weight 5000) was prepared. This was designated as B3.

  A1, B3, C1, and D1 were uniformly mixed at 95% by weight, 1% by weight, 2% by weight, and 2% by weight to obtain a solution P3. When this is dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder, the content of 940 dtex, 50 filaments, polyoxypropylene 2-ethylhexyl ether is 1% by weight. A 3000 g wound body of polyurethane yarn was obtained.

  Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. Spinnability was far superior to Comparative Example 1 in which B3 was not blended. Hot melt adhesiveness increased 1.17 times over Comparative Example 1 containing no B3.

[Example 4]
A DMAc dispersion (35% by weight) of polyoxyethylene polyoxypropylene 2-ethylhexyl ether (number average molecular weight 8000) was prepared. This was designated as B4.

  A1, B4, C1, and D1 were uniformly mixed at 95% by weight, 1% by weight, 2% by weight, and 2% by weight to obtain a solution P4. When this is dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder, the content of 940 decitex, 50 filaments, polyoxyethylene polyoxypropylene 2-ethylhexyl ether is 1 weight % Of polyurethane yarn of 3000 g was obtained.

  Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. Spinnability was far superior to that of Comparative Example 1 containing no B4. Hot melt adhesiveness increased 1.14 times compared to Comparative Example 1 containing no B4.

[Example 5]
A DMAc dispersion (35% by weight) of polyoxyethylene sorbitan trioleate (number average molecular weight 1000) was prepared. This was designated as B5.

  A1, B5, C1, and D1 were uniformly mixed at 95% by weight, 1% by weight, 2% by weight, and 2% by weight to obtain a solution P5. By spinning this at a speed of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder, a polyurethane yarn having a content of 940 dtex, 50 filaments, polyoxyethylene sorbitan trioleate of 1% by weight is obtained. 3000 g wound thread was obtained.

  Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. Spinnability was far superior to Comparative Example 1 in which B5 was not blended. Hot melt adhesiveness increased 1.11 times compared to Comparative Example 1 containing no B5.

[Comparative Example 1]
The polymer solution A1 and the additive solution C1 were mixed at 98% by weight and 2% by weight to obtain a uniform solution P6. This was dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder to obtain 3000 g of a 940 decitex, 50-filament polyurethane yarn. Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. The spinnability was poor and the hot melt adhesion was not satisfactory.

[Comparative Example 2]
The polymer solution A1 and the additive solutions C1 and D1 were mixed at 96 wt%, 2 wt%, and 2 wt% to obtain a uniform solution P7. This was dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder to obtain 3000 g of a 940 decitex, 50-filament polyurethane yarn. Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. The spinnability was not a problem, but the hot melt adhesion was not satisfactory.

[Comparative Example 3]
A1, B1, and C1 were mixed at 97 wt%, 1 wt%, and 2 wt% to obtain a uniform solution P8. This was dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder to obtain 3000 g of a 940 decitex, 50-filament polyurethane yarn. Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. Spinnability was poor.

[Comparative Example 4]
Polymer solution A1, additive solution C1, and titanium oxide E1 were mixed at 97.5 wt%, 2 wt%, and 0.5 wt% to obtain a uniform solution P9. This was dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder to obtain 3000 g of a 940 decitex, 50-filament polyurethane yarn. Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. The spinnability was poor and the hot melt adhesion was not satisfactory.

[Comparative Example 5]
A DMAc dispersion (35% by weight) of polyethylene oxide (number average molecular weight of 4500000) was prepared. This was mixed with A1, C1 at 3 wt%, 95 wt% and 2 wt% to obtain a uniform solution P10. This was dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder to obtain 3000 g of a 940 decitex, 50-filament polyurethane yarn. Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. The spinnability was poor and the hot melt adhesion was not satisfactory.

[Comparative Example 6]
A silicone mixture was prepared by mixing 100% by weight of silicone oil and 2.0% by weight of amino-modified silicone. Here, a silicone oil made of unmodified polydimethylsiloxane and having a viscosity at 25 ° C. of 20 × 10 ⁻⁶ m ² / S was used as the silicone oil. Next, 17.5% by weight of magnesium distearate is added to 100% by weight of the silicone mixture and mixed at 25 to 35 ° C. until uniform, and then wet milled using a horizontal bead mill to obtain magnesium distearate. A colloidally dispersed dispersion was prepared and used as a slurry modifier. This was mixed with A1, C1 at 2 wt%, 96 wt% and 2 wt% to obtain a uniform solution P11. This was dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder to obtain 3000 g of a 940 decitex, 50-filament polyurethane yarn. Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. In terms of hot melt adhesion, satisfactory results were not obtained.

[Comparative Example 7]
The uniform solution P6 was dry-spun at a speed ratio of 300 m / min with a speed ratio of 1.4 between the godet roller and the winder to obtain 3000 g of a polyurethane yarn of 940 decitex and 50 filaments of polyurethane yarn. Here, as the spinning oil, 75% of polypropylene glycol (number average molecular weight 700), 5% of isostearyl alcohol, 10% of mineral oil (15 centistokes), and 10% of dimethyl silicone (10 centistokes polydimethylsiloxane) 2.8% by weight was adhered to the fiber. Table 1 shows the spinnability and hot melt adhesion of the obtained yarn. Neither spinnability nor hot melt adhesion was satisfactory.

  The polyurethane yarn of the present invention is excellent in spinnability and contributes to improvement in productivity. Further, the gather using the polyurethane yarn of the present invention is excellent in hot melt adhesiveness. Because of having these excellent characteristics, the polyurethane yarn of the present invention can be used alone or in combination with various fibers, for example, socks, stockings, circular knitting, tricot, swimsuit, ski pants, work clothes, smoke fire. Clothes, clothes, golf trousers, wet suits, bras, girdles, fastening materials for various textile products such as gloves and socks, etc., fastening materials for preventing sanitary products such as paper diapers, fastening materials for waterproofing materials, imitation bait, artificial flowers, electricity It can be used for various applications such as insulating materials, wiping cloths, copy cleaners, and gaskets.

Claims (6)

A polyurethane yarn comprising a nonionic surfactant and silicone oil. The polyurethane yarn according to claim 1, wherein the nonionic surfactant is an ether type surfactant. The nonionic surfactant is at least one of a terminal-modified derivative of an ethylene oxide polymer, a terminal-modified derivative of a propylene oxide polymer, and a terminal-modified derivative of a copolymer of ethylene oxide and propylene oxide. The polyurethane yarn according to claim 1 or 2. The number average molecular weight of at least one of the terminal modified derivative of the ethylene oxide polymer, the terminal modified derivative of the propylene oxide polymer, and the terminal modified derivative of the copolymer of ethylene oxide and propylene oxide is 100 or more and 10,000 or less. The polyurethane yarn according to claim 3, wherein A method for producing a polyurethane yarn, characterized in that when a polyurethane yarn whose main constituents are a polymer diol and a diisocyanate is produced, it is spun by containing a nonionic surfactant and a silicone oil. The method for producing a polyurethane yarn according to claim 5, wherein the spinning method is a dry method.