JP4595775B2 - Polyurethane elastic fiber and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane elastic fiber. More specifically, the present invention relates to a polyurethane elastic fiber excellent in spinnability, coalescence property, and unwinding property, which is modified by blending a specific component into a spinning dope before dry spinning, and a method for producing the same.

  Polyurethane elastic fibers made of polyurethane or polyurethane urea are fibers that are easy to stick due to the inherent properties of the polymer. Therefore, when the spun fiber is wound up into a wound body, the fiber from the wound body is unwound. There was a problem that wrinkles were likely to get worse.

  Therefore, in order to improve the unraveling property and running stability, a metal soap such as magnesium stearate is added to the polymer before spinning and contained in the fiber, or the metal soap is added to the spinning oil. Thus, it has been proposed to apply to the fiber surface.

  For example, Patent Literature 1 and Patent Literature 2 describe that the former is spun after adding a metal soap into a polyurethane spinning solution and wound after applying an oil agent. As the latter, Patent Document 3 describes a method in which a specific oil agent obtained by adding metal soap to silicone oil is applied to polyurethane fibers in the spinning process.

  However, with the conventional method of adding metal soap to the polyurethane spinning solution before spinning, the unwinding property from the wound body is improved. In such a case, there is a problem in that the filaments are not sufficiently bonded to each other, and filament breakage or yarn breakage is likely to occur during the post-processing step or when using polyurethane fibers.

  In the method of applying oil agent added with metal soap to the fiber during spinning, the attached metal soap is unevenly distributed on the fiber surface, so the effect of metal soap is not fully exhibited, and the unwinding property is sufficiently improved It was difficult to do.

  In addition, a method has been proposed in which polyurethane fiber is spun and then separated using the lubricant effect of metal soap. For example, Patent Document 4 describes a method for obtaining a polyurethane filament having a very fineness by winding a plurality of filaments spun from a polyurethane spinning solution to which metal soap is added without bonding, and then separating the filaments. Yes. Also, 6 filaments, which are prepared by blending a hydrotalcite compound, metal soap and modified silicon compound in a polyurethane spinning solution and spinning them, are twisted with an air jet twisting machine two by two, and three of the two joined yarns are joined. Patent Document 5 describes a method of winding the yarns at the same time and then splitting them into three yarns.

  When the joining process is not performed during the spinning process as described in Patent Document 4, it is difficult to join the filaments together. In addition, when a hydrotalcite compound is added in combination as in Patent Document 5, the presence of hydrotalcite as an insoluble foreign matter in the fiber induces spinneret clogging or yarn breakage during spinning, resulting in poor spinnability. Therefore, there is a problem that scum generation increases, which is unsuitable for industrial production.

Japanese Patent Publication No. 58-44767 JP-A-57-51816 JP 2003-13362 A JP 2001-214332 A Japanese Patent Laid-Open No. 9-217227

  The object of the present invention is to solve the above-mentioned problems in the prior art, to prevent clogging of the die during spinning and thread breakage, to provide good spinning properties, and to prevent the yarn from sticking to each other in the wound body. Providing polyurethane elastic fibers with good toughness, in particular, even when a plurality of filaments are bonded together to produce a bonded polyurethane fiber yarn and wound, the unwindability is good and It is an object of the present invention to provide a polyurethane elastic fiber yarn that has sufficient filament coalescence in the yarn and hardly causes troubles such as filament breakage.

In order to achieve the above-described object, the polyurethane elastic fiber of the present invention comprises silicone oil, modified silicone, and metal soap, 0.1 to 10% by weight and 0.01 to 5.0% by weight, respectively, with respect to the polyurethane fiber. %, Ri name contains 0.05 to 5.0 wt%, modified silicone, amino-modified silicone, amide-modified silicones, carboxyamide modified silicone, both ends polyether-modified silicone, carbinol-modified silicones, and carboxyl-modified silicone is one or more of the one in which the content of the metal soap to the total content 100 parts by weight of silicone oil and modified silicone and wherein 5 to 100 parts by weight der Rukoto.

In addition, the method for producing a polyurethane elastic fiber according to the present invention includes adding a modifier obtained by mixing silicone oil, modified silicone, and metal soap to a polyurethane spinning stock solution, followed by dry spinning to thereby produce the polyurethane elastic fiber. it is characterized in that to produce a.

  Since the polyurethane elastic fiber of the present invention contains a predetermined amount of metal soap in the fiber, the unwinding tension from the wound yarn is small even in the inner layer portion, and each layer is excellent in unwinding property. In addition, despite the fact that metal soap is blended in the spinning dope, there is no trouble such as clogging in the die holes or yarn breakage during spinning, and the spinning property is good. Furthermore, even when a plurality of yarns are bonded in the spinning process, a wound body of bonded polyurethane elastic fiber yarns having good bonding properties between filaments and good unwinding properties and bonding properties is manufactured. can do. In addition, if the polyurethane elastic fiber of the present invention is used, it is possible to reduce scum adhesion and accumulation on the guides even in the processing step.

  Thus, the polyurethane elastic fiber of the present invention has high spinning continuity in the spinning process, and the resistance to unwinding (that is, the unwinding tension) from the wound body is from the outside to the inside of the wound body. It can be stably lowered, and an increase in the unwinding tension with time can be suppressed even when the wound body is stored for a long period of time.

  Therefore, when the polyurethane elastic fiber of the present invention is used in the production process of the fabric, the polyurethane elastic yarn can be supplied to the production process with a stable unwinding tension and can be used stably.

Hereinafter, the polyurethane elastic fiber of the present invention and the production method thereof will be described in detail.
The polyurethane elastic fiber of the present invention contains silicone oil, modified silicone, and metal soap, and the contents thereof are 0.1 to 10% by weight and 0.01 to 5.0% with respect to the polyurethane elastic fiber, respectively. % By weight, 0.05 to 5.0% by weight.

  Here, the silicone oil functions as a dispersion medium when adding metal soap to the spinning dope, and also functions to reduce troubles such as clogging of the base in the spinning process of the elastic fiber.

  The silicone oil is represented by polydimethylsiloxane. The 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. And polysiloxanes comprising methylphenylsiloxane units.

The silicone oil preferably has a viscosity at 25 ° C. of 10 × 10 ⁻⁶ to 10 × 10 ⁻¹ m ² / S. In the case of silicone oil having a viscosity that is too low (less than 10 × 10 ⁻⁶ m ² / S), the dispersion medium function is insufficient when preparing a modifier liquid containing metal soap before adding to the spinning dope. The metal soap is liable to settle and secondary agglomerate in the modifier liquid, and it is difficult to uniformly disperse the metal soap in the spinning dope, so troubles such as clogging of the mouthpiece due to the secondary agglomerate of the metal soap. Is likely to invite. Conversely, when the viscosity of the silicone oil is too high (exceeds 10 × 10 ⁻¹ m ² / S), the metal soap particle size is uniform and minute when the metal soap is dispersed in the silicone oil and used as a modifier. For example, the heat generation during wet pulverization is large, and the modifier itself may be altered, which is not preferable.

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).
This silicone oil is particularly necessary for enhancing the uniform fine dispersibility in the fiber of the metal soap added in combination, and its blending amount is 0.1 to 10% by weight based on the fiber. Among these, 0.5 to 5% by weight is preferable.

The modified silicone used in the present invention is a linear polyorganosiloxane containing a dimethylsiloxane unit and a siloxane unit having a modifying group as essential constituent units. The types of the modified silicone, amino-modified silicone, amide-modified silicones, carboxyamide modified silicone, both ends polyether-modified silicone, carbinol-modified silicone, carboxyl-modified silicone emissions mentioned, of one or more of these Used in a mixture .

  This modified silicone is particularly necessary for combining a plurality of filaments during spinning to form a polyurethane elastic fiber excellent in the yarn combining property, and the blending amount is 0.01 to 5. 0% by weight. Among these, 0.03 to 3.0% by weight is preferable.

The metal soap used in the present invention is an organic acid metal salt such as a higher fatty acid metal salt, and is preferably as fine as possible, for example, at a colloidal level. A colloid is a state in which a substance becomes fine particles and is mixed and dispersed in a liquid or the like. Therefore, colloidal particles generally have a dispersed particle size of about 10 ⁻⁷ to 10 ^−9. This refers to the case of about m particles. The average particle diameter of the metal soap used in the present invention is preferably less than 1 × 10 ⁻⁶ m (that is, less than 1.0 μm).

  Specific examples of the metal soap include stearic acid, palmitic acid, myristic acid, aicosanoic acid, docosanoic acid, lauric acid, 12-hydroxystearic acid, arachidic acid, behenic acid, octanoic acid, tall oil fatty acid and other fatty acids. , Resin acids such as abietic acid, neoabietic acid, d-pimaric acid, iso-d-pimalic acid, podocarp acid, agatendicarboxylic acid, benzoic acid, cinnamic acid, p-oxycinnamic acid, diterpenic acid, or naphthenic acid A metal salt (saponified product) of an organic acid such as

  As the type of metal constituting the metal salt, metals other than alkali metals are preferable, for example, aluminum, calcium, zinc, magnesium, silver, barium, beryllium, cadmium, cobalt, chromium, copper, iron, mercury, manganese, Examples include nickel, lead, tin, and titanium.

  In the present invention, one or more of these types of metal soaps may be used. Among them, higher fatty acid metal salts are preferable, and magnesium stearate, calcium stearate and the like are particularly preferable.

  By blending this metal soap in the spinning dope and making it a polyurethane elastic fiber with metal soap dispersed in the polymer, the polyurethane fiber obtained by spinning has properties such as breaking strength and chemical resistance. In addition, the yarns are prevented from sticking to each other in the wound body, and the unwinding property from the wound body, particularly the unwinding property in the inner layer part, is greatly improved, from the outer layer part to the inner layer part of the wound body. It becomes possible to unwind with a stable unwinding tension. Therefore, when this polyurethane elastic fiber is used for clothes or the like, stretchable fiber products having an excellent balance of appearance quality and the like can be manufactured. In order to exert these effects, the metal soap needs to have a fiber content of 0.05 to 5.0% by weight, especially 0.1 to 2.0% by weight. Is preferred.

  In terms of suppressing thixotropy when silicone oil, modified silicone, and metal soap are mixed in the spinning dope, and suppressing changes in viscosity such as thickening during storage of the modifier before addition, it is modified with silicone oil. The mixing ratio with silicone is preferably (100/50) to (100 / 0.5) (weight ratio).

  The amount of the metal soap relative to the silicone mixture (total of silicone oil and modified silicone) is preferably 5 to 100 parts by weight per 100 parts by weight of the silicone mixture. By setting this ratio, separation and settling of metal soap in the modifier can be suppressed to improve the stability of the modifier, and further, clogging of spinneret holes due to metal soap can be suppressed. A more desirable ratio is 10 to 70 parts by weight of metal soap per 100 parts by weight of the silicone mixture. Within this range, there is little change in the viscosity of the modifier, especially during long-term storage, and all of spinnability, coalescence, and scum suppression are excellent in a well-balanced manner.

The polyurethane-based elastic fiber of the present invention is a fiber produced by spinning a polyurethane polymer.
The polyurethane polymer may be a polyurethane-urea that also contains a urea bond, or may be a polyurethane that does not contain a urea bond. Further, it may be a mixed polymer or copolymer of polyurethane and polyurethane-urea.

  More specifically, this polyurethane polymer has two types of segments: (a) a soft segment such as a long-chain polyether segment or a polyester segment; and (b) an organic isocyanate and a diamine chain extender. Alternatively, a hard segment which is a relatively short chain segment derived by reaction with a diol chain extender is contained as a polymer constituent unit.

  Such polyurethane polymers are usually prepared by a prepolymer method in which a prepolymer product obtained by capping a hydroxyl-terminated soft segment precursor with an organic diisocyanate is chain-extended with a diamine or a diol, or all of these raw materials are in the same bath. It is produced by a one-shot method in which it is put into a polymer, but may be produced by other methods.

The soft segment is derived from a polymer diol compound such as a polyether diol compound or a polyester diol compound.
The polyether-based diol compound for deriving the polyether soft segment preferably includes a copolymerized diol compound containing a unit represented by the following general formula.

（但し、ａ、ｃは１〜３の整数、ｂは０〜３の整数、Ｒ１、Ｒ２はＨ又は炭素数１〜３のアルキル基)

(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 compound include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF). ) And 3-methyl-THF copolymer modified PTMG, THF and 2,3-dimethyl-THF copolymer modified PTMG, THF and neopentyl glycol copolymer modified PTMG, THF and Examples thereof include random copolymers in which ethylene oxide and / or propylene oxide are irregularly arranged. One kind of these polyether glycols may be used, or two or more kinds may be mixed or copolymerized. Among these, PTMG or modified PTMG is preferable.

  Typical polyester soft segments include (a) ethylene glycol, polytetramethylene ether glycol, 2,2-dimethyl-1,3-propanediol, and (b) dibasic acids such as adipic acid and succinic acid. And the like.

  The soft segment is preferably derived from the polyether-based diol compound or the polyester-based diol compound described above. In addition, a polycarbonate diol compound such as poly- (pentane-1,5-carbonate) diol, poly- ( It may be derived from a copolymerized diol compound such as a polyether ester formed from hexane-1,6-carbonate) diol or the like.

  As the organic diisocyanate used for polymerization of polyurethane in the present invention, usually, bis- (p-isocyanatophenyl) -methane (hereinafter abbreviated as MDI), tolylene diisocyanate, bis- (4-isocyanatocyclohexyl) -methane, Hexamethylene diisocyanate, 3,3,5-trimethyl-5-methylenecyclohexyl diisocyanate and the like are used. Among these, MDI is particularly preferable.

  Examples of the diamine chain extender used to form polyurethaneurea include various diamines such as ethylenediamine, 1,3-cyclohexanediamine, and 1,4-cyclohexanediamine. A chain terminator can be included in the reaction mixture to help control the final molecular weight of the polyurethaneurea. Usually, a monofunctional compound having active hydrogen, such as diethylamine, is used as the chain terminator.

  Moreover, the chain extender at the time of superposition | polymerization is not limited to the said diamine, You may use diol. For example, ethylene glycol, 1,3-propanediol, 4-butanediol, neopentyl glycol, 1,2-propylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4- Bis (β-hydroxyethoxy) benzene, bis (β-hydroxyethyl) terephthalate, paraxylylene diol, and the like. The diol chain extender is not limited to only one kind of diol, and may be composed of a plurality of kinds of diols. Moreover, you may use together with the compound containing one hydroxyl group which reacts with an isocyanate group.

  Furthermore, it is also preferred that the polyurethane used in the present invention includes 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 order to produce such a polyurethane, various methods such as a melt polymerization method and a solution polymerization method may be employed. The prescription for the polymerization is not particularly limited, and for example, a prepolymer method or a one-shot method may be used.

  The polyurethane elastic fiber of the present invention is provided with additives such as silicone oil, modified silicone, and metal soap in a polyurethane solution prepared by polymerization or a polyurethane solution in which polyurethane is dissolved in a solvent or dispersed in a dispersion medium. It is manufactured by mixing a fixed amount to obtain a spinning stock solution, and spinning from this spinning stock solution by an ordinary method. The spinning method may be any of a dry spinning method, a melt spinning method, a wet spinning method, and the like, but the dry spinning method is particularly preferable.

  The spinning conditions such as the temperature of the spinning dope, the atmospheric temperature, the discharge speed, the die shape, and the yarn take-up speed during dry spinning may be appropriately selected. For example, the number of holes in the spinneret is not particularly limited, but may be two or more in order to process a plurality of filaments in the spinning process.

  The polyurethane liquid used in the spinning step is preferably a polyurethane solution in which a polyurethane polymer is dissolved in a solvent, but may be a polyurethane dispersion using a dispersion medium. Further, a mixture of these may be used.

  The solvent or dispersion medium used for dissolving or dispersing the polyurethane polymer is not particularly limited as long as it is inert to polyurethane, but N, N-dimethylacetamide (highly soluble in polyurethane polymer) (Hereinafter abbreviated as DMAc), dimethylformamide, dimethyl sulfoxide, vinylpyrrolidone and the like are preferably used.

  In the synthesis of such polyurethane, catalysts such as amine catalysts and organometallic catalysts may be used alone or in combination.

  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.

  A means for blending a predetermined amount of silicone oil, modified silicone, and metal soap additives into this polyurethane solution is not particularly limited, but a fluid slurry is obtained by mixing silicone oil, modified silicone, and metal soap. A method of adding a modifier to the polyurethane solution and mixing the modifier is preferred.

  The method for producing the slurry modifier is not particularly limited, and for example, a predetermined amount of a solid metal soap such as magnesium stearate that is solid and a silicone component (silicone oil and modified silicone) that is liquid. And then wet pulverizing to disperse the metal soap in the liquid component. Here, as a pulverizer used for wet pulverization, various wet pulverizers such as a vertical bead mill, a horizontal bead mill, a sand grinder, a colloid mill, and a ball mill can be used.

  The time when this slurry modifier is added to and mixed with the polyurethane solution is a process for producing the spinning dope, that is, it may be added at any time after the polyurethane polymerization process until the spinning process. Especially, it is preferable to carry out at the stage just before a spinning process. As the addition means, an injection method, a batch method or the like can be selected.

  As described above, when a modifying agent in which additive components are mixed in advance is added to the spinning dope, the modifying agent is in a fluid slurry state when mixed with the spinning solution. This is preferred because it has the advantage that it requires less energy, can be mixed quickly and with relatively simple equipment.

  Thus, what is necessary is just to let the mixing ratio at the time of mix | blending a modifier with a polyurethane solution be a ratio that content of each component in the polyurethane-type elastic fiber manufactured becomes a predetermined value.

  The polyurethane concentration in the spinning dope is not particularly limited, but is usually preferably 25 to 80% by weight. More preferably, it is the range of 30-60 weight%, More preferably, it is the range of 35-55 weight%. When the polyurethane concentration is less than 25% by weight, spinning tends to be difficult because the amount of heat required for evaporation of the solvent and the like increases during dry spinning. On the other hand, if it exceeds 80% by weight, the stability of the spinning dope deteriorates, and the spinnability deteriorates. Even at such a high concentration, the yarn quality decreases if the degree of polymerization of the polymer is lowered in order to stabilize the spinning dope.

  The viscosity of the spinning dope is preferably 2500 to 5500 poise. If the viscosity is 2500 poises or more, yarn breakage due to a decrease in viscosity during dry spinning is small, and spinnability is good. Further, if the viscosity is 5500 poise or less, the pressure loss at the spinneret portion can be suppressed to some extent, so that the spinnability and yarn quality can be improved. The viscosity value is a value measured by a steel ball drop type viscosity measurement method at 40 ° C.

  In a preferred dry spinning process for producing the polyurethane elastic fiber of the present invention, a plurality of filaments (for example, 2 to 248 filaments) discharged from the spinneret are passed through a heated atmosphere to remove the solvent, A number of filaments are subjected to a coalescence treatment and, if necessary, an oil agent is applied, and then wound up to form a wound body of polyurethane fiber. As described above, it is preferable in the present invention to produce a polyurethane elastic fiber in a state in which a plurality of filaments are bonded by performing a bonding process in the spinning process. As means for the bonding process at this time, usual means such as provision of false twist and passage through a guide are applied.

  The fineness, the number of filaments, and the like of the polyurethane elastic fiber of the present invention thus produced may be appropriately determined according to the application.

  The polyurethane-based elastic fiber of the present invention may contain other additives such as various stabilizers, pigments, inorganic substances, and the like, if necessary, within a range that does not impair the effects of the present invention. You may make it contain. 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., “Ciba Geigy” 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. Also included are fluorine or silicone resin powders, bactericides containing silver, zinc and their compounds, deodorants, lubricants such as mineral oil, various antistatic agents such as betaine and phosphate. It may be. Moreover, these may be made to react with a polymer and contain. And especially in order to further improve durability to light, various nitric oxides, etc., for example, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd. may be blended.

  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.

  These other additives may be added when the spinning solution is prepared by mixing the polyurethane solution and the above-described modifier, or may be previously contained in the polyurethane solution or dispersion before mixing. You may keep it. The content of these additives is appropriately determined according to the purpose and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. The part in an Example and a comparative example represents a weight part, and% represents weight%.
In addition, each characteristic in an Example is based on the following evaluation method.

[Modifier dispersion stability]
Place 100 ml of the slurry modifier mixed in advance into a glass 100 ml graduated cylinder with a sealed stopper, and leave it at 40 ° C for 1 week and 1 month, and observe the appearance of the modifier after 1 week and 1 month. The dispersion stability of the slurry modifier was determined according to the following criteria.
A: The appearance was not changed in a uniform dispersion state.
A: A transparent layer of less than 5 ml was generated.
Δ: A transparent layer of 5 ml or more was generated.
X: Precipitation of metal soap occurred.

[Average particle diameter of metal soap]
To 100 ml of the slurry modifier mixed in advance, a silicone oil having a viscosity of 20 × 10 ⁻⁶ m ² / S at 25 ° C. was added and diluted so that the metal soap had a concentration of 1000 ppm to prepare a sample. . The area-based average particle diameter of this sample was measured at 25 ° C. using an ultracentrifugal automatic particle size distribution analyzer (CAPA-700 manufactured by Horiba, Ltd.).
[Evaluation of spinnability]
The frequency of yarn breakage during the dry spinning process was measured and displayed as the winding distance (fiber length) until yarn breakage occurred.

[Evaluation of adhesion]
The polyurethane elastic fiber is unwound while rolling the elastic fiber wound body. At this time, 200% stretched elastic yarn is fed at a feed rate of 50 m / min, and the yarn cracking portion is enlarged via the cross roll. Measure the number of cracks. Yarn breaks are observed as bent nodes. 100 windings were inspected to determine the number of occurrences of yarn breakage, the number of yarn breakage (average value) per 100 m of elastic fiber was determined, and evaluated according to the following criteria.
◎: Less than 1 place per 100 m ○: 1 place or more and less than 5 places per 100 m △: 5 places or more and less than 50 places per 100 m ×: 50 places or more per 100 m

[Strong elongation of elastic fiber]
A sample sample of the elastic yarn is subjected to a tensile test using an “Instron” 4502 tensile tester to measure the strength and elongation at the time of breaking.
That is, 300% elongation of a sample yarn having a sample length of 5 cm (L1) was repeated 5 times at a tensile speed of 50 cm / min. This length was then held for 30 seconds. Furthermore, it extended | stretched until the sample sample thread | yarn cut | disconnected 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 given by the following equation.

Strength = (G3)
Elongation = 100 × {(L3) − (L1)} / (L1)

[Unwinding tension of elastic fiber]
The unwinding tension is measured by the apparatus shown in FIG. The polyurethane elastic fiber wound body 1 wound around the tube 2 is fixed as shown in FIG. 1, and the polyurethane elastic fiber 3 is unwound from the side surface of the wound body 1 at a constant speed of 45.7 m / min. The unraveled traveling yarn 3 is passed through the guide 4 and the ceramic slot guide 5, and a trajectory bent at 90 degrees is drawn by the tensiometer roller 6, and the roller 12 is driven at 45.7 m / min. , Draw a trajectory bent at 90 degrees and let the soccer gun 13 suck. The free tensiometer roller 6 is connected to an electric strain gauge 7, and the electric signal is averaged by an integrator 9 through a conductor 8 and the data is stored in a recorder 11. This test is performed for 4 minutes and the average tension of the 183m yarn path is measured. The measurement temperature is 25 ° C. and 60% RH. The position of the wound thread body to be measured is the wound body surface layer, the center layer, and the innermost layer.

  Here, the wound body surface layer is a layer obtained by removing about 5 grams of yarn from the surface of the wound body. This is because the winding pattern on the surface of the wound body may be intentionally changed. The innermost layer is a layer where about 5 g of the wound yarn is left in the wound body. The center layer is a layer in the middle of the wound body surface layer and the innermost layer. As the wound body for measuring the unwinding tension, one stored at about 20 ° C. for 3 months or more after spinning was used.

[Evaluation of scum generation inhibition]
Ten wound yarns were prepared on a miniature warping machine, and wound at 1500 km at a yarn speed of 300 m / min in an atmosphere of 25 ° C. × 65% RH. At this time, the dropout and accumulation state of the scum with respect to the comb guide of the miniature warping machine was visually observed and evaluated according to the following criteria.
A: Almost no scum adhered.
○: Scum was slightly adhered, but there was no problem with stable yarn running.
X: There was much adhesion and accumulation of scum, and there was a big problem in the stable running of the yarn.

[Example 1]
Polymerization is performed from a polymerization raw material consisting of polytetramethylene ether glycol having a molecular weight of 2900, bis- (p-isocyanatophenyl) -methane, and ethylenediamine by a normal prepolymer method (comprising diethylamine as a terminal terminator) to form a polyurethane solution (solvent Prepared N, N′-dimethylacetamide (hereinafter abbreviated as DMAC), polyurethane concentration of 35% by weight) (A).

  Further, as an antioxidant, a polyurethane solution formed by the reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexylisocyanate) ("Megachlor" (registered trademark) 2462 manufactured by DuPont) (B) And a condensation polymer of p-cresol and divinylbenzene ("Megachlor" (registered trademark) 2390 manufactured by DuPont) in a ratio of 2 to 1 (weight ratio), and an antioxidant DMAc solution (concentration 35 wt.%). %), And this was used as the other additive solution (C).

  The polyurethane solution (A) and the other additive solution (C) were uniformly mixed at a ratio of 94% by weight and 6% by weight, respectively, to obtain a solution (D) once.

Separately, 100 parts by weight of silicone oil (S-1) and 2.0 parts by weight of amino-modified silicone (M-1) were mixed to obtain a silicone mixture. 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, 1100 parts by weight of magnesium distearate is added to 100 parts by weight of the silicone mixture and mixed at 25 to 35 ° C. until uniform, and then wet pulverized using a horizontal bead mill to obtain magnesium distearate. A colloidally dispersed dispersion was prepared and used as a slurry modifier (T-1). The composition and properties of the resulting slurry modifier are shown in Table 1.

  The slurry modifier (T-1) was uniformly mixed with the solution (D) by an injection method using a static mixer to obtain a spinning dope. The mixing ratio here was such that the modifier content in the fiber would be 4.0% by weight.

  The obtained spinning dope is discharged from the discharge holes (three) of the spinneret, passed through a heated atmosphere, the solvent is removed, and after coalescence treatment by air entanglement, oil is applied, and the godet roller and winder A dry spinning was performed under the conditions of a speed ratio of 1.20 and a winding speed of 600 m / min, and a polyurethane elastic fiber of 3 filaments 22 dtex was wound on a cylindrical paper tube having a length of 58 mm through a traverse guide that gave a width of 38 mm. And it wound up using the winder of the surface drive, and manufactured the 500 g winding body.

  Here, as the spinning oil, a normal oil mainly composed of silicone oil was used, and 5.0% by weight was adhered to the fiber.

  The obtained polyurethane elastic fiber was in a state where three filaments were bonded together, and the bonding property was excellent as shown in Table 2. As shown in Table 2, when spinnability, unwinding tension at the time of unwinding from a wound body, strong elongation characteristics of polyurethane elastic fiber, and scum generation suppression were evaluated, all were good.

  The slurry modifier used in Example 1 had good dispersion stability, and the metal soap had a small average particle size. In addition, the obtained polyurethane elastic fiber has a great effect of reducing the unwinding tension of the wound layer, particularly the inner layer part, and each layer has a low unwinding tension, excellent unwinding property, excellent coalescence, and spinnability. Also, there was almost no scum adhesion.

[Example 2]
In preparing the slurry modifier, the amount of amino-modified silicone (M-1) with respect to 100 parts by weight of silicone oil (S-1) was changed to 6.0 parts by weight, and magnesium distearate relative to 100 parts by weight of the silicone mixture. It mixed until it became uniform at 20-35 degreeC similarly to the case of Example 1 except having changed the quantity of salt (M-1) into 35.0 weight part (2 times amount in the case of Example 1). Thereafter, the mixture was wet pulverized using a horizontal bead mill to prepare a dispersion in which the magnesium distearate salt was colloidally dispersed, and this was used as a slurry modifier (T-2). Table 1 shows the composition and properties of the resulting slurry modifier.

  Using this slurry modifier (T-2), a polyurethane elastic fiber is produced in the same manner as in Example 1 except that the modifier content in the fiber is changed to 2.0 wt%. And evaluated. The results are shown in Table 2.

  The slurry modifier used in Example 2 had good dispersion stability, and the average particle size of the metal soap was relatively small. In addition, the obtained polyurethane elastic fiber has a great effect of reducing the unwinding tension of the wound layer, particularly the inner layer part, and each layer has a low unwinding tension, excellent unwinding property, excellent coalescence, and spinnability. Also, there was almost no scum adhesion.

[Example 3]
When preparing the slurry modifier, a slurry modifier (T-3) was prepared in the same manner as in Example 2 except that the modified silicone component was changed to carboxamide-modified silicone (M-2). . Table 1 shows the composition and properties of the resulting slurry modifier.
A polyurethane elastic fiber was produced and evaluated in the same manner as in Example 2 except that this slurry modifier (T-3) was used. The results are shown in Table 2.

  The slurry modifier used in Example 3 had good dispersion stability, and the average particle size of the metal soap was relatively small. In addition, the obtained polyurethane elastic fiber has a great effect of reducing the unwinding tension of the wound layer, particularly the inner layer part, and each layer has a low unwinding tension, excellent unwinding property, excellent coalescence, and spinnability. Also, there was almost no scum adhesion.

[Example 4]
A slurry modifier was prepared by the following method.
As the silicone oil component, a silicone oil (S-2) composed of unmodified polydimethylsiloxane and having a viscosity at 25 ° C. of 20 × 10 ⁻³ m ² / S is used. Ether-modified silicone was used. 100 parts by weight of this silicone oil (S-2) and 10 parts by weight of both terminal polyether-modified silicone (M-1) were mixed to obtain a silicone mixture.

  Next, 70 parts by weight of magnesium distearate is added to 100 parts by weight of the silicone mixture and mixed at 25 to 35 ° C. until uniform, and then wet pulverized using a horizontal bead mill to form colloidal magnesium distearate. A dispersion liquid was prepared and used as a slurry modifier (T-4). The composition and properties of the resulting slurry modifier are shown in Table 1.

Using this slurry modifier (T-4), a polyurethane elastic fiber was produced in the same manner as in Example 1 except that the modifier content in the fiber was changed to 2.0% by weight. And evaluated. The results are shown in Table 2.
The slurry modifier used in Example 4 had good dispersion stability and a small average particle size of the metal soap. In addition, the obtained polyurethane elastic fiber has a great effect of reducing the unwinding tension of the wound layer, particularly the inner layer part, and each layer has a low unwinding tension, excellent unwinding property, excellent coalescence, and spinnability. Also, there was almost no scum adhesion.

[Comparative Example 1]
The solution (D) prepared in Example 1 was used as it was without adding a slurry modifier, and this was used as a spinning dope. Using this spinning dope, polyurethane elastic fibers were produced and evaluated in the same manner as in Example 1. The results are as shown in Table 2, and the adhesion property is good, but the anti-sticking property between the yarns in the wound body is inferior, and the unwinding tension is particularly high in the inner layer part. It was unsatisfactory. Moreover, the scum suppressing effect was insufficient.

[Comparative Example 2]
A slurry modifier containing no silicone oil was prepared by the following method.
After adding 17.5 parts by weight of magnesium distearate to 100 parts by weight of amino-modified silicone (M-1) and mixing at 25 to 35 ° C. until uniform, it is wet pulverized using a horizontal bead mill and distearic acid. A dispersion in which a magnesium salt was colloidally prepared was prepared, and this was used as a slurry modifier (U-2). The composition and properties of the resulting slurry modifier are shown in Table 1.

  A polyurethane elastic fiber was produced and evaluated in the same manner as in Example 1 except that this slurry modifier (U-2) was used. The results are as shown in Table 2, and the adhesion property is good, but the anti-sticking property between the yarns in the wound body is inferior, and the unwinding tension is particularly high in the inner layer part. It was unsatisfactory. Moreover, there existed a problem that spinnability was inferior and there was much adhesion of scum.

[Comparative Example 3]
A slurry modifier containing no modified silicone was prepared by the following method.
3100 parts by weight of magnesium distearate is added to 100 parts by weight of silicone oil (S-1) made of unmodified polydimethylsiloxane and having a viscosity at 25 ° C. of 20 × 10 ⁻⁶ m ² / S. After mixing at 25 to 35 ° C. until uniform, wet pulverization is performed using a horizontal bead mill to prepare a dispersion in which magnesium distearate is colloidally dispersed, and this is used as a slurry modifier (U-3). ). The composition and properties of the resulting slurry modifier are shown in Table 1.

Using this slurry modifier (U-3), a polyurethane elastic fiber was produced in the same manner as in Example 1 except that the modifier content in the fiber was changed to 2.0% by weight. And evaluated. The results are shown in Table 2,
The slurry modifier used in Comparative Example 3 was inferior in dispersion stability and also had a large average particle size of the metal soap. Further, the obtained polyurethane elastic fiber had good unwinding properties from the wound body, but had poor adhesion, low spinnability, and had a problem in suppressing scum adhesion.

[Comparative Example 4]
A slurry modifier containing hydrotalcite without containing silicone oil was prepared by the following method.
70 parts by weight of magnesium distearate and 70 parts by weight of synthetic hydrotalcite (DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.) are added to 100 parts by weight of amino-modified silicone (M-1) used in Example 1. Were mixed at 25-35 ° C. until uniform, and then wet pulverized using a horizontal bead mill to prepare a dispersion in which the solid content was dispersed, and this was used as a slurry modifier (U-4). The composition and properties of the resulting slurry modifier are shown in Table 1.

Using this slurry modifier (U-3), a polyurethane elastic fiber was produced in the same manner as in Example 1 except that the modifier content in the fiber was changed to 1.0% by weight. And evaluated. The results are shown in Table 2,
The slurry modifier used in Comparative Example 4 was inferior in dispersion stability and had a large average particle size of the metal soap. In addition, the obtained polyurethane elastic fiber has relatively good unwinding properties from the wound yarn and has good bonding properties, but has a problem that spinnability is greatly inferior and scum adheres much.

[Comparative Example 5]
After mixing 17.5 parts by weight of magnesium distearate used in Example 1 and 100 parts by weight of DMAc at 25 to 35 ° C., a dispersion in which magnesium distearate was dispersed by wet pulverization using a horizontal bead mill ( U-5). Example 1 except that this dispersion (U-5) was used in place of the slurry modifier and was blended in the spinning dope so that the metal soap content in the fiber was 0.52% by weight. Similarly, polyurethane elastic fibers were produced and evaluated. The obtained polyurethane elastic fiber had good unwinding properties from the wound body, but had poor spinnability and was difficult to continuously spin. In addition, the fusing property was greatly inferior, and the yarn cracking phenomenon in which the multifilament single yarn was easily broken was observed, which was unsatisfactory.

[Comparative Example 6]
The amino-modified silicone (M-1) used in Example 1 was used in place of the slurry modifier, and was blended in the spinning stock solution so that the modified silicone content in the fiber was 0.07% by weight. Except for the above, polyurethane elastic fibers were produced and evaluated in the same manner as in Example 1. The obtained polyurethane elastic fiber was inferior in unwinding tension from the wound yarn, poor in unwinding property as in Comparative Example 1 without the addition of a modifier, and was completely unsatisfactory.

[Comparative Example 7]
The silicone oil (S-1) used in Example 1 was used in place of the slurry modifier, and was blended in the spinning dope so that the silicone oil content in the fiber was 1.40% by weight. Produced and evaluated polyurethane elastic fibers in the same manner as in Example 1. The obtained polyurethane elastic fiber was also inferior in unwinding tension from the wound yarn, poor in unwinding property as in Comparative Example 1 without the addition of a modifier, and completely unsatisfactory.

  Since the polyurethane-based elastic fiber according to the present invention has excellent properties such as high elongation properties, unwinding properties, and bonding properties, it can be used alone or in combination with various fibers, for example, socks, stockings, Sanitary products such as circular knitting, tricot, swimsuit, ski pants, work clothes, smoke fire clothes, clothes, golf pants, wet suits, bras, girdles, fastening materials for various textile products including gloves and socks, paper diapers and paper diapers It can be suitably used for various applications such as a leak-tightening fastening material, a waterproofing material fastening material, imitation bait, artificial flower, an electrical insulating material, a wiping cloth, a copy cleaner, and a gasket.

It is the schematic of the apparatus used when measuring unwinding tension | tensile_strength in an Example.

Explanation of symbols

1. 1. polyurethane elastic fiber wound body, 2. a tube; Running yarn, 4. Guide, 5. Slot guide, 6. 6. tension meter roller; Strain gauge, 8 and 10. 8. conducting wire, Integrator, 11. Recorder, 12. Roller, 13. Soccer gun

Claims (9)

Silicone oil, modified silicone, and a metal soap, respectively, from 0.1 to 10 wt% with respect to polyurethane fibers, 0.01 to 5.0 wt%, Ri name contains 0.05 to 5.0 wt%, The modified silicone is one or more of amino-modified silicone, amide-modified silicone, carboxyamide-modified silicone, double-ended polyether-modified silicone, carbinol-modified silicone, and carboxyl-modified silicone, and silicone oil and modified silicone polyurethane elastic fiber content of the metal soap relative to the total amount 100 parts by weight and wherein 5 to 100 parts by weight der Rukoto with.   2. The polyurethane elastic fiber according to claim 1, wherein the polyurethane elastic fiber is an elastic fiber yarn in which two or more filaments are bonded. The polyurethane elastic fiber according to claim 1 or 2, wherein the content of the metal soap is 17.5 to 100 parts by weight with respect to 100 parts by weight of the total content of the silicone oil and the modified silicone.   The weight ratio of the content of silicone oil and modified silicone is a ratio of silicone oil / modified silicone = (100/50) to (100 / 0.5). The polyurethane-based elastic fiber described in 1. Silicone oil, polyurethane elastic fiber according to any one of claims 1 to 4, wherein the viscosity at 25 ° C. is a silicone oil of ^{10 × 10 -6 ~10 × 10 -1} m 2 / S. Polyurethane elastic fiber according to any one of claims 1 to 5, the metal soap is characterized by a higher fatty acid metal salt. The polyurethane elastic fiber according to any one of claims 1 to 6 is produced by dry-spinning after adding a modifier formed by mixing silicone oil, modified silicone, and metal soap to the polyurethane spinning dope. A process for producing a polyurethane-based elastic fiber characterized by the above. The method for producing a polyurethane-based elastic fiber according to claim 7 , wherein the modifier is a slurry in which metal soap is dispersed in a colloidal form in a silicone mixture composed of silicone oil and modified silicone. The method for producing a polyurethane-based elastic fiber according to claim 7 or 8 , wherein in the dry spinning step, two or more filaments spun from the die are combined and then wound up.

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