DE112020004306T5 - Polyurethane elastic fiber, product containing the same and surface treatment agent for polyurethane elastic fiber - Google Patents

Abstract

The present invention provides: polyurethane elastic fibers with good unwindability even with low silicone oil content and with hardly any unraveling of a multifilament into individual strands; a product containing the same; and a surface-treating agent for polyurethane elastic fibers, the agent being suitable for the production of the polyurethane elastic fibers. Polyurethane elastic fibers characterized by containing 10 ppm to 10,000 ppm of a hydrocarbon compound represented by the formula (1) (wherein n is an integer of 2 to 5) based on the weight of the polyurethane elastic fibers ; a surface-treating agent for polyurethane elastic fibers, the agent being characterized by containing 0.10% to 25% by weight of the hydrocarbon compound; a fabric containing the elastic polyurethane fibers; and a sanitary material product.

Description

Area

The present invention relates to an elastic polyurethane fiber and a product containing the fiber and a surface treatment agent for elastic polyurethane fibers.

background

Elastic polyurethane fibers have high elongation and excellent elastic properties. However, since the polymer polyurethane is a flexible and sticky material, problems such as yarn breakage due to frictional resistance on guides or rollers during unwinding or running of a yarn from a package of elastic polyurethane fibers easily occur in the manufacturing process of products using elastic polyurethane fibers and production fluctuations. These problems are very significant, especially when a bobbin is used after long-term storage.

In order to solve these problems, there is known a method in which a treating agent composed of silicone oil is applied to the yarn. Since silicone oil is expensive, silicone oil is generally diluted using an inexpensive mineral oil to make a treating agent to be applied to the yarn. With a treating agent obtained by diluting silicone oil with a mineral oil, a cost reduction is possible, but the unwindability from a bobbin and the frictional properties of the elastic polyurethane fiber with the treating agent applied thereto are reduced, and thus sufficient unwindability and frictional property cannot be obtained will.

The following PTL 1 reports a method in which a specific amine and an organic acid are added to a surface treatment agent for polyurethane elastic fibers obtained by diluting silicone oil with a mineral oil. However, there is concern about the storage stability of a treating agent in the method in which a basic or acidic compound is added to mineral oil. There are also problems of increased labor in manufacture and an increase in cost.

The following PTL 2 reports on a method of applying a treating agent in which a hydrocarbon oil (mineral oil) having a specific viscosity range in a specific amount or more is used to a yarn as a means of improving unwindability by a surface treating agent for polyurethane elastic fibers , which is obtained by diluting silicone oil with a mineral oil. However, when a high-viscosity hydrocarbon oil is used, the viscosity of the treating agent itself becomes high and stably coating a yarn with the same becomes difficult. There are also problems of poor miscibility and storage stability due to the high viscosity of the treating agent itself.

The following PTL 3 reports a method for obtaining a polyurethane elastic fiber having good unwindability by dry-spinning a spinning dope into which a modifier composed of a silicone oil and a higher fatty acid metal salt is kneaded. Although there are clear technical improvements, the cohesion between individual yarns of a multifilament is weakened due to kneading of a modifier, and the phenomenon that individual yarns become detached from the multifilament (hereinafter referred to as single yarn untangling) is likely to occur. There is a problem of single yarn unraveling causing yarn breakage when the polyurethane elastic fibers are used in knitting, for example.

As described, a polyurethane elastic fiber in which unwindability is improved with a low silicone oil content and single-yarn untangling of a multifilament is low has yet to be obtained.

List of citations

patent literature

• [PTL 1] Japanese Patent Laid-Open (Kokai) No. 2007-270414
• [PTL 2] Japanese Patent Laid-Open (Kokai) No. 2017-110319
• [PTL 3] Japanese Patent Laid-Open (Kokai) No. 2009-287126

short description

Technical problem

In view of the above-described problems of the prior art, the object of the present invention is to provide a polyurethane elastic fiber having good unwindability and little single-yarn untangling of a multifilament even with a low silicone oil content, and a product containing the fiber and a surface treatment agent for polyurethane elastic fibers used for the production of the elastic polyurethane fiber is suitable to provide.

the solution of the problem

The inventors have conducted intensive studies and experiments in order to achieve the above object. As a result, the inventors unexpectedly found that the above object can be attained by incorporating a specific amount of a specific branched hydrocarbon compound in a polyurethane elastic fiber, thereby completing the present invention.

1. [1] Elastische Polyurethanfaser, die eine Kohlenwasserstoffverbindung, welche durch die folgende Formel (1) repräsentiert wird:
   
   wobei n eine ganze Zahl von 2 bis 5 ist, in einem Anteil von 10 ppm bis 10 000 ppm relativ zu dem Gewicht der elastischen Polyurethanfaser enthält.
2. [2] Elastische Polyurethanfaser gemäß [1], die die durch die Formel (1) dargestellte Kohlenwasserstoffverbindung, wobei n = 3 ist, in einem Anteil von 10 ppm bis 8000 ppm relativ zu dem Gewicht der elastischen Polyurethanfaser enthält.
3. [3] Elastische Polyurethanfaser gemäß [1] oder [2], die weiterhin eine andere Kohlenwasserstoffverbindung als die durch die Formel (1) repräsentierte Kohlenwasserstoffverbindung, wobei n eine ganze Zahl von 2 bis 5 ist, enthält.
4. [4] Elastische Polyurethanfaser gemäß einem der Punkte [1] bis [3], wobei die Fläche einer Komponente, die bei einer GC/MS-Messung eines Extrakts mit Hexan eine Retentionszeit benötigt, die länger als die Retentionszeit von Triacontan ist, weniger als 5% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
5. [5] Elastische Polyurethanfaser gemäß einem der Punkte [1] bis [4], wobei die Fläche einer Komponente, die bei einer GC/MS-Messung eines Extrakts mit Hexan eine Retentionszeit benötigt, die länger als die Retentionszeit von Octacosan ist, weniger als 5% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
6. [6] Elastische Polyurethanfaser gemäß einem der Punkte [1] bis [5], wobei die Fläche einer Komponente, die bei einer GC/MS-Messung eines Extrakts mit Hexan eine Retentionszeit benötigt, die kürzer als die Retentionszeit von Hexadecan ist, weniger als 5% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
7. [7] Elastische Polyurethanfaser gemäß einem der Punkte [1] bis [6], wobei die Fläche einer Komponente, die bei einer GC/MS-Messung eines Extrakts mit Hexan eine Retentionszeit benötigt, die kürzer als die Retentionszeit von Octadecan ist, weniger als 20% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
8. [8] Elastische Polyurethanfaser gemäß einem der Punkte [1] bis [7], wobei die Fläche einer Komponente, die bei einer GC/MS-Messung eines Extrakts mit Hexan eine Retentionszeit zwischen der von Octadecan und der von Octacosan benötigt, 80% oder mehr der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
9. [9] Textilstoff, der die elastische Polyurethanfaser gemäß einem der Punkte [1] bis [8] umfasst.
10. [10] Hygienematerialprodukt, das die elastische Polyurethanfaser gemäß einem der Punkte [1] bis [8] umfasst.
11. [11] Oberflächenbehandlungsmittel für elastische Polyurethanfasern, das eine Kohlenwasserstoffverbindung, welche durch die folgende Formel (1) repräsentiert wird:
    
    wobei n eine ganze Zahl von 2 bis 5 ist, in einem Anteil von 0,10 Gew.-% bis 25 Gew.-% enthält.
12. [12] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß [11], das die durch die Formel (1) dargestellte Kohlenwasserstoffverbindung, wobei n = 3 ist, in einem Anteil von 0,10 Gew.-% bis 20 Gew.-% enthält.
13. [13] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß [11] oder [12], das weiterhin eine andere Kohlenwasserstoffverbindung als die durch die Formel (1) repräsentierte Kohlenwasserstoffverbindung, wobei n eine ganze Zahl von 2 bis 5 ist, enthält.
14. [14] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß einem der Punkte [11] bis [13], wobei die Fläche einer Komponente, die eine Retentionszeit benötigt, welche länger als die Retentionszeit von Triacontan ist, bei einer GC/MS-Messung einer Lösung in Hexan weniger als 5% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
15. [15] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß einem der Punkte [11] bis [14], wobei die Fläche einer Komponente, die eine Retentionszeit benötigt, welche länger als die Retentionszeit von Octacosan ist, bei einer GC/MS-Messung einer Lösung in Hexan weniger als 5% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
16. [16] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß einem der Punkte [11] bis [15], wobei die Fläche einer Komponente, die eine Retentionszeit benötigt, welche kürzer als die Retentionszeit von Hexadecan ist, bei einer GC/MS-Messung einer Lösung in Hexan weniger als 5% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
17. [17] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß einem der Punkte [11] bis [16], wobei die Fläche einer Komponente, die eine Retentionszeit benötigt, welche kürzer als die Retentionszeit von Octadecan ist, bei einer GC/MS-Messung einer Lösung in Hexan weniger als 20% der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
18. [18] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß einem der Punkte [11] bis [17], wobei die Fläche einer Komponente, deren Retentionszeit zwischen der von Octadecan und der von Octacosan liegt, bei einer GC/MS-Messung einer Lösung in Hexan 80% oder mehr der Gesamtfläche eines von der Kohlenwasserstoffverbindung stammenden Peaks beträgt.
19. [19] Oberflächenbehandlungsmittel für elastische Polyurethanfasern gemäß einem der Punkte [11] bis [18], das weiterhin ein Silikonöl in einem Anteil von 20 Gew.-% bis 70 Gew.-% enthält.

The present invention is described as follows.

1. [1] Polyurethane elastic fiber containing a hydrocarbon compound represented by the following formula (1):
   
   where n is an integer of 2 to 5, in a proportion of 10 ppm to 10,000 ppm relative to the weight of the polyurethane elastic fiber.
2. [2] The polyurethane elastic fiber according to [1], which contains the hydrocarbon compound represented by the formula (1) where n=3 in a proportion of 10 ppm to 8000 ppm relative to the weight of the polyurethane elastic fiber.
3. [3] The polyurethane elastic fiber according to [1] or [2], which further contains a hydrocarbon compound other than the hydrocarbon compound represented by the formula (1) wherein n is an integer of 2-5.
4. [4] The polyurethane elastic fiber according to any one of [1] to [3], wherein the area of a component requiring a retention time longer than the retention time of triacontane in a GC/MS measurement of an extract with hexane is less than 5% of the total area of a peak originating from the hydrocarbon compound.
5. [5] The polyurethane elastic fiber according to any one of [1] to [4], wherein the area of a component requiring a retention time longer than the retention time of octacosane in a GC/MS measurement of an extract with hexane is less than 5% of the total area of a peak originating from the hydrocarbon compound.
6. [6] The polyurethane elastic fiber according to any one of [1] to [5], wherein the area of a component requiring a retention time shorter than the retention time of hexadecane in a GC/MS measurement of an extract with hexane is less than 5% of the total area of a peak originating from the hydrocarbon compound.
7. [7] The polyurethane elastic fiber according to any one of [1] to [6], wherein the area of a component requiring a retention time in a GC/MS measurement of an extract with hexane becomes shorter than the retention time of octadecane is less than 20% of the total area of a peak derived from the hydrocarbon compound.
8. [8] The polyurethane elastic fiber according to any one of [1] to [7], wherein the area of a component requiring a retention time between that of octadecane and that of octacosan in GC/MS measurement of an extract with hexane is 80% or is more of the total area of a peak originating from the hydrocarbon compound.
9. [9] A fabric comprising the polyurethane elastic fiber according to any one of [1] to [8].
10. [10] A sanitary material product comprising the polyurethane elastic fiber according to any one of [1] to [8].
11. [11] A surface-treating agent for polyurethane elastic fibers, which contains a hydrocarbon compound represented by the following formula (1):
    
    where n is an integer from 2 to 5, in an amount of from 0.10% to 25% by weight.
12. [12] The surface-treating agent for polyurethane elastic fiber according to [11], which contains the hydrocarbon compound represented by the formula (1) where n=3 in a proportion of 0.10% by weight to 20% by weight.
13. [13] The surface-treating agent for polyurethane elastic fiber according to [11] or [12], which further contains a hydrocarbon compound other than the hydrocarbon compound represented by the formula (1) wherein n is an integer of 2-5.
14. [14] The surface treatment agent for polyurethane elastic fibers according to any one of [11] to [13], wherein the area of a component requiring a retention time longer than the retention time of triacontane in a GC/MS measurement of a solution in hexane is less than 5% of the total area of a peak originating from the hydrocarbon compound.
15. [15] The surface treatment agent for polyurethane elastic fibers according to any one of [11] to [14], wherein the area of a component requiring a retention time longer than the retention time of octacosane in a GC/MS measurement of a solution in hexane is less than 5% of the total area of a peak originating from the hydrocarbon compound.
16. [16] The surface treatment agent for polyurethane elastic fiber according to any one of [11] to [15], wherein the area of a component requiring a retention time shorter than the retention time of hexadecane in a GC/MS measurement of a solution in hexane is less than 5% of the total area of a peak originating from the hydrocarbon compound.
17. [17] The surface treatment agent for polyurethane elastic fibers according to any one of [11] to [16], wherein the area of a component requiring a retention time shorter than the retention time of octadecane in a GC/MS measurement of a solution in hexane is less than 20% of the total area of a peak originating from the hydrocarbon compound.
18. [18] The surface-treating agent for polyurethane elastic fibers according to any one of [11] to [17], wherein the area of a component whose retention time is between that of octadecane and that of octacosane in a GC/MS measurement of a solution in hexane is 80% or more of the total area of a peak derived from the hydrocarbon compound.
19. [19] The surface-treating agent for polyurethane elastic fibers according to any one of [11] to [18], which further contains a silicone oil in a proportion of 20% by weight to 70% by weight.

Advantageous Effects of the Invention

The polyurethane elastic fiber containing a specific amount of a specific branched hydrocarbon compound according to the present invention is a polyurethane elastic fiber having good unwindability even with a low silicone oil content and little single-yarn untangling of a multifilament. Therefore, the polyurethane elastic fiber according to the present invention can be suitably used for textile fabrics, sanitary material products, and so on.

character list

• 1 Fig. 12 is a graph showing a calculation example of total peak area in GS/MS measurement of hydrocarbon compounds.
• 2 Fig. 12 is a graph showing a calculation example of the area of a component having a shorter retention time than octadecane in the total peak area of hydrocarbon compounds.
• 3 Fig. 12 shows a calculation example of the area of a component having a retention time between that of octadecane and that of octacosane measured by GS/MS of an extract in hexane in the total peak area of hydrocarbon compounds.
• 4 Fig. 14 is an explanatory drawing showing a state of single yarn unraveling.

Description of Embodiments

Embodiments for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the present invention.

wobei n eine ganze Zahl von 2 bis 5 ist, in einem Anteil von 10 ppm bis 10 000 ppm relativ zu dem Gewicht der elastischen Polyurethanfaser.In one embodiment of the present invention, a polyurethane elastic fiber contains a hydrocarbon compound (hereinafter referred to as “specific compound”) represented by the following formula (1):

where n is an integer of 2 to 5, in a proportion of 10 ppm to 10,000 ppm relative to the weight of the polyurethane elastic fiber.

wobei n eine ganze Zahl von 2 bis 5 ist, in einem Anteil von 0,10 Gew.-% bis 25 Gew.-%.In another embodiment of the present invention, a surface-treating agent for polyurethane elastic fibers contains a hydrocarbon compound represented by the following formula (1):

wherein n is an integer from 2 to 5, in an amount from 0.10% to 25% by weight.

In the polyurethane elastic fiber of the present embodiment, the reason why the unwindability is improved by adjusting the content of the specific compound to the specific range is unclear. However, it is considered that the specific compound can thereby be localized more easily on the surface of the polyurethane elastic fiber and the unwindability can be improved due to the high fluidity of the specific compound on the surface.

If the content of the specific compound is less than 10 ppm, it is difficult to obtain a sufficient effect of improving unwindability. From the aspect of achieving higher unwindability, the content is preferably 30 ppm or more. When the content is more than 10,000 ppm, single yarn untangling is more likely to occur and unwindability tends to deteriorate with time. The upper limit of the content of the specific compound is preferably 9000 ppm or less, and more preferably 5000 ppm or less.

As the state of the specific compound contained in the polyurethane elastic fiber, the specific compound may be contained within the polyurethane elastic fiber, it may be deposited on the surface thereof. As a method for incorporating the specific compound into the polyurethane elastic fiber, one of the following methods can be used: The specific compound or a mixture consisting of the specific compound and a hydrocarbon compound other than the specific compound is directly kneaded into the spinning liquid, or the specific compound or a mixture consisting of the specific compound and a hydrocarbon compound other than the specific compound is added to the surface-treating agent and the yarn surface is coated therewith.

The content of the specific compound in the surface-treating agent is preferably 0.10% to 25% by weight. From the viewpoint of suppressing single yarn unraveling, the content of the hydrocarbon mixture is preferably 20% by weight or less, and more preferably 17% by weight or less.

The compound is preferably a hydrocarbon compound represented by the formula (1) where n = 2 to 3, and more preferably a compound where n = 3, i.e., phytan, from the viewpoint of suppressing single yarn unraveling and smoothness.

The polyurethane elastic fiber of one embodiment preferably contains the hydrocarbon compound represented by the formula (1) where n=3 in a proportion of 10 ppm to 8000 ppm relative to the weight of the polyurethane elastic fiber.

The surface-treating agent for polyurethane elastic fiber, which is another embodiment, preferably contains the hydrocarbon compound represented by the formula (1) where n=3 in a proportion of 10% by weight to 20% by weight .

The polyurethane elastic fiber of the present embodiment is a fiber obtained by spinning a polyurethane polymer. As a method for producing the polyurethane polymer, a well-known polyurethane reaction method can be used. A polymer polyol, for example, polyalkylene ether glycol, and a diisocyanate are reacted under excess diisocyanate conditions to synthesize a urethane prepolymer having a terminal isocyanate group, and then the urethane prepolymer is subjected to a chain extension reaction with an active hydrogen-containing compound such as a bifunctional amine , to obtain a polyurethane polymer. If necessary, a monofunctional active hydrogen atom can be mixed with the bifunctional amine and used as an end capping agent. From the viewpoint of obtaining a uniform polymer with less gelation, the molar ratio of the diisocyanate to the polymer polyol is preferably 1.70 or less, more preferably 1.65 or less, and most preferably 1.60 or less.

Examples of the polymer polyol are various diols composed of substantially linear homo- or copolymers such as polyester diols, polyether diols, polyesteramide diols, polyacrylic diols, polythioester diols, polythioether diols, polycarbonate diols, mixtures thereof and copolymers thereof; and preferably polyalkylene ether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyoxypentamethylene glycol, copolymerized polyether glycol consisting of a tetramethylene group and a 2,2-dimethylpropylene group, copolymerized polyether glycol consisting of a tetramethylene group and a 3-methyltetramethylene group, and mixtures thereof. Among these polymer polyols are polytetramethylene ether glycol and copolymerized polyether glycol consisting of a tetramethylene group and a 2,2-dimethylpropylene group, particularly preferred from the viewpoint of superior elastic function.

In order to obtain superior elastic properties, the number-average molecular weight calculated from the hydroxy value of the polymer polyol is preferably 500 or more, more preferably 1,000 or more, and most preferably 1,500 or more. The number-average molecular weight is preferably 5,000 or less from the aspect of obtaining a yarn having high heat resistance. In order to obtain more superior heat resistance, the number-average molecular weight is preferably 3,000 or less, and more preferably 2,500 or less.

Examples of the diisocyanate are aliphatic, alicyclic and aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, m- or p-xylylene diisocyanate, α,α,α ',α'-Tetramethylxylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1,3- or 1,4-cyclohexylene diisocyanate, 3-(α-isocyanatoethyl)phenyl isocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, mixtures thereof and copolymers thereof. Of these, 4,4'-diphenylmethane diisocyanate is particularly preferred.

Examples of the active hydrogen-containing compound, i.e., the chain extender having a polyfunctional active hydrogen atom, are low-molecular diols such as hydrazine, polyhydrazine, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol and phenyldiethanolamine; or bifunctional amines such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 2-methyl-1,5-pentanediamine, triethylenediamine, m-xylenediamine, piperazine, o-, m- or p-phenylenediamine, 1,3 -diaminocyclohexane, 1,4-diaminocyclohexane, 1,6-hexamethylenediamine and N,N'-(methylenedi-4,1-phenylene)bis[2-(ethylamino)urea].

The above compounds can be used alone or in combination. Bifunctional amines are preferable to low molecular weight diols. Ethylenediamine mixtures containing 5 to 40 mol% of at least one selected from the group consisting of ethylenediamine, 1,2-propylenediamine, 1,3-diaminocyclohexane and 2-methyl-1,5-pentadiamine are preferable . Ethylenediamine alone is particularly preferred.

Examples of the endcapping agent having a monofunctional active hydrogen atom are monoalcohols such as methanol, ethanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol and 3-methyl-1-butanol; monoalkylamines such as isopropylamine, n-butylamine, t-butylamine and 2-ethylhexylamine; or dialkylamines such as diethylamine, dimethylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, di-2-ethylhexylamine and diisopropylamine. These can be used alone or in combination. Monoalkylamines and dialkylamines, which are monofunctional amines, are preferred over monoalcohols.

Regarding the process of the polyurethaneization reaction, amide-based polar solvents such as dimethylformamide, dimethylsulfoxide and dimethylacetamide can be used during the urethane prepolymer synthesis and the reaction between the urethane polymer and the active hydrogen-containing compound. Dimethylacetamide is preferable.

The polyurethane polymer composition may contain various stabilizers, pigments, etc., for example, antioxidants based on hindered phenols, benzotriazoles, benzophenones, phosphorus, or various hindered amines; metallic soaps such as magnesium stearate; inorganic substances such as titanium oxide, iron oxide, zinc oxide, cerium oxide or magnesium oxide; Carbon black, various pigments, silver, zinc, antibacterial agents containing these compounds; Deodorants, antistatic agents, nitrogen oxide scavengers, thermal oxidation stabilizers or light stabilizers, which may also be contained in combination.

An ester compound or a phosphoric acid ester compound composed of a condensate of an alcohol and a carboxylic acid or phosphoric acid may be contained in order to suppress single yarn unraveling. Preferable examples of the ester compound and the phosphoric acid ester compound are trimethyl citrate, bis(2-ethylhexyl) adipate, methyl benzoate, benzyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, trimethyl trimellitate, dibutyl phthalate, tricresyl phosphate and diphenyl-2-ethylhexyl phosphate, or two or more of each of the compounds can be used in combination are used.

The polyurethane polymer thus obtained can be formed into a fiber by a well-known dry spinning, melt spinning or wet spinning method to obtain an elastic polyurethane fiber. Polyurethane polymers polymerized using various raw materials can be blended in a spun state to be spun. The spinning process is preferably dry spinning of a polyurethane dope obtained by dissolving the polyurethane polymer in an amide-based polar solvent. Compared to melt spinning and wet spinning, dry spinning can form the strongest physical crosslinks due to hydrogen bonding between hard segments.

The polyurethane elastic fiber of the present embodiment can be used by containing a surface treatment agent to reduce resistance during unwinding and friction during use. The surface-treating agent may be pre-kneaded into the spinning liquid, or it may be applied to the fiber by a well-known method such as roller oils or guide oils before it is wound on a paper tube during spinning. Alternatively, the surface-treating agent may be applied after winding, without applying the surface-treating agent, at the time of winding to make another package. When the surface-treating agent is incorporated into the elastic polyurethane fiber, the content of the surface-treating agent relative to the weight of the elastic polyurethane polymer is preferably 1.0% by weight to 4.0% by weight from the viewpoint of cost and quality. The surface-treating agent preferably exhibits the desired effect in the entire range of the above percentages.

The composition of the surface treatment agent is not particularly limited. Well-known surface-treating agents, for example, silicone oils such as polydimethylsiloxane, polyester-modified silicone, polyether-modified silicone, and amino-modified silicone; hydrocarbon compounds to be described later; fine mineral particles such as silica, colloidal alumina and talc; powders of higher fatty acid metal salts such as magnesium stearate and calcium stearate; higher aliphatic carboxylic acids, higher aliphatic alcohols, and solid waxes at room temperature such as paraffin and polyethylene can be used in combination. The silicone oil is preferably polydimethylsiloxane. The kinematic viscosity at 25°C is preferably 15 mm ² /s or less from the viewpoint of reducing friction. The silicone oil content relative to the polyurethane elastic fiber is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, and particularly preferably 1.0% by weight or less, from the viewpoint of suppressing single yarn unraveling .

The hydrocarbon compound contained in the polyurethane elastic fiber of the present embodiment is a compound composed only of carbon and hydrogen. The polyurethane elastic fiber of the present embodiment may contain a hydrocarbon compound other than the specific compound.

The elastic polyurethane fiber of the present embodiment is based on the total area of the peaks derived from the hydrocarbon compound, which is determined by the sum of the peak areas measured by a method described later by GC/MS of the specific compound of a hexane-extracted solution and the peak area of the specific compound various hydrocarbon compound is represented. The area of a component having a longer retention time than that of triacontane measured under the same conditions is preferably less than 5%. If the area of the component with a retention time longer than the retention time of triacontane is less than 5% of the total area of the peaks originating from the hydrocarbon compound, the fluidity of the specific compound is of formula (1), where n = 2 to 5 is good. It is considered that the specific compound of the formula (1) wherein n=2 to 5 can thereby be localized more easily on the surface of the polyurethane elastic fiber and the unwindability can be further increased. The area of the component having a longer retention time than triacontane is most preferably less than 3%.

The elastic polyurethane fiber of the present embodiment is based on the total area of the peaks derived from the hydrocarbon compound, which is determined by the sum of the peak areas measured by a method described later by GC/MS of the specific compound of a hexane-extracted solution and the peak area of the specific compound various hydrocarbon compound is represented. The area of a component having a longer retention time than that of octacosan measured under the same conditions is preferably less than 5%. If the area of the component having a retention time longer than the retention time of octacosane is less than 5% of the total area of the peaks derived from the hydrocarbon compound, the flowability of the specific compound is of formula (1) where n = 2 to 5 is good. It is considered that the specific compound of the formula (1) wherein n=2 to 5 can thereby be localized more easily on the surface of the polyurethane elastic fiber and the unwindability can be further increased. The area of the component having a longer retention time than octacosane is more preferably less than 3%.

The elastic polyurethane fiber of the present embodiment is based on the total area of the peaks derived from the hydrocarbon compound, which is determined by the sum of the peak areas measured by a method described later by GC/MS of the specific compound of a hexane-extracted solution and the peak area of the specific compound various hydrocarbon compound is represented. The area of a component having a shorter retention time than that of hexadecane measured under the same conditions is preferably less than 5%. When the area of the component having a retention time shorter than the retention time of hexadecane is less than 5% of the total area of the peaks derived from the hydrocarbon compound, the flowability of the hydrocarbon compound is poor. Thus, it is considered that single yarn unraveling and yarn breakage are less likely to occur in the polyurethane elastic fiber. The area of the component having a shorter retention time than hexadecane is more preferably less than 3%.

The elastic polyurethane fiber of the present embodiment is based on the total area of the peaks derived from the hydrocarbon compound, which is determined by the sum of the peak areas measured by a method described later by GC/MS of the specific compound of a hexane-extracted solution and the peak area of the specific compound various hydrocarbon compound is represented. The area of a component having a shorter retention time than that of octadecane measured under the same conditions is preferably less than 20%. When the area of the component having a retention time shorter than the retention time of octadecane is less than 20% of the total area of the peaks derived from the hydrocarbon compound, the flowability of the hydrocarbon compound is poor. Thus, it is considered that single yarn unraveling and yarn breakage are less likely to occur in the polyurethane elastic fiber. The area of the component having a shorter retention time than octadecane is more preferably less than 15%.

The elastic polyurethane fiber of the present embodiment is based on the total area of the peaks derived from the hydrocarbon compound, which is determined by the sum of the peak areas measured by a method described later by GC/MS of the specific compound of a hexane-extracted solution and the peak area of the specific compound various hydrocarbon compound is represented. The area of a component having a retention time between those of octadecane and octacosane measured under the same conditions is preferably 80% or more. When the area of the component having a retention time between those of octadecane and octacosane is 80% or more of the total area of the peaks derived from the hydrocarbon compound, the fluidity of the hydrocarbon compound is poor. Thus, the effect of improving unwindability can be further increased without increasing the occurrence frequency of single yarn untangling. The area of the component having a retention time between those of octadecane and octacosane is preferably 90% or more, and more preferably 95% or more.

The area of each component measured by GC/MS is the same for the surface treating agent which is another embodiment of the present invention.

The hydrocarbon compound other than the specific compound is not particularly limited as long as the compound consists only of carbon and hydrogen. Examples thereof are light isoparaffin, synthetic squalane, vegetable squalane, squalane, ceresin, paraffin, petroleum jelly, machine oil, spindle oil, naphthenic oil, liquid paraffin, liquid isoparaffin, poly(alpha-olefin), polyisobutylene and polybutene and these may be used alone or in a combination of two or more can be used. The specific compound can be preliminarily included in the hydrocarbon compounds. As a preferred example where a synergistic effect occurs with the specific compound of formula (1) where n = 2 to 5, the hydrocarbon compound is preferably liquid paraffin and more preferably liquid paraffin having an average molecular weight of less than 450. Additionally the hydrocarbon compound preferably consists only of saturated carbons hydrogens. The paraffin/naphthene ratio is particularly preferably in the range from 50/50 to 80/20. Most preferably, and when the liquid paraffin is prepared by removing impurities by sulfuric acid washing instead of a hydrogenation process, a hydrocarbon compound having the properties described above can be easily obtained. From the aspect of suppressing single yarn unraveling, the total content of the specific compound and the hydrocarbon compound other than the specific compound is preferably 2.0% by weight or less, more preferably 1.5% by weight or less relative to the yarn.

High-quality fabrics without unevenness can be obtained by combining the polyurethane elastic fibers of the present embodiment with natural fibers such as cotton, silk or wool, polyamide fibers such as nylon 6 or nylon 66, polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate or polytetramethylene terephthalate, cationically dyeable polyester fibers, copper floss , viscose and acetate floss, or by coating, entangling or twisting them to form processed yarns using these fibers and thereafter weaving the processed yarns. Textile fabrics using polyurethane elastic fibers, in particular, have a large production volume and are supplied as bare yarns, and thus are suitable for warp knitting, which is greatly influenced by the quality of the yarn. The warp knit fabrics include a bodice tulle, semi-atlas, Russell tapes, two-way tricot, etc. By using the polyurethane elastic fiber of the present embodiment, a high-quality fabric having few stripes in the warp direction can be obtained.

The fabric using the polyurethane elastic fiber of the present embodiment can be used in applications such as swimwear, belts, brassieres, stockings, pantyhose, waistbands, bodies, leggings, stretch sportswear, stretch streetwear, medical wear, and stretch lining fabric.

The polyurethane elastic fiber of the present embodiment can be suitably used in sanitary material products such as sanitary ware and diaper paper, and has good smoothness and little variation in frictional property, so that high productivity and product stability can be obtained. Due to the effect of the specific compound of the formula (1) where n = 2 to 5 and improvement of unwindability, the amount of silicone oil, which is an inhibitor of stickiness in various bonding methods, can be reduced. Thus, the polyurethane elastic fiber is also suitable for various bonding methods in sanitary material manufacturing equipment, such as hot-melt adhesives, hot-pressing and ultrasonic bonding. A sanitary material product having high extensibility and little occurrence of a phenomenon called slip-in, which is one of product defects causing problems such as leakage of urine in the elastic polyurethane fiber, can be obtained.

Another embodiment of the present invention, as already described, is a surface-treating agent for polyurethane elastic fibers, which contains the specific compound represented by the formula (1) wherein n is an integer of 2 to 5 in a proportion of 0.10% by weight. % to 0.25% by weight. The reason for improving the unwindability of the polyurethane elastic fiber by adjusting the content of the specific compound of the formula (1) where n is an integer of 2 to 5 to the specific range above is unclear. However, it is considered that the specific compound can thereby be more easily localized on the surface of the polyurethane elastic fiber and the unwindability can be improved due to the high content of the specific compound on the surface. From the aspect of achieving higher unwindability, the content of the specific compound is preferably 0.10% to 20% by weight, and more preferably 0.10% to 17% by weight.

The hydrocarbon compound contained in the surface-treating agent for fibers of the present embodiment is a compound composed only of carbon and hydrogen. The surface-treating agent for fibers of the present embodiment may also contain a hydrocarbon compound other than the specific compound. Examples of hydrocarbon compounds other than the specific compound are light isoparaffin, synthetic squalene, vegetable squalene, squalene, ceresin, paraffin, vaseline, machine oil, spindle oil, naphthenic oil, liquid paraffin, liquid isoparaffin, poly(alpha-olefin), polyisobutylene and polybutene, and these can be used alone or in a combination of two or more. The specific compound may or may not be tentatively included in the hydrocarbon compounds. As a preferred example where a synergistic effect occurs with the specific compound of formula (1) where n = 2 to 5, the hydrocarbon compound is preferably liquid paraffin and more preferably liquid paraffin having an average molecular weight of less than 450. Additionally consists of the hydrocarbon compound tion preferably only from saturated hydrocarbons. The paraffin/naphthene ratio is particularly preferably in the range from 50/50 to 80/20. Most preferably, the liquid paraffin is prepared by removing impurities by sulfuric acid washing rather than a hydrogenation process.

The surface-treating agent for fibers of the present embodiment preferably further contains a silicone oil in a proportion of 20% by weight to 70% by weight. By containing the specific compound of the formula (1) where n = 2 to 5 and further adjusting the silicone oil content within the above range, the surface-treating agent, although having a silicone oil content of 70% by weight or less, have an unwinding property equal to or greater than that of a fiber surface treatment agent having a silicone oil content of more than 70% by weight. Since the silicone oil content is small, the occurrence of single yarn unraveling can be suppressed. Since the amount of use of the expensive silicone oil can be reduced, a cost reduction effect can be expected in comparison with a surface treatment agent for fibers in which the silicone oil content is more than 70% by weight. If the silicone oil content is less than 20% by weight, sufficient unwinding property cannot be obtained. When the silicone oil content is more than 70% by weight, single yarn unraveling is likely to occur and cost becomes a problem. The silicone oil can be polydimethylsiloxane. From the viewpoint of reducing friction, the kinematic viscosity at 25°C is preferably 15 mm ² /s or less.

As the surface-treating agent for fibers of the present embodiment, well-known surface-treating agents such as the above-described silicone oil, the specific compound, besides hydrocarbon compounds other than the specific compound, polyester-modified silicone, polyether-modified silicone, and amino-modified silicone; fine mineral particles, e.g. silica, colloidal alumina and talc, powders of metal salts of higher fatty acids, e.g. magnesium stearate and calcium stearate, higher aliphatic carboxylic acids, higher aliphatic alcohols, typically isostearyl alcohol, and waxes solid at room temperature such as paraffin and polyethylene can be used in combination .

An ester compound or a phosphoric acid ester compound composed of a condensate of an alcohol and a carboxylic acid or phosphoric acid may be contained in the surface-treating agent for fibers in order to suppress single-yarn unraveling. Preferable examples of the ester compound or phosphoric acid ester compound are trimethyl citrate, bis(2-ethylhexyl) adipate, methyl benzoate, benzyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, trimethyl trimellitate, dibutyl phthalate, tricresyl phosphate and diphenyl 2-ethylhexyl phosphate. Two or more of the above compounds can also be used in combination.

The surface-treating agent of the present embodiment can be applied by a well-known method such as roller oiling, guide oiling or spraying oiling.

examples

The present invention is specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples. The measurement methods and evaluation methods used in the following examples and comparative examples are as follows.

(1) Method of identifying/quantifying the specific compound of formula (1) wherein n=2-5

Elastic polyurethane fibers weighed accurately to the nearest 2 g were immersed in 50 g of hexane. After 10 minutes of extraction by application of ultrasonic waves, hexane was distilled off with an evaporator. Subsequently, the polyurethane elastic fibers after the extraction were then again immersed in 50 g of hexane in the same container. After 10 minutes of extraction by application of ultrasonic waves, the elastic polyurethane fibers were removed and hexane was distilled off with an evaporator to obtain a hexane extract. A sample from the extract diluted with hexane to a concentration of 1600 ppm served as an extract sample for GC/MS measurement. Note that when the amount of the extract is small, the amount of the elastic polyurethane fibers can be increased accordingly to carry out the same process.

• Gerät: Agilent 6890 GC, MSD-5973
• Säule: DB-5MS (30 m, 0,25 µm, ID 0,25 mm)
• Ofen: 40 °C (2 Minuten) - 8 °C/Minute - 320 °C (5 Minuten)
• INJ/DET: 325 °C/325 °C
• Gas: Helium
• Strömungsgeschwindigkeit: 1,0 ml/Minute
• Injektionsvolumen: 1,0 µl
• Injektionsverfahren: 10:1 aufgeteilt

The detailed conditions of GC/MS were as described below.

• Instrument: Agilent 6890 GC, MSD-5973
• Column: DB-5MS (30 m, 0.25 µm, ID 0.25 mm)
• Oven: 40°C (2 minutes) - 8°C/minute - 320°C (5 minutes)
• INJ/DET: 325°C/325°C
• Gas: helium
• Flow rate: 1.0 ml/minute
• Injection volume: 1.0 µl
• Injection method: 10:1 split

(2) Calculation of each area of hydrocarbon compounds in GC/MS measurement

The extract from the elastic polyurethane fiber was measured by GC/MS in the same manner as in (1) above. It was calculated in percentages that the area of the component with a longer retention time than triacontane was the area of the component with C30 or more; the area of the component having a longer retention time than octacosane was the area of the component having C28 or more; the area of the component having a shorter retention time than hexadecane was the area of the component having C16 or less; the area of the component having a shorter retention time than octadecane was the area of the component having C18 or less; the area of the component with a retention time between the retention times of hexadecane and triacontane was the area of the component with C16 to C30; the area of the component with a retention time between the retention times of octadecane and triacontane was the area of the component with C18 to C30; and the area of the component having a retention time between the retention times of octadecane and octacosane was the area of the C18 to C28 component relative to the total peak area derived from the hydrocarbon compound. Components not derived from the hydrocarbon compound were removed in the calculation of each area by GC/MS. Peaks of hydrocarbon compounds can be detected broadly in the case of a mixture. In this case, the point where the peak starts to rise was set as the start point, the point where the detected value of the peak starts to disappear to a negligible level was set as the end point, and the area was calculated from the baseline showing the connects the start point and the end point with a straight line.

(3) Calculation of each area of a hydrocarbon compound in surface treatment agents for fibers in GC/MS measurement

The surfactant was diluted to 1600 ppm with hexane. The value of each component in the surface-treating agent was calculated in the same manner as in (1) and (2) above. When the raw material was obtained before mixing the surface treatment agent, the hydrocarbon compound itself was diluted to 1600 ppm with hexane for ease of measurement. The measurement was carried out in the same manner as in (1) and (2) above.

(4) unwindability

• 7: Weniger als 10 g
• 6: 10 g bis weniger als 13 g
• 5: 13 g bis weniger als 15 g
• 4: 15 g bis weniger als 25 g
• 3: 25 g bis weniger als 30 g
• 2: 30 g bis weniger als 35 g
• 1: 35 g oder mehr oder Reißen des Garns

After the polyurethane elastic fiber was wound on a paper tube so that the winding width was 60 mm and the total weight was 3 kg, the polyurethane elastic fiber was left to stand for 2 days in an environment of 20°C and 60%RH. Thereafter, the yarn was peeled off the paper tube to within 2 cm to prepare a measurement sample; the yarn was passively unwound at 15 m/min toward the end face of the test sample; the tension at that time was measured for 5 minutes; the mean value was taken as the unwind tension; and determination was made in 7 stages according to the following evaluation criteria. It is expected that the lower the unwinding tension, the smoother the polyurethane elastic fiber is unwound and the less likely the yarn is to break during unwinding. “Passive unwinding” refers to a vertical unwinding process.

• 7: Less than 10g
• 6: 10g to less than 13g
• 5: 13g to less than 15g
• 4: 15g to less than 25g
• 3: 25g to less than 30g
• 2: 30g to less than 35g
• 1: 35g or more or yarn breakage

(5) Frequency of occurrence of single yarn untangling (%)

• 7: Häufigkeit des Auftretens 0% bis weniger als 3%
• 6: Häufigkeit des Auftretens 3% bis weniger als 5%
• 5: Häufigkeit des Auftretens weniger als 5%
• 4: Häufigkeit des Auftretens 5% bis weniger als 10%
• 3: Häufigkeit des Auftretens 10% bis weniger als 15%
• 2: Häufigkeit des Auftretens 15% bis weniger als 20%
• 1: Häufigkeit des Auftretens 20% oder mehr

Ten multifilaments with a length of 40 mm lined up in parallel were set in a demapper tester, stretched in the yarn length direction until the length reached 240 mm and relaxed back to the original 40 mm. The stretching process was repeated 5000 times at a frequency of 200 rpm. In a state where a multifilament of 40 mm in length was laid flat as shown in 4 shown, it was determined that single yarn untangling took place when a single yarn unraveling occurred by a distance of 0.5 mm or more at maximum from a part of the multifilament where most of the single yarns converged, or when a single yarn broke. The measurement was carried out 5 times on a quantity of 10 yarns from the same sample; the number of unraveled yarns out of a total of 50 yarns was determined; the frequency of occurrence was calculated; and the evaluation was made in the following 7 stages. It is expected that the lower the frequency of occurrence of single yarn unraveling when the polyurethane elastic fiber is used, the less likely it is to break a yarn due to single yarn unraveling.

• 7: frequency of occurrence 0% to less than 3%
• 6: frequency of occurrence 3% to less than 5%
• 5: frequency of occurrence less than 5%
• 4: frequency of occurrence 5% to less than 10%
• 3: frequency of occurrence 10% to less than 15%
• 2: frequency of occurrence 15% to less than 20%
• 1: Frequency of occurrence 20% or more

[Examples 1 to 12 and Comparative Examples 1 to 7 by kneading the specific compound of the formula (1) wherein n = 2 to 5 into spinning liquid]

[Example 1]

2000 g of polytetramethylene ether glycol having a number average molecular weight of 2000 and 400 g of 4,4'-diphenylmethane diisocyanate were reacted for 3 hours with stirring at 60°C in a dry nitrogen atmosphere to obtain a polyurethane prepolymer and finally capped with isocyanate. After cooling to room temperature, dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution. An amine solution in which ethylenediamine and diethylamine had been dissolved in dry dimethylacetamide was separately prepared and added into the polyurethane prepolymer solution so that the ratio of isocyanate groups in the urethane prepolymer to amino groups in the amine solution was 1:1.03, and reacted with cooling to 10°C. A polyurethane solution having a polyurethane solid content concentration of 30% by mass and a viscosity of 450 Pa·s (30°C) was obtained.

1 wt% 4,4'-butylidenebis(3-methyl-6-t-butylphenol) and 0.5 wt% 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, based on polyurethane solids content, 0.5% by weight polydimethylsiloxane having a kinematic viscosity at 25°C of 10 mm ² /s, relative to yarn weight, and 50 ppm phytane (n=3), relative to yarn weight, as a specific compound of formula (1), where n = 2 to 5, were weighed, dissolved in dimethylacetamide and then mixed with a polyurethane solution to give a uniform solution, which was then defoamed at room temperature under reduced pressure, whereby a spinning liquid was obtained.

The spinning dope was dry-spun at a winding speed of 500 m/minute and a hot air temperature of 300°C using a 48-hole spinneret, and the fibers were bundled with an effect twister using compressed air. Then the elasti s polyurethane fibers wound on paper tubes made of paper, giving a wound package of elastic polyurethane fibers of 470 dt / 48 filaments.

[Examples 2 to 12]

Except that a hydrocarbon mixture composed of the specific compound and a hydrocarbon compound other than the specific compound was respectively contained so as to obtain the content of the specific compound and the area ratios of the hydrocarbon compound shown in Table 1 below each of the polyurethane elastic fibers was obtained in the same manner as in Example 1.

[Comparative Example 1]

The polyurethane elastic fiber was obtained in the same manner as in Example 1 except that phytan was not contained.

[Comparative Example 2]

The polyurethane elastic fiber was obtained in the same manner as in Comparative Example 1 except that the polydimethylsiloxane content was changed to 1.0% by weight.

[Comparative Examples 3 to 6]

Except that a hydrocarbon mixture composed of the specific compound and a hydrocarbon compound other than the specific compound and a hydrocarbon compound other than the specific compound were respectively contained so that the content of the specific compound and the area ratios of the hydrocarbon compound are shown in the following Table 1, each of the polyurethane elastic fibers was obtained in the same manner as in Example 1.

[Comparative Example 7]

Except that the polydimethylsiloxane content was adjusted as shown in Table 1, the polyurethane elastic fiber was obtained in the same manner as in Comparative Example 4. Table 1 Polydimethylsiloxane content (wt%) Content of compound of formula 1 in fiber (ppm) Each area of hydrocarbon compound in GC/MS measurement on hexane extract from fiber (%) valuation n Total for n = 2 to 5 C16 or less C18 or less C28 or more C30 or more C16-30 C18-30 C18-28 settleability Frequency of occurrence of single yarn untangling (%) 1 2 3 4 5 6 or more Ex 1 0.5 0 0 50 0 0 0 50 0 0 0 0 100 100 100 7 7 Ex 2 0.5 0 10 30 10 0 0 50 0 0 1 0 100 100 99 7 7 Ex 3 0.5 0 5 15 5 0 0 25 2 9 1 0 98 91 90 6 7 Ex 4 0.5 0 100 300 100 0 0 500 2 9 1 0 98 91 90 7 7 Ex 5 0.5 0 1800 5400 1800 0 0 9000 2 9 1 0 98 91 90 7 5 Ex 6 0.5 0 0 100 300 100 0 500 0 0 6 2 98 98 94 6 7 Ex 7 0.5 0 0 0 100 400 0 500 0 0 7 4 96 96 93 5 6 Ex 8 0.5 0 0 0 0 500 0 500 0 0 10 7 93 93 90 4 6 Ex 9 0.5 100 300 100 0 0 0 400 7 11 0 0 93 89 89 7 5 Ex 10 0.5 300 200 0 0 0 0 200 9 28 0 0 91 72 72 7 4 Ex 11 0.5 100 100 100 100 100 0 400 13 27 9 6 81 67 64 4 4 Ex 12 0.0 0 1800 5400 1800 0 0 9000 2 9 1 0 98 91 90 5 6 Comp. Ex. 1 0.5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 3 Comp. Ex. 2 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4 3 Comp. Ex. 3 0.5 0 0 0 0 0 0 0 0 0 0 0 100 100 100 4 2 Comp. Ex. 4 0.5 0 2900 8700 2900 0 0 14500 0 0 1 0 98 91 90 4 2 Comp. Ex. 5 0.5 100 0 0 0 0 0 0 100 100 0 0 0 0 0 3 2 Comp. Ex. 6 0.5 0 0 0 0 0 100 0 0 0 100 100 0 0 0 2 3 Comp. Ex. 7 0.0 0 2900 8700 2900 0 0 14500 0 0 1 0 98 91 90 2 3

[Examples 13 to 20 and Comparative Examples 8 to 12 which are production processes for surface-treating agents for polyurethane elastic fibers]

Polydimethylsiloxane and the specific compound, a mixture of hydrocarbons consisting of the specific compound and a hydrocarbon compound other than the specific compound, or a hydrocarbon compound other than the specific compound were appropriately mixed so that the content of the specific compound and the area ratios of the Hydrocarbon compound shown in the following Table 2 were obtained and mixed for 30 minutes at room temperature by means of stirring paddles to obtain surface-treating agents for polyurethane elastic fibers. Table 2 Polydimethylsiloxane content (wt%) Content of compound of formula 1 in fiber surface treatment agent (% by weight) Each area of hydrocarbon compound contained in fiber treatment agent (%) raw material costs n Total for n = 2 to 5 C16 or less C18 or less C28 or more C30 or more C16-30 C18-30 C18-28 1 2 3 4 5 6 or more Ex 13 99 0 0 1 0 0 0 1.0 0 0 0 0 100 100 100 H Ex 14 60 0 0 1 0 0 0 1.0 0 0 1 0 100 100 99 N Ex. 15 60 0 0 0.1 0 0 0 0.1 0 0 1 0 100 100 99 N Ex. 16 60 0 0 15 0 0 0 15.0 0 0 1 0 100 100 99 N Ex 17 50 0 0.1 0.3 0.1 0 0 0.5 0 0 1 0 100 100 99 N Ex. 18 50 0 0 0 0 0.5 0 0.5 0 0 10 7 93 93 90 N Ex. 19 30 0 0.3 0.9 0.3 0 0 1.5 0 0 1 0 100 100 99 N Ex. 20 10 0 1 3 1 0 0 5.0 0 0 1 0 100 100 99 N Comp. Ex. 8th 100 0 0 0 0 0 0 0.0 0 0 0 0 0 0 0 H Comp. Ex. 9 60 0 0 0 0 0 0 0.0 0 0 0 0 100 100 100 N Comp. Ex. 10 60 0 7 21 7 0 0 35.0 0 0 1 0 98 91 90 N Comp. Ex. 11 60 0.2 0 0 0 0 0 0.0 100 100 0 0 0 0 0 N Comp. Ex. 12 60 0 0 0 0 0 0.2 0.0 0 0 100 100 0 0 0 N

In Table 2, a surface treatment agent for polyurethane elastic fibers with a polydimethylsiloxane content greater than 70% was marked "H" for high raw material cost, and one with less than 70% was marked "N" for low raw material cost.

[Examples 21 to 28 and Comparative Examples 13 to 18 of Polyurethane Elastic Fibers Coated with a Surface Treatment Agent for Polyurethane Elastic Fibers]

2,000 g of polytetramethylene ether glycol having a number-average molecular weight of 2,000 and 400 g of 4,4'-diphenylmethane diisocyanate were reacted with stirring at 60°C for 3 hours in an atmosphere of dry nitrogen to obtain an isocyanate-end-capped polyurethane prepolymer. After cooling to room temperature, dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution. An amine solution in which ethylenediamine and diethylamine were dissolved in dry dimethylacetamide was prepared separately and added to the polyurethane prepolymer solution such that the ratio of isocyanate groups in the urethane prepolymer to amino groups in the amine solution was 1:1.03. and reacted with cooling to 10°C. A polyurethane solution having a polyurethane solid content concentration of 30% by mass and a viscosity of 450 Pa·s (30°C) was obtained.

1 wt% 4,4'-butylidenebis(3-methyl-6-t-butylphenol) and 0.5 wt% 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole in terms of polyurethane solid content was weighed, dissolved in dimethylacetamide and then mixed with a polyurethane solution to form a uniform solution, which was then defoamed at room temperature under reduced pressure to obtain a spinning dope.

The spinning dope was dry-spun at a winding speed of 500 m/minute and a hot air temperature of 300°C using a spinneret having 48 perfectly circular holes, and the fibers were bundled with an effect twister using compressed air. Thereafter, surface-treating agents of the application amounts and types shown in Table 3 were applied to the elastic polyurethane fibers by jet oiling. The elastic polyurethane fibers were then wound onto paper tubes to obtain a wound pack of elastic polyurethane fibers of 470 dent/48 filaments.

[Example 29 and Comparative Example 19]

Except that the treating agent for polyurethane elastic fibers was kneaded into the spinning liquid instead of performing jet oiling, each of the wound packages of polyurethane elastic fibers of 470 dt/48 filaments was obtained in the same manner as in Examples 21 to 28 and Comparative Examples 13 to 18. Table 3 fiber treatment agent Amount of fiber treatment agent applied (weight) Content of compound of formula 1 in fiber (ppm) Each area of hydrocarbon compound in GC/MS measurement on hexane extract from fiber (%) valuation n Total for n = 2 to 5 C16 or less C18 or less C28 or more C30 or more C16-30 C18-30 C18-28 settleability Frequency of occurrence of single yarn untangling (%) 1 2 3 4 5 6 or more Ex. 21 Ex 13 1.0 0 0 100 0 0 0 100 0 0 0 0 100 100 100 7 5 Ex 22 Ex 14 1.0 0 0 100 0 0 0 100 0 0 1 0 100 100 99 7 7 Ex 23 Ex. 15 1.0 0 0 10 0 0 0 10 0 0 1 0 100 100 99 6 6 Ex. 24 Ex. 16 1.0 0 0 1500 0 0 0 1500 0 0 1 0 100 100 99 7 7 Ex. 25 Ex 17 1.0 0 10 30 10 0 0 50 0 0 1 0 100 100 99 7 7 Ex 26 Ex. 18 1.0 0 0 0 0 50 0 50 0 0 10 7 93 93 90 4 6 Ex 27 Ex. 19 1.0 0 30 90 30 0 0 150 0 0 1 0 100 100 99 6 6 Ex. 28 Ex. 20 1.0 0 100 300 100 0 0 500 0 0 1 0 100 100 99 5 6 Ex. 29 Ex. 14 (kneaded) 1.0 0 0 100 0 0 0 100 0 0 1 0 100 100 99 7 7 Comp. Ex. 13 Comp. Ex. 8th 1.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4 3 Comp. Ex. 14 Comp. Ex. 8th 2.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 3 Comp. Ex. 15 Comp. Ex. 9 1.0 0 0 0 0 0 0 0 0 0 0 0 100 100 100 4 3 Comp. Ex. 16 Comp. Ex. 10 4.0 0 2800 8400 2800 0 0 14000 0 0 1 0 98 91 90 4 3 Comp. Ex. 17 Comp. Ex. 11 1.0 20 0 0 0 0 0 0 100 100 0 0 0 0 0 3 3 Comp. Ex. 18 Comp. Ex. 12 1.0 0 0 0 0 0.2 0 0 0 0 100 100 0 0 0 3 3 Comp. Ex. 19 Comp. Ex. 9 (kneaded) 1.0 0 0 0 0 0 0 0 0 0 0 0 100 100 100 4 3

Commercial Applicability

The polyurethane elastic fiber containing a specific amount of the specific branched hydrocarbon compound according to the present invention is a polyurethane elastic fiber having good unwindability even with a low silicone oil content and low single-yarn untangling of a multifilament. Therefore, the polyurethane elastic fibers of the polyurethane elastic fiber according to the present invention can be suitably used for textile fabrics, sanitary material products, and so on.

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• JP 2007270414 [0007]
• JP 2017110319 [0007]
• JP2009287126 [0007]

Claims (19)

Polyurethane elastic fiber containing a hydrocarbon compound represented by the following formula (1):

where n is an integer of 2 to 5, in a proportion of 10 ppm to 10,000 ppm relative to the weight of the polyurethane elastic fiber. Elastic polyurethane fiber according to claim 1 containing the hydrocarbon compound represented by the formula (1) where n=3 in a proportion of 10 ppm to 8000 ppm relative to the weight of the polyurethane elastic fiber. Elastic polyurethane fiber according to claim 1 or 2 which further contains a hydrocarbon compound other than the hydrocarbon compound represented by the formula (1) wherein n is an integer of 2 to 5. Elastic polyurethane fiber according to any one of Claims 1 until 3 , wherein the area of a component requiring a retention time longer than the retention time of triacontane in a GC/MS measurement of an extract with hexane is less than 5% of the total area of a peak derived from the hydrocarbon compound. Elastic polyurethane fiber according to any one of Claims 1 until 4 , wherein the area of a component requiring a retention time longer than the retention time of octacosane in a GC/MS measurement of an extract with hexane is less than 5% of the total area of a peak derived from the hydrocarbon compound. Elastic polyurethane fiber according to any one of Claims 1 until 5 , wherein the area of a component requiring a retention time shorter than the retention time of hexadecane in a GC/MS measurement of an extract with hexane is less than 5% of the total area of a peak derived from the hydrocarbon compound. Elastic polyurethane fiber according to any one of Claims 1 until 6 , wherein the area of a component requiring a retention time shorter than the retention time of octadecane in a GC/MS measurement of an extract with hexane is less than 20% of the total area of a peak derived from the hydrocarbon compound. Elastic polyurethane fiber according to any one of Claims 1 until 7 , wherein the area of a component requiring a retention time between that of octadecane and that of octacosane in a GC/MS measurement of an extract with hexane is 80% or more of the total area of a peak derived from the hydrocarbon compound. Textile fabric comprising the elastic polyurethane fiber according to any one of Claims 1 until 8th includes. Sanitary material product containing the polyurethane elastic fiber according to any one of Claims 1 until 8th includes. A surface-treating agent for polyurethane elastic fibers, which contains a hydrocarbon compound represented by the following formula (1):

where n is an integer from 2 to 5, in an amount of from 0.10% to 25% by weight. Surface treatment agent for polyurethane elastic fibers according to claim 11 containing the hydrocarbon compound represented by the formula (1) wherein n=3 in a proportion of 0.10% by weight to 20% by weight. Surface treatment agent for polyurethane elastic fibers according to claim 11 or 12 which further contains a hydrocarbon compound other than the hydrocarbon compound represented by the formula (1) wherein n is an integer of 2 to 5. Surface treatment agent for elastic polyurethane fibers according to any one of Claims 11 until 13 , wherein the area of a component requiring a retention time longer than the retention time of triacontane in a GC/MS measurement of a solution in hexane is less than 5% of the total area of a peak derived from the hydrocarbon compound. Surface treatment agent for elastic polyurethane fibers according to any one of Claims 11 until 14 , wherein the area of a component requiring a retention time longer than the retention time of octacosane is less than 5% of the total area of a peak derived from the hydrocarbon compound in a GC/MS measurement of a solution in hexane. Surface treatment agent for elastic polyurethane fibers according to any one of Claims 11 until 15 , wherein the area of a component requiring a retention time shorter than the retention time of hexadecane is less than 5% of the total area of a peak derived from the hydrocarbon compound in a GC/MS measurement of a solution in hexane. Surface treatment agent for elastic polyurethane fibers according to any one of Claims 11 until 16 , wherein the area of a component requiring a retention time shorter than the retention time of octadecane is less than 20% of the total area of a peak derived from the hydrocarbon compound in a GC/MS measurement of a solution in hexane. Surface treatment agent for elastic polyurethane fibers according to any one of Claims 11 until 17 , wherein the area of a component whose retention time is intermediate between that of octadecane and that of octacosane in a GC/MS measurement of a solution in hexane is 80% or more of the total area of a peak derived from the hydrocarbon compound. Surface treatment agent for elastic polyurethane fibers according to any one of Claims 11 until 18 , which further contains a silicone oil in an amount of 20% by weight to 70% by weight.

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