JP5936292B1 - Dry-spun polyurethane elastic fiber - Google Patents

Abstract

A polyurethane-based elastic fiber that simultaneously imparts excellent unwinding properties, daily unwinding properties, anti-falling properties, and scum-deposition properties to polyurethane-based elastic fibers whose calorific value by DSC measurement is in a specific range. And a method for treating a polyurethane elastic fiber using the treatment agent. The following treatment agent for polyurethane elastic fiber comprises the following smoothing agent and the following unwinding improver, and the following smoothing agent exceeds 99.7% by mass and the following unwinding property. What contained the improver in the ratio of less than 0.3 mass% (total 100 mass%) was used. Polyurethane-based elastic fiber: Polyurethane-based elastic fiber smoothing agent having a calorific value at 150 to 300 ° C. measured by differential scanning calorimeter (DSC) of 40 mJ / mg or more and less than 150 mJ / mg: selected from silicone oil, mineral oil and ester At least one unwinding improver: a silicone resin having a mass average molecular weight of 3000 to 100,000 and having a trifunctional siloxane unit and / or a tetrafunctional siloxane unit as a constituent unit in the molecule, and an alkali of a fatty acid having 10 to 22 carbon atoms At least one selected from earth metal salts

Description

  The present invention relates to a dry-spun polyurethane elastic fiber, and more particularly, to a dry-spun polyurethane elastic fiber to which excellent unwinding property, daily unwinding property, anti-falling property and scum accumulation property are simultaneously imparted.

  Conventionally, as a dry-spun polyurethane-based elastic fiber, a treatment agent containing a modified silicone having an end-capped polyether group is attached (for example, see Patent Document 1), or a treatment agent containing a water-soluble silicone is attached. Containing a treatment agent containing polyalkylene ether diol, higher alcohol, mineral oil and dimethyl silicone (eg see Patent Document 3), mineral oil and an aliphatic ester compound Various types are known, such as those having a treatment agent attached thereto (see, for example, Patent Document 4). However, in these conventional dry-spun polyurethane elastic fibers, the calorific value obtained by measurement with a differential scanning calorimeter (hereinafter referred to as DSC) is given to the polyurethane elastic fibers in a specific range, and the unwinding and daily There is a problem that unraveling resistance, fall resistance, and scum resistance are insufficient.

JP-A-9-296377 JP 10-158938 JP 2005-344215 A JP 2011-42891 A

  The problem to be solved by the present invention is that the polyurethane-based elastic fiber having a calorific value measured by DSC measurement has excellent unwinding property, daily unwinding property, anti-falling property and scum-detaining property. Is to provide a dry-spun polyurethane-based elastic fiber to which is simultaneously applied.

  As a result of researches to solve the above-mentioned problems, the present inventors have determined that a specific smoothing agent and a specific unwinding improver are used at a specific ratio for polyurethane-based elastic fibers whose calorific value by DSC measurement is in a specific range. It has been found that a specific treatment agent contained in a specific proportion is correctly suitable.

  That is, the present invention relates to a dry-spun polyurethane-based elastic fiber characterized in that the following treatment agent is attached to the following polyurethane-based elastic fiber at a ratio of 0.1 to 10% by mass.

  Polyurethane elastic fiber: Polyurethane elastic fiber whose calorific value at 150 to 300 ° C. is 40 mJ / mg or more and less than 150 mJ / mg as measured by a differential scanning calorimeter (DSC).

  Treatment agent: composed of the following smoothing agent and the following unraveling improver, and more than 99.7% by weight of the following smoothing agent and less than 0.3% by weight of the following unraveling improving agent (total of 100% by weight) %))

  Smoothing agent: at least one selected from silicone oil, mineral oil and ester

  Peptide improver: Alkaline earth metal of a silicone resin having a weight average molecular weight of 3000 to 100,000 and a fatty acid having 10 to 22 carbon atoms having a trifunctional siloxane unit and / or a tetrafunctional siloxane unit as a constituent unit in the molecule At least one selected from salt

In the dry-spun polyurethane elastic fiber according to the present invention (hereinafter referred to as the elastic fiber of the present invention), the target polyurethane elastic fiber has a calorific value at 150 to 300 ° C. by DSC measurement of 40 mJ / mg to 150 mJ / mg. It is a polyurethane-based elastic fiber that is less than. There are a plurality of reports on DSC measurement of polyurethane-based elastic fibers (Japanese translations of PCT publication No. 2010-509512, international publication WO 2004/113599, etc.). In the elastic fiber of the present invention, the calorific value at 150 to 300 ° C. by DSC measurement of the polyurethane elastic fiber is from −50 ° C. to 300 ° C. after the sample is cooled from 25 ° C. to −50 ° C. at 10 ° C./min. It can obtain | require by measuring the emitted-heat amount in 150-300 degreeC when it heats up at 10 degreeC / min. The DSC 6200 manufactured by Seiko Instruments Inc. is used as the DSC, the polyurethane elastic fiber sampling amount is 3 mg, and Al ₂ O ₃ is used as a reference.

  The treatment agent attached to the polyurethane-based elastic fiber whose calorific value at 150 to 300 ° C. by DSC measurement as described above is in a specific range is composed of a smoothing agent and a deflocculating agent. The smoothing agent used is at least one selected from silicone oil, mineral oil and ester.

Specific examples of silicone oil used as a smoothing agent include trade name KF-96-10cs manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF-96-20cs manufactured by Shin-Etsu Chemical Co., Ltd., and trade name KF- manufactured by Shin-Etsu Chemical Co., Ltd. 96-50cs, Shin-Etsu Chemical Co., Ltd. trade name KF-50-100cs, Shin-Etsu Chemical Co., Ltd. trade name KF-4003, Shin-Etsu Chemical Co., Ltd. trade name KF-4917, Momentive Performance Materials Product name TSF451-10, product name TSF451-20 manufactured by Momentive Performance Materials, product name SH200-10CS manufactured by Toray Dow Corning, product name SH510-100CS manufactured by Toray Dow Corning, etc. It is done. These are all polydimethylsiloxane, polyalkylsiloxane, polyalkylphenylsiloxane and the like having a viscosity at 25 ° C. of ² to 100 mm ² / s, and one or more of them can be used.

There is no particular limitation on the mineral oil used as the smoothing agent, and a commercially available product can be used. Examples of such commercially available products include the product name Semtol 40 manufactured by Witoco, the product name Carnation manufactured by Witoco, and Cosmo Oil Lubricants. Cosmo Pure Spin D, Cosmo Oil Lubricants Cosmo Pure Spin RC, Cosmo Oil Lubricants Cosmo Pure Spin RB, Fuji Kosan Co., Ltd., Fukkor NT-60, Fuji Kosan Product name FUCOL NT-100, S-OIL product name Ultra-S2, S-OIL product name Ultra-S3, SK Lubrants product name YUBASE3, SK Lubrants product name YUBASE4, a product name made by Idemitsu Kosan Co., Ltd. A. W8, Idemitsu Kosan's trade name Diana Fresia W32, Idemitsu Kosan's trade name Diana Fresia G9, Idemitsu Kosan's trade name Diana Fresia K8, ExxonMobil's trade name Cristol N72, etc. 25 Examples thereof include spindle oil and liquid paraffin having a viscosity at ² ° C. of ² to 100 mm ² / s, and these can be used alone or in combination of two or more.

Furthermore, there is no restriction | limiting in particular also in the ester used as a smoothing agent, The ester manufactured from the various fatty acids and alcohol which are illustrated below is mentioned, These can use 1 type (s) or 2 or more types, but 25 Those having a viscosity at ² ° C. of ² to 100 mm ² / s are preferred.

  The fatty acid used as the raw material for the ester is not particularly limited in terms of its carbon number, presence or absence of branching, valence, etc., and it may be a higher fatty acid, a cyclic fatty acid, or a fatty acid having an aromatic ring. May be. Such fatty acids include caprylic acid, 2-ethylhexyl acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, arachidic acid, behenic acid, lignoceric acid, adipic acid, sebacin An acid, a benzoic acid, etc. are mentioned.

  The alcohol used as the raw material for the ester is not particularly limited in terms of the number of carbon atoms, presence or absence of branching, valence, etc., and it may be a higher alcohol, a cyclic alcohol, or an alcohol having an aromatic ring. It may be. Such alcohols include octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, ethylene glycol, hexanediol, glycerin, triglyceride, Examples include methylolpropane, pentaerythritol, sorbitol, sorbitan and the like.

  The unraveling improver used for the treating agent is a silicone resin having a mass average molecular weight of 3000 to 100,000 and a fatty acid having 10 to 22 carbon atoms, having a trifunctional siloxane unit and / or a tetrafunctional siloxane unit as a constituent unit in the molecule. Selected from alkaline earth metal salts. These can use 1 type (s) or 2 or more types. The mass average molecular weight can be determined in terms of polystyrene by gel permeation chromatography (hereinafter referred to as GPC) measurement.

The type of silicone resin to be used is not particularly limited as long as it is as described above, but is preferably selected from MQ silicone resin, MDQ silicone resin, T silicone resin and MTQ silicone resin. MQ silicone resin, MDQ Those selected from silicone resins and MTQ silicone resins are more preferred. Especially, when using what is chosen from MQ silicone resin, MDQ silicone resin, and MTQ silicone resin as a silicone resin, it is especially preferable to use the thing whose M / Q ratio is 0.5-1.1. Note that M, D, T, and Q crowned on the silicone resin are generally used as a notation method for the siloxane unit constituting the silicone resin, and M is represented by the general formula R ¹ R ² R ³ SiO _{1 /} monofunctional siloxane unit represented by _2, D is the general formula ^R 4 ^R 5 2-functional siloxane unit represented by _{SiO 2/2,} T is a trifunctional siloxane general formula is represented by ^R 6 _{SiO 3/2} The unit, Q, is a tetrafunctional siloxane unit having the general formula SiO _4/2 . Here, R ^{1 to} R ⁶ are hydrocarbon groups having 1 to 24 carbon atoms, and the general formula is —R ⁷ NHR ⁸ NH ₂ (R ⁷ and R ⁸ are hydrocarbon groups having 2 or 3 carbon atoms) or —R ^9. An organic amino group, a vinyl group, a carbinol group, or the like represented by NH ₂ (R ⁹ is a hydrocarbon group having 2 or 3 carbon atoms) or the like.

  There is no particular limitation on the alkaline earth metal salt of a fatty acid having 10 to 22 carbon atoms used as a peptizer, and capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid And calcium salts such as linoleic acid and magnesium salts, among which magnesium stearate is preferable. Commercially available products can be used as the magnesium stearate. Examples of such commercially available products include the product name SAK-MS-P manufactured by Sanace, the product name SAK-MS-P / USP manufactured by Sanace, and NOF Corporation. Product Name Magnesium Stearate G, NOF Product Name Magnesium Stearate GF-200, NOF Product Name Magnesium Stearate GR, NOF Product Name Magnesium Stearate, NOF Corporation Date Examples include local magnesium stearate, trade name Mg-St manufactured by Nitto Kasei Kogyo, and trade name Mg-LF manufactured by Nitto Kasei Kogyo.

  The treatment agent is composed of the above-described smoothing agent and the unraveling improver, and the smoothing agent exceeds 99.7% by mass and the unraveling improver is less than 0.3% by mass (total of 100% by mass). However, the smoothing agent is more than 99.7% by mass and not more than 99.999% by mass and the unraveling improver is not less than 0.001% by mass and less than 0.3% by mass (total 100% by mass). %) Is preferable.

  The treatment agent is composed of the above-described smoothing agent and unraveling improver, but other components may be used in combination as needed for the purpose. This includes, for example, wettability improvers, ultraviolet absorbers, antioxidants, preservatives and the like. The content of such other components can be appropriately determined according to the purpose within a range not impairing the purpose of the present invention, but is preferably as small as possible.

  The method for preparing the treatment agent described above is not particularly limited, and a known method can be applied to this.

  The treatment agent described above is adhered to the polyurethane elastic fiber in a neat state without being diluted. As an adhesion method, known methods such as a roller oil supply method, a guide oil supply method, and a spray oil supply method can be applied. The attaching step is preferably a spinning step. Examples of the spinning method in the spinning process include a dry spinning method, a melt spinning method, a wet spinning method, and the like, and the dry spinning method is applied. The amount of the treatment agent attached to the polyurethane elastic fiber is 0.1 to 10% by mass, but preferably 1 to 8% by mass. The form of the polyurethane elastic fiber is not particularly limited, and can be applied to a filament type or a span type.

  According to the present invention described above, the heat release at 150 to 300 ° C. by DSC measurement is superior to 40 mJ / mg or more and less than 150 mJ / mg of polyurethane-based elastic fiber. There is an effect that a dry-spun polyurethane-based elastic fiber to which twill resistance and scum deposition resistance are simultaneously imparted can be obtained.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following examples, “part” means “part by mass” and “%” means “% by mass”.

Test category 1 (Preparation of silicone resin as an agent for improving peptization)
Preparation of SIR-1 82.338 g (7.9 mol) of trimethylmethoxysilane, 800 g of water, 2.0 g of methanesulfonic acid and 2083.3 g (10 mol) of tetraethoxysilane were charged into a reaction vessel and heated to react. The temperature of was kept at 65 ° C. and heated and stirred for 24 hours. Next, 1.78 g of sodium hydrogen carbonate was added for neutralization, and then the mixture was refluxed for 5 hours and aged. Further, 2000 g of xylene was added, and methanol and ethanol by-produced by the reaction with water were distilled off and replaced with a xylene solution. After adjusting the effective concentration (silicone resin concentration in the xylene solution) of the obtained filtrate to 50%, the total amount and N- (2-aminoethyl) -3-iminopropylmethyldimethoxysilane 20.636 g (0. 1 mol) and 10 g of water were charged into another reaction vessel and reacted at 80 ° C. for 1 hour. Xylene, water and methanol were distilled off from the reaction solution to obtain a silicone resin SIR-1. When the following analysis was performed on the silicone resin SIR-1, this silicone resin SIR-1 has a general formula of R ¹ R ² R ³ SiO when R ¹ , R ² , and R ³ are all methyl groups. The general formula when the monofunctional siloxane unit / R ⁴ represented by _1/2 is an N- (2-aminoethyl) -3-iminopropyl group and R ⁵ is a methyl group is R ⁴ R ⁵ SiO _{2 A} bifunctional siloxane unit represented by / 2, a tetrafunctional siloxane unit represented by SiO _4/2 in general formula = 7.9 / 0.1 / 10 (molar ratio) and a silicone resin having a mass average molecular weight of 20000 Met.

-Analysis of the siloxane unit which comprises a silicone resin Silicone resin SIR-1 was used for the NMR spectrum analysis, and the molar ratio of the siloxane unit which comprises a silicone resin was computed. Similarly, the molar ratio of siloxane units constituting other silicone resins was also calculated.

Preparation of SIR-2 729.54 g (7 mol) of trimethylmethoxysilane, 800 g of water, 2.0 g of methanesulfonic acid and 2083.3 g (10 mol) of tetraethoxysilane were charged into a reaction vessel and heated to the temperature of the reaction system. The mixture was kept at 65 ° C. and heated and stirred for 24 hours. Next, 1.78 g of sodium hydrogen carbonate was added for neutralization, and then the mixture was refluxed for 5 hours and aged. Further, 2000 g of xylene was added, methanol and ethanol by-produced by the reaction with water and the reaction were distilled off and replaced with a xylene solution, and the whole was filtered, and further xylene was distilled off to obtain a silicone resin SIR-2. This silicone resin SIR-2 was analyzed. As a result, when R ¹ , R ² and R ³ are all methyl groups, the general formula is represented by R ¹ R ² R ³ SiO _1/2 It was a silicone resin having a mass average molecular weight of 11000 and having a tetrafunctional siloxane unit represented by SiO _4/2 = _7/10 (molar ratio).

Preparation of SIR-3 1042.2 g (10 mol) of trimethylmethoxysilane, 800 g of water, 2.0 g of methanesulfonic acid and 2083.3 g (10 mol) of tetraethoxysilane were charged into a reaction vessel and heated to the temperature of the reaction system. The mixture was kept at 65 ° C. and heated and stirred for 24 hours. Next, 1.78 g of sodium hydrogen carbonate was added for neutralization, and then the mixture was refluxed for 5 hours and aged. Further, 2000 g of xylene was added, and methanol and ethanol by-produced by the reaction with water and the reaction were distilled off and replaced with a xylene solution. The whole was filtered, and further xylene was distilled off to obtain a silicone resin SIR-3. This silicone resin SIR-3 was analyzed. As a result, when R ¹ , R ² and R ³ are all methyl groups, the general formula is represented by R ¹ R ² R ³ SiO _1/2 It was a silicone resin having a mass average molecular weight of 8000, which is a tetrafunctional siloxane unit represented by SiO _4/2 = _1/1 (molar ratio).

Preparation of SIR-4 1042.2 g (10 mol) of trimethylmethoxysilane, 800 g of water, 2.0 g of methanesulfonic acid and 2083.3 g (10 mol) of tetraethoxysilane were charged in a reaction vessel and heated to the temperature of the reaction system. The mixture was kept at 65 ° C. and heated and stirred for 24 hours. Next, 1.78 g of sodium hydrogen carbonate was added for neutralization, and then the mixture was refluxed for 5 hours and aged. Further, 2000 g of xylene was added, and methanol and ethanol by-produced by the reaction with water were distilled off and replaced with a xylene solution. After adjusting the effective concentration (silicone resin concentration in the xylene solution) of the obtained filtrate to 50%, the total amount and N- (2-aminoethyl) -3-iminopropylmethyldimethoxysilane 206.36 g (1 mol) ) And 10 g of water were charged into another reaction vessel and reacted at 80 ° C. for 1 hour. Xylene, water and methanol were distilled off from the reaction solution to obtain a silicone resin SIR-4. This silicone resin SIR-4 was analyzed. As a result, when R ¹ , R ² and R ³ are all methyl groups, the general formula is represented by R ¹ R ² R ³ SiO _1/2 Bifunctional siloxane unit represented by the general formula R ⁴ R ⁵ SiO _2/2 when R ⁴ is an N- (2-aminoethyl) -3-iminopropyl group and R ⁵ is a methyl group / general It was a silicone resin having a weight-average molecular weight of 7000 and having a tetrafunctional siloxane unit represented by SiO _4/2 = _10/1/10 (molar ratio).

Preparation of SIR-5 A reaction vessel was charged with 2063.5 g (10 mol) of hexyltrimethoxysilane, 800 g of water, and 2.0 g of methanesulfonic acid, heated to maintain the temperature of the reaction system at 65 ° C., and heated for 24 hours. Stir. Next, 1.78 g of sodium hydrogen carbonate was added for neutralization, and then the mixture was refluxed for 5 hours and aged. Further, 2000 g of xylene was added, water and methanol by-produced by the reaction were distilled off and replaced with a xylene solution, the whole amount was filtered, and further xylene was distilled off to obtain a silicone resin SIR-5. When the silicone resin SIR-5 was analyzed, it was a silicone resin having a mass-average molecular weight of 4500 consisting of a trifunctional siloxane unit represented by R ⁶ SiO _3/2 in the general formula when R ⁶ is a hexyl group.

Preparation of SIR-6 N- (2-aminoethyl) -3-iminopropyltrimethoxysilane (223.6 g, 10 mol) and water (800 g) were charged into a reaction vessel and heated to keep the temperature of the reaction system at 65 ° C. The mixture was stirred at reflux for 24 hours. Subsequently, water and methanol by-produced by the reaction were distilled off to obtain silicone resin SIR-6. When the silicone resin SIR-6 was analyzed, the general formula in the case where R ⁶ is an N- (2-aminoethyl) -3-iminopropyl group consists of a trifunctional siloxane unit represented by R ⁶ SiO _3/2 It was a silicone resin having a mass average molecular weight of 5000.

Preparation of SIR-7 Reaction of 312.66 g (3 mol) of trimethylmethoxysilane, 206.35 g (1 mol) of hexyltrimethoxysilane, 800 g of water, 2.0 g of methanesulfonic acid and 1041.65 g (5 mol) of tetraethoxysilane The vessel was charged and heated to keep the temperature of the reaction system at 65 ° C., and heated and stirred for 24 hours. Next, 1.78 g of sodium hydrogen carbonate was added for neutralization, and then the mixture was refluxed for 5 hours and aged. Further, 2000 g of xylene was added, methanol and ethanol by-produced by the reaction with water and the reaction were distilled off and replaced with a xylene solution, the whole amount was filtered, and further xylene was distilled off to obtain a silicone resin SIR-7. When the silicone resin SIR-7 was analyzed, the monofunctional siloxane unit / R represented by the general formula R ¹ R ² R ³ SiO _1/2 when R ¹ , R ² , and R ³ are all methyl groups is shown. ^In the case where ⁶ is a hexyl group, a trifunctional siloxane unit having a general formula of R ⁶ SiO _3/2 / a tetrafunctional siloxane unit having a general formula of SiO _4/2 = _3/1/5 (molar ratio) ) Is a silicone resin having a weight average molecular weight of 30,000.

Test Category 2 (Preparation of treatment agent)
Preparation of treatment agent (E-1) 69.9 parts of polydimethylsiloxane (L-1: trade name KF-96-10cs manufactured by Shin-Etsu Chemical Co., Ltd.) listed in Table 1 as a smoothing agent and mineral oil (L-2) : Idemitsu Kosan Co., Ltd. trade name Diana Fresia W8) 30 parts, and MDQ silicone resin (SIR-1) 0.1 part described in Table 2 as a deflocculating improver, and uniformly mixed with the above treatment agent ( E-1) was prepared.

Preparation of Treatment Agent (E-7) 89.8 parts of polydimethylsiloxane (L-1: trade name KF-96-10cs manufactured by Shin-Etsu Chemical Co., Ltd.) listed in Table 1 as a smoothing agent and mineral oil (L-2) : Idemitsu Kosan Co., Ltd. trade name Diana Fresia W8) 10 parts, and 0.1 parts of MDQ silicone resin (SIR-1) listed in Table 2 as a peptizer and magnesium stearate (S -1: 0.1 part of Sanace brand name SAK-MS-P) and the above were uniformly mixed and then treated with a wet disperser to prepare a treating agent (E-7).

Preparation of treatment agent (E-8) 99.8 parts of polydimethylsiloxane (L-1: trade name KF-96-10cs, manufactured by Shin-Etsu Chemical Co., Ltd.) listed in Table 1 as a smoothing agent As described in Table 3, 0.2 parts of magnesium stearate (S-1: trade name SAK-MS-P manufactured by San Ace Co., Ltd.) was uniformly mixed and then treated with a wet disperser to obtain a treating agent (E -8) was prepared.

Preparation of treatment agent (E-9) 29.9 parts of polydimethylsiloxane (L-1: trade name KF-96-10cs manufactured by Shin-Etsu Chemical Co., Ltd.) described in Table 1 as a smoothing agent and mineral oil (L-2) : Idemitsu Kosan Co., Ltd. trade name Diana Fresia W8) 70 parts, and T silicone resin (SIR-5) 0.1 part described in Table 2 as a peptizer, and uniformly mixed with the above treatment agent ( E-9) was prepared. In Test Category 3 described later, a combination of 1 part of lauryl diethanolamine and 1 part of cetyl alcohol phosphoric acid diester was used per 100 parts of this treating agent (E-9).

Preparation of Treatment Agent (E-10) 89.75 parts of polydimethylsiloxane (L-1: trade name KF-96-10cs manufactured by Shin-Etsu Chemical Co., Ltd.) listed in Table 1 as a smoothing agent and mineral oil (L-3) : SK Lubricants trade name YUBASE 3) 10 parts, and T silicone resin (SIR-6) 0.25 parts listed in Table 2 as a peptizer, and uniformly mixed with the treatment agent (E- 10) was prepared. In Test Category 3 described later, a combination of 0.5 part of amino-modified silicone (trade name KF-861 manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of the treatment agent (E-10) was used.

Preparation of treating agents (E-2) to (E-6), (R-1) to (R-6) and (R-8) In the same manner as treating agent (E-1), smoothing agent and unraveling The property-improving agent was uniformly mixed to prepare treating agents (E-2) to (E-6), (R-1) to (R-6) and (R-8).

Preparation of processing agents (R-7), (R-9) and (R-10) In the same manner as the processing agent (E-7), a smoothing agent and a peptizer are mixed uniformly, and then a wet disperser Then, treating agents (R-7), (R-9) and (R-10) were prepared. The contents of the treatment agents prepared above are summarized in Table 4.

Test category 3 (evaluation)
-Production of dry-spun polyurethane elastic fiber First, 35 of N, N'-dimethylacetamide (hereinafter referred to as DMAc) of polyurethane composed of tetramethylene ether glycol having a molecular weight of 2900, bis- (p-isocyanatophenyl) -methane and ethylenediamine. % Solution was polymerized to obtain a solution (A).

  Next, polyurethane (trade name Metachlor (registered trademark) 2462 manufactured by DuPont) produced by the reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexylisocyanate), p-cresol and divinylbenzene A 35% solution of DMAc in a 2 to 1 (mass ratio) mixture with a condensation polymer (trade name Metacral (registered trademark) 2390, manufactured by DuPont) was prepared to obtain a solution (B).

  The solution (A) and the solution (B) were uniformly mixed at a ratio of 96: 4 (mass ratio) to obtain a spinning dope.

  Using the spinning dope thus obtained, a 44 dtex / 3 fil multifilament polyurethane elastic fiber was spun by a dry spinning method used in known spandex, and the treatment agent (E-1) was fed from the oiling roller before winding. ) To (E-10) and (R-1) to (R-10) were roller-oiled as they were neat. The roller oiled in this way is wound using a surface drive winder through a traverse guide that gives a winding width of 38 mm to a 58 mm long cylindrical paper tube at a winding speed of 600 m / min, and is dry-type A 500 g package of spun polyurethane elastic fibers was obtained. The adhesion amount of the polyurethane-based elastic fiber treatment agent was adjusted to 5% with respect to the polyurethane-based elastic fiber by adjusting the number of rotations of the oiling roller. DMAc was volatilized by a nitrogen stream during the spinning process. The higher the temperature at this time and the higher the elongation ratio during winding, the higher the elastic modulus of the polyurethane-based elastic fiber obtained, which was measured at 150 to 300 ° C. The lower the temperature when volatilizing DMAc and the lower the expansion ratio at the time of winding, the lower the heat generation amount at 150 to 300 ° C. by DSC measurement of the obtained polyurethane elastic fiber. Although it became large, the polyurethane type elastic fiber of each example which has the emitted-heat amount as described in Table 4 was obtained by changing these as described in Table 4. The resulting dry-spun polyurethane elastic fiber package was subjected to the following measurements and evaluations, and the results are summarized in Table 5.

・ Measurement of calorific value at 150 to 300 ° C. by DSC measurement of polyurethane elastic fiber A sample taken from the dry-spun polyurethane elastic fiber package immediately after spinning obtained above from 10 ° C./min from 25 ° C. to −50 ° C. Then, the temperature was raised from −50 ° C. to 300 ° C. at 10 ° C./min, and the calorific value at 150 to 300 ° C. at this time was measured. In addition, the product name DSC6200 manufactured by Seiko Instruments Inc. was used as the DSC, the sampling amount of the polyurethane elastic fiber was 3 mg, and Al ₂ O ₃ was used as a reference.

・ Evaluation of unraveling property The first drive roller on one side and the first free roller that is always in contact with the first feed roller constitute the feed section, and the opposite side is wound up by the second drive roller and the second free roller that is always in contact with this. The winding part was installed 20 cm apart in the horizontal direction with respect to the delivery part. The dry-spun polyurethane-based elastic fiber package obtained immediately after spinning was mounted on the first driving roller, unwound until the thickness of the bobbin became 2 mm, and wound around the second driving roller. While fixing the feed speed of the polyurethane elastic fiber from the first driving roller at 50 m / min, the winding speed of the polyurethane elastic fiber to the second driving roller is gradually increased from 50 m / min to increase the polyurethane elastic fiber. Was forcibly resolved from the package. At the time of such forced unwinding, the winding speed V (m / min) when the polyurethane elastic fiber no longer dances between the sending portion and the winding portion is measured, and the unwinding property ( %) And evaluated according to the following criteria.

Evaluation standard for unraveling ◎: Unraveling is less than 120% (can be solved stably without any problem)
○: Unwinding property is 120% or more and less than 180% (although there is some resistance to pulling out the yarn, there is no occurrence of yarn breakage and it can be stably unwound)
×: Unwinding property is 180% or more (there is resistance to pulling out the yarn, yarn breakage, and there is a problem in operation)

・ Evaluation of daily unwinding property Evaluation of unwinding property except that a dry-spun polyurethane elastic fiber package stored for 6 months after spinning was used instead of the dry-spun polyurethane elastic fiber package immediately after spinning. The same evaluation was performed.

・ Evaluation of traversing resistance The number of yarn breaks caused by traversing of the package when the dry-spun polyurethane elastic fiber package obtained immediately after spinning as described above is sent out at 20 m / min and wound up at 1000 m at 40 m / min. And evaluated according to the following criteria.

Evaluation criteria for traversing resistance ◎: thread breakage due to traversal is 0 times ○: thread breakage due to traversal is 1 time or more and less than 3 times ×: thread breakage due to traversal is 3 times or more

-Evaluation of scum accumulation resistance Ten dry-spun polyurethane elastic fiber packages obtained as described above were prepared on a miniature warping machine and wound at 1500 km at a yarn speed of 300 m / min in an atmosphere of 65% RH at 25 ° C. I took it. At this time, the dropout and accumulation state of the scum in the comb guide of the miniature warping machine was visually observed and evaluated according to the following criteria.

Evaluation criteria for resistance to scum accumulation A: Almost no scum accumulated.
○: Scum was slightly accumulated, but there was no problem with stable yarn running.
X: There was much accumulation of scum, and there was a big problem in the stable running of the yarn.

In Table 1,
Viscosity: Kinematic viscosity at 30 ° C. L-1: Trade name KF-96-10cs manufactured by Shin-Etsu Chemical Co., Ltd.
L-2: Product name Diana Fresia W8 manufactured by Idemitsu Kosan Co., Ltd.
L-3: Product name YUBASE 3 manufactured by SK Lubricants

In Table 2,
M1: Monofunctional siloxane unit in which the general formula is R ¹ R ² R ³ SiO _1/2 and R ¹ , R ² and R ³ are all methyl groups D1: General formula is R ⁴ R ⁵ Bifunctional siloxane unit represented by SiO _2/2 and R ⁴ and R ⁵ are both methyl groups D2: General formula is represented by R ⁴ R ⁵ SiO _2/2 , R ⁴ is methyl group, R ⁴ Bifunctional siloxane unit when ⁵ is an N- (2-aminoethyl) -3-iminopropyl group T1: 3 when the general formula is R ⁶ SiO _3/2 and R ⁶ is a hexyl group Functional siloxane unit T2: Trifunctional siloxane unit when the general formula is R ⁶ SiO _3/2 and R ⁶ is an N- (2-aminoethyl) -3-iminopropyl group Q1: SiO _{4 /} tetrafunctional structure units represented by ₂

  As is clear from the results in Table 5 corresponding to Tables 1 to 4, according to the present invention, the polyurethane-based elastic fibers having a calorific value measured by DSC measurement are excellent in unwinding and aging. Thus, a dry-spun polyurethane-based elastic fiber that is simultaneously imparted with excellent unwinding property, twill resistance and scum deposition resistance is obtained.

Claims (6)

To polyurethane elastic fibers below, dry spinning Polyurethane based elastic textiles characterized in that the treatment agents described below are deposited in a proportion of 0.1 to 10 mass%.
Polyurethane elastic fiber: Polyurethane elastic fiber whose calorific value at 150 to 300 ° C. is 40 mJ / mg or more and less than 150 mJ / mg as measured by a differential scanning calorimeter (DSC).
Treatment agent: composed of the following smoothing agent and the following unraveling improver, and more than 99.7% by weight of the following smoothing agent and less than 0.3% by weight of the following unraveling improving agent (total of 100% by weight) %)) Treatment agent leveling agent: at least one selected from silicone oils, mineral oils and esters Peeling improver: trifunctional siloxane units and / or tetrafunctional siloxane units in the molecule At least one selected from a silicone resin having a mass average molecular weight of 3000 to 100,000 as a constituent unit and an alkaline earth metal salt of a fatty acid having 10 to 22 carbon atoms Silicone resin unwinding properties improver, MQ silicone resin, MDQ silicone resin, T silicone resin and a dry spinning Polyurethane based elastic textiles at least is one according to claim 1 wherein is selected from MTQ silicone resin. Solution silicone resin舒性enhancer, MQ silicone resin, MDQ silicone resin and a dry spinning Polyurethane based elastic textiles at least is one according to claim 1 wherein is selected from MTQ silicone resin. Silicone resin unwinding properties improver, dry spinning Polyurethane based elastic textiles of the is claim 3, wherein for the case M / Q ratio of 0.5 to 1.1. Unwinding property alkaline earth metal salt of a fatty acid enhancer, dry spinning Polyurethane based elastic textiles of any one of the preceding of claims 1 to 4 is magnesium stearate. Treatment agent, you in a proportion of flat lubricant less than 99.7 mass percent 99.999 mass% or less and the unwinding property improver 0.001 wt% 0.3 wt% (total 100 wt%) dry spinning polyurethane based elastic textiles of any one of the preceding description of the 請 Motomeko 1-5 is intended.