JP2020117838A - Treatment agent for polyurethane-based elastic fiber, method for treating polyurethane-based elastic fiber, and polyurethane-based elastic fiber - Google Patents

Abstract

To improve dispersion stability of higher fatty acid salt and also improve quality of processing of a workpiece by reducing defect of a winding shape if made into a wound yearn body.SOLUTION: A treatment agent for polyurethane-based elastic fiber includes a smoothing agent, a specific amide modified silicone and a specific higher fatty acid metal salt. The smoothing agent contains, besides the specific amide modified silicone, at least one of silicone oil, mineral oil, fatty acid ester and liquid polyolefin. A kinematic viscosity of the smoothing agent is 5-50 mm/s.SELECTED DRAWING: None

Description

The present invention relates to a treatment agent for polyurethane-based elastic fibers that is used by being attached to polyurethane-based elastic fibers, a method for treating polyurethane-based elastic fibers, and a polyurethane-based elastic fiber.

Conventionally, a treatment agent for elastic fibers containing an amino-modified polysiloxane in which hydrogen atoms, an alkyl group, a carboxyl group, and an alkylene oxide group are localized at both ends (see, for example, Patent Document 1), a metal soap having a specific particle size ( Higher fatty acid salt) and an amino-modified silicone having a methyl group at the end (see, for example, Patent Document 2), an elastic fiber treatment agent containing a highly polymerized amino-modified silicone (for example, Patent Document) 3) has been proposed, but these conventional treatment agents for elastic fibers have poor dispersion stability of higher fatty acid salts, cannot obtain an excellent winding shape, and cannot meet the requirements of high processing quality. There is.

JP, 10-053960, A JP, 2000-144578, A JP, 2003-201678, A

The problem to be solved by the present invention is to improve the dispersion stability of a higher fatty acid salt, suppress a defective winding shape in the case of a wound body, and improve the processing quality of a processed product. A treatment agent for a polyurethane-based elastic fiber for obtaining a fiber and a method for treating a polyurethane-based elastic fiber are provided. Another object of the present invention is to provide a polyurethane-based elastic fiber capable of improving the dispersion stability of a higher fatty acid salt, suppressing a defective winding shape when a wound body is formed, and improving the processed quality of a processed product.

As a result of research to solve the above problems, the present inventors have improved the dispersion stability of higher fatty acid salts, suppressed the defective winding shape in the case of a wound body, and improved the processed quality of the processed product. In order to obtain a polyurethane-based elastic fiber that can be used, it is correct and preferable to use an elastic fiber treatment agent in which a specific higher fatty acid metal salt is colloidally dispersed in a specific smoothing agent and a specific modified silicone. I found it.

A treatment agent for polyurethane-based elastic fibers that solves the above problems is a treatment agent for polyurethane-based elastic fibers that is used by being attached to polyurethane-based elastic fibers, and includes a smoothing agent, an amide-modified silicone represented by the following chemical formula 1, and It contains a higher fatty acid metal salt represented by Chemical Formula 3 below, and the smoothing agent contains at least one of a silicone oil other than the amide-modified silicone, a mineral oil, a fatty acid ester, and a liquid polyolefin. The kinematic viscosity is 5 to 50 mm ² /s.

In Chemical formula 1, X ¹ and X ² are a methyl group, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and at least one of X ¹ and X ² is an alkoxy group having 1 to 4 carbon atoms or It is a hydroxyl group. X ³ is an amide-modifying group represented by the following chemical formula 2. R ¹ is an alkyl group having 1 to 5 carbon atoms. p is an integer of 4 to 1200. q is an integer of 1 to 100.

In Chemical formula 2, R ² and R ³ are alkylene groups having 2 to 5 carbon atoms. R ⁴ is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent carboxylic acid. r is 0 or 1.

In Chemical formula 3, R ⁵ is a residue obtained by removing one carboxyl group from a fatty acid having 12 to 22 carbon atoms. M is a metal atom having an valence of n, and n is an integer of 1 to 3.
In the above polyurethane-based elastic fiber treating agent, in the amide-modified silicone, X ¹ and X ² in Chemical formula ¹ are methyl groups or hydroxyl groups, and at least one of X ¹ and X ² is a hydroxyl group. It is preferably in some cases.

In the above polyurethane-based elastic fiber treating agent, it is preferable that the amide-modified silicone is one in which X ¹ and X ² in Chemical formula ¹ are hydroxyl groups.
In the polyurethane-based elastic fiber treating agent, the amide-modified silicone is preferably one in which p in Chemical formula ¹ is an integer of 15 to 700 and R ¹ is a methyl group.

In the above polyurethane-based elastic fiber treating agent, in the amide-modified silicone, p in Chemical formula 1 is an integer of 100 to 500, q is an integer of 1 to 10, and the amide equivalent is 3000 to 30000 g/mol. In some cases, it is preferable.

In the above polyurethane-based elastic fiber treating agent, when the total content of the leveling agent, the amide-modified silicone, and the higher fatty acid metal salt is 100% by weight, the leveling agent is 85 to 99.8% by weight, and It is preferable to contain the amide-modified silicone in an amount of 0.1 to 5% by mass and the higher fatty acid metal salt in an amount of 0.1 to 10% by mass.

In the method for treating a polyurethane elastic fiber for solving the above problems, the treatment agent for a polyurethane elastic fiber is adhered to the synthetic fiber in an amount of 0.1 to 10% by mass relative to 100% by mass.

The polyurethane elastic fiber for solving the above-mentioned problems has the above-mentioned treatment agent for polyurethane elastic fiber attached thereto.

ADVANTAGE OF THE INVENTION According to this invention, while improving the dispersion stability of a higher fatty acid salt, suppressing the defective winding shape when it is made into a wound body, and obtaining the polyurethane type elastic fiber which can improve the processed quality of a processed product. You can

First, the processing agent for polyurethane elastic fibers according to the present invention (hereinafter referred to as the processing agent of the present invention) will be described. The treating agent of the present invention comprises a leveling agent, a specific amide-modified silicone represented by the following chemical formula 4 and a specific higher fatty acid salt represented by the following chemical formula 6.

(Smoothing agent)
The leveling agent used in the treatment agent of the present invention is one or more selected from silicone oils other than the amide-modified silicone represented by Chemical formula 4, mineral oils, fatty acid esters and liquid polyolefins, and has a kinematic viscosity at 25°C. Is 5 to 50 mm ² /s. Specific examples of silicone oils other than the amide-modified silicone represented by Chemical Formula 4 include (1) polydimethylsiloxanes having repeating units of dimethylsiloxane units, (2) repeating units having dimethylsiloxane units and 2 to 2 carbon atoms. Examples of the known products include polydialkylsiloxanes composed of a dialkylsiloxane unit having an alkyl group of 4 and (3) polysiloxanes composed of a dimethylsiloxane unit and a methylphenylsiloxane unit as repeating units. Has the following:

Polydimethylsiloxane having a kinematic viscosity at 25° C. of 5 mm ² /s (trade name KF-96L-5cs manufactured by Shin-Etsu Chemical Co., Ltd.), polydimethylsiloxane having a kinematic viscosity at 25° C. of 10 mm ² /s (Shin-Etsu Chemical KF-96-10cs manufactured by Kogyo Co., Ltd., polydimethylsiloxane having a kinematic viscosity of 20 mm ² /s at 25° C. (KF-96-20cs manufactured by Shin-Etsu Chemical Co., Ltd.), kinematics at 25° C. Polydimethylsiloxane having a viscosity of 30 mm ² /s (trade name KF-96-30cs manufactured by Shin-Etsu Chemical Co., Ltd.), polydimethylsiloxane having a kinematic viscosity at 25° C. of 50 mm ² /s (manufactured by Shin-Etsu Chemical Co., Ltd. Trade name KF-96-50cs).

Examples of the mineral oil include general petroleum fractions containing a paraffin component, a naphthene component, an aroma component, and the like, and known examples of the products include the following. Mineral oil having a kinematic viscosity of 10 mm ² /s at 25° C. (trade name: Cosmo Pure Spin D manufactured by Cosmo Oil Lubricants Co., Ltd.), mineral oil having a kinematic viscosity of 15 mm ² /s at 25° C. (manufactured by Fuji Kosan Co., Ltd. Product name of Fucor NT-60), and a mineral oil having a kinematic viscosity at 25° C. of 40 mm ² /s (Fucoal NT-100 manufactured by Fuji Kosan Co., Ltd.).

Examples of the fatty acid ester include an aliphatic monohydric alcohol and an aliphatic monocarboxylic acid such as butyl stearate, octyl stearate, oleyl laurate, oleyl oleate, isotridecyl stearate, and isopentacosanyl isostearate. Of 1,6-hexanediol didecanoate, trimethylolpropane monooleate monolaurate, trimethylolpropane trilaurate, castor oil and other natural fats and oils and aliphatic monocarboxylic acids Examples thereof include esters, dilauryl adipate, dioleyl azelate and the like, and esters of an aliphatic monohydric alcohol with an aliphatic polyvalent carboxylic acid.

Examples of liquid polyolefins include poly-α-olefins obtained by polymerizing 1-butene, 1-hexene, 1-decene and the like. Among them, those containing silicone oil such as polydimethylsiloxane are preferable.

The kinematic viscosity of the leveling agent is determined by a method using a Canon Fenske viscometer described in JIS-K2283 (Kinematic viscosity test method for petroleum products), and a kinematic viscosity at 25° C. of 5 to 50 mm ² /s is used. be able to.

(Specific amide-modified silicone)
The specific amide-modified silicone used for the treating agent of the present invention is represented by the following chemical formula 4.

X ¹ and X ² in Chemical formula 4 are an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a protoxy group and a butoxy group, a methyl group or a hydroxyl group, and at least one of X1 and X2. Is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms. Of these X ¹ and X ² is a methyl group or a hydroxyl group, and is preferably a case where at least one of X ¹ and X ² is a hydroxyl group, more those when X ¹ and X ² is a hydroxyl group preferable.

X ^{3 in} Chemical formula 4 is an amide-modifying group represented by Chemical formula 5 below.

R ² and R ^{3 in} Chemical formula 5 are alkylene groups having 2 to 5 carbon atoms such as an ethylene group, a propylene group, a butylene group, and a pentylene group, and r is 0 or 1. R ⁴ is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent carboxylic acid, and the carboxylic acid is not particularly limited in its carbon number, presence or absence of branching, valence, etc., and may be a higher fatty acid. , A cyclic fatty acid or an aromatic ring-containing fatty acid may be used. Examples of the fatty acid include caprylic acid, 2-ethylhexylic 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, sebacine. Acid, benzoic acid, etc. are mentioned.

R ¹ in the above Chemical Formula 4 is an alkyl group having 1 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group, and a pentyl group, p is an integer of 4 to 1200, and q is 1 to Although it is an integer of 100, it is preferable that p is an integer of 15 to 700, and R ¹ is a methyl group, p is an integer of 100 to 500, and q in Chemical formula 4 is The case where it is an integer of 1 to 10 is more preferable.

The amide-modified silicone represented by Chemical Formula 4 may be a random copolymer or a block copolymer.
Specific examples of the amide-modified silicone represented by Chemical Formula 4 include amide-modified silicone modified with hydroxyl groups at both ends having a 3-fatty acid amide propyl group and N-(2-fatty acid amide ethyl)-3-aminopropyl group in the side chain. Among them, amide-modified silicone modified with hydroxyl groups at both ends having N-(2-fatty acid amidoethyl)-3-aminopropyl group in the side chain is more preferred.

The amide-modified silicone represented by Chemical Formula 4 has an amide equivalent determined by a general titration method in which a sample is precisely weighed in a 1:1 mixed solvent of isopropyl alcohol and xylene and titrated with a 0.1N hydrochloric acid aqueous solution. It is preferably from 3000 to 30000 g/mol.

(Specific higher fatty acid salt)
The specific higher fatty acid salt used in the treating agent of the present invention is represented by the following chemical formula 6.

R ^{5 in} Chemical formula 6 is the residue obtained by removing one carboxyl group from a fatty acid having 12 to 22 carbon atoms such as lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid and behenic acid. And M is (1) a metal atom having a monovalent valence such as lithium, sodium and potassium, and (2) a divalent valence such as beryllium, magnesium, calcium, barium, manganese, nickel and zinc. And (3) a metal atom having a trivalent valence such as aluminum, iron and cerium, and n is an integer of 1 to 3.

Specific examples of the higher fatty acid salt represented by Chemical formula 6 include potassium laurate, sodium laurate, lithium laurate, potassium myristate, sodium myristate, lithium myristate, potassium palmitate, and palmitine. Acid sodium salt, lithium palmitate salt, potassium stearate salt, sodium stearate salt, lithium stearate salt, potassium arachiate salt, sodium arachiate acid, lithium arachiate salt, potassium behenate salt, sodium behenate salt, behen Acid lithium salt, magnesium dilaurate salt, calcium dilaurate salt, zinc dilaurate salt, magnesium dimyristate salt, calcium dimyristate acid, zinc dimyristate acid, magnesium dipalmitate salt, calcium dipalmitate salt, diamine salt Zinc palmitate, magnesium distearate, calcium distearate, zinc distearate, magnesium diarachinate, calcium diarachinate, zinc diarachiate, magnesium dibehenate, calcium dibehenate, zinc dibehenate, Myristic acid magnesium palmitate, Myristic acid calcium palmitate, Myristic acid zinc palmitate, Myristic acid magnesium stearate, Myristic acid calcium stearate, Myristic acid zinc stearate, Palmitic acid magnesium stearate, Palmitic acid Examples thereof include calcium stearate, zinc palmitate stearate, aluminum tristearate and iron tristearate. Among them, magnesium dimyristate, magnesium dipalmitate, magnesium distearate, calcium distearate. Salt, myristic acid magnesium palmitate salt, palmitic acid magnesium stearate salt, palmitic acid magnesium stearate salt, calcium distearate calcium salt, stearic acid sodium salt, and mixtures thereof such that M in Formula 6 is 1 or 2 A metal atom having a valence, n being an integer of 1 and 2 and having an average particle diameter determined by a laser diffraction method of 0.1 to 1.0 μm is preferable.

(Other ingredients)
Other components may be used in combination with the treatment agent of the present invention, if necessary, within a range that does not impair the effects of the present invention. Examples of such other components include components known as fiber treatment agents such as antistatic agents, anti-sticking agents, binders, wettability improvers, ultraviolet absorbers, antioxidants and preservatives.

(Content ratio of smoothing agent, specific amide-modified silicone, and specific higher fatty acid salt)
The treating agent of the present invention preferably contains the leveling agent in a proportion of 56 to 99.8% by mass, and more preferably in a proportion of 76.5 to 99.8% by mass.

The treatment agent of the present invention preferably contains the amide-modified silicone represented by Chemical formula 4 in a proportion of 0.08 to 20% by mass, and more preferably in a proportion of 0.09 to 5% by mass.

The treatment agent of the present invention preferably contains the higher fatty acid salt represented by Chemical formula 6 in a proportion of 0.08 to 10% by mass, more preferably 0.09 to 10% by mass.
Further, in the treating agent of the present invention, when the total content of the leveling agent, the amide-modified silicone represented by Chemical formula 4 and the higher fatty acid salt represented by Chemical formula 6 is 100% by mass, the content of the smoothing agent is 70%. To 99.8% by mass, the content ratio of the amide-modified silicone shown in Chemical formula 4 is 0.1 to 20% by mass, and the content ratio of the higher fatty acid salt shown in Chemical formula 6 is 0.1 to 10% by mass. Is preferable, the content ratio of the leveling agent is 85 to 99.8% by mass, the content ratio of the amide-modified silicone shown in Chemical formula 4 is 0.1 to 5% by mass, and The content ratio of the fatty acid salt is more preferably 0.1 to 10% by mass.

Next, the method for treating the polyurethane elastic fiber of the present invention (hereinafter referred to as the treatment method of the present invention) will be described. The treatment method of the present invention is a neat lubrication method without diluting the treatment agent of the present invention, and a polyurethane lubrication fiber of 100% by mass is produced by a known method such as a guide lubrication device, a roller lubrication device, or a spray lubrication device. The treatment method is characterized in that the treatment is carried out by adhering so as to have a ratio of 0.1 to 10 mass %.

In the present invention, a polyurethane-based elastic fiber means an elastic fiber substantially having polyurethane as a main constituent, and is usually a fiber spun from a long-chain polymer containing 85% by mass or more of segmented polyurethane. means.

The long-chain polymer has so-called soft segments and hard segments. The soft segment is a relatively long-chain segment such as polyether, polyester, and polyether ester, and the hard segment is a relatively short-chain segment derived from the reaction of an isocyanate with a diamine or diol chain extender. .. Such long chain polymers are typically prepared by capping a hydroxyl terminated soft segment precursor with an organic diisocyanate to form a prepolymer and chain extending the prepolymer with a diamine or diol.

Regarding the soft segment, the above-mentioned polyethers include those derived from tetramethylene glycol, 3-methyl-1,5-pentanediol, tetrahydrofuran, 3-methyltetrahydrofuran, etc. Among them, derived from tetramethylene glycol. What is carried out is preferable. Further, the above polyesters include those derived from ethylene glycol, tetramethylene glycol, 2,2-dimethyl-1,3-propanediol and the like and dibasic acids such as adipic acid and succinic acid. Further, the above-mentioned polyether ester includes those derived from polyether and polyester.

Examples of the organic diisocyanate used for capping the soft segment precursor include bis-(p-isocyanatophenyl)-methane (MDI), tolylene diisocyanate (TDI), bis-(4-isocyanatocyclohexyl)-methane (PICM). ), hexamethylene diisocyanate, 3,3,5-trimethyl-5-methylenecyclohexyl diisocyanate and the like, among which MDI is preferred.

Examples of the diamine used for chain extension of the prepolymer include ethylenediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine and the like.
Examples of the diol used for chain extension of the prepolymer include ethylene glycol, 1,3-propanediol, 4-butanediol, neopentyl glycol, 1,2-propylene glycol, 1,4-cyclohexanedimethanol, 1, Examples thereof include 4-cyclohexanediol, 1,4-bis(β-hydroxyethoxy)benzene, bis(β-hydroxyethyl)terephthalate and paraxylylenediol. The long-chain polymer that is a raw material for the polyurethane elastic fiber has been described above, but the method for polymerizing the long-chain polymer is not particularly limited in the present invention.

The long-chain polymer used as the raw material for polyurethane-based elastic fibers is a benzotriazole-based UV absorber, a hindered amine-based weathering agent, a hindered phenol-based antioxidant, various pigments such as titanium oxide and iron oxide. , Barium sulfate, zinc oxide, cesium oxide, functional additives such as silver ions, and the like can be contained.

Examples of the solvent used when spinning a polyurethane elastic fiber using a long-chain polymer as a raw material include N,N-dimethylacetamide (DMAc), dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone. DMAc is preferred. It is suitable for the dry spinning method using a solvent that the concentration of the long-chain polymer is 30 to 40% by mass, particularly 35 to 38% by mass, based on the total mass of the solution.

Usually, when a diol is used as the chain extender, the polyurethane elastic fiber is spun by a melt spinning method, a dry spinning method or a wet spinning method, and when a diamine is used as the chain extender, the polyurethane elastic fiber is a dry type. It is spun by the spinning method. In the present invention, the spinning method is not particularly limited, but a dry spinning method using a solvent is preferable.

Finally, the polyurethane elastic fiber according to the present invention will be described. The polyurethane elastic fiber according to the present invention is a polyurethane elastic fiber to which the treating agent of the present invention is attached, and can be obtained by the treatment method described above.

According to the present invention described above, the dispersion stability of the higher fatty acid salt in the polyurethane elastic fiber treating agent is improved. Further, it is possible to obtain a polyurethane-based elastic fiber that can suppress defective winding shape when a wound body is formed and can improve the processed quality of a processed product.

In particular, when the amide-modified silicone represented by Chemical Formula 4 is one in which X ¹ and X ² are hydroxyl groups, the effect of improving the texture of the processed product becomes large.
When p is an integer of 15 to 700 and R ¹ is a methyl group is used as the amide-modified silicone represented by Chemical formula 4, the processing quality by suppressing scum generation during processing is improved. The effect to improve becomes large.

When p is an integer of 100 to 500, q is an integer of 1 to 10 and the amide equivalent is 3000 to 30000 g/mol as the amide-modified silicone represented by Chemical formula 4, At the same time, the viscosity stability of the polyurethane-based elastic fiber treatment agent is improved, and the effect of suppressing defective winding shape and the effect of improving the processed quality by suppressing yarn breakage due to improved smoothness and rubbing are achieved at a high level. It can be compatible.

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

Test Category 1 (Preparation of smoothing agent)
When it is composed of two or more components, they are mixed in the proportions (mass ratios) shown in Table 1 to prepare the smoothing agent shown in Table 1.

Details of each component shown in Table 1 are as follows.
S5: Polydimethylsiloxane having a kinematic viscosity of 5 mm ² /s at 25° C. S10: Polydimethylsiloxane having a kinematic viscosity of 10 mm ² /s at 25° C. S20: Polydimethyl having a kinematic viscosity of 20 mm ² /s at 25° C. Siloxane S30: Polydimethylsiloxane having a kinematic viscosity of 30 mm ² /s at 25° C. S50: Polydimethylsiloxane having a kinematic viscosity of 50 mm ² /s at 25° C. M6: Mineral having a kinematic viscosity of 6 mm ² /s at 25° C. Oil M10: Mineral oil having a kinematic viscosity of 10 mm ² /s at 25° C. M15: Mineral oil having a kinematic viscosity of 15 mm ² /s at 25° C. M21: Mineral oil having a kinematic viscosity of 21 mm ² /s at 25° C. M40 : Mineral oil having a kinematic viscosity at 25°C of 40 mm ² /s Test Category 2 (Synthesis of amide-modified silicone)
-Synthesis of amide-modified silicone (AS-1) 27,000 g of hydroxyl group-modified polydimethylsiloxane having both terminals at the siloxane repeating unit of 40, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g, potassium hydroxide 40% 3.3 g of the aqueous solution was placed in a glass reaction container, heated to 90° C. with stirring, and reacted for 4 hours. Then, 32 g of water was added, dehydration operation was performed under reduced pressure, and filtration was performed using Celite to obtain 27,000 g of amino-modified silicone. 2814 g of oleic acid was placed in 27,000 g of the amino-modified silicone obtained, and the temperature was raised to 120° C. with stirring and the reaction was carried out for 4 hours under a nitrogen stream. Then, the reaction product was cooled to obtain 27,000 g of amide-modified silicone (AS-1).

-Synthesis of amide-modified silicones (AS-2) to (AS-9) (AS-11) The repeating unit of the siloxane moiety is changed according to the values of p and q in the general formula shown in Chemical formula 4, and hydroxyl groups at both terminals are changed. In addition to the modified polydimethylsiloxane and the combined use, an amine and a fatty acid corresponding to the structure of X ³ were used, and synthesis was performed in the same manner as the amide modified silicone (AS-1).

-Synthesis of amide-modified silicone (AS-10) N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine was replaced with 3-(dimethoxymethylsilyl)propylamine, and synthesized in the same manner as amide-modified silicone (AS-1). I went.

-Synthesis of amide-modified silicone (AS-12) 30543 g of both-terminal silanol-modified polydimethylsiloxane having 40 siloxane repeating units, 1032 g of N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine, 40% potassium hydroxide 4.0 g of the aqueous solution was placed in a glass reaction container, heated to 90° C. with stirring, and reacted for 4 hours. After that, 135 g of water was added and dehydration operation was carried out under reduced pressure, then 60 g of dimethyldimethoxysilane was added, reaction was carried out at 90° C. for 2 hours while stirring, demethanol was carried out under reduced pressure, and filtration was carried out using Celite. , 31,000 g of amino-modified silicone was obtained. 85 g of terephthalic acid was added to 31000 g of the amino-modified silicone obtained, and the temperature was raised to 120° C. with stirring in a glass reaction container, and the reaction was performed for 4 hours under a nitrogen stream. Then, the reaction product was cooled to obtain 31000 g of an amide-modified silicone (AS-12).

-Synthesis of amino-modified silicone (Ras-1) Hexamethyldisiloxane 162, water 18g, potassium hydroxide 40% aqueous solution 10.3g, octamethylcyclotetrasiloxane 13320g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, filtered using Celite, and amino-modified silicone (Ras). -1) 13000g was obtained.

Synthesis of amino-modified silicone (Ras-2) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 0.4 g, dimethyldimethoxysilane 361 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g The mixture was placed in a glass reaction vessel, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, filtered using Celite, and amino-modified silicone (Ras-2 was used. ) 500 g was obtained.

-Synthesis of amide-modified silicone (Ras-3) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 5.2 g, octamethylcyclotetrasiloxane 5932 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 413 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, and filtered using Celite to obtain 6400 g of amino-modified silicone. Obtained. To 6400 g of the amino-modified silicone obtained, 291 g of adipic acid was placed in a glass reaction vessel, heated to 120° C. with stirring, and reacted for 4 hours under a nitrogen stream. Then, the reaction product was cooled to obtain 6655 g of amide-modified silicone (Ras-3).

-Synthesis of amide-modified silicone (Ras-4) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 2.4 g, octamethylcyclotetrasiloxane 2225 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 413 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, and filtered using Celite to obtain 2700 g of amino-modified silicone. Obtained. To 2700 g of the obtained amino-modified silicone, 419 g of trimellitic acid was placed in a glass reaction container, heated to 120° C. with stirring, and reacted under a nitrogen stream for 4 hours. Then, the reaction product was cooled to obtain 3082 g of an amide-modified silicone (Ras-4).

-Synthesis of amide-modified silicone (Ras-5) 2505 g of methylhydrogenpolydimethylsiloxane (composed of 2 methylhydrogensiloxane units, 30 dimethylsiloxane units, 1 trimethylsiloxane unit and 1 trimethylsilyl unit) 897 g of pentanoyl polyalkylene glycol monoallyl ether (polyalkylene glycol in which 3 ethyleneoxy units and 3 propyleneoxy units are randomly bonded), 0.1 g of platinum chloride hexahydrate as a catalyst and 2000 ml of toluene as a reaction vessel The temperature of the reaction system was kept at 110° C., and the addition reaction was carried out for 10 hours. After xylene was distilled off under reduced pressure from the reaction system, the catalyst was filtered off to obtain a polyether-modified silicone as an intermediate. Separately, 490 g of 3-aminopropylmethyldimethoxysilane and 144 g of water were charged into a reaction vessel, the temperature of the reaction system was kept at 40° C., a polymerization reaction was performed for 2 hours, and then dehydration treatment under reduced pressure was performed at 80° C. for 2 hours to obtain an intermediate. As a result, an amino group-containing polysiloxane was obtained. 1701 g of the polyether-modified silicone thus obtained and 135 g of the amino group-containing polysiloxane were charged into a reaction vessel and uniformly mixed, and then 0.1 g of potassium hydroxide was added to the reaction system to keep the temperature of the reaction system at 98° C. for 24 hours. Was done. After neutralizing the reaction product with acetic acid, 193 g of trimellitic anhydride was further added, and the temperature of the reaction system was adjusted to 150 to 175° C. to carry out an amidation reaction for 6 hours to obtain an amide-modified silicone (Ras-5).

-Synthesis of amide-modified silicone (Ras-6) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 10.4 g, octamethylcyclotetrasiloxane 11123 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, filtered using Celite, and 11000 g of amino-modified silicone was obtained. Obtained. 160 g of terephthalic acid was placed in 11,000 g of the obtained amino-modified silicone in a glass reaction container, and the temperature was raised to 120° C. with stirring, and the reaction was carried out under a nitrogen stream for 4 hours. Then, the reaction product was cooled to obtain 11142 g of amide-modified silicone (Ras-6).

The constitution of each modified silicone is shown in Table 2.

In Table 2, "B-1" is _- a ^{_{"C 3 H 6 -COO-Y 1}} -OC-C 4 H 9 " polyether-modified group represented by and, three ^{Y 1} is propyleneoxy units It is a polyether-modified group in the case where it is a polyalkyleneoxy group in which 3 ethyleneoxy units are randomly bonded.

Test Category 3 (Preparation of polyurethane type elastic fiber treatment agent)
-Example 1
A mixture of 49 parts of polydimethylsiloxane (S20) having a viscosity of 20 mm ² /s at 25° C. and 49 parts of mineral oil (M21) having a viscosity of 21 mm ² /s at 25° C. shown in Table 3 as a leveling agent. 98 parts of a smoothing agent (L-1), 1 part of an amide-modified silicone (AS-1) shown in Table 2, and 1 part of magnesium distearate magnesium salt (SM-P manufactured by Sakai Chemical Co., Ltd.) as a higher fatty acid salt were added, The mixture was mixed at a temperature within the range of 20 to 35° C. until uniform, and then wet pulverized using a horizontal bead mill to prepare a colloidally dispersed polyurethane elastic fiber treatment agent.

-Examples 2-18 and Comparative Examples 1-3
In the same manner as the elastic fiber treatment agent of Example 1, the polyurethane elastic fiber treatment agents of Examples 2 to 18 and the polyurethane elastic fiber treatment agents of Comparative Examples 1 to 3 were prepared. The contents of these are summarized in Table 3.

Details of each component shown in Table 3 are as follows.
L-1 to L-9: Smoothing agent described in Table 1 M-1: Magnesium stearate M-2: Calcium distearate M-3: Sodium stearate M-4: Magnesium dicaprylate M-5 : Zinc distearate salt AS-1 to AS-12, Ras-1 to Ras-6: Amino-modified silicone and amide-modified silicone shown in Table 2 Ras-7: Viscosity 900 mm ² /s (25° C.), functional group equivalent 2700 g/mol amide polyether modified silicone Test Category 4 (Evaluation of polyurethane-based elastic fiber treatment agent)
The average particle size of the higher fatty acid salt, the dispersion stability, and the increase in viscosity of the polyurethane-based elastic fiber treating agents of each example prepared in Test Category 2 were evaluated as follows. The results are summarized in Table 3.

-Measurement method of average particle size Polyurethane-based elastic fiber treating agent was added to polydimethylsiloxane having a viscosity at 25°C of 10 mm ² /s, and the concentration of dispersoid in the polyurethane-based elastic fiber treating agent was 1000 mg/ It was diluted to L and the diluted solution was subjected to a laser diffraction type particle size distribution measuring device at a liquid temperature of 25° C. to measure a volume-based average particle diameter.

-Evaluation of dispersion stability 100 ml of the polyurethane type elastic fiber treating agent of each example was put into a 100 ml graduated cylinder made of glass with a sealed stopper, left at 40°C for 1 month, and immediately after preparation and after 1 month of polyurethane type The appearance of the treatment agent for elastic fibers was observed and evaluated according to the following criteria.

⊚: There is no change in appearance in a uniformly dispersed state.
◯: A transparent layer of less than 5 ml was generated.
X: A transparent layer of 5 ml or more was generated or precipitation was generated.

-Evaluation of change in viscosity Using an E-type viscometer (DVH-E type, manufactured by TOKIMEC), the viscosity at 30°C of the polyurethane-based elastic fiber treating agent of each example immediately after preparation was measured with a rotor E and 20 rpm. , Initial viscosity V ₁ (Pa·s). Further, the polyurethane-based elastic fiber treatment agent of each example was placed in a glass container with a hermetically sealed stopper, allowed to stand at 40° C. for 6 months, the viscosity at 30° C. was measured again, and the viscosity V ₂ (Pa·s ). Then, V ₂ /V ₁ was calculated and evaluated according to the following criteria.

⊚: V ₂ /V ₁ is less than 1.3 ◯: V ₂ /V ₁ is 1.3 or more and less than 1.5 ×: V ₂ /V ₁ is 1.5 or more, as is clear from the results in Table 3. The treatment agent of the present invention maintains the initial state for a long period of time and is excellent in dispersion stability and viscosity stability. The treatment agent of the present invention has little change in properties during long-term storage and transportation, and maintains excellent dispersion stability and viscosity stability, and thus is easy to use.

In addition, as the amide-modified silicone represented by Chemical formula 4, p is an integer of 100 to 500, q is an integer of 1 to 10, and the amide equivalent is 3000 to 30000 g/mol. In No. 6, the viscosity stability is further improved as compared with Examples 7 to 12 in which those that do not meet the requirements are used.

・Test Category 5 (Adhesion and evaluation of treatment agent for polyurethane elastic fiber to polyurethane elastic fiber)
Adhesion of polyurethane elastic fiber treatment agent to polyurethane elastic fiber A mixture of bis-(p-isocyanatephenyl)-methane/tetramethylene ether glycol (number average molecular weight 1800)=1.58/1 (molar ratio) was added. After reacting at 90° C. for 3 hours by a conventional method to obtain capped glycol, this capped glycol was diluted with N,N′-dimethylacetamide (hereinafter referred to as DMAc). Next, a DMAc solution containing ethylenediamine and diethylamine was added to the DMAc solution of the above-mentioned capped glycol, mixed at room temperature using a high-speed stirring device, and chain-extended to obtain a polymer. Further, DMAc was added to obtain a DMAc solution having a polymer concentration of about 35% by mass. Titanium oxide was added to the polymer in a DMAc solution of 4.7% by mass, a hindered amine-based weather-resistant agent was 3.0% by mass, and A hindered phenolic antioxidant was added to 1.2% by mass and mixed to prepare a uniform polymer mixed solution. Using this polymer mixed solution, a 44 dtex elastic yarn consisting of 4 single yarns was spun by a dry spinning method used in a known spandex, and a processing agent for polyurethane-based elastic fibers of each example was obtained from an oiling roller before winding. Was oiled in a neat state. The roller-lubricated material was wound at a winding speed of 550 m/min, and wound on a cylindrical paper tube having a length of 57 mm through a traverse guide giving a winding width of 42 mm, using a surface drive winder, and dry spinning. A polyurethane elastic fiber package was obtained. The amount of the polyurethane-based elastic fiber treatment agent deposited was adjusted by adjusting the rotation speed of the oiling roller, and the target value of 5.5% was applied.

-Measurement and Evaluation The dry-spun polyurethane-based elastic fiber package obtained above was subjected to the following measurements and evaluations, and the results are summarized in Table 3.

-Evaluation of shape of wound body With respect to the above-mentioned package (1 kg winding), the maximum value (Wmax) and the minimum width (Wmin) of the winding width are measured, and the bulge is obtained from the difference (Wmax-Wmin) between them, and the following criteria are used. It was evaluated by.

A: The bulge is less than 4 mm.
◯: Bulge is 4 to 10 mm.
X: Bulge is 10 mm or more.

-Evaluation of scum generation during processing Ten pieces of the package (1 kg wound) wound body were made into a miniature warping machine and wound up at 25°C in an atmosphere of 65% RH at a yarn speed of 300 m/min for 1500 km. At this time, the accumulation state of scum on the comb guide of the miniature warping machine was visually observed and evaluated according to the following criteria.

⊚: Scum hardly adhered.
◯: The scum was slightly attached, but there was no problem in the stable running of the yarn.
X: A large amount of scum was attached and accumulated, and there was a great problem in stable running of the yarn.

・Evaluation of smoothness Using a friction measurement meter (SAMPLE FRICTION UNIT MODEL TB-1 manufactured by Eiko Sokki Co., Ltd.), a chrome-plated satin finish pin with a diameter of 1 cm and a surface roughness of 2S is arranged between two free rollers, and this chrome is used. The contact angle of the polyurethane elastic fiber withdrawn from the above-mentioned package (roll of 500 g) was 90 degrees with respect to the plated satin finish pin. Under the condition of 25% and 60% RH, the initial tension (T ₁ ) of 5 g is applied on the inlet side, and the secondary tension (T ₂ ) on the outlet side when running at a speed of 100 m/min is set every 0.1 seconds. It was measured for 1 minute. The friction coefficient was calculated from the following equation 1 and evaluated according to the following criteria.

A: The coefficient of friction is 0.150 or more and less than 0.220.
◯: The coefficient of friction is 0.220 or more and less than 0.260.
Δ: The coefficient of friction is 0.260 or more and less than 0.300.

X: The friction coefficient is 0.300 or more.
-Evaluation of texture A woven fabric stretch fabric was produced using the sample yarn, post-processing such as dyeing was performed, and the appearance quality was evaluated. First, the sample yarn was covered with a cationic dyeable polyester yarn (168 dtex/48 fil). At that time, the covering yarn was obtained with a twist number of 450 t/m and a draft of 3.0 for the weft yarn, and a twist number of 700 T/M and a draft of 3.5. The covering yarn was used for the vertical yarn. Next, the obtained covering yarns were respectively used as a weft yarn and a warp yarn, and after warping the warp yarns with 5100 warp yarns (1100 warp winding warp yarns), the fabrics were woven with a 2/1 twill design using a Levia loom. .. The weaving machine obtained by weaving is subjected to scouring processing, intermediate setting (185°C) and weight reduction processing according to a conventional method, and further dyeing processing using a cationic dye, drying, finishing agent treatment, and 180°C, cloth 20 m/min, Finishing setting was performed under the condition of the set zone 24 m.

The texture of the stretched fabric after the post-processing in this way was evaluated based on the following criteria, mainly focusing on the waviness of the fabric.
⊚: No waviness and smooth texture

◯: Rippling, but hardly noticeable.
X: Wavy and worrisome to the touch.
As is clear from the results of Table 3, according to the treatment agent and the treatment method of the present invention, a package having a good winding shape can be obtained in the production of polyurethane elastic fibers, and scum is generated in the post-processing. It is possible to obtain a polyurethane-based elastic fiber in which the yarn breakage due to abrasion or abrasion is small, and as a result, the surface of the knitted fabric is smooth and the processed quality is excellent.

Particularly, Examples 1 to 14 using the amide-modified silicone represented by Chemical Formula 4 in which X ¹ and X ² are hydroxyl groups are compared with Examples 15 to 17 using those not satisfying the requirements. And the texture is further improved.

In addition, in Examples 1 to 12 in which p is an integer of 15 to 700 and R ¹ is a methyl group, the amide-modified silicone represented by Chemical Formula 4 is used. Compared to Examples 13 to 14, scum generation during processing is further suppressed.

In addition, as the amide-modified silicone represented by Chemical formula 4, p is an integer of 100 to 500, q is an integer of 1 to 10, and the amide equivalent is 3000 to 30000 g/mol. In No. 6, as compared with Examples 7 to 12 in which those that do not meet the requirements are used, the effect of suppressing defective winding shape and the effect of improving the smoothness of the synthetic fiber are compatible at a high level.

The present invention relates to a treatment agent for polyurethane-based elastic fibers that is used by being attached to polyurethane-based elastic fibers, a method for treating polyurethane-based elastic fibers, and a polyurethane-based elastic fiber.

Conventionally, a treatment agent for elastic fibers containing an amino-modified polysiloxane in which hydrogen atoms, an alkyl group, a carboxyl group, and an alkylene oxide group are localized at both ends (see, for example, Patent Document 1), a metal soap having a specific particle size ( Higher fatty acid salt) and an amino-modified silicone having a methyl group at the end (see, for example, Patent Document 2), an elastic fiber treatment agent containing a highly polymerized amino-modified silicone (for example, Patent Document) 3) has been proposed, but these conventional treatment agents for elastic fibers have poor dispersion stability of higher fatty acid salts, cannot obtain an excellent winding shape, and cannot meet the requirements of high processing quality. There is.

JP, 10-053960, A JP, 2000-144578, A JP, 2003-201678, A

The problem to be solved by the present invention is to improve the dispersion stability of a higher fatty acid salt, suppress a defective winding shape in the case of a wound body, and improve the processing quality of a processed product. A treatment agent for a polyurethane-based elastic fiber for obtaining a fiber and a method for treating a polyurethane-based elastic fiber are provided. Another object of the present invention is to provide a polyurethane-based elastic fiber capable of improving the dispersion stability of a higher fatty acid salt, suppressing a defective winding shape when a wound body is formed, and improving the processed quality of a processed product.

As a result of research to solve the above problems, the present inventors have improved the dispersion stability of higher fatty acid salts, suppressed the defective winding shape in the case of a wound body, and improved the processed quality of the processed product. In order to obtain a polyurethane-based elastic fiber that can be used, it is correct and preferable to use an elastic fiber treatment agent in which a specific higher fatty acid metal salt is colloidally dispersed in a specific smoothing agent and a specific modified silicone. I found it.

A treatment agent for polyurethane-based elastic fibers that solves the above problems is a treatment agent for polyurethane-based elastic fibers that is used by being attached to polyurethane-based elastic fibers, and includes a smoothing agent, an amide-modified silicone represented by the following chemical formula 1, and It contains a higher fatty acid metal salt represented by Chemical Formula 3 below, and the smoothing agent contains at least one of a silicone oil other than the amide-modified silicone, a mineral oil, a fatty acid ester, and a liquid polyolefin. kinematic viscosity Ri 5 to 50 mm ² / s der, wherein the amide-modified silicone, amide equivalent Ru 3000~30000g / mol der.

In Chemical formula 1, X ¹ and X ² are hydroxyl groups . X ³ is an amide-modifying group represented by the following chemical formula 2. R ¹ is an alkyl group having 1 to 5 carbon atoms. p is an integer of 100 to 500 . q is an integer of 1-10 .

In Chemical formula 2, R ² and R ³ are alkylene groups having 2 to 5 carbon atoms. R ⁴ is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent carboxylic acid. r is 0 or 1.

In Chemical formula 3, R ⁵ is a residue obtained by removing one carboxyl group from a fatty acid having 12 to 22 carbon atoms. M is a metal atom having an valence of n, and n is an integer of 1 to 3.

In the above polyurethane-based elastic fiber treating agent, in the amide-modified silicone, X ¹ and X ² in Chemical formula ¹ are methyl groups or hydroxyl groups, and at least one of X ¹ and X ² is a hydroxyl group. It is preferably in some cases.

In the above polyurethane-based elastic fiber treating agent, when the total content of the leveling agent, the amide-modified silicone, and the higher fatty acid metal salt is 100% by weight, the leveling agent is 85 to 99.8% by weight, and It is preferable to contain the amide-modified silicone in an amount of 0.1 to 5% by mass and the higher fatty acid metal salt in an amount of 0.1 to 10% by mass.

In the method for treating a polyurethane elastic fiber for solving the above problems, the treatment agent for a polyurethane elastic fiber is adhered to the synthetic fiber in an amount of 0.1 to 10% by mass relative to 100% by mass.

The polyurethane elastic fiber for solving the above-mentioned problems has the above-mentioned treatment agent for polyurethane elastic fiber attached thereto.

ADVANTAGE OF THE INVENTION According to this invention, while improving the dispersion stability of a higher fatty acid salt, suppressing the defective winding shape when it is made into a wound body, and obtaining the polyurethane type elastic fiber which can improve the processed quality of a processed product. You can

First, the processing agent for polyurethane elastic fibers according to the present invention (hereinafter referred to as the processing agent of the present invention) will be described. The treating agent of the present invention comprises a leveling agent, a specific amide-modified silicone represented by the following chemical formula 4 and a specific higher fatty acid salt represented by the following chemical formula 6.

(Smoothing agent)
The leveling agent used in the treatment agent of the present invention is one or more selected from silicone oils other than the amide-modified silicone represented by Chemical formula 4, mineral oils, fatty acid esters and liquid polyolefins, and has a kinematic viscosity at 25°C. Is 5 to 50 mm ² /s. Specific examples of silicone oils other than the amide-modified silicone represented by Chemical Formula 4 include (1) polydimethylsiloxanes having repeating units of dimethylsiloxane units, (2) repeating units having dimethylsiloxane units and 2 to 2 carbon atoms. Examples of the known products include polydialkylsiloxanes composed of a dialkylsiloxane unit having an alkyl group of 4 and (3) polysiloxanes composed of a dimethylsiloxane unit and a methylphenylsiloxane unit as repeating units. Has the following:

Polydimethylsiloxane having a kinematic viscosity at 25° C. of 5 mm ² /s (trade name KF-96L-5cs manufactured by Shin-Etsu Chemical Co., Ltd.), polydimethylsiloxane having a kinematic viscosity at 25° C. of 10 mm ² /s (Shin-Etsu Chemical KF-96-10cs manufactured by Kogyo Co., Ltd., polydimethylsiloxane having a kinematic viscosity of 20 mm ² /s at 25° C. (KF-96-20cs manufactured by Shin-Etsu Chemical Co., Ltd.), kinematics at 25° C. Polydimethylsiloxane having a viscosity of 30 mm ² /s (trade name KF-96-30cs manufactured by Shin-Etsu Chemical Co., Ltd.), polydimethylsiloxane having a kinematic viscosity at 25° C. of 50 mm ² /s (manufactured by Shin-Etsu Chemical Co., Ltd. Trade name KF-96-50cs).

Examples of the mineral oil include general petroleum fractions containing a paraffin component, a naphthene component, an aroma component, and the like, and known examples of the products include the following. Mineral oil having a kinematic viscosity of 10 mm ² /s at 25° C. (trade name: Cosmo Pure Spin D manufactured by Cosmo Oil Lubricants Co., Ltd.), mineral oil having a kinematic viscosity of 15 mm ² /s at 25° C. (manufactured by Fuji Kosan Co., Ltd. Product name of Fucor NT-60), and a mineral oil having a kinematic viscosity at 25° C. of 40 mm ² /s (Fucoal NT-100 manufactured by Fuji Kosan Co., Ltd.).

Examples of the fatty acid ester include an aliphatic monohydric alcohol and an aliphatic monocarboxylic acid such as butyl stearate, octyl stearate, oleyl laurate, oleyl oleate, isotridecyl stearate, and isopentacosanyl isostearate. Of 1,6-hexanediol didecanoate, trimethylolpropane monooleate monolaurate, trimethylolpropane trilaurate, castor oil and other natural fats and oils and aliphatic monocarboxylic acids Examples thereof include esters, dilauryl adipate, dioleyl azelate and the like, and esters of an aliphatic monohydric alcohol with an aliphatic polyvalent carboxylic acid.

Examples of liquid polyolefins include poly-α-olefins obtained by polymerizing 1-butene, 1-hexene, 1-decene and the like. Among them, those containing silicone oil such as polydimethylsiloxane are preferable.

The kinematic viscosity of the leveling agent is determined by a method using a Canon Fenske viscometer described in JIS-K2283 (Kinematic viscosity test method for petroleum products), and a kinematic viscosity at 25° C. of 5 to 50 mm ² /s is used. be able to.

(Specific amide-modified silicone)
The specific amide-modified silicone used for the treating agent of the present invention is represented by the following chemical formula 4.

X in chemical formula 4 ¹ , X ^Two Is a hydroxyl group.

In addition, as a reference example , X ¹ and X ² in Chemical formula 4 are an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a protoxy group, and a butoxy group, a methyl group or a hydroxyl group, and X1, and The case where at least one of X2 is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group is exemplified . Of these X ¹ and X ² is a methyl group or a hydroxyl group, and is preferably a case where at least one of X ¹ and X ² is a hydroxyl group, more those when X ¹ and X ² is a hydroxyl group preferable.

X ^{3 in} Chemical formula 4 is an amide-modifying group represented by Chemical formula 5 below.

R ² and R ^{3 in} Chemical formula 5 are alkylene groups having 2 to 5 carbon atoms such as an ethylene group, a propylene group, a butylene group, and a pentylene group, and r is 0 or 1. R ⁴ is a residue obtained by removing one hydroxyl group from a monovalent to tetravalent carboxylic acid, and the carboxylic acid is not particularly limited in its carbon number, presence or absence of branching, valence, etc., and may be a higher fatty acid. , A cyclic fatty acid or an aromatic ring-containing fatty acid may be used. Examples of the fatty acid include caprylic acid, 2-ethylhexylic 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, sebacine. Acid, benzoic acid, etc. are mentioned.

R ¹ in the above Chemical Formula 4 is an alkyl group having 1 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group, a pentyl group, p is an integer of 100 to 500 , and q is 1 to It is an integer of 10 .

As a reference example, p is an integer of 4 to 1200 and q is an integer of 1 to 100. Among them, p is an integer of 15 to 700, and R ¹ Is a methyl group, p is an integer of 100 to 500, and q in Chemical formula 4 is more preferably an integer of 1 to 10.

The amide-modified silicone represented by Chemical Formula 4 may be a random copolymer or a block copolymer.
Specific examples of the amide-modified silicone represented by Chemical Formula 4 include amide-modified silicone modified with hydroxyl groups at both ends having a 3-fatty acid amide propyl group and N-(2-fatty acid amide ethyl)-3-aminopropyl group in the side chain. Among them, amide-modified silicone modified with hydroxyl groups at both ends having N-(2-fatty acid amidoethyl)-3-aminopropyl group in the side chain is more preferred.

Amide-modified silicone emission represented by Formula 4, 1 of isopropyl alcohol and xylene: 1 sample was precisely weighed in a mixed solvent, the amide equivalent determined by a general titrimetric method of performing titration with 0.1N aqueous hydrochloric acid solution It is 3000 to 30000 g/mol .

(Specific higher fatty acid salt)
The specific higher fatty acid salt used in the treating agent of the present invention is represented by the following chemical formula 6.

R ^{5 in} Chemical formula 6 is the residue obtained by removing one carboxyl group from a fatty acid having 12 to 22 carbon atoms such as lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid and behenic acid. And M is (1) a metal atom having a monovalent valence such as lithium, sodium and potassium, and (2) a divalent valence such as beryllium, magnesium, calcium, barium, manganese, nickel and zinc. And (3) a metal atom having a trivalent valence such as aluminum, iron and cerium, and n is an integer of 1 to 3.

Specific examples of the higher fatty acid salt represented by Chemical formula 6 include potassium laurate, sodium laurate, lithium laurate, potassium myristate, sodium myristate, lithium myristate, potassium palmitate, and palmitine. Acid sodium salt, lithium palmitate salt, potassium stearate salt, sodium stearate salt, lithium stearate salt, potassium arachiate salt, sodium arachiate acid, lithium arachiate salt, potassium behenate salt, sodium behenate salt, behen Acid lithium salt, magnesium dilaurate salt, calcium dilaurate salt, zinc dilaurate salt, magnesium dimyristate salt, calcium dimyristate acid, zinc dimyristate acid, magnesium dipalmitate salt, calcium dipalmitate salt, diamine salt Zinc palmitate, magnesium distearate, calcium distearate, zinc distearate, magnesium diarachinate, calcium diarachinate, zinc diarachinate, magnesium dibehenate, calcium dibehenate, zinc dibehenate, Myristic acid magnesium palmitate, Myristic acid calcium palmitate, Myristic acid zinc palmitate, Myristic acid magnesium stearate, Myristic acid calcium stearate, Myristic acid zinc stearate, Palmitic acid magnesium stearate, Palmitic acid Examples thereof include calcium stearate, zinc palmitate stearate, aluminum tristearate and iron tristearate. Among them, magnesium dimyristate, magnesium dipalmitate, magnesium distearate, calcium distearate. Salt, myristic acid magnesium palmitate salt, palmitic acid magnesium stearate salt, palmitic acid magnesium stearate salt, calcium distearate calcium salt, stearic acid sodium salt, and mixtures thereof such that M in Formula 6 is 1 or 2 A metal atom having a valence, n being an integer of 1 and 2 and having an average particle diameter determined by a laser diffraction method of 0.1 to 1.0 μm is preferable.

(Other ingredients)
Other components may be used in combination with the treatment agent of the present invention, if necessary, within a range that does not impair the effects of the present invention. Examples of such other components include components known as fiber treatment agents such as antistatic agents, anti-sticking agents, binders, wettability improvers, ultraviolet absorbers, antioxidants and preservatives.

(Content ratio of smoothing agent, specific amide-modified silicone, and specific higher fatty acid salt)
The treating agent of the present invention preferably contains the leveling agent in a proportion of 56 to 99.8% by mass, and more preferably in a proportion of 76.5 to 99.8% by mass.

The treatment agent of the present invention preferably contains the amide-modified silicone represented by Chemical formula 4 in a proportion of 0.08 to 20% by mass, and more preferably in a proportion of 0.09 to 5% by mass.

The treatment agent of the present invention preferably contains the higher fatty acid salt represented by Chemical formula 6 in a proportion of 0.08 to 10% by mass, more preferably 0.09 to 10% by mass.
Further, in the treating agent of the present invention, when the total content of the leveling agent, the amide-modified silicone represented by Chemical formula 4 and the higher fatty acid salt represented by Chemical formula 6 is 100% by mass, the content of the smoothing agent is 70%. To 99.8% by mass, the content ratio of the amide-modified silicone shown in Chemical formula 4 is 0.1 to 20% by mass, and the content ratio of the higher fatty acid salt shown in Chemical formula 6 is 0.1 to 10% by mass. Is preferable, the content ratio of the leveling agent is 85 to 99.8% by mass, the content ratio of the amide-modified silicone shown in Chemical formula 4 is 0.1 to 5% by mass, and The content ratio of the fatty acid salt is more preferably 0.1 to 10% by mass.

Next, the method for treating the polyurethane elastic fiber of the present invention (hereinafter referred to as the treatment method of the present invention) will be described. The treatment method of the present invention is a neat lubrication method without diluting the treatment agent of the present invention, and a polyurethane lubrication fiber of 100% by mass is produced by a known method such as a guide lubrication device, a roller lubrication device, or a spray lubrication device. The treatment method is characterized in that the treatment is carried out by adhering so as to have a ratio of 0.1 to 10 mass %.

In the present invention, a polyurethane-based elastic fiber means an elastic fiber substantially having polyurethane as a main constituent, and is usually a fiber spun from a long-chain polymer containing 85% by mass or more of segmented polyurethane. means.

The long-chain polymer has so-called soft segments and hard segments. The soft segment is a relatively long-chain segment such as polyether, polyester, and polyether ester, and the hard segment is a relatively short-chain segment derived from the reaction of an isocyanate with a diamine or diol chain extender. .. Such long chain polymers are typically prepared by capping a hydroxyl terminated soft segment precursor with an organic diisocyanate to form a prepolymer and chain extending the prepolymer with a diamine or diol.

Regarding the soft segment, the above-mentioned polyethers include those derived from tetramethylene glycol, 3-methyl-1,5-pentanediol, tetrahydrofuran, 3-methyltetrahydrofuran, etc. Among them, derived from tetramethylene glycol. What is carried out is preferable. Further, the above polyesters include those derived from ethylene glycol, tetramethylene glycol, 2,2-dimethyl-1,3-propanediol and the like and dibasic acids such as adipic acid and succinic acid. Further, the above-mentioned polyether ester includes those derived from polyether and polyester.

Examples of the organic diisocyanate used for capping the soft segment precursor include bis-(p-isocyanatophenyl)-methane (MDI), tolylene diisocyanate (TDI), bis-(4-isocyanatocyclohexyl)-methane (PICM). ), hexamethylene diisocyanate, 3,3,5-trimethyl-5-methylenecyclohexyl diisocyanate and the like, among which MDI is preferred.

Examples of the diamine used for chain extension of the prepolymer include ethylenediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine and the like.
Examples of the diol used for chain extension of the prepolymer include ethylene glycol, 1,3-propanediol, 4-butanediol, neopentyl glycol, 1,2-propylene glycol, 1,4-cyclohexanedimethanol, 1, Examples thereof include 4-cyclohexanediol, 1,4-bis(β-hydroxyethoxy)benzene, bis(β-hydroxyethyl)terephthalate and paraxylylenediol. The long-chain polymer that is a raw material for the polyurethane elastic fiber has been described above, but the method for polymerizing the long-chain polymer is not particularly limited in the present invention.

The long-chain polymer used as the raw material for polyurethane-based elastic fibers is a benzotriazole-based UV absorber, a hindered amine-based weathering agent, a hindered phenol-based antioxidant, various pigments such as titanium oxide and iron oxide. , Barium sulfate, zinc oxide, cesium oxide, functional additives such as silver ions, and the like can be contained.

Examples of the solvent used when spinning a polyurethane-based elastic fiber using a long-chain polymer as a raw material include N,N-dimethylacetamide (DMAc), dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone. DMAc is preferred. It is suitable for the dry spinning method using a solvent that the concentration of the long-chain polymer is 30 to 40% by mass, particularly 35 to 38% by mass, based on the total mass of the solution.

Usually, when a diol is used as the chain extender, the polyurethane elastic fiber is spun by a melt spinning method, a dry spinning method or a wet spinning method, and when a diamine is used as the chain extender, the polyurethane elastic fiber is a dry type. It is spun by the spinning method. In the present invention, the spinning method is not particularly limited, but a dry spinning method using a solvent is preferable.

Finally, the polyurethane elastic fiber according to the present invention will be described. The polyurethane elastic fiber according to the present invention is a polyurethane elastic fiber to which the treating agent of the present invention is attached, and can be obtained by the treatment method described above.

According to the present invention described above, the dispersion stability of the higher fatty acid salt in the polyurethane elastic fiber treating agent is improved. Further, it is possible to obtain a polyurethane-based elastic fiber that can suppress defective winding shape when a wound body is formed and can improve the processed quality of a processed product.

In particular, when the amide-modified silicone represented by Chemical Formula 4 is one in which X ¹ and X ² are hydroxyl groups, the effect of improving the texture of the processed product becomes large.
When p is an integer of 15 to 700 and R ¹ is a methyl group is used as the amide-modified silicone represented by Chemical formula 4, the processing quality by suppressing scum generation during processing is improved. The effect to improve becomes large.

When p is an integer of 100 to 500, q is an integer of 1 to 10 and the amide equivalent is 3000 to 30000 g/mol as the amide-modified silicone represented by Chemical formula 4, At the same time, the viscosity stability of the polyurethane-based elastic fiber treatment agent is improved, and the effect of suppressing defective winding shape and the effect of improving the processed quality by suppressing yarn breakage due to improved smoothness and rubbing are achieved at a high level. It can be compatible.

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

Test Category 1 (Preparation of smoothing agent)
When it is composed of two or more components, they are mixed in the proportions (mass ratios) shown in Table 1 to prepare the smoothing agent shown in Table 1.

Details of each component shown in Table 1 are as follows.

S5: Polydimethylsiloxane having a kinematic viscosity of 5 mm ² /s at 25° C. S10: Polydimethylsiloxane having a kinematic viscosity of 10 mm ² /s at 25° C. S20: Polydimethyl having a kinematic viscosity of 20 mm ² /s at 25° C. Siloxane S30: Polydimethylsiloxane having a kinematic viscosity of 30 mm ² /s at 25° C. S50: Polydimethylsiloxane having a kinematic viscosity of 50 mm ² /s at 25° C. M6: Mineral having a kinematic viscosity of 6 mm ² /s at 25° C. Oil M10: Mineral oil having a kinematic viscosity of 10 mm ² /s at 25° C. M15: Mineral oil having a kinematic viscosity of 15 mm ² /s at 25° C. M21: Mineral oil having a kinematic viscosity of 21 mm ² /s at 25° C. M40 : Mineral oil having a kinematic viscosity at 25°C of 40 mm ² /s Test Category 2 (Synthesis of amide-modified silicone)
-Synthesis of amide-modified silicone (AS-1) 27,000 g of hydroxyl group-modified polydimethylsiloxane having both terminals at the siloxane repeating unit of 40, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g, potassium hydroxide 40% 3.3 g of the aqueous solution was placed in a glass reaction container, heated to 90° C. with stirring, and reacted for 4 hours. Then, 32 g of water was added, dehydration operation was performed under reduced pressure, and filtration was performed using Celite to obtain 27,000 g of amino-modified silicone. 2814 g of oleic acid was placed in 27,000 g of the amino-modified silicone obtained, and the temperature was raised to 120° C. with stirring and the reaction was carried out for 4 hours under a nitrogen stream. Then, the reaction product was cooled to obtain 27,000 g of amide-modified silicone (AS-1).

-Synthesis of amide-modified silicones (AS-2) to (AS-9) (AS-11) The repeating unit of the siloxane moiety is changed according to the values of p and q in the general formula shown in Chemical formula 4, and hydroxyl groups at both terminals are changed. In addition to the modified polydimethylsiloxane and the combined use, an amine and a fatty acid corresponding to the structure of X ³ were used, and synthesis was performed in the same manner as the amide modified silicone (AS-1).

-Synthesis of amide-modified silicone (AS-10) N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine was replaced with 3-(dimethoxymethylsilyl)propylamine, and synthesized in the same manner as amide-modified silicone (AS-1). I went.

-Synthesis of amide-modified silicone (AS-12) 30543 g of both-terminal silanol-modified polydimethylsiloxane having 40 siloxane repeating units, 1032 g of N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine, 40% potassium hydroxide 4.0 g of the aqueous solution was placed in a glass reaction container, heated to 90° C. with stirring, and reacted for 4 hours. After that, 135 g of water was added and dehydration operation was carried out under reduced pressure, then 60 g of dimethyldimethoxysilane was added, reaction was carried out at 90° C. for 2 hours while stirring, demethanol was carried out under reduced pressure, and filtration was carried out using Celite. , 31,000 g of amino-modified silicone was obtained. 85 g of terephthalic acid was added to 31000 g of the amino-modified silicone obtained, and the temperature was raised to 120° C. with stirring in a glass reaction container, and the reaction was performed for 4 hours under a nitrogen stream. Then, the reaction product was cooled to obtain 31000 g of an amide-modified silicone (AS-12).

-Synthesis of amino-modified silicone (Ras-1) Hexamethyldisiloxane 162, water 18g, potassium hydroxide 40% aqueous solution 10.3g, octamethylcyclotetrasiloxane 13320g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, filtered using Celite, and amino-modified silicone (Ras). -1) 13000g was obtained.

Synthesis of amino-modified silicone (Ras-2) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 0.4 g, dimethyldimethoxysilane 361 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g The mixture was placed in a glass reaction vessel, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, filtered using Celite, and amino-modified silicone (Ras-2 was used. ) 500 g was obtained.

-Synthesis of amide-modified silicone (Ras-3) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 5.2 g, octamethylcyclotetrasiloxane 5932 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 413 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, and filtered using Celite to obtain 6400 g of amino-modified silicone. Obtained. To the obtained amino-modified silicone (6400 g), 291 g of adipic acid was placed in a glass reaction vessel, heated to 120° C. with stirring, and reacted under a nitrogen stream for 4 hours. Then, the reaction product was cooled to obtain 6655 g of amide-modified silicone (Ras-3).

-Synthesis of amide-modified silicone (Ras-4) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 2.4 g, octamethylcyclotetrasiloxane 2225 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 413 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, and filtered using Celite to obtain 2700 g of amino-modified silicone. Obtained. To 2700 g of the obtained amino-modified silicone, 419 g of trimellitic acid was placed in a glass reaction container, heated to 120° C. with stirring, and reacted under a nitrogen stream for 4 hours. Then, the reaction product was cooled to obtain 3082 g of an amide-modified silicone (Ras-4).

-Synthesis of amide-modified silicone (Ras-5) 2505 g of methylhydrogenpolydimethylsiloxane (composed of 2 methylhydrogensiloxane units, 30 dimethylsiloxane units, 1 trimethylsiloxane unit and 1 trimethylsilyl unit) Pentanoyl polyalkylene glycol monoallyl ether (897 g of polyalkylene glycol in which 3 ethyleneoxy units and 3 propyleneoxy units are randomly bonded), 0.1 g of platinum chloride hexahydrate as a catalyst, and 2000 ml of toluene in a reaction vessel The temperature of the reaction system was kept at 110° C., and the addition reaction was carried out for 10 hours. After xylene was distilled off under reduced pressure from the reaction system, the catalyst was filtered off to obtain a polyether-modified silicone as an intermediate. Separately, 490 g of 3-aminopropylmethyldimethoxysilane and 144 g of water were charged into a reaction vessel, the temperature of the reaction system was kept at 40° C., a polymerization reaction was performed for 2 hours, and then dehydration treatment under reduced pressure was performed at 80° C. for 2 hours to obtain an intermediate. As a result, an amino group-containing polysiloxane was obtained. 1701 g of the polyether-modified silicone thus obtained and 135 g of the amino group-containing polysiloxane were charged into a reaction vessel and uniformly mixed, and then 0.1 g of potassium hydroxide was added to the reaction system to keep the temperature of the reaction system at 98° C. for 24 hours. Was done. After neutralizing the reaction product with acetic acid, 193 g of trimellitic anhydride was further added, and the temperature of the reaction system was adjusted to 150 to 175° C. to carry out an amidation reaction for 6 hours to obtain an amide-modified silicone (Ras-5).

-Synthesis of amide-modified silicone (Ras-6) Hexamethyldisiloxane 162 g, water 54 g, potassium hydroxide 40% aqueous solution 10.4 g, octamethylcyclotetrasiloxane 11123 g, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine 206 g was placed in a glass reaction container, heated to 90° C. with stirring, reacted for 4 hours, dehydrated and demethanol under reduced pressure, filtered using Celite, and 11000 g of amino-modified silicone was obtained. Obtained. 160 g of terephthalic acid was placed in 11,000 g of the obtained amino-modified silicone in a glass reaction container, and the temperature was raised to 120° C. with stirring, and the reaction was carried out under a nitrogen stream for 4 hours. Then, the reaction product was cooled to obtain 11142 g of amide-modified silicone (Ras-6).

The constitution of each modified silicone is shown in Table 2.

In Table 2, "B-1" is _- a ^{_{"C 3 H 6 -COO-Y 1}} -OC-C 4 H 9 " polyether-modified group represented by and, three ^{Y 1} is propyleneoxy units It is a polyether-modified group in the case where it is a polyalkyleneoxy group in which 3 ethyleneoxy units are randomly bonded.

Test Category 3 (Preparation of polyurethane type elastic fiber treatment agent)
-Example 1
A mixture of 49 parts of polydimethylsiloxane (S20) having a viscosity of 20 mm ² /s at 25° C. and 49 parts of mineral oil (M21) having a viscosity of 21 mm ² /s at 25° C. shown in Table 3 as a leveling agent. 98 parts of a smoothing agent (L-1), 1 part of an amide-modified silicone (AS-1) shown in Table 2, and 1 part of magnesium distearate magnesium salt (SM-P manufactured by Sakai Chemical Co., Ltd.) as a higher fatty acid salt were added, The mixture was mixed at a temperature within the range of 20 to 35° C. until uniform, and then wet pulverized using a horizontal bead mill to prepare a colloidally dispersed polyurethane elastic fiber treatment agent.

-Examples 2-6, reference examples 1-11, and comparative examples 1-3
Similar to the treatment agent for elastic fiber of Example 1, the treatment agent for polyurethane type elastic fiber of Examples 2 to 6 , the treatment agent for polyurethane type elastic fiber of Reference Examples 1 to 11, and the polyurethane type treatment agent of Comparative Examples 1 to 3 are used. A treatment agent for elastic fibers was prepared. The contents of these are summarized in Table 3.

Details of each component shown in Table 3 are as follows.

L-1 to L-9: Smoothing agent described in Table 1 M-1: Magnesium stearate M-2: Calcium distearate M-3: Sodium stearate M-4: Magnesium dicaprylate M-5 : Zinc distearate salt AS-1 to AS-12, Ras-1 to Ras-6: Amino-modified silicone and amide-modified silicone shown in Table 2 Ras-7: Viscosity 900 mm ² /s (25° C.), functional group equivalent 2700 g/mol amide polyether modified silicone Test Category 4 (Evaluation of polyurethane-based elastic fiber treatment agent)
The average particle size, dispersion stability, and viscosity increase of the higher fatty acid salt of the polyurethane elastic fiber treating agents of each example prepared in Test Category 2 were evaluated as follows. The results are summarized in Table 3.

-Measurement method of average particle size Polyurethane-based elastic fiber treating agent was added to polydimethylsiloxane having a viscosity at 25°C of 10 mm ² /s, and the concentration of dispersoid in the polyurethane-based elastic fiber treating agent was 1000 mg/ It was diluted to L and the diluted solution was subjected to a laser diffraction type particle size distribution measuring device at a liquid temperature of 25° C. to measure a volume-based average particle diameter.

-Evaluation of dispersion stability 100 ml of the polyurethane type elastic fiber treating agent of each example was put into a 100 ml graduated cylinder made of glass with a sealed stopper, left at 40°C for 1 month, and immediately after preparation and after 1 month of polyurethane type The appearance of the treatment agent for elastic fibers was observed and evaluated according to the following criteria.

⊚: There is no change in appearance in a uniformly dispersed state.
◯: A transparent layer of less than 5 ml was generated.
X: A transparent layer of 5 ml or more was generated or precipitation was generated.

-Evaluation of change in viscosity Using an E-type viscometer (DVH-E type, manufactured by TOKIMEC), the viscosity at 30°C of the polyurethane-based elastic fiber treating agent of each example immediately after preparation was measured with a rotor E and 20 rpm. , Initial viscosity V ₁ (Pa·s). Further, the polyurethane-based elastic fiber treatment agent of each example was placed in a glass container with a hermetically sealed stopper, allowed to stand at 40° C. for 6 months, the viscosity at 30° C. was measured again, and the viscosity V ₂ (Pa·s ). Then, V ₂ /V ₁ was calculated and evaluated according to the following criteria.

⊚: V ₂ /V ₁ is less than 1.3 ◯: V ₂ /V ₁ is 1.3 or more and less than 1.5 ×: V ₂ /V ₁ is 1.5 or more, as is clear from the results in Table 3. The treatment agent of the present invention maintains the initial state for a long period of time and is excellent in dispersion stability and viscosity stability. The treatment agent of the present invention has little change in properties during long-term storage and transportation, and maintains excellent dispersion stability and viscosity stability, and thus is easy to use.

In addition, as the amide-modified silicone represented by Chemical formula 4, p is an integer of 100 to 500, q is an integer of 1 to 10, and the amide equivalent is 3000 to 30000 g/mol. In No. 6 , the viscosity stability is further improved as compared with Reference Examples 1 to 6 in which those that do not meet the requirements are used.

・Test Category 5 (Adhesion and evaluation of treatment agent for polyurethane elastic fiber to polyurethane elastic fiber)
Adhesion of polyurethane elastic fiber treatment agent to polyurethane elastic fiber A mixture of bis-(p-isocyanatephenyl)-methane/tetramethylene ether glycol (number average molecular weight 1800)=1.58/1 (molar ratio) was added. After reacting at 90° C. for 3 hours by a conventional method to obtain capped glycol, this capped glycol was diluted with N,N′-dimethylacetamide (hereinafter referred to as DMAc). Next, a DMAc solution containing ethylenediamine and diethylamine was added to the DMAc solution of the above-mentioned capped glycol, mixed at room temperature using a high-speed stirring device, and chain-extended to obtain a polymer. Further, DMAc was added to obtain a DMAc solution having a polymer concentration of about 35% by mass. Titanium oxide was added to the polymer in a DMAc solution of 4.7% by mass, a hindered amine-based weather-resistant agent was 3.0% by mass, and A hindered phenolic antioxidant was added to 1.2% by mass and mixed to prepare a uniform polymer mixed solution. Using this polymer mixed solution, a 44 dtex elastic yarn consisting of 4 single yarns was spun by a dry spinning method used in a known spandex, and a processing agent for polyurethane-based elastic fibers of each example was obtained from an oiling roller before winding. Was oiled in a neat state. The roller-lubricated material was wound at a winding speed of 550 m/min, and wound on a cylindrical paper tube having a length of 57 mm through a traverse guide giving a winding width of 42 mm, using a surface drive winder, and dry spinning. A polyurethane elastic fiber package was obtained. The amount of the polyurethane-based elastic fiber treatment agent deposited was adjusted by adjusting the rotation speed of the oiling roller, and the target value of 5.5% was applied.

-Measurement and Evaluation The dry-spun polyurethane-based elastic fiber package obtained above was subjected to the following measurements and evaluations, and the results are summarized in Table 3.

-Evaluation of shape of wound body With respect to the above-mentioned package (1 kg winding), the maximum value (Wmax) and the minimum width (Wmin) of the winding width are measured, and the bulge is obtained from the difference (Wmax-Wmin) between them, and the following criteria are used. It was evaluated by.

A: The bulge is less than 4 mm.
◯: Bulge is 4 to 10 mm.
X: Bulge is 10 mm or more.

-Evaluation of scum generation during processing Ten pieces of the package (1 kg wound) wound body were made into a miniature warping machine and wound up at 25°C in an atmosphere of 65% RH at a yarn speed of 300 m/min for 1500 km. At this time, the accumulation state of scum on the comb guide of the miniature warping machine was visually observed and evaluated according to the following criteria.

⊚: Scum hardly adhered.
◯: The scum was slightly attached, but there was no problem in the stable running of the yarn.
X: A large amount of scum was attached and accumulated, and there was a great problem in stable running of the yarn.

・Evaluation of smoothness Using a friction measurement meter (SAMPLE FRICTION UNIT MODEL TB-1 manufactured by Eiko Sokki Co., Ltd.), a chrome-plated satin finish pin with a diameter of 1 cm and a surface roughness of 2S is arranged between two free rollers, and this chrome is used. The contact angle of the polyurethane elastic fiber withdrawn from the above-mentioned package (roll of 500 g) was 90 degrees with respect to the plated satin finish pin. Under the condition of 25% and 60% RH, the initial tension (T ₁ ) of 5 g is applied on the inlet side, and the secondary tension (T ₂ ) on the outlet side when running at a speed of 100 m/min is set every 0.1 seconds. It was measured for 1 minute. The friction coefficient was calculated from the following equation 1 and evaluated according to the following criteria.

A: The coefficient of friction is 0.150 or more and less than 0.220.

◯: The coefficient of friction is 0.220 or more and less than 0.260.
Δ: The coefficient of friction is 0.260 or more and less than 0.300.
X: The friction coefficient is 0.300 or more.

-Evaluation of texture A woven fabric stretch fabric was produced using the sample yarn, post-processing such as dyeing was performed, and the appearance quality was evaluated. First, the sample yarn was covered with a cationic dyeable polyester yarn (168 dtex/48 fil). At that time, the covering yarn was obtained with a twist number of 450 t/m and a draft of 3.0 for the weft yarn, and a twist number of 700 T/M and a draft of 3.5. The covering yarn was used for the vertical yarn. Next, the obtained covering yarns were respectively used as a weft yarn and a warp yarn, and after warping the warp yarns with 5100 warp yarns (1100 warp winding warp yarns), the fabrics were woven with a 2/1 twill design using a Levia loom. .. The weaving machine obtained by weaving is subjected to scouring processing, intermediate setting (185°C) and weight reduction processing according to a conventional method, and further dyeing processing using a cationic dye, drying, finishing agent treatment, and 180°C, cloth 20 m/min, Finishing setting was performed under the condition of the set zone 24 m.

The texture of the stretched fabric after the post-processing in this way was evaluated based on the following criteria, mainly focusing on the waviness of the fabric.
⊚: No waviness and smooth texture

◯: Rippling, but hardly noticeable.
X: Wavy and worrisome to the touch.
As is clear from the results of Table 3, according to the treatment agent and the treatment method of the present invention, a package having a good winding shape can be obtained in the production of polyurethane elastic fibers, and scum is generated in the post-processing. It is possible to obtain a polyurethane-based elastic fiber in which the yarn breakage due to abrasion or abrasion is small, and as a result, the surface of the knitted fabric is smooth and the processed quality is excellent.

In particular, as an amide-modified silicone represented by Formula 4, X ^1, and Example X ² is used as a hydroxyl group 1-6, Reference Example 1-8, the reference example was used that do not meet the requirements Compared with 9-11 , the texture is further improved.

In addition, Examples 1 to 6 and Reference Examples 1 to 6 in which p is an integer of 15 to 700 and R ¹ is a methyl group as the amide-modified silicone represented by Chemical Formula 4 satisfy the requirements. Compared with Reference Examples 7 to 8 in which no scum was used, scum generation during processing was further suppressed.

In addition, as the amide-modified silicone represented by Chemical formula 4, p is an integer of 100 to 500, q is an integer of 1 to 10, and the amide equivalent is 3000 to 30000 g/mol. In No. 6 , as compared with Reference Examples 1 to 6 in which materials that do not meet the requirements are used, the effect of suppressing defective winding shape and the effect of improving the smoothness of the synthetic fiber are compatible at a high level.

Claims (8)

A treatment agent for polyurethane elastic fibers which is used by being attached to polyurethane elastic fibers,
Containing a leveling agent, an amide-modified silicone represented by the following chemical formula 1, and a higher fatty acid metal salt represented by the following chemical formula 3,
The leveling agent contains at least one of silicone oil other than the amide-modified silicone, mineral oil, fatty acid ester, and liquid polyolefin,
A treatment agent for polyurethane elastic fibers, wherein the kinematic viscosity of the smoothing agent is 5 to 50 mm ² /s.
(In chemical formula 1,
X ¹ , X ² : a methyl group, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and at least one of X ¹ and X ² is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group X ³ : An amide-modified group R ¹ represented by Chemical formula 2: an alkyl group having 1 to 5 carbon atoms p: an integer of 4 to 1200 q: an integer of 1 to 100)
(In chemical formula 2,
^{R 2,} R ^3: an alkylene group having 2 to 5 carbon atoms R ^4: residues except one hydroxyl group from monovalent to tetravalent carboxylic acid r: 0 or 1)
(In chemical formula 3,
R ⁵ : a residue obtained by removing one carboxyl group from a fatty acid having 12 to 22 carbon atoms, M: a metal atom having a valence of n, n: an integer of 1 to 3) The amide-modified silicone is one in which X ¹ and X ² in Chemical formula ¹ are a methyl group or a hydroxyl group, and at least one of X ¹ and X ² is a hydroxyl group. The processing agent for polyurethane-based elastic fibers described. The polyurethane-based elastic fiber treating agent according to claim 1 or 2, wherein the amide-modified silicone is one in which X ¹ and X ^{2 in the} chemical formula 1 are hydroxyl groups. The polyurethane-based elastic fiber according to any one of claims 1 to 3, wherein the amide-modified silicone is one in which p in Chemical formula ¹ is an integer of 15 to 700 and R ¹ is a methyl group. Processing agent. The amide-modified silicone is one in which p in Chemical formula 1 is an integer of 100 to 500, q is an integer of 1 to 10, and the amide equivalent is 3000 to 30000 g/mol. The processing agent for polyurethane elastic fibers according to any one of 1. Assuming that the total content of the leveling agent, the amide-modified silicone, and the higher fatty acid metal salt is 100% by mass, the leveling agent is 85 to 99.8% by mass, and the amide-modified silicone is 0.1 to 5% by mass. %, and the higher fatty acid metal salt in an amount of 0.1 to 10% by mass, the polyurethane-based elastic fiber treatment agent according to any one of claims 1 to 5. The polyurethane-based treatment agent for elastic fibers according to any one of claims 1 to 6 is adhered to the synthetic fiber in an amount of 0.1 to 10 mass% with respect to 100 mass% of the synthetic fiber. Elastic fiber treatment method. A polyurethane-based elastic fiber having the treatment agent for polyurethane-based elastic fiber according to any one of claims 1 to 6 attached thereto.