JPH11229277A - Polyurethane elastic fiber and its elastic fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane elastic fiber having excellent unwindability and durability and not causing the accumulation of scams on fiber guides by imparting a specific mixture treating agent to a specific polyurethane elastic fiber. SOLUTION: This polyurethane elastic fiber is obtained by producing a polyurethane elastic fiber from 100 pts.wt. of a polyurethane polymer and 0.1-10 pts.wt. of one or more kinds of metal compounds selected from the group consisting of the (compound) oxide, hydroxide and hydrotalcite compounds of a metal selected from Mg, Zn and Al, and subsequently treating the polyurethane elastic fiber with 0.5-10 pts.wt. of a mixture treating agent obtained by adding 0.01-10 pts.wt. of a phosphate ester compound of the formula [R is a 1-3C alkyl, an alkoxy, a polyoxyalkylene or a 5 or 6C cycloalkyl substituted with a 1-10C alkyl group; (n) is an integer of 1-2] to 100 pts.wt. of a treating agent comprising a polyalkylsiloxane having a viscosity of 5-30 cst at 25 deg.C and a mineral oil having a viscosity of 5-30 cst at 25 deg.C in a ratio of 100/0 to 50/50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane elastic fiber comprising a polyurethane polymer obtained from an organic diisocyanate, a polymer diol and a chain extender having a polyfunctional active hydrogen atom, and an elastic fabric thereof. More specifically, it has excellent de-splitting properties from the winding package, and there is no breakage of the yarn and no scum accumulation on the yarn conductor during running of the yarn. The present invention relates to a polyurethane elastic fiber having improved chlorine durability and improved chlorine durability and handleability of yarn, and an elastic fabric comprising the same and a polyamide-based fiber or a polyester-based fiber.

[0002]

2. Description of the Related Art Polyurethane elastic fibers generally called spandex have moderate rubber elasticity and have excellent properties. For this reason, cross-knitted fabrics that are mixed and knitted, mixed and woven with various fibers such as polyester and polyamide, and dyed are now being used more and more widely as various stretch material clothing and sports clothing. The present invention relates to a polyurethane elastic fiber having excellent operability and chlorine resistance at the same time in a processing step, and an elastic fabric thereof. When repeatedly exposed to chlorine water having a concentration of active chlorine for sterilization of 0.5 to 3 ppm in the pool, the polyurethane elastic fiber is deteriorated by chlorine and its physical performance is reduced. As a result, in the swimsuit made of the elastic cloth, when the wearing pressure on the human body is reduced when the swimsuit is worn and the swimsuit is displaced from the skin or further deteriorates due to water pressure or current during swimming, the polyurethane elastic fiber in the swimsuit fabric is cut off. There was a problem in that the power of the fabric was reduced and the fabric became thin and could be seen through.

[0003] In order to improve the chlorine durability of polyurethane elastic fibers, it has been proposed to add various chlorine deterioration inhibitors. For example, zinc oxide (JP-B-60-4344)
No. 4), magnesium oxide, aluminum oxide (JP-B-61-35283), hydrotalcite compounds (JP-A-59-133248), and a solid solution of magnesium oxide and zinc oxide (JP-A-6-81215). A method has been proposed for improving the chlorine durability by adding a metal compound such as that disclosed in U.S. Pat. The present applicant has also proposed a metal compound having excellent chlorine resistance to polyurethane elastic fibers (Japanese Patent Application No. 09-029170). However, when a thin polyurethane elastic fiber of 40 denier or less is cross-knitted / cross-woven with another natural fiber, a chemical fiber, or a synthetic fiber and dyed into a fabric, the loosening property from the winding package is poor. If the decomposing stress is high, thread breakage occurs frequently, making it difficult to perform warping and knitting.

[0004] In order to improve the processability of such polyurethane elastic fibers, various oil agents for polyurethane elastic fibers have been studied. For example, JP-A-7-173770
And JP-A-9-49167, an alkyl phosphate metal (Na,
(K, Li, etc.) salts and alkyl phosphate amine salts have been proposed. However, with these alkyl phosphate metal salts, when used for a long time, scum accumulates in the yarn path, causing yarn breakage and unevenness in tension, resulting in a problem that the handleability is lowered and the surface quality of the knitted surface of the fabric is lowered. there were.

Furthermore, it has been difficult to stably and uniformly disperse and mix a metal salt of an alkyl phosphate in a spinning oil. As a result, the polyurethane elastic fiber may cause uneven adhesion in the yarn length direction. In addition,
Japanese Patent No. 38622 also proposes a method in which an alkyl phosphate metal salt is dispersed and mixed in a polymer and spinning is performed. However, in order to prevent clogging of a spinneret or a filter due to poor solubility or poor dispersibility in a spinning solution. However, there is a problem in production stability during spinning. Further, there is a problem that the alkyl phosphate metal salt becomes scum in the warping step and the knitting step. Therefore, it has not yet reached the stage where the handleability and fabric quality of the polyurethane elastic fiber can be improved and the chlorine resistance can be satisfied at the same time.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the production of polyurethane elastic fibers, to improve the handleability in the knitting process of knitted and woven fabrics, and at the same time, to improve the polyurethane resistance to chlorine. It is an object of the present invention to provide an elastic fabric having improved elastic fiber and fabric quality and chlorine resistance as a product.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve these problems, and as a result, have adhered a specific amount of a specific treatment agent to a polyurethane elastic fiber containing a specific amount of a specific metal compound. The present inventors have found that the above polyurethane elastic fiber solves the above problems, and have completed the present invention. That is, the present invention relates to an elastic fiber comprising a polyurethane polymer which satisfies the following (a), wherein a mixed treatment agent satisfying the following (b) is added to the elastic fiber:
It is a polyurethane elastic fiber adhered by 0.5 to 10 parts by weight with respect to parts by weight.

(A) 100 parts by weight of a polyurethane polymer, 0.1 to 10 parts by weight of Mg as a metal compound,
Oxides and composite oxides of metals selected from Zn and Al;
An elastic fiber containing one or more metal compounds selected from the group consisting of hydroxides and hydrotalcite compounds. (B) The ratio of 5-30 cst polyalkylsiloxane to 5-30 cst mineral oil at 25 ° C. is 100 / 0-50.
/ 100 parts by weight of the treating agent, the amount of the phosphate compound represented by the following formula (1) is 0.01 to
10 parts by weight of a mixed treatment agent.

[0009]

Embedded image (Where R is a linear or branched alkyl group having 1 to 30 carbon atoms, an alkoxypolyoxyalkylene group, a cycloalkyl group having 5 to 6 carbon atoms, 1 to 10 carbon atoms)
A cycloalkyl group having 5 to 6 carbon atoms substituted by an alkyl group, and n represents an integer of 1 or 2. )

Preferably, the metal compound contained in the polyurethane elastic fiber is ZnO, MgO, ZnO and MgO.
Complex oxide, divalent metal M (where M is Zn and Mg
Represents at least one selected from ), And a polyurethane elastic fiber comprising one or more selected from the group consisting of a composite oxide and a hydrotalcite compound, in which the molar ratio of the divalent metal M to Al is 1 to 5 containing Al. Further, the present invention is an elastic fabric comprising the polyurethane elastic fiber of the present invention and a polyamide-based fiber or a polyester-based fiber.

The high molecular weight diol which is one of the raw materials of the polyurethane polymer of the present invention is a substantially linear polymer having a molecular weight of 500 to 5,000 having hydroxyl groups at both ends, for example, polyoxyethylene. Homopolyether diols such as glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, or 2 having 2 to 6 carbon atoms
Copolymerized polyether diols composed of at least two kinds of oxyalkylenes each having a hydroxyl group at both ends; adipic acid,
Sebacic acid, maleic acid, itaconic acid, azelaic acid,
One or more dibasic acids such as malonic acid and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3 A polyester diol obtained from one or more glycols such as butanediol, hexamethylene glycol, diethylene glycol, 1,10-decanediol, 1,3 dimethylolcyclohexane, and 1,4 dimethylolcyclohexane; or a polyesteramide diol; Polyester ether diols; polylactone diols such as poly-ε-caprolactone diol and polyvalerolactone diol; and polycarbonate diols. Preferred are polyoxytetramethylene glycol, copolymerized poly (tetramethylene neopentylene) ether diol, and copolymerized poly (tetramethylene-2-methylbutylene) ether diol.

As the organic diisocyanate, for example, any of aliphatic, alicyclic and aromatic diisocyanates which are soluble or liquid under the reaction conditions can be applied. For example, methylene-bis (4-phenyl isocyanate),
Methylene-bis (3-methyl-4-phenyl isocyanate), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-xylylene diisocyanate , M- and p-phenylenediisocyanate, 4,4'-dimethyl-1,3-xylylenediisocyanate, 1-alkylphenylene-2,4 and 2,6-diisocyanate, 3- (α-isocyanatoethyl) phenyl isocyanate, 2, 6-diethylphenylene-1,4-diisocyanate, diphenyl-dimethylmethane-4,4 diisocyanate,
Diphenyl ether-4,4'-diisocyanate, naphthylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate), 1,3- and 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetra Examples include methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Preferably, it is methylene-bis (4-phenylisocyanate).

Examples of the chain extender having a polyfunctional active hydrogen atom include hydrazine, polyhydrazine, and linear or branched aliphatic, alicyclic and aromatic active hydrogen having 2 to 10 carbon atoms. Examples of the compound having an amino group include ethylenediamine, 1,2-propylenediamine, diamines such as diamines having a urea group described in JP-A-5-155814, hydroxylamine, and water, and low-molecular-weight glycols. For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10-decanediol 1,3 dimethylol cyclohexene Sun, can be used 1,4-dimethylol cyclohexane, and the like. Preferably, they are ethylenediamine and 1,2-propylenediamine.

As a terminal terminator having a monofunctional active hydrogen atom, for example, dialkylamine such as diethylamine is used. These chain extenders and terminal stoppers may be used alone or in combination of two or more. Regarding a method for producing a polyurethane polymer using a polyalkylene ether diol, a diisocyanate compound, and a diamine compound, a known polyurethane-forming reaction technique can be used. For example, a polyalkylene ether diol and an organic diisocyanate are mixed at a ratio of 1: 1.2
To 2.0, preferably 1: 1.3 to 1.8 (molar ratio) to synthesize a urethane prepolymer having isocyanate groups at both ends to obtain a urethane moiety. Next, the urethane prepolymer is subjected to a chain elongation reaction with a diamine compound and a glycol compound to obtain a polyurethane polymer.

Regarding the operation of the polyurethane conversion reaction, a solvent such as dimethylformamide, dimethylsulfoxide and dimethylacetamide may be used at the time of synthesizing the urethane prepolymer or at the time of reacting the urethane prepolymer with the active hydrogen-containing compound. In addition, the stoichiometric ratio of the various compounds used in the present invention is such that the sum of the hydroxyl groups of the polyalkylene ether diol and the active hydrogens of the diamine compound and the like is 1.00 to 1.07 with respect to the isocyanate group of the isocyanate compound. Desirably, it is an amount.

The metal compound used in the present invention is Mg, Z
Oxides, composite oxides, hydroxides and hydrotalcite compounds of metals selected from n and Al are one or more metal compounds. As such a metal compound,
For example, magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide, aluminum oxide, aluminum hydroxide, hydrotalcite compounds (for example, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O )
And a divalent metal M (where M represents at least one selected from zinc and magnesium) and aluminum, and the molar ratio of the divalent metal to aluminum is 1
-5. Particularly preferred metal compounds include MgO, ZnO, composite oxides of MgO and ZnO, hydrotalcite compounds, and the following composite oxides represented by the following formulas, for example.

[0017]

Embedded image 2ZnO.ZnAl ₂ O ₄ 3ZnO.ZnAl ₂ O ₄ 4ZnO.ZnAl ₂ O ₄ 5ZnO.ZnAl ₂ O ₄ These composite oxides can be obtained, for example, by firing a hydrotalcite compound ( Japanese Patent Publication No. 51-376
No. 40 and Japanese Patent Publication No. 51-20997).
It is not limited to this.

The metal compounds used in the present invention may be added at the same time as the raw material monomers at the time of polymerization of the polyurethane, or may be added at any stage before the step of spinning the polyurethane elastic fiber in order to enhance the effect of preventing chlorine deterioration. Can be added. Generally, it is preferable to add it after completion of polyurethane polymerization. The amount added is 0.1 to 10.0 parts by weight, preferably 0.5 to 7.0 parts by weight, based on 100 parts by weight of the polyurethane polymer. Excessive addition of these metal compounds in an amount of 10.0 parts by weight or more is not preferable because it adversely affects spinning stability during production and elastic recovery of polyurethane elastic fibers. A sufficient effect cannot be expected.

In the present invention, these metal compounds are preferably fine powders having an average particle size of 1 μm or less from the viewpoint of spinning stability. In some cases, the surface of the inorganic metal compound particles may be surface-treated with a fatty acid, a fatty acid ester, a silane coupling agent, a titanate coupling agent, or a mixture thereof. The thus obtained polyurethane polymer containing a metal oxide is subjected to dry spinning, melt spinning, and wet spinning in the usual manner, and before being wound into a paper tube package, roll oiling and guide oiling are performed on the polyurethane elastic fiber. A predetermined amount of the mixed treatment agent of the present invention can be applied by a known method such as spray oiling or the like.

As a method of adhering the mixed treatment agent to the elastic fiber, a polyalkylsiloxane, a mineral oil, and a phosphate compound may be adhered in a stepwise manner. That is, the polyalkylsiloxane and the mineral oil may be attached after the phosphate compound is first attached, or the phosphate compound may be attached after the polyalkylsiloxane and the mineral oil have been attached in advance, It may be simultaneously attached to the polyurethane elastic fiber as a mixing agent.

The mixed processing agent used in the present invention has a main component having a ratio of polyalkylsiloxane of 5 to 30 cst to mineral oil of 5 to 30 cst at 25 ° C. of 100/0 to 50 / c.
50. A representative example of a polyalkylsiloxane is dimethylsiloxane. More preferred viscosities of the polyalkylsiloxane and mineral oil are each 8 to 15 cst at 25C. Phosphate compound used in the present invention,
It is a compound represented by the formula (1).

Preferred examples of the phosphoric ester include mono- or dimethyl acid phosphate, mono- or diethyl-acid phosphate, mono- or di-propyl acid phosphate, mono- or di-isopropyl acid phosphate, mono- or dibutyl acid phosphate, mono- or dibutyl acid phosphate. Dilauryl acid phosphate, mono or distearyl acid phosphate, mono or di (2-ethylhexyl) acid phosphate, mono or diisodecyl acid phosphate, mono or dibutoxyethyl acid phosphate, mono or dioleyl acid phosphate, Mono or ditetradecyl acid phosphate, mono or di (2-hydroxyethyl) methacrylate acid phosphate, polyoxyalkylene glycol alkylene Chromatography ether acid phosphate compound can be mentioned. These phosphoric esters may be used in a mono- or di-form, alone or in combination of different kinds.

The phosphate compound is a compound represented by the formula (1)
Of 1 to 30 carbon atoms, preferably 3 to 3 carbon atoms
25 are preferred. More preferably, it has 10 to 2 carbon atoms.
0. The ratio of the phosphate compound to the polyalkylsiloxane and the mineral oil alone or in the mixed treating agent in the mixed treating agent of the present invention is 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the treating agent. It is in the range of 1 to 5 parts by weight. When the phosphate ester, the polyalkylsiloxane, and the mineral oil are used as a mixture, if the phosphate ester is in a liquid state, it can be uniformly dispersed or dissolved by high-speed stirring using a homomixer or the like. .

If the phosphoric acid ester is solid at room temperature, the phosphoric acid ester is heated above the melting point of the polyalkylsiloxane and mineral oil alone or in a state where the phosphoric acid ester is heated to the melting point or higher while being added to or mixed with the treating agent. The mixture can be uniformly dispersed or dissolved by high-speed stirring using a homomixer or the like. Polyurethane elastic fiber 1
With respect to 00 parts by weight, the phosphate compound of the present invention,
The effect can be exhibited by adhering 0.5 to 10 parts by weight of a mixed treatment agent comprising a polyalkylsiloxane and a mineral oil. Preferably it is in the range of 1 to 8 parts by weight, more preferably 2 to 6 parts by weight.

Although the effects of the present invention are not clear, it is presumed that the metal compound of the present invention near the fiber surface contained in the elastic fiber reacts with a part of the phosphate compound contained in the mixed treatment agent, The metal salt of the present invention of a phosphate ester on the fiber surface effectively, for example, the phosphate ester Zn
It is considered that a salt, a Mg salt, and the like are formed, and the phosphate metal salt can be effectively present only in the vicinity of the yarn surface. Therefore, it is presumed that problems such as filter clogging in fiber production caused by the phosphoric acid ester metal salt can be solved by the present invention, and that the lubricating properties and the chlorine resistance of the fibers have been simultaneously improved.

In the polyurethane polymer composition, in addition to the above-mentioned inorganic metal compounds, additives of known organic or inorganic compounds used for polyurethane elastic fibers, for example, heat stabilizers, antioxidants, ultraviolet absorbers, yellowing An inhibitor, a thermal discoloration inhibitor, an antiblock agent, a pigment, an antistatic agent, a fungicide, a colorant, a filler, and the like may be added in combination. The polyurethane polymer composition thus obtained is spun by a known dry, melt, or wet spinning method.

[0027] In addition to the mixed treatment component of the present invention, the spun polyurethane elastic fiber may further contain polyester-modified silicone, polyether-modified silicone, polyorganosiloxane, amino-modified silicon, aminoether-modified silicon, mineral oil, talc, silica, Mineral particles such as colloidal alumina, higher fatty acid metal salt powders such as magnesium stearate and calcium stearate, higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffins, waxes that are solid at room temperature such as polyethylene, etc. It may be provided as long as it is not damaged. The polyurethane elastic fiber used in the present invention is not knitted or woven alone, but is knitted and knitted with other natural fibers, chemical fibers, and synthetic fibers to form a fabric.

The polyurethane elastic fiber in the present invention comprises:
Do not select any other fibers that will be a knitted fabric. However,
Synthetic fibers are widely used at present because of their durability against wear and stretch fatigue when wearing swimwear products, the comfort of the texture felt by the human body when worn, and the form stability of the products. As synthetic fibers, polyethylene terephthalate,
Polytrimethylene terephthalate, polytetramethylene terephthalate, copolymerized polyterephthalate containing polytetramethylene glycol and ethylene glycol as main components as diol components, and their cationic dyeable polyester fibers, polyamides such as nylon 6, nylon 66, and polyacrylic , Polypropylene, polyvinyl chloride, synthetic fibers such as polyvinyl alcohol and the like, copper ammonia rayon, viscose rayon, regenerated cellulose fibers such as purified cellulose fibers, regenerated protein fibers,
Natural fiber materials such as semi-synthetic fibers, cotton, silk, and wool are also included. Preferably, it is a polyamide fiber or a polyester fiber.

The polyurethane elastic fiber of the present invention may be used together with these fiber materials together with covering, corespun yarn,
In the state of air-covering, ply-twisting, twist-twisting, interlaced conjugate fibers and / or their respective fibers as they are, knitting or knitting such as circular knitting fabric, weft knitting fabric, warp knitting, or cross-weaving, and dyeing are performed. Processed into dough and used for various purposes. Various knitting methods are used to produce a knitted fabric composed of polyurethane elastic fibers and other natural fibers, chemical fibers, and synthetic fibers. The knitted knitted fabric may be warp knit or weft knit, and examples thereof include tricot, Russell, and circular knit. Further, the knitting structure may be any knitting structure such as half knitting, reverse half knitting, double atlas knitting, and double Denby knitting. In addition, from the viewpoint of texture, it is preferable that the surface of the knitted fabric is made of other natural fibers, chemical fibers, and synthetic fibers.

The woven fabric composed of polyurethane elastic fibers and other natural fibers, chemical fibers and synthetic fibers is woven by a usual method. The fabric may be either one-way stretch using polyurethane elastic fiber only for warp or weft, or two-way stretch used for both warp and weft. Fabrics using the polyurethane elastic fiber of the present invention include girdle, bra, intimate products, various stretch foundations such as underwear, sock mouth rubber, tights, pantyhose, waistband, body suit, spats, swimwear, stretch sportswear, Applications include stretch fabrics, stretch outers, bandages, supporters, medical wear, stretch linings, disposable diapers and the like. The fabric of the present invention is particularly suitable for swimwear used in pools. In particular, polyamide fibers and polyester fibers are generally subjected to a fixing treatment using natural or synthetic tannin after dyeing in order to improve the fastness to chlorine dyeing.

For example, in the case of a cross-knitted fabric of polyamide fibers and polyurethane elastic fibers, in order to fix the dye after dyeing, a fixing treatment is performed with natural tannin as a natural polyphenol compound and synthetic tannin as a synthetic polyphenol compound. In a cross-knit fabric of polyester fibers and polyurethane elastic fibers, a dye fixing treatment may be performed with natural tannin or synthetic tannin before or after or simultaneously with the dyeing of the polyurethane elastic fibers. In any of the fixing treatments, the pH of the treatment bath is adjusted to 3 to 7, and the treatment is carried out at 80 ° C. to 130 ° C. after a normal temperature raising process. The longer the processing time, the better, but preferably 20 to 60 minutes. If necessary, a scum inhibitor and a softening agent in the bath may be mixed in the treatment bath. When the elastic cloth is dye-fixed, the utility of the polyurethane elastic fiber and the elastic cloth of the polyurethane fiber and the polyamide fiber or polyester fiber in the present invention is particularly high.

[0032]

Next, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples and the like. In addition, the measuring method described in an Example is as follows. (1) Method of evaluating the repellency of elastic fiber After winding up 400 g of 40 denier / 5 filament elastic fiber into a paper tube, it was dried at 25 ° C. and 65% RH in an atmosphere of 30%.
After standing for a day, the paper tube is placed on a satin finish roller, and the elastic fiber is sent out at a roller surface speed of 40 m / min while rotating the roller. The sent out elastic fiber is wound up on a satin roller having the same diameter installed at a position 50 cm away. The surface speed on the take-up roller is gradually decreased from 80 m / min, and the elastic fiber is entangled with the paper tube on the paper roller on the sending-out roller and reversely wound, and the speed Sm / at the time when the elastic fiber is cut and no longer sent out. Measure minutes. The smaller the value of Sm / min, the better the separation of the elastic yarn from the paper tube, and it is judged that the removability is good.

In general, polyurethane elastic yarns tend to stick to each other because the polymer itself has properties similar to rubber, and thus have poor disintegration properties. However, if the yarn separation is too good, the outer layer of the elastic fiber wound on the paper tube is liable to drop when transporting the polyurethane elastic fiber wound on the paper tube, causing a handling problem. In this measurement, S (hereinafter referred to as SO) of the elastic fiber of the preferable cheese outer layer is used.
Is SO = 45 to 55 m / min, and S (hereinafter referred to as SI) of the elastic fiber of the cheese inner layer is SI = 50 to 65 m / min. If the values of SI and SO are out of this range, and if the values are small, the yarn is liable to drop during transportation or in the warping process. Conversely, if the value is large, reverse winding or yarn breakage to the cheese may occur frequently, Become.

(2) Evaluation method of the number of warping yarn breakage 400 g of 40 denier / 5 filament elastic fiber was wound up on a paper tube, and 588 fibers were attached to an elastic yarn warping machine manufactured by River Co., Ltd., and the elastic fiber delivery speed was 150 m. / Min, warping at a beam take-up speed of 300 m / min, warping of 14.7 kg of elastic fiber per beam for 16 beams, warping yarn breakage by the number of yarn breaks of the elastic fiber that occurred until the completion. The number of times was evaluated. However, even when a yarn break occurred, the broken yarn was tied and connected and restarted with 588 yarns. Also, when a plurality of yarn breaks occurred almost simultaneously, the number of yarn breaks was counted as one.

(3) Evaluation method of scum 400 g of 40 denier / 5 filament elastic fiber was wound around a paper tube, and then was wound at 25 ° C. and 65% RH in an atmosphere of 30%.
After standing for a day, the paper tube is placed on a satin finish roller, and the elastic fiber is sent out at a roller surface speed of 40 m / min while rotating the roller. The sent out elastic fiber is wound up on a satin roller having the same diameter installed at a position 50 cm away. A razor blade was set up at an intermediate point of 25 cm from the elastic yarn to be sent so as to have a yarn angle of 115 degrees, and the surface speed on the winding roller was set at 70 m / min. After running the elastic fiber on the razor blade for 1 hour, the amount of white scum adhering to the razor blade (NT-L type blade part number L-300, manufactured by NT Co., Ltd.) was visually inspected for grades 1 to 5. I made a decision.

Grade 5: No adhesion to razor blade. Grade 4: Very slight adhesion to the razor blade. Class 3: Slightly adhered to the razor blade. Grade 2: The razor blade has a slightly large amount of adhesion. Grade 1: A large amount of deposits on the razor blade.

(4) Method for measuring the breaking strength and elongation Tensile tester (UTM-3 manufactured by Orientec Co., Ltd.)
-100 type) in an atmosphere of 20 ° C. and 65% RH. It is measured at a strain rate of 1000% for 1 minute with a yarn sample length of 5 cm width.

(5) Evaluation of Raw Yarn (Evaluation of Chlorine Durability)
After treatment in boiling water of No. 7 for 60 minutes, the mixture was cooled at room temperature for 2 hours. Then, it is immersed in a chlorine water tank having a length of 1 m, a width of 1 m and a depth of 30 cm. The effective chlorine average concentration of this chlorine water tank was adjusted to 7.0 ppm, pH 7, and water temperature to 30 ° C.
The strength retention after air immersion for 18 hours after immersion for 30 hours is shown by the following formula. The higher the retention, the higher the chlorine durability. Strength retention (%) = (Strength of elastic fiber after immersion in chlorine water /
Strength of elastic fiber before immersion in chlorine water) x 100

(6) Fabric evaluation (chlorine durability evaluation) Polyurethane elastic fiber and polyamide fiber 50 denier / 17 filament obtained by melt-spinning polyhexamethylene adipamide are knitted using a tricot machine. And a warp knit 2-way tricot. Knitting structure is half, knitting is polyamide fiber at the front and polyurethane elastic fiber at the back, 28 gauge, front runner 160 cm / 480 course, back runner 80
cm / 480 courses, 15 kg / 1 reaction.
The number of yarn breaks in the polyurethane elastic fiber when knitting 20 in this step was evaluated.

Further, the obtained two-way tricot greige was scoured, relaxed, dried and heat-set for dyeing. Dyeing was performed using Irgalan Black as a dye.
BGL 2.7% owf, ammonium sulfate 3% owf, acetic acid 0.
Treatment was performed at 95 ° C. for 30 minutes in a 2% owf bath (pH 5.5). The stained 2-way tricot was fixed with natural tannin containing tannic acid. The fixation treatment is performed using HiFix SLA (containing 30% tannic acid,
Dainippon Pharmaceutical Co., Ltd. (trade name) in 6% owf bath (pH
In 3.7), treatment was performed at 90 ° C. for 30 minutes.

A knitted fabric made of polyurethane elastic fiber and nylon 6 is stretched 50% in the weft direction, and is repeatedly immersed in a water tank having a length of 1 m and a width of 1 m and a depth of 0.5 m for 12 hours and air-dried for 12 hours. The average effective chlorine concentration during this 12 hour immersion is 2.0p
pm, pH 7, water temperature 35 ° C.
Time air drying is performed after rinsing with tap water. When the fabric is taken out from the 12-hour immersion, the presence or absence of a defect in the knitted fabric is confirmed, and the number of days until the occurrence of the defect is defined as the chlorine durability days of the knitted fabric.
The longer the chlorine durability days, the higher the chlorine durability.

(7) Effective chlorine concentration A 25 ml chlorine water sample is weighed in a 100 ml Erlenmeyer flask, and 2 g of dried potassium iodide is added thereto and shaken. Titration with a 1 / 100N sodium thiosulfate solution,
When the solution changes from orange to light yellow, the starch solution is added. 1/100 until blue color disappears due to iodine starch reaction
Titrate with N sodium thiosulfate solution. Separately, 25 ml of ion-exchanged water is sampled and titrated by the same operation as above to obtain a Planck titer. The effective chlorine concentration H is given by the following equation (1).

[0043]

(Equation 1) Here, H is the effective chlorine concentration (ppm), Vs is the titration amount (ml) of the 1 / 100N sodium thiosulfate solution when titrated with chlorinated water, and Vb is 1 / 100N when titrated with ion-exchanged water. Titration of sodium thiosulfate (ml),
f is the titer of 1 / 100N sodium thiosulfate, and Ws is the weight (g) of chlorine water.

[0044]

Example 1 400 g of polytetramethylene ether glycol having a number average molecular weight of 1800 and 91.7 g of 4,4′-diphenylmethane diisocyanate were reacted under a dry nitrogen atmosphere at 80 ° C. for 3 hours with stirring to obtain an isocyanate terminal. To give a polyurethane prepolymer capped. After cooling to room temperature, 720 g of dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution. On the other hand, 8.11 g of ethylenediamine and 1.37 g of diethylamine were added to dimethylacetamide 3
It was dissolved in 90 g and added to the prepolymer solution at room temperature to obtain a polyurethane solution having a viscosity of 4500 poise (30 ° C.).

In the polyurethane solution, 1% by weight of 4,4′-butylidenebis- (3-methyl-6-t-butylphenol) was added to the solid content of polyurethane.
0.5% of (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chloro-benzotriazole
By weight, 4.0% by weight of various metal compounds having an average particle size of 1 μm or less described in Table 1 were added to obtain a stock solution for spinning.

The spinning stock solution obtained in this manner was mixed with 1
Each of the spinnerets was extruded into hot air from five pores to evaporate the solvent. The dried yarn was false-twisted in the process of passing through a ring false twisting machine, and applied with a mixed treatment agent on an oiling roller via a godet roller. The mixing agent applied to the oiling roller is 10 cst at 25 ° C.
98 parts by weight of dimethylsiloxane, 10 cst at 25 ° C
1.5 parts by weight of mineral oil, and mono and di (1: 1) stearyl acid phosphate (trade name Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) 0.5
A mixed treatment agent consisting of parts by weight was supplied. The number of rotations of the oiling roll was adjusted so that the amount of the mixed treatment agent attached was 5 parts by weight with respect to 100 parts by weight of the yarn. The yarn to which the mixed treatment agent was applied was wound around a paper tube at a speed of 700 m / min.

Thus, the polyurethane elastic fibers (A) to (D) of the present invention having 40 denier / 5 filaments
I got Further, the polyurethane elastic fiber (E) of the present invention
Using the spinning stock solution to which the metal compounds described in Table 1 were added, 40 denier / 5 filaments were obtained in the same manner as described above, except that the mixing treatment applied to the oiling roller had the following composition. 99.5 parts by weight of dimethylsiloxane, 10 cst at 25 ° C., mono and di (1: 1)
Stearyl acid phosphate (Sakai Chemical Industry Co., Ltd.)
Made, trade name Phoslex A-1
8) A mixed treatment agent consisting of 0.5 parts by weight was supplied. The number of rotations of the oiling roll was adjusted so that the amount of the mixed treatment agent attached was 5 parts by weight with respect to 100 parts by weight of the yarn. Table 1 shows the evaluation results of the composition of the polyurethane elastic fiber, the repellency, etc. Table 1 also shows the results of evaluating various performances of the elastic fiber.

[0048]

Comparative Example 1 To a polyurethane solution polymerized according to the method of Example 1, 4% by weight of titanium oxide having an average particle diameter of 1 μ or less was added instead of a metal oxide to prepare a spinning dope.
This spinning stock solution was treated in the same manner as in Example 1 to obtain a polyurethane elastic fiber of 40 denier / 5 filaments to which a treating agent was attached. Table 1 shows the results of evaluating various performances of the elastic fiber.
Shown in

[0049]

Comparative Example 2 An undiluted spinning solution was prepared from a polyurethane solution polymerized according to the method of Example 1 by removing the metal compound.
That is, 1% by weight of 4,4′-butylidenebis- (3-methyl-6-t-butylphenol) and 2- (2′-hydroxy-3′-t-
0.5% by weight of (butyl-5'-methylphenyl) -5-chloro-benzotriazole was added to obtain a stock solution for spinning. This spinning stock solution was treated in the same manner as in Example 1 to obtain a polyurethane elastic fiber of 40 denier / 5 filaments to which a treating agent was attached. Table 1 shows the results of evaluating various performances of the elastic fiber.

[0050]

Comparative Example 3 Instead of the mixed treatment agent used in Example 1,
40 denier / 5 with a mixed treatment agent containing no phosphate compound attached thereto in the same manner as in Example 1.
A polyurethane elastic fiber of a filament was obtained. That is, the composition of the mixed treatment agent is as follows: 98 parts by weight of dimethylsiloxane of 10 cst at 25 ° C., and mineral oil of 10 cst at 25 ° C.
5 parts by weight and 0.5 parts by weight of magnesium stearate. Table 1 shows the results of evaluating various performances of the elastic fiber.

[0051]

Comparative Example 4 Instead of the mixed treatment agent used in Example 1,
A 40 denier / 5 filament polyurethane elastic fiber to which a mixed treatment agent having a ratio of 10 cst of polydimethylsiloxane to mineral oil of 40/60 at 25 ° C. was applied in the same manner as in Example 1 was obtained. That is, the composition of the mixed treatment agent is
39.5 parts by weight of dimethylsiloxane of 10 cst at 25 ° C., 60 parts by weight of mineral oil of 10 cst at 25 ° C., mono and distearyl acid phosphate (Phoslex A-1 manufactured by Sakai Chemical Industry Co., Ltd.)
8) 0.5 parts by weight. Table 1 shows the results of evaluating various performances of the elastic fiber.

[0052]

[Table 1] Here, in Table 1, 4% of metal oxide represents 4 parts by weight of metal oxide based on 100 parts by weight of polyurethane solid content. 5% of the mixed treatment agent represents 5 parts by weight of the adhesion amount to 100 parts by weight of the polyurethane elastic fiber.

[0053]

Example 2 Polyurethane elastic fibers were prepared in the same manner as in Example 1 by using a mixed treating agent using various alkyl acid phosphates shown in Table 2 instead of the mono- and distearyl acid phosphates of Example 1. (F)-(I)
I got Table 2 shows the results of evaluating various performances of these elastic fibers.

Comparative Example 5 A polyurethane elastic fiber was prepared in the same manner as in Example 2 by using the mixed processing agent in which the amount of the tridecyl acid phosphate of Example 2 in the mixed processing agent was increased from 0.5% to 12%. Obtained. Table 2 shows the results of evaluating various performances of the elastic fiber.

Comparative Example 6 Instead of the alkyl acid phosphate of Example 2, the metal (C
a) Salt (trade name LBT-182, manufactured by Sakai Chemical Industry Co., Ltd.)
0) A polyurethane elastic fiber was obtained in the same manner as in Example 2 using 1% by weight of the mixed treatment agent. Table 2 shows the results of evaluating various performances of the elastic fiber.

[0054]

[Table 2] Here, in Table 2, 4% of metal oxide represents 4 parts by weight of metal oxide based on the solid content of polyurethane. The percentages of the various phosphates represent parts by weight based on 100 parts by weight of the polyalkylenesiloxane and the mineral oil.

[0055]

Example 3 The polyurethane elastic fibers (A), (B) and (I) of Examples 1 and 2 and the polyurethane elastic fibers of Comparative Examples 1 and 3 were dyed by the method described in the above specification. A fabric obtained by performing a fixing treatment on a 2-way tricot knitted fabric with natural tannin containing tannic acid was obtained. The number of yarn breaks during the knitting process and, after dyeing, the number of days of chlorine resistance of the fabric to which natural tannin was fixed were evaluated. Table 3 shows the results.

[0056]

[Table 3]

[0057]

According to the present invention, the polyurethane elastic fiber is excellent in the openability from the paper tube package, does not break even when the yarn is running, and does not accumulate scum on the yarn guide. The chlorine endurance performance is improved for chlorine for use.
That is, the chlorine durability and the handling property of the yarn are simultaneously improved. The elastic cloth produced by the polyurethane elastic fiber of the present invention is suitable, for example, for a swimsuit for swimming that is frequently used in a chlorinated water environment such as in a swimming pool or an elastic cloth in which a chlorine bleach is used. .

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 13/292 D06M 13/292 // D01F 6/70 D01F 6/70 Z D06M 101: 38 D06M 11/12

Claims (3)

[Claims] 1. The following (a) comprising a polyurethane polymer:
An elastic fiber which satisfies the following (b):
A polyurethane elastic fiber, characterized in that 0.5 to 10 parts by weight of a mixed treatment agent satisfying the following conditions is adhered to 100 parts by weight of the elastic fiber. (A) 0.1 to 10 parts by weight of Mg, Zn, Al as a metal compound with respect to 100 parts by weight of a polyurethane polymer
Oxides, composite oxides, hydroxides of metals selected from:
One or two selected from the group of hydrotalcite compounds
Elastic fibers containing more than one metal compound. (B) The ratio of 5-30 cst polyalkylsiloxane to 5-30 cst mineral oil at 25 ° C. is 100 / 0-50.
/ 100 parts by weight of the treating agent, the amount of the phosphate compound represented by the following formula (1) is 0.01 to
10 parts by weight of a mixed treatment agent. Embedded image (Where R is a linear or branched alkyl group having 1 to 30 carbon atoms, an alkoxypolyoxyalkylene group, a cycloalkyl group having 5 to 6 carbon atoms, 1 to 10 carbon atoms)
A cycloalkyl group having 5 to 6 carbon atoms substituted by an alkyl group, and n represents an integer of 1 or 2. ) 2. The metal compound contained in the polyurethane elastic fiber is ZnO, MgO, a composite oxide of ZnO and MgO, a divalent metal M (where M represents at least one selected from Zn and Mg). .) And a composite oxide comprising Al and a molar ratio of the divalent metal M to Al of 1 to 5,
One or two selected from the group of hydrotalcite compounds
The polyurethane elastic fiber according to claim 1, comprising at least one kind. 3. An elastic fabric comprising the polyurethane elastic fiber according to claim 1 and a polyamide-based fiber or a polyester-based fiber.