JPH06200419A - Polyurethane elastic yarn - Google Patents

Abstract

(57) [Summary] [Purpose] To obtain a polyurethane-based elastic yarn having high elasticity and no unsticking property and excellent in unwinding property. [Structure] An oil agent containing a polyalkylsiloxane that is liquid at room temperature and a polyalkylsiloxane that is solid at room temperature as main components is attached to polyurethane fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastic yarn which has high elasticity and is free of stickiness and excellent in unwinding property.

[0002]

2. Description of the Related Art Conventionally, in order to prevent the thread stickiness, the higher fatty acid metal salt is dispersed in a spinning oil agent, and the thread soap oil agent is added to the thread to prevent the thread stickiness. The higher fatty acid metal salt is dispersed in the polymer in an amount of 0.3% by weight or more and spun to prevent sticking. These are intended to allow the higher fatty acid metal salt to be present on the surface of the polymer to prevent the sticking of the yarn. Further, Japanese Patent Publication No. 42-8438 describes that polyamyl siloxane is added as a component of an oil agent and the oil agent is applied to a yarn to prevent sticking.
Even if this polyamylsiloxane is added, the adhesiveness of the yarn cannot be sufficiently prevented, and the elastic yarn cannot be unwound smoothly from the cheese, and in particular, it is difficult to prevent the adhesiveness in the inner layer of the cheese. In many cases, problems such as uneven tension of the yarn and cutting of the yarn occur in the post-processing step of the elastic yarn.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an elastic yarn in which the elastic yarn is prevented from sticking, and in particular, the unwindability of the yarn in the inner layer of the elastic yarn cheese is improved. Dispersing a large amount of a higher fatty acid metal salt in a polymer not only makes it difficult to disperse, but also adversely affects the yarn convergence. That is, usually, the elastic yarn is spun as a multifilament and is converged by applying false twist or the like. If the convergence is not sufficient here, the yarn is cut by filament static electricity or the like while passing through post-processing steps such as warping, circular knitting, and covering steps. From this viewpoint, it is not preferable for the elastic yarn to disperse a large amount of the higher fatty acid metal salt in the polymer.

[0004]

The present invention relates to a yarn obtained by spinning a polyurethane-based polymer a. A polyalkylsiloxane that is liquid at room temperature and b. An elastic yarn obtained by applying an oil agent composed of a polyalkylsiloxane that is solid at room temperature and then winding it. The polyurethane polymer of the present invention contains a small amount of 0.1 to 0.
It is more preferable to contain 3 wt% of a metal salt of saturated higher fatty acid Mg and / or Ca. The saturated higher fatty acid used at this time is a fatty acid having 12 to 20 carbon atoms, and stearic acid is particularly preferable. In addition, fatty acids are used as magnesium or calcium salts. Magnesium stearate is preferably used.

Further, the polyurethane-based polymer constituting the yarn is, for example, an intermediate group having an isocyanate group at an end group by reacting a polyether glycol or polyester glycol having a number average molecular weight of 600 to 5000 with an excess mole of an organic diisocyanate compound. It can be obtained by obtaining a polymer, dissolving the intermediate polymer in an inert solvent, and then adding an organic diamine to cause a reaction. The polymer solution thus obtained is allowed to contain a higher fatty acid metal salt in a proportion of 0.1 to 0.3% by weight, and the polymer is dry-spun. As described above, when 0.3% by weight or more of the higher fatty acid metal salt is contained in the polymer, filament splitting or the like occurs and the post-process passability is reduced. If it is 0.1% or less, the synergistic effect with the oil agent used in the present invention often decreases. Examples of the polyether glycol include polytetramethylene ether glycol, polypropylene ether glycol, polyethylene ether glycol and the like. Polyester glycol, succinic acid, adipic acid and other organic fatty acids and ethylene glycol,
Some are obtained by polycondensation with an organic glycol such as propylene glycol, butanediol or hexanediol. Preferably, the number average molecular weight is 1,000 to 30.
00 polytetramethylene ether glycol is used.

The organic diisocyanate compound used in the present invention includes p, p'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate and 1,4-
Examples thereof include phenylene diisocyanate and 4,4′-dicyclohexylmethane diisocyanate. Especially p,
P'-diphenylmethane diisocyanate is preferred. Furthermore, the polyether glycol or polyester glycol and the organic diisocyanate compound are used in a ratio of isocyanate groups to hydroxyl groups of between 1.3 and 2.6. As the organic diamine, hydrazine, ethylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, 1,3-
Cyclohexyldiamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, m
Examples include diamines such as xylylenediamine and hydrogenated products thereof, p-xylylenediamine and hydrogenated products thereof, and mixtures thereof. As the inert solvent used in the polymerization reaction, N, N-dimethylformamide,
Examples of the polar solvent include N, N-dimethylacetamide, N, N, N ′, N′-tetramethylurea, N-methylpyrrolidone and dimethylsulfoxide. In addition to 0.1 to 0.3% by weight of the higher fatty acid metal salt, an antioxidant, an ultraviolet absorber, a pigment, a tertiary amino compound and the like are added to the obtained polymer solution, if necessary. Of course, a diol may be used in place of the diamine, the intermediate polymer may be sharply extended and melt-spun, but the method of solution polymerization by the above-mentioned method and dry-spinning is more preferable.

The polymer solution thus obtained is dry-spun by a usual method, and an oil agent is applied by which the filaments are converged by a method such as false twisting. The oil agent used in the present invention comprises a. A polyalkylsiloxane that is liquid at room temperature and b. It is composed of polyalkyl siloxane which is solid at room temperature. A polyalkylsiloxane that is liquid at room temperature is represented by dimethylsiloxane. Although the viscosity changes depending on the molecular weight, dimethylsiloxane having a viscosity of 5 cst to 20 cst at room temperature (25 ° C) is recommended. A polyalkylsiloxane that is solid at room temperature can be obtained as follows. A polyalkylsiloxane is obtained by reacting an alkyl-trialkoxysilane in an inert solvent such as toluene or xylene to dealcoholize. Dimethylsiloxane is added to the obtained polyalkylsiloxane solution and heated to distill off the solvent to finally obtain a dimethylsiloxane mixture of polyalkylsiloxane. Preferred polyalkyl siloxanes have a poly n-butyl siloxane skeleton.

Basically,-((n-Bu) SiO _3/2 )
It has a structure indicated by _n . Also, the viscosity of a mixture of poly n-butyl siloxane and dimethyl siloxane having a viscosity of 10 cst at 25 ° C. in a weight ratio of 20/80 is 15 to 40 c.
st (25 ° C.), especially n that is 20 to 30 cst
-Butylsiloxane is preferred. The higher the viscosity, the lower the compatibility with dimethylsiloxane. If the viscosity is low, it becomes a viscous liquid at room temperature and it is difficult to prevent the thread from sticking. This poly n-butyl siloxane is
It is added to the oil agent at a ratio of 2 to 3% by weight. Further, dimethylsiloxane is blended in the oil agent in a proportion of 98 to 60% by weight. Further, if necessary, modified silicone, mineral oil and the like can be mixed. The thread to which the oil agent is applied is wound around the bobbin by a usual method. In the elastic yarn thus obtained, the yarns are prevented from sticking to each other and the unraveling of the elastic yarn from the cheese is smooth. In particular, the unwinding of the elastic yarn from the cheese inner layer is improved.

In the present invention, a polyalkyl siloxane which is liquid at room temperature and a polyalkyl siloxane which is solid at room temperature are applied to an oil agent on the yarn surface, and a small amount of a higher saturated fatty acid metal salt is added to the polymer. It becomes more effective by including. Evaluation of unwinding of elastic yarn from cheese is performed as follows. Set the cheese on a 10 cm diameter satin-finished roller,
The surface speed of the roller is adjusted to 50 m / min. On one side, a bobbin for winding is set on the same satin-finished roller having a diameter of 10 cm. The elastic yarn sent out at 50 m / min is wound on one winding bobbin.
At that time, the wound elastic roller prepares the winding roller at a minimum speed at which the elastic yarn cannot be pulled up in the rotation direction of the cheese. The surface speed of the lowest roller is measured and the unwinding property is expressed as follows. Unwindability (%) = (S−S ₀ ) / S ₀ × 100 where S ₀ is the delivery speed of the elastic yarn (50 m / min) S is the lowest winding speed of the elastic yarn, that is, the unwindability is 0 % Means that the elastic yarn can be unwound from cheese without tension.
The unwinding property of the cheese inner layer being 0% indicates that it is difficult to maintain the shape of the cheese,
Usually, the value is 0% or more. The invention is illustrated in the examples below. It should be noted that these examples illustrate the present invention and are not limited thereto.
In the examples, the parts are weighted and the unwinding property is evaluated according to the above method. This unwinding value is 5-10
It is preferably in the range of 0%, more preferably in the range of 15 to 85% in the inner layer of cheese.

[0010]

【Example】

(Example 1) 10,000 parts of polytetramethylene ether glycol having a number average molecular weight of 2000 and 2500 parts of 4,4'-diphenylmethane diisocyanate were placed in a jacketed polymerization vessel and heated to 70 ° C while stirring. After heating for 1 hour, heating was stopped, 20354 parts of N, N-dimethylacetamide was added, and the reaction mixture was dissolved while cooling. When the internal temperature reaches 8 ℃,
333 parts of 1,2-diaminopropane and 17 parts of N, N-diethylamine were mixed with 5000 parts of N, N-dimethylacetamide.
The solution dissolved in the solution was gradually added dropwise with stirring.
After adding about 4000 parts, cooling was stopped and the amine solution was added dropwise. After adding a total amount of 5230 parts of the amine solution, 105 parts of N, N-diethylamine and N, N-
A solution of 1000 parts of dimethylacetamide was added.

Polymer solution 15 thus obtained
15% by weight of magnesium stearate in 000 parts
65 parts of N, N-dimethylacetamide dispersion was added,
1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethyl-benzyl) isocyanuric acid 49
Parts, 50 wt% N, N-dimethylacetamide solution of poly (N, N-diethylaminoethyl) methacrylate 1
47 parts and 656 parts of a 30% by weight titanium dioxide N, N-dimethylacetamide dispersion were added and stirred for 45 minutes to obtain a spinning dope. The spinning dope thus obtained was fed at a rate of 4.04 g / min to a spinneret having two pores. Then, it was extruded from the pores into hot air to evaporate the solvent. The dried yarn was passed through a false twisting machine that generates a swirling air flow to give false twist, and then contacted with an oiling roller. For oiling rollers, use poly n
20% by weight of butyl siloxane of 10 cst dimethylsiloxane mixture has a viscosity of 26 cst at 25 ° C.
An oil solution consisting of 5 parts of butyl siloxane and 95 parts of 10 cst dimethyl siloxane was fed. The surface speed of the oiling roller was adjusted so that the amount of the applied oil agent was 6% by weight based on the yarn. 6 minutes per minute for elastic thread with oil
The bobbin was wound up at a speed of 00 m.

Wound 400 g of elastic thread on the bobbin and
0 denier elastic yarn cheese was obtained. The obtained cheese is 45
After being left in an atmosphere of ° C for 24 hours, the unwinding property of the surface layer and the inner layer of the cheese was measured. As a result, the surface layer was 4% and the inner layer was 16%. In addition, the obtained cheese is set in a covering machine, and the elastic yarn is sent out at a speed of 6 meters per minute,
The nylon processed yarn was wound up and wound up at 21 m / min. As a result, the unraveling of the elastic yarn from the cheese was not taken up to the inner layer in the direction of rotation of the cheese. Further, the obtained cheese was placed on a roller, sent out at a speed of 200 m / min and combined with the nylon-processed yarn, and then the elastic yarn and the nylon-processed yarn were entangled with an air stream and wound up at a speed of 625 m / min. Also in this result, the unraveling of the elastic yarn from the cheese was performed without reaching the inner layer in the direction of rotation of the cheese.

(Example 2) 9000 parts of polytetramethylene ether glycol having a number average molecular weight of 1800,
Charge 2125 parts of 4'-diphenylmethane diisocyanate into a jacketed polymerization vessel and stir at 70 ° C.
Heated to. After heating for 80 minutes, stop heating,
18200 parts of N-dimethylacetamide was added, and the reaction mixture was dissolved while cooling. When the internal temperature reached 8 ° C, 151 parts of ethylenediamine, 47 parts of 1,2-diaminopropane, and 11 parts of N, N-diethylamine were dissolved in 4000 parts of N, N-dimethylacetamide, and the solution was gradually added dropwise with stirring. did. After adding about 3500 parts, the cooling was stopped and the amine solution was added dropwise. After adding a total of 4200 parts of amine solution, N,
A solution of 77 parts of N-diethylamine and 1000 parts of N, N-dimethylacetamide was added. To 15,000 parts of the polymer solution thus obtained, 65 parts of a 15% by weight magnesium stearate N, N-dimethylacetamide dispersion was added, and 1,3,5-tris (4-t-
Butyl-3-hydroxy-2,6-dimethyl-benzyl) isocyanuric acid 49 parts, 3-ethyl-1,5-dimethyl-3-azapentane-1,5-diol and 4,4 ′
68 parts of a 50% by weight N, N-dimethylacetamide solution of a polymer with -dicyclohexylmethane diisocyanate was added and stirred for 45 minutes to obtain a spinning dope.

The spinning dope thus obtained was spun in the same manner as in Example 1. To the oiling roller, 4 parts of poly (n-butyl siloxane) having a viscosity of 10 cst dimethyl siloxane mixture of 20% by weight of poly (n-butyl siloxane) of 26 cst at 25 ° C. and 60 parts by Redwood viscometer.
An oil solution comprising 20 parts of mineral oil having a viscosity of 10 seconds, 74 parts of dimethylsiloxane having a viscosity of 10 cst, and 2 parts of ethylene oxide / propylene oxide modified silicone was supplied. The surface speed of the oiling roller was adjusted so that the amount of the applied oil agent was 6% by weight based on the yarn. The elastic yarn to which the oil agent was applied was wound around a bobbin at a speed of 600 m / min. 20 g of 400 g of elastic thread is wound around the bobbin
A denier elastic yarn cheese was obtained. The obtained cheese is 45 ° C
After leaving it in the atmosphere for 24 hours, the unwinding property of the surface layer and the inner layer of the cheese was measured. As a result, the surface layer was 10% and the inner layer was 36%. In addition, the obtained cheese is set in a covering machine, and the elastic yarn is sent out at a speed of 6 meters per minute,
The nylon processed yarn was wound up and wound up at 21 m / min. As a result, the unraveling of the elastic yarn from the cheese was not taken up to the inner layer in the direction of rotation of the cheese. Further, the obtained cheese was placed on a roller, sent out at a speed of 200 m / min and combined with the nylon-processed yarn, and then the elastic yarn and the nylon-processed yarn were entangled with an air stream and wound up at a speed of 625 m / min. Also in this result, the unraveling of the elastic yarn from the cheese was performed without reaching the inner layer in the direction of rotation of the cheese.

(Example 3) The stock solution for spinning obtained in Example 1 was spun in the same manner as in Example 1. The following oil was supplied to the oiling roller. An oil formulation consisting of 5 parts of poly-n-butylsiloxane having a viscosity of 50% by weight of a 10 cst dimethylsiloxane mixture of 80 cst at 25 ° C. and 95 parts of dimethylsiloxane having a viscosity of 10 cst was fed. The surface speed of the oiling roller was adjusted so that the amount of the oil agent adhered was 6% by weight with respect to the yarn. The cheese was not taken in the rotating direction of the obtained cheese, but the inner layer was partially covered in the rotating direction of the cheese. I was seen to be seen. But,
The elastic thread was never cut. Similarly, in the case of the entangled yarn, the unraveling of the elastic yarn was not taken in the rotation direction of the cheese in the surface layer, but the elastic yarn was cut in the rotation direction of the cheese in the inner layer.

(Example 4) To 10,000 parts of the polymer solution obtained in Example 1, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethyl-benzyl) was added.
Isocyanuric acid 32 parts, poly (N, N-diethylaminoethyl) methacrylate 50% by weight N, N-dimethylacetamide solution 98 parts, titanium dioxide 30% by weight
437 parts of N, N-dimethylacetamide dispersion was added and stirred for 45 minutes to obtain a spinning dope. This spinning solution was spun in the same manner as in Example 1 to obtain elastic yarn cheese. The oil agent is also the same as in Example 1. The obtained cheese was evaluated for unwinding property, covering, and entangled yarn. As a result, the surface unwinding property was 65% and the inner layer unwinding property was 93%. When set on a covering machine, the unraveling of the elastic yarn was not taken in the direction of rotation of the cheese in the surface layer, but it was found that it was partly taken in the direction of rotation of the cheese in the interior. But,
The elastic thread was never cut. Similarly, in the case of the entangled yarn, the unraveling of the elastic yarn was not taken in the rotation direction of the cheese in the surface layer.

Example 5 10000 parts of the polymer solution obtained in Example 1 was mixed with 15 parts of magnesium stearate.
162 parts by weight of N, N-dimethylacetamide dispersion was added, and 1,3,5-tris (4-t-butyl-3) was further added.
-Hydroxy-2,6-dimethyl-benzyl) isocyanuric acid 32 parts, poly (N, N-diethylaminoethyl)
98 parts of a 50 wt% N, N-dimethylacetamide solution of methacrylate and 437 parts of a 30 wt% N, N-dimethylacetamide dispersion of titanium dioxide were added and stirred for 45 minutes to obtain a spinning dope. This spinning dope is used in Example 1.
An elastic yarn cheese was obtained by spinning in the same manner as in. The oil agent is also the same as in Example 1. The obtained cheese was evaluated for unwinding property, covering, and entangled yarn. As a result, the unwinding property of the surface layer was 0% and the unwinding property of the inner layer was 4%. When it was set on a covering machine, the filament was split into two filaments, one of which was wound on a delivery roller and cut. Even in the case of the entangled yarn, the filament was divided into two and the elastic yarn was cut.

Example 6 The spinning dope obtained in the same manner as in Example 2 was spun. Table 1 shows the results obtained by changing the oil agent as shown in Table 1 below.

[0019]

[Table 1]

[0020]

As described above, according to the present invention as shown in the examples, the sticking of elastic yarn with cheese is spun, and the process passability in the processing process is also improved. The effect of the oil agent of the present invention becomes more remarkable by adding 0.1 to 0.3% by weight of a higher fatty acid metal salt to the yarn.

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Claims (4)

[Claims] 1. A yarn obtained by spinning a polyurethane polymer, comprising: a. A polyalkylsiloxane that is liquid at room temperature, b. A polyurethane-based elastic yarn in which a polyalkylsiloxane that is solid at room temperature is added as an oil agent. 2. The polyurethane elastic yarn according to claim 1, wherein the polyalkylsiloxane which is liquid at room temperature is dimethylsiloxane having a viscosity of 5 cst to 20 cst. 3. The polyurethane elastic yarn according to claim 1, wherein the polyalkylsiloxane which is solid at room temperature is a polyalkylsiloxane having an n-butylsiloxane skeleton. 4. A. 60-98% by weight, b. Is 2-1
The polyurethane elastic yarn according to claim 1, wherein an oil agent of 0% by weight is added.