JP3280790B2 - Oil agent for polyurethane elastic yarn - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil agent used for preventing adhesion of polyurethane elastic yarn and reducing friction. More specifically, the present invention relates to an oil agent which has a small effect of deteriorating the polyurethane elastic yarn, has a necessary anti-adhesion effect, and gives a good rolled cheese.

[0002]

2. Description of the Related Art Conventionally, dry, wet and melt spinning methods have been used as methods for producing polyurethane elastic yarn. In the method of spinning these polyurethane elastic yarns, the wound cheese yarns easily adhere to each other, and when a general synthetic fiber oil agent is applied, the yarn breaks when the yarn is unwound in a later step, making it unusable. .

For this reason, various ideas have been devised for oil agents used for polyurethane elastic yarns. The urethane elastic yarn obtained by the dry or wet spinning method substantially does not contain active isocyanate groups in the yarn at the time of spinning, and the cause of adhesion is adhesion due to adhesion. JP-B-45-40719), a method of suspending metal soap (JP-B-41-286, 40-55)
57) and many other methods have been proposed.

On the other hand, the melt spinning method is advantageous because it does not require a solvent recovery and purification step, and generally has a high spinning speed, so that the production cost can be reduced. However, polyurethane elastic yarns produced by the melt spinning method have stronger adhesion between the yarns than those of the dry and wet spinning methods. This is because the polyurethane elastic yarn of the melting method has a strong reactive isocyanate group when it is wound on cheese, so that allophanate bonds and other chemical bonds are formed at the interface where the yarns adhere to each other, and the adhesive force between the yarns In order to further strengthen.
In order to solve this problem, it is effective to blend a compound having an amino group in the oil agent and chemically seal the isocyanate group, and an oil agent different from those for dry and wet polyurethane elastic yarns is proposed. Have been. For example,
16312 discloses an oil agent containing an aliphatic amine. However, although this aliphatic amine has a good effect of deactivating the isocyanate group on the yarn surface, it penetrates into the inner layer of the yarn, so that the recombination reaction after spinning reduces the isocyanate group which has the function of increasing the polymer molecular weight. ,
Therefore, the yarn physical properties decrease. Japanese Patent Publication No. 63-8233 discloses an oil containing an amino-modified silicone.
However, although this method also improves the unwinding property, it has the disadvantage that the friction between the urethane yarns is remarkably reduced, so that the shape collapses during winding and a large number of twill drops occur in a post-processing stage.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the shape of a polyurethane elastic yarn produced by a melt spinning method at the time of winding, a yarn breakage due to a twill drop in a post-processing stage, a decrease in yarn physical properties, and the like. An object of the present invention is to solve the problems and to provide an oil agent having a good adhesion preventing ability during spinning.

[0006]

According to the present invention, there is provided a polyurethane elastic yarn characterized by comprising 0.1 to 12% of a polyoxyalkyleneamine having a number average molecular weight of 300 to 4000 in order to solve the above problems. An oil agent is provided.

[0007] The oil agent for polyurethane elastic yarn of the present invention is used for producing polyurethane elastic yarn by a melt spinning method, and is mainly composed of a polyoxyalkyleneamine (hereinafter referred to as a mineral oil or a mixture of a mineral oil and a polyorganosiloxane). POAA).

The mineral oil used in the present invention can be used without any particular limitation, but has a viscosity at 25 ° C. of 3.5 to 30 _cst.
Are preferred. When the viscosity is 3.5 _cst or less, the weight loss due to evaporation is large, and when the viscosity is 30 _cst or more, the viscosity is too high at the time of winding, which is not preferable because the roller is wound around. Further, those having a flash point of 70 ° C. or more are preferred from the viewpoint of safety.

The polyorganosiloxane of the present invention is represented by the following general formula, wherein R is typically a CH ₃ group. 2. The viscosity at 25 ° C. is 3.
Those with 5 to 30 _cst are preferred.

[0010]

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The POAA of the present invention is a polyoxyalkyleneamine having a mono or diamino group at the end, and may be a monoamine or a diamine alone or a mixture of both. Polyoxyalkyleneamine can be obtained as a derivative in which the terminal of polyoxyalkylene glycol is a mono- or diamino group. As the polyoxyalkylene glycol, those obtained by adding propylene oxide to an active hydrogen compound such as methanol or propylene glycol are preferable because they have good solubility in mineral oil or a mixture of mineral oil and polyorganosiloxane. However, other alkylene oxides such as ethylene oxide and tetrahydrofuran may be copolymerized as long as the solubility is not impaired. The oxyalkylene group preferably contains at least 70% of an oxypropylene group from the viewpoint of solubility in an oil agent.

The number average molecular weight of POAA is 300 to 4.0.
00 is preferable, and if it is 300 or less, it penetrates into the inner layer of the yarn, and the recombination reaction after spinning reduces isocyanate which has the function of increasing the molecular weight of the polymer, thereby deteriorating the physical properties of the yarn. . On the other hand, if it is more than 4,000, the effect of preventing adhesion is reduced due to a decrease in the concentration of amino groups, which is not preferable.

The mixing ratio of the mineral oil and the polyorganosiloxane is arbitrary. When the mixing ratio of the polyorganosiloxane is high, the adhesion preventing ability and the friction performance are improved, but the solubility of POAA is reduced. ~ 3
0:70 is preferred.

The amount of POAA in the oil agent is 0.1%.
% To 12% by weight, preferably 1 to 10% by weight.
When the content is 0.1% by weight or less, the adhesion preventing ability becomes insufficient, and when the content is 12% by weight or more, phase separation occurs due to poor solubility, and the viscosity of the oil agent increases, resulting in poor winding. Bring.

The solubility of the oil agent of the present invention may be further increased by adding a compatibilizer such as a higher alcohol. Further, in order to further improve the friction characteristics and the adhesion preventing property, modified silicons such as polyether-modified silicon, alcohol-modified silicon, and alkyl-modified silicon may be added. or,
It may be used in combination with an aliphatic amine and amino-modified silicon. It is also effective to heat the oil agent to make it uniform.

The oil agent of the present invention may be supplied to a polyurethane elastic yarn by a conventional method. For example, a method in which the filament discharged from the spinneret is brought into contact with an oiling roller before being wound up, or a nozzle oiling method is used. The oil is applied to the filament from 1 to
10% by weight, preferably 2 to 7% by weight, are deposited. 1
% Or less, the anti-adhesion ability and friction performance are not sufficient.
If it is 0% or more, it is not preferable in terms of troubles due to separation and scattering of the oil in each processing step and oil cost.

[0017]

The adhesive agent of the present invention has a number-average molecular weight of 3
Since a high molecular weight amine of from 4000 to 4000 is blended, the permeability to the yarn is slower than that of a low molecular weight amine, so that it hardly reacts with the isocyanate group inside the yarn. This effect is exhibited by effectively sealing the isocyanate group which causes the adhesive force of the yarn, and by having a high ability to cover the yarn surface due to the large volume of the amine molecule. In addition, since the penetration into the inside of the yarn is slow and the recombination reaction of the isocyanate group inside the yarn is not hindered, a decrease in the physical properties of the yarn is also suppressed.

[0018]

EXAMPLES Examples 1 to 7 and Comparative Examples 1 to 6 71 parts of polyethylene propylene adipate having an average molecular weight of 2,000 (ethylene / propylene molar ratio 9/1) and 29 parts of 4,4'-diphenylmethane diisocyanate (MDI) Was charged into a jacketed reactor and reacted at 80 ° C. for 1 hour to obtain a prepolymer.

The prepolymer had an isocyanate group content of 6.65%. After defoaming, the prepolymer was continuously supplied with 1,4-butanediol at a weight ratio of 100: 6.3 to a cylindrical reactor having an internal volume of 600 cm ² and equipped with a stirrer and reacted. The reactor pressure was set at 5 kg / cm ² and the reaction temperature was 210 ° C. The discharged polymer was pressurized to 50 kg / cm ² by a pressure pump and supplied to a spinning head having eight nozzles. The discharge amount per nozzle was 2.67 g / min, and a winding machine having two godet rolls was used to obtain 40 d of elastic yarn at a spinning speed of 600 m / min. The head temperature was 205 ° C. The isocyanate group content in the discharged yarn was 0.5%.
The oil was heated to 40 ° C. and provided between the first and second godet rolls by an oiling roller method. The amount of the oil agent attached to the yarn was about 6%.

The compositions of the oils are as shown in Examples 1 to 7 and Comparative Examples 1 to 6 in Table 1.

[0021] Examples and Comparative Examples using component mineral oil (Matsumoto Yushi, T _PN -11) 25 ° C Viscosity 5 _cst polyorganosiloxane 25 ° C Viscosity 5 _cst (Shin-Etsu Silicone Co., KF-96L) Polyether modified Silicon (PO / EO modified) Viscosity at 25 ° C 1400 _cst (Matsumoto Yushi, SIE-49) Amino modified silicone: Amino modified silicon at both ends (Shin-Etsu Silicone, X-22-161A amine equivalent 840) Amino compound POAA (1 ): Amino-modified polypropylene glycol at both ends (manufactured by Texaco Mitsuishi, Jeffamine D-400, number average molecular weight 400) P0AA (2): Amino-modified polypropylene glycol at both ends (manufactured by Texaco, Jeffamine D-2000, number-average molecular weight 2000) P0AA (3): Amino-modified polypropylene glycol at one end (manufactured by Texaco Mitsuishi, Jeffamine M-600 number average molecular weight 600) A (4): one end amino-modified polypropylene glycol (Mitsuishi Texaco Ltd., JEFFAMINE M-2005 a number average molecular weight 2000)

Examples 8 to 13 and Comparative Examples 7 to 12 Spinning was carried out in the same manner as in Example 1 except that poly-3-methylpentane adipate (Kuraray P-2010) was used instead of polyethylene propylene adipate. Was.
The oil composition is shown in Examples 8 to 13 and Comparative Examples 7 to 12 in Table 1.

Examples 14 to 17 and Comparative Examples 13 to 14 Spinning was carried out in the same manner as in Example 1. The oil composition is shown in Table 2.

Measurement Results Table 3 shows the measurement results of Examples 1 to 13 and Comparative Examples 1 to 12 in terms of shape loss, adhesion, and strength retention. Examples 14 to 17, Comparative Example 13
Table 4 shows the similar measurement results of Nos. To 14.

Measurement method Cheese crumble: rolled on a paper tube with an outer diameter of 80 mm and a width of 57 mm with a width of 44 mm
Judgment was made based on the winding shape when 400 g was wound. Adhesion degree: After the wound cheese has been aged for more than one week, put it on a drawer / winder with a variable magnification and send it out at a speed of 50 m / min. Indicated by 1.3 or less is preferable. Deterioration in strength due to amine component: Take 1 g of elastic yarn immediately after spinning, immerse it in 20 g of oil agent, and let it stand for one day. After removal, the tenacity was measured and the retention was determined by comparing with the untreated yarn.
It is preferably at least 75%.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

As can be seen from the measurement results in Tables 3 and 4,
The oil agent of the present invention has the following advantages. (2) A good rolled cheese is obtained. And so on.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-58-132170 (JP, A) JP-A-4-24284 (JP, A) JP-A-58-180684 (JP, A) JP-A-2- 127570 (JP, A) JP-A-5-195442 (JP, A) JP-A-52-213 (JP, A) JP-B-46-16312 (JP, B1) JP-B-63-8233 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) D06M 13/00-15/715

Claims (8)

(57) [Claims] 1. An oil agent for polyurethane elastic yarns, comprising 0.1 to 12% of a polyoxyalkyleneamine having a number average molecular weight of 300 to 4000. 2. The oil agent for polyurethane elastic yarn according to claim 1, wherein the polyoxyalkyleneamine is a monoamine, a diamine, or a mixture of both. 3. The polyurethane according to claim 1, wherein the polyoxyalkyleneamine is a compound having a terminal amino group derived from polypropylene glycol or a copolymer of propylene oxide and another alkylene oxide other than propylene oxide. Oil agent for elastic yarn. 4. The oil agent for polyurethane elastic yarn according to claim 1, wherein the component other than the polyoxyalkyleneamine is mainly composed of mineral oil or a mixture of mineral oil and polyorganosiloxane. 5. The oil agent for polyurethane elastic yarn according to claim 2, wherein the alkylene oxide other than propylene oxide is one or more alkylene oxides selected from ethylene oxide and tetrahydrofuran. 6. The mineral oil has a viscosity of 3.5 to 30 at 25 ° C.
_The oil agent for polyurethane elastic yarn according to claim 4, which is _cst . 7. A polyorganosiloxane having a viscosity of 25 °
The oil agent for polyurethane elastic yarn according to claim 4, wherein C is 3.5 to 30 _cst . 8. The oil agent for polyurethane elastic yarn according to claim 1, wherein the polyurethane elastic yarn is produced by melt spinning.