JP2948950B2 - Oil agent for elastic fiber - 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 for elastic fibers, and more particularly to an oil agent having excellent anti-sticking properties and anti-roll-over properties.

[0002]

2. Description of the Related Art Elastic fibers are spun by a dry method, a wet method, or a melting method. However, in any of the methods, the polyurethane resin (polyurethane urea resin) used has a high content of an amorphous part, and thus is sticky. When wound up on a bobbin,
There is a problem that a bobbin on which an elastic fiber has been wound cannot be unwound stably because the fibers are strongly stuck together. Particularly in the melt spinning method, it is said that the yarn immediately after spinning has a part where urethane bonds are dissociated, and it is said that chemical bonding occurs between the fibers after winding on a bobbin. Problem. Further, since the elastic fiber has a low elastic modulus, there is a problem that even a slight friction during the process is elongated, and a spot is easily generated. As an oil agent for preventing such sticking and reducing friction, an oil agent in which fine particles such as talc and magnesium stearate are suspended in polydimethylsiloxane (silicone) or mineral oil (liquid paraffin) is disclosed in Japanese Patent Publication No. 41-286. Japanese Patent Publication No. 45-40719 discloses an oil agent in which polyether-modified silicone is blended with polydimethylsiloxane or mineral oil.
An oil agent in which an amino-modified silicone is blended with polyorganosiloxane or mineral oil is described in JP-B-63-8233.

[0003] However, oils using fine particles such as talc cannot be said to have sufficient anti-sticking properties, and in the processing step, fine particles accumulate in guides and cause scum, causing troubles such as yarn breakage and fluctuation in tension. May cause. or,
In the case of using an ether-modified silicone, the higher the degree of modification and the higher the hydrophilicity, the higher the anti-sticking effect.However, if the degree of modification begins to exhibit the anti-sticking effect, the compatibility with mineral oil and silicone becomes poor. Phase separation occurs. For dissolution, it is necessary to use a compatibilizer such as a higher alcohol or a low molecular ester. However, since the compatibilizer swells the polyurethane resin, the performance as spandex is remarkably reduced and the yarns are stuck together. Of course, it is possible to use a silicone having a modified degree of dissolution, but it is impossible to prevent sticking at all. Oils using amino-modified silicones have high anti-sticking performance, but they extremely reduce the coefficient of friction on the fiber surface. Cannot be rolled up.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oil agent for an elastic fiber which is excellent in anti-sticking property and unwinding property and free of scum and excellent in anti-collapse.

[0005]

According to the present invention, 89.0 to 99.8% by weight of a polyorganosiloxane, 0.1 to 10% by weight of an amino-modified polyorganosiloxane, and 0.1 to 10% by weight of an ether-modified polyorganosiloxane. An oil agent for elastic fibers comprising 0% by weight and having a viscosity at 30 ° C. of 30 centistokes or less.

The polyorganosiloxane referred to in the present invention is a compound having a structural unit represented by the following formula 1 as a repeating unit.

[0007]

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In the present invention, it is generally called a silicone or a silicone oil, and it means a polyorganosiloxane which is not substantially modified with an amino group or an ether. Among them, polydimethylsiloxane is widely used. The viscosity of the polyorganosiloxane used can be arbitrarily selected, but is preferably 5 to 15 centistokes in consideration of the viscosity resistance with the guides.
If it exceeds 15 centistokes, denier spots may be generated because the elastic yarn is stretched by resistance, and if it is less than 5 centistokes, a large amount of low boiling point is contained and loss due to evaporation and vaporization is large.

It is also effective to use a polyorganosiloxane in which a low-viscosity material (for example, 2 to 5 CS) and a high-viscosity material (for example, 10 to 30 CS) are blended and used to keep the loss in a processing step of an oil agent at a certain level. Means.

The amino-modified polyorganosiloxane used in the present invention is obtained by introducing an amino group into a polyorganosiloxane. The modification site of the amino group may be a side chain or a main chain. The amino equivalent of the amino-modified polyorganosiloxane (average molecular weight of amino-modified polyorganosiloxane / average number of amino groups per molecule) is as follows:
It is preferably from 50 to 200,000. When the amino equivalent is less than 50, the effect of lowering the friction coefficient of the fiber surface is large, so that the proportion of the amino-modified polyorganosiloxane in the oil agent of the present invention must be delicately controlled, making it difficult to adjust the oil agent.

When the amino equivalent exceeds 200,000, the difference from the unmodified polyorganosiloxane becomes small, the sticking is prevented, and the effect of reducing the frictional force is reduced. However, when the amino equivalent is small, the polymer is polymerized by carbon dioxide gas or the like, and a solidified product may be generated. Therefore, the most preferable range is 3,000 or more and 6,000 or less. The amino-modified polyorganosiloxane has a viscosity of 5 centistokes (hereinafter abbreviated as CS) and 5,000C.
S or less, particularly preferably 10 CS or more and 2,000 CS or less. Those having a low viscosity contain a large amount of a low-molecular-weight amino-modified polyorganosiloxane, have a stronger character as an amine than a silicone, and in very rare cases, may cause skin damage. Also 5,000
If it exceeds 0CS, there is a problem in achieving the viscosity range of 30CS or less of the oil agent of the present invention. Amino-modified polyorganosiloxane and polyorganosiloxane may not be compatible depending on their type, composition, and viscosity.However, by adjusting the viscosity and degree of modification of amino-modified polyorganosiloxane, the composition, type, and viscosity of polyorganosiloxane. Compatibility can be achieved. The ether-modified polyorganosiloxane referred to in the present invention means a chain ether having a structural unit represented by the following chemical formula 2, which forms a block copolymer or a graft copolymer with a polyorganosiloxane.

[0012]

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R ↓ 3 is preferably an alkylene group. Specific examples include ethylene oxide and / or propylene oxide-modified polydimethylsiloxane.
If the degree of ether modification is increased and the hydrophilicity is increased, the polyorganosiloxane may not be compatible with the polyorganosiloxane. In this case, if the compatibilizing agent is used, the physical properties of the elastic fiber are reduced as described above, so that the compatibilization should be performed by adjusting each composition. The viscosity of the ether-modified polyorganosiloxane should also be kept high to avoid the viscosity range of the oil agent of the present invention of 30 CS or less, and 3,000 CS or less, more preferably 1,500 CS or less. preferable.

In the present invention, the viscosity of the oil agent is 3
The viscosity at 0 ° C. (hereinafter, the viscosity at 30 ° C. is specified unless otherwise specified) is required to be 30 CS or less, more preferably 10 CS or less. This is because oil viscosity is 30
When CS is exceeded, the elastic fiber has an extremely low elastic modulus and high elongation, so it is taken up by rollers and guides at the time of winding up due to the viscosity of the oil agent, and it is wound up on a bobbin in a state where unevenness has occurred, This is because the yarn may be wound around the thread. Also, in the processing steps such as weaving and knitting, troubles such as generation of unevenness in extension due to friction due to the viscosity of the oil agent occur. Of course, if necessary, a viscosity reducing (diluting) agent, for example, a low-viscosity polydimethylsiloxane can be used in combination.

It is preferable that the oil agent is added in an amount of 1.0 to 10.0% by weight with respect to the polyurethane elastic fiber.
If it is less than 1.0% by weight, it is not sufficient in terms of prevention of sticking.
If it exceeds 0.0% by weight, it is not preferable from the viewpoint of prevention of collapse and cost.

When the oil agent of the present invention is applied to the following polyurethane elastic fiber, its effect is remarkably exhibited. The polyurethane elastic fiber is composed of a polyurethane obtained by polymerizing a polymer diol, an organic diisocyanate and a chain extender, and is preferably an elastic fiber composed of a polyurethane using a characteristic polymer diol shown below.

The high molecular weight diol is a diol unit represented by the formula -OR ↑ 4-O- (wherein R ↑ 4 represents a divalent organic group);

[0018]

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And / or a dicarboxylic acid unit represented by the formula:

[0020]

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Polyester diols, polycarbonate diols and polyester polycarbonate diols comprising a carbonyl unit represented by the following formula and having a diol unit bonded to both ends of the dicarboxylic acid unit and the carbonyl unit are preferred. Examples of the divalent organic group R # 4 contained in the diol unit include carbons such as tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, 3methylpentamethylene, and 2methyloctamethylene. An alkylene group of the number 4 to 10 is exemplified. Examples of the diol that provides the diol unit include 1,
4-butanediol, 1,6-hexanediol, 1,
7-heptanediol, 1,8-octanediol,
Examples include 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol. Preferably, it is 3-methyl-1,5-pentanediol.

The divalent organic group R # 5 contained in the dicarboxylic acid unit includes a carbon atom having 3 to 10 carbon atoms such as a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group and an octamethylene group. And a divalent saturated aliphatic hydrocarbon group having 6 to 10 carbon atoms such as an o-, m- or p-phenylene group, and a naphthylene group. As the compound providing a dicarboxylic acid unit, a dicarboxylic acid such as a saturated aliphatic or aromatic dicarboxylic acid having 5 to 12 carbon atoms is preferable,
Examples of the saturated aliphatic dicarboxylic acid include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, and isophthalic acid. Preferably, azelaic acid and sebacic acid are used. The molecular weight of these high molecular diols is 10
A range from 00 to 3000 is preferred.

Suitable organic diisocyanates used in the present invention include aliphatic, alicyclic or aromatic organic diisocyanates.
4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, toluylene diisocyanate,
Examples thereof include diisocyanates having a molecular weight of 500 or less, such as 1,5-naphthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. Preferred is 4,4'-diphenylmethane diisocyanate.

In the present invention, the chain extender used is a chain extender commonly used in the polyurethane industry,
That is, low molecular weight compounds having a molecular weight of 400 or less containing at least two hydrogen atoms capable of reacting with isocyanate, such as ethylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol,
Methyl-1,5-pentanediol, 1,4-bis (2
Diols such as -hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate, and xylene glycol. These compounds may be used alone or in combination of two or more. The most preferred chain extender is 1,4-
Butanediol and / or 1,4-bis (2-hydroxyethoxy) benzene.

With respect to the quantitative relationship between the polymer diol, the organic diisocyanate and the chain extender used for producing the polyurethane used in the present invention, the heat resistance and elastic recovery of the obtained polyurethane are particularly good. From the viewpoint, it is preferable that the amount of the organic diisocyanate be 0.9 to 1.2 times the molar number of the total of the polymer diol and the chain extender used. More preferably, 0.95
１．１1.15 times the number of moles.

It is known that polyurethane elastic fibers are produced by a wet spinning method, a dry spinning method and a melt spinning method. However, when the oil agent of the present invention is applied to elastic fibers obtained by a melt spinning method, The effect is remarkable.

[0027]

The oil agent of the present invention is made of an elastic fiber, especially an elastic fiber made of thermoplastic polyurethane (spandex).
By spinning after applying during spinning, not only can sticking be prevented, but also frictional resistance can be appropriately generated between the fibers to prevent collapse of winding. Further, the friction with guides, knitting needles, and the like in the processing step is reduced, and no scum is generated, so that a high-quality finished product such as a knitted fabric can be obtained. If necessary for the oil agent of the present invention, conventionally used fine particles, antioxidants, ultraviolet absorbers and the like can be used in combination.

The oil agent of the present invention is also useful for synthetic fibers such as polyester fibers, polyvinyl alcohol yarn fibers, acrylic fibers and nylon fibers, and natural fibers such as wool and hemp. Hereinafter, the embodiment will be described in detail.

[0029]

【Example】

Examples 1-4, Comparative Examples 1-6 Polytetramethylene glycol having a molecular weight of 1,000 /
4,4'-diphenylmethane diisocyanate / 1,4
A thermoplastic polyurethane resin obtained by reacting butanediol at a molar ratio of 1/3/2 is extruded by a single screw extruder, and is extruded from a 1.0φ spinning hole, and a spinning speed of 500
The oil was rolled up at m / min, and the oil shown in Table 1 was applied between the first codet roller and the second codet roller by an oiling roller, and then wound up on a bobbin. Further, the elastic yarn wound on the bobbin was aged at 100 ° C. for 18 hours. Regarding the wound elastic yarn, the anti-collapse property at the time of spinning, the stable unwinding rate when the aged yarn is unwound by a forced unwinding device, and the presence or absence of scum through a guide portion having an edge. Table 2 shows the results of the evaluation of.・ Stable unwinding rate = V ↓ 1/100 Unwinding speed at unwinding speed 100m / min, winding up at unwinding speed V ↓ 1, changing V ↓ 1 speed at which unwinding becomes unstable due to sticking etc. Take the ratio with 1.3
1.9 is a favorable range.

[0030]

[Table 1]

[0031]

[Table 2]

In Examples 1 to 3, since the present invention does not collapse and the adhesion is very small, the unwinding ratio in which the unwinding is stable is 1.3 to 1.9 and scum is generated. Did not. On the other hand, in Comparative Examples 1, 5, and 6, the amount of the amino-modified silicone added was large, so that sticking was prevented, but roll-up collapse and twilling occurred, and this was not practical. Comparative Example 2
There was scum and it was not practical. Comparative Example 3,
In No. 4, the viscosity of the system was too high, and in Comparative Example 3, the elastic yarn was taken on the codet roller and could not be taken up by the take-up machine. In Comparative Example 4, the unwinding behavior became unstable due to adhesion instead of sticking.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoshi Takeda 892 Sakuhi-shi, Saijo-shi, Ehime Pref. Kuraray Co., Ltd. Examiner Yoko Nakajima (56) Reference JP-A-3-146774 (JP, A) (58) Survey Field (Int.Cl. ⁶ , DB name) D06M 13/00-15/72 D01F 11/00-13/00

Claims (1)

(57) [Claims] 1. Polyorganosiloxane 89.0-9
9.8% by weight, amino-modified polyorganosiloxane 0.
An oil agent for elastic fibers comprising 1 to 1.0% by weight and 0.1 to 10.0% by weight of an ether-modified polyorganosiloxane and having a viscosity at 30C of 30 centistokes or less.