JP2955746B2 - 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 for obtaining polyurethane elastic fibers having good scourability and less occurrence of oil spots during dyeing.

[0002]

2. Description of the Related Art Conventionally, as a method for producing polyurethane elastic fibers, there are a melt spinning method, a dry spinning method, a wet spinning method and the like. However, if the oil agent for nylon is adhered, the sticking property cannot be sufficiently prevented, so that the cheese is poorly unwound from the cheese in the post-processing step, causing problems such as thread breakage.

[0003] Therefore, in the spinning process, dimethylpolysiloxane or mineral oil or a blend thereof is used as a base oil, and an oil agent obtained by adding various anti-stick agents to the base oil is applied to the fibers.

[0004] However, dimethylpolysiloxane has very poor refining properties, and often spends a lot of time in the refining process and often causes oil spots during dyeing.

[0005] In the case of mineral oil, although there is little problem with refining properties, it easily swells in polyurethane fibers, causing a problem of embrittlement of the fibers.

A method in which a metallic soap is used as a suspending agent added to the above base oil to exhibit a releasing effect by a method of suspending the soap (JP-B-41-286, JP-B-40-5557); A method using polyether-modified silicone as a liquid substance (Japanese Patent Publication No. 45-407)
19, JP-A-48-19893) and the like. However, in the former case, it is difficult to disperse the metal soap in the oil agent, and uneven adhesion to the yarn occurs.
Further, in the latter, since a compound in which a polyether group is introduced into a high molecular weight siloxane skeleton is used, the viscosity of the polyether-modified silicone itself is high, and the amount added is limited in order to maintain an appropriate viscosity of the oil agent. The effect was not satisfactory.

[0007]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide good refining properties, low occurrence of oil spots and the like during dyeing, and post-processing from spinning when producing polyurethane elastic fibers. It is an object of the present invention to provide an oil agent for polyurethane elastic fibers which can provide good operability in a process.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the production of polyurethane elastic fibers in order to obtain an oil agent for spinning having good refining properties. As a result, an oil agent containing a specific polyalkylene ether-modified siloxane in the spinning process was obtained. It has been found that the above problem can be solved by adhering the polymer to the fiber, and the present invention has been achieved.

That is, the present invention provides a polyalkylene ether-modified polysiloxane (A1) having a polyoxyethylene skeleton content of 20 to 80% by weight in a molecule, represented by the following general formula 1; Contains at least one polyalkylene ether-modified polysiloxane (A) selected from the group consisting of polyalkylene ether-modified polysiloxane (A2) and polyalkylene ether-modified polysiloxane (A3) represented by general formula 3. The present invention relates to a characteristic oil agent for polyurethane elastic fibers.

The poly of the present invention The content of polyoxyethylene groups in the molecule of the alkylene ether-modified polysiloxane is 20 to 80% by weight. When the amount is less than 20% by weight, it is difficult to exert the effect of the refining property. When the amount exceeds 80% by weight, the viscosity tends to be too high. In this case, the viscosity of the whole oil becomes too high, causing problems such as thread breakage, and when the viscosity of the whole oil is adjusted to an appropriate range, the compounding ratio to be mixed in all the oils decreases, and this feature, scouring It will be difficult to exert the sexual effect sufficiently.

The poly of the present invention The alkylene ether-modified polysiloxane (A) is a polysiloxane represented by the general formula 1.
Alkylene ether-modified polysiloxane (A1); Alkylene ether-modified polysiloxane (A2), a polysiloxane represented by general formula 3:
Any of the alkylene ether-modified polysiloxanes (A3) or a combination thereof.

The (A1) of the present invention is represented by the following general formula 1.

[0013]

Embedded image

In the general formula 1 in (A1), X ¹
Is a trialkylsiloxane group or a residue obtained by removing O bonded to Si from Y ² . The alkyl group of the trialkylsiloxane group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, a didecyl group, and an octadecyl group. But they may be different. Examples of the trialkylsiloxane group include a trimethylsiloxane group, a triethylsiloxane group, and a dimethylpropylsiloxane group. Of these, a preferred group is a trimethylsiloxane group.

In general formula 1, Y ¹ and Y ² are polyether group-containing groups represented by general formula 4. Here, Y ¹ and Y ² may be the same or different.

[0016]

Embedded image

In the general formula 4, X ⁴ and X ⁵ are each independently a monovalent hydrocarbon group or a trialkylsiloxane group. The monovalent hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-ethylhexyl group, didecyl group, octadecyl group, etc.), and aromatic hydrocarbon group. Examples include a hydrogen group (phenyl group, biphenyl group, naphthyl group, phenanthryl group, etc.), an alicyclic hydrocarbon group (cyclopropyl group, cyclohexyl group, etc.) and the like. The alkyl group as the trialkylsiloxane group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, a didecyl group, and an octadecyl group. They may be the same or different. Examples of the trialkylsiloxane group include a trimethylsiloxane group, a triethylsiloxane group,
And a dimethylpropylsiloxane group. Preferred groups among X ⁴ and X ⁵ are a methyl group and a trimethylsiloxane group.

In the general formula 4, R ³ is a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, a didecyl group, and an octadecyl group. A preferred group of R ³ is a hydrogen atom,
It is a methyl group.

In the general formula 4, A is usually an ethylene group or a propylene group, and OA is an oxyethylene group or an oxypropylene group. Although the repetition of OA may be the same or different, an oxyethylene group is indispensable, and an oxyethylene group alone or a combination of an oxyethylene group and an oxypropylene group may be used.
In the case of combined use, the mode of addition may be random addition or block addition.

In the general formula 4, p is a number of 1 to 50, preferably 2 to 20. If it is 0, it is difficult to exhibit the effect of the refining property, and if it exceeds 50, the viscosity tends to be too high. Can be difficult to do.

In the general formula 4, q is a number from 1 to 4.

In the general formula 1, R ¹ and R ² are each independently a monovalent hydrocarbon group. The monovalent hydrocarbon group is not particularly limited, and may be an aliphatic hydrocarbon group (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-ethylhexyl group, didecyl group, octadecyl group, etc.), and aromatic hydrocarbon group. Examples include a hydrogen group (phenyl group, biphenyl group, naphthyl group, phenanthryl group, etc.), an alicyclic hydrocarbon group (cyclopropyl group, cyclohexyl group, etc.) and the like. Among them, preferred groups are a methyl group and a phenyl group.

In the general formula 1, m is a number of 0 to 15, preferably 0 to 10. If it exceeds 15, the viscosity tends to be too high, so that the mixing ratio in all the oils is reduced, and it may be difficult to sufficiently exert the effect of the scouring property.

The (A2) of the present invention is represented by the following general formula 2.

[0025]

Embedded image

In the general formula 2 in (A2), X ²
Is a trialkylsilyl group, which has been described above (A1)
It is similar to those mentioned X ¹ in.

In the general formula 2, X ³ is a trialkylsiloxane group or Y ² . The alkyl group of the trialkylsiloxane group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, a didecyl group, and an octadecyl group. They may be the same or different. Examples of the trialkylsiloxane group include a trimethylsiloxane group, a triethylsiloxane group, and a dimethylpropylsiloxane group. Of these, a preferred group is a trimethylsiloxane group.

In the general formula 2, Y ¹ and Y ² may be the same as Y ¹ and Y ² in (A1) described above.
¹ and Y ² may be the same or different.

In the general formula 2, R ¹ may be the same as R ¹ in (A1) described above.

In the general formula 2, n is a number of 0 to 10, preferably 0 to 7. If it exceeds 10, the viscosity tends to be too high, so that the mixing ratio in all the oils decreases, and it may be difficult to sufficiently exert the effect of the refining property.

The (A3) of the present invention is represented by the following general formula 3.

[0032]

Embedded image

In the general formula 3 in (A3), X ³
May the same as X ³ in the previously described (A2). X ³ may be the same group or a different combination in the repeating unit.

In general formula 3, X ² is as described above (A
Or the same as X ² in 2).

In the general formula 3, Y ¹ and Y ² may be the same as Y ¹ and Y ² in (A1) described above.
¹ and Y ² may be the same or different.

In the general formula 3, k is a number from 0 to 7,
Preferably it is 0-5. If it exceeds 10, the viscosity tends to be too high, so that the mixing ratio in all the oils decreases, and it may be difficult to sufficiently exert the effect of the refining property.

The polyalkylene ether-modified polysiloxane of the present invention has a viscosity at 25 ° C. of 10 to 40.
0 centistokes, preferably 10-20
0 centistokes. Viscosity at 25 ° C is 1
If the content is less than 0 centistokes, the content of polyoxyethylene groups in the molecule is small, and it is difficult to exhibit the effect of scouring ability. To reduce
In some cases, it is difficult to sufficiently exert the effect of the refining property.

The number of Si atoms in the polyalkylene ether-modified polysiloxane of the present invention is 2 to 20, preferably 2 to 10. When the number of Si atoms exceeds 20, the viscosity becomes too high, so that the blending ratio in all the oils decreases, and it may be difficult to sufficiently exert the effect of refining.

The method for producing the polyalkylene ether-modified polysiloxane of the present invention is not particularly limited, but usually, an alkylene oxide adduct of allyl alcohol is added to a polysiloxane having a Si—H group under a platinum catalyst. It can be produced by a method or a method of reacting with a polysiloxane having a Si-H group by dehydrogenation with a polyether having a hydroxyl group at a molecular terminal.

The content of the polyalkylene ether-modified polysiloxane of the present invention is usually from 5 to 5
It is 80% by weight, preferably 10 to 80% by weight. If it is less than 5% by weight, the scouring effect is insufficient, and if it exceeds 80% by weight, the viscosity of the entire oil tends to increase significantly. May occur.

The viscosity of the oil agent of the present invention containing the polyalkylene ether-modified polysiloxane (A) is preferably not more than 100 centistokes at 25 ° C. from the viewpoint of uniform adhesion and prevention of winding around the roller.

The components used in combination with the polyalkylene ether-modified polysiloxane of the present invention do not hinder the effect of the refining properties in order to reduce friction with various rollers or guides in the post-spinning and post-processing steps. It is preferable to use a diorganopolysiloxane or a mineral oil in combination.

Examples of the diorganopolysiloxane for this purpose include dimethylpolysiloxane and those obtained by substituting some of the methyl groups of dimethylpolysiloxane with other alkyl groups and phenyl groups. In any case, the viscosity of the entire blended oil is usually 100 centistokes or less at 25 ° C, preferably 2 to 50 centistokes. If the viscosity is less than 2 centistokes, the volatility is high and the adhesion to the yarn tends to be difficult. If the viscosity exceeds 50 centistokes, the adhesion to the yarn may be difficult.

As a mineral oil, the viscosity of the entire blended oil is usually 100 centistokes or less at 25 ° C., preferably 1 to 100 centistokes.
50 centistokes. If the viscosity is less than 1 centistokes, the volatility tends to be high and the adhesion to the yarn tends to be difficult. If the viscosity exceeds 50 centistokes, the adhesion to the yarn may be difficult.

The oil agent for elastic fibers of the present invention may further comprise, if necessary, an anti-stick agent, for example, mineral solid fine particles such as talc, silica and colloidal alumina; metal powder salts of higher fatty acids; and paraffin and polyethylene. The performance of the polyalkylene ether-modified polysiloxane of the present invention, such as a solid wax at room temperature, or a modified silicone such as an epoxy-modified silicone, a polyether-modified silicone, an amino-modified silicone, or a silicone resin, or as a binder, an alcohol or a fatty acid ester. May be added to such an extent that is not impaired, and the addition can increase the anti-sticking effect. Further, components usually used in spinning oils, such as antistatic agents, antioxidants, and ultraviolet absorbers, can be added.

The oil agent of the present invention can be applied to the yarn by roller lubrication or nozzle lubrication at any position after spinning and before the yarn is wound in the polyurethane fiber spinning process. The oil agent of the present invention is generally added to the polyurethane elastic fiber in an amount of 0.5 to 10% by weight, preferably 1 to 8% by weight.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

The polys of Examples 1 to 3 and Comparative Examples shown in Table 1 The alkylene ether-modified polysiloxane was blended in the composition ratio shown in Table 2, and
6 and Comparative Examples 1 to 5 were prepared. Furthermore, (a) thread break, (b) stickiness, (c) scouring,
(D) Dyeability and (e) Swellability were evaluated. Table 2 also shows the evaluation results.

[0049]

[Table 1]

The test methods for yarn breakage, adhesiveness, dyeability and swelling of the yarns provided with the oil agents of the examples and comparative examples are as follows. (A) Thread breakage In the dry spinning method of the polyurethane fiber, an oil agent was applied by roller lubrication so that the amount of the oil agent adhered to 6% of the filament weight was wound around the cheese at 600 m / min. Until winding, it was visually determined whether or not a yarn break occurred. -Judgment criteria-○: No thread breakage occurred X: Thread breakage occurred

(B) Gluing property After aging the wound cheese for one week, the cheese is wound on a variable-magnification draw-out winding device at a speed of 50 m / min. Shown at the lowest possible magnification. 1.3 or less is preferable.

(C) Refining properties Refining was performed using the fibers used for the adhesive property under the following conditions. The amount of oil remaining on the fibers after scouring was measured, and the drop-off rate of the oil was calculated. Refining conditions: Refining agent (Gran Up VO50K; manufactured by Sanyo Chemical Industries, Ltd.) 2 g / l, sodium carbonate 0.5 g / l
(Bath ratio 1:20), put knitted fabric at 85 ° C, 3
After scouring for 0 minutes, the plate was washed with hot water of 80 ° C. for 10 minutes, washed with running water for 5 minutes, dehydrated and dried. -Judgment criteria-O: Oil dropout rate of 80% or more X: Oil dropout rate of less than 80%

(D) Dyeing property A knitted fabric is formed using a single covered yarn in which a nylon-processed yarn is wound in a coil shape on the fiber used for the adhesiveness, and after scouring under the above conditions, the dye is dyed under the following dyeing conditions. It was made to adhere and the stained spot was visually determined. Dyeing condition: Dye (CI Acid Blue 23)
0: Clariant Japan Co., Ltd.) 1% o. w. f
The cloth after scouring is immersed in a dyeing bath using a bath ratio of 1:15, 8
After staining at 0 ° C. for 15 minutes, the sample was washed with water to obtain a judgment sample. -Judgment criteria-○: Uniform dyeing △: Some uneven dyeing

(E) Swellability A commercially available urethane film was mixed with a prepared oil at 70 ° C. ×
After immersion for 10 minutes and taking out, wipe off the oil attached to the surface, measure the weight of the film before and after immersion,
The rate of weight increase was defined as the swelling rate. -Judgment criteria-A: Swelling ratio less than 5% X: Swelling ratio 5% or more

[0055]

[Table 2]

Dimethyl polysiloxane: SH-200 5cs (manufactured by Dow Corning Silicone Toray Co., Ltd.) Mineral oil: liquid paraffin 40S (manufactured by Chuo Kasei Co., Ltd.) Polyether-modified silicone: KF-352 (manufactured by Shin-Etsu Chemical Co., Ltd.) )

As is clear from Examples 1 to 6 in Table 2,
The poly of the present invention It can be seen that the oil agent containing the alkylene ether-modified polysiloxane has good scourability and significantly reduces the occurrence of oil spots and the like during dyeing.
In particular, even if it contains dimethylpolysiloxane, which has been pointed out as having a problem of scourability, although it has a friction reducing effect conventionally, It turns out that scourability can be improved by containing an alkylene ether-modified polysiloxane. In addition, it can be seen that the anti-adhesive property and the swelling property of the conventional oil agent are equal to or higher than those of the conventional oil agent. On the other hand, Comparative Example 1 (conventional oil based mainly on dimethylpolysiloxane), Comparative Example 2 (conventional oil based on mineral oil), Comparative Example 3 (polysiloxane having an oxyethylene group content in the molecule which is too small) Comparative example 4
(Oil agent using polysiloxane having too much oxyethylene group content in molecule), Comparative Example 5 (Oil agent using polysiloxane having too much oxyethylene group content in molecule and keeping viscosity of oil agent in an appropriate range) Does not satisfy all performance items.

Further, it can be seen that Examples 1 to 6 of the present invention also have an anti-adhesion property and a swelling property which are equal to or higher than those of conventional oil agents in terms of anti-adhesion property.

Conventionally, polyurethane elastic fibers are produced.
When using dimethylpolysiloxane as the main component
Processing is difficult, scouring is difficult
Problems, etc., and it is not possible to obtain stable operability
Was. However, the poly- Alkylene ether modified poly
Manufactured using oil agent for elastic fiber containing polysiloxane
Good scouring, less uneven dyeing,
Less swelling in fiber and excellent anti-sticking property between yarns
The polyurethane elastic fiber after spinning.
Manufacturing while maintaining stable operability in the processing process
It can be.

Claims (3)

(57) [Claims] 1. A polyalkylene ether-modified polysiloxane (A) having a polyoxyethylene skeleton content of 20 to 80% by weight in a molecule and represented by the following general formula 1.
1) one or more polyalkylene ether-modified polysiloxanes selected from the group consisting of polyalkylene ether-modified polysiloxanes (A2) represented by the general formula 2 and polyalkylene ether-modified polysiloxanes (A3) represented by the general formula 3 An oil agent for polyurethane elastic fibers, comprising (A). Embedded image (Wherein, X ¹ is a trialkylsilyl group or a residue obtained by removing O bonded to Si from Y ² ; Y ¹ and Y ² are represented by general formula 4)
Wherein R ¹ and R ² are each a monovalent hydrocarbon group which may be the same or different, and m is 0 to 15
Represents the number of ) (Wherein X ³ is a trialkylsiloxane group or Y ² ;
X ² is a trialkylsilyl group; Y ¹ and Y ² are polyether group-containing groups represented by the general formula 4, which may be the same or different; R ¹ is a monovalent hydrocarbon group;
Represents a number from 10 to 10. ) (Wherein X ³ is a trialkylsiloxane group or Y ² ;
X ² is a trialkylsilyl group; Y ¹ and Y ² are polyether group-containing groups represented by the general formula 4 and may be the same or different; k represents a number from 0 to 7; ) (Wherein X ⁴ and X ⁵ are monovalent hydrocarbon groups or trialkylsiloxane groups, which may be the same or different; R ³ is a hydrogen atom or an alkyl group; A is an ethylene group and / or a propylene group) OA represents an oxyethylene group and / or an oxypropylene group; p represents a number of 1 to 50; q represents a number of 1 to 4.) 2. The oil agent for elastic fibers according to claim 1, wherein the viscosity at 25 ° C. of the polyalkylene ether-modified polysiloxane (A) is 10 to 400 centistokes. 3. The oil agent for elastic fibers according to claim 1, wherein the number of Si atoms in the polyalkylene ether-modified polysiloxane (A) is 2 to 20.