JP2955749B2 - 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 elastic fibers, which is excellent in anti-sticking properties between fibers and has good aging stability for obtaining polyurethane elastic fibers excellent in unwinding property from cheese. Oil related.

[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.

A method in which a metallic soap is used as a suspending agent to be added to a base oil to exhibit a releasing effect by suspending and using a metal soap (Japanese Patent Publication Nos. 41-286 and 40-5557); A method using a branched polyether-modified silicone of a liquid substance (Japanese Patent Publication No. Sho 45-4)
No. 0719) has been proposed. However, in the former case, it is difficult to disperse the metal soap in the oil agent, and uneven adhesion to the yarn occurs. In addition, although the latter has anti-sticking properties, the end group of the polyether group is a hydroxyl group, the hydrophilicity is high, and the compatibility with the base oil is poor, so the stability of the oil itself over time is insufficient. Separation and sedimentation of the oil agent occur, causing problems such as uneven adhesion to the yarn. In addition, as a modified silicone having a polyether group having good compatibility with a base oil, a method of using a non-branched polyether-modified silicone in which a polysiloxane group is introduced into a polysiloxane portion as a main chain (Japanese Patent Laid-Open Publication No.
No. 41873) has been proposed. However, since it has a linear structure, the anti-sticking property is insufficiently expressed, and its effect is not satisfactory.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an oil agent which has good aging stability, good anti-sticking property between fibers, and a post-processing from spinning when producing polyurethane elastic fibers. An object of the present invention is to provide an oil agent for polyurethane elastic fibers that can provide good operability in the process over a long period of time.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to obtain a spinning oil having good aging stability and anti-sticking property during the production of polyurethane elastic fibers. The inventors have found that the above problems can be solved by attaching an oil agent containing a modified silicone having a group to fibers, and have reached the present invention.

That is, the present invention has a base oil comprising a diorganopolysiloxane (A1) and / or a mineral oil (A2) and a terminal-blocked polyether group represented by the general formula (1) or (2), The present invention relates to an oil agent for polyurethane elastic fibers, characterized in that the polyether group contains a modified silicone (B) which is a polyoxyalkylene group branched from a main chain.

[0008]

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[0009]

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Wherein A is an alkylene group having 2 to 4 carbon atoms; R is a monovalent hydrocarbon group; and n is a number of 1 to 100.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The oil agent for elastic fibers in the present invention comprises a base oil composed of diorganopolysiloxane (A1) and mineral oil (A2) and a modified silicone (B) having a specific structure as essential components.

Examples of the diorganopolysiloxane (A1) used in the present invention include dimethylpolysiloxane and those obtained by substituting some of the methyl groups of dimethylpolysiloxane with other alkyl groups and phenyl groups. In any case, any viscosity may be used as long as the viscosity of the entire blended oil (base oil and modified silicone) is usually 100 centistokes or less at 30 ° C, but preferably 2 to 50 centistokes. It is. Viscosity 2
If the viscosity is less than centistokes, the volatility tends to be high and adhesion to the yarn tends to be difficult. If the viscosity exceeds 50 centistokes, it may be difficult to control the viscosity of the entire blended oil.

[0013] The mineral oil (A2) used in the present invention includes the whole compounded oil (base oil and modified silicone).
Any viscosity may be used as long as the viscosity is usually 100 centistokes or less at 30 ° C., but preferably 1
~ 50 centistokes. If the viscosity is less than 1 centistoke, the volatility tends to be high and adhesion to the yarn tends to be difficult, and if it exceeds 50 centistokes, it may be difficult to control the viscosity of the entire blended oil. The base oil may be one or more diorganopolysiloxanes (A1), one or more mineral oils (A2), or a combination thereof, and the ratio of (A1) to (A2) depends on the thickness of the elastic fiber used. different. For example,
When applied to thick fibers, the weight ratio of (A1) / (A2) is usually 50/50 to 0/100, and when applied to thin fibers, the weight ratio of (A1) / (A2) is usually 100/0 to 0/100. 5
0/50.

The modified silicone (B) of the present invention has a terminal-blocked polyether group represented by the general formula (1) or (2), wherein the polyether group is a polyoxyalkylene group branched from the main chain. is there.

In the general formulas (1) and (2), A is an alkylene group having 2 to 4 carbon atoms (ethylene group, propylene group, butylene group, etc.), and OA is an oxyalkylene group having 2 to 4 carbon atoms. (Oxyethylene group, oxypropylene group, oxybutylene group, etc.). Of these, preferred are an oxyethylene group (EO) and an oxypropylene group (PO), and the repetition of OA may be the same or different, and more preferably a combination of EO and PO. When different groups are used in combination, the mode of addition may be random addition or block addition.

The monovalent hydrocarbon group for R is not particularly limited, and may be an aliphatic hydrocarbon group (eg, methyl, ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, didecyl, octadecyl, etc.). ), Aromatic hydrocarbon groups (phenyl group, biphenyl group, naphthyl group, phenanthryl group, etc.), alicyclic hydrocarbon groups (cyclopropyl group,
Cyclohexyl group). Among them, preferred groups are an alkyl group having 1 to 18 carbon atoms and a phenyl group. Particularly preferred is an alkyl group having 1 to 3 carbon atoms in the general formulas (1) and (2).

In the general formulas (1) and (2), n is 1
It is a number of -100, preferably 1-50. When the ratio is less than 1, the anti-sticking property is insufficient, and when it exceeds 100, the viscosity tends to be too high. Can be difficult to do.

The modified silicone (B) having an end-blocked polyether group of the present invention has the general formula (1) or (2)
Wherein the polyether group is a polyoxyalkylene group branched from the main chain. The bonding position between the polyether group of the modified silicone having an end-blocking type polyether group and the polysiloxane group as the main chain should be at least one at the branched position.
It is necessary that the polyether groups be located at more than one position, but when there are a plurality of polyether groups, the positions of the other polyether groups may be branched or located at the end of the polysiloxane group.

The structure of the polyether group capable of more effectively exhibiting the compatibility between the modified silicone (B) having a terminal-blocking polyether group of the present invention and a base oil (dimethylpolysiloxane or mineral oil) is EO. And PO
Are preferred, and the EO / PO molar ratio is 10 /
Those having 90 to 90/10 and the terminal group of which is blocked by an alkyl group having 1 to 3 carbon atoms are preferable. EO / P
If the molar ratio of O is less than 10/90, the hydrophobicity becomes too high, so that it may be difficult to achieve sufficient compatibility with the base oil. If the molar ratio exceeds 90/10, on the contrary, the hydrophilicity is too high. It may be difficult to dissolve in water.

The viscosity of the modified silicone (B) having an end-blocking polyether group of the present invention is usually 30 ° C.
20 centistokes to 20,000 centistokes, preferably 100 centistokes to 10,000
It is centistokes. If the density is less than 20 centistokes, the anti-sticking property may be insufficiently expressed.
When the viscosity exceeds 0 centistokes, the viscosity of the entire oil agent tends to increase remarkably, and a sufficient amount of anti-sticking property may be difficult to develop due to a small amount of the oil agent.

The method for producing the modified silicone (B) having an end-blocked polyether group of the present invention is not particularly limited, but is usually an alkylene oxide adduct of allyl alcohol to a polysiloxane having a Si—H group. Can be produced by a method in which a terminal alkyl ether is added under a platinum catalyst.

The content of the modified silicone (B) having an end-blocking polyether group of the present invention is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total weight of the oil. % By weight. When the amount is less than 0.1% by weight, the anti-sticking effect is insufficient, and when the amount exceeds 20% by weight, the viscosity of the whole oil tends to increase remarkably. Etc. may occur.

The viscosity of the oil agent for elastic fibers of the present invention is preferably 100 centistokes or less at 30 ° C. from the viewpoint of uniform adhesion and prevention of winding around the roller.

The oil agent for elastic fibers of the present invention may further comprise, if necessary, an anti-sticking 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. Room temperature solid wax or the like, or epoxy-modified silicone, polyether-modified silicone having a terminal hydroxyl group type polyether group, linear polyether-modified silicone,
Modified silicones such as amino-modified silicones and silicone resins, and as binders, alcohols, fatty acid esters, etc. may be added to the modified silicone (B) of the present invention so as not to impair the performance of the modified silicone (B). The prevention effect can be increased. Further, components usually used in spinning oils, such as antistatic agents, antioxidants, and ultraviolet absorbers, can be added.

The oil agent for elastic fibers of the present invention can be applied to the yarn by roller oiling or nozzle oiling 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 used in an amount of 0.5 to 10% by weight, preferably 1 to 10% by weight, based on the polyurethane elastic fiber.
-8% by weight.

[0026]

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.

Examples 1 to 4 were blended in the composition ratios shown in Table 1.
3 and Comparative Examples 1 and 2 were prepared. Further, Table 1 also shows the evaluation results of (a) chronological stability and (b) adhesiveness.

[0028]

[Table 1]

The following methods are used to test the stability of the oils obtained in the Examples and Comparative Examples with time and the adhesiveness of the yarns to which the oils are applied. (A) Stability over time Put the oil agent prepared at the composition ratio shown in Table 1 into a 100 ml glass bottle and place it in a thermostat at 40 ° C and 5 ° C.
After standing for a day, the appearance was visually observed, compared with the appearance immediately after preparation, and evaluated according to the following criteria. -Judgment criteria-○: No change △: Slight separation or precipitation occurs ×: Separation or precipitation occurs 6 for
%, And wound around cheese at 600 m / min to obtain a 40D polyurethane fiber. After aging the wound cheese for one week, the yarn was sent out at a speed of 50 m / min by using a drawer / winder with a variable magnification and the yarn was sent out at the lowest magnification at which the yarn could be sent out without being entangled due to sticking. 1.3 or less is preferable. .

Modified silicone-1 of the present invention: viscosity; 1000 centistokes / 30 ° C. polyether group; EO / PO molar ratio = 50/50 methyl group-blocked type Modified silicone-2 of the present invention: viscosity: 2000 centistokes / 30 ° C. polyether group; EO / PO molar ratio = 35/65 methyl group-blocked type Modified silicone of comparative example 1: branched polyether-modified silicone Viscosity: 2000 centistokes / 30 ° C. polyether group; EO / PO molar ratio = 50/50 Terminal hydroxyl group type Modified silicone-2 of Comparative Example: straight-chain (non-branched) polyether-modified silicone F-178-21 (Nihon Unicar Co.) Dimethyl polysiloxane: SH-200 5cs (Dow Corning Toray Toray) Co., Ltd.) mineral oil: liquid paraffin 40S (manufactured by Chuo Kasei Co., Ltd.) silicone resin: BY16-877 (Toray Dow Corning silicone over emissions Co., Ltd.)

As is apparent from Table 1, the oil agent of the present invention containing the modified silicone (B) having an end-blocking polyether group has good aging stability and is similar to the conventional oil agent in terms of adhesiveness. It turns out that it has the above-mentioned anti-sticking property.

In the past, oils which used polyether-modified silicone of a hydroxyl group type as an anti-sticking agent in the production of polyurethane elastic fibers had poor aging stability and caused separation and sedimentation. It was not possible to obtain stable operability over a long period of time, such as uneven adhesion to the surface. However, the modified silicone (B) having an end-blocked polyether group of the present invention
In the case of manufacturing using an oil agent for elastic fiber containing, since the oil agent itself has good aging stability and also has excellent anti-sticking property between yarns, polyurethane elastic fiber is used in the post-processing step from spinning. It can be manufactured while maintaining stable operability.

Claims (6)

(57) [Claims] 1. A base oil comprising a diorganopolysiloxane (A1) and / or a mineral oil (A2), and a polyether having an end-blocked polyether group represented by the general formula (1) or (2). An oil agent for polyurethane elastic fibers, comprising a modified silicone (B) whose group is a polyoxyalkylene group branched from the main chain. Embedded image Embedded image (Wherein, A represents an alkylene group having 2 to 4 carbon atoms; R represents a monovalent hydrocarbon group; n represents a number of 1 to 100) 2. The oil agent for elastic fibers according to claim 1, wherein R in the general formula (1) or (2) is an alkyl group having 1 to 18 carbon atoms or a phenyl group. 3. The polyether group of the modified silicone (B) comprises a copolymer of ethylene oxide (EO) and propylene oxide (PO), and has an EO / PO molar ratio of 10/90 to 90/10. The oil agent for elastic fibers according to claim 1 or 2. 4. The oil agent for elastic fibers according to claim 1, wherein the terminal hydroxyl group of the polyether group of the modified silicone (B) is blocked with an alkyl group having 1 to 3 carbon atoms. 5. The modified silicone (B) has a viscosity of 30 ° C.
And 20 to 20,000 centistokes.
5. The oil agent for elastic fibers according to any one of 4. 6. The oil agent for elastic fibers according to claim 1, wherein the content of the modified silicone (B) is 0.1 to 20% by weight based on the whole oil agent.