JPH05117976A - Lubricant for polyurethane fiber - Google Patents

Abstract

PURPOSE:To obtain the subject lubricant effective for reducing the agglutination and cheese collapse when applied in the spinning of a polyurethane fiber by adding two specific silicone resin components to a mineral oil and/or a polyorganosiloxane. CONSTITUTION:The objective lubricant for polyurethane fiber is produced by compounding 90-99.3wt.% (based on total lubricant) of a mineral oil and/or a polyorganosiloxane with 0.2-5wt.% of an aminoalkylsilicone resin of formula (R1 is 1-3C hydrocarbon group; R2 is 1-5C hydrocarbon group; R3 is 4-1-C hydrocarbon group; (n) is 0.1 to 0.5; (m) is 0.5 to 0.9; n+m=1; (t) is 5-50) and 0.5-5wt.% of an alkylsilicone resin. When the lubricant is applied to a polyurethane polymer after the extrusion from a nozzle and before the winding of the spun yarn, the agglutination of yarns and the collapse of cheese can be prevented to stabilize the processing operability. The alkylsilicone resin is e.g. hydrolytic condensation product of dimethylmethoxysilane and amylmethoxysilane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oil agent for polyurethane fibers.

[0002]

2. Description of the Related Art As a method for producing a polyurethane fiber, a melt spinning method, a dry spinning method, a wet spinning method and the like have hitherto been carried out. Recently, in order to improve stretchability and heat resistance of urethane yarn, Urethane elastomer and other fibers
A new method is being made by conjugating with (eg nylon). In any of these methods, when the fibers are wound during spinning, the fibers stick together,
Therefore, when unwinding and pulling out the thread from the cheese in a later step,
Due to sticking, it becomes difficult to pull out the thread, and thread breakage occurs, making stable operation impossible.

As a method for preventing this sticking, a method of adhering solid particles of talc, silica or the like to a fiber as an aqueous or oily slurry, and a method of dispersing a metal salt powder of a higher fatty acid in water or a mineral oil (Japanese Patent Publication No. 41). -286, Japanese Patent Publication No. 40-5557), higher temperature fatty acid carboxylic acid salts, higher fatty acid alcohols, paraffin, polyethylene and the like normal temperature solid wax is dispersed in an oil agent mainly mineral oil (Japanese Patent Publication No. 43-272). Japanese Patent Publication 43-995
No. 5, JP-B-44-8907), a method of using a polyalkylene oxide-modified silicone as a room temperature liquid substance in an anti-sticking agent (JP-B-45-40719, JP-B-48-19893, JP-B-5797). -12
No. 8270) and a method of dissolving amyl siloxane resin in dimethyl siloxane (Japanese Patent Publication No. 42-8438).

However, although these anti-sticking methods are excellent methods, they are not yet satisfactory methods for simultaneously satisfying the performance and the operability in terms of using an oil agent.

[0005] In the spinning of polyurethane fibers, the sticking between yarns is not only due to the rubber-like tackiness of polyurethane, but also the sticking due to a surface chemical reaction between the yarns due to the active isocyanate groups remaining on the yarn surface (arohanate bond,
Other chemical bond formation) occurs. This is generally called self-adhesion. As for the self-adhesive action, the more isocyanate groups are present on the polymer surface during spinning, the more the chemical reaction on the yarn surface proceeds, forming a stronger glue. Even with cheese in which the yarn can be unwound immediately after spinning, the self-adhesion action between the yarns progresses after several days, and the yarn cannot be unwound. In particular, this sticking phenomenon is severe when producing polyurethane fibers by melt spinning, and this tendency is remarkable in the method of mixing and spinning active diisocyanate prepolymers having both terminals at the time of spinning as a cross-linking agent. It is not possible to prevent sticking by itself.

In order to prevent the isocyanate group from sticking due to a chemical reaction, it is necessary to deactivate the isocyanate group, and a method using a component having an active hydrogen group has been proposed. As a method for this, a method in which a mineral oil in which a monoamine is dissolved is already applied during spinning (Japanese Patent Publication No. 46-163).
No. 12), a method of applying an oil agent containing a diamine.
(JP-A-58-132170) has been proposed.
However, in these methods, skin damage due to contact at the time of damage due to residual amine has become a major social problem. Therefore, a method of using an oil agent in which an amino-modified silicone oil is mixed instead of such an aliphatic amine has been proposed (Japanese Patent Publication No. Sho 63-008233).
Since the effect of reducing the fiber-fiber friction by this component is too large, the spinning bobbin and the cheese are severely crumbled, and the amount and structure of the amino-modified silicone oil used must be limited to maintain the shape.

As described above, various substances have been proposed for the anti-sticking agent, but those which can satisfy all of the anti-sticking properties and the operability in the spinning process and the post-processing process are still not available.
Not found.

[0008]

The method of the present invention is applied to the production of polyurethane fibers, and in particular, to the production of polyurethane fibers by mixing a prepolymer having isocyanate groups at both ends during spinning to produce a polyurethane fiber. It prevents bobbin sticking up, bobbin / cheese twilling and winding shape collapse, and provides good operability in the post-process from spinning. Specifically, it is to improve the usability of the amino-modified silicone oil and obtain excellent anti-sticking property by using the amino-alkyl modified silicone resin and the alkyl-modified silicone resin together.

[0009]

The present invention comprises (1) mineral oil and / or polyorganosiloxane; 90.0-99.3.
Weight% (2) Formula I:

[Chemical 2] [In the formula, R ₁ is a hydrocarbon group which may have a side chain having 1 to 3 carbon atoms, R ₂ is a hydrocarbon group which may have a side chain having 1 to 5 carbon atoms, R ₃ Is a saturated or unsaturated hydrocarbon group which may have a side chain having 4 to 10 carbon atoms; n is 0.1 to 0.1
0.5, and m is 0.5 to 0.9, n + m = 1; t is 5 to 5
Representing 0], an amino alkyl silicone resin of 0.2 to 5.0% by weight; and (3) an alkylsilicone resin of 0.5 to 5.0% by weight.

The present invention is an amino-modified silicone, amino.
By using alkyl silicone resin in combination, anti-sticking property and contradictory characteristics such as cheese collapse, which cannot be achieved by using alkyl silicone resin alone, are made possible.

The aminoalkyl silicone resin used in the present invention is represented by the above formula I.
In the formula, R ₁ represents a hydrocarbon group having 1 to 3 carbon atoms such as methylene, ethylene, trimethylene, propylene and vinylene. Preferred is ethylene. R ₂ is a hydrocarbon group having 1 to 5 carbon atoms such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, propylene, cyclopentylene and vinylene, preferably propylene.
R ₃ may have a side chain or an unsaturated group such as n-butyl, tert-butyl, sec-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, cyclopentyl, cyclohexyl, benzyl and phenyl. Alkyl,
It is a hydrocarbon group having 4 to 10 carbon atoms selected from aryl, aralkyl, cycloalkyl and the like, preferably an alkyl group which may have a side chain. In this range, both the function of preventing sticking and the function of preventing the cheese from losing its shape can be exhibited. Particularly preferred specific examples are n-butyl, n-hexyl,
Examples include n-octyl and cyclohexyl.

In the formula, n is 0.1 to 0.5, preferably 0.1.
To 0.2 and m is 0.5 to 0.9, preferably 0.8 to
0.9 and typically n≈0.1 and m≈0.9. n + m = 1. t is 5 to 50, more preferably 3
0 to 40.

The structure of the amino group is effective for both primary amines and secondary amines, but primary amines are effective from the standpoint of reactivity with the active cyanate group of the polyurethane polymer.
In particular, the amino group at the terminal is preferably a primary amine. Further, the larger the amount of amino groups, the more effective the anti-sticking property is, but it is restricted in terms of compatibility with the linear polyorganosiloxane. The amount of amino groups is quantitatively expressed by amino equivalents, and the smaller the amino equivalents, the larger the amount of amino groups in the molecule. The amino equivalent corresponds to the molecular weight of siloxane per amino group and is defined as follows. Definition of amino equivalent

[Equation 1] An amino-alkyl silicone resin having an amino equivalent of 5000 or less is suitable for obtaining excellent anti-sticking property. When the amino equivalent is 5000 or more, the anti-sticking property is inferior and the unwinding property of the yarn from the cheese is poor in the subsequent step, which is not preferable.

The amino-alkyl silicone resin used in the present invention is a polymer obtained by condensing a hydrolyzate such as N-β (alkylethyl) γ-aminopropyltrimethoxysilane or n-hexyltrimethoxysilane. It is a three-sensitivity reaction product that is collectively called varnish, resin, etc.

The amount of the amino-alkyl silicone resin used in combination varies depending on the amount of active isocyanate groups present on the fiber surface, but it is necessary to use an amount that does not cause an increase in sticking over time. Generally, 0.2 to
The content is preferably 10.0% by weight, and more preferably 0.2 to 5.0% by weight. If it is 0.2% or less, it is difficult to obtain excellent anti-sticking property, and if it is 10% or more, the fiber / fiber friction is lowered and the spun cheese is likely to lose its shape.

The amino-alkyl silicone resin used in the present invention deactivates the isocyanate group on the yarn surface by the active hydrogen of the amino group present in the molecule, and at the same time,
Due to the releasing effect due to the characteristics of the silicone resin, it exhibits extremely excellent anti-sticking property. However, the amino
The use of alkyl silicone resin alone can achieve almost the original purpose, but by using an appropriate amount of alkyl silicone resin in combination, it is possible to achieve a fiber / fiber friction force that cannot be achieved by amino / alkyl silicone resin alone. It was possible to maintain a high level, that is, prevent the cheese from collapsing. Even if the alkyl silicone resin is used alone, it exhibits excellent anti-sticking property immediately after spinning, but since the active isocyanate group cannot be deactivated, the anti-sticking property over time deteriorates and there is a problem in practical use. .. As described above, the present invention has some problems when the amino / alkyl silicone resin is used alone, and there are various problems when the alkyl silicone resin is used alone. It is what

The alkyl silicone resin used in the present invention can be prepared by any of the known methods described in the section of the prior art (Japanese Patent Publication No. S42).
-8438) and is obtained by condensing a hydrolyzate of alkyldimethoxysilane and alkyltrimethoxysilane.

The use of the amino-alkyl silicone resin provides anti-sticking property, but the shape of the cheese is inevitable depending on the amount used. This is not as bad in shape as the known amino-modified silicone (straight chain), but has the same tendency. Therefore, in order to increase the fiber-to-fiber friction and prevent the cheese from losing its shape without impairing the anti-sticking property of the amino-alkyl silicone resin, it is effective to use the above-mentioned alkyl silicone resin in combination. If it is too high, the yarn may wind around the roller due to sticking during spinning. Therefore, the viscosity at 30 ° C is usually 5
A material having a viscosity of 00 to 5000 cst is used,
It is preferably 700 to 3000 cst.

Typical alkyl silicone resins are hydrolyzed condensates of dimethyldimethoxysilane and amyltrimethoxysilane.

The amount of the alkyl silicone resin compounded varies depending on the amino equivalent and the amount of the amino alkyl silicone resin used in combination. As the amino equivalent is smaller and the combined amount is larger, it is necessary to increase the compounding amount,
In the present invention, it is preferably about 0.5 to 10.0% by weight, more preferably 0.5 to 5.0% by weight. 0.5
If the amount is less than 10% by weight, it is insufficient to prevent the fiber / interfiber friction lowering action of the amino alkyl silicone resin.
If it is 5% by weight or more, the fiber-to-fiber friction tends to be high, and the quality of the woven fabric in the subsequent step tends to be deteriorated. Therefore, it is preferable to determine the amino equivalent and the combined amount of the amino-alkyl silicone resin used in combination so that a proper anti-sticking property and a proper slip property can be obtained with a blending amount of 5% by weight or less.

In the present invention, the amino / alkyl silicone resin and the alkyl silicone resin are used by blending with a lubricating component. Typical lubricating components are mineral oils and / or polyorganosiloxanes.

The mineral oil used in the present invention may be of any composition, but for uniform attachment to the yarn and for preventing the yarn from winding around the roller due to the viscous resistance of the oil agent during spinning. The viscosity is preferably 5 to 20 cst at 30 ° C.

As the linear polyorganosiloxane used in the present invention, it is desirable to use dimethylpolysiloxane. Also in this case, it is better to have a low viscosity in terms of uniform adhesion and roller wrapping.
Those of t are preferred. When the viscosity of both mineral oil and dimethylpolysiloxane is 5 cst or less, the volatility is large, and after spinning, it is volatilized from the yarn surface, and the smoothness of the yarn and the sticking and spinning property are lowered, which is not preferable.

The mineral oil and the linear polyorganosiloxane can be appropriately blended depending on the solubility of the amino-alkyl silicone resin and the alkyl silicone resin used in the blending. When it is not possible to dissolve by mixing only mineral oil and linear polyorganosiloxane, fatty acid ester or higher alcohol of 10% by weight or less may be added.
From the viewpoint of anti-sticking property, mineral oil, fatty acid ester,
The higher the amount of higher alcohols contained, the lower the anti-sticking property, so it is preferable to use the linear polyorganosiloxane alone as much as possible.

As a method for adhering the oil agent of the present invention to polyurethane elastic fibers, a method of contacting with an oiling roller or refueling with a nozzle which is quantitatively discharged until the yarn discharged from the spinneret is wound up. The method of doing can be used. The oil agent of the present invention is usually 2-1 to the yarn.
By adhering 0% by weight, preferably 3 to 6% by weight, it has a proper fiber / fiber smoothness immediately after spinning,
Moreover, since it has a good anti-sticking property even after a lapse of time, it is possible to smoothly carry out operations such as rewinding, covering, warping, and steelmaking in the post-processing.

The present invention will be described below with reference to examples. Examples 1 to 3 and Comparative Examples 1 to 15 Oil agents for polyurethane fibers were prepared according to the formulations shown in Table 1.
Unwinding speed ratio, fiber /
The frictional force between fibers and the collapse of cheese were evaluated. Comparative example 2
The structure of the amino-modified silicone oil used in 3 and 3 is as shown in Formula II.

[Chemical 3] Each measuring method is as follows.

Preparation of test sample Commercially available 140de spandex yarn was continuously degreased by using an ultrasonic cleaner with n-hexane as a solvent, and experimental oil solution was adhered to it so that the target adhesion amount was 5%. 60 ° C
The sample was allowed to stand for 1 week at 40 ° C., and was subjected to accelerated aging, and then subjected to measurement.

Unwinding speed ratio: The cheese (1) to which the oil agent is added is set on the unwinding side of the unwinding speed ratio measuring machine, and the paper tube (2) is set on the winding side (see FIG. 1). After setting the winding speed to a constant speed, the rollers (3) and (4) are simultaneously activated. In this state, the yarn (5) has almost no tension, and the yarn sticks on the cheese and does not separate, so the unwinding point (6) is in the state shown in FIG. Since the unwinding point (6) of the yarn (5) from cheese changes by changing the unwinding speed, the unwinding speed is set so that this point coincides with the contact point (7) between the cheese and the roller. The unwinding speed ratio is calculated by the following formula.

[Equation 2] The smaller this value is, the better the unwinding property is.

Frictional force between fibers: An explanation will be given with reference to FIG. One end of the urethane thread (8) is fixed, a fixed load (9) (for example, 10 g) is applied to the other end, and the urethane thread (8) is hung through the roller (10). Separately, a urethane thread with a load (11) (eg, 2g) on one end
(12) is crossed at right angles with the urethane thread (8) (13) and is connected to the take-up roller (16) via the roller (15) attached to the U gauge (14). The urethane yarn (12) is wound at a constant speed (for example, 0.175 m / min), the tension fluctuation at that time is measured by a U gauge (14), and the fiber / fiber friction (μ) is measured.

Cheese crumble ... Visual judgment of crumble

[0031]

[Table 1]

[Table 2]

From the above test results, it is understood that the unwindability (speed ratio), cheese collapse, and fiber / fiber μs are well balanced, and excellent operability can be given.

[0033]

EFFECTS OF THE INVENTION By using the oil agent for urethane fiber of the present invention, it is possible to prevent the yarn from sticking to each other on the spun cheese during the production of the urethane fiber, and at the same time prevent the cheese from collapsing due to the slip of the yarn on the cheese. Therefore, it is possible to improve the unwinding property of the yarn in the subsequent processing step, to maintain the smoothness of the thread moderately, and to stabilize the operability in the processing step.

[Brief description of drawings]

FIG. 1 is an explanatory view of a method for measuring an unwinding speed ratio.

FIG. 2 is an explanatory view of a method for measuring a frictional force between fibers.

[Explanation of symbols]

 1. Cheese 2. Paper core 3. And 4. Roller 5. Thread 6. Unwinding point 7. Contact point 8. Urethane thread 9. Fixed load 10. Roller 11. Load 12. Urethane thread 13. Crossover of urethane threads (8) and (12) 14. U gauge 15. Roller 16. Take-up roller

Claims (5)

[Claims] 1. A mineral oil and / or polyorganosiloxane; 90.0-99.3% by weight. (2) Formula I: [In the formula, R ₁ is a hydrocarbon group which may have a side chain having 1 to 3 carbon atoms, R ₂ is a hydrocarbon group which may have a side chain having 1 to 5 carbon atoms, R ₃ Is a saturated or unsaturated hydrocarbon group which may have a side chain having 4 to 10 carbon atoms; n is 0.1 to 0.1
0.5, and m is 0.5 to 0.9, n + m = 1; t is 5 to 5
Representing 0], an oil agent for polyurethane fibers containing 0.2 to 5.0% by weight of an aminoalkyl silicone resin; and (3) 0.5 to 5.0% by weight of an alkyl silicone resin. 2. The oil agent according to claim 1, wherein n is 0.1 to 0.2 and m is 0.8 to 0.9. 3. The oil agent according to claim 1, wherein the amino-alkyl silicone resin represented by the general formula (I) has an amino equivalent of 5000 or less. 4. The compounding amount of the amino alkyl silicone resin represented by the general formula (I) is 0.2 to 5.
The oil agent according to claim 1, which is 0% by weight. 5. The oil agent according to claim 1, wherein the compounding amount of the alkyl silicone resin is 0.5 to 5.0% by weight based on the total weight of the oil agent.