JP2000144578A - Oiling agent for elastic yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricant capable of reducing decrease of spinning yield and shape defection of wound yarn form caused by coagulation of magnesium stearate in spinning and also decreasing thread breakage due to falling down of wiping form in warping and thread breakage due to poor frictionality with needles or guides in a knitting process. SOLUTION: This lubricant is obtained by including >=96.5 wt.% polydimethylsiloxane having 5-30 cSt viscosity, 0.12-0.45 wt.% amino-modified silicone 0.50-1.50 wt.% magnesium stearate having <=0.5 μm mean particle diameter and 1.5 μm maximum particle diameter based on the whole lubricant weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Polyurethane elastic yarns are wound up with an oil agent applied thereto, but the inner layer of the wound yarns tends to stick to each other with the passage of time, which tends to cause poor unwinding. As a method for preventing sticking, a method using a metal salt of a higher fatty acid such as magnesium stearate (Japanese Patent Publication No. 37-4586) has been proposed. However, even though this method is effective in preventing sticking of the polyurethane elastic yarn, the metal salt agglomerates and deposits on a roll or the like during spinning to cause yarn breakage, thereby lowering the spinning yield, or when using the warp knitting field. In knitting, the yarn accumulates in the guide portion, causing thread breakage, or the coefficient of friction between the yarns is too low, resulting in a poor wound thread body shape or loss of shape during unwinding, leading to yarn breakage. There was a drawback to do. Further, a method using an amino-modified silicone (Japanese Patent Publication No. 63-8233) has been proposed, but the effect of preventing sticking was insufficient.

In order to suppress aggregation of higher fatty acid magnesium salts such as magnesium stearate, there has been proposed a method in which an amino-modified silicone is used in an amount of 0.5 to 3.0% by weight (JP-A-10-259577). According to this method, the aggregation of the magnesium salt of the higher fatty acid is suppressed, but the friction coefficient between the elastic yarns is excessively reduced, and the shape of the wound body becomes poor, or when the yarn is unwound from the wound body. There is a problem that the shape of the thread body breaks and thread breakage occurs.
If the amount of the amino-modified silicone is reduced to improve this, thread breakage or the like due to aggregation of the magnesium salt of higher fatty acid frequently occurs.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to suppress the aggregation of magnesium stearate, and to reduce the friction coefficient between elastic yarns when amino-modified silicone is used. The purpose of the present invention is to provide an elastic yarn oil agent that does not cause collapse of the wound body or breakage of the yarn during unwinding.

Another object of the present invention is to provide an oil agent for an elastic yarn which does not cause a yarn breakage due to poor friction with a needle or a guide portion in a knitting process.

[0006]

According to the present invention, 96.5% by weight or more of polydimethylsiloxane having a viscosity of 5 to 30 centistokes and 0.12 to 0.45% by weight of an amino-modified silicone are used based on the total weight of the oil. And the average particle size is 0.5 μm
An oil agent for elastic yarns, comprising 0.50 to 1.50% by weight of magnesium stearate having a maximum particle size of 1.5 μm or less.

In the present invention, it is preferable that the ester-modified silicone be contained in an amount of 0.5 to 1.5% by weight based on the total weight of the oil agent. Further, the weight ratio of amino-modified silicon to magnesium stearate is preferably 0.10 to 0.45: 1. In achieving the object of the present invention,
It is extremely important to use magnesium stearate having a maximum particle size of 1.5 μm or less and to limit the proportion of the amino-modified silicone to a limited amount of 0.12 to 0.45% by weight.

The dimethyl siloxane used in the present invention is
In order to prevent uniform adhesion to the yarn and winding around the roller during spinning, those having a viscosity of 5 to 30 cst at 30 ° C are preferable. When the viscosity of dimethylsiloxane is 5 cst or less, the volatility becomes large and volatilizes from the yarn over time after spinning, resulting in a decrease in the smoothness of the yarn and a decrease in the anti-sticking property.

The oil agent of the present invention is obtained by dispersing a specific amount of magnesium stearate having a specific particle size in the above-mentioned dimethyl silicone in a colloidal form. The method of dispersing magnesium stearate in dimethyl silicone,
There is no particular limitation, and a known wet pulverizer can be used. The particle size of magnesium stearate in oils is
Average value is 0.5 μm or less, and maximum particle size is 1.5 μm
It must be: Average particle size 0.5 μm
If the average particle diameter exceeds 1.5 μm or the maximum particle diameter exceeds 1.5 μm, the particles tend to agglomerate and sediment, and are deposited on rolls in the spinning process, guides in the processing process, and the like, causing yarn breakage. In addition, since the particle size is small, magnesium stearate is uniformly dispersed on the yarn surface, and the effect of suppressing the sticking of the yarn is improved, but at the same time, the friction coefficient between the yarn and the yarn is reduced, and the content in the oil agent is increased. As a result, the shape of the wound body becomes worse, or the shape is broken at the time of unwinding, causing breakage of the thread. Therefore, the content of stearic acid is preferably 1.5% by weight or less, more preferably 1. 0% by weight or less. Also, when the particle size of magnesium stearate increases, aggregation occurs,
A large amount of an amino-modified silicone or the like is required as a dispersing agent because of easy precipitation.

The amino-modified silicone contained in the oil agent of the present invention is a linear polyorganosiloxane containing a dimethylsiloxane unit and a siloxane unit having an amino-modifying group, and is preferably the amino-modified silicone represented by the formula (1). .

[0011]

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The content of the amino-modified silicone in the oil is preferably 0.12 to 0.45% by weight. 0.45%
If it exceeds, the coefficient of friction between the yarns is reduced, the shape of the wound body is deteriorated, or the shape is lost at the time of unwinding, which may cause yarn breakage, which is not preferable. On the other hand, when the content is less than 0.12%, magnesium stearate is undesirably coagulated and deposited, causing yarn breakage during spinning or processing.

An ester-modified silicone can be contained for the purpose of suppressing yarn breakage during processing. The ester-modified silicone is contained in a large amount because it can reduce the friction coefficient with a needle or a guide at the time of processing without lowering the frictional resistance between the elastic yarns, but is preferably 1.5% or less for reasons of economy and the like. . It is possible to include an aminoether-modified silicone for the purpose of improving antistatic properties. However, in order to reduce the friction coefficient between elastic yarns, the content is preferably 0.2% by weight or less based on the total weight of the oil agent. preferable.

The polyurethane elastic yarn to which the present invention is applied is
A polyfunctional active hydrogen atom-containing chain extender and a monofunctional active hydrogen atom in an isocyanate-terminated prepolymer typically prepared with an organic diisocyanate and a substantially linear polymer diol It is obtained by dry spinning, wet spinning or melt spinning an elastic high molecular polymer having a urethane group in a molecule obtained by reacting an end-blocking agent in one or more stages.

As another method of preparing the polyurethane elastic yarn, a hydroxyl group having a hydroxyl group at both ends and a molecular weight of 400
A chain extender having a polyfunctional active hydrogen atom and a terminal stopper having a monofunctional active hydrogen atom in an isocyanate-terminated prepolymer comprising a substantially linear polymer having a molecular weight of up to 5,000 and an organic diisocyanate. It is obtained by spinning while reacting with an agent.

The polymer diol which is one of the raw materials for producing the polyurethane elastic yarn of the present invention is a substantially linear polymer having a hydroxyl group at both terminals and a number average molecular weight of 400 to 5,000. For example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, linear or random copolymerized polyalkylene ether diols having 1 to 8 carbon atoms, and the like. Polyether diols; one or more dibasic acids such as adipic acid, sebacic acid, maleic acid, itaconic acid, azelaic acid, malonic acid and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol , 2,2-dimethyl-1,3-propanediol, 1 One or more glycols such as 4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10-decanediol, 1,3-dimethylolcyclohexane, and 1,4-dimethylolcyclohexane Or a polyester diol, such as polyester amide diol, polyether ester diol, poly-ε-caprolactone diol, or polyvalerolactone diol, or a polycarbonate diol.

As the organic diisocyanate which is one of the raw materials for producing the polyurethane elastic yarn of the present invention, for example, an aliphatic, alicyclic or aromatic diisocyanate may be dissolved or liquid under the reaction conditions. Everything shown is applicable.
For example, methylene-bis (4-phenyl isocyanate), methylene-bis (3-methyl-4-phenyl isocyanate), 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, m- and p
-Phenylene diisocyanate, 4,4'-dimethyl-
1,3-xylylene diisocyanate, 1-alkylphenylene-2,4 and 2,6-diisocyanate, 3-
(Α-isocyanatoethyl) phenyl isocyanate, 2,6-diethylphenylene-1,4-diisocyanate, diphenyl-dimethylmethane-4,4-diisocyanate, diphenylether-4,4′-diisocyanate, Naphthylene-1,5-diisocyanate,
1,6-hexamethylene diisocyanate, methylene-
Bis (4-cyclohexyl isocyanate), 1,3-
And 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 3,3,5-trimethyl-5-
Examples thereof include methylenecyclohexyl diisocyanate, and preferred is methylene-bis (4-phenylisocyanate).

Examples of the chain extender having a polyfunctional active hydrogen atom, which is one of the raw materials for producing the polyurethaneurea elastomer of the present invention, include hydrazine, polyhydrazide, polyol, ethylenediamine, propylenediamine, bis- (4-aminocyclohexyl) methane, polyamines such as m-xylylenediamine, p-xylylenediamine, hydroxylamine, 1,4-butanediol,
Polyols such as 6-hexanediol, ethylene glycol and 1,8-octanediol, water and the like can be used.

As a terminator having a monofunctional active hydrogen atom, which is one of the raw materials for producing the polyurethane elastomer of the present invention, for example, dialkylamine such as diethylamine is used. These chain extenders and terminal terminators may be used alone or in combination of two or more. In the polyurethane polymer composition, if desired, an organic or inorganic compounding agent having a specific chemical structure used in a known polyurethane polymer composition, for example, a benzophenone-based compound, a benzotriazole-based compound, a hindered amine-based compound UV absorbers, antioxidants such as hindered phenolic compounds, fungicides; inorganic fine particles such as barium sulfate, magnesium oxide, magnesium silicate, calcium silicate, zinc oxide, hydrotalcite; magnesium stearate; An anti-adhesive such as calcium stearate, polytetrafluoroethylene, or organopolysiloxane may be appropriately compounded.

[0020]

EXAMPLES The present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The method of measuring the characteristic values in the examples will be described below. (Measurement of Particle Size Distribution of Magnesium Stearate) The oil agent is diluted with 10 cst of dimethyl silicone, and measured with a light scattering type particle size distribution measuring device (LA-910, manufactured by Horiba, Ltd.).

(Evaluation of Agglomeration and Deposition of Magnesium Stearate) 100 ml of the oil agent was placed in a 100 ml glass measuring cylinder with a stopper, and allowed to stand at 25 ° C. for 3 months. Determined from the transparency of the layer. If there is no transparent layer and no agglomeration is observed, it is evaluated as 、, if there is a transparent layer of less than 5 ml above, Δ if there is a transparent layer of 5 ml or more. (Evaluation of the shape of the wound body) The shape of the wound body wound on the paper core shown in FIG. 1, and the difference between the paper core length A and the winding width B is 6 mm or more, and ○ when the difference is less than 6 mm. Evaluate.

(Yarn breakage at the time of spinning) When the yarn breakage at the roll at the time of spinning is less than once per 100 million m, it is evaluated as ○, and at least one time x. (Thread breakage during warping and knitting) Back runner 75 cm, front runner 17 with 40 denier polyurethane elastic yarn on the back and nylon 50d / 17f on the front
Observe the number of thread breaks due to shape collapse during aging and the number of thread breaks in the needle and guide during knitting when preparing a 2-way tricot with 2 cm and 28 gauge.
If the number of thread breaks per 100 m is less than 1, ◎ if less than 4 times, evaluate as × if more than 4 times

[0023]

Examples 1 to 3 and Comparative Examples 1 to 5 <Preparation of polyurethane polyurea solution> Number average molecular weight 1,200
Of polytetramethylene glycol (parts by weight, hereinafter the same) and 312 g of methylene-bis (4-phenylisocyanate) were reacted while stirring at 95 ° C. for 90 minutes in a stream of nitrogen gas to obtain an isocyanate group residue. The base prepolymer was obtained. Next, after cooling to room temperature, 2,360 g of dry dimethylformamide was added and dissolved to obtain a prepolymer solution.

On the other hand, 23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 1,570 g of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature to obtain a polyurethane urea having a viscosity of 1,800 poise (30 ° C.). A solution was obtained. The thus obtained viscous polymer solution was added to 4,4′-butylidene-bis (3-methyl-6-methyl-3- (6-methyl-6-)) (based on the weight of polymer solids).
t-butylphenol) 2%), 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5
What added 0.7% of chloro-benzotriazole was used as a spinning dope.

Using this stock solution for spinning, dry spinning is carried out according to a conventional method, at a winding speed of 990 m / min and 40 d / 4.
An elastic yarn of f was obtained. At this time, an oil agent having a composition shown in Table 1 was applied to the oil agent so as to adhere to 6% by weight based on the total solid content.
In the table, StMg: magnesium stearate, AS
i: amino-modified silicone, EsSi: ester-modified silicon.

Table 1 shows the aggregation of magnesium stearate in the oil, the shape of the obtained wound body, and the yarn breakage during knitting of the two-way tricot.

[0027]

[Table 1]

As shown in Table 1, the average particle size of stearic acid exceeds 0.5 μm or the maximum particle size is 1.5 μm.
When the particle size exceeds the above range, the particles are liable to agglomerate and precipitate, and are deposited on rolls in the spinning step, guides in the processing step, and the like, causing the yarn to break. If the amount of the amino-modified silicon exceeds 0.45%, the coefficient of friction between the threads decreases, and the shape of the wound body deteriorates.
When unwound, it loses its shape and causes yarn breakage. Also,
If it is less than 0.10%, magnesium stearate is coagulated and deposited, and causes yarn breakage during spinning or processing.

It can be seen that by containing magnesium stearate having a specific particle size and amino-modified silicone in specific amounts, the friction coefficient between yarns can be controlled, yarn breakage can be suppressed, and a wound body can be improved.

[0030]

By using the oil agent of the present invention, it is possible to reduce the spinning yield due to the aggregation of magnesium stearate during spinning and to reduce the defective shape of the wound body. Further, it is possible to reduce the occurrence of thread breakage due to collapse of the winding form during aging and breakage of yarn due to poor friction with the needle or guide portion in the knitting process.

[Brief description of the drawings]

FIG. 1 is a view showing an example of the shape of a wound body according to the present invention.

Claims (3)

[Claims] 1. A polydimethylsiloxane having a viscosity of 5 to 30 centistokes in an amount of 96.5% by weight or more, an amino-modified silicone in an amount of 0.12 to 0.45% by weight, and an average particle size of 0.5 μm, based on the weight of the total oil. Below, and a maximum particle size of 1.5 μm or less magnesium stearate 0.50
An oil agent for an elastic yarn, comprising 1.50% by weight. 2. The oil agent for an elastic yarn according to claim 1, wherein the ester-modified silicone is contained in an amount of 0.5 to 1.5% by weight based on the total weight of the oil agent. 3. The oil agent for an elastic yarn according to claim 1, wherein the weight ratio of the amino-modified silicon and the magnesium stearate is 0.10 to 0.45: 1.