JP2002363866A - Oil agent for elastic yarn and elastic wound thread - Google Patents

Abstract

(57) Abstract: An oil agent for elastic yarns containing mineral oil and polydimethylsiloxane as main components, in particular, amino-modified silicone (A) 0.45% by weight or less based on the total amount of the oil agent,
For elastic yarns containing 1.0 to 4.0% by weight of alkyl silicone resin (B) which is a mono- and trifunctional co-hydrolyzed polymer and 2.0% by weight or less of magnesium stearate (C) Oil agent. [Effects] Suppression of yarn breakage due to poor unwinding, suppression of yarn breakage during spinning due to aggregation of magnesium stearate, and suppression of static electricity generation and yarn breakage due to frictional resistance between elastic yarn and knitting needle .

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 In general, polyurethane elastic yarns are wound with an oil agent applied thereto. However, the inner layer of the wound body tends to be agglutinated with the passage of time, so that unwinding failure in the inner layer tends to occur. A method using a metal salt of a higher fatty acid such as magnesium stearate as a method for preventing sticking (Japanese Patent Publication No. Sho 3)
No. 7-4586) 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. Also during knitting, the yarn accumulates in the guide section and causes thread breakage, and the coefficient of friction between the yarns decreases, resulting in a poor wound thread shape. There is a drawback that

[0003] A method using an amino-modified silicone (Japanese Patent Publication No. 63-8233) has also been proposed.
The anti-sticking effect is insufficient. In order to suppress aggregation of a higher fatty acid magnesium salt such as magnesium stearate, a method in which an amino-modified silicone is used in an amount of 0.5 to 3.0% by weight has been proposed (JP-A-10-259577).
No.). According to this method, the aggregation of the magnesium salt of the higher fatty acid is suppressed, but the coefficient of friction between the elastic yarns is excessively reduced, and the shape of the wound body becomes poor, or the winding is difficult when unwinding from the wound body. There is a problem that the shape of the thread body breaks and thread breakage occurs. Further, in this method, when a large number of amino groups are present on the surface of the elastic yarn, it causes yellowing of the yarn, or causes skin damage when worn. 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.

An oil agent containing a monofunctional or tetrafunctional alkylsilicone resin has also been proposed (Japanese Patent Application Laid-Open No. 9-1997).
No. 78460). According to this method, it is possible to prevent sticking of the elastic yarn. However, the elastic yarn to which the oil agent is attached has a large friction with the knitting needle, generates static electricity, and causes a problem of increased yarn breakage during knitting.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to suppress the aggregation of magnesium stearate and, at the same time, appropriately adjust the coefficient of friction between the elastic yarns and between the elastic yarns and the knitting needles. An object of the present invention is to provide an oil agent for elastic yarn that can suppress yarn breakage during processing.

[0006]

As a result of various studies on the above-mentioned problems, the present inventors have found that an oil agent for elastic yarns containing mineral oil and polydimethylsiloxane as main components, comprising (A) an amino-modified silicone, (B) an alkyl silicone resin which is a mono- and tri-functional co-hydrolyzed polymer,
(C) It has been found that the above problem can be solved by adding magnesium stearate.

Hereinafter, the present invention will be described in detail. The content of the components constituting the oil agent for elastic yarn of the present invention is as follows. Except for the mineral oil and polydimethylsiloxane, which are the main components, the content of the amino-modified silicone (A) is 0.45 wt% or less based on the total amount of the oil agent. An alkylsilicone resin (B), which is a co-hydrolyzed polymer composed of three functional groups, containing 1.0 to 4.0 wt%;
It is preferable that magnesium stearate (C) is 2.0 wt% or less. In the present invention, aggregation of magnesium stearate (C) can be suppressed by containing an amino-modified silicone (A) and a monofunctional or trifunctional alkyl silicone resin (B) in the oil agent, and
It has been found that since the anti-sticking action is enhanced, even if the content of magnesium stearate (C) in the oil agent is 2% or less, the sticking of the elastic yarn can be prevented. Furthermore, by containing a monofunctional or trifunctional alkyl silicone resin (B), the friction between the elastic yarn and the knitting needle can be kept small, so that the amount of static electricity generated by frictional charging can be reduced, and Yarn breakage can be reduced.

In the present invention, at the same time as preventing sticking of the elastic yarn,
The problems of the prior art, such as the coagulation of magnesium stearate (C), the collapse of the wound body, the yellowing of the thread, the skin disorder, and the suppression of thread breakage with a knitting needle, could be achieved. In order to achieve the object of the present invention, the content of the amino-modified silicone (A) in the oil is set to 0.45% by weight or less based on the total amount of the oil, and a mono- and tri-functional co-hydrolyzed polymer is used. It is very important to contain 1.0 to 4.0 wt% of a certain alkyl silicone resin (B).

When the amino group content in the amino-modified silicone (A) is less than 0.01% by weight, there is no effect on the dispersion stability of magnesium stearate (C), and when it exceeds 0.5% by weight, skin disorders and yellowing may occur. Problems arise. Therefore, the amino group content is 0.01 to 0.5% by weight, preferably 0.02% by weight.
０．３0.3 wt%. The content of the amino-modified silicone (A) in the oil agent is preferably 0.45% by weight or less based on the total amount of the oil agent. Content is 0.45wt%
If it exceeds, the coefficient of friction between the yarns decreases, the shape of the wound body deteriorates, and skin problems and problems of yellowing occur. The viscosity of the amino-modified silicone is 1,000 to 30,000 mm ² / s from the viewpoint of the dispersibility of magnesium stearate.
It is.

The monofunctional and trifunctional alkyl silicone resin (B) used in the present invention is a co-hydrolyzed polymer of two monomers represented by the following formula (1).

Embedded image (R ₁ in the formula represents a hydrocarbon group having 3 to 10 carbon atoms.) The content of the alkylsilicone resin (B) in the oil is preferably 1.0 to 4.0 wt% based on the total amount of the oil. If the content of the alkylsilicone resin (B) is less than 1.0 wt%, there is no effect on the anti-sticking property and antistatic property of the elastic yarn,
If it exceeds 4.0% by weight, the viscosity of the oil agent becomes high, and the problem of thread breakage during refueling occurs. 1.0 ~
3.0 wt% is more preferable.

Monofunctional and trifunctional alkyl silicone resins
In (B), the ratio of monofunctional / trifunctional is 1/5
Or less, more preferably 1/10 or less.
The monofunctional, trifunctional alkyl silicone resin itself has an anti-sticking effect, and has a smaller coefficient of friction between the elastic yarn and the metal than the monofunctional, tetrafunctional alkyl silicone resin. Frictional resistance can be reduced, and the generation of static electricity due to contact with the knitting needle can be reduced. For this reason, it is possible to solve the problem of increased knitting tension during knitting and yarn breakage due to generation of static electricity.

In the present invention, magnesium stearate is maintained on the elastic yarn while maintaining the anti-sticking effect.
It is preferable that the coagulation and sedimentation of (C) is small. The amino-modified silicone (A) of the present invention is added in an amount of 0.45 to the total amount of the oil.
wt% or less, and containing 1.0 to 4.0 wt% of a monofunctional or trifunctional alkyl silicone resin (B),
2.0 wt% magnesium stearate (C) content
By the addition of a small amount as described below, a sufficient anti-sticking effect and an anti-agglomeration effect can be exhibited. If the content of magnesium stearate (C) exceeds 2% by weight, the dispersion stability of magnesium stearate becomes insufficient. The average particle diameter of magnesium stearate (C) is preferably 0.01 to 1.0 μm from the viewpoint of dispersibility of particles and anti-sticking property of the elastic yarn,
More preferably, it is 0.1 to 0.8 μm. The water content in the magnesium stearate (C) used for the oil agent is preferably 1 to 5% by weight from the viewpoint of the viscosity stability of the oil agent,
More preferably, it is good to control it to about 2-4 wt%.
For example, in the case of a magnesium salt of a higher fatty acid, it can be used if the carbon number of the higher fatty acid is 10 to 30, but it is preferable to use magnesium stearate (C).

In the present invention, the amino-modified silicon (A)
And a monofunctional or trifunctional alkyl silicone resin (B),
The important point of each role of magnesium stearate (C) is that coexistence of monofunctional and trifunctional alkyl silicone resin (B) and magnesium stearate (C) for preventing sticking of elastic yarns. Even if the content of magnesium stearate (C) is small, sufficient anti-sticking effect can be obtained on the elastic yarn, and the addition of amino-modified silicon (A) necessary for dispersing this small amount of magnesium stearate Can be reduced to a small amount. Furthermore, monofunctional and trifunctional alkyl silicone resins
By using (B), the frictional resistance between the elastic yarn and the knitting needle can be reduced, and the generation of static electricity due to the contact with the knitting needle can be reduced.

The mineral oil in the oil agent is contained in order to lower the oil agent cost and to suppress the fly waste at the time of cotton knitting, but if it exceeds 50% by weight, the unwinding property of the wound body deteriorates. Therefore, the content of the mineral oil in the oil agent is preferably 5 to 50 wt%. More preferably, it is 8 to 40 wt%. The viscosity of the mineral oil at 25 ° C. is preferably in the range of 5 to 40 mm ² / s, more preferably 10 to 30 mm ² / s. The content of polydimethylsiloxane in the oil agent is preferably 43 wt% to 94 wt%, and more preferably 50 wt% to 90 wt%. To the oil agent of the present invention, if necessary, a trace amount of polyether-modified silicone, ester-modified silicone, carboxyl-modified silicone, mercapto-modified silicone, fluorine-modified silicone, or the like can be added. The oil agent of the present invention is generally used in an amount of 1 to 10% by weight, preferably 2 to 10% by weight, based on the polyurethane elastic yarn.
It is preferable that the content be given to ８8 wt%.

The elastic yarn to which the oil agent of the present invention is applied is not particularly limited. For example, polyurethane, polyetherester elastic yarn and the like can be used, but polyurethane elastic yarn is particularly preferable. Polyurethane elastic yarns are typically polyisocyanate-terminated prepolymers made from organic diisocyanates and substantially linear polymeric diols, with chain extenders having polyfunctional active hydrogen atoms and monofunctional It is obtained by dry spinning, wet spinning or melt spinning an elastic high molecular polymer having a urethane group in the molecule obtained by reacting an end-blocking agent having an active hydrogen atom in one or more steps. As another method for producing a polyurethane elastic yarn, a hydroxyl group at both ends described later and having a molecular weight of 4
A chain extender having a polyfunctional active hydrogen atom in an isocyanate-terminated prepolymer comprising an organic diisocyanate and a substantially linear polymer having a molecular weight of from 00 to 5,000, preferably from 800 to 4000; It is obtained by spinning while reacting with a terminal terminator having an active hydrogen atom.

The high molecular weight diol which is one of the raw materials for producing the polyurethane elastic yarn of the present invention has a substantially linear number average molecular weight of 400 to 5,000, preferably 800 to 4000, having hydroxyl groups at both ends. It is good to be a high polymer. For example, polyoxyethylene glycol,
Polyether diols such as polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, and copolymerized polyalkylene ether diols having linear or random ether bonds of 1 to 8 carbon atoms; adipic acid; Sebacic acid, maleic acid, itaconic acid, azelaic acid, one or more dibasic acids such as malonic acid and ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol, 1,10 A polyester diol obtained from one or more glycols such as decanediol, 1,3-dimethylolcyclohexane and 1,4-dimethylolcyclohexane; or polyesteramide diol, polyetherester diol, poly-ε- Examples include polylactone diols such as caprolactone diol and polyvalerolactone diol, and polycarbonate diols.

The organic diisocyanate which is one of the raw materials for the polyurethane elastic yarn of the present invention is, for example, an aliphatic, alicyclic or aromatic diisocyanate which is soluble or liquid under the reaction conditions. Everything can be applied. 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-methylenecyclohexyl diisocyanate and the like are exemplified, preferably methylene-bis (4-phenyl isocyanate).
It is.

Examples of the chain extender having a polyfunctional active hydrogen atom, which is one of the raw materials of the polyurethane urea elastic material of the present invention, include, for example, hydrazine, polyhydrazide, and polyhydrazine.
, Ethylenediamine, propylenediamine, bis-
(4-aminocyclohexyl) polyamines such as methane, m-xylylenediamine, p-xylylenediamine, polyols such as hydroxylamine, 1,4 butanediol, 1,6 hexanediol, ethylene glycol and 1,8 octanediol; Water or the like can be used. As a terminal stopper having a monofunctional active hydrogen atom, which is one of the raw materials for the polyurethane elastic material of the present invention, for example, a dialkylamine such as diethylamine is used.
These chain extenders and terminal terminators may be used alone or in combination of two or more.

The polyurethane polymer composition may optionally contain an organic or inorganic compounding agent having a specific chemical structure used in a known polyurethane polymer composition, for example, a benzophenone compound, a benzotriazole compound, UV absorbers such as hindered amine compounds; antioxidants such as hindered phenol compounds; fungicides;
Barium sulfate, magnesium oxide, magnesium silicate,
Inorganic fine particles such as calcium silicate, zinc oxide, hydrotalcite and the like; anti-adhesives such as magnesium stearate, calcium stearate, polytetrafluoroethylene, organopolysiloxane and the like can be appropriately blended.

[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. (Evaluation method of unwinding property) Measuring method of unwinding speed ratio: In FIG. 1, an elastic yarn wound body (1) with an oil agent attached is set on the unwinding side of the unwinding speed ratio measuring machine, and the winding side is set. The winding paper tube (2) is set in.
After setting the winding speed to a constant speed, the rollers (3) and (4) are simultaneously activated. In this state, almost no tension is applied to the yarn (5), so that the yarn sticks on the cheese and does not separate, and the unwinding point (6) is in the state shown in FIG. Since the unwinding point (6) of the yarn (5) from the 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 determined by the following equation (2). The smaller this value is,
It shows that the unwinding property is good. After winding on cheese and storing at room temperature for 30 days, the unwinding speed ratio is measured. Unwinding speed ratio (%) = (winding speed−unwinding speed) ÷ unwinding speed × 100 (2) Measurement method of knitting tension: In FIG. 2, cheese (8) and elastic yarn ( 9) through a compensator (10), a roller (11), a knitting needle (12), a roller (14) attached to a U cage (13), and a speedometer (1).
5) Connect to winding roller (16). Speedometer (1
The rotation speed of the winding roller (16) is adjusted so that the traveling speed in 5) is 100 m / min, and the winding roller (1) is adjusted.
Take up in 6), and use the U gauge (13)
And the friction (g) between the elastic yarn (9) and the knitting needle (12)
Is measured.

(Degree of sedimentation) An oil solution was placed in a 100-ml test tube with a stopper, allowed to stand for one month, and the height of the resulting supernatant portion was defined as A ₁ , and the height of the cloudy portion was defined as A _2. Oils with S less than 20 defined by the formula (3) were defined as sedimentation degree 〇, and oils with 20 or more as sedimentation degree x. S = A ₁ ÷ (A ₁ + A ₂ ) × 100 (3) (Yarn yellowing degree Δb) Sunshine weather meter [WE
L-SUN-HO type] After irradiating light for 72 hours with Suga Test Instruments Co., Ltd., spectral colorimeter CLR-710F (SHIMAZU C
(ORPORALTION) was used to measure the difference in Δb value.
A yarn having a Δb value of less than 3 has a yellowing degree, and a yarn having a value of 3 or more has a yellowing degree x
And (Amino% measuring method) (1) A 2 g sample is precisely weighed in a beaker having a capacity of 100 ml, 60 ml of ethyl alcohol and 20 ml of toluene are added, and a Teflon (registered trademark) rotor is put therein. (2) Using an automatic titrator, titrate with 0.25N alcoholic HCL. (3) Substitute the titer V (ml) into the following equation to determine the amino%. Amino% = (0.25 × F × V × 16 × 100) / 20
00 (F is the factor of the titrant)

[0022]

Examples 1 to 4 and Comparative Examples 1 to 5 <Preparation of polyurethane polyurea solution> Number average molecular weight 1,200
Of polytetramethylene glycol (parts by mass, hereinafter the same) and 312 g of methylene-bis (4-phenylisocyanate) were reacted at 95 ° C. in a nitrogen gas stream with stirring for 90 minutes 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 give a viscosity of 1,80 g.
A polyurethane urea solution of 0 × 10 ^-1 Pas (30 ° C.) was obtained. The thus obtained viscous polymer solution was added to (4% by weight of polymer solid content, the same applies hereinafter), 4,4′-butylidene-bis (3-methyl-6-t-butylphenol) 2
%, 2- (2'-hydroxy-3'-t-butyl-5 '
A solution obtained by adding 0.7% of (-methylphenyl) -5-chloro-benzotriazole was used as a stock solution for spinning. Using this spinning dope, dry spinning was carried out according to a conventional method to obtain an elastic yarn of 44 dtex / 4f at a winding speed of 1,000 m / min.

At this time, an oil agent having a composition shown in Table 1 was applied to the oil agent so as to adhere to the solid content by 5 wt%.

[Table 1] (Note) DMSi: Polydimethylsiloxane St-Mg: Magnesium stearate A-Si: Amino-modified silicone Si-R: Alkyl silicone resin MT: Alkyl silicone resin which is a co-hydrolyzed polymer consisting of monofunctional and trifunctional MG: Alkyl silicone resins that are mono- and tetra-functional co-hydrolyzed polymers

Table 2 shows the sedimentation degree of magnesium stearate in the oil, the skin irritation, the unwinding property of the shape of the obtained wound body, the knitting tension during knitting, and the amount of generated static electricity.

[Table 2]

As shown in Table 2, a monofunctional or tetrafunctional alkyl silicone resin (B) -containing oil agent
The friction between the elastic yarn and the knitting needle is large, the knitting tension increases, and the amount of generated static electricity increases. Increasing the amount of amino-modified silicone (A) in oils will increase magnesium stearate.
Although sedimentation of (C) can be suppressed, skin irritation is increased and thread yellowing occurs. When the amount of the alkyl silicone resin (B) is small, the unwinding property of the wound body becomes poor, and the yarn breakage due to poor unwinding occurs. In addition, when the content of magnesium stearate (C) in the oil is increased, the magnesium stearate (C) is coagulated and deposited, which causes yarn breakage during spinning or processing. As a result, 0.45 wt% or less of amino-modified silicone (A) was added to alkyl silicone resin (B), which is a mono- and tri-functional co-hydrolyzed polymer, at 1.0%.
~ 4.0 wt% magnesium stearate (C).
It can be seen that by containing 0 wt% or less, the unwinding property and the friction coefficient can be controlled, and trouble during processing can be suppressed.

[0026]

When the oil agent of the present invention is attached to the elastic yarn, yarn breakage during processing due to poor unwinding of the wound body can be suppressed. Further, yarn breakage during spinning and processing due to aggregation of magnesium stearate can be suppressed. Further, in the knitting process, occurrence of thread breakage due to poor friction with the needle and the guide portion can be reduced.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an apparatus for measuring an unwinding speed ratio.

FIG. 2 is an explanatory diagram of an apparatus for measuring knitting tension.

[Explanation of symbols]

 1, 8: cheese 2: take-up side paper tube 3, 4, 11, 14: roller 5, 9: elastic yarn 6: unwinding point 7: contact point between cheese and roller 10: compensator 12: knitting needle 13: U cage 15: Speedometer 16: Winding roller

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 169/04 C10M 169/04 D06M 13/02 D06M 13/02 13/188 13/188 // C10N 10: 04 C10N 10:04 40:00 40:00 Z D06M 101: 38 D06M 101: 38

Claims (5)

[Claims] 1. An oil agent for elastic yarns containing mineral oil and polydimethylsiloxane as main components, wherein (A) an amino-modified silicone and (B) an alkyl which is a mono- and tri-functional co-hydrolyzed polymer. An oil agent for elastic yarns, comprising a silicone resin and (C) magnesium stearate. 2. The oil agent for an elastic yarn according to claim 1, wherein the content of the amino-modified silicone (A) is 0.45% by weight or less based on the total amount of the oil agent. 3. The content of the alkyl silicone resin (B), which is a mono- and tri-functional co-hydrolyzed polymer, is 1.0 to 4.0 wt% based on the total amount of the oil agent. Item 3. The oil agent for elastic yarn according to item 1 or 2. 4. The oil agent for an elastic yarn according to claim 1, wherein the content of magnesium stearate (C) is 2.0% by weight or less based on the total amount of the oil agent. 5. An elastic wound thread body, wherein the oil agent according to claim 1 is attached in an amount of 1 to 10% by weight.