JP2669561B2 - High-speed spinning oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a spinning oil for synthetic fibers. More specifically, it relates to a high-speed spinning oil agent for synthetic fibers which can reduce yarn breakage due to yarn rubbing at high speed in a balloon control ring of a ring spinning machine, for example.

[Conventional technology and its problems]

The spinning process consists of processes such as opening, carding, drawing, roving, and spinning, and there are many processes through which fibers pass. The properties required of the spinning oil agent differ depending on each process, and the spinning oil agent needs to satisfy these required properties. Therefore, conventional spinning oils have been focused on satisfying these spinning characteristics. That is, it is an improvement in opening property, draft property and antistatic property.

Nowadays, however, competition is intensifying, and the need for streamlining and speeding up the spinning process is increasing. In particular, the productivity of the ring spinning process, in which the twisting speed, that is, the number of spindle rotations, is critical, and there is a strong demand for speeding up the ring spinning process.

The ring spinning has a very good yarn quality, but due to the mechanism, abrasion of the balloon control ring and the yarn at a high speed is unavoidable, and there are limits to speeding up due to problems such as dyeing spots, feathering, and yarn breakage. Can be

Therefore, adoption of new methods such as open-end spinning and air jet spinning has been attempted. However, in these new methods, although the spinning speed is high, a sufficiently high yarn quality has not yet been obtained.

[Means for solving the problem]

As a result of intensive studies to reduce yarn breakage in ring spinning, the present inventors have found that organic phosphate ester quaternary ammonium which is a good antistatic agent having good thermal stability and extreme pressure properties. The inventors have found that a high-speed rubbing in ring spinning can be remarkably reduced by combining a salt and an oxyalkylene polymer, which is a high molecular compound, and a spinning oil having good spinnability can be obtained, thereby completing the present invention.

That is, the present invention provides a high-speed spinning oil containing the following components A and B.

A: Quaternary ammonium salt represented by the general formula (1) [In the formula (1), R ₁ is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, (R ₅ represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, a represents an integer of 1 to 3) or a β-hydroxyalkyl group or alkenyl group having 10 to 24 carbon atoms, and R ₂ , R ₃ are each independently an alkyl group or an alkenyl group having 1 to 22 carbon atoms, a benzyl group or-(AO) _b-
H (A is an alkylene group having 2 to 4 carbon atoms, b is 1 to
Represents an integer of 20), or R ₂ and R ₃ are Forming a, R ₄ is - _{[CH (R 6) CH 2} ] c -OH (R 6 is H Matahaha alkyl group having 1 to 18 carbon atoms, c is an integer of 1 to 5).

X ⁻ is an anion of the organic phosphate ester represented by the general formula (2).

(In the formula (2), R ₇ is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, A is the same as described above, d is an integer of 0 to 20, and e is 1 or 2.) B: an oxyalkylene polymer represented by the general formula (3) R ₁₁ —O— (AO) _n H (3) (in the formula (3), R ₁₁ is H, an alkyl group or an alkenyl group having 1 to 20 carbon atoms) Represents an acyl group having 2 to 22 carbon atoms, an aryl group, a polyhydric alcohol group or a silyl group, A represents an alkylene group having 2 to 4 carbon atoms, and the molecular weight of the oxyalkylene polymer is 2,000 to 40,000.) The details of the mechanism for reducing thread breakage in the ring spinning process are not clear, but in order to reduce the occurrence of thread breakage, the lubricating oil film is maintained at high speed (2000 rpm) and the oil film breaks even if the oil film becomes thin. And lubricating components should be replenished with oil components entering the rubbing area. It is estimated that is necessary. For the former, a polymer compound is preferable, and for the latter, a linear molecule is preferable.

As a specific example, JP-A-62-22381, which uses a polyoxyalkylene polymer, discloses that when the gel portion of the wet spinning process in which a certain fiber of acrylic fiber is not yet formed, the compound is added and the polymer is added. It is characterized by preventing sticking at the time of formation. In addition, he is concerned that the compound may reduce the spinnability, and considers that the compound may be used in combination with a conventional spinning oil agent and suppresses the amount used, and there is no problem.

However, as a result of intensive investigations by the present inventors, as a characteristic of ananikara and the compound, they found a thread breakage prevention performance by metal abrasion at a high speed in a balloon spinning control ring of a ring spinning, The inventors have positively found its usefulness as a spinning oil component and have completed the present invention.

The quaternary ammonium salt represented by the general formula (1) of the component A according to the present invention can be easily produced by the method shown below. That is, the general formula (4) (In the formula, R ₁ , R ₂ and R ₃ are the same as those in the general formula (1) respectively) and the tertiary amine (a) represented by the general formula (2) (In the formula (2), R ₇ is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, d is an integer having 0 to 20 carbon atoms, e Is 1 or 2
It is. ) In the mixture with the organic phosphate ester (b) represented by (Wherein R ₆ is as described above). This reaction is preferably carried out at a molar ratio of (a) :( b) :( c) of 1: 0.9 to 1.2: 1.0 to 2.5. Alternatively, at the time of compounding the oil agent or preparing the oil agent emulsion, the acidic organic phosphoric acid ester or a salt thereof and the quaternary amine or a salt thereof are neutralized or salt-exchanged in a system to form a compound represented by the general formula (1). You may make it form a quaternary ammonium salt.

R ₁ in the formula (1) is octyl, decyl, lauryl, myristyl, palmityl, stearyl, oleyl,
Eicosyl, behenyl, 2-ethylhexyl, 2-octyldodecyl and the like can be mentioned.

Specific examples of the tertiary amine (a) represented by the general formula (4) include N, N-dimethyloctylamine, N, N-dimethyldecylamine, N, N-dimethyllaurylamine, N, N-dimethyl Myristylamine, N, N-dimethylpalmitylamine, N, N-dimethylstearylamine, N, N-dimethyloleylamine, N, N-dimethyleicosanylamine,
N, N-dimethyl-2-ethylhexylamine, N, N-dimethyl-2-octyldodecylamine, (In the formula, n ₁ + n ₂ = 2 to 10, and R ₁ is as described above.) And the like.

Organic phosphoric acid ester (b) represented by the general formula (2)
Is a compound obtained by phosphorylating a higher alcohol or its alkylene oxide adduct with a phosphorylating agent such as phosphorus pentoxide, orthophosphoric acid, polyphosphoric acid, phosphorus oxychloride, and specifically, sesquioctyl phosphate. Ester, sesquidecyl phosphate, sesquilauryl phosphate, sesquimyristyl phosphate, sesquipalmityl phosphate, sesquistearyl phosphate, sesquibehenyl phosphate, sesquioleyl phosphate, sesqui-2-ethylhexyl Phosphate ester, sesqui-2-octyldodecyl phosphate, bispolyoxyethylene (8 mol) dodecyl phosphate, polyoxypropylene (3 mol) (hereinafter POP
Abbreviated as (3)) stearyl phosphate, bisPOP (3)
Lauryl phosphoric acid and the like. In addition, a mono-body, a di-body, and an arbitrary mixture of a mono- and a di-corresponding to each are also exemplified.

Specific examples of the epoxy compound (c) represented by the general formula (5) used for producing the quaternary ammonium salt include ethylene oxide, propylene oxide, butylene oxide, 1,2-epoxyoctane, 1,2- Examples thereof include epoxide dodecane and 1,2-epoxy octadecane.

Specific examples of R _{11 in} the oxyalkylene polymer represented by the general formula (3) of the component B used in the present invention include methyl, ethyl, propyl and butyl as alkyl groups.
Amyl, octyl, decyl, lauryl, myristyl, palmityl, stearyl, behenyl, 2-ethylhexyl, 2-octyldodecyl and the like can be mentioned, and as the acyl group, an acetyl group, a caproic acid group, a caprylic acid group, a capric acid group, lauric acid. Group, myristic acid group, palmitic acid group, stearic acid group, oleic acid group, etc., and aryl groups such as nonylphenyl group, octylphenyl group, and polyhydric alcohol groups such as glycerin group, trimethylolpropane group, neopentyl group. And a glycol group. Specific examples of the epoxy compound used for oxyalkylenation include ethylene oxide, propylene oxide, butylene oxide and the like. Specific examples of A in the general formula (3) include a dimethylene group, a methyldimethylene group and an ethyldimethylene group.

The oxyalkylene polymer represented by the general formula (3) may be randomly polymerized or block polymerized. The molecular weight of such an oxyalkylene polymer is from 2000 to
The range of 40,000 is preferable, and the range of 6000-40,000 is more preferable. The molecular weight is measured by gel chromatography, and polystyrene with a known molecular weight is used as a standard (1000 weight average).
It is the value calculated by calibration as 0). When the molecular weight is 2000 or less, the oil film strength is low and the effect of preventing scratches is reduced. Further, when the molecular weight is large, handling such as solubility becomes difficult as an oil agent component, so the upper limit of the molecular weight is 40,000.

In carrying out the present invention, in addition to the components A and B of the present invention, any spinning oil component can be blended within a range that does not impair the effects of the present invention. As such optional components, non-ionic activators such as animal fats and oils, mineral oils, various fatty acid esters, fatty acids, higher alcohols, polyhydric alcohols, and ethylene oxide adducts of fatty acid esters are used. In particular, it is preferable to add a nonionic surfactant for the purpose of improving emulsion stability of the oil agent and handling of the oil agent to the extent that spinnability is not impaired. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, ethylene oxide- or propylene oxide-modified silicone surfactant, and the like.
The amount of the nonionic surfactant added is usually 60% or less, preferably 5 to 30%.

The spinning oil of the present invention can be applied to all synthetic fibers such as polyester fibers, polyacrylonitrile fibers, and polyamide fibers. In particular, since the polyacrylonitrile fiber is sensitive to the problem of high-speed ring spinning, the spinning oil of the present invention is considered to be highly useful for this fiber.

When the spinning oil agent of the present invention is treated by a dipping method, it is usually used as an aqueous emulsion.
It is suitable to use it as an emulsion having a concentration of 5 to 5% by weight, but it can also be used for treatment by a roller contact method or a spray method.

The amount of the spinning oil of the present invention attached to the fiber is generally 0.01.
-1% owf, preferably 0.1-0.8% owf.

Regarding the oil agent of the present invention, a quaternary ammonium salt (A)
Is 5 to 80% by weight, preferably 10 to 40% by weight, based on the solid content of the oil agent. If the content of A is less than 5% by weight, antistatic property and extreme pressure property are insufficient, and if it is 80% by weight or more, problems such as too strong bundling property occur. The content of the oxyalkylene polymer (B) is 5 to 70% by weight, preferably 10 to 40% by weight based on the solid content of the oil agent. When the content of B is 5% by weight or less, the effect of preventing scratching of the yarn is insufficient, and when it exceeds 70% by weight, the sliver cracking and the yarn breaking due to the insufficient sizing tend to occur.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

 In the examples,% is based on weight.

Example 1 Acrylic fiber staple degreased with a solvent (1.7d, 38m
The compounds of Table 2 were immersed in m) in the form of a solvent (ethanol: methylene chloride) solution (0.5%) and dried at 60 ° C. for 2 hours. After the oiled cotton was conditioned for a whole day and night, it was subjected to a spinning test by trial spinning with a spinning tester manufactured by Platt.

Evaluation of rubbing with a balloon control ring in spinning was performed as follows.

The rotation speed of the spinning machine made by Platt Co., Ltd. can be easily changed by using a continuously variable speed motor.

Using this spinning machine, spun yarn was trial-spun from staples provided with various oil agent compounds shown in Table 2. The fluff generated at this time is observed under a microscope, and the fluff is about 2000 per 100 m of the spun yarn.
The number of revolutions at the time of occurrence was evaluated as the limit number of revolutions. The limit rotation speed is conveniently indicated by the rotation speed of the motor. The correspondence between the limit rotation speed and the spindle rotation speed was assumed as shown in Table 1 below.

Table 2 shows the evaluation results.

Quaternary amine salt S: N, N, N-trimethyllauryl ammonium methosulfate complex X: N, N-dimethyl-N-2-hydroxyethyl stearyl ammonium sesquiethyl phosphate complex A: N, N-dimethyl-N-2- Hydroxyethyl lauryl ammonium sesquidecyl phosphate complex B: N, N-dimethyl-N-2-hydroxyethyl lauryl ammonium sesquilauryl phosphate complex C: N, N-dimethyl-N-2-hydroxyethyl lauryl ammonium sesquistearyl phosphate complex D : N, N-dimethyl-N-2-hydroxyethylstearyl ammonium sesquilauryl phosphate complex E: N, N-dimethyl-N-2-hydroxyethyl stearyl ammonium sesquistearyl phosphine Complex F: N, N-dimethyl-N-2-hydroxyethyllauryl ammonium sesqui-POE (3) lauryl phosphate complex G: N, N-dimethyl-N-2-hydroxyethyl lauryl ammonium sesqui-POE (3) stearyl phosphate EOPO : Ethylene oxide / Propylene oxide Further, R ₁₁ of each polymer (No. 9 to 18) in Table 2 is H.

Results From Table 2, due to the change in the molecular weight of the oxyalkylene polymer, the higher the molecular weight, the higher the rotational speed limit (good for high-speed spinning). If the molecular weight is less than 2000, high-speed spinning properties cannot be expected. Then, it can be seen that the effect is not so much improved. Also, ethylene oxide,
It can be seen that there is almost no difference between the propylene oxide block polymer and the random polymer.

Further, regarding the complex of quaternary amine and phosphate, there is a tendency that the limit rotational speed becomes slightly higher as the carbon chain length of phosphate becomes longer.

Example 2 Next, the interaction between oxyalkylene polymer and phosphate was examined.

The oxyalkylene polymer and phosphate shown in Table 3 were lubricated to acrylic fibers in the same manner as in Example 1 and the spinning test was conducted in the same manner as in Example 1.

The mixing ratio between the oxyalkylene polymer and the phosphate is 50/50 (weight ratio).

 Table 3 shows the results.

Results From Table 3, it can be seen that the compound is improved by about 500 rotations as a whole, compared with the level using each compound alone in Example 1, and that the high-speed spinning property which is the object of the present invention is exhibited. . In Experiment No. 19, the high-speed spinning property is also excellent, but even if this complex is not used after being synthesized, the complex is produced by salt exchange during compounding of the oil agent, and the same effect can be obtained. You can see that it can be done.

In addition, the effect is good even when the terminal of the oxyalkylene polymer is lauryl ether or nonylphenyl ether (No.38, 39), and the alkylene group is EOPO.
It can be seen that a good effect can be obtained even with BO (BO: butylene oxide) (No. 40).

Example 3 Next, the effect of the following blending oil agent was tested in consideration of the entire spinning process.

(Oil formulation) sorbitan stearate 40% stearylamide 10 hydrogenated castor oil ethylene oxide adduct 20 N, N-dimethyl-N-2-hydroxyethyl lauryl ammonium sesquilauryl phosphate 15 EOPO random polymer (R ₁₁ = H) 15 Acrylic fibers were lubricated in the same manner as in Example 1 using an oil agent, and spinning characteristics were measured.

As a result, there is no problem in the spinning process such as card electrification voltage and its passability, roller winding, etc.
It was 00 rpm, and it was found that the high-speed spinning property was excellent.

〔The invention's effect〕

The oil agent of the present invention has excellent anti-rubbing property against metal at high speed. Therefore, high-speed spinning can be prevented by preventing yarn breakage and yarn quality deterioration during high-speed spinning.

Claims (3)

(57) [Claims] 1. A spinning oil for high speed, which comprises the following components A and B: A: Quaternary ammonium salt represented by the general formula (1) [In the formula (1), R ₁ is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, (R ₅ represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, a represents an integer of 1 to 3) or a β-hydroxyalkyl group or alkenyl group having 10 to 24 carbon atoms, and R ₂ , R ₃ are each independently an alkyl group or an alkenyl group having 1 to 22 carbon atoms, a benzyl group or-(AO) _b-
H (A is an alkylene group having 2 to 4 carbon atoms, b is 1 to
Represents an integer of 20), or R ₂ and R ₃ are And R ₄ is — [CH (R ₆ ) CH ₂ ] _c —OH (R ₆ is H or an alkyl group having 1 to 18 carbon atoms, and c is an integer of 1 to 5). X ⁻ is an anion of the organic phosphate ester represented by the general formula (2). (In the formula (2), R ₇ is an alkyl group or an alkenyl group having 8 to 22 carbon atoms, A is the same as described above, d is an integer of 0 to 20, and e is 1 or 2.) B: an oxyalkylene polymer represented by the general formula (3) R ₁₁ —O— (AO) _n H (3) (in the formula (3), R ₁₁ is H, an alkyl group or an alkenyl group having 1 to 20 carbon atoms) Represents an acyl group, an aryl group, a polyhydric alcohol group or a silyl group having 2 to 22 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and the molecular weight of the oxyalkylene polymer is 2000 to 4000.) 2. The high-speed spinning oil composition according to claim 1, wherein the solid content of the oil solution contains 5 to 80% by weight of the quaternary ammonium salt (A) and 5 to 70% by weight of the oxyalkylene polymer (B). 3. The high-speed spinning oil composition according to claim 1, wherein the target fiber is a polyester fiber or an acrylic fiber.