JPS6197421A - Production of antistatic conjugated fiber - Google Patents

Abstract

PURPOSE:A fiber-forming thermoplastic polymer and another fiber-forming thermoplastic polymer containing a specific amount of a polyalkylene glycol or its derivative are subjected to conjugate spinning under specific conditions to improve fibrilation resistance and color development. CONSTITUTION:A fiber-forming thermoplastic polymer A (polyester or polyamide) and another fiber-forming thermoplastic polymer B containing 1-7 wt% of polyalkylene glycol or its derivative are subjected to cnjugate spinning so that the polymer B occupies 5-70% of the cross section area of the resultant fiber. The conjugate melt extrusion is effected using a spinneret for making dense fibers having more than 0.2 mm<2> hole area and satisfying the equation: S>=0.02Q<2> + 0.2 where S is hole area in mm<2> of each nozzle; Qis throughput in grams/min per nozzle.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing composite fibers having antistatic properties. More specifically, the present invention relates to a novel method for producing fibers with excellent antistatic properties from a fiber-forming thermoplastic polymer containing polyoxyalkylene glyco-A or its derivatives.

(Prior art) Synthetic fibers made from fiber-forming thermoplastic polymers, typified by polyester, have excellent mechanical strength and durability, but on the other hand, these synthetic fibers have a unique property of low electrical resistance. It has the fatal disadvantage of being extremely susceptible to static electricity. Many various methods have been proposed to completely prevent this tendency to be charged with static electricity. but,
Currently, none of the methods can satisfy all of the above requirements in terms of cost increase, spinning operation stability, quality stability, antistatic performance and durability, balance with other fiber properties, etc. For example, in a method in which an antistatic agent is applied on the surface of fibers, part or all of the antistatic agent disappears during washing or dyeing processes, and durable antistatic performance cannot be obtained. In addition, in order to obtain fibers with durable antistatic properties, antistatic agents such as polyoxyalkylene glycols or their derivatives (hereinafter abbreviated as POG) are added to the fiber-forming thermoplastic polymer prior to spinning. A method of incorporating fibers into fibers (for example, Japanese Patent Publication No. 39-5214)
has also been proposed, but when trying to obtain antistatic fibers by simply adding an antistatic agent such as POG to a fiber-forming thermoplastic polymer before spinning and melt-spinning it by a conventional method,
In order to obtain a fiber with practically sufficient antistatic performance, it is necessary to incorporate a large amount of POG, and the large amount of FOG does not impair the excellent mechanical properties of the fiber made from the fiber-forming thermoplastic polymer. Furthermore, the light fastness of the resulting dyed fibers becomes extremely poor, and in this method, the commercial value of the fibers is almost completely lost in order to obtain an antistatic effect.

The method for producing antistatic fibers by simply adding POG' to a fiber-forming thermoplastic polymer has the following drawbacks, and the present inventors have made several efforts to improve these drawbacks. We discovered a method to obtain fibers with practical antistatic performance using a large amount of POG.

A method of melt spinning a fiber-forming thermoplastic polymer containing POG using a spinneret having a single hole with a single hole opening area of 0.2 or more was proposed.

(Problems to be Solved by the Invention) The above method certainly provided excellent light resistance. Although it became possible to obtain fibers with practical control properties, subsequent studies revealed that these fibers had problems such as easy fibrillation and poor color development. It became clear.

(Means for solving the problems) The means for solving all the above-mentioned problems, that is, the structure of the present invention is as follows.

That is, it is composed of a fiber-forming thermoplastic polymer [A] and a fiber-forming thermoplastic polymer CB) containing a polyalkylene glycol or a derivative thereof in a 1- to 7-polymer relationship;
B] When performing composite spinning so that the proportion of the acid component in the cross section of the fiber is 5 to 70%.

Using a spinneret having a spinning hole for producing solid fibers in which the opening area of the single spinning hole is 0.2 or more, the opening area of the single spinning hole S (mm2) and the discharge amount per single hole QCf1 min) This is a method of performing composite melt spinning under conditions where the relationship between .

S≧0.0202 10.2...
(1) Component (A) and [B] as used in the present invention
The fiber-forming thermoplastic polymer constituting the acid component may be any thermoplastic polymer that can be formed into fibers by a melt-spinning method, and typical examples include 1, such as polyester #, polyamide, polystyrene, Examples include polyethylene, polypropylene, polyether ester, etc., but it goes without saying that the material is not limited to these examples.

Among the fiber-forming thermoplastic polymers mentioned above, the present invention is particularly applicable to polyesters mainly composed of repeating units represented by the general formula (where n is an integer of 2 to 6), and polyamides represented by nylon 6, nylon 66, etc. It exhibits excellent effects.

In particular, in the case of polyester, it is used as a copolymer component and exhibits excellent effects on basic dye-dyeable polyester.

The fiber-forming thermoplastic polymers constituting component CA) and component CB) may be the same type of thermoplastic polymer.

Component (A) and [B] may be different thermoplastic polymers.
In order to prevent acid component peeling, it is desirable to use the same or the same thermoplastic polymer.

Polyoxyalkylene glycol or its derivative (POG>) referred to in the present invention is used to impart antistatic properties by being mixed into thermoplastic synthetic fibers, for example in Japanese Patent Publication No. 39-5214.
As seen in Japanese Patent Publication No. 57-4724, etc., this term refers to all things that are generally known, and specific examples include polyethylene glycol, polypropylene glycol/I/, ethylene oxide and propylene oxide. random or block copolymers,
Polytewomethylene glycol, block copolymers obtained by adding ethylene oxide to polytetramethylene glycol, polyoxyalkylene compounds with hydroxyl groups at both ends such as compounds obtained by adding ethylene oxide to neopentyl glycol or bisphenol glycol, monophenoxy polyethylene Glyco)v, nonylphenoxypolyethylene glycol, sodium sulfophenoxypolyethylene glycol/I/, diphenoxypolyethylene glycol, compounds bonded with 2 moles of monophenoxypolyethylene glycol/11 moles of tolylene diisocyanate, or A polyoxyalkylene compound whose both ends are blocked via an ether bond,
polyethylene glycol laurate, polyethylene glycol phosphate or its partially alkaline salt,
Polyether compounds esterified at one or both ends, such as phosphonates of polyethylene glycol or partially alkali salts thereof, block copolymers of polyethylene glycol and polyethylene terephthalate, and combinations of polytetramethylene glycol and polyethylene terephthalate or polybutylene terephthalate. Block copolymer, polyethylene glycol block copolymer with ε-capramide 1 Polyethylene glycol with cyanoethylated at one end or both ends ~) V or polyethylene glycol with this cyano group as an amino group, 1
Compounds obtained by total addition of ethylene oxide to primary or secondary alkylamines and linear formula (z) t (m)
Examples include compounds represented by the formula +(II[).

It goes without saying that the polyether compound referred to in the present invention is not limited to the above specific examples, and may be a single compound or a mixture of two or more of these compounds.

Moreover, in the above POG, both ends are -OH.

In the case of a group having active hydrogen such as -COOH, -NH2, etc., the weight average molecular weight (hereinafter referred to as molecular weight) of the POG is preferably 6,000 or more. When one end is blocked by a group having active hydrogen and the other end is blocked by a group not having active hydrogen, the molecular weight of POG is 400.
It is preferable that it is 0 or more.

Further, when both ends of the POG are blocked with a group having no active water, the molecular weight of POG is preferably 1000 or more.

The POG to be used in the present invention is one or more sticky POGs.
It is fine as long as it is OG. Furthermore, this additional P to be contained
Antioxidants, ultraviolet absorbers, pigments, organic or inorganic ionic compounds, and other additives may be mixed in advance with OG.

The polyalkylene glycol or its derivative is contained in an amount of 1 to 7% by weight in the component CB) constituting the entire composite fiber. Here, if the concentration of polyalkylene glyco/L' or its derivative is less than 1% by weight, a sufficient antistatic effect cannot be obtained. Moreover, if it exceeds 7% by weight, light resistance and spinning operability will decrease.

Therefore, the concentration of polyalkylene glycol or its derivative is preferably 1 to 7% by weight.

The method of incorporating POG into the fiber-forming thermoplastic polymer is not limited as long as it is prior to spinning, and as long as it does not adversely affect spinnability etc., it can be added from the polymerization initiation stage of the thermoplastic polymer to spinning. Any point in the previous stage is acceptable.

In addition, a fiber-forming thermoplastic polymer [B
[Percentage of the area of the acid component in the cross section of the fiber, or 5 to 70%
It is. If it is less than 5%, sufficient antistatic effect cannot be obtained. Moreover, if it exceeds 70%, it is unsuitable because it tends to become fibrillated and the color development property deteriorates.

[A] Acid component [B] A conjugate fiber composed of acid component may have a similar shape. but.

The core-sheath type ([B] acid component core) is desirable for carpet applications that require strict performance such as abrasion resistance, but for general clothing applications that require performance that is strict in terms of color development and antistatic properties rather than abrasion resistance. A molded sheet in which at least a part of the component (CB) is exposed on the fiber surface is preferable.

The present invention uses a fiber-forming thermoplastic polymer comprising the acid component [A] and the acid component [B] in a spinneret for producing solid fibers having a larger opening area of a single spinning hole than those conventionally generally used. , and the opening area S of the single hole in the spinneret is
(mm2) and the discharge amount per single hole QCf1 minute) is a condition where the following formula (1) is fully satisfied.

Preferably, it is necessary to perform melt spinning under conditions that satisfy all of the following formula (2).

S≧0.02 Q2 + 0.2 ・
・・・・・・・・・(1) S≧0. I Q2+ 0.2
(2) Conventionally, in melt spinning of thermoplastic synthetic fibers, a spinneret for producing solid fibers has been used with a single spinning hole having an opening area of approximately 0.03-
POG fibers with single holes of about 0.13 mj are used, and the discharge rate per single hole is 0.8 f1 min to 3.05'/min. When spinning the containing fiber-forming thermoplastic polymer to produce antistatic fibers, POG't-
Satisfactory antistatic performance could not be obtained unless a large amount was contained.

However, a spinneret for producing solid fibers having a single spinning hole with an opening area of 0.2 TIj or more is used.

and the condition that the relationship between the opening area S (mm2) of the single hole of the spinneret and the discharge amount Q (2/min) per single hole satisfies the above formula (1), preferably the condition that the above formula (2) is completely satisfied. So (A
, L component and CB) component by melt spinning the POG content in component [B].
At ~7% by weight, fibers with surprising durable antistatic performance are obtained.

In determining the spinning conditions of the present invention, the opening area S of a single spinning hole and the discharge iQ per single hole are important factors. □・ The opening area S of the single spinning hole of the spinneret for producing solid fibers used in the present invention is not particularly limited as long as it is 0.2- or more, and it may be as large as it is as long as melt spinning is possible. . However, in practice, there are restrictions on the fiber denier depending on the purpose and use. Therefore 0.4
It is preferable to set it to 1.5-.

The spinneret in the present invention is for producing solid fibers,
As long as the opening area of the single spinning hole is 0.2- or more, the cross-sectional shape can be not only circular but also non-circular. Examples include, but are not limited to, a triangle, a quadrilateral, or a polygon larger than that, a cross, a cross, and a seven-figure shape.

However, those shaped to obtain fibers with hollow portions (hollow fibers) are excluded. Here, in the case of a fiber having a shape to obtain a fiber having a hollow part, if the melt spinning conditions according to the present invention are adopted, it becomes difficult to perform melt spinning with good spinning stability. Fibers with excellent properties cannot be stably obtained.

The upper and lower limits of the discharge amount Q per single hole in the present invention are not particularly limited, and as long as melt spinning is possible, no matter how large the discharge amount Q is, as long as the above formulas (1) and (2) are satisfied,
Furthermore, although it may be as small as possible, in practice there will be limitations from the viewpoint of fiber properties and productivity depending on the purpose and use. Therefore, it is preferable to set it as 0.1-52/min.

The winding speed in the present invention is not particularly limited, but is 500~
The speed is preferably 8000 m/min, preferably 1000 to 4000 m/min.

The present invention can also be applied when using a spinneret for producing mixed fiber yarn. In this case, the spinneret for producing mixed fiber yarn should have a single spinning hole with an opening area of 0.2 m7 or more.

The relationship between the opening area S and the discharge amount Q per single hole is curved (1
) The number of holes for producing fully satisfactory fibers is at least 1 or more, preferably 5% of the total number of holes in the spinneret.
Any material may be used as long as it accounts for 10% or more of the above, more preferably 10% or more.

(Examples) The present invention will be explained below using Examples, but the present invention is not limited to these Examples. In addition, in the examples, unless otherwise specified, percentages are 1 by weight.
Parts represent parts by weight. Further, in the examples, the half-life (hereinafter simply referred to as half-life) and light resistance were measured by the following methods.

(a) Half-life: The half-life is measured using the obtained filament knitted material according to the JIS standard.
-L-1094-1980 (Methods for testing electrification properties of woven and knitted materials) A method (half-life measurement method) was used for measurement.

In order to evaluate the durability of the antistatic property, the obtained filament was knitted, subjected to the washing treatment shown below, and after air-drying, it was used as a sample for the above-mentioned half-life measurement.

Washing treatment: All knitted fabrics were washed at 40°C with a 0.5f/II aqueous solution of neutral detergent.
Complete laundry using a home washing machine for 0 minutes.

After dehydrating, rinse under running water at room temperature for 20 minutes.

After dehydrating again, rinse with warm water at 40° C. for 5 minutes to dehydrate. The above operation was repeated 20 times, and after air drying, it was used as a sample for a chargeability test.

(b) Light resistance; Myramen 1il obtained in the same manner as above was knitted.

The knitted fabric before and after washing was treated with 1.0% owf of Resolin Blue FBL (disperse dye manufactured by Bayer) *Solution ratio 1:50.
After dyeing with a dye liquor at 130° C. for 60 minutes in a conventional manner, washing by reduction and air drying, the light fastness was measured by the method specified in JIS-L-0842-1971 (Carpon-Pook lighting fastness test method).

(c) Fibrillation test The filaments obtained in the same manner as above were knitted.

The knitted fabric after washing is processed according to JIS-L-1018-197.
After conducting a test according to 6.17 (abrasion strength) = C method (tapered shape method) specified in 7 (Knitted Fabric Testing Method), the state of fiber damage was determined. The degree of corrosion was rated 5th grade for ordinary filament yarns that did not contain POG'e (almost undamaged), 1st grade for the most severe, and 3rd grade for moderate damage.

Example 1 Polyethylene terephthalate was polymerized by a conventional method, and immediately before the completion of polymerization, polyethylene glycol (average molecular weight 20
．． 1, 3.5-) Rimethy/L/2, 4. OOO) which is a hindered phenol antioxidant.
6-) Lith(3,5-ditertiary-butyl-4-hydroxylbencyl)benzene (manufactured by Ciba Geigy, trade name Irganox 1330) was added in an amount of 1.0% and melted and mixed. 1POG content: 3. After completing one polymerization by adding 5%, it was discharged from the polymerization can and cut to obtain chips [B)'t-. This chip was used as one component of the composite yarn, and the other component was a regular polyethylene terephthalate chip (A), which was melted at 290°C under the spinning conditions shown in Table 1 using a side-pie-side type spinneret. Spinning was performed, the spun yarn was cooled and solidified, and the undrawn yarn having an area ratio of 20 in the cross section of the [B] acid component fiber was wound (winding speed 130 (1 portion). The resulting drawn fibers were knitted and the half-life, light resistance, degree of fibril formation, and color development were measured. The results of the measurements are shown in Table 1.

Part 1 Table According to the method of the present invention, as shown in Table 1.

It can be seen that a product with excellent antistatic properties, excellent fibrillation resistance, and excellent color development can be obtained.

Example 2 Spinning using only the CB) component of Example 1. Alternatively, the area of the single hole opening and the amount of POG added in the [B] component are
Fibers were produced and knitted in the same manner as in Example 1 except that the values shown in the table were used.

Half-life of the resulting knitting, extent of fibrils.

The evaluation results of color development are shown in Table 2.

As shown in Table 2, the POG content in the - component is 1 to 7.
%, the single pore opening area is 0.2- or more, and the area ratio of the POG-containing component to the fiber cross section is optimally 3 to 70%. In addition, samples without composite spinning tend to fibrillate and have poor color development.

Example 3 Chips (A) and [1,B) used in Example 1 were
Using a sheath-type spinneret, the yarn containing the core component k [:B] and the sheath component was spun under conditions such that the single hole opening area was 0.785 d and the discharge rate per single hole was 0.5 f/min. It was cooled and solidified, and rolled up at 1300 m/min (the mark on the cross section of the fiber contains 30% of the component). The obtained yarn was drawn in a conventional manner.

The resulting fibers were knitted. The half-life after 20 washes is 46
A fiber with excellent color development was obtained, the degree of fibrillation was 5th grade, the light resistance was 4th to 5th grade.

(Effects of the Invention) As described above, in the present invention, excellent antistatic properties can be achieved with less 2l-POGffl by using a spinneret for solid fibers with a larger opening area of a single spinning hole than those commonly used in the past. is obtained, so that the light resistance of the obtained fibers also poses no practical problems.

Moreover, since the fiber is a composite fiber and one component (A) does not contain incompatible POG, it is resistant to fiber IJ.
) The dyeing properties are greatly improved, and since there is a layer that does not contain POG components with different refractive indexes, the coloring property of the dyed product is very good.

Moreover, this composite fiber has a great effect on improving the mechanical properties of the fiber.

Claims (1)

[Scope of Claims] 1. Consisting of a fiber-forming thermoplastic polymer [A] and a fiber-forming thermoplastic polymer [B] containing 1 to 7% by weight of polyalkylene glycol or a derivative thereof; ] When performing composite spinning so that the proportion of the component in the fiber cross section is 5 to 70%, the opening area of a single spinning hole is 0.2 m.
Using a spinneret having spinning holes for producing solid fibers of m^2 or more, the relationship between the opening area S (mm^2) of the single hole of the spinneret and the discharge amount Q (g/min) per single hole is The following formula (1)
A method for producing an antistatic composite fiber characterized by melt spinning under conditions that satisfy the following. S≧0.02Q^2+0.2...(1) 2. The fiber-forming thermoplastic polymer constituting the component [A] and component [B] is polyester, according to claim 1. Method for producing antistatic composite fiber.