JPS59192719A - Antistatic polyester fiber - Google Patents

Abstract

PURPOSE:The titled fiber which is produced by dispersing a polyamide composition such as polyhexamethlene adipamide containing a specific amount of an inorganic electrolyte such as alkali or alkaline earth halide in a fiber-forming polyester in stripes or lines, thus showing high antistatic performance. CONSTITUTION:(A) 100pts.wt. of a fiber-forming polyester is mixed with (B) 1- 15pts.wt. of a polyamide composition such as a polyhexamethylene adipamide or poly-epsilon-capramide containing 0.1-5wt% of alkali or alkaline earth metal halide and melting at 170-210 deg.C, after the polyamide composition is passed through the filter A composed of sand 3 and both components pass through the paths 4 and 5 and they are kneaded in the kneading part having a hole 10 in which the static kneading element 9 is contained, then extruded out of the spinneret D to form the objective fiber where component B dispeses in stripes or lines in component A.

Description

Detailed Description of the Invention (a) Technical Field The present invention relates to polyester fibers with improved antistatic properties, and more particularly, to polyester fibers with improved antistatic properties.
The present invention relates to an antistatic polyester fiber formed by dispersing a polyamide composition containing an electrolyte in the form of stripes.

(B) Prior Art Polyester fibers, typified by polyethylene terephthalate fibers, are widely used in the fields of clothing, interior decoration, industrial materials, etc. due to their excellent properties, but their major drawback is the problem of static electricity generation. That is, polyester fibers are more easily charged with static electricity than cotton, rayon, etc., and when used for clothing, there are problems such as making a crackling discharge sound and clinging to the body, especially in the winter.

To address this drawback, a number of improvement methods, ie, antistatic methods, have been proposed.

For example, fibers made by spinning polyester copolymerized with polyethylene glycol have been proposed. However, in order to impart practical antistatic properties, it is necessary to copolymerize a relatively large amount of polyethylene glycol, resulting in a decrease in thermal stability and light fastness. Furthermore, methods have been proposed in which antistatic agents made of various polyalkylene glycol derivatives are added to polyester.

However, most of these do not have practical antistatic properties, or their antistatic properties do not last until after the dyeing process, washing, etc.

Furthermore, fibers made by dispersing polyester in which polyethylene glycol is block-copolymerized or polyamide in a polyester have been proposed (for example, JP-A-50-107206 and JP-B-Sho 48-10580). However, these also have problems arising from the thermal instability of polyethylene glycol and UV degradation. In addition, a technology has been proposed to prevent static electricity by blending an alkali metal halide into polyester5.
(Special Publication No. 45-29913). However, the antistatic properties of fibers obtained using this technology do not actually last until after the dyeing process and washing.

(c) Purpose of the invention As a result of intensive studies to overcome the problems of the prior art as described above, the present inventors have developed a polyamide composition in which a specific inorganic electrolyte is contained in a specific polyamide. It was discovered that the above problems could be overcome by dispersion, and the present invention was achieved. That is, an object of the present invention is to provide a polyester fiber that retains various excellent properties inherent to polyester and also has excellent antistatic properties.

B) Structure of the Invention The antistatic polyester fiber according to the present invention is made by dispersing 1 part by weight or more and less than 15 parts by weight of a polyamide composition containing an inorganic electrolyte in 100 parts by weight of a fiber-forming polyester (fiber-forming polyester fiber). (A) the inorganic electrolyte is an alkali metal halide or an alkaline earth halide, and (B) the inorganic electrolyte is contained in the polyamide composition in an amount of 0.00 parts by weight based on 100 parts by weight of the polyamide. 1 part by weight or more and less than 5 parts by weight, and (C) the polyamide is a random copolymerized polyamide mainly composed of polyhexamethylene adipamide or polyε-cabramide having a melting point of 1000 or more and less than 210C. shall be.

(e) Preferred embodiments The fiber-forming polyester used in the present invention includes polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, poly P-ethyleneoxybenzoate, polybutylene terephthalate, etc., or copolymers thereof, e.g. , polyethylene terephthalate/isophthalate copolymer.

Among these, polyethylene terephthalate and copolyester containing polyethylene terephthalate as a main component are preferred.

The polyamide used in the present invention has a polyamide of 1000 or more21
It is a random copolymerized polyamide mainly composed of polyhexamethylene adipamide or polyε-cabramide having a melting point of less than 0C. Specific examples include polyhexamethylene adipamide/ε-capramide copolymer (hereinafter abbreviated as "nylon 66/6 copolymer") with a melting point of 170C or more and less than 210C, poly-ε-cabramide/hexamethylene copolymer, and bacamide copolymer (hereinafter abbreviated as nylon 6/610 copolymer), polyhexamethylene adipamide,
Hexamethylene sebaamide conjugate (hereinafter referred to as nylon 6
6/61 D co-te (abbreviated as “coalescence”), polyε-cabramide/hexamethylene adipamide, hexamethylene sebacamide co-polymer (hereinafter referred to as “nylon 6/66/610
(abbreviated as "copolymer"), etc. Of course, Isophthal iX?・Terephthalic acid, etc. can also be a copolymerization component.

On the other hand, copolyamides or monopolyamides whose main components are polyhexamethylene adipamide, polyundecaneamide, etc. cannot obtain sufficient antistatic properties even if their melting points are in the range of 1000 to 210C. So I don't like it. Furthermore, a polyamide copolymer obtained by block copolymerizing a large amount (for example, 15 to 85 weight percent) of polyethylene glycol chains is not preferred because of the disadvantages caused by polyethylene glycol, as described with respect to the prior art. The melting point of the copolyamide of the present invention must be 1000 or more and less than 210C. More preferably 1000 or more2
It is less than 00C. If the melting point is less than 170C, it will be difficult to withstand hot water in the dyeing process of polyester fibers.

On the other hand, if the melting point is 210C or higher (t)? 1, the prevention effect is insufficient. Among these copolyamides, nylon 6, which has a melting point of 1000 or more and less than 200C,
6/6 or nylon 66/6/610 random copolymer (nylon 6 or nylon 66 may be the main component) is more preferable, especially 1000 or more 20
A nylon 6/66/610 random copolymer having a melting point of less than 0C and containing nylon 6 as a main component is most preferred from the viewpoint of hot water resistance and antistatic properties.

The inorganic electrolyte used in the present invention is an alkali metal halide or an alkaline earth metal halide. Specific examples include lithium chloride, lithium bromide,
Sodium chloride, sodium bromide, sodium iodide,
Examples include potassium chloride, potassium bromide, potassium iodide, magnesium chloride, magnesium bromide, calcium chloride, etc., preferably lithium bromide, sodium bromide, potassium iodide, and more preferably potassium iodide. . Of course, these inorganic electrolytes may be used alone or in combination of two or more. On the other hand, if the inorganic electrolyte is an inorganic electrolyte other than an alkali metal halide compound or an alkaline earth metal halide compound, or an organic electrolyte such as alkylbenzenesulfonic acid (IJium), sufficient antistatic properties cannot be obtained.

The content of the inorganic electrolyte in the polyamide composition is at least 11 parts by weight and less than 5 parts by weight of the inorganic electrolyte per 100 parts by weight of the polyamide. If it is less than 0.1 part by weight, sufficient establishment property cannot be obtained, and if it is more than 5 parts by weight, no further substantial improvement in the antistatic effect can be expected. .1.

Practical antistatic properties are obtained only when the inorganic electrolyte is contained in polyamide, and even if it is contained in fiber-forming polyester or evenly contained in both fiber-forming polyester and polyamide, Sufficient antistatic properties cannot be obtained.

As schematically shown in FIG. 1, in the fiber according to the present invention, the polyamide composition A containing an inorganic electrolyte is contained in the fiber-forming polyester B in a longitudinal direction along the axis of the fiber (← direction). It must be dispersed in a sushi-like manner. As schematically shown in Figure 2, polyamide composition A is dispersed in polyester B in the form of particles, and polyamide composition is observed as an independent phase and is dispersed to a very uniform degree. does not have sufficient antistatic properties. Regarding the striped dispersion, the longer the stripes are, the more preferable it is, and in particular, it is most preferable that the striped dispersion be substantially continuous, as schematically shown in FIG.

In the present invention, the proportion of the polyamide composition containing an inorganic electrolyte and the fiber-forming polyester is 1 part by weight or more and less than 15 parts by weight, preferably 6 parts by weight or more and less than 16 parts by weight, per 100 parts by weight of the latter. be. If the polyamide composition is less than 1 part by weight, sufficient antistatic properties cannot be obtained, and if it is more than 15 parts by weight, when the fiber of the present invention is spun, the coloring becomes noticeable, the spinning becomes sharp, and the resulting product is not obtained. The physical properties of the resulting fibers are significantly lower than those inherent to polyester.

A specific method for producing the antistatic polyester of the present invention is as follows.

Inorganic in polyamide? In order to obtain a total of 1 including 1 likely solute, (
A.) A method in which an inorganic electrolyte is added as a powdered aqueous solution during polymerization of polyamide, (B) A method in which the polyamide is melted after polymerization and a powdered inorganic electrolyte is added. F can. Particularly preferred are the method of adding an electrolyte aqueous solution during polymerization of polyamide and the method of impregnating polyamide with a heated electrolyte aqueous solution, since the inorganic electrolyte is finely and uniformly dispersed.

The method for producing the antistatic polyester t(η) of the present invention is to pelletize (A) the FA-free electrolyte-containing polyamide composition, premix it with pelletized fiber-forming polyester, and then feed it to a melt spinning machine. How to spin (
B) A method in which an inorganic electrolyte-containing polyamide composition and a fiber-forming polyester are separately melted, and then the melts are mixed and spun. Particularly, in method (B), the method in which two melts are introduced into a static kneading element, mixed, and then spun is easy to obtain a substantially continuous sushi-like dispersion state, and the difference between polyamide and polyester is This is preferable because it causes less reaction and reduces melt viscosity and coloring of the spun product.

Figure fJ4 is a sectional view of a main part showing a typical example of a spinneret device used for producing the antistatic fiber of the present invention. In the same figure, the copolyamide composition and the fiber-forming polyester are introduced sequentially from the introduction holes 15 and 16 into the r-vortex portion A1.
The blending part B1 has 0 kneading agent and is spun out through the spinneret part. f vortex part A includes sand 3, sand pack 1, and sand holding wire mesh 2
It consists of The merging section B is composed of a liquid passage plate 6 provided with a copolyamide flow path 5 and a polyester flow path 4, and a liquid passage plate 8 provided with a flow path 7 for combining the two polymer flows. . The cross section 0 is a static kneading element 9
The kneading batten 11 is provided with holes 10 incorporating the kneading battens, and the connecting battens 16 and 14 are provided with grooves 12 for connecting these holes in sequence.

The fibers obtained in this manner may be stretched several times to adjust the strength and elongation, heat treated or shaped to transform into processed yarn, etc., or subjected to dyeing or alkali reduction i1 processing, as necessary. All conventionally known processing techniques such as these can be applied.

Further, the antistatic polyester 1 of the present invention may contain suitable light stabilizers, heat stabilizers, matting agents, dyes and pigments, etc. These can be added in advance to the fiber-forming polyester or polyamide composition, or added at the time of mixing the fiber-forming polyester and polyamide composition.

(f) Effects of the Invention In most of the conventional antistatic property imparting technologies, antistatic properties were obtained using polyethylene glycol (or polyethylene), whereas the antistatic polyester fiber of the present invention uses polyamide and an inorganic electrolyte. The combination produces antistatic properties, and there are no adverse effects caused by polyethylene glycol.
That is, problems such as a decrease in heat resistance and light fastness can be overcome. In addition, since the inorganic electrolyte is water-soluble, the antistatic polyester kJA fiber of the present invention can be dyed or washed with 7M.
There was a concern that antistatic properties would be lost due to this, but surprisingly, these techniques fIi! It is possible to maintain sufficient antistatic properties for practical use even after passing through.

(G) Examples The following is a detailed description of examples. Note that the measurement method used in the examples is as follows.

[Half-life]

The half-life method was used to measure antistatic properties.

Immediately, the obtained fibers were made into a net fabric and scoured for 30 minutes in a score roll well 400 (manufactured by Sanyo Chemical Industries, Ltd.) 21/stone aqueous solution at a water temperature of 60 U, and then the fibers were dyed. As the dye, disperse dye Re5olin BlueFBL (manufactured by Bayer) was used, and the concentration was 1% owf.

Dyeing was carried out at 130C with a bath ratio of 1:50. D as a dispersant
isper TL (manufactured by Meisei Chemical Industry Co., Ltd.)
P/-e was added and the pH was adjusted to 6 with acetic acid.

Next, the dyed silk fabric was submerged for 7 hours using a 12% OWF warm water solution (40C) at a bath ratio of 1:240 (manufactured by Kao Soap Co., Ltd.).

After washing, the knitted fabric was washed with water, dried, and left in an atmosphere of 23 tT and 43% relative humidity for 24 hours to moisten fi+4, and the half-life of this sample was measured using an honest meter (manufactured by Mito Shokai). .

[Melting point]

The melting point of the copolyamide was measured using a DSO-2C differential scanning calorimeter (manufactured by PERK N-ELMER) at a heating rate of 20 C/min, and the temperature at the peak position of the endothermic curve obtained was measured by It was taken as the melting point.

[Light fastness]

A dyed silk fabric prepared to measure antistatic properties was used as a sample, and a 6.
3 tl;, a 27-hour dew test was conducted. The degree of discoloration of the sample after the test was compared with that of ordinary polyethylene terephthalate fiber tested under the same conditions at 6 N, and was visually observed.

Example 1 ε-caprolactam 75-fold 1-Tsujiyaku-6 Hegisamethylene diammonium adipate (hereinafter abbreviated as "AH salt")
A mixture of 15 parts by weight of a 40% by weight aqueous solution and 10 parts by weight of a 30% by weight aqueous solution of hexamethylene diammonium sebacate (hereinafter abbreviated as 1-sH salt) was mixed with
80t:'' while controlling the internal pressure to remove the solvent water and condensed water, and use the conventional polyamide melting method to obtain 1.1°!J E-/'J'7'*7°h.
---s-r'''j l f k >7') S 4
Hexamethylene sebamide (nylon 6/66/
610) A random copolymer was produced and granulated into pellets. The melting point of the polyamide copolymer was measured. The melting point was 180C. 4ky of the copolymer pellets, 1
The sample was immersed in an aqueous solution of potassium iodide (1) dissolved in water (5) for impregnation at a boiling temperature of νH'c for 40 minutes, and then dried. After the treatment, the potassium iodide in the pellets was analyzed and found that the amount of potassium iodide in the pellets was 6 parts by weight per 100 parts by weight of the copolymer. Using a spinning machine with an extruder, one extruder was fed with the polyamide composition and extruded at 250C, and the other extruder (3') was fed with polyethylene terephthalate fibers having an intrinsic viscosity I of 90.61 ( 205% by weight of polyethylene terephthalate) was supplied as a matting agent and extruded at 290G.A spinneret with 16 discharge holes and a static cross-wire element having a structure as shown in Fig. 4 was used. is the installation.A spinning machine was used.The molten polyamide composition was passed through the introduction hole 15 in FIG.
The mixture was combined by a static kneading element 9, mixed, and spun. The discharge speed of each molten polymer was adjusted so that the mixing ratio of the polyamide composition and polyethylene terephthalate was 9:100 by weight. The spun yarn was wound at a speed of 1200 m/min to form an undrawn yarn of 170 denier 16 filaments. Furthermore, 12
0t? Stretched 3.67 times using a heat plate of 50
A fiber of denier 16 filament was obtained. When the antistatic properties of this fiber were measured, the half-life was 48 seconds, showing excellent antistatic properties.
had sex. Further, when the light fastness of a dyed product of this fiber was determined at 7 inches, no fading was observed, similar to the polyethylene terephthalate 1-fjAQ fiber, and it had excellent light fastness. When this fiber 1 (Ij:) was observed using an optical @microscope, continuous streak-like dispersion was observed as shown in Figure @5.

Comparative example 1'! In Bit Example 1, all of the samples were real/I, except that the copolyamide was not impregnated with potassium iodide.
A fiber consisting of a mixture of copolyamide and polyethylene terephthalate was produced in the same manner as in Example 1. When the antistatic properties of this fiber were measured, the half-life exceeded 6 minutes, and no substantial antistatic properties were observed.

Comparative Example 2 In Example 1, polyamide was used instead of copolyamide.
In the same manner as in Example 1 except for using ε-cabramide,
A Fl fiber was produced consisting of a mixture of a polyamide composition and polyethylene terephthalate.

This fiber regulation? When the II property was measured, the half-life was over 6 minutes.

Comparative Example 3 A nylon 6/66/610 copolymer was produced in the same manner as in Example 1 from a mixture of 65 parts by weight of ε-caprolactam, 23 parts by weight of Al (salt) and 17 parts by weight of SH (salt) and pelletized. The t111 point of this copolymer was 16.
[It was 1'C. This copolymer pellet was prepared in Example 1.
When the copolymer pellets were impregnated with potassium iodide using the same method as above, the copolymer pellets dissolved in the boiling aqueous solution, making it impossible to produce potassium iodide-containing polyamide composition pellets.

Example 2 ε-caprolactam 40 weight, AH salt 70 weight (4
A nylon 66/6 copolymer composition containing potassium iodide was produced in the same manner as in Example 1 from a mixture of scrap potassium iodide (used as an aqueous solution of 0 weight Jit%),
It was granulated into pellets.

The melting point of this polyamide was 195C. Next, this polyamide composition was mixed and spun with polyethylene terephthalate and drawn in the same manner as in Example 1 to produce fibers. When the antistatic properties of this fiber were measured, the half-life was 58 seconds.

Furthermore, continuous streak-like dispersion was observed in microscopic observation of this fiber.

Comparative Example 4 When producing polyethylene terephthalate from dimethyl terephthalate and ethylene glycol by conventional transesterification and polycondensation reactions, potassium iodide was added to the ester in a ratio of 0.5 parts by weight to 100 parts by weight of polyethylene terephthalate. The potassium iodide-containing polyethylene terephthalate composition (
Polyethylene terephthalate (reduced viscosity = 0.61) was produced. Next, in Comparative Example 1, a fiber made of a mixture of a copolyamide polyamide and a polyethylene terephthalate composition was produced in the same manner as in Comparative Example 1, except that the polyethylene terephthalate composition was used instead of polyethylene terephthalate. When the antistatic properties of this fiber were measured, the half-life was over 6 minutes. It can be seen that antistatic properties are not exhibited when potassium iodide is contained in polyethylene terephthalate rather than in copolymerized polyamide.

Examples 3 to 5, Comparative Examples 5 to 8 Polyamide compositions made of combinations of various copolyamides shown in Table 1 and various inorganic electrolyte types and substances were polymerized in the same manner as in Example 2. Manufactured by These polyamide compositions and polyethylene terephthalate were mixed and spun in the same manner as in Example 2 in the proportions shown in Table 1, and various fibers were produced by drawing. The antistatic properties of these fibers were measured. The results are shown in Table 1.

Margin below

[Brief explanation of the drawing]

FIGS. 1 to 6 are diagrams schematically showing the state in which the copolymerized polyamide composition can be soaked in tL (a rag), and among these, FIGS. Figure 2 shows fibers that do not fall under the present invention. In each figure, A is the copolyamide composition of the present invention, and B is the fiber-forming polyester. Figure 4 shows the antistatic fiber of the present invention. 1 is a cross-sectional view of main parts showing a typical example of a spinneret device having a static kneading element section used for manufacturing. A: filtration section, B+combination section, C: kneading section, D
:0 metal part, 1: sand pack, 2: wire mesh for holding sand, 6: sand, 4: polyester channel, 5: copolyamide channel, 6: liquid passage plate, 7: combining two polymer streams 8: Liquid passage plate, 9: Static kneading element, 10:
Hole incorporating static mixing element, 11: Kneading batten, 12
: groove for connecting each hole in sequence, 15.14
: Connection batten, 15: Copolyamide introduction hole, 16:
Polyester introduction hole. FIG. 5 is a photograph of the polyester antistatic fiber of the present invention observed with an optical microscope. Patent applicant Asahi Kasei Kogyo Co., Ltd. Patent agent Akira Aoki Patent attorney Kazuyuki Nishidate Patent attorney Yukio Uchida Patent attorney Akira Yamaguchi) 1 Figure 2 Figure 3 11214

Claims (1)

[Claims] 1. Fiber-forming polyester 100@i part inorganic 11
A fiber obtained by dispersing 1 part by weight or more and less than 15 parts by weight of a polyamide composition containing solutes in a sushi-like shape,
) the inorganic electrolyte is an alkali metal chloride or an alkaline earth metal halide; and (B) the content of the inorganic electrolyte in the polyamide composition is polyamide 10.
0 parts by weight or more and less than 5 parts by weight,
(An antistatic polyester fiber characterized in that the CI polyamide is a random copolyamide mainly composed of polyhexamethylene adipamide or polyε-cabramide having a melting point of 17 DC or more and less than 210'C.