KR19980021395A - Antistatic polyester resin composition and polyester prepared therefrom - Google Patents

Abstract

The present invention relates to an antistatic polyester resin composition and a polyester yarn prepared therefrom. The polyester resin composition of the present invention is prepared by adding polyalkylene glycol or a derivative thereof and an ionic organic compound to a predetermined amount of glycol. A water-in-oil emulsion is prepared by injecting it into a polyester polymerization process. When the resin composition thus prepared is melted and spun, the polyalkylene glycol or its derivative is uniform in the form of an independent island component with high orientation in the longitudinal direction. It is dispersed and formed to improve the ion conduction effect of the yarn, and since polyalkylene glycol or its derivatives and ionic organic compounds are introduced in the form of an emulsion, they have physical bonding strength, so that the antistatic agent is not detached even after a process such as weight loss, dyeing or washing. It is possible to produce an antistatic polyester yarn having durability.

Description

Antistatic polyester resin composition and polyester yarn prepared therefrom

The present invention relates to an antistatic polyester polymer composition, and more particularly, to an antistatic polyester polymer composition having excellent quality stability under reduced weight processing and laundry durability.

As a method of imparting antistaticity to a polyester, there exists a method of mixing a polyalkylene glycol or its derivative (s) with a polyester matrix, or the method of mix | blending an ionic organic compound with this (Japanese Unexamined Patent Publication No. 39-5214, 44-31828, 47-11280, 47-10246).

However, in order to obtain the antistatic fiber through the conventional melt spinning by including the above antistatic agent in the polyester, a large amount of the antistatic agent must be included. In this case, since the excellent property of the polyester is impaired, the poly The amount of antistatic agent contained in the ester should be less than 5% by weight.

In addition, antistatic agents such as polyalkylene glycol, which have been conventionally used, are easily detached from the polyester matrix by alkali reduction, dyeing process, or washing so that the antistatic durability is poor and the hydrophobicity of the antistatic agent is increased to prevent the antistatic property itself. Has the disadvantage of greatly deteriorating.

The present invention overcomes the problems of the prior art, and has a sufficient antistatic property even at an amount of less than 3% by weight of the antistatic agent, and is capable of producing an antistatic fiber having excellent quality stability and wash durability under weight reduction processing. It is for that purpose to manufacture.

The antistatic polyester resin composition of the present invention for achieving the above object is a fixed amount of 0.1 to 5 parts by weight of polyalkylene glycol or derivatives thereof and 0.1 to 3 parts by weight of an ionic organic compound relative to 100 parts by weight of the total polyester resin composition. A water-in-oil emulsion prepared by adding to the glycol in advance and stirring is prepared during the polyester polymerization process.

Hereinafter, the present invention will be described in detail.

The polyester matrix used in the present invention is an aromatic polyester having an aromatic ring in a repeating unit of the polymer, a combination obtained through the reaction of a bifunctional aromatic acid or its ester forming derivative with glycol or its ester forming derivative to be.

Preferred aromatic polyesters include copolymerized polyesters such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, copolymers of polyethylene isophthalate and polyethylene terephthalate. Especially preferred are polyethylene terephthalate, polypropylene terephthalate and polybutyl terephthalate having excellent moldability.

Aromatic polyesters are synthesized by any method. For example, in the description of polyethylene terephthalate, glycol esters of terephthalic acid and / or oligomers thereof may be formed by directly reacting terephthalic acid with ethylene glycol or by transesterifying lower alkyl esters of terephthalic acid such as dimethyl terephthalate with ethylene glycol. It is prepared through a one step of producing a step, followed by a two step reaction in which the product is heated under reduced pressure to condensation polymerization until the desired degree of polymerization is reached. The polyester resin composition may contain another thermoplastic polymer in a range in which the original properties of the polyester are not lost.

As the glycol used in the present invention, aliphatic glycols such as ethylene glycol, trimethylene glycol, butylene glycol, aliphatic aromatic glycols, or aromatic diols and mixtures thereof are preferable.

Examples of the difunctional aromatic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like, and terephthalic acid is particularly preferable. You may use together 2 or more types of these bifunctional aromatic acids. Moreover, you may use together 1 type (s) or 2 or more types of 5-sodium sulfoisophthalic acid etc. with these aromatic acids.

In the present invention, the water-in-oil emulsion composed of polyalkylene glycol / ionic organic compound / glycol may be prepared in a reactor capable of temperature control and continuous stirring of 200 RPM or more, and is prepared before the polymerization reaction and kept in a stable state. It is desirable to put it.

The glycol which comprises the said emulsion may use any of the above-mentioned glycol, and the weight is preferable to set it as 80-200 weight part with respect to 100 weight part of polyalkylene glycol and its derivative (s) added. When the amount is less than 80 parts by weight, phase transition occurs, so that oil-in-water emulsions are easily formed, and even when water-in-oil emulsions have a problem of poor stability. When it is more than 200 parts by weight, the ionic organic compound serving as an emulsifier is dispersed too widely, making it difficult to form micelles.

As the polyalkylene glycol or derivatives thereof used in the present invention, all kinds of compounds conventionally proposed to add antistatic properties to the manufacturing process of thermoplastic resins are possible. If the average molecular weight of the polyalkylene glycol or its derivatives is less than 2,000, when the polyester resin composition is made of fibers, it is difficult to form a sufficiently long dispersed phase in the fiber axis direction, so that the antistatic property is poor. Since dispersion | distribution becomes uneven and antistatic property deteriorates within, it is preferable that the average molecular weight is between 2,000 and 30,000. The amount of polyalkylene glycol or derivatives thereof is appropriately 0.1 to 5 parts by weight relative to the appetizer polyester composition. If it is less than 0.1 part by weight, sufficient antistatic property is not obtained. If it exceeds 5 parts by weight, the antistatic property is improved, but the physical properties, light resistance, and the like of the polyester resin composition or the fiber produced therefrom are deteriorated. Polyalkylene glycol or its derivative (s) may be used together 2 or more types.

Examples of the ionic organic compound used in the present invention include sulfonic acids such as undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and tridecylbenzenesulfonic acid, and sulfonic acid alkali metal salts such as sodium dodecyl sulfite composed of sulfonic acids and alkali metals. . The amount of the ionic organic compound is suitably 0.1 to 3 parts by weight relative to the total polyester composition. When the amount is less than 0.1 part by weight, the improvement of the antistatic property is insignificant. When the amount is more than 3 parts by weight, the whiteness and dyeing property of the polyester resin composition or the fiber produced therefrom deteriorates.

In the present invention, the temperature at the time of preparing the emulsion is preferably maintained between the melting point of the polyalkylene glycol or its derivative and the melting point of + 30 ° C. At temperatures below the melting point, the polyalkylene glycol or derivatives thereof are not dissolved or the viscosity is high, making emulsions impossible. At temperatures above the melting point of + 30 ° C., there is a possibility that by-products are generated by the reaction of the polyalkylene glycol or the derivatives themselves. have.

In the present invention, the emulsion prepared in advance may be added at any stage of polymerization of the polyester resin composition, or may be added in one whole amount or dispersedly added several times.

Melting and spinning the antistatic polyester resin composition of the present invention yields an antistatic polyester yarn in which polyalkylene glycol or a derivative thereof is uniformly dispersed in an independent island component having a size of less than 1 μm in any fiber cross section. Can be.

In this case, the dispersion in an independent island component in any fiber section means that the polyalkylene glycol or derivative thereof is evenly dispersed in the fiber with a sufficient length in the fiber axis direction and these dispersions are polyester when viewed from any cross section. It is meant to appear in a form that is identifiable with respect to the matrix.

The magnitude of the island component means the diameter in the case of circular shape, the diameter of the circumscribed circle in the case of polygon, and the length of the long axis in the case of elliptical shape. The size of the conductive component is maintained at a predetermined size or more when the polyalkylene glycol or derivatives thereof is contained in 0.1 parts by weight or more. When the conductive component having a size of 1 μm or more is present, the antistatic property is good, but the whiteness and the light resistance are good. Becomes worse and the process becomes unstable.

The polyester resin composition of this invention can mix | blend antioxidants, such as a hindered phenol type, a sulfide type, and a phosphite type, ultraviolet absorbers, such as a benzophenone type and a benzotriazole type. For example, when an antioxidant is blended, the fall of the antistatic property due to the thermal decomposition of polyalkylene or its derivatives in the melt spinning process can be suppressed.

In addition, the polyester resin composition of the present invention may be flame retardant, fluorescent brightener, titanium dioxide, zinc sulfate, barium sulfate, colorant, inert fine particles such as silica, alumina, calcium carbonate, calcium phosphate, and other optional additives. You may add to the arbitrary steps from superposition | polymerization of a polyester resin composition to a spinning process separately, or mixed previously.

It is preferable that the intrinsic viscosity [micro] of the polyester resin composition of this invention is 0.50 or more. If the intrinsic viscosity is less than 0.50, when the polyester resin composition is made of fibers, the elongation viscosity after exiting the spinneret is too low, so that the alkylene oxide chain in the polyalkylene glycol or its derivative is sufficiently long in the polyester fiber. It becomes difficult to take the form of dispersion in the direction, so that the antistatic property is insufficient, crystallization is likely to occur by heat, and the toughness tends to be weakened and weak, and thus the wear resistance is insufficient.

There is no particular limitation on the denier of the fiber produced from the polyester resin composition described in the present invention, and the cross-sectional shape exhibits antistatic properties even when any one of circular, triangular, flat, and hollow forms of these forms is adopted.

According to the present invention, an antistatic resin composition is obtained which has excellent antistatic properties even when a small amount of antistatic agent is used and exhibits excellent durability even when passing through processes such as weight loss, dyeing and washing.

The reason why the fiber produced from the polyester resin composition of the present invention exhibits excellent antistatic properties is that polyalkylene glycol or its derivatives are introduced into the emulsion to obtain a uniform dispersed state in the polyester matrix, This is because the ion conduction effect is increased by forming an independent conductive component having a high degree of orientation.

The durability is improved because polyalkylene glycol or its derivatives or ionic organic compounds are introduced in an emulsion state, and thus have a physical bonding force, and thus are relatively difficult to be removed even if they pass through a process such as weight loss, dyeing or washing. In addition, since the antistatic agent is uniformly dispersed, even in a harsh process, the antistatic agent is less detached compared to the fiber in which the antistatic agent is concentrated on the surface, thereby exhibiting excellent durability.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples. However, the present invention is not limited by the examples.

(Example 1)

A water-in-oil emulsion was prepared by adding 2 parts by weight of polyethylene glycol having an average molecular weight of 20,000 and 1 part by weight of sodium dodecyl sulfite to 3.5 parts by weight of glycol. The prepared emulsion was added during a conventional polyester polymerization process to prepare a polyester resin composition having an average molecular weight of 10,000. Through spinning process, a fiber having 75/24 denier and fineness was produced, and the plain weave fabric composed of these fibers was kept in a constant temperature and humidity chamber at 20 ° C. and 40% relative humidity for 24 hours, followed by Kanebo friction according to KS-K-0555 method. The triboelectric voltage and the half-life were measured with a voltmeter. In addition, the plain weave fabric made of these fibers was weight-reduced for 10 minutes in a 5% aqueous solution of sodium hydroxide, and then pretreated under the same conditions in the constant temperature and humidity chamber, and the friction band voltage and half-life were measured. Further, the fabric weight-reduced under the above conditions was washed 50 times, dried, and then pretreated under the same conditions in the constant temperature and humidity chamber, and the friction band voltage and half-life were measured. In addition, the cross section of the prepared fiber was observed with a transmission electron microscope to determine the size of the island component. The results are shown in Table 1.

division Fairness Size of island component (㎛) Friction band voltage (volts) / half life (seconds) Weight loss After weight loss Before washing After 50 washes Example 1 Good 0.8 300 / 0.1 700 / 0.2 1,000 / 0.2 Example 2 Good 0.8 400 / 0.1 1,000 / 0.2 2,000 / 0.5 Comparative Example 1 Bad 1.5 or more Not measurable Not measurable Not measurable Comparative Example 2 Bad 1.0 600 / 0.1 4,000 / 5.5 8,000 / 10 minutes or more Comparative Example 3 Good 1.2 500 / 0.2 1,000 / 0.2 2,700 / 1.3 Comparative Example 4 Good 1.3 500 / 0.1 3,000 / 4.2 3,000 / 3.3

Not measurable: Antistatic measurement is impossible due to process defect

(Example 2)

A polyester resin composition having the same composition as the polyester resin composition of Example 1, except for the differences shown in Table 2, was tested in the same manner as in Example 1. The results are shown in Table 1.

division Emulsification Polyethylene glycol (parts by weight) Sodium dodecyl sulfite (parts by weight) Glycol (part by weight) Example 1 ○ 2 One 3.5 Example 2 ○ 2 0.5 3.5 Comparative Example 1 ○ 6 0.5 10.5 Comparative Example 2 ○ 2 0.05 3.5 Comparative Example 3 × 2 One 3.5 Comparative Example 4 × 2 0.5 3.5

※ parts by weight: parts by weight relative to 100 parts by weight of the total polyester composition

(Comparative Examples 1-4)

A polyester resin composition having the same composition as the polyester resin composition of Example 1, except for the differences shown in Table 2, was tested in the same manner as in Example 1. The results are shown in Table 1.

Claims (3)

0.1 to 5 parts by weight of polyalkylene glycol or a derivative thereof and 0.1 to 3 parts by weight of an ionic organic compound are added to glycol, and a water-in-oil emulsion prepared by stirring with respect to 100 parts by weight of the total polyester composition. Antistatic polyester resin composition made into. The antistatic polyester resin composition according to claim 1, wherein the ionic organic compound is an undecylbenzenesulfonic acid, a dodecylbenzenesulfonic acid, a tridecylbenzenesulfonic acid or a sulfonic acid alkali metal salt. Antistatic property containing a water-in-oil emulsion prepared by adding and stirring 0.1 to 5 parts by weight of polyalkylene glycol or a derivative thereof and 0.1 to 3 parts by weight of an ionic organic compound to 100 parts by weight of the total polyester composition. An antistatic polyester yarn, wherein said polyalkylene glycol, produced by melting and spinning a polyester resin composition, is uniformly dispersed in an independent conductive component having a size of less than 1 m in an arbitrary fiber cross section.