KR940011540B1 - Manufacturing process of polyester fiber having an excellent antistatic property - Google Patents

Abstract

(a) adding a slurry mixed with terephthalic acid and ethylene glycol into a polymerization tank contg. polyethylene terephthalate, and reacting the mixt. to make an oligomer; (b) adding an antimony trioxide, a polyoxyalkylene amine cpd. of formula (I) [R1 = hydrocarbon; R2 = alkylene; n = 20-40 and a cpd. of formula (II) [R3 = H,CH3,OH or CH2CH2OH; M = K or Li to the oligomer, and reacting the mixt. to a polyester; and (c) melt-spinning and drawing the polyester. The polyester fiber has a good hydrolysis resistance against an alkali.

Description

Manufacturing method of polyester fiber excellent in antistatic property

The present invention relates to a method for producing a polyester fiber having excellent antistatic properties and excellent hydrolysis resistance to alkali.

Polyester fiber is widely used due to its excellent properties, but has high electrical resistance and high static electricity, which adversely affects workability during spinning and processing, and has a problem of discomfort to the user even when using the final product. Conventionally, a method of copolymerizing and spinning polyethylene glycol has been proposed as a method for solving such a problem, but in order to impart practical antistatic properties, a large amount of polyethylene glycol components should be copolymerized, and as a result, thermal stability and light resistance are degraded. I have a problem.

In addition, a method of adding an antistatic agent composed of various polyalkylene glycol derivatives to polyester has been developed, but it has not been put to practical use due to problems in the dyeing process or loss of antistatic properties after washing. As another method, a technique using a block polyalkylene ether amide obtained by block copolymerization of a polyamide obtained by modifying a polyalkylene glycol copolymerized polyester and a polyalkylene glycol modified polyamide having a carboxyl group and an amine group as an antistatic agent is Japanese Patent. It was introduced in Announcements 44-16178, 46-7213. Further, Japanese Patent Publication Nos. 48-20380 and 50-107206 for dispersing a block polyalkylene etheramide and a block polyalkylene ether ester in a polyester, and a Japanese patent publication using a block polyalkylene etheramide and an organic electrolyte together So 45-17547 was introduced. The methods listed above require a separate process and equipment to obtain a polyalkylene ether block copolymer polymer, and a general polyester melt polymerization has a disadvantage in that pyrolysis occurs and does not easily solidify after discharge. Recently, the most widely used method is a technique using an antistatic agent in which polyethylene glycol having a molecular weight of 10,000 to 30,000 is mixed with a metal sulfonic acid compound. Since the metal component is made of sodium, it is generally performed in the post-processing process of polyester fiber. Paper has a problem that is vulnerable to weight loss processing by sodium hydroxide.

Accordingly, the present inventors have made a thorough study to solve the above problems, and have therefore reached the method of the present invention for introducing an ether group into a polyester polymer chain which is easy to apply to a general process of polyester.

That is, the present invention polymerizes a polyester by adding a blocked polyoxyalkylene amine compound and a compound of the following general formula (2) per polymer in the following general formula (1) to polymerize the polyester: It relates to a method for producing an ester fiber.

R ₁ O (R ₂ O) n NH ₂ . (One)

(Wherein R _{1 is a} hydrocarbon, R _{2 is an} alkylene group, and n is an integer of 20 to 40).

(Wherein one of R ₃ : H, CH ₃ , OH, CH ₂ CH ₂ OH, M: K or Li)

The single-ended block polyoxyalkylene amine compound of the general formula (1) used in the present invention can significantly alleviate the vacuum line clogging caused by the polycondensation reaction of polyester, and the preferred dosage is based on the polyester component. It is 0.5-7 weight%, More preferably, it is 2-5 weight%, As for the range of n in formula, 20-40 are preferable as defined above. If n is less than 20, there is a weakness of the antistatic performance after washing, and a considerable amount of the antistatic effect can be obtained to obtain a satisfactory antistatic effect. In addition, if n is 40 or more, the compatibility with polyester is lost, and homogeneous mixing is not performed during the reaction.

When the compound of the general formula (2) used in the present invention is subjected to the polyester polymerization reaction using only the compound of the general formula (1), the polymerization time is long, resulting in a decrease in color and it is difficult to obtain a melt viscosity suitable for weaving. In order to solve the above problems and to produce an amorphous portion of the fibrous polymer chain, the compound substituted with K or Li is considered to be susceptible to sodium hydroxide hydrolysis. By using it, improved results were obtained. In the present invention, the compound of formula (2) is characterized in that 10 to 50% by weight compared to the compound of formula (1).

If it is less than 10% by weight, the above-described effects of the present invention are difficult to obtain, and if it is more than 50% by weight, the relative intrinsic viscosity is lowered due to an abnormal increase in melt viscosity, which is not preferable.

For obtaining antistatic properties of polyester used for the polyester polymer obtained by the above polymerization process, the radial stretching by an ordinary melt-spinning method, whereby the specific gravity of the fibers is a 1.360~1.370g / cm ³ specific gravity of the regular polyester 1.375~1.385g remarkably smaller than / cm ³ . That is, many amorphous parts are advantageous in terms of electrical conductivity. In the present invention, since the electrical conductivity of the fiber polymer is not the surface conductivity but the volume conductivity, it is preferable to spin the hollow with 5 to 10% of the hollow fiber in order to maximize the discharge effect. If the porosity is less than 5%, the electric discharge area, that is, the surface area effect is small, and if it exceeds 10%, it is difficult to obtain a yarn of excellent quality. The antistatic polyester yarn of the present invention has good characteristics in the manufacturing process and has excellent antistatic properties, and has a characteristic of about 1.1 times better than that of general polyester fibers by hydrolysis rate by sodium hydroxide.

EXAMPLE

<Measurement method>

(ηrel) is the ratio of the viscosity of the diluted polyester solution in the solvent (3: 2 mixture of phenol and tetrachloroethane) and the solvent viscosity measured at 25 ° C, and C represents the concentration of polyester in the solvent.

(2) Diethylene glycol (DEG): Pyrolyse polyester with hydrazine hydrate, which is measured by gas chromatography.

(3) Loss rate (%): Put polyester fiber sample in a solution of 5g of sodium hydroxide in 1L of water, hold it at 100 ℃ for 30 minutes, and measure by weight loss ratio.

(4) Electrical resistance: Measured by using an electric resistance measuring instrument of TOA of Japan in constant temperature and humidity room.

(5) Friction band voltage: Measured using a Kanebo friction belt voltage meter.

Example 1

While maintaining a polymerization tank containing 10 kg of polyethylene terephthalate oligomer at 260 ° C., a slurry in which 8645 g of terephthalic acid and 3875 g of ethylene glycol were well mixed was added over 6 hours to prepare 20 kg of oligomer, and then 10 kg was transferred to another polymerization tank. 5 g of antimony trioxide and 300 g of a compound of formula (1) having R ₁ : CH ₃ , R ₂ : CH ₂ CH ₂ , n = 40 and (3) of R ₃ : CH ₃ , n = 30 100 g of a compound having a metal (M) of K was added, and the reaction was carried out at 280 ° C. while reducing the pressure from 760 mmHg to 1 mmHg or less in 1 hour to prepare a polyester of the present invention.

The obtained polymer was dried in a conventional manner, and spun at a rate of 1000 m / min at 295 ° C. using a mold having 36 round spherical balls having a diameter of 0.25 mm. The obtained non-twisted yarn was stretched at a drawing speed of 1070 m / min by a heating roller maintained at 80 ° C. and a hot plate maintained at 120 ° C. to produce 75 d / f drawn yarn.

[Examples 2, 3, 4 and Comparative Example 1]

Polymerization and sacrifice were carried out in the same manner as in Example 1, except that the compounds in the following table were used.

[table]

Comparative Example 1

The same procedure as in Example 1 was carried out except that 350 g of polyethylene glycol having a weight average molecular weight of 10,000 and 175 g of sodium dodecylbenzenesulfonate were used as the copolymerization component.

Comparative Example 3

It was carried out in the same manner as in Example 1 with a general polyester without using a copolymerization component.

The physical properties of the yarn samples prepared above were evaluated and summarized in the following table.

[table]

Claims (3)

In polymerizing polyester, the polyester fiber excellent in antistatic property characterized by adding and polymerizing the single-ended block | blocked polyoxyalkylene amine compound of General formula (1) and the compound of following General formula (2) as a copolymerization component. Manufacturing method. R ₁ O (R ₂ O) n NH ₂ . (One) (Wherein R _{1 is a} hydrocarbon, R _{2 is an} alkylene group, and n is an integer of 20 to 40). (Wherein one of R ₃ : H, CH ₃ , OH, CH ₂ CH ₂ OH, M: K or Li) According to claim 1, wherein the compound of formula (1) is 0.5 to 7% by weight based on the polyester component, the compound of formula (2) is 10 to 50% by weight relative to the compound of formula (1) A method for producing a polyester fiber having excellent antistatic properties, which is used in combination. ^3. The antistatic property according to claim 1 or 2, wherein the final specific gravity of the polyester fiber obtained is 1.360 to 1.370 g / cm ³ and the hollow portion having a hollow ratio of 5 to 10% in the fiber length direction. Method for producing this excellent polyester fiber.