KR860000288B1 - Manufacturing method of antistatic electricity polyester fiber - Google Patents

Abstract

Polyester fiber having an anti-electrostatic property is manufactured from polyester copolymer of sulfonic acid salt (I) or phosphoric acid salt (II) by blending it with a copolymer of polyalkylene oxide and a polyamide-forming monomer, and by adding an epoxy compd. having formula (III) or (IV) where: R, R' = -H, -(CH2)nH or -(CH2)nOH; n = 1-6; Me = alkyli metal; and R", R'" = alkyl gp. The composition of acid salt, copolymer of polyalkylene oxide and polyamide, and epoxy compd. are 0.01 - 5.0 wt.%, 0.1-20 wt.%, and 0.5 - 10 wt.%, respectively.

Description

Manufacturing method of antistatic polyester fiber

The present invention relates to a method for producing an antistatic polyester fiber which imparts antistatic properties without impairing the excellent intrinsic properties of polyester fibers in imparting antistatic performance to polyester fibers. will be.

Generally so-called polyester fibers obtained from polyethylene terephthalate or its copolymers, poly-1,4-cyclohexane dimethyl terephthalate or its copolymers and polyesters obtained from paraoxyethoxy benzoic acid, or their copolymers are highly It has excellent performance in crystallinity, elongation, flexural strength, chemical resistance, light resistance and heat resistance, so it has great value not only for clothing but also for industrial use.

On the other hand, however, the dyeing property is poor, the static electricity is easily generated by the friction, the peeling (pilling) is likely to occur, and sweat has a drawback and the like. Particularly, the obstacle caused by static electricity is one of the major drawbacks. It is wound around the body due to the static electricity generated by friction when worn as clothing, it gives discomfort when undressing, and in severe cases, electric shock occurs. In addition, it is easily stained by adsorption of dust and the like, making it impossible to wear for a long time. This is true even when the polyester fiber is not only used alone, but also mixed with other fibers such as cotton, wool, and rayon.

To date, many tests have been conducted to improve the defects of polyester fibers and to solve the electrostatic disturbance, and have been proposed without antistatic.

For example, a method of post-processing polyester fibers with an aqueous solution of polyethylene amine as in Japanese Patent Application No. 39-14650, or a method of copolymerizing alkylglycidyl ether as in Hungarian Patent No. 150851, and also in Japanese Patent Application Although methods for mixing polyalkylene glycols have been introduced as in SO 46-22200, they are insufficient to impart permanent antistatic performance and are easy to damage the excellent physical properties of polyester fibers.

Further, as a known fact, it is possible to thin the copolymer of polyalkylene oxide and polyamide in polyester filament by imparting permanent antistatic performance to polyester fibers, as in Japanese Patent Offices 45-39179 and 47-27804. It is also widely known to discharge the static electricity generated by friction by dispersing in a long line to the outside. However, these methods were effective in providing permanent antistatic performance, but problems such as coloring of yarns of polyester fibers or lowering of elongation occurred. This is because when the polyester is mixed with the polyalkylene oxide polyamide copolymer and spun, the polyester melts to generate a decomposition gas mainly composed of aldehyde, which acts on the amide group of the polyalkylene oxide and polyamide copolymer. The copolymer is partially decomposed, thus causing problems such as coloring of the polyester and lowering of elongation.

Therefore, the present invention solves this problem in imparting antistatic performance to the polyester fiber, a method of producing an antistatic polyester fiber excellent in antistatic effect without coloring the yarn or impairing the excellent properties of the polyester fiber The purpose is to provide.

The present invention will be described in detail as follows.

In the present invention, in the preparation of polyester fibers, the sulfonic acid represented by the following general formula (I) and / or general formula (II) before completion of polymerization of the polyester

Phosphoric acid method represented by ( _wherein R and R 'are -H,-(CH ₂ ) _n H or-(CH ₂ ) _n OH where n is an integer of 1 to 6 and Me is an alkali metal atom) The mixture obtained by copolymerizing a polyester obtained by copolymerizing a monomer which forms a polyamide in a polyalkylene oxide and melt-spun was mixed, wherein the following general formula (III) or general formula (IV)

(Wherein R ″ and R ″ ′ are alkyl groups)

It is a method of manufacturing the antistatic polyester fiber characterized by adding an epoxy compound having one functional group represented by.

According to the present invention, when these two copolymers, that is, polyester and polyalkylene oxide copolymer are mixed and melt-spun, the epoxy compound having high reactivity acts on the decomposition gas mainly containing aldehyde and decomposes by adding an epoxy compound. By preventing the gas from reacting with the polyalkylene oxide copolymer, it is possible to solve problems such as coloring of the fiber of polyester fibers or lowering of elongation.In addition, metal salts are added to the polyester to introduce ionic groups to transfer charges. It is easily synergized with the polyalkylene oxide copolymer to give a better permanent antistatic performance.

The polyester used in the present invention is a polyester capable of forming a fiber mainly composed of terephthalic acid, and specific examples thereof include polyethylene terephthalate, polyethylene terephthalate-inphthalate copolymer and polycyclohexane dimethyl terephthalate. It is not limited to.

In addition, the sulfonate and phosphate added thereto have a structure capable of bonding with polyester, for example, as follows.

According to the present invention, when the sulfonate and phosphate are added to the polyester, the amount of addition is about 0.01-5.0 Wt%, and the addition time may be any time before the polymerization of the polyester.

At this time, when the amount of sulfonate and phosphate added is less than 0.01 Wt%, it does not affect the improvement of the antistatic performance, and when it exceeds 5.0Wt%, the degree of polymerization is lowered, which adversely affects the excellent original properties of the polyester.

Therefore, sulfonate and phosphate are added to the polyester so that about 0.01-5.0Wt% is copolymerized to improve the dispersion state of the copolymer of polyalkylene oxide and polyamide and synergize with it to give better antistatic performance. Will be.

On the other hand, the polyalkylene oxide used in the copolymer of alkylene oxide and polyamide has a molecular weight of 100 or more and preferably 2000 or more, and specifically, for example, polyethylene glycol, methoxy polyethylene glycol, nonylphenol ethylene glycol, nonylphenol Ethylene oxide adducts, polypropylene glycol, polytetra hydrofran or copolymers thereof, but are not necessarily limited thereto.

Examples of the polyamide copolymerized with the polyalkylene oxide include copolyamides in homopolymers such as nylon 6, nylon 8, nylon 12, and copolymers thereof. In the preparation of such an alkylene oxide and a polyamide copolymer, the sock end of the polyalkylene oxide is cyanoethylated and then hydrogenated to make a polyalkylene ether diamine, which is obtained by polycondensation with the equivalents forming the polyamide. Can be. Moreover, the polyalkylene oxide which has an amino group at the terminal with a carboxyl group or an amino group, and a carboxyl group, and the polyamide which has a carboxyl group, an amino group, or an amino group and a carboxyl group at the terminal can also be obtained by polycondensation in solution or molten state. In addition, it can also be obtained using a known block copolymer production method.

In the present invention, in order for the polyester to have excellent antistatic performance, these block copolymers must be evenly dispersed in the polyester in a thin and long line state, and in order to do so, their relative viscosity needs to be 2.3 or more and 2.7 or less. In the present invention, the content of polyalkylene oxide in the copolymer of polyalkylene oxide and polyamide is 15-75 Wt%, and preferably 30-50 Wt%. In addition, the influence of the copolymer on the total polyester is preferably 0.1-20 Wt%. In the present invention, when the polyalkylene oxide is added, the antistatic effect is less than 0.1 Wt% and the physical properties of the polyester are easily damaged at 20Wt% or more.

Specific examples of the epoxy compound having one functional group used in the present invention include the following.

However, it is not necessarily limited to the above examples.

According to the present invention, the amount of polyester added of the epoxy compound is preferably 0.5-10 Wt%, preferably 1.0-5.0 Wt%.

In the present invention, when the functional group of the epoxy compound is two or more, crosslinking with the polyester is formed, which adversely affects the physical properties of the polyester, which is not preferable.

On the other hand, in the present invention, the method of mixing the polyalkylene oxide copolymer and the polyester of the epoxy compound is dried by a conventional method after the dipolyalkylene oxide copolymer is in a chip state, which is dried polyester. Melt spinning is carried out by a conventional method using a chip and a screw-type melt spinning machine.

Hereinafter, the present invention will be described in detail with reference to Examples.

The intrinsic viscosity of the polyester and the relative viscosity of the polyalkylene oxide and the polyamide copolymer, the electrical resistivity friction voltage and the degree of color change of the polyester fiber yarn is measured by the following method.

Intrinsic viscosity of polyester

The sample was dissolved in 0-chlorophenol and measured at 25 ° C. as an Ostwald viscometer.

The sample obtained by extracting and drying the relative viscosity equivalent of the polyalkylene oxide copolymer was dissolved in a catcher solution at a concentration of 1% to obtain a value obtained by measuring at 25 ° C. with a ubled viscometer and dissolving the value. It is divided by the measured value of the viscosity of the catcher crotal undiluted | stock solution which was not made.

-Frictional high voltage

It was measured by ROTARY STATIC TESTER (product of Heung-A Sangho, Japan). The sample washed with LOUNDER-O-METER was dried and left at 20 ℃ ± 2 ℃ for 43 ± 2% RH for 24 hours. It is a value measured by static electricity generated by friction by rotating at the speed of.

Electrical resistivity

The sample was washed for 2 hours with 0.175% detergent (New Beads (Day)) using an electric washing machine, washed with water, and left to dry for 48 hours at a condition of 20 ± 43% RH.

This dried sample is 10 cm long and has a fineness of 1000 D. Then, the resistance measured by a capacitive electrometer (VE-40 TERA OHM METER) is calculated by the following equation.

Where ρ is the volume resistivity of the sample (Ωcm)

SG is the density of the sample (g / cm ³ )

f is correction factor = 1

R is the electrical resistance (Ω)

D is the denia (D) of the sample

L is the length of the sample (cm)

-Color change of the thread (Lab value)

Samples washed with LOUNDER-O-METER are measured by HUNTER LAB COLOR METER (model D 2SA-2).

L value: White is 100 and black is 0. L value is displayed.

a value: Redness when +

0 is gray

-Greeness

b-value: Yellowness when +

0 is gray

When is Blueness

Example 1-6

Before the polymerization of polyethylene terephthalate is completed

로

in

를 같이 혼합하여 용융방사한다. 각 실시예로 표 1에서와 같이 A폴리머에 대하여 각종 조성물의 첨가량을 변화하여 용응방사를 실시하였으며 그 결과를 표 2에 나타내었다. 일반적으로 정전기에 의한 문제가 없으려면 마찰대전압이 1000V이나, 반감기가 30초 이상이거나 마찰대전압이 300V이하, 반감기가 10초이하 이어야 한다. 따라서 표 2에서 볼수 있듯이 본 발명에 의해 만족할만한 대전방지성을 얻을 수 있다.The alkali metal salt represented was added 1.0 Wt% to this polyterephthalate to synthesize a polyester (hereinafter referred to as a polymer) after polymerization was completed. The intrinsic viscosity at this time was 0.64. Moreover, acrylonitrile is made to react with polyethyleneglycol (number average molecular weight 400) under an alkali catalyst, hydrogen is added, and 95% or more synthesize | combine the polyethylene ether amine which has an amino group. Adipinic acid was reacted to make polyethylene ether diamine adipic acid salt, and then mixed with ε-caprolactam to melt polycondensation to synthesize block polyetheramide (hereinafter referred to as B polymer) having a proportion of 45% by weight of polyethylene ether chain portion. It was. The relative viscosity of this polymer was 2.5. As the epoxy compound of the present invention, when the chips of two polymers A and B dried by a method are mixed and spun normally

Mix together and melt spin. In each example, as shown in Table 1, the amount of the various compositions added to the polymer A was changed to melt spinning, and the results are shown in Table 2. In general, to avoid problems caused by static electricity, the frictional voltage should be 1000V, but the half-life should be more than 30 seconds, the frictional voltage should be less than 300V, and the half-life should be less than 10 seconds. Therefore, as shown in Table 2, satisfactory antistatic property can be obtained by the present invention.

TABLE 1

TABLE 2

Comparative Example 1

를 30Wt%혼합한 후 방사연신하여 75데니아, 36필라멘트의 연신사를 얻었다. 이 연신사의 비저항은 4.8×10⁹Ω·cm 마찰대전압은 3200V, 반감기는 47.0초였으며 b치는 2.0이었다.As in Example 1-6, block polyether amide was synthesized as an antistatic agent. This is mixed at a ratio of 4.0 Wt% to the polyester without addition of the alkali metal salt, and this is melted into an epoxy compound during melt spinning.

After 30Wt% of the mixture was blended and radially stretched to obtain a stretched yarn of 75 denia and 36 filaments. The specific resistance of this stretched yarn was 4.8 × 10 ⁹ Ω · cm friction voltage, 3200V, half-life 47.0 seconds and b value 2.0.

Comparative Example 2

Before the completion of polyethylene terephthalate polymerization

를 첨가하여

By adding

Synthesized polyester to make a chip. Here, the same block polyetheramide as in Example 1-6 is mixed and melt spun at a ratio of 3.3 Wt%. At this time, the specific resistance was 1.2 × 10 ⁹ Ω · cm large voltage 100V and half life was 12.5 seconds, but the antistatic property was good.However, the properties of the stretched yarn were 3.9g / D elongation 24% and b value was 11.3. The phenomenon appeared.

Example 7-11

As in Comparative Example 2, a polyester to which an alkali metal salt was added was synthesized. Intrinsic viscosity at this time was 0.65%. A block polyether amide having a relative viscosity of 2.5 was synthesized, in which a salt of polyethylene ether diamine having a number average molecular weight of 300 and sefasin acid was mixed with ε-caprolactam for polymerization. When the two polymers were mixed and spun at a ratio of 25: 1, various epoxy compounds of the present invention were mixed and melt spun in a predetermined amount, and the results are shown in Table 3.

As described above, the polyester fiber prepared according to the present invention, unlike the conventional one, does not impair the original excellent properties of the polyester fiber by adding an epoxy compound when melt-spun spinning polyester and polyalkylene oxide. It was possible to have an antistatic property, and to produce a high quality antistatic polyester fiber without discoloration of polyester fiber yarn.

Claims (5)

In preparing polyester fiber, sulfonate represented by the following general formula (I) or general formula (II) before completion of the polymerization of the polyester

(Wherein R and R 'are -H,-(CH ₂ ) _n H or-(CH ₂ ) _n OH (n is an integer of 1-6), Me is an alkali metal atom) A polyester obtained by copolymerization and a structure obtained by copolymerizing a monomer capable of forming a polyamide in a polyalkylene oxide are mixed and melt-spun, wherein the following general formula (III) or general formula (IV)

A method for producing an antistatic polyester fiber characterized by adding an epoxy compound having one functional group represented by (wherein R " and R " 'are alkyl groups). The method according to claim 1, wherein the amount of sulfonic acid or phosphate added to the polyester is 0.01-5.0 Wt%. The method of claim 1 wherein the content of polyalkylene oxide in the copolymer of polyalkylene oxide and polyamide is 15-75 Wt%. The method according to claim 1 or 3, wherein the copolymer of polyalkylene oxide and polyamide has a relative viscosity of 2.3-2.7 and contains 0.1-20 Wt% of the total polyester. The method according to claim 1, wherein the amount of epoxy compound added to the polyester is 0.5-10 Wt%.