KR950008906B1 - Method of manufacturing polyester fiber having high anti-static and hygroscopic property - Google Patents

Abstract

The polyester fiber having a good antistatic property and moisture-absorbing property is produced by (a)condenation-polymerizing a polyoxyalkylene glycol cpd. of R1O(R2O)n1H[R1=C1-13 alkyl or H; R2=C2-16 alkylene; n1=20-150 having 2000-3000 average molecular wt., a nonreactive polyalkyl sulfonic acid metal salt of R3SO3Me[R3=C3-25 alkyl or C7-30 aryl; Me=Li, k or Na , a silicone cpd. (SiO2) particle and a phosphate cpd. of MHn2(PO4)n3 [M=K, Na, Al or NH4; n2=0-4; n3=1-2 as a dispersing agent with an antimony trionide(Sb2O3) at 280 deg. c for 2hr, and (b)drying a polyester, spinning and drawing it.

Description

Manufacturing method of polyester fiber excellent in antistatic property and hygroscopicity

The present invention relates to an improved manufacturing method of an antistatic agent that imparts antistatic performance and imparts hygroscopicity by suppressing generation of static electricity, which is a disadvantage of conventional polyester fibers, while maintaining the advantages of general polyester fibers.

Polyester fiber is attracting much attention for medical use because of its excellent physical properties such as heat resistance, chemical resistance, elongation, crystallinity, and flexural strength, but it is used in lining, lingerie, foundation, and other dust-free clothing in areas with low temperature and low humidity. In order to use it as a special functional clothing such as sportswear or the like, dust is easily adsorbed and contaminated by the generation of static electricity due to friction, and also has a problem in that a shock or discomfort is given to the wearer due to the weak property of absorbing sweat or moisture. Many methods have been proposed to solve the problem of electrostatic disturbance and weak hygroscopicity. For example, methacrylate or bisphenol is used for the polyoxyalkylene glycol, and there is a method of imparting antistatic function by post-processing by plasma method, but this method has a disadvantage in that the antistatic property is sharply inferior after washing. In order to solve this problem of washing resistance and to impart permanent antistatic properties, a method of modifying a polymer using polyalkylene glycol and sodium alkyl sulfonate introduced in Japanese Patent Laid-Open Nos. 52-47071 and 52-47072 is disclosed. This has been used a lot lately. Sodium alkyl sulfonate has an advantage of introducing an ionic group into the polymer to promote charge transfer and to express excellent antistatic performance by synergistic action with the copolymer of polyalkylene glycol.

In addition, SiO ₂ may be used to create a multi-column groove through a weight loss process to increase hygroscopicity and antistatic performance. However, poor dispersion of SiO ₂ results in poor dispersibility inside the polymer and increases pack pressure during spinning. In addition, sodium metal salts and SiO ₂ remain inside the spinning nozzles, resulting in poor spinning and short exchange cycles, resulting in poor spinning workability and poor dispersibility in the polymer.

On the other hand, in order to impart hygroscopicity, there are grafting of the surface of the fiber and surface treatment due to hydrophilic properties and saponification treatment of the surface, but there is a disadvantage in that the washing resistance is poor and the hygroscopicity is not permanently expressed. The present invention solves this problem and described in detail as follows.

The present invention relates to a polyoxyalkylene glycol compound, a non-reactive alkylsulfonic acid metal salt, a colloidal SiO ₂ and a phosphate compound, and a copolymerization of a dispersant to a polyester fiber having excellent antistatic properties and hygroscopicity.

Phosphate compound-based dispersant used in the present invention is the same as the general formula (1), the content is preferably 0.05 to 5% by weight relative to the silicon compound to be described later.

If less than 0.05% by weight, the effect of the dispersant is greatly reduced, the silicon fine particles are not uniformly dispersed, the formation of large aggregated particles is increased. In addition, when it exceeds 5% by weight, a problem occurs that the object property after spinning is lowered.

MHn ₂ (PO ₄ ) n ₃ (1)

(Herein, a compound selected from the group consisting of M: K, Na, Ca, Al, NH ₄ , an integer of n ₂ : 0-4, an integer of n ₃ : 1-2)

Specific examples of the compound of formula (1) used as a dispersant in the present invention include NaH ₂ PO ₄ , Na ₂ HPO ₄ , Na ₃ PO ₄ , KH ₂ PO ₄ , K ₂ HPO ₄ , K ₃ PO ₄ , CaH ₄ (PO ₄ ) ₂ , CaHPO ₄ , NH ₄ H ₂ PO ₄ , (NH ₄ ) ₂ HPO _4, and the like.

In the present invention, the polyoxyalkylene glycol compound is a compound of the following general formula (2) having a number average molecular weight of 2,000 to 3,000 and copolymerized at the terminal of the polyester main chain by adding 0.01 to 3.5% by weight to the total amount of polyester in the condensation polymerization period. .

If the amount is less than 0.01% by weight, the antistatic property is extremely low, and if the content exceeds 3.5% by weight, the basic physical properties of the yarn is lowered.

R ₁ O (R ₂ O) n ₁ H (2)

(Wherein R ₁ : C ₁ ~ C ₁₃ alkyl group or H, R ₂ : C ₂ ~ C ₁₆ alkylene group, n ₁ : 20 ~ 150 integer)

In the present invention, the non-reactive alkylsulfonic acid metal salt is preferably a non-reactive polyalkylsulfonic acid metal salt of the following general formula (3), the amount of which is 0.01 to 2% by weight relative to the total polyester.

R ₃ SO ₃ Me (3)

(Herein, an alkyl group having R ₃ : C ₃ ~ C ₂₅ or an aryl group having C ₇ ~ C ₃₀ , Me: Li, K, Na)

At this time, when the content of the polyalkyl sulfonate metal salt exceeds 2% by weight, the content of diethylene glycol (DEG) increases, so that when the polymer is discharged at the same melt viscosity, the intrinsic viscosity becomes high and the elongation of the object is too low. When it is generated and less than the weight%, the viscosity is low, making it difficult. Therefore, the preferable addition amount is weight%.

The addition amount of the silicon compound (SiO ₂ ) fine particles used in the present invention is suitably set to a weight percent of polyester. If less than 0.1% by weight, the number of surface unevenness is small, the deep color effect and hygroscopicity is lowered during dyeing, there is a problem that the objectivity is significantly reduced when added to exceed the%.

The present invention can also increase the thermal stability by reacting for 2 hours after adding ~ ppm Sb ₂ O ₃ as a catalyst during the condensation polymerization and 10 ~ 200ppm of the phosphorus compound as described below.

_Wherein R _{4 to 6} : H or an alkyl group

In the present invention, in the slurry production method, a dispersant of the general formula (1) is added to a SiO ₂ dope solution dispersed in ethylene glycol (EG) at 30% by weight, and the EG / TPA molar ratio is adjusted to 1.1. After the addition of ethylene glycol (EG) and stirred to make a uniformly dispersed silicon fine particle ethylene glycol solution and left for about 10 hours, terephthalic acid (TPA) to the EG / TPA molar ratio of 1.1 to prepare a slurry.

In the polymerization process of the present invention, the alkylsulfonate metal salt and polyoxyalkylene glycol are introduced at the initial stage of condensation polymerization, and vacuum is applied to 0.5 torr over about 1 hour, and then polymerized at 0.5 tor or less for 2 hours at 280 ° C. to polymerize the polyester. Make a polymer.

As described above, the polyester antistatic yarn according to the present invention can be widely used in medical and functional clothing having excellent antistatic performance, excellent hygroscopicity, deep colorability, and good gloss feel without impairing the physical properties of polyester fibers.

An example is given and described below.

EXAMPLE

<Measurement method>

(1) Water absorption: Measure the weight (W1) by drying the eluted sample at 110 ° C for 60 minutes, and dehydrate the sample precipitated in water with a dehydrator for 5 minutes and then measure the weight (W2). Calculated by.

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

(3) Friction band voltage, half-life: Measured using a Kanebo friction belt voltage meter.

* The specific resistance, friction voltage, and half-life were measured at 20 ± 2 ℃ and 40 ± 2RH% humidity.

Example 1

While maintaining a polymerization tank containing 10 kg of polyethylene terephthalate oligoma at 260 ° C., 8645 g of terephthalic acid, 3875 g of ethylene glycol, and 400 g of SiO ₄ having a particle size of 50 ml were prepared according to the method described above. Slurry well mixed with 4 g of calcium phosphate anhydride [CaH (PO ₄ )] in the compound of (1) was added over 6 hours to prepare 20 kg of oligomer, and 5 kg of this was transferred to another polymerization tank. 5 g of antimony trioxide, 100 g of compound C ₁₂ H ₂₅ O (C ₂ H ₄ O) H of formula (21) and 10 g of compound C ₁₂ H ₂₅ SO ₃ Li of formula () were added to the oligomer, followed by 280 ° C. Reaction was carried out to prepare the polyester of the present invention. After drying the obtained polymer in a conventional manner, the unstretched yarn obtained by spinning at a hollow rate of 20% 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 obtain 75 d / 36f. To prepare a drawn yarn and to evaluate the physical properties it is shown in Table 1 below.

EXAMPLES 2-6 AND COMPARATIVE EXAMPLES 1-4

The composition ratio of the copolymerized components is as shown in Table 1, except that in Example 2 and Comparative Examples 1 and 2 are C ₁₂ H ₂₅ SO ₃ K as a compound of the general formula (3), Examples 3 to 6 are C ₁₂ H ₂₅ SO ₃ Na is used, and Example 4 is NaHPO ₄ , Example 5 is Al (H ₂ PO ₄ ) ₃ , and Example 6 is NH ₄ H ₂ PO ₄ as a compound of Formula (1). 3 is not using the compound of formula (1), Comparative Example 4 is carried out and evaluated in the same manner as in Example 1 except that the compound of SiO ₂ and the formula (1) is not used together with Table 1 Indicated.

* Compounds (2) and (3) are% of PET, and (1) compounds are% of SiO400g.

[Examples 7-8, Comparative Examples 5-6]

Except for changing the addition amount of the compound of the general formula (2) as shown in Table 2 was carried out and evaluated in the same manner as in Example 1 and shown in Table 2 below.

[Examples 9-10, Comparative Examples 7-8]

Except for changing the addition amount of the compound of the general formula (3) as shown in Table 2 was carried out and evaluated in the same manner as in Example 1 shown in Table 2 below.

Claims (4)

Preparation of polyester fiber with excellent antistatic property and hygroscopicity, characterized by addition copolymerization of phosphate compound as a dispersant with polyoxyalkylene glycol compound, non-reactive alkylsulfonic acid metal salt and SiO ₂ (0.1-10% by weight of polyester) Way. The polyester fiber having excellent antistatic property and hygroscopicity according to claim 1, wherein the phosphate compound is at least one selected from compounds represented by the following general formula (1) and is added in an amount of 0.05 to 5% by weight based on the amount of SiO _2. Manufacturing method. MHn ₂ (PO ₄ ) n ₃ (1) (Herein, a compound selected from the group consisting of M: K, Na, Ca, Al, NH ₄ , an integer of n ₂ : 0-4, an integer of n ₃ : 1-2) The method of claim 1, wherein the polyoxyalkylene glycol compound is a compound of the general formula (2) having a number average molecular weight of 2,000 to 3,000, the antistatic property, characterized in that added to 0.01 to 3.5% by weight relative to the total amount of polyester And a method for producing a polyester fiber having excellent hygroscopicity. R ₁ O (R ₂ O ₄ ) n ₁ H... … … … … … … … … … … … … … … … … … … … … … (2) (Here, an alkyl group having R ₁ : C ₁ to C ₁₃ or an alkylene group having H, R ₂ : C ₂ to C ₁₆ , an integer of n ₁ : 20 to 150) According to claim 1, wherein the non-reactive alkali metal salt of non-reactive polyalkyl phosphonic acid of the general formula (3) is an antistatic and hygroscopic, characterized in that the addition amount of 0.01 to 2% by weight relative to the total amount of polyester Method for producing this excellent polyester fiber. R ₃ SO ₃ Me... … … … … … … … … … … … … … … … … … … … … … … … (3) (Herein, an alkyl group having R ₃ : C ₃ ~ C ₂₅ or an aryl group having C ₇ ~ C ₃₀ , Me: Li, K, Na)