KR970010708B1 - Process for preparing polyester fiber - Google Patents

Abstract

Keeping polymer vessel which has polyethylene terephthalate oligomer l0[kg , at 260 degree C, a slurry is made with a terephthalic acid and an ethyleneglycol and SiO2 of which particle size is 0.05 micrometer, among the metal which has high electric property, SiO2 of which particle size is 0.02 micrometer, a calcium phosphate anhydride is fed in the slurry for 6 hours and an oligomer 20[kg is produced. To produced oligomer, an antimony trioxide, C12H250(C2H40)40H and C12H25SO3Na are thrown in and reacted at 280 degree C and then a polyester fiber is produced.

Description

Method for producing polyester fiber

The present invention relates to an improved manufacturing method of an antistatic agent that imparts antistatic performance and provides absorbency while 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 clothing because it has excellent properties such as heat resistance, chemical resistance, elongation, crystallinity, and flexural strength, but in low temperature and low humidity areas, it is lining, lingerie, foundation, and other dust-free clothing in winter. 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 there is a problem in that 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 this problem of electrostatic failure and weak absorption. There is a method of imparting antistatic function by post-processing by using methacrylate or bisphenol in polyoxyalkylene glycol and plasma method, this method has a disadvantage in that the antistatic property is sharply reduced 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 expressing excellent antistatic performance by introducing ionic paper into the polymer to promote charge transfer and synergy 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 salt and SiO ₂ remain inside the spinning nozzle, resulting in poor spinning and short cycle of pack replacement, resulting in poor spinning workability and poor dispersibility in the polymer, which can lead to poor dyeing.

On the other hand, in order to impart hygroscopicity, there are surface treatment and surface saponification treatment due to grafting and hydrophilic properties of the fiber surface, but there is a disadvantage in that it does not express hygroscopicity permanently due to poor washing resistance. The present invention is to solve this problem is characterized in that to increase the antistatic performance by adding a metal particle with a high dielectric constant.

That is, the present invention, in the production of polyester fibers based on polyethylene terephthalate (PET), polyoxyalkylene glycol compound, non-reactive polyalkylsulfonic acid metal salt, colloidal SiO ₂ , phosphate-based dispersant and high dielectric constant The manufacturing method of the polyester fiber excellent in the antistatic property and hygroscopicity produced from the polyester obtained by addition-copolymerization of the metal fine particle of (1).

MexOy… … … … … … … … … … … … … … … … … … … … … … … … … … … … … (One)

(Where Me is a 3- or 4-cycle transition metal element or a compound selected from In, Sn, Sb, Ge, Al, Ga, and x and y are integers from 0 to 5.)

The metal fine particles of the formula (I) having a high dielectric constant used in the present invention have a particle size of 0.001 µm to 1 µm, which increases the pack pressure during spinning and causes radiation failure. If the amount is less than 0.01 to 10% by weight compared to the preferred amount less than the antistatic effect is not great, if added more than this will result in poor radiation and lower the objectivity.

On the other hand, the dispersant used to facilitate the dispersion of the silicon compound and metal fine particles in the present invention is as shown in the following formula (2).

MHn ₂ (PO ₄ ) n ₃ . … … … … … … … … … … … … … … … … … … … … … … … … … … (2)

(Here, M is a compound selected from the group consisting of K, Na, Ca, Al, NH 4; n ₂ is an integer of 0 to 4, n ₃ is an integer of 1 to 2.)

The compound of formula (2) used as a dispersant in the present invention is 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 can be exemplified.

At this time, the use content is preferably 0.05 to 5% by weight of SiO ₂ to be described later. If less than 0.05% by weight, the effect of the dispersant is greatly reduced, the metal and silicon fine particles are not uniformly dispersed, the formation of large aggregated particles is increased. In addition, when 5% by weight or more, the problem of deterioration of the object after spinning occurs.

The polyoxyalkylene glycol compound in the present invention is a compound of formula (3) having a number average molecular weight of 2,000 or more and 30,000 or less and copolymerized at the end of the polyester backbone by condensation polymerization of 0.01 to 3.5% by weight relative to PET. Preferably, when the amount is 0.01% by weight or less, the antistatic properties and hygroscopicity is extremely inferior, and when 3.5% by weight or more, the basic physical properties of the yarn is lowered.

R ₁ O (R ₂ O) n ₁ H... … … … … … … … … … … … … … … … … … … … … … … … … … … … (3)

(Herein, R ₁ is C ₁ -C ₁₃ alkyl group or H, R ₂ is C ₂ -C ₁₃ alkylene group, n ₁ is an integer of ₂₀ to 150.)

The reaction temperature at the time of the condensation polymerization is controlled at an initial stage of 260 ° C. over 1 hour and 30 minutes and maintained at the end of the oligomer reaction. On the other hand, the polyalkylsulfonic acid metal salt of the present invention uses a non-reactive polyalkylsulfonic acid metal salt of formula (4), the amount of which is preferably 0.01 to 2% by weight relative to PET.

R ₃ SO ₃ Me... … … … … … … … … … … … … … … … … … … … … … … … … … … … … … (4)

(Wherein R ₃ is a C ₃ ~C ₂₅ alkyl group or a C ₇ ~C ₃₀ aryl group, Me is Li, K, Na.)

At this time, when the content of the polyalkyl sulfonate metal salt is more than 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 is too low in the object. When less than 0.01 weight%, a viscosity becomes difficult and it is difficult. Therefore, the preferred amount is 0.01 to 2% by weight compared to PET.

In addition, as is generally known, thermal stability can be enhanced by adding 200-400 ppm of Sb ₂ O ₃ as a catalyst during condensation polymerization, adding 10-200 ppm of the following phosphorus compounds, and reacting for 2 hours.

(Wherein R ₄ to ₆ are H or an alkyl group)

The amount of silicon fine particles (SiO ₂ ) used in the present invention is suitably 0.1 to 10% by weight compared to PET. When less than 0.1% by weight, the number of surface irregularities is small, there is a problem that the deep color effect and hygroscopicity when dyeing, and when added more than 10%, the objectivity is significantly reduced.

In the present invention, in the slurry production method, a dispersant of the general formula (2) is added to a SiO ₂ dope liquid 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 ethylene glycol liquid 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 alkyl sulfonate metal salt and polyoxyalkylene glycol are introduced at the initial stage of the 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. The polyester antistatic yarn obtained according to the present invention can be widely used in clothing and functional clothes having excellent antistatic performance, excellent hygroscopicity, deep colorability and gloss feel without sacrificing the inherent properties of polyester fibers.

An example is given and described below.

(How to measure)

(1) Moisture regain: Measure the weight (W1) by drying the eluted sample at 110 ° C for 60 minutes, and measure the weight of the sample (W2) left at room temperature (25 ° C, 60% RH) for 12 hours.

Calculate

(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.

※ Specific resistance, friction band 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 oligomer (PET) at 260 ° C., 8645 g of terephthalic acid, 3875 g of ethylene glycol, 400 g of SiO ₂ having a particle size of 0.05 μm, and a high dielectric constant metal fine particle (1) had a particle size of 0.02 μm. Prepare 200g of SnO ₂ according to the method described above, but dispersing agent was added 20g of 6g of calcium phosphate anhydride [CaH (PO ₄ )], one of the compounds (2), over 6 hours After preparing the oligomer of 10kg was transferred to another polymerization tank. The compounds of antimony trioxide 4g and formula (3) in the oligomer _{C 12 H 25 O (C 2} H 4 O) was charged into the compound C ₁₂ H ₂₅ SO ₃ Na 50g of ₄₀ H 100g and expression (4), 280 ℃ 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. The drawn yarn was manufactured.

(Examples 2-5, Comparative Examples 1-5)

The composition of the copolymerization components is shown in Table 1, and Examples 2 to 3 and Comparative Example 1 were to change the content of the compound (1), and Examples 4, 5, and 6 were (1) compounds, respectively, TiO ₂ and MoO. ₃ , a compound coated with SnO ₂ with Sb ₂ O ₃ was used, Comparative Examples 2 and 3 were to change the compound content of (2), Comparative Example 4 is not using the compound (1), Comparative Example 5 was carried out in the same manner as in Example 1 except that Compounds (1) and (2) were not used.

As can be seen in Table 1, Examples 1 to 6 according to the present invention can be seen that the overall hygroscopicity, antistatic properties and the objectability compared to Comparative Examples 1 to 5.

TABLE 1

Compounds (1), (3) and (4) are weight percent based on polyethylene terephthalate (PET), and (2) compounds are weight percent compared to 400 g of SiO _2.

Claims (5)

In preparing polyester fiber using polyethylene terephthalate (PET), polyoxyalkylene glycol compound, non-reactive polyalkyl sulfonate metal salt during copolymerization, metal fine particles of formula (1) having a high dielectric constant, SiO ₂ (compared to PET) 0.1 to 10% by weight) and a polyester obtained by copolymerization by adding a phosphate compound as a dispersing agent is used. MexOy… … … … … … … … … … … … … … … … … … … … … … … … … … … … … (One) (Me here is a three- or four-cycle transition metal element or one of In, Sn, Sb, Ge, Al, Ga, x, y is an integer of 0-5.) The method for producing a polyester fiber according to claim 1, wherein the metal fine particles have a particle size of 0.001 µm to 1 µm and 0.01 to 10% by weight of polyethylene terephthalate. The method of claim 1, wherein the phosphate compound is at least one member and method of producing a polyester fiber which is characterized by adding 0.05 to 5%, based on the weight of SiO ₂ that satisfies the following formula (2). MHn ₂ (PO ₄ ) n ₃ . … … … … … … … … … … … … … … … … … … … … … … … … … … (2) (Wherein M is one species of K, Na, Ca, Al, NH4, n 2 is an integer of 0 to 4, n ₃ is an integer of 1-2.) The polyoxyalkylene glycol compound according to claim 1, wherein the polyoxyalkylene glycol compound is a compound of formula (3) having a number average molecular weight of 2,000 or more and 30,000 or less, wherein 0.01 to 3.5% by weight of polyethylene terephthalate is added to A method for producing a polyester fiber, characterized in that copolymerized at the end. R ₁ O (R ₂ O) n ₁ H... … … … … … … … … … … … … … … … … … … … … … … … … … … … (3) (Wherein R ₁ is C ₁ ~C ₁₃ alkyl group or H, R ₂ is C ₂ ~C ₁₃ alkyl group, n ₁ is an integer of 20-150.) The method of producing a polyester fiber according to claim 1, wherein the non-reactive polyalkylsulfonic acid metal salt is a compound represented by the following formula (4), and the amount added is 0.01 to 2% by weight relative to polyethylene terephthalate. R ₃ SO ₃ Me... … … … … … … … … … … … … … … … … … … … … … … … … … … … … … (4) (Herein, R ₃ is C ₃ -C ₂₅ alkyl group or C ₇ -C ₃₀ aryl group, Me is one of K, Li and Na.)