KR0152762B1 - Method of manufacturing polyester fiber with fire retardant and anti-pilling properties - Google Patents

Abstract

The present invention is a method for producing a polyester fiber having flame retardancy and anti-pilling properties.

The present invention polymerizes a polyester polymer with a dicarboxylic acid component and a diol component, and melt-spun and stretches the polymer to produce polyester fibers.At the time of polyester polymerization, a flame retardant of the following general formula (I) and a general formula It is a method characterized by superposing | polymerizing by adding the antifilling agent of (II).

Provided that R is ethyl or methyl is n or 0

Description

Manufacturing method of polyester fiber having flame retardancy and anti-pilling property

The present invention relates to a method for producing a polyester fiber having both flame retardancy and anti-pilling property.

As is well known, polyester has excellent mechanical properties, chemical resistance, heat resistance, etc., so it is used in fiberglass, film, etc., but it is inherently flammable material, so it is easy to ignite and burn.

In particular, in Europe and the United States, flame retardant standards are prescribed by law for clothes for children and the elderly, curtains, carpets, and the like.

The flame retardant method of polyester introduced so far can be divided into the method of adding a material which has a flame retardant effect during polymerization, and the post-processing method using a flame retardant component mixed with a fiber emulsion. First, the post-processing method has economic advantages, while the surface of the product is rough and the flame retardant component is dropped due to washing off of the flame retardant component. In addition, the flame-retardant substance used for the method of adding a flame-retardant substance at the time of superposition | polymerization is the inorganic, halogen-type, and phosphorus organic substance in general. Antimony trioxide is a representative example of the inorganic flame retardant component. In this case, it is restricted to use because it is incompatible with polyester, which is organic. Countries are restricting their use. Next, there are cases of using a flame retardant of phosphorus. Examples include U.S. Patent No. 3,941,752, Japanese Patent Application No. 55-41610, and Korean Patent Publication 83-59, and others Japanese Patent Application No. 38-1750, Small 45-9197, Small 52 * 17050, U.S. Patent No. 3,076,010 and 4,157,436, etc., but the process is complicated and the residual rate of the phosphorus compound is substantially low, thus reducing the activity of the catalyst or the melting point of the polymer when the excess phosphorus compound is administered. There are problems such as poor workability and bad mechanical properties.

In addition, when the polyester fiber is used in clothing, a portion of the fiber surface of the fabric is cut by friction during use, and a wool is formed, and these wools are entangled with each other and are attached to the fabric surface with a roof. What happens in the fabric is called a fill and what appears in the fabric of the filament is called a snack (in the present invention, it is called a pilling phenomenon).

This peeling phenomenon is remarkably increased in garments composed mainly of synthetic fibers, such as polyester fibers, compared to natural fibers, and this phenomenon greatly reduces the appearance and feel of the garments. Giving.

Generally, as a means for suppressing peeling phenomenon, first, a method of reducing the occurrence of cows, second, a method of minimizing the entanglement or entangling of the cows, third, a method of easily dropping the generated cows and the formed pill (pill) Etc.

The first method is to suppress the movement of fibers by increasing the binding force between the fibers, which requires sufficient consideration of the thickness, length, number of twists and the fabric, density, and processing of the fabric.

The second method is to increase the bending resilience of the fiber and to suppress the formation of the peel. The method of eliminating the mechanical crimp by heat treatment and manufacturing the special crimped fiber straightening the crimp of the fiber tip part, etc. There is this.

The third method is an aggressive method of anti-pilling means, which promotes peeling of the peel due to friction by lowering the strength of the fiber. For example, the low-polymerization method proposed in Japanese Patent Application No. 35-8562 is a method of lowering the strength of fibers by lowering the degree of polymerization or lowering the viscosity of the melt, resulting in poor radioactivity and many problems in post-processing. -22617 describes a method of lowering the elongation by breaking the inner structure of the fiber by stretching the unstretched toe after cooling it to 10 to 30 ° C., and according to this method, the inner structure of the fiber is uniform. Since it is not destroyed, short fibers are generated in the spinning process, and workability and productivity are reduced due to the cooling process.

In addition, in the past, techniques for imparting anti-pilling property to polyester flame retardant yarn have been introduced in US Pat. Nos. 5,180,793, 5,145,941 and 5,151,494. However, since the methods are a method of adding a large amount of flame retardant, Deteriorated physical properties and there was a problem that could not be produced polyester fibers with excellent anti-pilling properties.

The present invention solves the problems of the prior art as described above, even if the addition of a small amount can be obtained a sufficient flame retardant effect and at the same time a method that can greatly improve the anti-pilling properties using a compound having three functional groups, will be described in detail below Is as follows.

The present invention relates to a compound of formula (I) having phosphorus (P) and nitrogen (N) atoms together as a flame retardant imparting component when polymerizing a polyester using a dicarboxylic acid component and a diol component. It is a method of preparing by polymerizing by adding a compound of formula (II) having three functional groups as a peeling imparting component and then spinning and stretching the polymer by a conventional method.

R is ethyl or ethyl n is 0 or 1

[Trimellitic Anhidride]

The compound of formula (I) used in the present invention is relatively simple in structure, has good reactivity due to its inherent ring strain, and has both phosphorus and nitrogen components, thereby reducing the physical properties of the polyester fiber in a small amount. It can give a sufficient flame retardant effect with little generation.

The compound of the general formula (I) is usually obtained by reacting ethylene or propylene glycol with phosphorus hexaalkyltriamide at low temperature (0 to 10 ° C) using a benzene or diethyl ether as a solvent, or a cyclic It is obtained by reacting chloro anhydride with ethylene or propylene glycol at low temperature (0 to 10 DEG C) under a base catalyst using benzene or diethyl ether as a solvent.

Polyesters having excellent flame retardancy and anti-pilling properties according to the present invention are prepared from the dicarboxylic acid component, the diol component, the compound of the general formula (I) and the compound of the formula (II), wherein the reaction conditions, that is, transesterification The reaction, esterification, and condensation reaction conditions are the same as those in the known method. Among them, in the case of producing polyester using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the diol component, By using a known alkali metal or alkaline earth metal or a metal compound such as zinc, manganese, titanium or cobalt as a catalyst to perform a transesterification reaction at a temperature of 140 ℃ to 240 ℃ by using a metal compound as the catalyst used in the transesterification reaction naejineun naejineun atmospheric pressure and 200 ℃ of 5kg / cm ² Jin the esterification reaction under a temperature condition of 280 ℃ , At which time under the presence of metal compounds such as certain of the reaction product of antimony or germanium or titanium obtained 1 Torr (torr) naejineun 250 ℃ in vacuum by the following polycondensation under a temperature condition of 320 ℃ to prepare the desired polyester.

In the present invention, the input amount of the general formula (I) has a sufficient flame retardant effect when 0.25% or more on the basis of phosphorus, and when it exceeds 0.6% by weight, the color and reaction time are affected due to the excessive injection. In addition, the amount of the compound of formula (II) which provides anti-pilling property is suitably in the range of 0.03 mol% or more and 3 mol% or less with respect to the total acid component, and in the case of less than 0.03 mol%, the anti-pilling property is insufficient and more than 3 mol%. In this case, it is difficult to control the reaction and the fiber properties because the increase of the melt viscosity during polymerization is sharply increased.

The fiber produced as described above has not only a sufficient flame retardancy suitable for the flame retardant yarn evaluation criteria in the field of clothing and non-clothing in Japan and Europe and the United States, but also has an excellent anti-pilling property.

As the method used for the analysis of the polymer, the degree of polymerization was shown as the ultimate viscosity (IV), and the physical property was decreased by the content of diethylene glycol (DEG), and the coloring was compared by measuring the color value (b).

Intrinsic viscosity (IV) was measured at 25 ° C. using an ortho chlorophenol solution. The content of DEC was determined by hydrolyzing the polyester polymer, followed by ethylene glycol (EG) and diethylene glycol DEG according to the gas chromatograph method. After quantification, the amount of DEG relative to the total glycol was expressed in mol%.

On the other hand, flame retardancy was expressed as the average value of five times the number of times of contact in the 45 ° Coil method according to the method indicated in the Korean Fire Code.

In addition, anti-pilling property was the rotation time was 5 hours using the ICI tester specified in JIS L1076, and the occurrence of peel and dropping condition of the generated peel were classified into 1-5 grades, and the average value was shown.

Example 1

In a stainless steel reactor equipped with a condenser and agitator designed to reflux, dimethyl terephthalate and ethylene glycol were molar ratio of 1: 1.5, and then the compound of formula (I) was 0.25 wt% based on phosphorus based on polymer. After adding 0.03 mole% of the compound of (II) to the dimethyl terephthalate, a transesterification catalyst is added and the mixture is heated and stirred to carry out the transesterification while raising the temperature from 220 ° C to 230 ° C.

When the transesterification reaction is completed, a commonly used polycondensation catalyst is added and the temperature is gradually raised to a final temperature of 265 ° C. to 285 ° C., and the pressure is gradually reduced to a final pressure of 0.2torr or less to proceed with the reaction for 100 minutes. A polymer having an intrinsic viscosity of 0.61 was obtained.

The polymer was spun, stretched and cut in the usual manner to form a staple fiby and spun and dipped to measure flame retardancy and anti-pilling. The measurement results are shown in Table 1.

[Examples 2 to 6 and Comparative Examples 1 to 4]

Except for the addition of the compounds of the general formula (I) and (II) in the amount shown in Table 1 to obtain a fabric in the same manner as in Example 1, measured and evaluated the physical properties and the results are shown in Table 1.

Claims (2)

Flame retardancy and anti-pilling property characterized by polymerizing dicarboxylic acid and diol component, and spinning and stretching to prepare polyester fiber, by adding the following compound of general formula (I) and general formula (II) Method for producing a polyester fiber having a. Provided that R is ethyl or methyl is n or 0 The amount of the flame retardant represented by the general formula (I) is 0.25 to 0.6% by weight based on phosphorus, and the amount of the anti-pilling imparting substance represented by the general formula (II) is 0.03 to the total acid component. Method for producing a polyester fiber having a flame retardancy and anti-pilling, characterized in that 3 mol%.