KR0166447B1 - 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 dicarboxylic acid 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 ( The method is characterized in that the polymerization is carried out by adding the anti-pilling agent of II).

Description

Manufacturing method of flame retardant and anti-filling polyester fiber

The present invention relates to a method for producing a polyester fiber having 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 fiber, 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 established by law for infants and the elderly, curtains, carpets, and the like. In order to develop applications in these fields, the flame retardancy of polyester is urgently required.

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, in the case of post-processing, there are economic advantages, but the surface of the product is rough and flame retardant components are dropped by washing, etc., and thus the flame retardant durability is lowered. In addition, the flame retardant material used for the method of adding a flame retardant substance at the time of superposition | polymerization is the inorganic, halogen-based, and phosphorus organic substance in general. Antimony trioxide is a representative example of the inorganic flame retardant component. In this case, it is restricted from use because it is not compatible with the organic polyester. Halogen-based flame retardants generate toxic gases during coloring and thermal decomposition of polymers. The situation is imposing restrictions on their use. Next, there are cases of using a flame retardant having a turnover. Examples include U.S. Patent No. 3,941,752, Japanese Laid-Open Patent Application 55-41610, and Korean Patent Laid-Open Publication 83-59. 9197, JP 52-17050, U.S. Patent No. 3,076,010, and 4,157,436, but many of them have to be administered because the process is complicated and the residual rate of phosphorus compounds is low. Or lowering the melting point of the polymer, which leads to poor workability during processing and poor mechanical properties.

In addition, when polyester fiber is used for clothing, a part of the fiber surface of the fabric is cut by mutual 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 shape. It is called a pill and what appears on the filament fabric is called a snack. (In the present invention, it is referred to as a pilling phenomenon.)

This peeling phenomenon occurs remarkably in garments composed mainly of synthetic fibers such as polyester fibers as compared to natural fibers, which not only significantly reduces the appearance and feel of the garments, but also significantly restricts the material design and product design of the synthetic products. Is giving.

Generally, as a means for suppressing the peeling phenomenon, first, to reduce the occurrence of cows, second, to minimize the tangling or entangling of the cows, third, the method of easily falling off the generated cows and the formed pill (pill), etc. There is this.

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

The second method is to suppress the formation of the peel by increasing the bending resilience of the fiber, a method of eliminating the mechanical crimp by heat treatment and a method for producing a special crimped fiber straightening the crimp of the tip of the fiber Etc.

The third method is an active method of anti-pilling means, in which the peel due to friction promotes dropping by lowering the strength of the fiber. For example, the low-polymerization method proposed in Japanese Special Office 35-8562 is a method of reducing the strength of fibers by lowering the degree of polymerization, and this method causes not only poor radioactivity due to low melt viscosity, but also causes many problems in post processing. The method of Japanese Patent Application No. 50-22617 is a method of deteriorating the stiffness by destroying the internal structure of the fiber by stretching the unstretched tow and cooling it to 10-30 ° C. According to this method, the internal 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, conventional techniques for imparting anti-pilling properties to polyester flame retardant yarns have been introduced in US Patent Nos. 5,180,793 and 5,145,494, but the above methods are a method of adding a large amount of flame retardant to reduce the physical properties of the polyester fiber. And there was a problem that could not produce a polyester fiber excellent anti-pilling properties.

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

The present invention is a general formula (II) having three functional groups as an anti-pilling imparting component together with a phosphorus compound of the following general formula (I) as a flame retardant imparting component when polymerizing polyester using a dicarboxylic acid component and a diol component. The polymer is added and polymerized, followed by spinning and stretching the polymer in a conventional manner to produce the polymer.

[Trmelitic Anhydride]

Since the compound of general formula (I) used in the present invention has good reactivity due to high list rain, the remaining amount to the input amount is large so that a sufficient flame retardant effect can be obtained even if a small amount is added, and the molecular structure is very simple as a linear structure. Unlike the conventional copolymerized flame retardant, which was very complicated in three dimensions and inhibited the orientation and crystallization of the fiber, it does not degrade the inherent physical properties of the polyester.

The compound of the general formula (I) is usually diethylene phosphite by adding ethylene glycol and reacted at 140 ℃ for 10 hours with sodium alkoxy sodium as a catalyst, after removing excess ethylene glycol and distilled under vacuum of 5 Torr (Torr) Get by

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 in the known method, among which terephthalic acid is used as the dicarboxylic acid component and ethylene glycol is used as the diol component. By using a known alkali metal or alkali 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 ℃ using a metal compound as the catalyst used in the transesterification reaction The esterification reaction proceeds under a pressure of 5 kg / cm 2 and a temperature of 200 ° C. to 280 ° C., The desired reaction product was polycondensed under a temperature condition of 250 ° C. to 320 ° C. under vacuum of 1 Torr in the presence of a metal compound such as antimony, germanium or titanium to prepare a desired polyester.

In the present invention, the dosage of the general formula (I) is preferably 0.3% by weight to 0.8% by weight based on phosphorus. If less than 0.3% by weight, insufficient flame retardant effect and more than 0.8% by weight will affect the color and reaction time. In addition, the amount of the compound of formula (II) that 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. If exceeded, the melt viscosity increases rapidly during the polymerization, and the reaction and the fiber properties are difficult to control.

The fiber produced as described above has not only sufficient flame retardancy that meets the flame retardant yarn evaluation criteria in the field of clothing and non-clothing in Korea and Japan, and also in Europe and the United States, as well as excellent anti-pilling property.

The present invention will be described in detail with reference to the following Examples.

Intrinsic viscosity (IV) was measured at 25 ° C using a chlorophenol solution. The phosphorus content of the synthesized polymer was quantified according to the fluorescence X-ray method after dissolving the polymer, and the color value (b) was 140 ±. Crystallized at 2 ° C. for one hour and measured with a colorimeter.

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

In addition, anti-pilling property was set to 5 hours using the ICI tester specified in JIS L1076, and the occurrence of peeling and dropping of peeled peels were classified into 1-5 grades and measured five times.

Example 1

In a stainless steel reactor equipped with a condenser and an agitator designed to reflux, dimethyl terephthalate and ethylene glycol are at a molar ratio of 1: 1.5, and then the compound of formula (I) is 0.3% by weight based on phosphorus based on the polymer. After adding 0.03 mol% of the compound of formula (II) to dimethyl terephthalate, a conventional transesterification catalyst is added and heated and stirred to carry out the transesterification reaction while raising the temperature from 220 ° C to 230 ° C.

When the transesterification reaction is completed, a conventional polycondensation catalyst is added and the temperature is gradually raised to a final temperature of 265 ° C to 285 ° C. A polymer of 0.62 was obtained.

The polymer was spun, stretched and cut in accordance with conventional methods to form staple fibers, spun and woven to measure flame retardancy and anti-pilling.

The measurement results are shown in Table 1 below.

[Examples 2-4, Comparative Examples 1-4]

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 retardance and anti-pilling characterized in that the polyester is prepared by the conventional method using the dicarboxylic acid component and the diol component, followed by polymerization by adding a compound of the following formulas (I) and (II): Method for producing a polyester polyester fiber. The amount of the flame retardant represented by the general formula (I) is 0,3-0.8 wt% based on phosphorus, and the amount of the anti-pilling imparting substance represented by the general formula (II) is 0.33-3 mol%. Method for producing a flame retardant and anti-pilling polyester fiber, characterized in that.