KR100546460B1 - Atmospheric salting polyester fiber and its manufacturing method. - Google Patents

Abstract

The present invention relates to atmospheric pressure salting polyester fiber and a method for producing the same.

The present invention is to prepare a polyester fiber by polycondensation of a dicarboxylic acid component and trimethylene glycol, which is a terephthalic acid or an ester derivative thereof, a metal sulfonic acid of the general formula (I) at any time before completion of the polycondensation reaction. 0.8 to 8 mol% of the derivatives are added to the total content of the dicarboxylic acid to copolymerize to prepare atmospheric salt-containing polyester fibers.

In formula (I), A is an ester reactor and M is a monovalent metal.

Description

Atmospheric salting polyester fiber and its manufacturing method.

The present invention relates to atmospheric pressure salting polyester fiber and a method for producing the same.

Specifically, the present invention relates to a polyester fiber capable of dyeing with a basic dye at atmospheric pressure and having excellent touch and alkali resistance and a method for producing the same.

As a conventional method for producing basic dye saltable polyester fibers, a method of preparing fibers by copolymerizing an isophthalic acid component containing a metal sulfonic acid group, for example, 5-sodium sulfoisophthalic acid component, is disclosed in Japanese Patent Publication No. 34-34. Known as 10497.

However, in order to increase the dyeability to a satisfactory level, the method requires copolymerizing at least 3 mol% of an isophthalic acid component containing a metal sulfonic acid group as well as attaching a metal sulfonate group to the copolymer component, thereby preventing the regular alignment of the polymer. there is a problem.

Therefore, the fiber produced by the above method has a problem that the weight loss process for improving the feel is difficult because not only the strength is lowered but also the alkali resistance is weak because there are more defects than the conventional polyester fiber. This is because the alkali aqueous solution is easily penetrated into the glycol ester portion of isophthalic acid having a metal sulfonate group.

Meanwhile, prior art US Pat. Nos. 3,959,213, 4,496,716 and UK Pat. No. 62,370,79 disclose a method of copolymerizing polyalkylene oxides with isophthalic acid components containing metalsulfonic acid groups. This method improves the strength and alkali resistance of the yarn because the amount of the isophthalic acid component containing the metal sulfonic acid group is reduced compared to the case where only the isophthalic acid component containing the metal sulfonic acid group is conventionally used, and the poly used together Alkylene oxide can enhance the dyeability to basic dyes by promoting the penetration of dyes in the fiber. However, also in this case, since the content of the isophthalic acid component containing the metal sulfonic acid group can be reduced only within the range not exceeding the allowable minimum dyeing amount by the basic dye, the strength and alkali resistance improvement of the yarn is insignificant, and the dyeability is improved. There is also a problem that the polyalkylene oxide used for lowering the physical properties of the fiber.

Meanwhile, the prior art Korean Patent Application No. 89-18179 discloses (i) a compound having one metal sulfonic acid group and two ester reactors and 28 ') one metal sulfonic acid group and one ester reactor before the completion of the polyester polymerization. A method of combining and copolymerizing an appropriate amount of a polyalkylene oxide having a molecular weight of 300 to 5,000 with a compound is proposed. However, such a method also has a problem in that physical properties and leveling properties of the fiber are deteriorated when the amount of polyalkylene oxide used for improving dyeing property is large.

Meanwhile, Korean Patent Publication 93-7625 proposes a method of adding diethylene glycol together with a metal sulfonate compound and a polyalkylene oxide before the completion of the polyester polycondensation reaction. This method has the effect of diethylene glycol to reduce the crystallinity of the polymer and the regularity of the crystal to improve the dyeability, but the dyeability is not improved to the level capable of dyeing with a basic dye at normal pressure. In addition, it is not possible to obtain the effect of improving the touch, there are also a lot of types of copolymers added during the polycondensation reaction process, there is also an uneconomical problem.

Accordingly, an object of the present invention is to provide a polyester fiber which can be dyed with a basic dye at normal pressure and has excellent touch and alkali resistance.

The present invention can be dyed with a basic dye at normal pressure, it is low in the initial modulus to provide a polyester fiber excellent in the touch and improved alkali resistance and a method for producing the same.

The present invention relates to a polyester fiber excellent in colorability and dyeable with a basic dye at normal pressure, and excellent in touch and alkali resistance, and a method for producing the same.

Hereinafter, the present invention will be described in detail.

First, the present invention is to prepare a polyester fiber by polycondensation reaction of dicarboxylic acid component and trimethylene glycol, which is terephthalic acid or ester derivative thereof, at any time before completion of the polycondensation reaction. It is characterized in that the copolymerization is performed by adding 0.8-8 mol% of the phonic acid derivative to the total content of dicarboxylic acid.

In formula (I), A is an ester reactor and M is a monovalent metal.

Terephthalic acid, isophthalic acid, diphenyl dicarboxylic acid or naphthalene dicarboxylic acid may be used as the dicarboxylic acid component in the polycondensation reaction. On the other hand, trimethylene glycol is used as a glycol component.

When polycondensation of terephthalic acid and trimethylene glycol, which are one of the dicarboxylic acid components, a polyester having a structure as shown in the following general formula (II), specifically polytrimethylene terephthalate, is prepared.

Polytrimethylene terephthalate has a very similar polymerization method and chemical structure to polyethylene terephthalate, but there are many differences in thermal and mechanical properties.

Polytrimethylene terephthalate is superior in polyethylene terephthalate and polybutylene terephthalate in particular in elasticity, touch, alkali resistance and dyeing property.

Polytrimethylene terephthalate exhibits a soft hand with a relatively low initial modulus to nylon levels. As a result, there is no need for alkali weight loss processing to improve the feel, such as polyethylene terephthalate. In addition, polytrimethylene terephthalate has excellent elasticity and alkali resistance, it is possible to dye disperse dyes at less than 100 ℃, dyeing fastness is also very good. Polytrimethylene terephthalate has a glass transition temperature of 45 ° C. to 65 ° C., similar to polyamide, and a melting point of 228 ° C. The crystallization temperature is at 65 ° C. and the crystallization rate is fast. Moreover, it decomposes thermally at high temperature 300 degreeC or more. Due to these thermal properties, polytrimethylene terephthalate can be easily spun and stretched in the normal spinning and stretching zone. The stretching temperature is 60 ° C to 160 ° C and the stretching magnification is about 2.5 to 3.5.

On the other hand, the mechanical properties of the polytrimethylene terephthalate, the birefringence is 0.073, the density is 1.33g / ㎠, the process water content is 0.15, the strength and elongation is similar to the polyamide.

As described above, the present invention is characterized by improving the dyeability, feel and alkali resistance of the polyester itself by using trimethylene glycol as the glycol component in the polycondensation reaction.

On the other hand, the present invention is characterized in that the copolymerization by adding 0.8-8 mol% of the metal sulfonic acid derivative of the general formula (I) to the total dicarboxylic acid content at any time before the polycondensation reaction is completed.

In formula (I), A is an ester reactor and M is a monovalent metal.

Examples of the compound of general formula (I) used in the present invention include 5-sodium sulfo dimethyl isophthalate, 5-sodium sulfo isophthalic acid, 5-sodium sulfo bis, β-hydroxy ethyl isophthalate, and the like.

When the metal sulfonic acid derivative of the general formula (I) is added less than 0.8 mol% based on the total dicarboxylic acid content, the effect of improving dyeing properties is somewhat insufficient, and when it is added more than 8 mol%, the mechanical properties of the yarn, etc. This lowers.

On the other hand, polyester polycondensation reaction with at least one component selected from the group consisting of isophthalic acid or its ester derivative, adipic acid or its ester derivative, butanediol and polyethylene glycol together with the metal sulfonic acid derivative of formula (I) 1-5 mol% may be added and copolymerized at arbitrary time points before completion.

The addition time of the metal sulfonic acid derivative of general formula (I) is preferably added before the polycondensation reaction is completed in order to obtain uniform dispersion of the additive compound and high degree of polymerization. In addition, an appropriate amount of additives such as light stabilizers, heat stabilizers, quenchers, pigments, and dyes may be added to prepare polyesters by adapting to the present invention.

Thus, polyester fiber copolymerized with the metal sulfonate derivative of general formula (I) etc. is spun and stretched under normal conditions, and polyester fiber is manufactured.

The polyester fiber of the present invention is a dicarboxylic acid component which is a terephthalic acid or an ester derivative thereof, and a polysulfonic acid derivative of the general formula (I) is an essential component of a polyester produced by polycondensation of trimethylene glycol. It is copolymerized with 0.8-8 mol% with respect to the acid total content.

The polyester fibers of the present invention can be dyed with basic dyes at normal pressure and have excellent touch and alkali resistance. These results are also attributable to copolymerization of the metal sulfonic acid derivative of the general formula (I) during the polycondensation step, but also to the use of trimethylene glycol as the glycol component during polyester polycondensation. The result is a combination of the two factors.

The method of evaluating various physical properties in the present invention is as follows.

Intrinsic viscosity

It measures at 30 degreeC using the same weight compound of phenol and ethane tetrachloride as a solvent.

· Dyeing [dye adsorption rate,%]

Refined tubular letters or plain weaves made of malachite-green (Kantao Chemical) 5% owf (On the weight of fiber), 0.5 ml / l acetate, 0.2 g / l sodium acetate After dyeing for 60 minutes in a 1: 100 hot water solution (temperature: 80 ° C), the dye is lifted and then the dye concentration in the dyeing residue is measured to determine the dye adsorption rate of the dye.

Homogenous

Place the plain fabric dyed in the same way as the dyeing process for the evaluation of dyeability under fluorescent lighting and carefully check the following items.

-Salt spot: Observe spots caused by thick and salt of dye on the same filament. If the level is not visible, it is 0. If it is not visible, it is invisible, but if you look up close, it is 15, and if it is visible, it is 50.

-Difference in salt: The difference in dyeing and salting between neighboring filaments.The degree is visually 10% darker +10 points, 20% darker +20 points, 10% lighter -10 points, 20% lighter -20 points It is done.

Alkali resistance [loss rate,%]

1 part by weight of the tubular letter is immersed in 50 parts by weight of a boiling aqueous solution of sodium hydroxide (4% by weight) for 1 minute, treated with stirring for 60 minutes, washed with water, then neutralized in 1% acetic acid solution, washed with water and dried again. After drying the letter before alkaline aqueous solution in hot air at 100 ℃ for 20 minutes, measure the weight, and dry the same letter after alkaline aqueous solution treatment at 100 ℃ for 20 minutes to measure the weight. Obtain

% Reduction = × 100

Where A is the letter weight before alkali reduction and B is the letter weight after alkali reduction.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

150 parts by weight of terephthalic acid, 3 parts by weight of 5-sodium sulfo dimethyl isophthalate (hereinafter referred to as DMIS), 4 parts by weight of adipic acid, 70 parts by weight of trimethylene glycol, 0.04 parts by weight of zinc acetate and 0.014 parts by weight of sodium acetate It is put into a broth and heated up to 140-250 degreeC, and the by-product methanol is removed. After methanol has escaped 97% or more, 0.02 parts by weight of triphenylphosphate as a stabilizer and 0.03 parts by weight of antimony trioxide as a polymerization catalyst were continued for 2 hours under vacuum at 290 ° C and 0,5 mmHg, and then a polymer having an intrinsic viscosity of 0.55 To prepare. The polymer thus obtained is spun by a conventional melt spinning method to produce an undrawn yarn. The undrawn yarn is drawn and heat treated to produce polyester fibers. The letter of the tubular shape was prepared by using the polyester fiber, and then it was prepared using a malachite green dye (5% owf), 0.5 ml / l acetate, and 0.2 g / l soda acetate. Stain for 60 minutes in a hot aqueous solution.

The results obtained by evaluating the dyeability, leveling resistance, alkali resistance and feel of the dyed letter by the aforementioned method are shown in Table 2.

Comparative Example 1

Except for changing the content of DMIS, etc., during polycondensation, polyester fibers and dyed letters are manufactured under the same process and conditions as in Example 1.

The results obtained by evaluating the dyeability, leveling resistance, alkali resistance and feel of the dyed letter by the aforementioned method are shown in Table 2.

Comparative Example 2

Ethylene glycol is used instead of trimethylene glycol during polycondensation, and polyester fiber and dyeing letter are prepared in the same process and conditions as in Example 1 except that adipic acid is not added as shown in Table 1 below.

The results obtained by evaluating the dyeability, leveling resistance, alkali resistance and feel of the dyed letter by the aforementioned method are shown in Table 2.

<Table 1> Manufacturing conditions

<Table 2> Property Evaluation Results

Polyester fiber of the present invention can be dyed with a basic dye at normal pressure to simplify the dyeing process and reduce the dyeing cost.

In addition, the polyester fiber of the present invention is excellent in the touch and alkali resistance can be usefully used in the production of clothing, carpets and artificial leather.

Claims (2)

In preparing a polyester fiber by polycondensation of a dicarboxylic acid component which is terephthalic acid or an ester derivative thereof and trimethylene glycol, a metal sulfonic acid derivative of the general formula (I) is decayed at any time before completion of the polycondensation reaction. At least one component selected from the group consisting of isophthalic acid or its ester derivatives, adipic acid or its ester derivatives, butanediol and polyethylene glycol is copolymerized with addition of 0.8 to 8 mol% of the total amount of the carboxylic acid. A method for producing an atmospheric pressure saltable polyester fiber characterized in that the copolymerization by adding 1 to 5 mol% at any time before the completion of the ester polycondensation reaction. In formula (I), A is an ester reactor and M is a monovalent metal.] In the polytrimethylene terephthalate prepared by polycondensation of a dicarboxylic acid component which is terephthalic acid or an ester derivative thereof and trimethylene glycol, a metal sulfonic acid derivative of the general formula (I) below is an essential component and the total dicarboxylic acid content 0.8-8 mol% copolymerized with respect to 1-5 mol% copolymerized with at least one component selected from the group consisting of isophthalic acid or ester derivatives thereof, adipic acid or ester derivatives thereof, butanediol and polyethylene glycol. Atmospheric salting polyester fiber. In formula (I), A is an ester reactor and M is a monovalent metal.