KR102410767B1 - Cationic-dyeable polyester-based elastic resin and cationic-dyeable polyester-based elastic fiber with improved dyeing property using the same - Google Patents

Abstract

In the present invention, in the cationic dyeable polyester-based elastic resin formed of a hard segment and a soft segment, the hard segment is formed of diol and dicarboxylic acid, and the soft segment is formed of polyol. It relates to a cationic dyeable polyester-based elastic resin, characterized in that the sulfonate is copolymerized during polymerization of the polyester-based elastic resin.

Description

Cationic dyeable polyester-based elastic resin and cationic dyeable polyester-based elastic fiber with improved dyeability using the same }

The present invention relates to a cationic dyeable polyester-based elastic resin and cationic dyeable polyester-based elastic fibers with improved dyeability using the same. It relates to an elastic resin and cationic dyeable polyester-based elastic fibers with improved dyeability using the same.

Polyurethane-based spandex is the most common thermoplastic elastic yarn. Spandex is known to have superior strength, elongation and elastic recovery compared to other materials. However, spandex has disadvantages such as poor heat resistance, chlorine resistance, and light resistance. In the case of polyester-based elastic yarn developed to compensate for these shortcomings, heat resistance, chlorine resistance, light resistance, etc. have superior advantages over spandex, but the elongation and elastic recovery power are inferior compared to spandex.

In the case of spandex, it is a polyurethane series, and polyurethane is a form of a hard segment composed of a urethane functional group and a soft segment composed of a polyol structure. Due to the flexible structure of the soft segment, high elongation can be expressed.

On the other hand, due to the strong intermolecular bonding force between neighboring polyurethane molecules due to the hydrogen bonding between the hydrogen atom and the oxygen atom of the urethane functional group of the hard segment, the elastic recovery force that is restored to the original state after stretching is expressed.

In the case of polyester-based elastic yarn, high elongation was possible by mimicking the structure of polyurethane, replacing the hard segment with a polyester functional group and using a similar polyol for the soft segment. Since it can only be dyed, there is a drawback that a vivid and deep color cannot be easily obtained.

Most of the cationic dyed polyester resins currently on the market are atmospheric pressure dyeing, and basically, atmospheric dyeing is possible at 100°C or less. The cationic dyed polyester has excellent deep dyeing and clarity, and complements the drawbacks of disperse dye dyeing, and the strength characteristics are generally worse than regular types, but properties close to those of ordinary polyester fibers are obtained by the improvement of polymer and weaving technology. will lose

Japanese Patent Laid-Open No. 2008-069490 relates to dyed polyester having excellent clarity, and provides a polyester fiber that can be dyed with a cationic dye, has vividness close to that of acrylic fibers, and has high practicality and excellent sharpness. As a fiber composed of polyester whose main repeating unit is ethylene terephthalate, the polyester contains 5-sodium sulfoisophthalic acid and/or sulfoisophthalic acid as a copolymerization component, so that the total amount of their copolymerization is 4 to 20 mol. % of polyester fibers are provided.

Japanese Patent Application Laid-Open No. 2011-196006 relates to atmospheric pressure cationic dyeable polyester and fibers composed therefrom, wherein the isophthalic acid component containing a metal sulfonate group for the acid component is 2.0 to 5.5 mol%, and adipinesine for the total acid component Normal pressure cationic flammability, characterized in that it contains 3 to 10 ppm of a titanium compound soluble in the polyester as a titanium element as a polyester containing 3.0 to 6.0 mol% of a component, and 5 to 40 ppm of a phosphorus compound in terms of an elemental element A polyester and fibers constructed therefrom are provided.

As described above, most of conventional cationic dyeable polyester fibers use sulfoisophthalic acid metal salts to impart cationic dyeability to polyester.

The conventional cationic dyeable polyester using only the sulfoisophthalic acid metal salt alone has a very high viscosity in the molten state due to the interaction between the metal salts of the sulfoisophthalic acid, and at the same time the shear thinning behavior is large. happens Shear thinning refers to a behavior in which a polyester resin exhibits the same melt viscosity up to a specific shear rate, but decreases at a high shear rate. It can be explained by the phenomenon that molten polyester is a material with viscosity and elasticity.

Conventional polyester resins have little shear thinning behavior, but cation-dyed polyester has very large shear-thinning due to the bond between salts having the function of cation-salting. This increases the stirrer power load in the polymerization process, making it difficult to achieve high molecular weight, and increases the extruder temperature and filter pressure in the spinning process. That is, the melt viscosity is high, but the polymer intrinsic viscosity is relatively low, which causes the strength of the yarn to decrease during spinning.

An object of the present invention is to provide a polyester-based elastic resin having cationic dyeability by using a sulfonate salt that was invented to solve the problems of the prior art as described above.

In addition, an object of the polyester elastic resin is to provide a cationic dyeable polyester elastic fiber with improved dyeability that can be manufactured in fineness due to little shear thinning behavior.

In the present invention, in the cationic dyeable polyester-based elastic resin formed of a hard segment and a soft segment, the hard segment is formed of diol and dicarboxylic acid, and the soft segment is formed of polyol. It provides a cationic dyeable polyester-based elastic resin, characterized in that the sulfonate is copolymerized during polymerization of the polyester-based elastic resin.

In addition, the diol is ethylene glycol (EG) and/or 1,4-butanediol, and the dicarboxylic acid is terephthalic acid (TPA) or an ester derivative thereof. A polyester-based elastic resin is provided.

In addition, the polyol (Polyol) is poly (tetramethylene ether) glycol (PTMG), polyethylene glycol (PEG) and polypropylene glycol (PPG), characterized in that it contains any one or more cationic dyeable polyester-based elasticity resin is provided.

In addition, the compound of [Formula 1] provides a cationic dyeable polyester-based elastic resin, characterized in that 0.1 to 10 mol% of the total polyester-based elastic resin is copolymerized.

In addition, the polyol provides a cationic dyeable polyester-based elastic resin, characterized in that the number average molecular weight is 1,000 ~ 3,000.

In addition, the sulfonate is dimethyl 5-sulfoisophthalate sodium salt (DMS), a compound of the following [Formula 1], any one or two or more compounds of dimethyl-5 sulfoisophthalic acid tetrabutylphosphonium salt (DMSP) It provides a cationic dyeable polyester-based elastic resin, characterized in that.

[Formula 1]

[Wherein, R ₁ , R ₂ are the same or different, and each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a β-hydroxyethyl group]

In addition, there is provided a cationic dyeable polyester elastic fiber with improved dyeability, characterized in that it is formed of the above cationic dyeable polyester-based elastic resin.

As described above, the cationic dyeable polyester-based elastic resin according to the present invention contains a sulfonate to increase cationic dyeability and direct dyeability, thereby reducing the maximum dyeing time.

In addition, cationic dyeable polyester-based composite fibers with improved dyeability that can be manufactured into fine fibers by producing cationic dyeable polyester-based elastic resins with less shear thinning behavior of the polyester elastic resins has the effect of being able to manufacture

Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the gist of the present invention.

As used herein, the terms 'about', 'substantially' and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and serve to enhance the understanding of the present invention. To help, precise or absolute figures are used to prevent unfair use by unscrupulous infringers of the stated disclosure.

In the present invention, in the cationic dyeable polyester-based elastic resin formed of a hard segment and a soft segment, the hard segment is formed of diol and dicarboxylic acid, and the soft segment is formed of polyol. It is characterized in that the sulfonate is copolymerized during polymerization of the polyester-based elastic resin.

As the diol forming the hard segment, ethylene glycol (EG) or 1,4-butanediol or ethylene glycol (EG) and 1,4-butanediol may be used, and the diol may be selected according to the use. will be.

As the dicarboxylic acid, terephthalic acid (TPA) or an ester derivative thereof may be used, and terephthalic acid (TPA) or dimethylene terephthalate (DMT) may be used.

The hard segment is formed by an esterification reaction by inputting the molar fraction of dicarboxylic acid and diol in a ratio of 1 to 1.0 to 1.8 during manufacture. The excessively added diol component is polycondensation reaction Most of them are recovered through a medium pressure reduction process, and dicarboxylic acid and diol have a value of 30 to 99% by weight of the total elastic resin composition.

The polyol forming the soft segment is formed to include any one or more of poly(tetramethylene ether) glycol (PTMG), polyethylene glycol (PEG), and polypropylene glycol (PPG).

The polyol is a generic term for a high molecular compound having a hydroxyl group, and imparts elasticity to the polyester elastic resin and improves dyeability.

In addition, in order to maintain a high elastic recovery rate, the content of the soft segment should be maintained at 40 to 70 wt% based on the total weight of the polymer. Since the length of the soft segment is too long, the polymerization reaction time may be delayed, it may be preferable to use a polyol having a number average molecular weight of 1,000 to 3,000.

In the polyester elastic resin, the content of the soft segment is an important resin that exhibits elastic properties. When the content of the soft segment is low, the elastic repulsion force is high but the elongation is low. For optimal elastic repulsion and elongation, the soft segment content should be maintained in an appropriate amount, and the soft segment content should preferably be 40 to 70 wt%.

In the cationic dyeable polyester-based elastic resin of the present invention, a sulfonate is copolymerized for cationic dyeability.

As the sulfonate, any one or two or more compounds of dimethyl 5-sulfoisophthalate sodium salt (DMS), a compound of the following [Formula 1], and dimethyl-5 sulfoisophthalic acid tetrabutylphosphonium salt (DMSP) may be used. There will be.

[Formula 1]

[Wherein, R ₁ and R ₂ are the same or different, and each independently represents an alkyl group having 1 to 5 hydrogen atoms or a β-hydroxyethyl group]

Conventional polyester resins have little shear thinning behavior, but when producing cationic dyeable polyester resins using only sulfoisophthalic acid metal salts such as dimethyl 5-sulfoisophthalate sodium salt, the metal salts of sulfoisophthalic acid The viscosity of the melt state is very high due to the interaction of

When the compound of [Formula 1] is used together with a sulfonic acid salt such as dimethyl 5-sulfoisophthalate sodium salt in the preparation of the polyester-based elastic resin, cationic salting is possible and It is preferable to copolymerize the sulfonate containing the compound of the above [Formula 1] during polymerization of the polyester-based elastic resin as it is possible to produce a polyester elastic resin with low melt viscosity and low shear thinning behavior of the resin at the same time will be.

The sulfonic acid salt is preferably copolymerized in an amount of 0.1 to 10 mol% based on the mole of the total polyester-based elastic resin. When the sulfonate is copolymerized with less than 0.1 mol%, the cationic dyeability effect is low, and when the sulfonate is copolymerized in excess of 10 mol%, the poly The physical properties of the ester elastic fiber may be deteriorated.

As an example of the compound of the [Formula 1], the compound (BTP) of the following [Formula 2] may be used.

[Formula 2]

The cationic dyeable polyester-based elastic resin of the present invention in which the sulfonate is copolymerized as described above is imparted with cationic dyeability to improve dyeability.

In addition, because polyol is contained, cationic dyeability and dyeability for direct dyes are improved, and dyeability of textile products manufactured by mixing with cellulosic fibers such as cotton and rayon is improved.

Hereinafter, examples of a method for producing a cationic dyeable polyester-based elastic resin and a cationic dyeable polyester-based elastic fiber having improved dyeability according to the present invention are shown, but the present invention is not limited to the examples .

Example 1

8.2 moles of poly(tetramethylene ether) glycol (PTMG) having a molecular weight of 2,000, 53.8 moles of butanediol, 41.6 moles of dimethylene terephthalate (DMT), 0.6 moles of dimethyl 5-sulfoisophthalate sodium salt (DMS) (1.5 moles of total ester content) mol%) was put into the reactor in a slurry state, and the transesterification reaction was carried out while raising the temperature from 150°C to 200°C.

A resin was prepared by polycondensing the esterified oligomer together with a conventional polycondensation catalyst at 250° C. while gradually reducing the pressure to a final degree of reduced pressure of 0.1 mmHg.

The resin prepared as described above was composite spun into a sheath-core structure with polyethylene terephthalate as the outside and polyethylene terephthalate as the inside to prepare elastic yarns, and the physical properties thereof are shown in Table 1.

Example 2

A slurry of 8.2 moles of poly(tetramethylene ether) glycol (PTMG) having a molecular weight of 2,000, 53.8 moles of butanediol, 41.6 moles of dimethylene terephthalate (DMT), and 0.6 moles of BTP of [Formula 2] (contains 1.5 mole% of the total ester content) The transesterification reaction proceeds while raising the temperature from 150°C to 200°C. Thereafter, the procedure is the same as in Example 1.

Example 3

8.2 moles of poly(tetramethylene ether) glycol (PTMG) having a molecular weight of 2,000, 53.8 moles of butanediol, 41.4 moles of dimethylene terephthalate (DMT), 0.4 moles of dimethyl 5-sulfoisophthalate sodium salt (DMS) (1.0 of the total ester content) mol%), and 0.4 mol of BTP (containing 1.0 mol% of the total ester content) of [Formula 2] are put into the reactor in a slurry state, and the transesterification reaction is carried out while raising the temperature from 150°C to 200°C. Thereafter, the procedure is the same as in Example 1.

Example 4

8.2 moles of poly(tetramethylene ether) glycol (PTMG) having a molecular weight of 2,000, 53.8 moles of butanediol, 41.6 moles of dimethylene terephthalate (DMT), 0.4 moles of dimethyl 5-sulfoisophthalate sodium salt (DMS) (1.0 of the total ester content) mol%), 0.21 mol of dimethyl-5 sulfoisophthalic acid tetrabutylphosphonium salt (DMSP) (containing 0.5 mol% of the total ester content) was added to the reactor in a slurry state, and transesterified while raising the temperature from 150°C to 200°C proceed with the reaction. Thereafter, the procedure is the same as in Example 1.

Example 5

8.1 moles of poly(tetramethylene ether) glycol (PTMG) having a molecular weight of 2,000, 53.8 moles of butanediol, 41.4 moles of dimethylene terephthalate (DMT), 0.4 moles of dimethyl 5-sulfoisophthalate sodium salt (DMS) (1.0 of the total ester content) mol%) and 0.4 mol of dimethyl-5 sulfoisophthalic acid tetrabutylphosphonium salt (DMSP) (containing 1.0 mol% of the total ester content) were put into the reactor in a slurry state and transesterified while raising the temperature from 150°C to 200°C proceed with the reaction. Thereafter, the procedure is the same as in Example 1.

Comparative Example 1

After adding terephthalic acid and ethylene glycol to the ester reactor, the reaction is conducted at a temperature of 258° C. in a conventional manner to prepare an esterified oligomer, and dimethyl 5-sulfoisophthalate sodium salt (DMS) is added to the esterified oligomer to the total ester content. was added so as to be 1.5 mol% of

The esterified oligomer was subjected to a polycondensation reaction together with a conventional polycondensation catalyst while raising the temperature to 285° C. while gradually reducing the pressure to a final degree of reduced pressure of 0.1 mmHg to prepare a cationic dyeable polyester resin.

It was prepared into long fibers by single spinning by a conventional method, and its physical properties are shown in Table 1.

Comparative Example 2

8.2 moles of poly(tetramethylene ether) glycol (PTMG) having a molecular weight of 2,000, 53.8 moles of butanediol, and 42.3 moles of dimethylene terephthalate (DMT) were put into the reactor in a slurry state, and the transesterification reaction was carried out while raising the temperature from 150°C to 200°C. do. Thereafter, the procedure is the same as in Example 1.

Comparative Example 3

7.0 moles of poly(tetramethylene ether) glycol (PTMG) having a molecular weight of 2,000, 71.8 moles of butanediol, and 52.5 moles of dimethylene terephthalate (DMT) were put into the reactor in a slurry state, and the transesterification reaction was carried out while raising the temperature from 150°C to 200°C. do. Thereafter, the procedure is the same as in Example 1.

※ How to measure fiber properties

◎ Tensile strength and elongation at break: ASTM D638 (The tensile strength and elongation at break are measured with an elastic yarn of 15 cm in length)

◎ Elastic recovery rate

- Recovery rate analysis method: After fixing one end of the yarn to a length of 15 cm, a 1 kg weight was hung on the other side to fix it and left for 10 minutes. After removing the weight, the recovery rate was analyzed by comparing the increased length compared to the initial length.

Elastic recovery rate (%) = Recovered length/Extended length when force is applied × 100

◎ Dyeing Concentration (K/S): Measure the surface reflectance at the maximum absorption wavelength of the dyed fabric using a colorimeter (GretagMacbeth Color-Eye 7000A) and calculate the dyeing concentration (K/S) according to the Kubelka-Munk equation for each condition Compare the dye concentration of dyed fabrics according to

K/S = (1-R) ² ÷ (2R)

(Where K is the extinction coefficient, S is the scattering coefficient, and R is the reflectance)

division DMS (mol%) BTP (mol%) DMSP (mol%) Strength (g/d) Elongation (%) Elastic recovery rate (%) Dyeability (K/S) Example 1 1.5 0 0 1.21 433 88 28.5 Example 2 0 1.5 0 1.59 357 83 27.1 Example 3 1.0 1.0 0 1.11 415 87 30.2 Example 4 One 0 0.5 1.33 476 89 26.8 Example 5 One 0 One 1.29 473 88 27.8 Comparative Example 1 1.5 0 0 3.3 30 23 22 Comparative Example 2 0 0 0 1.35 484 89 - Comparative Example 3 0 0 0 1.76 382 83 -

As shown in Table 1, it can be seen that Examples 1 to 5 containing a sulfonate salt have better dyeability than Comparative Examples 2 and 3 without a sulfonate salt, and in particular, the dyeability is superior to Comparative Example 1 containing a sulfonate salt. it can be seen that

In addition, it can be seen that the cationic dyeable polyester-based elastic resin of the present invention contains a polyol and has excellent elongation at break and elastic recovery rate.

Claims (7)

In the cationic dyeable polyester-based elastic resin formed of a hard segment and a soft segment,
The hard segment is formed of diol and dicarboxylic acid, and the soft segment is composed of poly (tetramethylene ether) glycol (PTMG),
A sulfonate is copolymerized during polymerization of a polyester-based elastic resin,
The sulfonate salt is characterized in that any one or two or more of dimethyl 5-sulfoisophthalate sodium salt (DMS), a compound of the following [Formula 1], and dimethyl-5 sulfoisophthalic acid tetrabutylphosphonium salt (DMSP) A cationic dyeable polyester-based elastic resin.
[Formula 1]

[Wherein, R ₁ , R ₂ are the same or different, and each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a β-hydroxyethyl group] The method of claim 1,
The diol is ethylene glycol (EG) and/or 1,4-butanediol, and the dicarboxylic acid is terephthalic acid (TPA) or an ester derivative thereof. Ester-based elastic resin. delete delete The method of claim 1,
The poly(tetramethylene ether) glycol (PTMG) is a cationic dyeable polyester-based elastic resin, characterized in that the number average molecular weight is 1,000 to 3,000. delete A cationic dyeable polyester elastic fiber with improved dyeability, characterized in that it is formed of the cationic dyeable polyester-based elastic resin of any one of claims 1, 2, and 5.