KR20200040519A - Cationic-dyeable polyester resin and cationic-dyeable polyester fiber using the same - Google Patents

Abstract

The present invention relates to a cationic-dyeable polyester resin and a cationic-dyeable polyester fiber using the same. More specifically, the present invention relates to: a cationic-dyeable polyester resin, in which a sulfoisophthalic acid metal salt and a compound of chemical formula 1 are copolymerized to provide cationic-dyeable properties, while being capable of fine-defining; and a cationic-dyeable polyester fiber using the same.

Description

Cationic flame-retardant polyester resin and cationic flame-retardant polyester fiber using the same {CATIONIC-DYEABLE POLYESTER RESIN AND CATIONIC-DYEABLE POLYESTER FIBER USING THE SAME}

The present invention relates to a cationic flame-retardant polyester resin and a cationic flame-retardant polyester fiber using the same, and a cationic flame-retardant polyester resin capable of fine-degrading while providing cationic flame-resistance using a sulfoisophthalate metal salt and the same The cationic flame-retardant polyester fiber used.

Cationic dye is a new type of basic dye developed for acrylic fibers. It is very vivid and beautifully dyed in acrylic and resistant to sunlight and heat. The cationic dye can also be dyed polyester (cationic quenched polyester), which is an improved material.

The polyester fiber typified by polyethylene terephthalate has a drawback that it is difficult to obtain a clear and deep color because it can only be dyed with a disperse dye or an azoic dye from its chemical properties. The biggest challenges of polyester (PET) were lack of color development (clarity), high pressure and high temperature dyeing.

A solution for solving the above problems was cationic dye salting by copolymerization or internal addition of sulfoisophthalic acid salt.

Most of the cationic flame-retardant polyester resins currently on the market are atmospheric pressure-salt, and can be dyed at normal pressure below 100 ℃. The cationic dyeing polyester has excellent dyeing and clarity and compensates for the defects of disperse dyeing, and its strength characteristics are generally worse than that of the regular type, but by improving the polymer and weaving technology, characteristics similar to normal polyester fibers are obtained. Lose.

Japanese Unexamined Patent Publication No. 2008-069490 relates to a flame-retardant polyester having excellent clarity, and can be dyed by a cationic dye, has a sharpness close to that of an acrylic fiber, and further provides a polyester fiber having excellent clarity. Fibers composed of ethylene terephthalate as the main repeating unit, and the polyester contains 5-sodium sulfoisophthalic acid component and / or sulfoisophthalic acid component as a copolymerization component, and the total amount of their copolymerization is 4 to 20 mol. % Polyester fibers.

Japanese Unexamined Patent Publication No. 2011-196006 relates to a cationic flame-retardant polyester at normal pressure 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 adipinecin for all acid components. Atmospheric pressure cationic flame-retardant, characterized in that the component contains 3.0 to 6.0 mol% of polyester, and the titanium compound soluble in polyester contains 3 to 10 ppm in terms of titanium element and 5 to 40 ppm in phosphorus compound in terms of elemental element. Polyesters and fibers constructed therefrom.

As described above, most of the conventional cationic flame-retardant polyester fibers use a metal salt of sulfoisophthalate to give the polyester a cationic flame-retardant function.

The cationic flame-retardant polyester using only the conventional sulfoisophthalic acid metal salt as described above has a very high viscosity in a molten state due to interaction between metal salts of sulfoisophthalic acid, and has a large shear thinning behavior. Happens. Shear thinning refers to a behavior in which a polyester resin exhibits the same melt viscosity up to a specific shear rate, and at a high shear rate, the melt viscosity decreases. It can be explained as a phenomenon that appears because molten polyester is a material having viscosity and elasticity.

Conventional polyester resins have little shear thinning behavior, but cationic flame-retardant polyesters have very large shear thinning due to inter-salt bonds with the function of cationic salts. This makes it difficult to achieve high molecular weight by weighting the stirrer power value load in the polymerization process, 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 deteriorate during spinning.

More specifically, in the molten state, the viscosity is high, so it is difficult to handle in the process, and when cooled in the form of a yarn, the molecular weight is small, so the strength is lowered, which makes it difficult to manufacture fine fibers.

The present invention was invented to solve the problems of the prior art as described above, while using a metal salt of sulfoisophthalic acid for cationic flame retardancy in a polyester resin, cationic with less shear thinning behavior of the polyester resin. It is an object to provide a flame-retardant polyester resin.

In addition, an object of the present invention is to provide a cationic flame-retardant polyester fiber having improved strength and fineness through a cationic flame-retardant polyester resin having a low shear thinning behavior of the polyester resin.

The present invention provides a cationic flame-retardant polyester resin characterized in that a sulfoisophthalic acid metal salt and a compound of the following [Chemical Formula 1] are copolymerized with a polyester resin.

[Formula 1]

[In Formula 1, n is 3 or more carbons, and α is an integer. It is composed of an aliphatic linear chain, and may include double bonds and triple bonds in some cases.]

The sulfoisophthalate metal salt provides a cationic flame-retardant polyester resin, characterized in that 0.1 to 3 mol% of the total polyester mole is copolymerized.

The compound of [Formula 1] provides a cationic flame-retardant polyester resin, characterized in that 1 to 20 mol% of the total polyester moles are copolymerized.

The compound of [Formula 1] provides a cationic flame-retardant polyester resin, which is a compound of [Formula 2] below.

[Formula 2]

It provides a cationic flame-retardant polyester fiber, characterized in that it is formed of the cationic flame-retardant polyester resin.

The cationic flame-retardant polyester fiber provides a cationic flame-retardant polyester fiber characterized in that the mono fineness is 0.4 to 3.5 denier.

As described above, the cationic flame-retardant polyester resin according to the present invention improves processability by using a sulfoisophthalic metal salt for cationic flame-retardancy in the polyester resin, but has less shear thinning behavior of the polyester resin. It works.

In addition, the shearing behavior of the cationic flame-retardant polyester resin is small, so that the strength is improved and there is an effect of producing a cationic flame-retardant polyester fiber that can be produced with fineness.

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 will be omitted so as not to obscure the subject matter of the present invention.

As used herein, the terms 'about', 'substantially', etc. are used in or at a value close to that value when manufacturing and substance tolerances specific to the stated meaning are presented, and the understanding of the invention To aid, accurate or absolute figures are used to prevent unconscionable abusers from unduly using the disclosed disclosure.

Conventional polyester resins have little shear thinning behavior, but when the cationic flame-retardant polyester resin is prepared by using only the sulfoisophthalic metal salt alone, the viscosity of the molten state is caused by interaction between the metal salts of sulfoisophthalic acid. Very high and at the same time, shear thinning behavior is large.

In the present invention, by using a metal salt of sulfoisophthalate and a compound of the following [Chemical Formula 1], it is possible to cation the cationic at normal pressure, and the melt viscosity of the cationic flame-retardant polyester resin is lowered, and at the same time, the shear thinning behavior of the resin is less It relates to an ester resin.

[Formula 1]

[In Formula 1, n is 3 or more carbons, and α is an integer. It is composed of an aliphatic linear chain, and may include double bonds and triple bonds in some cases.]

The compound molecular structure of [Formula 1] copolymerized with polyester, such as the sulfoisophthalic acid metal salt, has a divalent carboxylic acid capable of polyester condensation polymerization, and has a long chain of hydrocarbons. It is grafted between the metal salts to give a distance between metal salts, thereby suppressing the increase in the melt viscosity.

The sulfoisophthalic acid metal salt may be a sulfoisophthalic acid metal salt in which X in Chemical Formula 3 below is an alkali cation or alkaline earth metal cation.

[Formula 3]

[In the formula, R represents a hydrogen atom or a hydroxyl group or an alkyl group having 1 to 5 carbon atoms or a β-hydroxyethyl group.]

It is preferable that the sulfoisophthalic acid metal salt copolymerized with the cationic flame-retardant polyester resin of the present invention is copolymerized with 0.1 to 3 mol% of the total polyester mole, and the cationic ion when the sulfoisophthalate metal salt is copolymerized with less than 0.1 mol%. The reactivity with the dye may be lowered, and the cationic flame retardancy may be reduced, and when the copolymerization exceeds 3.0 mol%, the physical properties of the polyester fiber may be reduced.

The compound of [Formula 1] is preferably 1 to 20 mol% of the total polyester moles to be copolymerized. If the compound of [Formula 1] is less than 1 mol%, the shear thinning behavior due to the compound of [Formula 1] phenomenon The inhibitory effect of may be lowered, and when it is copolymerized in excess of 20 mol%, the physical properties of the polyester fiber may be lowered.

As an example of the compound of Formula 1, the compound of Formula 2 below may be used.

[Formula 2]

As described above, the cationic flame-retardant polyester resin of the present invention in which the sulfoisophthalic acid metal salt and the compound of [Formula 1] are copolymerized are polyester resins with low shear thinning behavior, and are conventional sulfoiso when produced from polyester fibers. The strength of the fiber is improved as compared to a cationic flame-retardant polyester fiber formed of a cationic flame-retardant polyester resin using only a phthalic acid metal salt.

In addition, the cationic flame-retardant polyester fiber formed of the cationic flame-retardant polyester resin of the present invention is capable of fine-seaming according to strength improvement, so that the cationic salt of the present invention can be produced with a fineness of less than 1 denier. The cationic flame-retardant polyester fiber formed of a sex polyester resin will preferably have a mono fineness of 0.4 to 3.5 denier depending on the purpose of use.

Hereinafter, an example of a method for preparing a cationic flame-retardant polyester resin and a cationic flame-retardant polyester fiber according to the present invention is shown, but the present invention is not limited to the examples.

<Production of cationic flame-retardant polyester resin>

Example 1

Terephthalic acid and ethylene glycol were added to the ester reactor and reacted at a temperature of 258 ° C in a conventional manner to prepare an esterified oligomer, and the metal salt of sulfoisophthalic acid sodium salt as the metal salt was 1.8 moles compared to the total polyester mole. %, DDSA of the following [Formula 2] is added so that it is 1 mol% compared to the total polyester mol.

The esterified oligomer was combined with a conventional polycondensation catalyst, and subjected to a condensation polymerization reaction while gradually increasing the pressure to 285 ° C. while gradually reducing the final pressure to 0.1 mmHg to prepare a cationic flame-retardant polyester resin.

Examples 2 to 12

The Examples 2 to 12 were prepared by polymerization in the same manner as in Example 1, but were prepared by differently adding DDSA content. Table 2 shows the DDSA content of Examples 2 to 12 and the polymer properties of the polyester resin.

Comparative example

In the same manner as in Example 1, a cationic flame-retardant polyester resin was prepared, but only 1.8 mol% of a metal salt, sulfoisophthalate sodium salt, was added, and a cationic flame-retardant polyester resin was prepared without DDSA.

※ Method for measuring polymer properties

* Intrinsic Viscosity (IV): Measured by using a Uberod-type viscometer in a constant temperature bath at 30 ° C after sufficiently dissolving the polymer in a concentration of 0.5% in a solvent mixed with phenol: tetrachloroethane at 100 ° C in a 1: 1 ratio. .

* Melting Viscosity (MV): Measured using a plate type RDA from TA.

* Shear Thinning: The behavior of a polymer that has a constant melt viscosity up to a specific shear rate (rad / s) and decreases the melt viscosity at high shear rates. In the present invention, 100 rad at a melt viscosity of 10 rad / s. Measure the difference in melt viscosity at / s

* Melting point (℃): The melting point (℃) of the copolymerized polyester resin was measured using a thermal differential scanning calorimeter (Perkin Elmer, DSC-7).

division Input composition Polymer properties Metal salt
(mole%) DDSA
(mole%) IV
(dl / g) MV
(Poise) Flyer
(10-100rad / s) Melting point (℃) Comparative example 1.8 - 0.557 3525 794 242.9 Example 1 1.8 One 0.561 3412 773 241.7 Example 2 1.8 2 0.566 3359 754 240.2 Example 3 1.8 3 0.556 3210 721 238.7 Example 4 1.8 4 0.563 3086 676 236.9 Example 5 1.8 5 0.557 2971 613 235.1 Example 6 1.8 6 0.565 2841 535 233.6 Example 7 1.8 7 0.554 2663 448 231.6 Example 8 1.8 8 0.563 2448 344 229.5 Example 9 1.8 9 0.558 2267 232 227 Example 10 1.8 10 0.574 2011 107 224.5 Example 11 1.8 15 0.588 1642 95 211.7 Example 12 1.8 20 0.591 1301 91 198.3

As shown in Table 1, the shear thinning of the comparative example is 794, but it can be seen that the melt viscosity (MV) and the shear thinning behavior are also effectively reduced as the content of DDSA increases.

<Production of cationic flame-retardant polyester fiber>

After drying the cationic flame-retardant polyester resins of Examples 1 to 12 and Comparative Examples, fibers were prepared by a conventional method for preparing cationic flame-retardant polyester fibers.

The mono fineness, strength, and dyeability of the prepared cationic flame-retardant polyester fiber were measured and are shown in Table 2.

※ Method for measuring physical properties of cationic flame-retardant polyester fiber

* Intensity: Using an Instron device under constant temperature and humidity conditions at a temperature of 20 ° C and a humidity of 65%, measure the average value after measuring 5 times under the condition of a sample length of 200mm and a cross head speed of 400mpm.

* Dyeing property (K / S): Cationic flame-retardant polyester fiber is made of circular knitted fabric and dyed with a cationic blue dye (1 OWF%) for IR dyeing at 110 ° C for 30 minutes to specify the K / S value at the maximum wavelength . In the present invention, the value at 620 nm is read. It can be obtained from the reflectance R at each wavelength by the following Kubelka-Munk equation.

K / S = (1-R) ² / 2R (K: absorption coefficient, S: scattering coefficient)

division Mono fineness
(denier) burglar
(g / d) Dyed
(K / S) Comparative example 3.3 3.4 22.5 Example 1 2.7 3.5 22.4 Example 2 3.4 3.4 23.2 Example 3 3.2 3.6 24.5 Example 4 2.9 3.8 24.7 Example 5 3.1 3.9 25.5 Example 6 3.1 4.2 25.7 Example 7 2.8 3.8 25.8 Example 8 2.8 3.6 26.7 Example 9 3.1 3.1 27.3 Example 10 2.7 2.9 28.3 Example 11 3.5 2.3 30.5 Example 12 3.4 1.8 32

As shown in Table 2, it can be seen that when the shear thinning behavior of the cationic flame-retardant polyester resin is reduced, the strength of the cationic flame-retardant polyester fiber is improved.

In Examples 3 to 8, that is, when DDSA is 3 to 8 mol%, it can be seen that the strength and dyeability are excellent, and since DDSA is 9 or more in which the amount exceeds 8 mol%, the strength is It is estimated that DDSA lowers the crystallinity of the polyester resin and lowers the strength through lowering the melting point of the polyester resin.

K / S dyeability increases as the DDSA content increases, and it can be seen that the amorphous region in the polyester resin increases, making cationic dye penetration easier.

<Production of Cationic flame-retardant polyester fiber of fineness>

The cationic flame-retardant polyester fiber having mono fineness of 3D, 1D, and 0.5D was prepared with the cationic flame-retardant polyester resin of Example 6, which had excellent strength among the comparative examples and examples.

Table 3 shows the fiber properties and spinning processability of the prepared cationic flame-retardant polyester fibers.

division Input composition (mol%) Fiber properties Spinning fairness Metal salt DDSA Mono fineness
(denier) burglar
(g / d) General Ambassador
(time) yield
(%) Comparative Example-1 1.8 - 3.4 3.5 2 97 Comparative Example-2 1.8 - One 2.6 11 88 Comparative Example-3 1.8 - 0.54 1.1 12 or more times Bad Example 6-1 1.8 6 3.1 4.2 0 98 Example 6-2 1.8 6 One 3.7 2 97 Example 6-3 1.8 6 0.49 3.9 3 97

As shown in Table 3, the cationic flame-retardant polyester fiber prepared by using only 1.8 mol% of the sulfoisophthalate sodium salt as in Comparative Examples-1 to Comparative Example-3 had low strength and poor processability during fine summing.

However, the cationic flame-retardant polyester fiber made of the cationic flame-retardant polyester resin of Example 6 according to the present invention is excellent in spinning processability without deteriorating strength even when made of 1 denier and 0.5 denier fibers. It can be seen that the cationic flame-retardant polyester resin can be overcome and the high-strength fine fiber cationic flame-retardant polyester fiber can be produced.

Claims (6)

Cationic flame-retardant polyester resin, characterized in that a sulfoisophthalic acid metal salt and a compound of the following [Formula 1] are copolymerized with the polyester resin.
[Formula 1]

[In Formula 1, n is 3 or more carbons, and α is an integer. It is composed of an aliphatic linear chain, and may include double bonds and triple bonds in some cases.] According to claim 1,
The sulfoisophthalate metal salt is a cationic flame-retardant polyester resin, characterized in that 0.1 to 3 mol% of the total polyester mole is copolymerized. According to claim 1,
The compound of [Chemical Formula 1] is a cationic flame-retardant polyester resin, characterized in that 1 to 20 mol% of the total polyester mole is copolymerized. According to claim 1,
The compound of [Formula 1] is a cationic flame-retardant polyester resin, characterized in that the compound of [Formula 2] below.
[Formula 2]

Cationic flame-retardant polyester fiber, characterized in that it is formed of a cationic flame-retardant polyester resin according to any one of claims 1 to 4. The method of claim 5,
The cationic flame-retardant polyester fiber is a cationic flame-retardant polyester fiber, characterized in that the mono fineness is 0.4 to 3.5 denier.