JPH07189031A - Polyester fiber excellent in light resistance - Google Patents

Abstract

PURPOSE:To produce a bisphenol A ethylene oxide addition copolyester fiber remarkably improved in light resistance. CONSTITUTION:A copolyester synthesized from acid components composed mainly of an aromatic carboxylic acid and glycol components composed mainly of the bisphenol A ethylene oxide addition compound represented by formula I (m and n are each an integer of 1 or 2) and an aliphatic glycol is subjected to melt spinning to obtain a polyester fiber. A benzotriazole compound expressed by formula II (R1 and R2 are each an alkyl. they may be same or mutually different. they may be each a straight chain group or a branched chain group) is adsorbed and blended in the polyester fiber so that the mol% (B) of the copolymerized compound represented by formula I and the wt.% (U) of the contained compound expressed by formula II may satisfy both the formulae 0.25-0.5<U<=B - 1 and 2<=B<=6, thus improving light resistance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has good light fastness,
The present invention also relates to a polyester fiber that gives a woven or knitted fabric excellent in swelling feeling, soft feeling, drapeability, firmness and elasticity, and a fiber product thereof.

[0002]

2. Description of the Related Art Conventionally, as a highly shrinkable mixed shrinkage yarn made of polyester fiber, 2,2-bis [4- (β-hydroxyethoxy) phenyl] propane (hereinafter referred to as BA-
Polyethylene terephthalate (hereinafter abbreviated as PET) in which a specific amount of EO is copolymerized (Japanese Patent Publication No. Sho 60-35450, Japanese Patent Laid-Open No. 55-57013), or as a high shrinkage yarn. Mixed fiber using PET in which BA-EO and isophthalic acid are copolymerized in a specific amount (Japanese Patent Laid-Open No. 19528/1990).
No. 2-19539). However, these copolymerized PETs have a problem that the light fastness of the polyester is remarkably deteriorated because BA-EO is copolymerized, which is not preferable in terms of dyeability particularly for light-colored products.

Therefore, P obtained by copolymerizing such BA-EO
In the case of a mixed fiber yarn in which ET is a high shrinkage yarn, even if it is satisfied with all of swelling, softness, drapeability, firmness, and firmness,
Since the above-mentioned light resistance is poor, its use is limited in terms of commercial value.

[0004]

DISCLOSURE OF THE INVENTION The object of the present invention is to have good light fastness, and to swell, soft feel, drape,
An object of the present invention is to provide a polyester fiber having excellent elasticity and elasticity and a fiber product made of the same.

[0005]

The present invention relates to a polyester system comprising an aromatic dicarboxylic acid as a main acid component and an ethylene oxide adduct of bisphenol A represented by the following formula (I) and an aliphatic glycol as a main glycol component. A polyester system having good light resistance, which is a fiber containing a benzotriazole compound represented by the following formula (II) in an amount satisfying the following formulas (III) and (IV): It is a fiber.

[0006]

[Chemical 3] (In the formula, m and n are integers of 1 or 2)

[0007]

[Chemical 4] (In the formula, R ₁ and R ₂ are lower alkyl groups,
They may be the same group or different groups, and may be linear or branched.)

[0008]

[Equation 2] (In the formula, B is mol% of the compound represented by the formula (I), and U is wt% of the compound represented by the formula (II))

The present invention will be described in detail below. B
The reason why the polyester copolymerized with A-EO is inferior in light resistance is considered to be a decrease in light resistance based on the skeleton of the molecular structure of BA-EO. That is, according to the examination results of the present inventors, a quinone radical is generated at the BA-EO terminal in the polyester by ultraviolet light in sunlight, and the quinone radical causes various oxidation reactions. It seems that the light resistance is reduced. In particular, it has been found that when the BA-EO copolyester is shielded from light of 350 mμ or more in the near-ultraviolet region, the light resistance is not lowered. Then, as a result of extensive studies on various ultraviolet absorbers, a benzotriazole compound represented by the above structural formula (II) in which the absorption spectrum is on the long wavelength side,
It has been found to be effective for the BA-EO copolyester. It has also been found that the light resistance is significantly improved by adding the compound especially at the time of dyeing.

In the present invention, BA represented by the formula (I)
-Copolymerization amount of EO with respect to polyester is 2 to 6 mol%
Is the range. When the copolymerization amount of BA-EO is less than 2 mol%, the light resistance of the polyester is not deteriorated by the copolymerization of BA-EO, so that it is not necessary to add the benzotriazole compound of the present invention. On the other hand, if the copolymerization amount of BA-EO exceeds 6 mol%, no effect of improving the light resistance can be seen no matter how much the benzotriazole compound of the present invention is added.

The content of the benzotriazole compound represented by the formula (II) in the polyester fiber has a deep relationship with the copolymerization amount of BA-EO, as represented by the formula (III). When the added amount U of the benzotriazole-based compound is less than (0.25B-0.5), the effect of improving the light resistance is not observed. On the other hand, when the added amount of U exceeds (B-1), The amount of the benzotriazole-based compound added is too large, and coloring due to the compound is observed, and it becomes impossible to dye a desired hue particularly in light-color dyeing.

The above-mentioned benzotriazole type compound is BA-
The timing of addition to the EO copolyester is not particularly limited. Before polymerizing the BA-EO copolyester,
It may be added at any time during the polymerization, after the polymerization, before spinning the polyester, during the dyeing, etc., but considering the coloring of the polyester or the fiber made of the polyester, the dyeing is preferable. The benzotriazole compound in the present invention is added to the dyeing bath because it melts in hot water, especially 110 ° C. or higher, and what should be powder at room temperature liquefies in hot water. The added compound can be adsorbed on the fiber composed almost entirely of BA-EO copolyester together with the disperse dye molecule which is a dye. Therefore, the content of the benzotriazole-based compound contained in the polyester fiber in the present invention,
It is the amount of the benzotriazole-based compound adsorbed on the polyester fiber, not the amount of the benzotriazole-based compound added to the reaction system or the like.

In the present invention, in particular, in the case of the mixed yarn using the BA-EO copolyester fiber as the high shrinkage yarn, the BA-EO copolymer which is more easily dyed than the PET fiber used as the low shrinkage yarn is used. Since it is selectively adsorbed on the polymerized polyester side, it has a remarkable effect on the improvement of light resistance.

The benzotriazole compound used in the present invention is represented by the formula (II), and specific examples include 2- (3,
5-di-t-butyl-2-hydroxyphenyl) -5-
Examples include chlorobenzotriazole. Further, when the compound is used by being added at the time of dyeing, it is convenient in terms of use to disperse and emulsify it using an anionic or nonionic activator.

The effect of improving the light fastness in the present invention is particularly remarkable in light color dyeing, and it is recognized that the light fastness is improved by about 2 or more. PET which is not copolymerized with BA-EO has little improvement effect, and the improvement effect level is about 0.5 to 1.0 grade. The effect of improving the light resistance is shown by a factor of 2 ^X (x: grade), which is 2 times that of PET.
On the other hand, the BA-EO copolyester shows an effect of 4 times or more, and this improving effect is considered to be a unique effect of the BA-EO copolyester.

The BA-EO copolymerized polyester fiber containing the above-mentioned benzotriazole compound in the present invention can be made into a cloth by using 100%, or a different shrinkage mixed fiber using the polyester fiber as a high shrinkage yarn. The yarn may be a cloth, but is not limited thereto. BA as a high shrinkage yarn that constitutes a different shrinkage mixed yarn
In the main chain of the —EO copolyester, 2,2-bis [4- (β-hydroxyethoxy) phenyl] sulfone, diol compounds such as diethylene glycol and 1,4-dibutanediol, adipic acid, azelaic acid, isophthalic acid An acid, a dicarboxylic acid compound such as 5-sulfoisophthalic acid, or the like may be copolymerized. As the low shrinkage yarn, PE obtained by copolymerizing the above diol and dicarboxylic acid
Examples thereof include T, PET, polybutylene terephthalate, and the like, and these may contain inorganic fine particles such as silica, titanium oxide, and barium sulfate. Furthermore, as the polyester yarn of the low shrinkage yarn, a partially drawn yarn including a thick and thin portion may be used, or a composite fiber having an irregular cross section or various composite shapes may be used. Examples of the conjugate fiber include conjugate fibers such as a core-sheath cross section, a bonded cross section, a multi-layer composite cross section, and a sea-island composite cross section. Depending on each selection condition of the two components of the composite polymer,
Fibers and the like that can be eluted and divided to make them ultrafine are included. Examples of this elution method include organic solvent extraction and alkali treatment.

The polyester fiber in the present invention means
Long fibers such as monofilaments, short fibers such as staples,
It may be any of filament yarns, spun yarns, blended yarns of the fibers of the present invention with natural fibers, semi-synthetic fibers, other synthetic fibers, and other processed yarns such as plied yarns, entangled yarns and crimped yarns. . Furthermore, the fiber product in the present invention may be any of woven and knitted fabrics, nonwoven fabrics, final clothing, and fiber products such as towels formed by using the fibers and threads as a part or the whole thereof.

[0018]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.
In addition, each physical property in an Example was measured by the following method.

(1) Intrinsic viscosity of polymer ([η] dl /
g): 0.25 g / dl of the target polymer using an equal weight mixed solvent of phenol and tetrachloroethane,
It was determined from the reduced viscosities of the three types measured at a temperature of 30 ° C. for solutions of three types of concentrations of 0.5 g / dl and 1.0 g / dl.

(2) Adsorption amount (content) (wt%) of the ultraviolet absorber in the fiber: A certain amount of the fiber treated in a solution containing a benzotriazole compound is dissolved with orthochlorophenol. , The absorbance of the solution at the maximum absorption wavelength in the ultraviolet was measured using an ultraviolet spectrophotometer, and the content of the ultraviolet absorber in the fiber (weight) was determined from the calibration curve of the separately prepared orthochlorophenol solution. %).

(3) Constant light fastness: JIS-L0824
According to Shimadzu's carbon arc lamp type,
The degree of discoloration and fading of the blue scale by the second exposure method described in JIS-L0824 was examined under an irradiation atmosphere with a black panel temperature of 63 ° C. and an irradiance of 464 W / m ² , and graded.

(4) Evaluation of hue of woven fabric: A product having a strong yellow coloration was regarded as abnormal, and a product having no coloration or a coloration that did not interfere with commercial products was judged to be normal.

Examples 1 to 3 and Comparative Examples 1 to 10 Terrephthalic acid and ethylene glycol were added in a predetermined amount of BA-
The mixture was added to a slurry tank containing EO, mixed, transferred to an esterification tank, subjected to an esterification reaction at 280 ° C. and a pressure of 2.5 kg / cm ² for 2 hours, and then an ethylene glycol solution of antimony trioxide was used as a catalyst. Added as a temperature of 2
Polymerization was carried out by gradually reducing the pressure to 0.1 mmHg while raising the temperature from 40 ° C to 280 ° C over 45 minutes. Then, chips were produced by a conventional method, and [η] was 0.7 dl.
/ G of BA-EO copolymerized PET was obtained. This copolymer PE
T was used to perform direct spinning and drawing at a spinning speed of 5000 m / min. The BA-EO copolyester fiber obtained was used as a high shrinkage yarn, and the ordinary PET stretched yarn was used as a low shrinkage yarn.
A different shrinkage mixed yarn was obtained by imparting entanglement of individual pieces / m. A Z300T / M twist was applied to the different shrinkage mixed yarn, and a twill fabric using this twisted yarn as a warp and a weft was woven. Then,
Desizing, preset at 180 ° C., and alkali weight reduction treatment were performed to make a fabric with a weight loss rate of about 15%. For twill fabrics composed of ordinary PET fibers not copolymerized with BA-EO and each of the above fabrics, 1 in the following dye bath to which each benzotriazole compound shown in Table 1 was added:
Dyeing was performed at 30 ° C. for 40 minutes. BA that constitutes the dyed product
When the content weight (%) of the benzotriazole compound in the -EO copolyester fiber was measured, the compound added to the dyeing bath was adsorbed by 100%. The results of light fastness and hue are shown in Table 1.

Dyeing bath composition Disperse dye: Sumikaron Blue E-RPD (Sumitomo Chemical Co., Ltd.) 0.1% owf Dispersant: Disper TL (Meisei Chemical Co., Ltd.) 1 g / liter pH adjusting agent: acetic acid 0.5 cc / liter Bath ratio : 50: 1

[0025]

[Table 1]

As shown in Table 1, BA-EO is added in an amount of 2 to
The benzotriazole compound represented by the formula (II) was added to the polyester fiber copolymerized within the range of 6 mol% with the formula (II
Adsorption / blending with a content within the range indicated by I) shows an effect of improving the light fastness of the fourth class. Also BA-EO
In the case of PET in which is not copolymerized, the improvement is only about 0.5 grade. That is, it is understood that only the polyester obtained by copolymerizing a specific amount of BA-EO has a remarkable improving effect. In addition, the above-mentioned improvement of the fourth grade means, in other words, an effect of the light resistance on the irradiation time, that is, a time until the color fading is extended by 16 times, and from this, it can be seen that there is a remarkable effect.

<< Example 4 and Comparative Example 11 >> Different shrinkage mixed yarns were obtained in the same manner as in Example 1, and a twill using twisted yarns obtained by twisting the mixed yarns as warps was woven, and then carried out. Relaxation, presetting, and alkali reduction treatment were performed under the same conditions as in Example 1. For the woven fabric after the preset, 2- (3-t-) was used as a benzotriazole compound.
Butyl-5-methyl-2-hydroxyphenyl) -5-
Dyeing was carried out using chlorobenzotriazole, using the same dye and dispersant as in Example 1 at the addition amounts and temperatures shown in Table 2. The results are shown in Table 2.

[0028]

[Table 2] As shown in Table 2, when a benzotriazole-based compound is added to a dyeing bath at 110 ° C. for dyeing treatment, 100% of the compound added to the dyeing bath is adsorbed and light fastness is improved. When it was added to a 100 ° C. dyeing bath for dyeing treatment, only 20% of the compound added to the dyeing bath was adsorbed, and no improvement in light fastness was observed.

[0029]

According to the present invention, by containing a specific amount of a benzotriazole compound having a specific structure in the BA-EO copolymerized polyester fiber, the light fastness can be remarkably improved, and the BA-EO copolymer can be significantly improved. The applications of the polymerized polyester fiber can be expanded.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Naomi Nitta 7471 Tamashima Otoshima, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.

Claims (1)

[Claims] 1. An aromatic dicarboxylic acid as a main acid component,
A polyester fiber comprising an ethylene oxide adduct of bisphenol A represented by the following formula (I) and an aliphatic glycol as a main glycol component, wherein the benzotriazole compound represented by the following formula (II) is A polyester fiber having good light resistance, characterized in that it is contained in an amount satisfying III) and formula (IV). [Chemical 1] (In the formula, m and n are integers of 1 or 2) (In the formula, R ₁ and R ₂ are lower alkyl groups,
They may be the same group or different groups, and may be linear or branched.) (In the formula, B is mol% of the compound represented by the formula (I), and U is wt% of the compound represented by the formula (II))