KR960000083B1 - Method for manufacturing of polyester fiber - Google Patents

Abstract

The polyester fiber is produced by reacting a diol with dicarboxylic acid(or its ester deriv.) to obtain polyester, reacting the polyester with 2.0˜6.0parts colloidal silica sol prepared by dispersing 50˜100nm spherical silica in ethylene glycol and 1.0˜3.0parts slurry prepared by dispersing 0.1˜0.3 micron titanium oxide into ethylene glycol to obtain a polyester chip, mixing the polyester chip with a ultraviolet absorbing agent of formula (I), (II) and (III) and a thermal stabilizer, and spinning the mixture. In the formulas, R1 and R2 are each H, OH, methoxy or ethoxy; A1 is C1-5 alkyl; A2 is C1-3 aliphatic hydrocarbon. The polyester fiber has a good UV shieldability and bathochromic affect.

Description

Method for producing polyester fiber

The present invention relates to a method for producing a polyester fiber having excellent UV protection and deep colorability, and more particularly, in preparing a polyester produced by the reaction of a diol and dicarboxylic acid or an ester-forming derivative thereof. It is characterized by improving the UV blocking performance and deep color by kneading and spinning the polymer reacted by adding silica sol dispersed in ethylene glycol during the exchange reaction and the compound represented by the following general formulas (I), (II) and (III): It relates to a method for producing a polyester fiber.

Wherein R ₁ and R ₂ are each selected from hydrogen, hydroxy, methoxy or ethoxy groups, A ₁ is a compound containing an alkyl group of 1 to 5 carbon atoms, and A ₂ contains an aliphatic hydrocarbon group of 1 to 3 carbon atoms. It is a compound.

The polyester fiber itself has excellent mechanical strength, various physical properties, and chemical properties, but has a problem that the light reflection amount of the fiber surface is large and the color depth is degraded. For example, a representative method for imparting color depth is a method of coating a low refractive resin on the surface of polyester fiber, a method of imparting irregularities on the surface by plasma processing the fiber surface, and adding an additive during the polymerization process The method of imparting color depth due to surface irregularities by performing alkali reduction treatment after spinning is known. However, considering the general characteristics and economic aspects of the fiber, the method of imparting color depth using polymerization modification and alkali reduction method has been put into practical use, and such a manufacturing method is disclosed in Japanese Patent Laid-Open Nos. 56-45922, 56-47428-, 58-13717, 60-59171, 61-258018 and the like, but satisfactory color depth and radioactivity could not be obtained.

On the other hand, the ozone layer is destroyed by the use of Freon around the world, and because of this, the amount of ultraviolet rays reaching the earth is increasing. Therefore, there is an increasing need to protect the skin from ultraviolet rays. Ultraviolet rays with a wavelength range of 180nm to 400nm in the sunlight are classified into UV-A, B and C waves according to the wavelength range. Among them, UV waves of 290nm to 400nm, which are long-wavelength regions, increase melanin, collagen and polysaccharides, etc. Reduction may cause skin cancer or skin aging. In particular, the ultraviolet rays most harmful to the human body is a UV B wave that can cause skin cancer, and a fiber having a blocking property over a wide range of ultraviolet rays is required, centering on the UV B wave in the range of 290 to 320 nm.

As a method of imparting ultraviolet ray blocking function to polyester fiber products, a method of attaching an ultraviolet ray blocking material to the fiber surface by a post-processing method has been mainly used. As a technical means, a dust reduction method and a padding method are used, In terms of molecular weight, it is easy to be solubilized in the fiber, and the UV-blocking material should have low melting point due to its high melting point and low skin irritation such as toxicity, and it is difficult to stably fix the UV-blocking material. In addition, even if the UV protection processing, the gap between the yarn and the yarn, between the fiber and the fiber between the fibers can not penetrate properly, there is a limit to the blocking effect. Another post-processing method is fabric coating or laminating method, but it has excellent UV blocking effect, and is relatively easy in consideration of durability of processing agent and adhesion to fiber, but it has a problem of greatly deteriorating touch. This particularly required apparel use is not practically applicable. Therefore, research and development is mainly progressed by incorporating a sunscreen material directly into the fiber. The direct method of incorporation into the fiber has many advantages, such as superior durability and post-processing, which does not impair the feel of the textile product.However, since the manufacturing method requires high technology, polymerization, spinning, It is necessary to secure core technologies such as weaving and high-order processing. The sunscreen used for direct incorporation into the fiber is classified into an inorganic sunscreen material and an organic sunscreen material. As the inorganic sunscreen material, mainly zinc oxide and titanium oxide are used. Dispersion technology and particle size control have a great influence on post-processability and quality. In the use of organic sunscreen materials, thermal stability and human stability should be considered first.

For example, Japanese Patent Laid-Open No. 5-323218 discloses a method of injecting and emitting inorganic UV-blocking materials such as titanium oxide, zinc oxide, silicon-based and organic-blocking materials having ultraviolet absorption characteristics during polymerization. Problem of controlling dispersibility due to slurrying during the injection process, trimming occurs during spinning due to secondary aggregation between inorganic particles due to exothermic reaction during a long time during polymerization process, weaving defect due to excessive particles, and dyeing defect during dyeing process Has problems such as;

Accordingly, an object of the present invention is to improve the color degradation and UV blocking performance due to the problem of excessive input of inorganic particles in the polymerization and the degradation of the thermal stability of the ultraviolet absorber due to the addition of the ultraviolet absorber during polymerization, the problem of deep colorability and It is to provide a method for producing a polyester fiber excellent in UV protection performance.

In order to achieve the above object as well as another object that can be easily expressed in the present invention, the diol and dicarboxylic acid or ester-forming derivatives thereof are reacted, but transesterified, silica sol dispersed in ethylene glycol during the transesterification reaction. Was added to react and polycondensation to obtain a polymer, and the polyester fiber excellent in deep color and UV blocking performance by kneading and spinning the polymer and the compounds represented by the general formulas (I), (II) and (III). Can be obtained.

The present invention will be described in more detail as follows.

In preparing polyester by reacting diol with dicarboxylic acid or ester forming derivatives thereof, a colloidal silica sol in which spherical silica having an average particle diameter of 50 to 100 nm is dispersed in ethylene glycol is produced during a transesterification reaction. Produced a slurry obtained by dispersing 2.0 to 6.0 parts by weight of titanium oxide and an average particle diameter of 0.1 to 0.31 titanium oxide in ethylene glycol, and reacted by adding 1.0 to 3.0 parts by weight based on titanium oxide to polyester to react. After manufacturing the polyester chip, the deep color polyester chip, organic blocker and special thermal stabilizer are kneaded and radiated to stabilize the radioactivity and object property, have thermal stability and high UV protection, and cool due to visible light blocking effect. A polyester fiber having both cooling and deep color effects was prepared.

The average particle diameter and the input content of the spherical silica used in the present invention are important criteria for determining the interrelationship between radioactivity, color depth, and UV blocking property. When the average particle diameter is less than 50 nm or the input amount is 2.0 parts by weight or less, alkali reduction is performed. Depth of concave-convexity which affects color depth is decreased, or the number of concave-convexities is decreased, so deep color performance is deteriorated and UV-blocking property is deteriorated due to light scattering efficiency deterioration. The problem of poor radioactivity due to coagulation and coarsening is caused. In addition, in the case of titanium dioxide introduced in parallel, the average particle size is 0.1 to 0.31 and the dose is 1.0 to 3.0 parts by weight in consideration of the interrelationship between ultraviolet ray shielding, radioactivity and color depth.

When light is irradiated on a polymer material having a high refractive index agent or a UV absorber, UV blocking by both the high refractive index agent and the ultraviolet absorber occurs in the ultraviolet region of 180 to 400 nm, and in the visible region, scattering or reflection is caused by the high refractive index agent. In the case of the ultraviolet absorber, the visible light is blocked, and transmission is mainly known to block the hot wire. In particular, in the case of the ultraviolet absorber, the selection of the absorbent added is an important factor in providing the UV blocking effect. Generally, the ultraviolet absorber is mainly a compound represented by the following general formula (I), (II) or (IV).

Wherein, R ₁ and R ₂ is hydrogen, hydroxy, methoxy or will each selected from an ethoxy group, A ₁ is a compound containing an alkyl group of a carbon number of 1 ~ 5, R ₃ is an alkyl group of hydrogen or C ₁ ~ C ₁₀ to be.

Representative examples of the compound represented by the general formula (I) include a compound in which R ₁ is hydrogen and R ₂ is -OH, R ₁ is hydrogen and R ₂ is a methoxy group, or a compound in which R ₁ and R ₂ are methoxygin Examples of the compound represented by the general formula (II) include A ₁ being methyl, ethyl, butyl or t-butyl. Examples of the compound represented by the general formula (IV) include a compound wherein R ₃ is hydrogen. _There are compounds in which R ₃ is -C ₈ H ₁₇ or compounds in which R ₃ is t-butyl.

However, in the case of the compound of formula (I), it is highly available for the fiber which can be ion-bonded due to the fact that the -OH group can be freely controlled by the reactor, but has the disadvantage of being expensive. Although it does not have a reactor, it is considerably restricted in its use, but it is inexpensive, has low toxicity, and has been used due to its relatively high solubility in high temperature water, and has a low melting point in the case of the general formula (IV) compound. It has low practicality due to its strong sublimation and low absorption wavelength.

As a conventional method for imparting a sunscreen effect, a benzophenone-based compound represented by the general formula (I) or a bezotriazole-based compound represented by the general formula (II) was used alone during the polycondensation reaction. In many cases, the absorbent itself decomposes due to high heat during the polymerization reaction, resulting in loss of UV blocking performance and deterioration of color tone of the chip and color tone of the fiber.

Therefore, in the present invention, the ultraviolet absorber is added to the kneading spinning without polymerization, but is represented by the benzophenone compound represented by general formula (I) having high reactivity with polyester and general formula (II) having excellent thermal stability. The benzotriazole-based compound was mixed and mixed before kneading to increase the UV blocking effect and prevent color deterioration of chips and fibers.

The mixing ratio of the general shin (I) compound and the general formula (II) compound was 10: 1 ~ 0.1: 1, preferably 7: 1 ~ 1.5: 1, which was effective in terms of UV protection and fiber properties. The amount added is preferably 0.1 to 0.5 parts by weight based on the resulting polymer.

However, when the mixed sunscreen and the molten polymer are mixed during kneading, embrittlement of the polymer chain due to thermal oxidation occurs, thereby causing a problem in that the color tone changes. Hindered represented by the following general formula (III) in the present invention. The addition of (hindered) phenolic compounds prevents rapid color deterioration and melt viscosity drop due to oxidation.

Here, A <_1> is a compound containing a C1-C5 alkyl group, and A <_2> is a compound containing a C1-C3 aliphatic hydrocarbon group.

Compound of formula (III) not only shows the effect of secondary antioxidants by decomposing hydroperoxide and blocking radical progression, but also progresses oxidation by reacting with peroxy radicals and stopping chains. The effect of delaying primary antioxidants is also shown. The compound of formula (III) is effective to use 0.2 ~ 0.6 parts by weight with respect to the polyester chip, and when the content exceeds 0.6 parts by weight, there is no synergistic effect according to the addition, when less than 0.2 parts by weight Low.

The following examples and comparative examples further illustrate the present invention, but do not limit the scope of the present invention.

Example 1

100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 0.083 parts by weight of manganese acetate, and 0.038 parts by weight of antimony trioxide were placed in a transesterification reactor and heated slowly at 140 ° C. When the temperature inside the reactor reached 170 ° C., 4.0 parts by weight of a 15% silica dispersion (colloidal silica sol) containing spherical silica having an average particle diameter of 65 nm dispersed in ethylene glycol was added to silica, and then the methanol discharge amount was 75%. % Of titanium dioxide (TiO2) (manufactured by Fuji Corporation) with an average particle diameter of 0.25 u was added 3.0 parts by weight of a 14% slurry solution dispersed in ethylene glycol, based on titanium oxide. When the final internal temperature reached 240 ℃, the transesterification reaction was terminated, the product was transferred to a polycondensation reaction tank, and after 5 minutes, 0.035 parts by weight of phosphorous acid was added, and the reaction was carried out at a temperature of 285 ℃ for about 2 hours 30 minutes under reduced pressure to 0.1mmHg. A colored polyester chip was prepared. The high viscosity of the chip was 0.655 ~ 0.658, and the chip was dried at 150 ° C. for 6 hours using a vacuum dryer to maintain a moisture content of 40 ppm after drying.

While the dried chip is melt-extruded using a general polyester melt spinning equipment under a spinning temperature of 285 ° C., the temperature in a separate vessel is maintained at a temperature of 195 ° C. to give 2-2'-dihydroxy-4-. 0.24 part by weight of 4'-dimethoxybenzophenone, 0.06 part by weight of 2 (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) -benzotriazole, triethyleneglycol-bis-3 (3 0.3 parts by weight of -tert-butyl-4-hydroxy-5-methylphenyl) -propionate was stirred in a vessel and melted, followed by melting with a molten polymer using a static mixer for static kneading (HI-MIXER, Japan). After kneading, an undrawn yarn was prepared at a spinning temperature of 280 ° C., followed by a drawn yarn FY 75 denier / 36 filament.

The yarn was used as both light and weft yarns to weave palace fabrics with a weft twist of 2,750T / M, a warp density of 170 / inch, a weft density of 98 / inch, and a weight of 85 g / yd. Alkaline reduction was performed with a 50% NaOH solution at 23% reduction, and then dyed by high temperature and high pressure using black and colored general dispersible dyes at 130 ° C. for 1 hour.

The deep reflectivity was evaluated by measuring the surface reflectance (L ^* ) of the fabric, and UV transmission (T%) was measured by using a SHADAD magnetic spectrophotometer (Model: UV-3101). Sex evaluation was performed and the result is shown in Table 1.

Example 2

The experiment was carried out under the same conditions and in the same manner as in Example 1, except that 6.0 parts by weight of silica having an average particle size of 100 nm was used, and the evaluation results are shown in Table 1.

Example 3

The amount of titanium dioxide was 1.5 parts by weight, 0.2 parts by weight of 2-2'-dihydroxy-4-4'-dimethoxybenzophenone and 2 (2'-hydroxy-3'-tert-butyl-5 ' Except having made -methyl-phenyl)-benzotriazole into 0.1 weight part, it carried out similarly to Example 1, and shows the evaluation result in Table 1.

Example 4

The evaluation results are shown in Table 1 except that 3.0 parts by weight of silica having an average particle diameter of 50 nm and 2.0 parts by weight of titanium dioxide having a particle diameter of 0.11 were used.

Comparative Example 1

The evaluation results are shown in Table 1 except that 2-2'-dihydroxy-4-4'-dimethoxybenzophenone is added at 0.3 parts by weight alone as a sunscreen.

Comparative Example 2

As the sunscreen agent, 2 (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) -benzotriazole was added in 0.3 parts by weight alone, and the same procedure as in Example 1 was carried out. 2 is described.

Example 5

Except for adding 0.6 parts by weight of triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionate, the same procedure as in Example 1 was carried out and the evaluation results are shown in Table 1. It was.

Comparative Example 3

5 minutes after the completion of the transesterification reaction, 0.035 parts by weight of phosphorous acid was added thereto, 0.24 parts by weight of 2-2'-dihydroxy-4-4'-dimethoxybenzophenone, and 2 (2'-hydroxy-3'-tert. 0.06 parts by weight of -butyl-5'-methyl-phenyl) -benzotriazole and 0.3 parts by weight of triethylene glycol-bis-3 (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionate After completion of the reaction, the reaction was completed at a temperature of 285 ° C. for about 2 hours and 30 minutes under reduced pressure to 0.1 mmHg, and the same procedure and conditions as in Example 1 were carried out, and the physical properties were evaluated. Described.

[Comparative Example 4]

After vacuum drying a general semi-Dull type PET chip having an intrinsic viscosity of 0.658 and 0.4 parts by weight of titanium dioxide, a non-drawn yarn was produced at a spinning temperature of 285 ° C., followed by obtaining a drawn yarn FY 75/36. Weaving, dyeing, and evaluation were carried out under the same conditions and methods as described above. The results are shown in Table 1.

TABLE 1

* Property evaluation method

1) Inner pack pressure: It indicates the pressure in the pack when melt extruded polymer. In case of polyester, 15 ~ 190kgf / ㎠ is most appropriate.

2) Winding rate: It is related to the number of trimming thread broken in the spinning and drawing process at spinning speed of 3,000m / min.

3) Four-color tone: sample L and measure L value (whiteness: whiteness) and b value (yellowness: yellowness) using colorimeter, and L value decreases, especially b value rises due to poor heat resistance. There is this.

4) Deep color: ㆍ L *: The reflectance (L *) is measured by colorimeter measurement. The better the color depth, the smaller this value.

How to judge by water supply: Forge made of deep yarn and plain yarn of the same tissue are dyed with the same dye and dyeing conditions. Color results are visually compared and judged.

Α = K / S = (kubelka-Munk 式)

: It determines by measuring the reflectance R by spectrophotometer measurement. The larger the value of α, the better the color depth (wherein K is the extinction coefficient of the sample, S is the light scattering coefficient of the sample, and R is the reflectance of the monochromatic light).

5) UV protection and visible light blocking property: In order to compare the fabric of the same yarn and the same tissue with the UV blocking fabric, a UV spectrophotometer with an integrating sphere is used, and an ultraviolet region having a wavelength of 180 nm to 400 nm and a visible ray having a wavelength of 400 nm to 790 nm Calculate the blocking rate by measuring the transmittance in the ray region.

Claims (4)

In preparing a polyester by reacting diol with dicarboxylic acid or an ester-terminating derivative thereof, a colloidal silica sol dispersed in ethylene glycol is added and reacted during a transesterification reaction to obtain a polyester chip. A method for producing a polyester fiber characterized by kneading and spinning a compound represented by formulas (I), (II) and (III). Wherein R ₁ and R ₂ are each selected from hydrogen, hydroxy, methoxy or ethoxy groups, A ₁ is a compound containing an alkyl group of 1 to 5 carbon atoms, and A ₂ contains an aliphatic hydrocarbon group of 1 to 3 carbon atoms. It is a compound. The method for producing a polyester fiber according to claim 1, wherein the silica is spherical silica having an average particle diameter of 50 to 100 nm, and its input range is 2.0 to 6.0 parts by weight based on the produced polyester. The method of claim 1, wherein the mixing ratio of the general formula (I) and (II) compound is 7: 1 to 1.5: 1, the input range is 0.1 to 0.5 parts by weight of the production of polyester fibers Way. The method of producing a polyester fiber according to claim 1, wherein the compound of formula (III) is added in an amount of 0.2 to 0.6 parts by weight.