JP3053248B2 - Polyester composition having ultraviolet shielding performance, method for producing the polyester composition, and fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition having an ultraviolet shielding property and a fiber comprising the polyester composition, for example, blouse, summer suit, sports clothing, curtain, parasol, canvas, automobile cover, etc. The present invention relates to a fiber suitably used for clothing and industrial materials.

[0002]

BACKGROUND OF THE INVENTION A resin composition which absorbs and blocks ultraviolet rays, more specifically, a resin composition which absorbs light having a wavelength of 380 nm or less almost completely and substantially blocks ultraviolet rays is formed into a film or a bottle. It is used for preventing discoloration of photographs and the like, preventing deterioration of foods and chemicals, and as window glass. Conventionally, organic compounds such as benzotriazole and benzophenone, and inorganic compounds such as zinc oxide, titanium oxide, talc, kaolin, and sodium carbonate have been known as additives imparting the ability to absorb and block ultraviolet rays. Organic compounds such as benzotriazole and benzophenone have excellent ultraviolet absorbing ability, but have a high melting point and, when melt-kneaded into a thermoplastic resin, have thermal stability.
Many have problems in sublimation resistance, compatibility with organic substances, and the like. Some organic UV absorbers and dyes and pigments have a certain level of UV absorption effect, but they generally have a very large absorption in the visible light wavelength range. However, it is necessary to pay attention to the fact that this is limited to the case where it is permitted, or that the decomposition product itself may cause skin damage. Next, white, high-refractive-index inorganic powders that have no absorption in the visible region are used as pigments in the paint and ink industries, as well as in the plastics industry. Among them, titanium oxide, zinc oxide, talc, kaolin It has been known that calcium carbonate or the like has an ultraviolet shielding effect.

[0003]

However, when an attempt is made to impart an ultraviolet ray shielding effect to fibers made of a thermoplastic resin, even if the above-mentioned inorganic particles are used, the process stability such as spinnability and the like is required. In order to maintain the above, there are various restrictions such that only a small amount of particles can be blended, or particles having a large particle size cannot be used, and a fiber having a satisfactory and excellent ultraviolet shielding effect has not yet been obtained. Is the current situation. An object of the present invention is to provide a polyester fiber having an excellent ultraviolet shielding effect, and to provide a polyester composition suitable for the fiber.

[0004]

That is, the present invention provides a polyester containing 1 to 10% by weight of zinc oxide and titanium oxide having an average particle size of 0.1 to 3 μm and a molecular weight of 5 to 5%.
500 or more of a phenolic compound and / or a phenylphosphite compound are
A polyester composition characterized by containing 10,000 ppm and a fiber containing the polyester composition as at least one component, and a zinc oxide having an average particle diameter of 0.1 to 3 μm when producing the polyester composition. Is added to the reaction system after the esterification reaction and before the polycondensation reaction, and a phenolic compound and / or a phenylphosphite compound having a molecular weight of 500 or more is added to the reaction system simultaneously with or before the addition of zinc oxide. It is a method for producing a polyester composition, characterized by being added.

[0005] In the present invention, both zinc oxide and titanium oxide must coexist in the polyester composition, and even if one of them is missing, an excellent ultraviolet shielding effect cannot be achieved. And both are 1 to 1 in total
It must be contained in the polyester composition in the range of 0% by weight. If the content is less than 1% by weight, a sufficient ultraviolet shielding effect cannot be obtained, and if it exceeds 10% by weight, the viscosity decreases significantly during spinning and spinning becomes impossible. Further, the average particle diameter of both is 0.1 to 3 μm, preferably 0.3 to 1 μm. If the particle size is less than 0.1 μm, thermal aggregation occurs during the polymerization of the polyester, and the filter is clogged in the process from the polymerization to the formation of fibers. On the other hand, when the particle size exceeds 3 μm, the filter is clogged and the spinning becomes unstable. Or, even if the spinning can be performed, it often causes troubles such as winding of the roller and generation of fluff in the stretching process. In the present invention, the weight ratio of titanium oxide to zinc oxide is not particularly limited, but it is preferable that the amount of titanium oxide is large, and specifically, titanium oxide: zinc oxide = 90: 10 to 50:50, particularly 7
It is preferably from 0:30 to 50:50.

Next, in the present invention, attention must be paid to the method of adding zinc oxide in order to disperse zinc oxide uniformly in the polyester. For example, it is not preferable to add zinc oxide particles directly to the reaction system, because remarkable aggregation of the particles easily occurs. In addition, there is a method of adding a slurry in which particles are dispersed in ethylene glycol.However, even in this case, it is not possible to add the slurry at an arbitrary stage during the polymerization of the polyester. It is easy to occur, and conversely, if it is added later than the polycondensation reaction, the depolymerization of the polymer tends to occur, which is not preferable. Therefore, zinc oxide must be added to the reaction system after the esterification reaction and before the polycondensation reaction. The concentration of zinc oxide in the slurry is not particularly limited, but is preferably 20 to 50% by weight. Further, insufficient dispersion of zinc oxide in ethylene glycol causes clogging of filters due to generation of aggregates and poor dispersion in fibers. It is desirable to disperse for about 5 hours. In addition, the timing of adding titanium oxide is not particularly limited,
Usually, it may be added at the time of preparation.

In the present invention, it is difficult to obtain satisfactory dispersibility even if the timing of adding zinc oxide is specified as described above. Prior to that, a phenolic compound having a molecular weight of 500 or more and / or a phenylphosphite-based compound must be added to the reaction system. The phenol compound having a molecular weight of 500 or more and the phenylphosphite compound used herein include 1,
1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane (manufactured by Sanyo Chemical Industries, Ltd., antioxidant F), 1,1,3-tris (2-
Methyl-4-hydroxy-5-t-butylphenyl) butane (Topanol CA, manufactured by ICI), 1,3,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene (Ionox 330, manufactured by Shell Chemical Company), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′hydroxyphenyl) propionate] methane (Nippon Ciba Geigy) (Irganox 1010), bis- [3,
3'-Bis- (4'hydroxy-3'-t-butylphenyl) butyric acid] glycol ester (manufactured by Hoechst, AntioxidantHoechst T
MOZ), triphenylphosphite (Sumitomo Chemical Co., Sumilizer TPP), diphenylisodecylphosphite (manufactured by Sanko Chemical Co., DPDP), phenyldiisodecylphosphite (Sakai Chemical Co., Chelex-
D), 4,4'-butylidene-bis (3-methyl-6-
t-butylphenyl-di-tridecyl) phosphite (manufactured by Asahi Denka Co., Mark 260), tris (nonylphenyl) phosphite (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer TN)
And compounds such as P). Since these compounds have been conventionally known as antioxidants, they are not only effective in preventing oxidation, but also extremely effective in dispersing zinc oxide. That was never known before.

It is important to add these compounds to the reaction system during the preparation of raw materials before esterification or during the period after esterification until the start of polycondensation. The addition amount is 500 to 100 with respect to the weight of the finally obtained polyester.
It may be added so as to be 00 ppm, preferably 1000 to 5000 ppm. If the added amount is less than 500 ppm, the color of the polymer may be changed, or the light resistance after fiberization may be poor,
In the case where the physical properties of the fiber decrease, etc., on the other hand, when it exceeds 10,000 ppm, the discoloration of the polymer is also caused, which is not preferable.

The polyester composition of the present invention preferably further contains 1,000 to 20,000 ppm of an ultraviolet absorber in order to exhibit higher light-shielding performance and heat-shielding performance. Known compounds can be used as the ultraviolet absorber. However, in consideration of heat stability and ultraviolet absorption performance, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′- Hydroxy-5
'-T-butylphenyl) benzotriazole, 2-
Benzotriazole compounds such as (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- It is preferable to use an ultraviolet absorber of a benzophenone-based compound such as octoxybenzophenone and 2,2'-dihydroxy-4-methoxybenzophenone. If the amount of the compound is less than 1000 ppm, the effect of absorbing ultraviolet rays is low, and if it exceeds 20,000 ppm, discoloration of the polymer occurs, which is not preferable. If this compound is added before the ester polycondensation starts, the effect of addition may not be expected in some cases. Therefore, it is preferable to add this compound after the ester polycondensation is completed.

The polyester in the present invention refers to a polyester such as polyethylene terephthalate or polybutylene terephthalate, or a copolymerized polyester obtained by modifying these with a third component. Examples thereof include terephthalic acid, isophthalic acid, and naphthalene 2,6-dicarboxylic acid. Acid, phthalic acid, aromatic dicarboxylic acid such as α, β- (4-carboxyphenoxy) ethane, 4,4′-dicarboxydiphenyl-5-sodium phosphophthalic acid, or aliphatic such as adipic acid, sebacic acid Dicarboxylic acids or their esters and diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, polyethylene glycol, and polytetramethylene glycol A fiber-forming polyester synthesized from a product according to a conventional method. In the present invention, a polyester in which 80 mol% or more, particularly 90 mol% or more of its constituent units are composed of ethylene terephthalate units or butylene terephthalate units is preferable. . Further, a small amount of additives such as a flame retardant, an antibacterial agent, a deodorant, a fluorescent brightener, and a stabilizer may be contained in the polyester.

The fiber of the present invention comprising such a polyester composition is not limited in its production method as long as it contains the above-mentioned polyester in an effective amount, and it is possible to employ a conventionally known fiberization technique. Regarding the cross-sectional shape of the fiber, various cross-sectional fibers such as a round cross-section, a flat cross-section, a dog bone cross-section, a T-shaped cross-section, a 3-6 hexagonal cross-section, a 3-14 leaf cross-section, a hollow cross-section, a side-by-side type, and a core sheath are also available. It is possible to use other component fibers such as a mold, a multilayer bonding type, a random composite type, a sea-island type, and various variations. However, in the present invention, a T-shaped cross section or a flat multi-lobed fiber having about 8 to 14 leaves is used. It is preferable from the viewpoint of the glossiness of the obtained fiber.

[0012]

According to the polyester composition of the present invention, titanium oxide and zinc oxide particles are uniformly dispersed as fine particles without aggregation by adding a specific compound during polymerization. When performing fiberization, it is possible to extremely stably produce fibers excellent in ultraviolet shielding performance without clogging or breakage of the filter. In addition, even when producing a film other than the fiber, it is possible to produce a film with good ultraviolet shielding performance and few spots.

[0013]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the examples, the evaluation of ultraviolet transmittance and light fastness is based on the following methods. Ultraviolet transmittance: Nonwoven fabric sample (100 g / m
↑ 2 hot pressed at 180 ° C for 3 minutes)
, And simultaneously measure the ultraviolet rays without attaching a sample to the other sensor unit, and determine the ultraviolet transmittance by the following equation. Ultraviolet transmittance (%) = (U / U0) × 100 U: Ultraviolet ray on the sample side U0: Ultraviolet ray on the non-sample side Light resistance: Evaluated according to JISL0842 using Shimadzu Fade Tester CF-202 type (manufactured by Shimadzu Corporation). did.
The main condition was to irradiate a sample of raw cotton, which had been appropriately stretched and flattened, under the conditions of 83 ± 3 ° C. × 200 hours, and determined the strength retention and elongation retention after irradiation. Whiteness: Measured according to JIS L1015 7.17 (Method B).

Example 1 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, 0.04 part by weight of antimony trioxide, titanium oxide having an average particle diameter of 0.5 μm (manufactured by Titanium Industry Co., Ltd.)
2 parts by weight, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-
t-butylphenyl) butane (manufactured by Sanyo Chemical Industries, Ltd.)
Trade name: 0.1 part by weight of antioxidant F) is charged into a transesterification can and an esterification reaction is carried out while gradually raising the temperature to 160 to 240 ° C. 2 parts by weight of zinc oxide (manufactured by Honjo Chemical Co., Ltd.) was dispersed in a small amount of ethylene glycol and added.
Then, the esterification reaction product was transferred to a polycondensation reaction tank, and the pressure was gradually reduced from normal pressure to 1 mmHg or less over 1 hour,
At the same time, the temperature was raised to 280 ° C., polycondensed to a predetermined degree of polymerization at 280 ° C. and 1 mmHg or less, and then vacuum-ruptured with nitrogen. A part by weight is dispersed in a small amount of ethylene glycol and added, followed by stirring for 15 minutes and 2 kg / cm
加 圧 Pressurized to 2G and granulated chips. 285
After being melt-extruded at a spinning temperature of 1,000 ° C., it was taken up at a take-off speed of 1000 m / min, bundled into a 1.2 million denier tow, stretched at a bath temperature of 94 ° C. and a stretch ratio of 3.2 times.
After heat treatment at 30 ° C. and cutting, raw cotton of 2 denier × 51 mm was obtained. As a result of observing the dispersibility of titanium oxide and zinc oxide in the fiber with a microscope, the dispersion was in an extremely good state. Then, the raw cotton is woven in a conventional manner using a non-woven fabric (100 g / m @
2, thickness 1 mm), and the ultraviolet transmittance was measured. As a result, an excellent ultraviolet shielding effect as shown in Table 1 was recognized.

[0015]

[Table 1]

Example 2 1 part by weight of zinc oxide having an average particle size of 0.5 μm, 3 parts by weight of titanium oxide having an average particle size of 0.5 μm, and 0.1 part of antioxidant F.
Polymerization was carried out in the same manner as in Example 1 except that 1% of UVA 635 L was added at 5000 ppm, and spinning and stretching were performed to obtain a 2 denier × 51 mm raw cotton. Further, a nonwoven fabric having the same basis weight and the same thickness as in Example 1 was prepared using the raw cotton, and the ultraviolet transmittance of the nonwoven fabric was measured. As shown in Table 1, an excellent ultraviolet shielding effect was recognized. .

Comparative Example 1 A fiber was formed in the same manner as in Example 2 except that the antioxidant F and the ultraviolet absorber were not used. When the obtained fiber was observed under a microscope, it was found that zinc oxide was aggregated and had extremely poor dispersibility. A nonwoven fabric was prepared from the fibers in the same manner as in Example 2, but only a non-woven fabric having poor light resistance was obtained.

Comparative Example 2 A polyester was polymerized in the same manner as in Example 2 except that zinc oxide was added at the time of charging the raw materials, but clogging of aggregates of zinc oxide and titanium oxide in the intermediate filter from the esterification tank to the polymerization tank. Occurred. Further, the dispersibility of zinc oxide and titanium oxide was extremely poor, and thread breakage and winding occurred frequently in the spinning process, which was unsatisfactory.

Comparative Example 3 A polyester was polymerized in the same manner as in Example 2 except that 25,000 ppm of antioxidant F was added. As a result, the color of the fiber became yellowish and the light resistance was remarkably poor.

Normal polyester fiber (2 denier × 5)
1 mm), the same nonwoven fabric as that of Example 1 was prepared, and the ultraviolet transmittance was measured. As a result, it was 50%.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI C08K 3:22 5:13 5:52) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 67/00- 67/04 D01F 6/92

Claims (4)

(57) [Claims] 1. A phenolic compound and / or a phenylphosphite compound having an average particle diameter of 0.1 to 3 μm and containing 1 to 10% by weight of zinc oxide and titanium oxide in a polyester and having a molecular weight of 500 or more. A polyester composition comprising 500 to 10000 ppm based on polyester. 2. An ultraviolet absorber is added to the polyester in an amount of 100
The polyester composition according to claim 1, which is contained in an amount of 0 to 20,000 ppm. 3. A process for producing the polyester composition according to claim 1, wherein zinc oxide having an average particle size of 0.1 to 3 μm is added to the reaction system after the esterification reaction and before the polycondensation reaction, and And adding a phenolic compound having a molecular weight of 500 or more and / or a phenylphosphite compound to the reaction system at the same time as or before the addition of zinc oxide. 4. A fiber comprising the polyester composition according to claim 1 as at least one component.