JPH11124732A - Weather-resistant, flame-retardant polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester fiber maintaining the strength and elongation of an ordinary polyester fiber and having good weather resistance and flame retardancy. SOLUTION: This weather-resistant, flame-retardant polyester fiber whose all portions or whose sheath portion is produced from a composition obtained by copolymerizing or compounding polyethylene terephthalate or a polyester containing the polymer as a main component with a phosphorous compound in a phosphorus atom content of 5300-7200 ppm and subsequently adding 1-10 wt.% of a polyarylate to the copolymer or mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester fiber which maintains the strength and elongation characteristics of ordinary polyester fiber and has weather resistance and flame retardancy.

[0002]

2. Description of the Related Art Fibers made of polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate have a high melting point, a high elastic modulus, excellent heat resistance and chemical resistance, and are widely used as fibers for clothing and industrial materials. I have.

[0003] Polyester fiber has relatively good weather resistance, and its mechanical properties are less deteriorated by ultraviolet light and the like than nylon fiber, which is another general-purpose material. However,
For applications such as automotive interior materials, outdoor reinforcements, and safety nets, higher weather resistance is required, and further, flame retardancy is required from the viewpoint of fire prevention.

Hitherto, various attempts have been made to improve the light resistance of polyethylene terephthalate fiber.
For example, Japanese Patent Publication No. 47-24249 proposes a light-resistant polyester fiber composed of a composition containing polyethylene terephthalate and polyarylate.

Japanese Patent Application Laid-Open No. 7-258520 discloses fine particles which are obtained by copolymerizing a polyester with a bifunctional organic phosphorus compound and comprising cerium oxide and silica or cerium oxide and talc, the surface of which is coated with amorphous silica. There has been proposed a polyester fiber having light resistance and flame retardancy, which is composed of a composition containing the same.

However, the polyester fibers as described above have high strength and are used for automobile interior materials, outdoor reinforcing materials,
It was insufficient for use in fields requiring high weather resistance and flame retardance, such as safety nets.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester fiber which maintains the high elongation of ordinary polyester fibers and has weather resistance and flame retardancy.

[0008]

The present invention solves the above-mentioned problems, and the gist thereof is as follows. 1. Polyethylene terephthalate or a polyester based on this, the phosphorus compound has a phosphorus atom content of 5300 ~
A weather-resistant, flame-retardant polyester fiber comprising a composition which is copolymerized or blended in an amount of 7200 ppm and contains 1 to 10% by weight of polyarylate. 2. Polyethylene terephthalate or a polyester based on this, the phosphorus compound has a phosphorus atom content of 5300 ~
A composition containing 1 to 10% by weight of polyarylate and being copolymerized or blended in an amount of 7200 ppm constitutes a sheath component, and a sheath-core structure in which polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate constitutes a core component. A weather-resistant, flame-retardant polyester fiber characterized by having:

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In the present invention, polyethylene terephthalate is preferred as the polyester, but it may be a polyester which is mainly used and contains a small amount of a copolymer component. As the copolymerization component, isophthalic acid, phthalic anhydride, 5-sodium sulfoisophthalic acid, naphthalenedicarboxylic acid,
Adipic acid, sebacic acid, 1,3-propanediol, 1,
4-butanediol, 1,6-hexanediol, 1,4-
Cyclohexane dimethanol, diethylene glycol,
Polyethylene glycol, 4-hydroxybenzoic acid, ε
-Caprolactone, pentaerythritol and the like.

As the phosphorus compound used in the present invention, there are phosphoric acid, phosphonic acid, phosphinic acid and derivatives thereof, and two or more of them can be used in combination. Specific examples of phosphoric acid derivatives include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, and the like. Specific examples of phosphonic acid and derivatives thereof include phenylphosphonic acid, dimethylphosphonic acid, and diethylphosphonic acid, and phosphinic acid and derivatives thereof. Specific examples of phosphorane, 9,10-dihydro-9-oxa-
Ethylene carbonate was added to a maleic acid adduct or itaconic acid adduct of 10-phosphaphenanthrene-10-oxide, an ethylene glycol ester of 3-methylphosphinicopropionic acid, or a reaction product of diphenylphosphine oxide and p-benzoquinone. Compounds.

The phosphorus compound may be used in the form of a monomer, oligomer or polymer reacted with an acid component such as terephthalic acid or isophthalic acid.

The phosphorus compound can be contained in the polyester by a conventional method. That is, when the phosphorus compound is copolymerized, the phosphorus compound may be added at the time of esterification or transesterification and at any stage up to the initial stage of the polycondensation reaction when producing the polyester. The phosphorus compound may not necessarily be copolymerized with the polyester, and in that case, the phosphorus compound may be added at the time of producing the polyester or at any stage after the production.

The amount of the phosphorus compound to be added is such that the phosphorus atom content in the polyester is 5300 to 7200 ppm, preferably 5600 to 7200 ppm.
It is necessary to reach 7000 ppm. If the amount of the phosphorus compound is too small, the flame retardancy becomes insufficient, and if the amount is too large, the mechanical properties of the obtained polyester fiber may be impaired, which may cause problems in the physical properties of the polyester.

In order to obtain a high-strength fiber that can be practically used, it is preferable that the polyester containing the phosphorus compound has a relative viscosity of 1.30 to 1.80 by a measurement method described later.

The term "polyarylate" refers to a wholly aromatic polyester comprising an aromatic dicarboxylic acid component and an aromatic diol component. The polyarylate may be produced by any of an interfacial polymerization method, a solution polymerization method, and a melt polymerization method.

The polyarylate preferably used in the present invention comprises an isophthalic acid component and / or a terephthalic acid component and a bisphenol A component. A part of the bisphenol A component is converted to 4,4'-dihydroxy-diphenyl ether, 4,4'-dihydroxy-diphenylthioether, 2,2 '-(4,4'-dihydroxy-3,5,3', 5 ' Polyarylate substituted with another aromatic diol component such as (tetrabromodiphenyl) propane can also be used.

The polyarylate preferably has a relative viscosity of 1.50 to 2.00 as measured by a measurement method described later. If the relative viscosity is not within an appropriate range, it is difficult to form a uniform molten mixture with the polyester, and high-strength fibers cannot be obtained.

The amount of polyarylate to be added to polyethylene terephthalate or polyester mainly composed of
It needs to be 1 to 10% by weight, preferably 2 to 5% by weight. If the compounding amount is larger than this, not only fibers having the desired high elongation degree cannot be obtained, but also it is uneconomical. On the other hand, if the amount is less than this, sufficient weather resistance cannot be exhibited.

As a method for incorporating the polyarylate into the polyester, there are a method of adding the polyarylate at the time of polymerization of the polyester and a method of melt-kneading the polyester and the polyarylate at the time of spinning, and any method may be used.

In the present invention, when it is particularly necessary to use a high-strength fiber, a composite fiber having polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate in the core may be used.

In the case of composite fibers, the ratio of the core component is 70% by weight.
It is desirable to make the following. If the ratio of the core component is too large, the weather resistance and the flame retardancy become insufficient, or the core component is partially exposed on the fiber surface to cause unevenness in the weather resistance, which is not preferable.

In the case of a conjugate fiber, it is desirable to include a phosphorus compound in the core component, if necessary, in order to obtain a sufficiently flame-retardant fiber.

The cross-sectional shape of the fiber of the present invention is not particularly limited, and may be a circular cross section, a flat cross section, a six-lobed cross section, a triangular cross section, or a modified cross section.

The fiber of the present invention can be produced by a usual melt spinning method. That is, first, the spinning temperature 290-31
After melt-spinning at 0 ° C and passing the spun yarn through a heating cylinder,
It is cooled to a temperature below the glass transition point and is drawn at a speed of 500 to 5000 m / min to obtain an undrawn yarn. The temperature and length of the heating cylinder, the temperature of the cooling air, the blowing amount, and the take-up speed are appropriately adjusted depending on the discharge amount and the number of holes in the base.

The obtained undrawn yarn is subjected to hot drawing, and the drawing can be carried out by a two-step method in which the undrawn yarn is once wound and then drawn, or a direct spin drawing method in which the undrawn yarn is continuously drawn without winding. Is also good.

The hot stretching is performed by a one-stage stretching method or a multi-stage stretching method of two or more stages. As a heating means in hot stretching,
A heating roller, a heat plate, a steam jet device, or the like can be used, and these can be used in combination as appropriate. The drawn yarn is subjected to a heat treatment or a relaxation treatment as necessary.

The fiber of the present invention has a weather resistance of 70% or more in strength retention and 65% or more of elongation retention according to the measurement method described below, and a flame retardancy of 3.5 or more ignition counts in the measurement method described below. It is desirable to select the composition of the composition constituting the fiber so that the flame time is within 2.0 seconds. Fibers that do not satisfy such conditions have insufficient weather resistance and / or flame retardancy, and are insufficient for use in fields requiring high weather resistance and flame retardancy.

The processing conditions of the fiber of the present invention are not particularly limited, and the fiber can be processed in the same manner as a normal polyester fiber, but the pigments, dyes and auxiliaries used are weather-resistant and flame-retardant. It is preferable to use a material having good

The polyester fiber of the present invention may contain, if necessary, a heat-resistant agent, a light stabilizer, a fluorescent agent, an antioxidant,
Various additives such as a matting agent, an antistatic agent, a pigment, a plasticizer, and a lubricant can be contained.

[0031]

Next, the present invention will be described specifically with reference to examples. In addition, the measuring method of a characteristic value is as follows. (a) Relative viscosity of polyester Using a mixture of phenol and tetrachloroethane in an equal weight mixture as a solvent, a solution having a concentration of 0.5 g / dl was measured using an Ubbelohde type viscosity tube at a temperature of 20 ° C. (b) Relative viscosity of polyarylate Using a mixture of phenol and tetrachloroethane in a weight ratio of 6/4 as a solvent, a solution having a concentration of 1.0 g / dl was measured at a temperature of 25 ° C. using an Ubbelohde type viscosity tube. (c) Strength and elongation Measured according to the method of JIS L-1017 7.5. (d) Weather resistance Sunshine Weather O Meter WB manufactured by Suga Test Instruments Co., Ltd.
Using L-SUN-HC type, black panel temperature 63 ± 3 ℃,
A cycle of irradiating ultraviolet rays with rainfall conditions of 18 minutes out of 120 minutes is repeated 75 times, a total of 150 hours of ultraviolet irradiation,
The strength and elongation of the fiber before and after irradiation were measured by the above method, and the strength retention and elongation retention were determined. (e) Flame retardancy Measured according to the method of JIS L-1091 6.4.

Example 1 The ethylene glycol ester of 3-methylphosphinicopropionic acid was used to reduce the phosphorus atom content in the polyester.
A polyethylene terephthalate-based polyester copolymerized at 6900 ppm was produced, formed into chips, and dried under reduced pressure. (Relative viscosity of polyester 1.72) On the other hand, polyarylate was produced by an interfacial polymerization method from a methylene chloride solution of a mixed acid dichloride having a molar ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1/1 and an aqueous alkali solution of bisphenol A, and After washing with water,
Chips were formed and dried under reduced pressure. (Relative Viscosity of Polyarylate 1.71) Next, the above polyester and polyarylate were mixed at a ratio such that the content of polyarylate became 3% by weight, and supplied to an extruder-type melt spinning apparatus to be melt-spun.
The spinneret has 48 spinning holes with a diameter of 0.4 mm, a single-phase type with a circular cross section, and spun at a spinning temperature of 300 ° C.
After passing through a heating cylinder with a length of 20 cm and a temperature of 350 ° C. placed directly below the base, the wind speed is increased by a horizontal cooling device with a length of 90 cm.
The yarn was cooled by blowing cooling air at a temperature of 15 ° C. at a rate of 0.5 m / min. Further, after an oil agent mainly composed of an aliphatic ester was applied by an oiling roll, the oil was taken out by a take-off roller at room temperature. Between the take-up roller and the first stretching roller
The film was stretched 1.01 times, and then stretched between the first stretching roller and the second stretching roller at 230 ° C. so that the total stretching ratio was 6.1. Next, after performing a relaxation heat treatment at a tension ratio of 0.98 between the second stretching roller and the heat treatment roller at 160 ° C.,
After winding, a polyester fiber of 250d / 48f was obtained. Table 1 shows the weather resistance and flame retardancy of the obtained fibers.

Example 2 and Comparative Examples 1-2 Polyester fibers were obtained in the same manner as in Example 1 except that the content of polyarylate was changed as shown in Table 1. Table 1 shows the weather resistance and flame retardancy of the obtained fibers.

Comparative Example 3 A polyethylene terephthalate having a relative viscosity of 1.62 without copolymerizing a phosphorus compound was used as the polyester.
A polyester fiber was obtained in the same manner as in Example 1. Table 1 shows the weather resistance and flame retardancy of the obtained fibers.

[0035]

[Table 1]

In Examples 1 and 2, the strength is large and
Polyester fibers excellent in both weather resistance and flame retardancy were obtained. On the other hand, in Comparative Example 1, the polyarylate was not contained, so that the weather resistance was inferior. In Comparative Example 2, the amount of polyarylate was too large, so that the strength was inferior. Also,
In Comparative Example 3, since the polyester containing no phosphorus compound was used, the flame retardancy was inferior.

Example 3 Polyethylene terephthalate having a relative viscosity of 1.72 was used as a core component,
The mixture of polyester and polyarylate in a weight ratio of 97/3 in Example 1 was used as a sheath component, and the core / sheath composite weight ratio was
A 60/40 concentric core / sheath composite fiber was produced by the method according to Example 1. Table 2 shows the weather resistance and flame retardancy of the obtained fibers.

Example 4 A composite fiber was produced in the same manner as in Example 3 except that the polyester in Example 1 was used as a core component and the mixture of polyester and polyarylate in Example 1 having a weight ratio of 97/3 was used as a sheath component. Table 2 shows the weather resistance and flame retardancy of the obtained fibers.

[0039]

[Table 2]

[0040]

According to the present invention, it is possible to produce a polyester fiber which maintains the high elongation of a normal polyester fiber and has weather resistance and flame retardancy.

Claims (2)

[Claims] 1. A composition comprising polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate or a polyester comprising a copolymer or blend of a phosphorus compound in an amount of 5300 to 7200 ppm of a phosphorus atom and containing 1 to 10% by weight of a polyarylate. A weather-resistant, flame-retardant polyester fiber comprising: 2. A composition comprising polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate or a polyester comprising a copolymer or blend of a phosphorus compound in an amount of 5300 to 7200 ppm of a phosphorus atom and containing 1 to 10% by weight of a polyarylate. Is a sheath component, and has a sheath-core structure in which polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate constitutes a core component.