JPH07268191A - Flame-retardant polyester resin composition - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a molding material which is excellent in mold releasability at the time of molding and suppresses the bleed-out phenomenon and has good moisture resistance. [Structure] 100 parts by weight of thermoplastic polyester,
Halogen compound 3 to 50 parts by weight, antimony compound 1 to
A flame-retardant polyester resin composition comprising 30 parts by weight and 0.01 to 10 parts by weight of beeswax.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant thermoplastic polyester resin composition. Specifically, it has excellent releasability,
In addition, the present invention relates to a resin composition in which bleeding out of a flame retardant on the surface of a molded article is suppressed and mechanical strength and wet heat resistance are improved.

[0002]

BACKGROUND OF THE INVENTION Thermoplastic polyester resins, such as polyethylene terephthalate, have mechanical, electrical,
It has excellent physical properties, chemical resistance, dimensional stability, etc. and is widely used for electrical / electronic parts, mechanical parts, automobile parts, etc. However, the thermoplastic resin is a flammable polymer as it is, and is not suitable for applications requiring flame retardancy.

However, particularly in the fields of electricity and electronics, there is an increasing demand for safety against fires, and it has become necessary to make the resins used flame-retardant.

[0004]

It is known to add various flame retardants in order to make a resin flame-retardant. As such a flame retardant, a halogen compound or a combination thereof with a certain metal compound such as antimony trioxide is typically known. In addition, for molded products such as electric and electronic parts, the demand for moisture resistance is increasing year by year. In response to such demand, attempts have been made to improve the terminal functional group of the material polymer, and in general, bisphenol is generally used. It is known that the moisture resistance is improved by adding an A-type epoxy resin, a silane coupling agent and the like.

However, in the case of blending these organic compounds, the compound bleeds out on the surface of the molded product, so that the compound tends to adhere to the mold and the releasability tends to deteriorate, and the surface of the molded product tends to decrease. There is a problem that the appearance remarkably deteriorates.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have found that a flame-retardant heat having excellent releasability at the time of molding, suppressing the bleed-out phenomenon of a flame retardant, etc., and improving the mechanical strength and the resistance to moist heat. As a result of intensive studies to provide a plastic polyester resin composition, by adding beeswax together with a flame retardant,
The inventors have found that such an object can be achieved and arrived at the present invention.

That is, the gist of the present invention is to add 3 to 50 parts by weight of a halogen compound, 1 to 30 parts by weight of an antimony compound, and 0.01 to 0.01 parts of beeswax to 100 parts by weight of a thermoplastic polyester.
A flame-retardant polyester resin composition comprising 10 parts by weight. Hereinafter, the present invention will be described in detail.

The thermoplastic polyester resin used in the present invention includes terephthalic acid or its esters, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol and cyclohexanediene. Terephthalic acid type thermoplastic polyester obtained from glycols such as methanol, hydroquinone, bisphenol A, 2,2-bis (4-hydroxyethoxyphenyl) propane, 1,4-dimethyloltetrabromobenzene or TBA-EO Resins are preferred.

Of these, polyethylene terephthalate and polybutylene terephthalate are preferable, and polybutylene terephthalate is most preferable. Furthermore, in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (weight ratio 5: 5), one having an intrinsic viscosity [η] measured at 30 ° C. of 0.6 to 1.5 dl / g , Mechanical strength, fluidity during melting, short shot of molded products,
Excellent in terms of surface gloss.

Examples of the halogen compound used in the present invention include halogenated epoxy resin, halogenated phenoxy resin, halogenated polycarbonate resin, halogenated polystyrene resin, halogenated polyphenylene oxide resin, halogenated polyester resin and the like. A halogenated epoxy resin is preferable, and a halogenated epoxy resin having an epoxy equivalent of 1,000 to 30,000, preferably 2,000 to 20,000 is preferable. Further, bromine is most preferable as the halogen, and a brominated epoxy resin, particularly an epoxy equivalent of 1000 to 300
A brominated epoxy resin of 00, preferably 2000 to 20000 is good.

The halogen compound is added in an amount of 3 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin. Within this range, a sufficient flame retardant effect can be obtained, and the mechanical strength is less likely to decrease. Examples of the antimony compound used in the present invention include antimony trioxide, antimony tetraoxide,
Examples thereof include antimony pentoxide, alkali metal oxides thereof, alkaline earth metal oxides, sodium pyroantimonate, and the like, of which antimony trioxide and antimony pentoxide are preferable. It is also preferable to use antimony trioxide and antimony pentoxide together.

The amount of antimony compound used is preferably in the range of 1 to 30 parts by weight, more preferably 2 to 20 parts by weight. When the amount used is in this range, the flame retardant effect is high, and the mechanical strength of the composition is not significantly reduced. Furthermore,
When antimony pentoxide is used, one containing at least one selected from alkali metal oxides and alkaline earth metal oxides in an amount of 0.2 to 1.5 mol per mol of antimony pentoxide is more preferable. preferable. Examples of such metal oxides include Na ₂ O.

The present invention is characterized by blending beeswax in addition to the above-mentioned flame retardant. Beeswax is known as a release agent, but when used in combination with a flame retardant, it is possible to unexpectedly suppress bleed-out of the flame retardant and obtain a molded product having a good surface appearance. Such an effect is obtained by using other commonly used release agents, for example, butyl stearate, stearic acid monoglyceride, stearic acid sorbitan ester and other aliphatic ester type release agents, and polyolefin wax type release agents such as polyethylene wax. Not available when using.

The amount of beeswax used is preferably 0.0
It is in the range of 1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. Within this range, the effect of lowering the mechanical strength of the composition and suppressing the bleed-out of the components to the surface is high.
In addition to the above-mentioned components, a hindered phenol-based stabilizer may be used in the composition of the present invention. The amount used is preferably 0.1 to 10 parts by weight, more preferably 0.1. Is in the range of 5 parts by weight. Within this range, sufficient thermal stability is obtained, and the mechanical strength of the composition is not significantly reduced.

As the hindered phenol heat stabilizer, N, N-hexamethylene bis (3,5-di-ter) is used.
t-butyl-4-hydroxy-hydrocinnamamide),
3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diester), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-) Hydroxybenzyl) benzene, 1,6-hexanediol-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythrityl-tetra-kis (3- (3,5- The-
tert-butyl-4-hydroxyphenyl) propionate), tris- (3,5-di-tert-butyl-
4-hydroxybenzyl) -isocyanurate and the like can be mentioned.

Among these, pentaerythrityl-tetra-
Kiss (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and Tris-
(3,5-Di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like are preferable. Further, the composition of the present invention may be reinforced by adding various fillers. As the reinforcing filler, known and conventional ones can be used, but typical ones are glass fiber, carbon fiber, potassium titanate fiber, metal fiber, ceramic fiber, aramid fiber, PPS fiber, calcium carbonate, calcium silicate. , Magnesium silicate, calcium sulfate, barium sulfate, iron oxide, graphite, carbon black, mica,
Examples include asbestos, ceramic powder, metal flakes and glass beads.

Further, these reinforcing materials are preferably surface-treated with a silane coupling agent, a titanium coupling agent, or the like. For example, an aminosilane system such as γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyldimethoxymethylsilane and the like;
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane and other epoxysilanes; and titanium coupling agents such as isopropyltrisstearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, and tetraisopropylbis (dioctylphosphite) titanate.

Further, in the composition of the present invention, as other additives, a crystal nucleating agent, a pigment, a dye, a plasticizer, a lubricant, a heat resistance stabilizer, an antioxidant, an ultraviolet absorber, a foaming agent, an antistatic agent. ,
Alternatively, a coupling agent or the like may be used, or another flame retardant may be used in combination. The method for producing the composition of the present invention is not particularly limited, but is preferably a single-screw or multi-screw extruder at a temperature equal to or higher than the melting point of the thermoplastic polyester resin after uniformly mixing the components of the composition. Is melt-kneaded by using, and then cut with a cutter to be used as pellets. The obtained pellets can be subjected to molding by any known method such as generally known injection molding and extrusion molding.

Such a composition of the present invention is not only excellent in flame retardancy and releasability, but also has a very good surface appearance of a molded article and is also excellent in hydrolysis resistance. Therefore,
It has an extremely high industrial value and can be used for molding applications such as mechanical and mechanical parts, electric and electronic parts, and automobile parts.

[0020]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples without departing from the gist thereof. Example 1 and Comparative Examples 1 to 3 [η] was added to 100 parts by weight of a polybutylene terephthalate (hereinafter abbreviated as PBT) resin having 0.85 dl / g.
Various halogen compounds shown in Table 1, antimony compounds,
Beeswax and glass fiber are pre-mixed uniformly and then 250
After kneading with a 35 mmφ twin-screw extruder set to ° C, it was drawn out as a strand and cooled. Then, it cut with a cutter and the resin pellet was obtained.

From the pellets, using an injection molding machine, a strip type test piece having a thickness of 1/32 inch and a dumbbell No. 1 test for a tensile test having a thickness of 3.2 mm at a molding temperature of 250 ° C. and a mold temperature of 100 ° C. Created a piece. Here, the injection molding machine is Nestal SG-75 manufactured by Sumitomo Heavy Industries Ltd., and the mold is a 100 mm × 100 mm × 1 mmt flat plate, and the mold stains due to the flame-retardant or the like coming out of the mold are visually observed. The effect of suppressing bleedout was evaluated by observation. The judgment criteria are as follows.

◯: There is almost no mold stain even after molding several times, and the appearance of the molded product is good. Δ: Staining of the mold is not observed at the beginning of molding, but stains of the mold become visible within several moldings. X: Staining of the mold was observed from the beginning of molding, and the appearance of the molded product was also poor.

The flame retardancy was measured according to the fire test of UL-94 standard. AST for tensile strength
It measured according to MD-638. Regarding the moist-heat resistance test, after performing a treatment at 120 ° C. × 2 atm for 100 hours, a tensile test was performed according to ASTM-D-638 and measurement was performed. The results are shown in Table 1. All blending amounts in the table are parts by weight unless otherwise specified.

[0024]

[Table 1] * 1) Brominated bisphenol A type epoxy resin: Epoxy equivalent = 2500 * 2) Brominated bisphenol A type epoxy resin: Epoxy equivalent = 10000 * 3) Antimony pentoxide flame retardant (Sb ₂ O ₅ : Na
₂ O: H ₂ O = 84.2: 116: 4.0, Sb ₂ O ₅ / N
a ₂ O (molar ratio) = 0.73) * 4) Polyethylene wax: trade name HW-410P
(Mitsui Petrochemical Co., Ltd.) * 5) Beeswax: Product name Golden Brand Powder (Noda Wax Co., Ltd.) * 6) Chopped strands

[0025]

INDUSTRIAL APPLICABILITY The composition of the present invention is used in various molded articles as a molding material having excellent releasability at the time of molding and suppressing the bleed-out phenomenon and having good moisture resistance.

Claims (2)

[Claims] (1) A thermoplastic compound comprising 100 parts by weight of a halogen compound (3 to 50 parts by weight), an antimony compound (1 to 30 parts by weight), and beeswax (0.01 to 10 parts by weight). Flammable polyester resin composition. 2. A halogen compound having an epoxy equivalent of 1000.
The flame-retardant polyester resin composition according to claim 1, which is a halogenated bisphenol A type epoxy resin of -30000.