JP3164175B2 - Polyester resin composition - 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 resin composition, more particularly to a flame-retardant resin composition having excellent tracking resistance, and is used as an insulator for electric parts.

[0002]

2. Description of the Related Art Conventionally, thermoplastic polyester resins have been
Because of its good electrical and mechanical properties, it is widely used for electrical components. However, the tracking resistance, which is the insulation durability when the surface is contaminated, is not sufficient. When the flame retardant is used, the degree of the reduction depends on the type of the flame retardant, but it further decreases. There are limitations in applications where resistance is required. Attempts have also been made to blend thermoplastic polyester resins flame-retarded with widely used halogen-based flame retardants with polypropylene resins having high tracking resistance, but improvements have been made. Could not be obtained. Further, as a result of diligent studies, the use of a specific compatibilizing agent significantly improved the dispersion, but the tracking resistance was slightly improved and did not improve as expected. Also, there has been a demand for the development of a flame-retardant thermoplastic polyester having excellent tracking resistance as well as other electrical properties for heat-resistant electrical components whose surfaces are contaminated, such as automotive distributors and factory switch components.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to develop a flame-retardant thermoplastic polyester resin composition having excellent trackability as a forming material for parts used for electrical insulation and the like. It was done.

[0004]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, blended a specific amount of a polypropylene resin and red phosphorus with a thermoplastic polyester resin. The present inventors have found that a flame-retardant thermoplastic polyester resin composition having excellent tracking resistance can be obtained by adding a rubber or a reinforcing material, and completed the present invention. That is, the present invention relates to Thermoplastic polyester resin 10
0 parts by weight; B. 1 to less than 80 parts by weight of a polypropylene resin and / or a modified polypropylene resin;
1 to 50 parts by weight of red phosphorus, 0 to 150 parts by weight of an inorganic reinforcing material, A thermoplastic polyester resin composition comprising 0 to 15 parts by weight of a compatibilizer between a polyester resin and a polypropylene resin.

The thermoplastic polyester resin as the component A used in the present invention contains at least one selected from terephthalic acid, isophthalic acid, naphthalene 1,4 or 2,6 dicarboxylic acid, adipic acid and the like as an acid component. , As glycol components ethylene glycol, butylene glycol, propylene glycol, diethylene glycol,
It is a thermoplastic polyester resin or a thermoplastic copolymer polyester resin comprising at least one selected from neopentyl glycol, cyclohexane dimethanol, polyethylene glycol, polytetramethylene glycol, and the like. Preferably, a thermoplastic polyester resin comprising 80 mol% or more of ethylene terephthalate or butylene terephthalate repeating unit or a combination thereof is used. The thermoplastic polyester resin used in the present invention has an intrinsic viscosity of 0.4 or more measured at 30 ° C. in a phenol / tetrachloroethane mixed solvent (6/4 weight ratio), and is 0.5 or more. The above is preferred.

The polypropylene resin and / or the modified polypropylene resin as the component B used in the present invention may be any of isotactic and atactic, but isotactic is preferred. In addition to the homopolymer, a propylene component of 8
A random or block copolymer with another olefin containing 0 mol% or more can also be used. Polypropylene resin is ASTM D-1238-62T (230 ° C.
2160 g) has a melt flow rate of 0.1 to 150 g / 10 min. Are preferred, especially 0.5 to 7
5 g / 10 min. Is preferred. In the present invention, a modified polypropylene resin is also used. Preferred modifications include epoxy modification, carboxylic acid or carboxylic anhydride modification, and imino ether modification, and are performed by copolymerization or graft modification with an organic peroxide. As a denaturing agent,
A monomer having these functional groups and an unsaturated bond, or a monomer having these functional groups and a hydrocarbon group activated by a radical is used. More specifically, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, 2,2′-methylenebis (2 -Oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline) and the like. Can be. When these modified polypropylene resins are used in the present invention, the compatibility between the polyester resin and the polypropylene resin is good, so that it is not necessary to use a compatibilizer in particular.

In the present invention, red phosphorus as the component C is added in an amount of 1 to 100 parts by weight of the thermoplastic polyester resin.
５０50 parts by weight. If it is less than 1 part by weight, the flame retardancy is insufficient, and if it exceeds 50 parts by weight, the physical properties are undesirably deteriorated. Note that red phosphorus is mixed with a resin or made into a master from the viewpoint of handling. In the present invention, phenolic resin, red phosphorus coated with epoxy resin or polyester resin, polyphenylene sulfide resin, thermoplastic polyester resin, polyamide resin,
Red phosphorus mastered with a polyolefin resin, an acrylonitrile-styrene copolymer, a polystyrene copolymer or the like is preferable.

The compatibilizing agent for the thermoplastic polyester resin and the polypropylene resin, which are the E component, which is used as required in the present invention, includes a monomer having an affinity or reactivity with the thermoplastic polyester resin and an affinity with the polypropylene resin. A block copolymer or a graft copolymer with a monomer having the following is preferred. More specifically, olefin-glycidyl methacrylate copolymer or graft copolymer, methyl methacrylate graft copolymer of olefin-glycidyl methacrylate copolymer, acrylonitrile-styrene graft copolymer of olefin-glycidyl methacrylate copolymer , Anhydride or acid-modified polyolefin. Among them, olefins
A methyl methacrylate graft copolymer of a glycidyl methacrylate copolymer is particularly preferred.

In the present invention, examples of the inorganic reinforcing material which is a D component optionally added include fiber reinforcing materials such as glass fibers and carbon fibers, whiskers such as potassium titanate and gypsum fibers, talc, clay and wollastonite. , Montmorillonite, mica, bentonite, and calcium carbonate. Glass fiber, talc and wollastonite are particularly preferable, and two or more kinds are often used in combination. The blending amount of the inorganic reinforcing material is selected depending on the required performance regarding dimensions, heat resistance and strength rigidity, but is 1 to 100 parts by weight of the thermoplastic polyester resin.
If the amount exceeds 50 parts by weight, the moldability deteriorates and the appearance of the molded product deteriorates, which is not preferable.

[0010] The method for obtaining the composition of the present invention is not particularly limited, and may be carried out by any method. For example, after pre-mixing all components, a method of kneading in an extruder or a kneader, or a pellet obtained by previously kneading and mixing an arbitrary number of components in an extruder or a kneader, further kneading and mixing other components. Method and the like.

The composition of the present invention may further contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a lubricant, an antistatic agent, a release agent and a colorant, depending on the purpose and application. Further, the composition of the present invention does not require a special molding method or molding conditions, and can be molded under ordinary thermoplastic polyester molding conditions, in addition to various molded articles, tubular articles, containers,
Used in plate form.

[0012]

[Action] It is still clear why a certain amount of red phosphorus is added to a polymer alloy of thermoplastic polyester resin and polypropylene resin to obtain a flame-retardant resin with excellent tracking resistance as well as dielectric strength and volume resistivity. However, red phosphorus is an effective flame retardant for both polyester resin and polypropylene resin, and both have good dispersibility, and the benzene ring distance increases due to the fact that the polypropylene resin is finely dispersed in the polyester resin. It is considered as a reason. Ordinary flame-retardant resin promotes carbonization of the surface during combustion to prevent combustion, and often involves combustion under high voltage.Therefore, tracking resistance is greatly reduced by flame retardancy. Because of the generality, compatibility between tracking resistance and flame retardancy was unexpected.

[0013]

The present invention will be specifically described below with reference to examples. The parts and percentages in the examples are on a weight basis,
Each physical property value was measured by the following method. (1) Tracking resistance: IEC pub. According to the 112 standard, a constant voltage is applied to an electrode set at a tip interval of 4 mm so as to form 60 ° with an interval of 4 mm. After measuring, a voltage corresponding to 50 drops was determined and defined as a tracking resistant voltage. The measurement was made for a thickness of 3 m.
m of injection molded articles. (2) Flammability: 12.7 mm width according to UL94 standard
A vertical combustion test was performed on five injection-molded products each having a length of 127 mm and a thickness of 1.6 mm, the first and second after-flame times were measured, and the total time of 10 times was calculated.

Examples 1 to 12 Comparative Examples 1 to 8 Polyethylene terephthalate resin ( EM manufactured by Toyobo Co., Ltd.)
C500-01, hereinafter referred to as PET ), polybutylene terephthalate resin ( Toyobo Co., Ltd. EMC700-01, hereinafter referred to as PBT)
Say), polypropylene resin (Sumitomo Chemical Co., Ltd. Sumitomo No
Bren Y101, hereinafter referred to PP), glycidyl methacrylate 1.5% modified polypropylene resin (Sumitomo Chemical Co.,
Sumitomo Noprene Y101 with 1.5% of methacrylic acid methacrylate and simulmil peroxide
1% by weight modified with kraft , hereinafter referred to as PP-GMA
U), and 0.3% maleic anhydride by Sumitomo Nofu Bu Ren Y101 manufactured maleic 0.3% modified polypropylene resin anhydride (Sumitomo Chemical Co.,
Shi Bu Kumiruha ° Okisaito Bu 0.5 those click Bu raft modified by wt%, or less P
P-MAH ), phenylenebis (2oxazoline) 0.3% modified polypropylene resin ( Sumitomo Chemical Co., Ltd.)
The manufacturing Sumitomo Nofu Bu Ren Y101 phenylene bis (2 Okisaso Bu phosphorus) of 0.3% and shea Bu Kumiruha゜ｰ
Those click Bu raft modified by Oki site Bu 0.5 wt%, or less PP-PB
O ), red phosphorus I (Nova Excel 150 Rin Kagaku Kogyo KK), red phosphorus master II (Nova pellet PE)
T Rin Kagaku Kogyo Co., Ltd.), polyethylene glycidyl methacrylate copolymer methyl methacrylate graft copolymer (PE-GMA-PMMA , Modiper 42)
00 manufactured by NOF Corporation), maleic acid 0.3% modified polyethylene anhydride a (Mitsui Petrochemical Co. Haise Bu box 2100J
Also click Bu raft modified with 0.3% maleic acid and shea Bu Kumiruha ° Okisaito Bu 0.5 wt%
(Hereinafter referred to as PE-MAH ), talc ( Hayashi Kasei Co., Ltd.)
Ltd. Tarkan PK, hereinafter referred to as TA), glass fiber (Asahi file
Iha Bu chromatography click Bu class Co. 486A, hereinafter referred to as GF), montanic acid esters (WAX E), polycarbonate oligomer (Teijin Chemicals of tetrabromobisphenol A (Co.)
Ltd. FG7000, hereinafter referred FG), brominated poly scan switch <br/> Len (FERRO Corporation (USA) Pas Gray check 68PB, less
PB ), antimony trioxide ( Nippon Seiko Steel Co., Ltd.
Tox S (hereinafter referred to as SbO ) was preliminarily mixed at the ratios shown in Tables 1 and 2, and then charged into a hopper of a twin-screw extruder and melt-kneaded at a cylinder temperature of 265 ° C. to obtain compound chips. After drying these compound chips at 140 ° C. for 4 hours, test pieces were molded using an injection molding machine adjusted to 265 ° C., and the flammability and tracking resistance were evaluated. The results are shown in Tables 1 and 2.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

As is clear from Tables 1 and 2, the polyester resin composition of the present invention is a flame-retardant resin having excellent tracking resistance. Accordingly, the molded article obtained from the composition of the present invention has insulation durability even in an environment where the surface is contaminated with electrolyte, and thus is useful for automobile distributor parts and outdoor electric parts. It is great to contribute to.

Claims (1)

(57) [Claims] 1. A. With respect to 100 parts by weight of the thermoplastic polyester resin, B.I. B. 1 to less than 80 parts by weight of a polypropylene resin and / or a modified polypropylene resin; 1 to 50 parts by weight of red phosphorus, 0 to 150 parts by weight of inorganic reinforcing material,
E. FIG. A polyester resin composition comprising 0 to 15 parts by weight of a compatibilizer between a polyester resin and a polypropylene resin.