JP3204325B2 - 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 non-bleed, non-drip, flame-retardant polyester composition, which has good heat resistance and electric characteristics, and therefore has excellent heat resistance and electric properties, and is therefore an insulating material for electric parts and electronic parts, a part for heat appliances, and an electric equipment for automobiles. Widely used for parts.

[0002]

2. Description of the Related Art It is well known that chlorine or bromine flame retardants are effective for making polyester resins flame retardant. Japanese Patent Publication No. 62-37057 discloses that non-bleed, non-drip flame retardant materials are generally preferably high melting point and high molecular weight flame retardants. However, when the melting point of the flame retardant is high or the molecular weight is high, the dispersion of the flame retardant is large, so it is necessary to increase the blending amount to ensure the quality. Not only is it uneconomical. The present invention provides a high-quality and economical polyester resin composition by increasing the dispersibility of a flame retardant by blending a flame retardant with a high dispersibility with a high molecular weight and a special dispersant to a polyester resin. It is intended to be.

[0003]

That is, an object of the present invention is to develop a non-bleed, non-drip flame-retardant composition having high physical properties by increasing the efficiency of a flame retardant and reducing the amount thereof.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have intensively studied to obtain a high quality polyester composition with a relatively small amount of flame retardant by increasing the efficiency by uniformly dispersing a high molecular weight flame retardant. As a result, the present invention has been finally completed. That is, 100 parts by weight of the thermoplastic polyester resin, an inorganic reinforcing material 0 to 120 parts by weight, the oxide 20 parts by weight of antimony, a number average molecular weight of 5000 or less of polyals <br/> sharp glycol derivatives and / or aliphatic polyester Derivative 0.1-20 parts by weight, number average molecular weight 5000
A polyester resin composition comprising 1 to 50 parts by weight of the above brominated phenoxy resin (however,
Excluding the metal sulfonic acid salt represented by the formula (1)) .

Embedded image (In the above general formula (1), R is a group having 6 to 60 carbon atoms.
Machine, m is the number of charges of metal M, n is an integer from 1 to 4, M is gold
Indicates a genus atom. )

The polyester resin used in the present invention includes terephthalic acid, isophthalic acid, naphthalene 1,4 or 2,6 dicarboxylic acid, diphenyl ether 4,4 dicarboxylic acid, adipic acid, sebacic acid and the like as acid components. Among them, polyesters containing terephthalic acid in an amount of 80 mol% or more are preferred from the viewpoints of flame retardancy, heat resistance and moldability. The glycol component is composed of one or more selected from ethylene glycol, butylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol and the like. Of these, ethylene glycol and butylene glycol are particularly preferred. For the purposes of the present invention, polyethylene terephthalate, polybutylene terephthalate or combinations thereof are particularly preferred. The polyester resin used in the present invention has an intrinsic viscosity of 0.4 or more, preferably 0.5 or more, measured at 30 ° C. with a phenol / tetrachloroethane mixed solvent (6/4 weight ratio).

Examples of the inorganic reinforcing material blended in the present invention include fibrous reinforcing materials such as glass fiber and carbon fiber, whiskers such as potassium titanate and gypsum fibers, talc, clay, wollastonite, mica, and pentonite. , Montmorillonite, and calcium carbonate. In particular, glass fiber, talc or walathnite, or a combination of two or more thereof is preferred. The amount of the inorganic reinforcing material is 1 to 100 parts by weight of the polyester resin.
If it exceeds 20 parts by weight, the moldability deteriorates, which is not preferable.

The antimony oxide compounded in the present invention includes antimony trioxide, antimony pentoxide and the like.
It is 1 to 20 parts by weight with respect to 0 parts by weight. If the amount is less than 1 part by weight, it is insufficient as a flame retardant auxiliary, and if it exceeds 20 parts by weight, the strength is undesirably reduced.

Next, polyalkylene glycol derivatives and / or aliphatic polyester derivatives having a number average molecular weight of 5,000 or less to be blended in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyethylene glycol / polypropylene glycol copolymer. , Polylactone, polyethylene adipate, pributylene adipate, and those whose ends are blocked by esterification or etherification, and glycidyl ether or glycidyl esterified derivatives. Of these, polyethylene glycol, polybutylene adipate, and derivatives in which the terminal of polylactone is esterified or glycidyl etherified are particularly preferable. The effect of polyalkylene glycol derivatives and aliphatic polyester derivatives is to increase the dispersibility and distribution of high molecular weight brominated phenoxy resin in polyester resin, and to reduce the required amount of brominated phenoxy resin due to its improved effectiveness. It is presumed that this was made possible.
If the number average molecular weight exceeds 5,000, the effect of increasing the dispersibility of the brominated phenoxy resin is small, and on the contrary, the flame retardancy is rather lowered due to the properties of the resin, which is not preferable. If the amount is more than 20 parts by weight based on 100 parts by weight of the polyester resin, the strength and heat resistance are undesirably reduced.

Further, the brominated phenoxy resin blended in the present invention includes tetrabromobisphenol A
And a polyhydroxyether having a number average molecular weight of 5,000 or more, which is obtained by a reaction between the compound and epichlorohydrin. If the molecular weight is less than this, bleeding occurs on the surface of the molded article during use, which is not preferable. Also, when the number average molecular weight increases, dispersibility and dispersibility in the polyester resin tend to decrease,
According to the present invention, even if the number average molecular weight is 5,000 or more, the number average molecular weight remains 5 μm or less, the effect of imparting flame retardancy is enhanced, and 1 to 50 parts by weight is blended with 100 parts by weight of the polyester resin to meet the demand for non-bleed. Thus, a non-drip type flame-retardant molding material can be obtained. The molecular weight of the brominated phenoxy resin is particularly preferably from 30,000 to 100,000.

The polyester resin 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 according to the purpose and use. preferable.

The method for producing the polyester resin composition of the present invention is not particularly limited, and any method can be used. For example, after all components are premixed, a method of kneading in an extruder or a kneader, or a pellet obtained by previously kneading and mixing arbitrary or several components in an extruder or a kneader, and further melt-mixing other components. The method etc. can be raised. 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 products, it is used in the form of a tube, container, or plate. You.

[0012]

The present invention will be described below in detail with reference to examples. Parts and% in the examples are on a weight basis. The evaluation of the flame retardancy was performed on a 1.6 mm thick test piece by UL.
The flame retardancy and drip properties were determined according to the VO grade pass / fail criteria of the vertical combustion test shown in No. 94. The test piece was treated at 120 ° C. for 200 hours to observe the bleeding property.

Examples 1 to 14 Comparative Examples 1 to 6 Polyethylene terephthalate resin ( manufactured by Toyobo Co., Ltd.)
VILOPET EMC500-01 or below, referred to as PET), polybutylene terephthalate resin ( manufactured by Toyobo Co., Ltd.,
Loppet EMC700-01 or below, referred to as PBT), polyethylene glycol dibenzoate ( manufactured by Sanyo Chemical Co., Ltd.)
Hereinafter, it is referred to as PEGDBA. Molecular weight 610, 2021
0), polyethylene glycol diglycidyl ether ( manufactured by Nagase Kasei Kogyo Co., Ltd., hereinafter referred to as PEGDGE) (molecular weight 514), and polylactone diglycidyl ether ( manufactured by Nagase Kasei Kogyo Co., Ltd., hereinafter referred to as PLDGE) (molecular weight: 1114) And polybutylene adipate dibenzoate ( manufactured by Toyobo Co., Ltd., hereinafter referred to as PBADGE) (molecular weight: 1114), glass fiber (Asahi Glass Co., Ltd.)
Made, Asahi fiber glass, 3mm cut , Talc (Hayashi
Chemical Micron White # 5000) , antimony trioxide, antimony pentoxide, brominated phenoxy resin ( Toto Kasei Co., Ltd., molecular weight 3000, 20,000, 6 )
0000) was preliminarily mixed at the ratio shown in Table 1, and then charged into a hopper of a twin- screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) , and melt-kneaded at a cylinder temperature of 265 ° C. to obtain a compound chip. The compound chip was dried at 140 ° C. for 4 hours, and then 127 × by an injection molding machine (Nissei Plastic Industries FS75) adjusted to a cylinder temperature of 265 ° C.
A 12.7 × 1.6 mm test piece was molded and evaluated for flame retardancy by the above method. The results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

[0014]

As is clear from Tables 1 and 2, the total burning time of the composition of the present invention is as long as 11 seconds at most, and no drip, cotton ignition and bleed are confirmed at all. Is very good. In other words, the composition of the present invention is non-drip, non-bleed, and has good heat resistance and electric characteristics, and is therefore widely used for insulating materials for electric parts and electronic parts, parts for heating appliances, electric parts for automobiles, and the like. It is a great contribution to the world.

Claims (1)

(57) [Claims] To 1. A 100 parts by weight of the thermoplastic polyester resin, an inorganic reinforcing material 0 to 120 parts by weight, the oxide 20 parts by weight of antimony, a number average molecular weight of 5000 or less of polyals <br/> sharp glycol derivatives and / Or 0.1 to 20 parts by weight of an aliphatic polyester derivative, number average molecular weight of 5,000
A polyester resin composition comprising 1 to 50 parts by weight of the above brominated phenoxy resin (however,
(It does not contain the metal sulfonic acid salt represented by the formula (1)) . Embedded image (In the above general formula (1), R is a group having 6 to 60 carbon atoms.
Machine, m is the number of charges of metal M, n is an integer from 1 to 4, M is gold
Indicates a genus atom. )