JPH05311053A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyester resin composition having stable qualities for long-term use at any temperature. CONSTITUTION:The composition is prepared by mixing 0.1-5.0 pts.wt. bisoxazoline compound with a total of 100 pts.wt. resin composition comprising 50-98 pts.wt. aromatic saturated polyester, 1-25 pts.wt. butadiene elastomer and 1-25 pts.wt. polyolefin.

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 which has excellent mechanical properties such as molding appearance, impact strength and toughness and has improved long-term heat stability and high temperature heat resistance. ..

[0002]

2. Description of the Related Art Aromatic polyesters represented by polyethylene terephthalate (hereinafter referred to as PET) and polybutylene terephthalate (hereinafter referred to as PBT) have hitherto been used in a wide range of fields such as electric and electronic device parts and automobile parts due to their excellent properties. It is used. However, with the expansion and diversification of applications, it is often necessary for the resin to have higher performance and peculiarities. One of these properties is heat stability, especially at high or low temperatures. Increasingly, there is a demand for quality stability for long-term use. For example, in the automobile industry, due to safety requirements, it has excellent mechanical properties at low temperatures, especially toughness such as flexibility and impact resistance, and its physical properties are retained even during long-term use at high temperatures. Is required.

[0003]

In order to meet the above requirements, thermoplastic polyester resins have conventionally been blended with thermoplastic elastomers such as polycarbonate or olefin polymers, rubber-like polymers, and epoxy resins,
A method of using polycarbodiimide and the like in combination has been proposed. However, the polyester resin containing such an elastomer and an additive has mechanical properties improved to some extent, but has a surface peeling phenomenon due to poor compatibility, and also has a decrease in physical properties in high temperature long-term use, Due to the problem of thermal discoloration, its use is limited to some extent. Therefore, in order to solve the above-mentioned drawbacks, various compounding agents have been proposed. For example, a method of adding an elastomer obtained by graft-modifying a thermoplastic elastomer such as an olefin polymer or a rubber-like polymer with an unsaturated carboxylic acid or a derivative thereof has been proposed. Although somewhat improved by these methods, for example, flexibility, toughness such as impact resistance, heat resistance stability required for connectors of automobiles, electrical equipment, etc.
It is not sufficient to meet the requirements for high temperature and long-term physical properties, and there is a strong demand for its solution.

[0004]

[Means for Solving the Problem] As a result of intensive research and study for solving the above problems, the present inventors finally completed the present invention. That is, the present invention relates to (A) 50 to 98 parts by weight of an aromatic saturated polyester, (B) 1 to 25 parts by weight of a butadiene-based elastic body, and (C) a polyolefin 1-2.
The polyester resin composition is characterized in that 0.1 to 5.0 parts by weight of the (D) bisoxazoline compound is added to 100 parts by weight in total of 5 parts by weight.

The polyester resin as the component (A) in the present invention is polyethylene terephthalate or a copolymerized polyester containing at least 80% or more, preferably 90% or more ethylene terephthalate repeating units,
A conventionally known dicarboxylic acid component, glycol component and / or oxycarboxylic acid component can be used as the copolymerization component. That is, examples of the copolymerization component include acid components such as isophthalic acid, naphthalene 1,4- or 2,6-dicarboxylic acid, diphenyl ether 4,4′-dicarboxylic acid, adipic acid and sebacic acid, propylene glycol, and ptyrene. Glycol, diethylene glycol,
Examples thereof include glycol components such as neopentyl glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, oxycarboxylic acids such as P-oxybenzoic acid and P-hydroxyethoxybenzoic acid. The polyester was mixed with phenol / tetrachloroethane mixed solvent (6/4 weight ratio) at 30 ° C.
It is preferable that the intrinsic viscosity measured by the method of 0.5 is 0.5 or more, further preferably 0.55 or more.

Next, the butadiene type elastic copolymer which is the component (B) in the present invention is one kind selected from methacrylic acid ester, acrylic acid ester and aromatic vinyl compound in the presence of a rubber containing butadiene. It is obtained by copolymerizing the above monomers. Examples of the rubber containing butadiene include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic acid ester copolymer and the like. As the methacrylic acid ester and the acrylic acid ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate,
Examples thereof include octyl acrylate. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like. These elastic copolymers may be produced by any of soul-like polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and the copolymerization method may be either single-stage grafting or multi-stage grafting. Further, it may be a mixture with a copolymer containing only a graft component produced as a by-product during the production, or a mixture of two or more kinds of elastic copolymers.

Commercially available components (B) include Metaprene-C-100 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), Metaprene-C-202 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), Kane Ace B-12 (trade name, manufactured by Kanebuchi Chemical Co., Ltd.), Kane Ace B-22 (trade name, manufactured by Kanefuchi Chemical Co., Ltd.), BTA (trade name, Kureha Chemical Industry Co., Ltd.)
Manufactured), HIA (trade name, manufactured by Kureha Chemical Industry Co., Ltd.), HN
(Trade name, manufactured by Kureha Chemical Industry Co., Ltd.) and the like.

The polyolefin as the component (C) in the present invention is a homopolymer of α-olefin, a copolymer of α-olefins, and a copolymer with another monomer copolymerizable with α-olefin. In any case, the copolymer may be a random copolymer, a block copolymer, or a graft copolymer. Specific examples of α-olefins include ethylene, propylene, butene-1, isobutylene, pentene-1, hexene-1, heptene-1 and the like, among other monomers copolymerizable with α-olefins. Specific examples include glycidyl acrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid, acrylic acid amide, acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinylidene chloride, vinyl acetate,
Examples thereof include tetrafluoroethylene and difluoroethylene. Preferred examples of the polyolefin (C) include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / glycidyl methacrylate copolymer, and ethylene / ethyl acrylate copolymer, and particularly preferred examples are ethylene / ethyl. An acrylate copolymer can be mentioned.

The bisoxazoline compound which is the component (D) used in the present invention is represented by the following general formula (I), and specific examples thereof include 2,2'-methylenebis (2-
Oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-)
Oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octa Methylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylene Bis (4,4-dimethyl-2-oxazoline), 2,2 '
-P-phenylenebis (4-phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2)
-Oxazoline), 2,2'-m-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'-
m-phenylenebis (4-phenyl-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-phenylbis (4-methyl-2-oxazoline), 2,2 ' -Bis (2-oxazoline),
2,2'-bis (4-methyl-2-oxazoline),
2,2'-bis (4-methyl-2-oxazoline),
2,2'-bis (4-phenyl-2-oxazoline) and the like can be mentioned. Such bisoxazoline compounds may be used alone or in combination of two or more kinds.

[0010]

[Chemical 1] (In the formula, R represents a divalent organic group, and the hydrogen atom may be substituted with an alkyl group or an aryl group.)

In the present invention, the blending amount of each of the above components is 50 to 98 parts by weight, preferably 70 to 95 parts by weight of the component (A) based on 100 parts by weight of the total of (A) to (C).
Parts by weight, 1 to 25 parts by weight of component (B), preferably 3 to
15 parts by weight, 1 to 25 parts by weight of the component (C), preferably 3 to 15 parts by weight. Bisoxazoline compound (D)
Is 0.1 to 5.0 parts by weight, preferably 0.3 to 5.0 parts by weight, based on 100 parts by weight of the components (A) to (C).
2.0 parts by weight. If this amount is too small, the effect will not be exhibited, and if it is too large, the viscosity will extremely rise, and adverse effects such as discoloration during long-term use will occur.

In the composition of the present invention, fibrous and granular fillers and reinforcing agents (for example, glass fiber, carbon fiber, metal fiber, potassium whisker titanate, glass beads, glass, etc.) are used within a range not impairing the object of the present invention. flake,
Mica, asbestos, clay, talc, wollastonite, montmorillonite, sericite, barium sulfate, calcium carbonate, etc.), antioxidants, heat stabilizers, UV absorbers, lubricants, release agents, colorants including dyes and pigments, One or more conventional additives such as nucleating agents can be added.

Particularly in electric appliances, automobiles and the like, flame retardancy is often required depending on the use environment, and it is often essential to mix a flame retardant and a flame retardant aid. As the flame retardant, known halogen-containing compound flame retardants such as brominated polycarbonate, brominated epoxy compound, brominated diphenyl, brominated diphenyl ether can be used. Also,
As the flame retardant aid, an antimony compound such as antimony trioxide or antimony halide, a metal compound containing zinc or bismuth, a clay silicate such as magnesium hydroxide or asbestos, and the like can be used.

The method for producing the resin composition of the present invention is not particularly limited, and a commonly known method can be used. From an industrial point of view, each component is generally a tumbler,
Examples thereof include a method of dry blending with a blender and a Nauta mixer and the like, followed by a method of kneading and kneading and extruding, and a method of kneading with an extruder equipped with an automatic weighing feeder. In any case, the conditions and equipment may be selected so that the respective components are sufficiently dispersed and mixed.

[0015]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The flexural property values of the compositions obtained in the respective examples were measured according to ASTM D-790.

Examples 1 to 4 Comparative Examples 1 to 3 (A) Polyethylene terephthalate, (B) Butanediene elastomer, (C) Polyolefin, and (D) Bisoxazoline compound were blended in the blending ratios shown in Table 1 respectively. And dry blended, then vented extruder (30 mmφ, L / D = 25, cylinder temperature: 265
(° C) was melt-extruded into pellets. The pellets were dried at 145 ° C. for 5 hours or more with a hot air dryer, and a test piece for measuring physical properties was molded with an injection molding machine, and each physical property value was measured. The results are shown in Table 1. The molding conditions of the test piece are as follows: cylinder temperature: 260 ° C., injection pressure: 50 kg / cm.
² (gauge), mold temperature: 80 ° C., molding cycle: injection 15 seconds cooling 15 seconds.

[0017]

[Table 1] In Table 1, (A) PET: Toyobo Co., Ltd. RE530 (intrinsic viscosity 0.62) (B) Butanediene-based elastic body: Kureha Chemical Co., Ltd. HIA
-28 (C) Polyolefin: Nippon Unicar Co., Ltd. EEA (M
B-870) (Ethylene / ethyl acrylate copolymer) (D) Oxazoline compound: Takeda Yakuhin Co., Ltd. 1.3PB
O (2,2 '-(1,3 phenylene) -bis (2-oxazoline) * 1): measuring temperature 23 ° C * 2): after heating at 150 ° C for 500 hours, measuring temperature 23 ° C

[0018]

As is apparent from Table 1, the composition of the present invention obtained by blending PET with a butanediene elastomer, a polyolefin and a bisoxazoline compound is a PET resin containing a conventional impact modifier and the like. Compared to the composition,
It can be seen that it is possible to obtain a molded product having good heat stability and long-term high-temperature quality without impairing the mechanical properties and moldability. Therefore, according to the present invention, the range of application thereof is widened, and the present invention can be suitably used for, for example, connectors, switches, relays, etc., which greatly contributes to the industrial world.

Claims (1)

[Claims] 1. (A) Aromatic saturated polyester 50 to 98
100 parts by weight, 1 to 25 parts by weight of (B) butadiene-based elastic material, and 1 to 25 parts by weight of (C) polyolefin.
(D) Bisoxazoline compound 0.1 to 0.1 part by weight
A polyester resin composition comprising 5.0 parts by weight.