JP3226052B2 - 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 which is excellent in mechanical properties such as molded appearance, impact strength and toughness, and has improved long-term heat stability and high-temperature heat resistance. .

[0002]

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

[0003]

In order to meet the above demand, a thermoplastic polyester resin is blended with a thermoplastic elastomer such as a polycarbonate or an olefin-based polymer or a rubber-like polymer.
A method using polycarboimide and the like in combination has been proposed. However, polyester resins in which such elastomers, additives, etc. are blended, although the mechanical properties are improved to some extent, there are surface peeling phenomena due to poor compatibility, and the physical properties decrease in long-term use at high temperatures, Due to the problem of thermal discoloration, its use is rather limited. Then, in order to solve the above-mentioned drawbacks, various compounding agents have been proposed. For example, there has been proposed a method of adding an elastomer obtained by graft-modifying a thermoplastic elastomer such as an olefin-based polymer or a rubber-like polymer with an unsaturated carboxylic acid or a derivative thereof. Although somewhat improved by these methods, for example, flexibility required for connectors of automobiles, electrical equipment, etc., toughness such as impact resistance, heat stability,
It is not yet sufficient for the required performance in terms of high-temperature long-term physical properties and the like, and there is an urgent need for a solution.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies and studies to solve the above-mentioned problems, and as a result, have finally completed the present invention. That is, the present invention relates to a total of 100 parts by weight of (A) 50 to 98 parts by weight of an aromatic saturated polyester, (B) 1 to 25 parts by weight of a butadiene-based elastic material, and (C) 1 to 25 parts by weight of an unmodified polyolefin. , (D) 0.1 to 5.0 parts by weight of a bisoxazoline compound.

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,
As the copolymerization component, a conventionally known dicarboxylic acid component, glycol component and / or oxycarboxylic acid component can be used. 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, sebacic acid, propylene glycol, and butylene Glycol, diethylene glycol,
Examples include glycol components such as neopentyl glycol, cyclohexanedimethanol, and 2,2-bis (4-hydroxyphenyl) propane, and oxycarboxylic acids such as P-oxybenzoic acid and P-hydroxyethoxybenzoic acid. In addition, polyester is 30 degreeC with a phenol / tetrachloroethane mixed solvent (6/4 weight ratio).
Is preferably 0.5 or more, more preferably 0.55 or more.

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

[0007] Components (B) which are commercially available 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 Kanegafuchi Chemical Co., Ltd.), Kane Ace B-22 (trade name, manufactured by Kanebuchi Chemical Co., Ltd.), BTA (trade name, Kureha Chemical Industry Co., Ltd.)
HIA (trade name, manufactured by Kureha Chemical Industry Co., Ltd.), HN
(Trade name, manufactured by Kureha Chemical Industry Co., Ltd.).

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

The bisoxazoline compound (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.

[0010]

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

In the present invention, the amount of the component (A) is 50 to 98 parts by weight, preferably 70 to 95 parts by weight 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, component (C) is 1 to 25 parts by weight, preferably 3 to 15 parts by weight. Bisoxazoline compound (D)
Is from 0.1 to 5.0 parts by weight, preferably from 0.3 to 5.0 parts by weight, based on 100 parts by weight of the total of components (A) to (C).
2.0 parts by weight. If the amount is too small, no effect will be exhibited, and if it is too large, the viscosity will extremely increase and adverse effects such as discoloration will occur during long-term use.

In the composition of the present invention, fibrous and granular fillers and reinforcing agents (for example, glass fiber, carbon fiber, metal fiber, potassium whisker, glass beads, glass beads, etc.) as long as the object of the present invention is not impaired. flake,
Colorants including mica, asbestos, clay, talc, wallastenite, montmorillonite, sericite, barium sulfate, calcium carbonate), antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, dyes and pigments, One or more conventional additives such as a nucleating agent can be added.

In particular, electrical equipment, automobiles, and the like often require flame retardancy depending on the use environment, and it is often necessary to blend a flame retardant and a flame retardant auxiliary. As the flame retardant, known halogen-containing compound flame retardants such as brominated polycarbonate, brominated epoxy compound, brominated diphenyl, and brominated diphenyl ether can be used. Also,
Examples of the flame retardant aid include antimony compounds such as antimony trioxide and antimony halide, metal compounds containing zinc and bismuth, and clayey silicates such as magnesium hydroxide and asbestos.

Next, the method for producing the resin composition of the present invention is not particularly limited, and an ordinary known method is used. From an industrial point of view, generally each component is tumbled,
A method of dry-blending with a blender and a Nauta mixer or the like and then kneading and kneading and extruding, or a method of kneading with an extruder equipped with an automatic measuring feeder, and the like can be mentioned. In any case, the conditions and apparatus may be selected so that the components are sufficiently dispersed and mixed.

[0015]

EXAMPLES The present invention will now be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the bending property value of the composition obtained in each Example was measured according to ASTM D-790.

Examples 1 to 4 Comparative Examples 1 to 3 (A) Polyethylene terephthalate, (B) butanediene-based elastic material, (C) polyolefin, and (D) bisoxazoline compound were blended at blending ratios shown in Table 1. After dry blending, the extruder with vent (30 mmφ, L / D = 25, cylinder temperature: 265)
C) to form a pellet. The pellet was dried at 145 ° C. for 5 hours or more with a hot air drier, and a test piece for measuring physical properties was molded by an injection molding machine, and each physical property value was measured. Table 1 shows the results. The molding conditions of the test piece were 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 material: Kureha Chemical Co., Ltd. HIA
-28 (C) Polyolefin: Nippon Unicar Co., Ltd. EEA (M
B-870) (Ethylene / ethyl acrylate copolymer) (D) Oxazoline compound: 1.3 PB by Takeda Pharmaceutical Co., Ltd.
O (2,2 ′-(1,3 phenylene) -bis (2-oxazoline) * 1): Measurement temperature 23 ° C. * 2): After heating at 150 ° C. for 500 hours, the measurement temperature was 23 ° C.

[0018]

As is clear from Table 1, the composition of the present invention comprising PET and a butanediene-based 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 a molded article having good heat stability and high-temperature long-term quality can be obtained without impairing the mechanical properties and moldability. Therefore, according to the present invention, its application range is widened and, for example, it is suitably used for connectors, switches, relays, and the like, which greatly contributes to the industry.

Claims (1)

(57) [Claims] 1. An aromatic saturated polyester (A) 50 to 98.
0.1 to 5.0 parts by weight of (D) bisoxazoline compound based on 100 parts by weight of (B) 1 to 25 parts by weight of butadiene-based elastic material and (C) 1 to 25 parts by weight of unmodified polyolefin A polyester resin composition characterized by blending parts.