JPS59204656A - Thermoplastic polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition giving a molded article having improved surface smoothness and excellent physical properties even after the use for a long period, without lowering the moldability and the initial physical properties of the base resin, by compounding a thermoplastic polyester resin with epoxidized linseed oil and/or epoxidized soybean oil. CONSTITUTION:(A) 100pts.wt. of a thermoplastic polyester resin is compounded with (B) 0.1-4pts.wt., preferably 0.5-2pts.wt. of an epoxidized linseed oil and/or epoxidized soybean oil. The component (A) is preferably polyethylene terephthalate resin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic polyester resin composition. More specifically, the present invention relates to a thermoplastic polyester resin composition that improves the surface properties of a molded article and the deterioration of physical properties during long-term use by introducing a specific amount of a specific epoxy compound into the thermoplastic polyester resin.

Thermoplastic polyester resins have a high softening point and excellent electrical and mechanical properties, including heat resistance, chemical resistance, and light resistance, so they are widely used in fibers, films, and molded products. There is. However, in actual injection molding, the surface properties of the molded product are not necessarily good, and when physical property tests are conducted assuming long-term use,
It had the disadvantage that the measured values tended to vary widely and the physical property values tended to decrease significantly. Hitherto, there has been a demand for thermoplastic polyester resin compositions that do not cause such phenomena.

As a result of intensive studies based on this viewpoint, the present inventors surprisingly found that by introducing a specific amount of a specific epoxy compound into a thermoplastic polyester resin, moldability and initial physical properties are impaired. It has been discovered that it is possible to obtain a composition with excellent surface properties of molded articles and physical properties during long-term use without the above-mentioned conditions, and has thus arrived at the present invention. That is, the gist of the present invention is a thermoplastic polyester resin composition containing (al) 100 parts by weight ('b) of a thermoplastic polyester resin, and 0.1 to 4 parts by weight of epoxidized linseed oil and/or epoxidized soybean oil. .

In the present invention, a thermoplastic polyester resin (al means a dicarboxylic acid component in which at least 90 mol% is terephthalic acid, and at least 90 mol% is ethylene glycol, propane-1,3-diol, butane-
Obtained by direct esterification or transesterification with diol components such as 1,4-diol, pentane-1,5-diol, hexane-1,6-diol, and cyclohexane-1,4-dimetatool, followed by polycondensation. is also p. O~1 of dicarboxylic acid component of thermoplastic polyester resin
0mo) v% is another aromatic dicarboxylic acid having 6 to 14 carbon atoms, an aliphatic dicarboxylic acid having 4 to 8 carbon atoms, or 8 to 1 carbon atoms.
It may also be an alicyclic dicarboxylic acid of No. 2.

Examples of such dicarboxylic acids include phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4-
diphenyldicarboxylic acid, diphenylethane-4,4-
Dicarboxylic acid, adipic acid, sebacin or diol component 0-1o-! :/L/% may be another aliphatic diol having 3 to 10 carbon atoms, another alicyclic diol having 6 to 15 carbon atoms, or an aromatic diol having 6 to 12 carbon atoms. Examples of such diols include 2,2-dimethylpropane-1,3-diol, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,2-bis-(4
'-Hydroxyphenyl)propane, hydroquinone, etc. Furthermore, oxycarboxylic acids, e.g.
-Oxycaproic acid, hydroxybenzoic acid, etc. may be copolymerized. Of course, the thermoplastic polyester resin may be branched with trivalent or tetravalent alcohols or tribasic or tetrabasic acids; examples of suitable branching agents include trimesic acid, trimellitic acid, trimellitic acid, Examples include methylolpropane and pentaerythritol.

From an industrial standpoint, polyethylene terephthalate resins, polypropylene terephthalate resins, polybutylene thenephthalate resins, and the like are preferred. These thermoplastic polyester resins may be used alone or in a blend of two or more. Furthermore, for the purpose of increasing crystallinity, organic acid salts such as sodium acetate, sodium benzoate/sodium hydrogen phthalate, disodium phthalate, magnesium stearate, 1-lium stearate, calcium stearate, etc. ; Inorganic salts including sodium carbonate, calcium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, etc.; Nucleating agents such as metal oxides including zinc oxide, magnesium oxide, titanium oxide, etc. It is also possible to copolymerize or mix polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. It may contain a compound having a structure. It may also contain aliphatic polyester oligomers of dibasic acids, such as adipic acid, and cyonopes, such as butanediol, and so-called ionomers such as sodium salts of ethylene/acrylic acid copolymers. It's okay. Historically, for the purpose of improving the mechanical and electrical properties of thermoplastic polyester resins, polyamide polymers, polycarbonate polymers, etc. may be contained, diene rubbers, acrylic rubber thread polymers, etc. , butyl rubber-based polymer, ethylene-propylene rubber-based copolymer, ethyl V-vinyl acetate thread copolymer, urethane rubber, epichlorohydrin rubber, silicone rubber, and other thermoplastic rubbers may be contained.

In the present invention, epoxidized linseed oil/epoxidized soybean oil (1)) refers to epoxidized linseed oil/soybean oil, and all types of commercially available oils can be used.

Generally, it is produced by reacting linseed oil or soybean oil with peroxide, and it is a compound that belongs to the category of plasticizers having epoxy groups.

It is known that epoxy compounds are added to thermoplastic polyester resins, but for example, when a compound such as bisphenol A diglycidyl ether is added to polyethylene terephthalate resin, there are many problems during extrusion processing, and the heat distortion temperature (1-IDT,). In the case of the epoxidized linseed oil and epoxidized soybean oil of the present invention, these phenomena do not occur, and moreover, the surface properties of molded products are improved, and they show excellent results in physical property tests assuming long-term use. The amount added is 0.1 to 4 parts by weight, preferably 0.5 to 2 parts by weight. If the amount is less than 0.1 part by weight, the above effect will not be obvious, and if it exceeds 4 parts by weight, the initial physical properties will be deteriorated.
Cannot withstand use as a resin.

If necessary, a reinforcing filler can be added to the composition of the present invention to further improve its physical properties. Suitable reinforcing fillers include glass fibers, mineral fibers, talc, mica, kaolin, and the like. Further, a flame retardant can be added to the composition of the present invention to impart flame retardance, if necessary. Suitable flame retardant,! =Halogenated diphenyl ether compound, halogenated polycarbonate compound, halogenated polyphenylene oxide compound, halogenated bisphenol resin, halogen-containing S-triazine compound, halogenated polystyrene compound, red phosphorus flame retardant In addition to these,
If necessary, a flame retardant aid such as antimony trioxide or zinc borate may be added to develop a synergistic effect.

To produce the composition of the present invention, a thermoplastic polyester resin and epoxidized linseed oil and/or epoxidized soybean oil may be mixed by a known method. Examples include a method of adding and blending during the production of thermoplastic polyester resin, and a method of mixing and extruding using an extruder. Furthermore, other additives such as thermal antioxidants, light stabilizers, pigments, dyes, nucleating agents, plasticizers, lubricants, etc. may be added to the extent that the physical properties are not impaired.

In this way, it is possible to obtain a composition that has excellent surface properties of molded articles and physical properties during long-term use without impairing moldability or initial physical properties.

The composition of the present invention can be widely used for molding various molded parts, pipes, containers, etc., and is particularly suitable for electrical parts, building material parts, automatic tank parts, etc., and can also be used for fibers, films, and sheets. be.

The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. In the examples, the tensile strength of the molded product is ASTM-I) 638, and the heat distortion temperature (ts, 6/c+ya) is ASTM-D6.
48.

As a long-term physical property test, the molded body was tested at 180% for heat resistance.
Tensile strength retention after being left in a °C oven for 7 days.
For humidity resistance, the molded body is heated to 50°C1 relative humidity 90-95%.
The tensile strength retention rate after being left in an oven for 500 hours was evaluated. Further, the amount added in each example is in parts by weight.

Examples 1-2, Comparative Example 1 Polyethylene terephthalate tiM resin (PET),
After extrusion mixing epoxidized soybean oil (oxirane oxygen 6.6%) and glass fiber (fiber length 3 mm) at various ratios shown in Table 1, injection molding was performed at a mold temperature of 120'C to obtain test pieces. I got it. As shown in Table 1, the results were excellent in surface properties and long-term physical property tests without any deterioration in initial physical properties. In addition, as Comparative Example 1, a similar test was conducted without using epoxidized soybean oil, which is also shown in Table-1. No. 79646 2, Title of the invention: Shutake-type, IL-i, °'Noesthenon Kendoku Gokan-i Honji-sho 3, Relationship with the case of the person making the amendment Patent applicant (IEv'/i'; Kita-ku, Osaka City Nakanoshima 3-chome 2-4 M1'''; name) (094-) Kanebuchi Chemical Industry Co., Ltd., upper representative, 1st year of high school), 4th grade, agent & contents of amendment 15Pf4 tt Ibijo-IQ lower lI・1
To BU, Tsukiichi lp ~ φ7 Moroyaki 1121 joins.

(Attachment) Examples 3-4. Comparative Example 2 Polyethylene terephthalate resin (pET) copolymerized with 10% by weight of polyethylene glycol monotrimellitic acid ester disodium salt having an average molecular weight of 11,740, epoxidized linseed oil (oxirane oxygen 9.2%), and fiber length 3 mm. Glass fibers were extruded and mixed at various ratios shown in Table 2, and then injection molded at a mold temperature of 90°C to obtain test pieces.

As shown in Table 2, the results were excellent in surface properties and long-term physical property tests without any deterioration in initial physical properties.

A similar test was conducted for a case in which epoxidized linseed oil was not used as Comparative Example 2, but as shown in Table 2, the surface properties and long-term physical property tests were poor.

Table-2

Claims (2)

[Claims] (1) A thermoplastic polyester resin composition containing 100 parts by weight of (al thermoplastic polyester resin) (b) 0.1 to 4 parts by weight of epoxidized linseed oil and/or epoxidized soybean oil. (2) The composition according to claim 1, wherein the thermoplastic polyester resin is a polyethylene terephthalate resin.