JPS59174645A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A composition that is composed of an ethylene terephthalate polyester resin, a polyphenylene ether resin and a styrene resin, thus giving moldings of very high heat distortion temperature, less anisotropy in strength and contraction, and good surface smoothness. CONSTITUTION:The objective composition is composed of 5-95wt% of polyester resin of ethylene terephthalate units, 95-5wt% of a polyphenylene ether resin and 0.2-50wt% of a styrene resin. The polyester resin contains more than 80mol% of ethylene terephthalate recurring units. As the polyphenylene ether resin, is used poly-2,6-dimethyl-1,4-phenylene ether.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition, and more specifically to an ethylene terephthalate polyester resin,
The present invention relates to a thermoplastic resin composition having excellent polyphenylene ether resin properties, heat resistance, and molding fluidity.

Polyethylene terephthalate resin has a high melting point and excellent mechanical properties, and is used in large quantities for applications such as fibers and films. On the other hand, polyethylene terephthalate as a molding material has an extremely low heat distortion temperature under load despite its high melting point, so polyethylene terephthalate is usually blended with a large amount of glass fiber to increase the heat distortion temperature under load. There is. However, polyethylene terephthalate resin reinforced with glass fibers produces molded products with poor surface properties, and orientation of the glass fibers occurs during molding, resulting in extremely large strength anisotropy and poor shrinkage anisotropy. Therefore, the molded product has the disadvantage of causing warp deformation.

The present inventors have improved the drawbacks of polyethylene terephthalate resin, and have created a polyester molding material that has a high heat distortion temperature of molded products, has little anisotropy in strength and shrinkage rate, and has excellent surface smoothness. That is, the present invention is a thermoplastic resin composition comprising a polyester resin mainly containing ethylene terephthalate repeating units, a poly7-ethylene ether resin, and a styrene resin. It has a uniform strength and molding shrinkage rate at a uniform deformation temperature, has few defects such as strength anisotropy and warp deformation, and can provide molded products with excellent surface properties.

The polyester resin used in the present invention includes:
It is a polyester resin mainly composed of ethylene terephthalate repeating units, and it contains not only polyethylene terephthalate but also acid components such as isophthalic acid, P-oxybenzoic acid, diphenylmethane dicarboxylic acid, naphthalene dicarboxylic acid, adipic acid, and sebacic acid, or glycol components. Examples include ethylene terephthalate polyester resins copolymerized with tetrapyrene glycol, tetramethylene glycol, hexamethylene glycol, neopen-y-ruglycol, diethylene glycol, Schiff tetrahexane dimetatool, bisphenol A, and the like. The content of ethylene terephthalate repeating units is preferably 80 mol% or more, and particularly preferably 96 mol% or more. Also, an ester-forming component with trifunctionality or more is copolymerized within a range that does not impair moldability. It may also be a polyester resin.

Furthermore, by blending two or more types of polyester resins, the resulting blend of polyester resins containing ethylene terephthalate repeating units as a main component may be used. In addition,
The polyester resin usually has an intrinsic viscosity of 0.4 or more, preferably 0.5, as measured at 30°C in a mixed solvent of phenol/tetralacv2a ethane (6/4 weight ratio).
That's all.

Furthermore, examples of the polyphenylene ether resin used in the present invention include resins having a unit structure represented by the general formula.

Here, RI N R2, R3 and R4 are hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, cyano group, alkoxy group, phenoxy group or nitro group, and n indicates the degree of polymerization. Specific examples of R1% R2, R3 and R4 include hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bpmmethyl, cyanoethyl, cyano, methoxy, ethoxy, Examples include groups such as phenoxy and nitro. Specifically, toeha, poly a, S-dimethyl-1,4-phenylene ether, poly-2,6-diethyl-1,4-phenylene ether, poly-2,6-diprobyl-1,4-phenylene ether, Poly-2,6-
Dimethoxy-1,4-phenylene ether, poly-2,
6-dimethyl-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether, poly-, P! , 6-dydrilu 1.4-7
Enylene ether, poly-2,6-dichloro-1,4-
Phenylene ether and poly-2,5-dimethyl-1
, 4-phenylene ether, poly-2,6-dipendylene-1,4-phenylene ether, etc. cause vignetting.

A preferable poly7 ethylene ether resin is a polymer in which R1 and R4 in the general formula have an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and n is usually or preferably 0 or more. The styrene resin used and the female usually have a general formula (wherein R is hydrogen, a lower alkyl group, e.g. 1 to 4 carbon atoms).
represents an alkyl group or halogen, 2 represents hydrogen, halogen or a lower alkyl group, p is 0 or Ul
- at least 25% by weight of the polymer of units derived from vinyl aromatic hydrocarbons represented by (representing an integer of a)
Examples of the above resins include homopolymers such as polystyrene, polychlorotetrastyrene, polyα-methylstyrene, rubber-modified polystyrene, such as styrene-butadiene rubber-modified polystyrene, and DEPJ! 'M 71t Core A Modified t' restyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-α methylstyrene copolymer,
Various copolymers such as styrene-acrylic nitrile-butadiene copolymer and styrene-maleic acid copolymer are exemplified. Moreover, an olivemer having two or more repeating units may be used. These styrene resins in the present invention may be copolymerized with polyphenylene ether resins.

In the present invention, the blending ratio of polyester resin, polyphenylene ether resin, and styrene resin is 5 to 95% by weight of polyester resin, 95 to 5% by weight of polyphenylene ether resin, and 0% of styrene resin to the total composition.
．． 2 to 50% by weight, preferably 10 to 90% by weight of polyester resin, 90 to 90% of polyphenylene ether resin
xoitan% and styrenic resin 0.5 to 20% by weight.

In the present invention, by blending a small amount of styrene resin, the polyester resin and polyphenylene ether resin are uniformly dispersed and mixed, and their compatibility is significantly improved. As a result, it has the feature of obtaining an extremely high heat distortion temperature. If too much styrene resin is blended, not only will the effect of improving heat distortion temperature be lost, but performance such as chemical resistance will be significantly deteriorated.

The composition of the present invention may further include crystal nucleating agents for the polyester resin, such as talc, mica, titanium oxide, carbon black, etc., and crystallization accelerators, such as compatible polyoxyalkylene-based agents, depending on the use and purpose. Compounds, polyhydric alcohol promoters, higher fatty acid esters, higher fatty acid metal salts, high molecular weight aliphatic polycarboxylic acid salts, carboxylic acid metal base-containing polymers, etc. may be blended. Usually, the amount of the crystal nucleating agent is up to about 50% by weight based on the composition, and the amount of the crystallization promoter is preferably up to about 10% by weight based on the composition. As the crystallization promoter, polyoxyalkylene compounds are particularly preferred. Specifically, polyoxyalkylenes such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide/pyrene oxide random or block copolymers, alkylene oxide adducts of polyhydric alcohols, and alkylene oxide adducts of polyhydric carboxylic acids. 7 of polyether glycols with chains or their mono-diethers, mono-diesters, polyether glycols
Compounds with an anionic group introduced at the end of the polyoxyalkylene chain such as taric acid ester, diglycolic acid ester, polyoxyalkylene phenyl ether sulfonic acid, and their metal salts, and benzyl alcohol, etc. polyether compounds with unsaturated groups such as esters esterified with esters, unsaturated alcohol ethers of polyether glycol, unsaturated acid esters, partial polyalkylene glycol esters of polymers containing carboxylic acid groups, and polyoxyalkylene chains. Examples include epoxy compounds, which can be used alone or in combination of two or more.

We also supply stabilizers such as antioxidants, UV LSG&absorbents, hydrolysis resistance improvers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, conductivity imparting agents, colorants, polyfunctional crosslinking agents, inorganic fillers other than those mentioned above, fibrous reinforcing agents, impact modifiers (for example, Tg of 0°C or less, particularly preferably -20°C)
Additives such as the following reactive group-containing olefin copolymers, polyester polyether elastomers, polyester polylactone elastomers, etc.), sliding property improvers (solid lubricants, liquid lubricants), foaming agents, etc. It can also be blended.

Additionally, other thermoplastic resins may be blended in amounts and types that do not detract from the objectives of the present invention.

The method for producing the composition of the present invention is not particularly limited, and any method may be used. For example, they can be blended by mechanical kneading using an extruder, roll mill, Banbury mixer, or the like.

The present invention will be explained below using examples.

Example 1-10: Comparative Examples 1 to 3 Poly-2,6-dimethylphenylene-1,4-ether (ppo) powder with [η] of 0.58 (measured at 30°C in tetraroform) A predetermined amount of polyethylene terephthalate (pxT) powder with a quantitative [η] of 0.63 and a predetermined amount of various styrene resins were mixed in a blender, and a 30-pore φ
The mixture was cross-extruded using a twin-screw extruder (POM-30, manufactured by Ikegai Tekko Co., Ltd.) at a cylinder temperature of 295° C. to obtain pellets. The obtained pellet was dried in a vacuum dryer at 120°C for 5 hours,
A molded product was produced using an injection molding machine (Nissei Jushi Kogyo Co., Ltd., Model FI9-'15). The cylinder temperature at this time was 280°C. Moreover, the mold temperature was 70°C.

The various measurements in the example were conducted using the following methods.

(1) Heat distortion temperature According to ASTM D-e4a, load 18.6#/cj
Measured at Measurements are taken after molding, and measurements are taken at 140℃ after molding.
Measurements were taken after heat treatment in a car oven for 1 hour.

(2) Flowability Molding was performed using a mold as shown in Figure 1 at a mold temperature of 70°C, a cylinder temperature of 290°C, and an injection pressure of 1000 #/Cd, and the flow length was measured.

The results are shown in Table 1.

Table 1* 100℃×2 hr! i Annealing samples Various styrenic resins> Polystyrene Stysine 683 (no chemical formation! I,)A
BS Diapet AE8 (Mitsubishi Rayon Co., Ltd.) A19 Tyril 783
(Asahi Kasei) H Engineering PH Nisprite 500A
(Sumitomo FFJ) Styrene oligomer Picolastic A-75 (Esso Kagaku) Polyethylene Asahi Dow polythousyrene yg+io (Asahi Kasei) As is clear from Table 1, the heat distortion temperature is significantly improved by the combination of styrene resin. I can't get a molded product. Styrenic resin blending amount (If it is too large, the effect of improving heat distortion temperature will be lost and, although not shown in the table, there will be disadvantages such as decreased chemical resistance, durability, etc.)

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of the mold used in the fluidity evaluation, and point A) indicates the ilm gate. Patent applicant: Toyobo Co., Ltd. No. 11! l 2'Continuation of WL Kou page 1 ■Int, C1, 3 identification code Internal reference number (C
08L 67102 1104 55102 ) (7-fold person Toshio Hiramatsu 2-1-1 Katata, Otsu City)

Claims (1)

[Scope of Claims] L A thermoplastic resin composition comprising a polyester resin mainly containing ethylene terephthalate repeating units, a polyphenylene ether resin, and a styrene resin. z The blending ratio of polyester resin, polyphenylene ether resin, and styrene resin is 5 to 95% by weight of polyester resin, 95 to 5% by weight of poly7 ethylene ether resin, and 0.2 to 50% by weight of styrene resin, based on the total composition. % of the thermoplastic resin composition according to claim 1.