JPH036259A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To prepare a polyphenylene ether resin compsn. of which the dependency of melt viscosity on shear rate is increased by compounding a specified amt. of a specific compd. into a compsn. obtd. by compounding a polyphenylene ether partially modified with an acid (anhydride) with a styrene resin. CONSTITUTION:0.01-5 pts.wt. polyvalent epoxy compd. (e.g. an epoxidized polystyrene) and/or polyamine (e.g. melamine) is compounded into 100 pts.wt. compsn. obtd. by compounding a polyphenylene ether at least partially modified with an acid (anhydride) with styrene resin (e.g. a rubber-reinforced styrene resin).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyphenylene ether resin composition, and particularly to a polyphenylene ether resin composition having excellent blow moldability.

[Conventional technology]

Polyphenylene ether resin compositions have excellent heat resistance and are also excellent in mechanical strength, electrical properties, water resistance, flame retardance, etc., and have various uses as resin materials for molding. However, polyphenylene ether resin compositions have major drawbacks such as poor moldability due to high melt viscosity, and poor solvent resistance and impact resistance.

In order to improve this problem, a composition in which a styrene resin is blended with a polyphenylene ether resin to improve moldability and impact resistance is known, for example, N0RYL (trademark: General Electric Company). However, this resin composition was mainly used for injection molding and not for blow moldability. In recent years, blow molding has begun to take advantage of the excellent properties of engineering plastics, and it has become necessary to improve blow moldability.

Although conventionally known borifuerene ether resin compositions have sufficient injection moldability, it has been difficult to use them in blow molding for producing relatively large blow molded products. This is because during blow molding, the molten resin, ie, the parison, sag under its own weight, resulting in a so-called drawdown phenomenon in which the thickness, dimensions, etc. of the molded product become extremely uneven.

When blow molding is performed using an ordinary extrusion screw type blow molding machine, in order to reduce the load on the extruder screw and to prevent melt fracture from occurring when the molten polymer is discharged from the die at high speed, Low viscosity is desirable. On the other hand, in order to obtain a molded article with uniform wall thickness and dimensions without causing the drawdown phenomenon of the parison, it is desirable that the melt viscosity be high.

In order to satisfy these two contradictory demands, the polymer should have a low melt viscosity under high shear rates and a high melt viscosity under low shear rates. However, the melt viscosity of conventional polyphenylene ether resin compositions had a small dependence on shear rate, resulting in insufficient blow moldability.

[Problem to be solved by the invention]

The present invention aims to solve the problems associated with the above-mentioned prior art, and aims to improve a polyphenylene ether resin composition consisting of polyphenylene ether and styrene resin, and to make it possible to mold large-sized molded products by blow molding. The aim is to improve the properties by increasing the shear rate dependence of the melt viscosity.

[Means to solve the problem]

The present invention provides that (1) a composition containing a polyphenylene ether at least partially modified with an acid or an acid anhydride and a styrene resin is combined with either a polyepoxy compound or a polyvalent amine compound; One side is 0.
(2) a polyphenylene ether at least partially modified with an epoxy;
(a) for a composition blended with a styrene resin;
It is characterized by a polyphenylene ether resin composition containing 0.01 to 5 parts by weight of either a polyvalent carboxylic acid compound or (b) a polyvalent amine compound.

The polyphenylene ether used here is, for example,
General formula (wherein R1, RZ, R:l and R4 are hydrogen, halogen, alkyl group, alkoxy group, haloalkyl group and haloalkoxy group having at least 2 carbon atoms between the halogen atom and the phenyl ring) , represents a monovalent substituent selected from those that do not contain a tertiary α-carbon, and n is an integer representing the degree of polymerization), and is a general term for polymers represented by the above general formula. The polymer may be used alone or as a copolymer of two or more kinds.

In preferred embodiments, R5 and R2 have 1 to 4 carbon atoms.
is an alkyl group. For example, poly(2,6-dimethyl-
1,4-phenylene) ether, poly(2゜6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(
2-Methyl-6-broby-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-ethyl-6-broby-1.4)
-phenylene) ether, etc. Also I'P
As the E copolymer, an alkyl trisubstituted phenol, for example, 2,3
．． A copolymer partially containing 6-trimethylphenol can be mentioned. Moreover, a copolymer in which a styrene compound is grafted onto these polyphenylene ethers (hereinafter abbreviated as "rppg") may also be used. The styrene compound-grafted polyphenylene ether is a copolymer obtained by graft polymerizing a styrene compound such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, etc. to the above 1'PE.

This polyphenylene ether is at least partially modified with an acid or acid anhydride such as citric acid, malic acid, or agaricic acid, or an epoxy such as glycidyl acrylate, glycidyl methacrylate, itaconic acid, glycidyl esters, or allyl glycidyl ether. It is necessary to be present. Such modification can be performed by melt-mixing the polyphenylene ether and the additive composition.

In addition, the styrenic resin used in the present invention is -(in the formula, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and Z represents a substituent that is a halogen or an alkyl group having 1 to 4 carbon atoms. , p is an integer of 1 to 5.) A repeating structural unit derived from a vinyl aromatic compound represented by
The styrenic polymer must contain a small amount (25% or more by weight) of the polymer.
For example, homopolymers of styrene or its derivatives, and also, for example, polybutadiene, polyisoprene, butyl rubber, EPDM.

Ethylene-propylene copolymers, styrenic polymers mixed with or modified with elastomeric materials such as natural rubber, and styrene-containing copolymers such as styrene-acrylonitrile copolymers (SAN) and styrene-butadiene copolymers. Examples include styrene-maleic anhydride copolymer, and styrene-acrylonitrile-butadiene copolymer (ABS). Preferred styrenic resins for the present invention are homopolystyrene and rubber reinforced polystyrene.

The polyvalent epoxy compound used in the present invention is a compound having two or more epoxy groups in the molecule, and is, for example, a bisphenol-type epoxy compound obtained by reacting bisphenol A and epiglylhydrin in various proportions. Compounds, nophorac type epoxy compounds obtained from nophorac resin and epicrylhydrin, polyglycidyl esters obtained from polycarboxylic acid and epicrylhydrin, alicyclic compounds such as alicyclic epoxy compounds obtained from dicyclobencune, alcohols. glycidyl ethers obtained from aliphatic compounds having a functional hydroxyl group (e.g. butadiol, glycerin, etc.) and epichlorohydrin;
Examples include epoxidized polybutadiene, and copolymers containing epoxy group compounds consisting of an unsaturated monomer having an epoxy group and another unsaturated monomer. Preferred examples of these polyvalent epoxy compounds include bisphenol A-type epoxy compounds, such as compounds represented by (where n is a number from 0 to IO), and Ebo-11 group-containing co-In combinations. C is ethylene/glycidyl methacrylate co-i [
ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/carbon oxide/glycidyl methacrylate copolymer, ethylene/acrylic acid copolymer, etc. Among them, ethylene/glycidyl methacrylate copolymer is preferred. .

Some of the polyvalent amine compounds include compounds having two or more amine groups in the molecule, such as polymethylenediamine, polyetherdiamine, diethylenetriamine, triethylenetetramine, and N-aminoethylethanolamine. Aliphatic polyvalent amine, metaphenylenediamine, aromatic polyvalent amine such as 1-silenediamine, 4.4°-diaminodiphenyl ether, 4.4′-diaminodiphenylamine, 4.4′-diaminodicyclohexylmethane, 4, Alicyclic polyvalent amines such as 4'-diaminodicyclohexyl ether, melamine,
Heterocyclic polyvalent amines such as benzoguanamine, α, ω-
It is an organic silane compound such as bis(aminopropyl)polydimethylsiloxane.

Examples of polyvalent carboxylic acid compounds include compounds having two or more carboxylic acid groups in the molecule, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, itaconic acid, Aliphatic polycarboxylic acid compounds (or their salts or anhydrides) such as citraconic acid, mesaconic acid, malic acid, citric acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid aromatic polyhydric carboxylic acids (or their salts or anhydrides), such as
It is a carboxylic acid group-containing copolymer (eg, polystyrene, polyolefin, etc.).

The blending amount of the polyvalent amine compound or polyvalent carboxylic acid compound is preferably 0.01 to 5 parts by weight, and if it is less than o or oi parts by weight, the effect of improving the shear rate dependence of the melt viscosity is small;
Moreover, if it is more than 5 parts by weight, it is not preferable because it causes increased viscosity and poor appearance.

〔Example〕

50 parts of polyphenylene ether (PI'E-1) whose terminal was modified with an acid anhydride group or polyphenylene ether (PP[E-2) whose terminal was modified with an epoxy group,
A polyvalent epoxy compound, a polyvalent amine compound, or a polyvalent carboxylic acid compound shown in Table 1 was melt-kneaded to a composition consisting of 50 parts of rubber-reinforced styrene resin (IIIPs) to obtain a pellet.

The melt viscosity characteristics of each pellet obtained were measured by the following method. Using a capillary flow characteristic tester, shear rate 1
The melt viscosity (MV) of each was measured at sec"" and 10Osec""1. What is the ratio between these two fakes? It is called tV ratio. In blow molding, MV at low shear rates of the molten resin is used to reduce parison drawdown.
The higher the MY, the better; on the other hand, the lower the MY at high shear rates, the better, in order to reduce the load on the extruder screw. This means that the larger the MV ratio value, the more the resin composition exhibits viscosity characteristics suitable for blow molding.

Table 1 shows the measurement temperatures and results.

In addition, as a comparative example, unmodified polyphenylene ether (
PPE) and rubber-reinforced styrene resin only.

It can be seen that all of the compositions with the formulations shown in the Examples show a higher Nv ratio than the Comparative Examples, and the blow moldability is improved.

Table 1

Claims (2)

[Claims] (1) For 100 parts by weight of a composition containing a polyphenylene ether at least partially modified with an acid or an acid anhydride and a styrene resin, (a) a polyepoxy compound or (b) a polyvalent A polyphenylene ether resin composition, characterized in that it contains 0.01 to 5 parts by weight of either one of the amine compounds. (2) For 100 parts by weight of a composition containing a polyphenylene ether at least partially modified with epoxy and a styrene resin, add (a) a polyvalent carboxylic acid compound or (b) a polyvalent amine compound. A polyphenylene ether resin composition characterized by containing 0.01 to 5 parts by weight of either one.