JPS62129342A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition with highly good balance between impact resistance, heat resistance and processability, by blending a polyphenylene ether resin, polyester, specific modified ethylene-alpha-olefin copolymer and specific styrene copolymer. CONSTITUTION:The objective composition can be obtained by blending (A) 3.5-95 (pref. 10-50)wt% of a polyphenylene ether resin, (B) 95-3.5 (pref. 80-35)wt% of a polyester, (C) 1-50 (pref. 5-25)wt% of either unsaturated acid anhydride - or unsaturated acid-modified ethylene-alpha-olefin copolymer and (D) 0.5-90 (pref. 0.5-40)wt% of a copolymer from styrene monomer and unsaturated compound selected from unsaturated dicarboxylic acid anhydride, unsaturated acid, epoxy group-contg. unsaturated compound and amino group-contg. vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a thermoplastic resin composition having excellent processability, impact resistance, and heat resistance.

``Prior art'' Polyphenylene ether resin has excellent mechanical properties, electrical properties, and IIV1 thermal properties, as well as good dimensional stability, so it has attracted attention as a resin suitable for a wide range of applications. However, moldability, IIJ#j
The major drawback is that the impact strength is low. It has been proposed in Japanese Patent Publication No. 51-21664 to incorporate polyester in order to improve the moldability of polyphenylene ether resin, but polyphenylene ether resin IYI
and polyester have very poor compatibility, and the resulting resin composition has poor mechanical properties (significantly inferior when the polyester content exceeds 20% in 41F). , had very low impact resistance. In addition, in order to improve the impact resistance of the above resin composition, an ethylene-propylene co-adhesive compound (
Even if attempts were made to add EPR (hereinafter referred to as EPR), the impact resistance would hardly be improved.

"Problems to be Solved by the Invention" As a result of intensive studies to obtain a resin composition that has excellent processability, impact resistance, and heat resistance and can be used in a wide range of applications, the inventors discovered that polyphenylene ether and polyester The present invention has been achieved based on the discovery that a thermoplastic resin composition having unprecedented performance can be obtained by further blending two specific resins in a specific ratio.

"Means for Solving the Problems" That is, the present invention provides (a) 3.5 to 95% by weight of polyphenylene ether resin, (b) 95 to 3.5% by weight of polyester, and (c) ethylene-α-olefin resin. 1 to 50% by weight of a polymer (d) 0.5 to 90% by weight of a styrenic polymer, wherein component (c) is at least one selected from unsaturated acid anhydrides and unsaturated acids. an ethylene-α-olefin copolymer modified with a species, (d)
Ingredients are styrenic monomer and unsaturated dicarboxylic anhydride,
Unsaturated acids, epoxy group-containing unsaturated compounds, and amino group-containing vinyl systems? This is a mature plastic resin composite acid product characterized by being a copolymer with at least one unsaturated compound selected from 11-mers.

The present invention will be explained in detail below.

The polyphenylene ether resin (a) I & used in the final step 11 has the general formula (I) (wherein R1, R2, R3, Ra are the same or different alkyl groups, aryl groups, halogens, hydrogen, etc.). and n represents the degree of polymerization. Specific examples thereof include poly(2,6-dimethylphenylene-1,4-z-tel), poly(2,
6-ethylphenylene-1,4-ether), poly(
2,6-diprophenylene-1,4-ether), poly(2-methyl-6-ethylphenylene-1,4-27,11/).

Poly(2-chloro-6-methylphenylene-1゜4-ether), Poly(2-methyl-6-isopropylphenylene-1,4-ether), Poly(2,6-di-n-propylphenylene-1, 4-ether), poly(2-chloro-6-promphenylene-1,4-ether), poly(2-chloro-6-ethylphenylene-1,4-ether), poly(2-methylphenylene-1 , 4-ether), poly(2-chlorophenylene-1,4-ether), poly(2-phenylphenylene-1,4-ether), poly(2-methyl-6-phenylphenylene-1,
4-ether), poly(2-bromo-6-phenylphenylene-1,4-ether), poly(2,4'-methylphenylphenylene-1,4-ether), and their copolymers and their It is a styrene compound graft copolymer.

The blending amount of the polyphenylene ether resin in the thermoplastic resin composition of the present invention is 3.5 to 95% by weight, preferably 8 to 60% by weight, and more preferably 10 to 50% by weight.

Polyphenylene ether resin company 3.51+, 1%
If it is less than that, it will improve the heat resistance! No in effect was observed, 95
If the weight exceeds 1%, the workability will be poor.

The polyester component (b) used in the present invention includes:
Aliphatic polyesters, aromatic polyesters, wholly aromatic polyesters, etc. are used.

Preferred polyesters include the following general formula (II):
[In the formula, n is an integer and represents 2, 4.6.

Ar is ◎, O○, CH◎, 〇-人〇〇, and aromatic groups directly added with alkyl, halogen, alkoxy groups, etc. ] It is produced by condensation polymerization of a dicarboxylic alcohol component and a diol component, which are represented by the following formula.

The dicarboxylic acid and diol components may be used alone or in combination of two or more.

Particularly preferred polyesters are polyethylene terephthalate, polybutylene terephthalate and modified products thereof.

The polyester may be used alone or two or more polyesters may be used in combination.

The amount of component (b) used is 95 to 3.5% by weight, preferably 90 to 25% by weight, and more preferably 80 to 35% by weight.

If the amount of component (b) exceeds 95% by weight, no significant effect on improving heat resistance will be observed, and if it is less than 3.5% by weight, processability will be poor.

Component (c) of the present invention is ethylene-α modified with at least one selected from unsaturated acid anhydrides and unsaturated acids.
-Olefin copolymers, and particularly preferred among these are ethylene-α-olefin copolymers (where the polymer is copolymerized with at least one selected from unsaturated acids and unsaturated acid anhydrides, especially It is made by graft polymerization.

The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, pentene-1, hexene-1
, heptene-1,4-methylbutene-1,4-methylpentene-1, etc., but propylene is particularly preferred.

Although it is possible to copolymerize the component (c) of the present invention with a polyene compound, it is preferable from the viewpoint of processability that a polyene compound is not copolymerized.

The polyene compound used here includes l.

4-pentadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 3,3-dimethy, IL/-1
,5-hexadiene, l,7-octadiene, 1.9-
Decadiene, 6-methyl-1,5-hexadiene, l,
4-hexadiene, 7-methyl-1,6-octadiene, 9-methyl-1,9-undecane, isoprene, 1.
3-pentadiene, 1,4.9-decatriene, 4-vinyl-1-cyclohexane, cyclopestadiene, 2-
Methyl-2,5-norbornadiene, 5-methyl-? −
Flubornene, 5-ethylidene-2-norbornene, 5
-Impropylidene-2-norbornene, 5-impropenyl-2-norbornene, dicyclopentadiene, tricyclopentadiene, and the like.

Mul-195 of ethylene and α-olefin: 5-5
:95, preferably 95;5-20:80, more preferably 92:8-60:40. Particularly preferably 85:
15-70:30.

ff1m ratio of ethylene and α-olefin: 20: s
.

~30: Particularly good workability is in the range of 70.

Heavy weight ratio of ethylene and α-olefin: 80:20
Impact resistance is particularly good in the range of 70:25.

When the above polyene compound is used, the iodine value is 2 to 40.
(c) J&min of the range is used.

Ethylene-α-olefin Mooney clay (ML+,
4. +00°C) is 5 to 200 in terms of IN impact resistance.
The range is preferably 5 to 100. More preferably, it is 5-50. Impact resistance is particularly good when Mooney clay is in the range of 10 to 30.

In addition, the ethylene-α-olefin co-ff (combined cyclohexane insoluble corporation) affects the processability and impact resistance of the undeveloped thermoplastic resin composition, and is less than 50% by weight, preferably less than 5!ll1it%. It is.

In Section 1!11 (c) d;i, minutes, examples of unsaturated acids used for modification, such as grafting, include acrylic acid, methacrylic acid, tarotonic acid, cinnamic acid, itaconic acid, maleic acid, etc. Preferred are acrylic acid and methacrylic acid. These unsaturated acids may be used alone or in combination of two or more.

Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, dichloromaleic anhydride, 1% aqueous citraconic acid,
Examples thereof include butenyl co/\hydric anhydride, tetrahydrophthalic anhydride, and the particularly preferred l,X unsaturated acid anhydride is maleic anhydride. These unsaturated acid-free materials may be used alone or in combination of two or more.

The above-mentioned unsaturated compounds used for modifying the ethylene-α-olefin copolymer may be used in combination.

Component (c) of the present invention is obtained by mixing the ethylene-α-olefin copolymer, the unsaturated compound or the unsaturated compound mixture, and a peroxide at a temperature of, for example, 100 to 300°C (preferably 150 to 250°C). It can be obtained by heat treatment (kneading) for 0.5 to 30 minutes (preferably 1 to 10 minutes).

These reactions can be carried out using an extruder, Nigu, Banbury mixer, or the like. Alternatively, it can also be obtained by dissolving the ethylene-α-olefin copolymer and the organic peroxide in an organic solvent and heating the solution.

The solvent used in this 11ν is a hydrocarbon having 6 to 12 carbon atoms, a halogenated hydrocarbon having 1 to 12 carbon atoms, tetrahydrofuran, or the like. The heating temperature varies depending on the type of organic peroxide used, but is usually 40 -
The temperature is 300°C, preferably 50-200°C, and the heating time is 1 minute to 10 hours, preferably 5 minutes to 5 hours.
After the reaction is completed, the polymer, such as alcohol, is put into an intolerant solvent and solidified, or solidified by steam stripping and then dried.

Further, other vinyl m-L forms copolymerizable with the unsaturated compounds and unsaturated acids can be used.

Other copolymerizable vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylate.

Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-
Acrylic acid alkyl esters such as ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate,
Methacrylic acid alkyl esters such as ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, pencil methacrylate, styrene, α-methylstyrene, Methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, cyfuromstyrene, p
- Aromatic M vinyl compounds such as tert-methylstyrene, ethylstyrene, and vinylnaphthalene. Maleimide, N-
Methylmaleimide, N-ethylmaleimide, N-butylmaleimide.

N-laurylmaleimide, N-phenylmaleimide, N
There are maleimide compounds such as -(p-plumophenyl)maleimide, and other copolymerizable vinyl monomers are used alone or in combination of two or more.

The above-mentioned other copolymerizable vinyl monomers may be mixed with the above-mentioned unsaturated compound and subjected to a modification reaction by the above-mentioned graft polymerization method, or may be mixed with the above-mentioned other copolymerizable vinyl monomers in advance. A copolymer with the unsaturated compound may be polymerized, and the occupied polymer may be subjected to a modification reaction according to the graft polymerization method or the like described above.

As the peroxide used in the production of (c) I&, all known organic peroxides are used.

For example, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2
,5-di(tert-butylperoxy)hexane, 2
．． 2'-bis(tart-butylperoxy)-p-diisopropylbenzenedicumyl peroxide, di-t
ert-butyl peroxide.

tart-butylperoxybenzoate, 1,1-bis(tert-butylperoxy)-3,3,5-)
Limethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, azobisisobutyronitrile, etc., preferably 2,5-dimethyl-2,5-
di(tert-butylperoxy)hexane, 2.5-
Dimethyl-2,5-di(tert-butylperoxy)hexyne-3.

The amount of organic peroxide used here is 0.05 to 2 parts by weight per 100 parts by weight of the ethylene-α-olefin copolymer.
Part by weight, preferably 0.1 to 1 part by weight.

The amount of the unsaturated compound reacted with the ethylene-α-olefin copolymer is preferably 0.01-50% by weight, more preferably 0.1-10% based on the ethylene-α-olefin copolymer. Heavy stitching percentage, particularly preferably 0.2~
It is 5% by weight. If the amount of modification is too large or too small, the impact resistance will be poor.

The amount of the component (c) used in the thermoplastic resin composition of the present invention is 1 to 50% by weight, preferably 2 to 30% by weight.
, more preferably 5 to 25% by weight. If it is less than 1% by weight, no improvement in impact resistance will be observed, and if it exceeds 50% by weight, processability will be poor.

Component (d) of the present invention is a styrene monomer and at least one selected from unsaturated dicarboxylic anhydrides, unsaturated acids, epoxy group-containing unsaturated compounds, and amine group-containing vinyl monomers. The unsaturated compound is preferably 0.1 to 30
It is copolymerized by weight%.

Unsaturated dicarboxylic acid anhydride used here.

As the unsaturated acid, the above-mentioned saturated dicarboxylic anhydride and unsaturated butyric acid are used.

The epoxy group-containing unsaturated compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule.

For example, unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, evodialkenes, and p-glycidylstyrenes represented by the following general formulas (II), (m), and (rV). be.

旙(R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond.) (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. 6.X is -CH2-0- 1-O-o - or -〇-.) R' Example 1-(Buto ('') (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. R' is hydrogen or methyl ) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2-
Methylallyl glycidyl ether, styrene-p-glycidyl ether, 3゜4-epoxybutene, 3.4-epoxy-3-methyl-1-butene, 3.4-epoxy-
Examples include 1-pentene, 3.4-dipoxy-3-methylpentene, 5.6-epoxy-1-hexene, vinylcyclohexene monoxide, and p-glycidylstyrene. These can be used alone or in combination of two or more.

As the amino group-containing vinyl rt'-a form, the general formula (
However, in the formula, R1 represents hydrogen, a methyl group, ethylene, (, and R2 represents hydrogen, an alkyl group having 1 to 12 carbon atoms, a furukayl group having 2 to 12 carbon atoms, a phenyl group having 6 to 12 carbon atoms, and a phenyl group having 6 to 12 carbon atoms. 6 to 12 cycloalkyl groups or their derivatives), (or a vinyl spinning wheel having at least one substituted amine group), specific examples include aminoethyl acrylate, acrylic acid Alkyl ester derivatives of acrylic acid or methacrylic acid such as propylaminoethyl, dimethylamine ethyl methacrylate, aminopropyl methacrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate, N-vinyldiethylamine and N-acetyl Vinylamine derivatives such as vinylamine, allylamine derivatives such as allylamine, methacrylamine and N-methylallylamine, acrylamide derivatives such as acrylamide and N-methylacrylamide, and amide/styrenes such as p-aminostyrene are used. Among them, allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, etc. are particularly preferably used because they can be obtained economically on an industrial scale.

These unsaturated compounds containing an amino group or a substituted amine 7 group may be used alone or in combination of two or more.

As the styrene monomer, all of the above-mentioned aromatic vinyl compounds are used.

Component (d) of the present invention is in addition to the above-mentioned essential components.

This can be achieved by copolymerizing other beer monomers that can be copolymerized with these.

As other vinyl monomers used here, the vinyl cyanide compounds, the acrylic acid alkyl esters, the methacrylic acid alkyl esters, and the maleimide compounds are all used. These monomers may be used alone or in combination of two or more.

Component (d) of the present invention is emulsion polymerization, which is a known polymerization method,
It can be obtained by bulk polymerization, solution combination, suspension polymerization, etc.

The amount of component (d) used in the present invention is 0.5 to 9
0% by weight, preferably 0.5-60% by weight, preferably 0.5-40% by weight.

If the amount is less than 0.5% by weight, the impact resistance will be poor, and if it exceeds 90% by weight, the heat resistance will be poor.

The thermoplastic resin composition of the present invention can be obtained by kneading it using various extruders, Henley mixers, kneaders, rolls, etc.

During the above-mentioned kneading, the composition of the present invention may be obtained by mixing all the components of the present invention, or after mixing and kneading one or more of the components and a portion of each component. The thermoplastic resin composition of the present invention may be obtained by further blending and kneading the remaining components.

In addition, from the viewpoint of impact resistance and processability, it is better to first knead component (a) / (c) component / (d) component, and then add component (d) and knead it further. (a) Ingredients/
A method in which 50% by weight or less of component (b) is added to component (c)/component (d) and kneaded, and then the remaining component (b) is added and further kneaded also yields favorable results. It will be done.

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as wallasnite, calcium carbonate, talc, and barium sulfate can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 lm and a fiber length of 30 lm or more.

These Qj fillers are preferably contained in an amount of 5 to 150 parts by weight per 100 parts of the thermoplastic resin composition.

Additionally, known additives such as flame retardants, oxide 11-agents, plasticizers, colorants, and lubricants may be added.

Preferred flame retardants and antioxidants are phosphorus compounds.

Excellent impact resistance can be obtained by using other polymers, such as polyesters such as PBT and PET, with an undeveloped 1JI thermal fi (less than 50% by weight of the polyamide used in the plastic 11M composition). So S.

Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, BR, NBR, SBR, 5
-B-S block copolymer, hydrogenated 5-B-3, polystyrene, AS resin, HIPS, ABS resin, AES resin,
Polysulfone, polyether sulfone, N-phenylmaleimide Jl1 styrenic resin, MBS, methyl methacrylate-styrene copolymer, 5-I-S block copolymer polyimide, PPS, polyether ether ketone, vinylidene fluoride Polymers and the like can be blended as appropriate.

The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, sheet extrusion, J''L air molding, foam molding, etc.

The various molded products obtained by the above-mentioned molding method can be used for automobile outer bags, interior parts, electrical and electronic related parts, housings, etc. by taking advantage of their distinct properties.

"Example J" The present invention will be explained in more detail with reference to Examples and Production Examples, but these are merely illustrative and do not limit the scope of the present invention.

In each of the following, parts and % indicate parts by weight and % by weight, respectively.

Polyphenylene ether used in Examples and Comparative Examples was obtained by the following method.

1) Production of Polymer A-1 (Polyphenylene Ether) Oxygen blowing device, cooling coil, ) at the bottom of the reactor! N
After filling and purging the inside of a stainless steel reactor equipped with nitrogen with nitrogen, 3.6 g of 2115 bromide, 1110 g of di-n-butylamine, and 8.75 kg of 2,6-xylenol dissolved in 40 g of toluene were added. . After stirring to make a homogeneous solution, polymerization was carried out for 90 minutes while rapidly blowing oxygen into the reaction vessel. During the zero polymerization, water was circulated through a cooling coil to maintain the internal temperature at 30°C. After the polymerization was completed, 30ml of toluene was added, and a 20% aqueous solution of 430g of trisodium ethylenediaminetetraacetate dissolved in water was added to stop the reaction.

? ') was born Ij2. The combined heavy liquid phase was removed from the mixture by centrifugation. While vigorously squeezing the combined solution phase, methanol was slowly added to the slurry to form a slurry. After separation, the mixture was dried to obtain Polymer A-1.

2) ff<combination A-z (polyphenylene ether)
In the production of violet polymer A-1, a phenol compound was added to 2.
Polymerization was performed in place of 6-xylenol/2,3.6-)limethylphenol = 90/10 (mole ratio), and polymer A
-2 (star).

Production Example-2 Component (c) of the present invention used in Examples and Comparative Examples was obtained by the following method.

Ethylene propylene rubber (JSRE manufactured by Japan Go1 & Co., Ltd.)
PO2P, Mooney viscosity M L +・4noo'c)2
4) 100? For B, 1 part of maleic anhydride, 0.
Three parts were premixed in advance and heat treated using a 55 mmφ extruder (1 car, full-flight type screw) at 200°C and screw rotation a30 rpm (residence time about 4 minutes).

The resulting reaction product was extracted with acetate (2 hours at the freezing point), the polymer was formed into a film, and the amount of maleic anhydride grafted was determined by infrared spectroscopic analysis. The grafting rate of maleic anhydride was 0.5 parts by weight per 10 parts by weight of ethylene propylene.

2) Polymers B-2 to B-8 Polymers B-2 to B-4 under the manufacturing conditions of Polymer B-1
is a variation of the amount of maleic anhydride. B-6, B
-7 is one in which the ethylene propylene copolymer species was changed. In B-5 and B-8, maleic anhydride was replaced with styrene acrylate-maleic anhydride copolymer. The results are shown in Table-1.

Table-1 Etile 7-fi hydromaleic acid polymer
Propylene rubber type OuyhE: (Part) B-
2JSREP-02P 1, IB
-3JSREP-02P 2B -
4jsREP-02P O, IB-
5JSREP-02P 0,5(7
Acrylic acid) B-6JSREP-911P
0, 5 (Moon viscosity ML114 (
100'c) :l5)B-7JSREP-9+2
P 0, 5(
Mooney viscosity ML 4(loo'c) :1O)B
-8JSREP-02P
2, 0 (sunareshi maleic anhydride co-detached °) B-9JSREP-02P ---
(2) Wood: Tyraturk (manufactured by Arco Polymer) Production Example-3 Component (d) of the present invention used in Examples and Comparative Examples was prepared by the following method.

Wl After purging the interior of a stainless steel autoclave with nitrogen, 45 parts of styrene, 5 parts of glycidyl methacrylate, and 0 tert-dodecyl mercaptan were added in a nitrogen stream.
．． 2 parts, 1.0 part of dodecylbenzenesulfone buty soda,
140 parts of ion-exchanged water was added. 70℃ on jacket
While circulating hot water, an aqueous solution of 1.0 part of potassium persulfate dissolved in 20 parts of ion-exchanged water was added at an internal temperature of 60°C. 2
After carrying out a polymerization reaction for a period of time, 45 parts of styrene, 5 parts of glycidyl methacrylate, 0.2911 parts of tert-dodecyl mercaptan, 1.0 parts of dodecylbenzenesulfonic acid sorter.
An emulsion consisting of 0 parts and 90 parts of ion-exchanged water was added.

The polymerization reaction was further carried out for 2 hours. Add calcium chloride aqueous solution to the obtained polymer latex and wash.

After dehydration and drying, polymer D-1 was obtained.

Polymerization was performed under the conditions for producing Polymer D-1, replacing glycidyl methacrylate fi and glycidyl methacrylate with acrylic acid, p-7 minostyrene, and allylamine.

Table 2 shows glycidyl methacrylate, acrylic acid content,
p-Aminostyrene and allylamine ψ are shown.

D-215 (glycidyl methacrylate) D-33 (glycidyl methacrylate) D-43 (acrylic acid) D-53 (p-aminostyrene) D-63 (allylamine) 3) Polymer D-7 Styrene-maleic anhydride copolymer (Dyrata ■-ku 232, manufactured by Arcopolymer) 4) Polymer D-8 ■ Polystyrene (Tobolex 500-51゜ manufactured by Mitsui Toatsu Co., Ltd.) Examples and Comparative Examples The various polymers described above had the compositions shown in Table 3. They were mixed in the same proportions and melted and kneaded in a co-rotating twin-screw extruder at a barrel temperature of 220°C to 280°C for a residence time of 3 to 5 minutes to obtain a pelletized thermoplastic structural composition. .

After sufficiently drying in a vacuum dryer, a test piece was produced using an injection molding machine, and impact resistance, 11il+# heat resistance, etc. were measured using the following method. The results are shown in Table-3.

In addition, in Example-21, the mixing method was changed to the composition ratio of Example-1. First, a blend of components (a), (c), and (d) was passed through an extruder, and component (b) was added midway through the extruder to obtain an MI acid compound having the same composition ratio as in Example-1. It is something.

Shock resistance: Hitting rod tip R = 1/ with DuPont impact tester
2'' and a thickness of 2.4 mm (7).The falling weight impact strength was determined.

Using a UL test piece with a negative ridge thickness of 1/8", the length of the molded product after being left in an atmosphere of 150° C. for 2 hours was measured, and the heat shrinkage rate was determined according to the following calculation.

Heating shrinkage rate (%) = (Length of initial test piece - Length of test piece after heating and standing) x
100/(Initial length of test piece) Measured using a Shukosha Koka type flow tester at a nozzle diameter of 1 mmΦ, thickness of 2 mm, temperature of 280° C., and load of 30 kg.

Comparative Example 6 is a known composition, and although it has excellent moldability and heat resistance, it is a brittle resin with very low impact resistance, and has extremely low industrial value.

In contrast, the composition according to the present invention has significantly improved impact resistance as shown in the Examples, and has highly balanced physical properties such as impact resistance, heat resistance, and moldability.

Therefore, since the composition of the present invention has highly balanced physical properties, high quality is required. P
It can be used for exterior and interior parts of l+ +l+-, various parts related to air/electronics, and molded products such as housings.

``Effects of the Invention'' As is clear from 2 below, according to the present invention, by blending polyphenylene ether and polyester with two specific resins in specific ratios, it is possible to achieve advantages that are not found in conventional polyphenylene ether resin compositions. Highly balanced heat resistance, heat resistance, and moldability
i (It became possible to provide a plastic resin composition.

Claims (1)

[Claims] (a) 3.5 to 95% by weight of polyphenylene ether resin (b) 95 to 3.5% by weight of polyester (c) 1 to 50% by weight of ethylene-α-olefin copolymer (d ) A composition consisting of 0.5 to 90% by weight of a styrenic polymer, in which component (c) is an ethylene-α-olefin modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. (d)
Ingredients are styrenic monomer and unsaturated dicarboxylic anhydride,
A thermoplastic resin composition characterized in that it is a copolymer with at least one unsaturated compound selected from unsaturated acids, epoxy group-containing unsaturated compounds, and amino group-containing vinyl monomers.