JPS59140257A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent heat resistance and mechanical strength and useful as an engineering resin, consisting of a polyphenylene ether resin, a modified ethylene/alpha-olefin copolymer and a specified block copolymer. CONSTITUTION:The titled compsn. is obtd. by blending 1-100pts.wt. modified ethylene/alpha-olefin copolymer (A) having an MFR (190 deg.C) of 0.1-50 and contg. 0.3-50pts.wt. graft monomer per 100pts.wt. ethylene/alpha-olefin copolymer obtd. by graft copolymerizing a graft monomer selected from among styrene hydrocarbons onto part or the whole of an ethylene/alpha-olefin copolymer obtd. by copolymerizing 70-7mol% of a 3-18C alpha-olefin, and 1-100pts.wt. styrene hydrocarbon block/olefin elastomer block copolymer (B) with 100pts.wt. polyphenylene ether resin or compsn. (C) consisting of said resin and a styrene resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition with improved impact resistance.

Polyphenylene ether resins have extremely excellent heat resistance and mechanical strength, and are useful as so-called engineering resins.

But endurance? Since the fjqJf property is poor, various proposals have been made for improving it.

For example, JP-A No. 57-139140 discloses that a modified olefin polymer having a draft ratio of 2 to 40%, obtained by grafting a styrene monomer to an olefin polymer resin, is mixed with a polyphenylene ether resin. By,
It has been proposed to improve the moldability of polyphenylene ether while maintaining practical mechanical strength. However, the effect of improving impact resistance is insufficient only with the modified polyolefin polymer resin disclosed herein, and the effect varies depending on the type of mistyrene-modified polyolefin. Furthermore, in order to improve impact resistance, it is necessary to increase the mixing ratio of styrene-modified polyolefin resins, which often impairs the excellent heat resistance and mechanical strength that are characteristic of polyphenylene ether resins. .

Furthermore, JP-A-57-139140 discloses an example in which a modified elastomer obtained by reacting a styrene monomer with an ethylene-α-olefin copolymer elastomer is mixed with a polyphenylene ether resin together with a polystyrene resin. It is shown.

However, in order to obtain a composition with good compatibility and no layer peeling property, it is necessary to graft a large amount of styrene-based monox to the ethylene-α olefin copolymer elastomer. However, since the grafting reaction of the styrene monomer is accompanied by a crosslinking reaction of the ethylene-α-olefin copolymer elastomer, uniform dispersion is difficult even when mixed with the polyphenylene ether resin and the polystyrene resin. It has the disadvantage that it is inferior in impact resistance improvement effect, especially at O'C or lower. Furthermore, δ often impairs the excellent heat resistance that characterizes polyphenylene ether resins.On the other hand, styrenic hydrocarbon polymers, which are commercially available under the names of Kraton (Shell Chemical Company), etc. It is also known to mix a block copolymer of a block and an olefinic elastomer to improve the melt processability of polyphenylene ether resins and to improve the impact resistance of molded articles obtained from the mixture.

For example, JP-A-53-71158, JP-A-54-889
No. 60 contains polyphenylene ether resin alone or in combination with styrene resin.
B'ij & Koborie Chire? A composition is disclosed in which a block copolymer is mixed with a block copolymer and a block copolymer.

However, with unmodified poly-a-olefin resin, even if the above block copolymer is used in combination, there is a limit to the mixing ratio of the unmodified poly-a-olefin resin and the above block copolymer. When the mixing ratio of the unmodified poly-α-olefin resin to the polyolefin resin increases, there is a drawback that the impact resistance decreases and layered peeling occurs. Also, in the bulletin,
There is no mention or suggestion of any modification of the poly-α-olefin resin used.

The present invention is a polyphenylene ether resin with improved impact resistance, which is made by combining a specific modified ethylene-α-olefin copolymer and a styrene hydrocarbon polymer block-olefin elastomer block copolymer with a polyphenylene ether resin. The present invention relates to a resin composition.

That is, the present invention provides (A) a polyphenylene ether-based resin (A1) or a composition of a polyphenylene ether-based resin and a styrene-based resin (A2) (B) an α-olefin with fLPJt of 3 to 18 containing 70
Ethylene-α copolymerized at a ratio of 7 to 7 mol%
- A modified ethylene-α-olefin copolymer obtained by graft copolymerizing a graft monomer selected from styrenic hydrocarbons to part or all of an olefin copolymer, wherein the proportion of the graft monomer is ethylene- 〇-0.6 to 50 parts by weight per 100 parts by weight of olefin copolymer
Parts by weight, melt flow rate (MFR (190°
C) Copolymer (C) Styrenic hydrocarbon polymer block-olefin elastomer in which C) is 0.1 to 50. Consisting of ivy copolymer, (B) is blended in a ratio of 1 to 100 parts by weight to 10'O parts by weight of (A), and (0) is blended in a ratio of 1 to 100 parts by weight. The present invention relates to a polyphenylene ether resin composition.

The polyphenylene ether resin to which the present invention is applied is a polymer obtained by condensation polymerization of at least one monocyclic phenol represented by the general formula (1). The modified polyphenylene ether carbon may be a homopolymer of one type or a copolymer of two or more types, and furthermore, it can be obtained by graft copolymerizing a vinyl compound.

3 (wherein, R1 is a lower alkyl group having 1 to 6 carbon atoms, R
and R6 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. ) Examples of the monocyclic phenol represented by the general formula (1) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2- Ethyl-6-propylphenol, m-cresol, 2,3-dimethylphenol, 2,3-diethylphenol h2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-
Methyl-5-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-6-propylphenol, 2-propyl-3-methylphenol, 2-propyl-6-ethylphenol, 2.3-6-) Dimethylphenol, 2,3.6- ) diethylphenol, 2,
3.6-dribrovirphenol, 2,6-dimethyl-
Examples include 6-ethylphenol, 2,6-dimethyl-6-propylphenol, and the like.

Polyphenylene ethers obtained by condensation polymerization of these monocyclic phenols include phos(2,6-dimethyl-1,4-phenylene) ether and poly(2,6-cymethyl-1,4-phenylene) ether.
diethyl-1,4-phenylene)ether-poly(2,
6-diprobyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-brobyl-1,4-7 enylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, -ethyl-6-broby-1,4-phenylene) ether, 2,6-dimethylphenol/2,3.6-)dimethylphenol copolymer,
2,6-dimethylphenol/2,3.6-triethylphenol copolymer, 2+6-diethylphenol/
2.3.6-drimethylphenol copolymer, 2.6-
Examples include diprobylphenol/2,3.6-)dimethylphenol copolymer.

Another embodiment of the polyphenylene ether resin to which the present invention is applied is a modified polyphenylene ether obtained by graft copolymerization of the polyphenylene ether and a vinyl compound.

Vinyl compounds include styrene derivatives such as styrene, methylstyrene, dimethylstyrene, α-methylstyrene, and t-7-methylstyrene; unsaturated ester compounds such as vinyl acetate, methyl acrylate, butyl acrylate, and methyl methacrylate; Examples include unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, and tolyl, and one or more of them may be used as necessary. In the present invention, styrene derivatives are particularly preferably used.

For graft copolymerization, any known polymerization method such as bulk polymerization, solution polymerization, or suspension polymerization can be used.

The proportion of vinyl monomer in the modified polyphenylene ether is generally about 1 to about 500 parts by weight, particularly preferably about 10 to about 300 parts by weight, per 1 oo g of polyphenylene ether.

When the proportion of the vinyl monomer exceeds 500 parts by weight, the heat resistance of the composition decreases, and when it falls below 1 part, the effect of improving moldability becomes small.

The styrenic resin that may be used in the present invention is a resin containing at least 25% by weight of a structural unit represented by the following general formula 〇) in its polymer, and 4 (wherein R4 is a hydrogen atom or (lower alkyl group, 2 represents a halogen atom or lower alkyl group, P is 0 or a positive integer of 1 to 3.) For example, polystyrene, high-impact polystyrene, styrene-butadiene copolymer,
Examples include 4-styrene-butadiene-acrylonitrile copolymer and styrene-α-methylstyrene copolymer.

Among them, impact-resistant polystyrene is preferably used, and polybutadiene, butadiene-styrene (combined rubber, F
; Also includes comb-modified polystyrene modified with a rubber component such as PDM.

The blending ratio of styrene resin to polyphenylene ether resin depends on the type of polyphenylene ether resin,
In particular, it can be changed depending on whether or not it is a modified polyphenyl ether that has already been graft-copolymerized with a vinyl compound, and further depending on the type of styrene resin.

Zunawaji, when using a modified polyphenylene ether resin made by graft copolymerizing styrene derivatives, (
b) It is desirable to reduce the proportion of methene-based resin or not to mix it.

When unmodified polyphenylene ether is used, the amount of the styrene polymer is about 0 to about 500 parts by weight, particularly preferably about 10 to about 600 parts by weight, per 100 parts by weight of the polyphenylene ether resin. It is preferable.

In either case, the proportion of the structural unit represented by the general formula (2) in the composition consisting of the polyphenylene ether resin and the styrene resin blended as necessary is about 0 to about 80% by weight, especially about 0 to about 7
It is desirable to set it to 0% by weight. If it exceeds 80% by weight, the heat resistance of the composition will decrease.

The modified ethylene-α-olefin copolymer (B) used in the present invention is a modified ethylene-α-olefin copolymer obtained by graft copolymerizing a specific amount of a graft monomer.

The ethylene-α-olefin copolymer to be subjected to graft modification needs to have an ethylene content in the range of 30 to 93 mol%, more preferably 40 to 90 mol%.
It is preferable that it is in the range of . Even if the ethylene content of the ethylene-α-olefin copolymer becomes greater than 9'5 mol% or less than 30 mol%, the ethylene-α-olefin copolymer becomes highly crystalline and the copolymer becomes highly crystalline. Even if a graft modified product of a polymer is blended into a polyphenylene ether resin, it cannot be said that the effect of improving the impact resistance of the composition is sufficient. melt flow rate) (MF
R, value measured at 190°C with a load of 2160g (AST
MD 1238, E conditions)] or 0.1 to 50g/
It is desirable that the amount be in the range of 0.2 to 20 g/10 minutes, and particularly preferably in the range of 0.2 to 20 g/10 minutes.

The MFR of the ethylene-d-olefin copolymer is 0.1
Even if it is smaller than 50 g/10 minutes or larger than 50 g/10 minutes, the difference in melt viscosity between the modified ethylene-α-olefin copolymer obtained from the copolymer and (A) tends to increase. The dispersion effect of the kraft modified product (A)- is not necessarily sufficient, and the effect of improving impact resistance tends to be reduced. Further, the density of the ethylene-〇-olefin copolymer is preferably within the range of 0.90 g/on2LJ, more preferably 0.85 g/on2LJ.
and 0.89 g/O12. Furthermore, it is preferable that the ethylene-α-olefin copolymer has low crystallinity or non-quality properties, and its crystallinity is usually in the range of 0 to 50%, and the degree of crystallinity is usually in the range of 0 to 40%. It is.

The α-olefin component units constituting the ethylene-α-olefin copolymer include α-olefins having 5 to 18 carbon atoms;
Examples of the ole)yne include propylene, 1-butene, 1-hexene, 4-megaben, 1-benzene, and 1-thecene, and it is one type or a mixture of two or more of these. The ethylene-α-olefin copolymer is usually a copolymer of an ethylene component and a (K-olefin), but it may contain a diene component in an amount of 5 mol % or less.

The graft monomer to be graft copolymerized to the ethylene-α-olefin copolymer is one or more compounds selected from styrenic hydrocarbons.

The styrenic hydrocarbon has the general formula (3) (wherein R4 is a hydrogen atom or a lower alkyl group, Z is a halogen atom or a lower alkyl group, and P is 0 or a positive integer from 1 to 3). This is the compound represented. Specifically, styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene, p-ethylstyrene, 0-isopropylstyrene, m-isopropylstyrene, p-
Examples include isopropylstyrene. Among these styrene hydrocarbon components, the 7-styrene component and the m- or p-methylstyrene component are preferred.

The grafting ratio of the grafting monomer is 1 ethylene-〇-
It is necessary that the amount is in the range of 0.3 to 50 parts by weight, and more preferably in the range of 1 to 20 parts by weight, based on 100 parts by weight of the olefin copolymer. When the grafting ratio of the styrene hydrocarbon is less than 0.3 parts by weight, the compatibility with the polyphenylene ether resin becomes poor, delamination tends to occur, and the effect of improving impact resistance becomes small. Furthermore, if the grafting ratio of the styrenic hydrocarbon exceeds 50 parts, the graft-modified product no longer exhibits the properties of a rubber-like elastic body, and the effect of improving the impact resistance of the polyphenylene ether resin decreases. Furthermore, the styrenic hydrocarbon kraft enalene
Melt flow rate h (MFR) of α-olefin copolymer
The value measured at s load of 2160 g and 190°C] is 0.
It ranges from 1 to 50/10 minutes, preferably from 0.2 to 20 g/10 minutes.

The modified ethylene/α-olefin copolymer used in the present invention can be prepared by directly melting the above-mentioned -ethylene/α-olefin copolymer or dissolving it in a solvent, and adding a radical initiator and the above-mentioned graft polymer/mer to carry out a graft reaction. It is desirable to prepare by performing the following steps. A reactor, an extruder, a kneader, etc. are used for the graft reaction. Examples of radical initiators include organic peroxides, organic peresters, such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-
Butyl peroxide, 2,5-dimethyl-2,5-di(
Peroxide benzoe, -hexyne-3,1,4-
Bis(tert-butylperoxoisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert
-butylperoxy)hexane-6,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylperbenzony), tert-butylperphenylacetate\tert-butylperisobutyrate, These include tert-butylperu-5ec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, as well as other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate. Among these, dicumyl peroxide, di-1θrt-butyl peroxide, 2,5-dimethyl-2,5-di(tert
Dialkyl peroxides such as -butylperoxy)hexane-6,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred.

(E) The blending ratio of modified ethylene-α-olefin copolymer is about 1 to about 100 parts by weight per 100 parts by weight of (A).
Parts by weight, especially about 2 to about 50 parts by weight, are preferred. If it exceeds 100 parts by weight, the quality (rigidity, thermal deformation) will decrease, and if it is less than 1 part by weight, impact resistance will decrease.

Furthermore, in the present invention, a composition with improved dispersibility can be obtained by using (B) a modified ethylene-α-olefin copolymer together with (c) a styrene-based hydrocarbon polymer Bronqu olefin-based elastomer block copolymer. is obtained. (C) The styrene-based uncarbonized polymer floc-olefin-based elastomer block copolymer is exemplified by the one disclosed in JP-A-55-71158, in which the styrenic hydrocarbon block (X) and (X) and conjugated gene block (Y) (however, X and X may be the same or different), X-Y-X, X-(-Y-X-Y-)
nXXX%Y-X-), Y(X→4Y% Y-(1-X
)4 or Y((X-Y-)4Y)4 (in the formula, n is an integer from 1 to 10), and hydrogenated block copolymers obtained by hydrogenating each of these are used.

The end blocks of these copolymers prior to hydrogenation are pomopolymers or fuborimers, preferably made from styrenic hydrocarbons (the aromatic portion may be monocyclic or polycyclic).

Typical styrenic hydrocarbons used here include styrene, cI-methylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof, and conjugated dienes include butadiene, isoprene, 1.6-pentagene or 2
, 3-dimethylbutadiene, halogenated derivatives thereof, and mixtures thereof.

The terminal blocks of these block copolymers may be the same or different. The central block can have a linear, sequential or teleradial structure.

In these CC) block copolymers, the molecular weight of the central block should be greater than the molecular weight of the end blocks, but can vary widely as required. It is particularly preferred to form terminal X blocks with an average molecular weight R of 4,000 to 115,000 and central blocks Y1 with an average molecular weight of 2 D D 00 to 45 CIC 100, for example hydrogenated polybutadiene.

More preferably, the terminal block is 8,000 to 60
The hydrogenated polybutadiene polymer block has an average molecular weight of 50,000 to 300,000. The terminal blocks contain 2 to 60 or more, preferably 15 to 4, polymers of the total block.
Preferably it contains 0% by weight.

stomach. Preferred copolymers are those formed from copolymers having hydrogenated/saturated polybutadiene central blocks such that 5 to 55% or more, preferably 30 to 50%, of the butadiene carbon atoms are vinyl side chains. be.

The hydrogenated copolymer has an average degree of unsaturation reduced to less than 20% of its original value. 10% of its original value
It is preferred to have the degree of unsaturation of the central block Y reduced to below, preferably to 5%.

(0) The block copolymer is hydrogenated and used by a method well known to those skilled in the art. Examples of hydrogenation catalysts include nickel, diatomaceous earth, Raney nickel, silver dichromate,
This can be done using molybdenum sulfide and finely ground platinum or other precious metals on a low surface area gear.

Hydrogenation can be carried out at any temperature or pressure, e.g. from atmospheric pressure to 20°C.
It can be carried out at a pressure of 0 atmospheres, usually 5 to 70 atmospheres, and a temperature of 24°C to 620°C for about 0.1 to about 24 hours, preferably about 0.2 to about 8 hours.

These (C) styrenic hydrocarbon polymer blocks-
Among the olefinic elastomer block copolymers, Kraton G-6500, Kraton G-6521, Kraton G-1650, and Kraton G-1652, available from Shell Chemical Company, and Hydrogen, available from Phillips Company, are particularly useful. Sol'Drene is useful.

(0) The blending ratio of the block copolymer can be changed as appropriate depending on the type and blending ratio of (to) the modified ethylene-α-olefin copolymer, but it is usually 100 parts by weight in total of (A). About 1 to about 100 parts by weight, particularly about 2 to about 50 parts by weight, is preferred.

Even if the amount exceeds about 100 parts by weight, there is no significant difference in the effect of improving dispersibility, and if the amount added is small, the effect of improving dispersibility becomes small.

Also, (B) + (C) for 100 parts by weight of (A)
The total of about 2 to 150 heavy weight gold, especially about 5
It is preferable to adjust the amount to about 80 parts by weight. 150
If it exceeds 2 parts by weight, the effect of improving stiffness and heat distortion temperature will decrease, and if it is less than 2 parts by weight, impact resistance will decrease.

Optionally, the compositions of the invention further include one or more other additives, such as (A) (B) (0) additives that may be used in each component, such as phenolic or amine antioxidants; UV absorbers and photoprotectants, phosphite stabilizers, peroxide decomposers, polyamide stabilizers, basic co-stabilizers, polyvinyl chloride stabilizers, nucleating agents, plasticizers, lubricants, emulsifiers, antistatic agents , flame protectants, pigments, carbon black, asbestos, glass fibers, kaolin and talc. Therefore, the present invention includes multi-component compositions that together contain one or more additives.

Examples of suitable additives mentioned above are selected from the following group: In particular, the composition of the present invention containing the antioxidants exemplified below, as well as the thickening inhibitors and ultraviolet absorbers exemplified below, provides very effective stability.

These additives include, for example, the compounds described in Japanese Patent Publication No. 56-34036, which serve as antioxidants.
6-dialkylphenol, e.g. 2,6-ditertiarybutyl-4-methylphenol, alkylated hydroquinone derivatives, e.g. 2,5-ditertiarybutyl-hydroquinone, hydroxylated thiodiphenyl ether, e.g. 2,2-thiobis-(6 -tert-butyl-4
-methylphenol), alkylidene-bisphenols, such as 2,2'-methylene-bis(6-tert-butyl-4-methylphenol), 0-1N- and S
-benzyl compounds, such as s-5,s's'-tetratert-butyl-4,4'-dihydroxypencyl ether, 4-hydroxy-6,5-dimethylbenzyl-
Mercaptoacetic acid octadecyl ester, hydroxybenzylated malonic acid ester, e.g.
5'-ditertiarybutyl-2-hydroxybenzyl)
-Malonic acid dioctadecyl ester, 2-(3-tert-butyl-4-hydroxy-5-methylpencyl)-
Malonic acid dioctadecyl ester, hydroxybenzyl-aromatic hydrocarbon, e.g. 1,3,5-tri(6,5
-ditert-butyl-4-hydroxybenzyl)-2
, 4,6-trimethylbenzene, S-') IJ azine compounds, such as 2,4-bisoctylmercapto-6-
(3,5-ditertyabutyl-4-hydroxyanilino)-8-triazine, 3,5-ditertyabutyl-
Amides of 4-hydroxyphenylpropionic acid, e.g. 1.3.5-)su(6,5-ditertibutyl-
4-Hydroxyphenyl-propionyl)-hexahydro-8-triazine, 6,5-ditertiarybutyl-4
Esters of -hydroxyphenyl-propionic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, octadeca-7-
1,6-hexane-diol, 1,9-nonanediol A ethylene glycol, 1,2-propane-diol 1 diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, trimethylolpropane, 5-tert-butyl- Esters of 4-hydroxy-6-methylphenylpropionic acid and monohydric or polyhydric alcohols 1 For example, methanol,
Ethanol, octadecanol, 1.6-hexanediol, 1.9-nonanediol, ethylene glycol,
1.2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, trimethylolpropane, i5-
ditertiarybutyl-4-hydroxyphenylacetic acid and 1
Esters with hydrohydric or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-
7 Nanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glyconyl, neopendel glycol, pentaerythritol, trimethylolpropane, aminoaryl derivative\Example, t4;i:, °Phenyl-1-naphthylamine.
Phenyl-2-naphthylamine, ultraviolet absorbers and photoprotective agents include 2-(2-hydroxyphenyl)-benztriazole derivatives and 2,4-bis(couhydroxyphenyl)-6-alkyl-8-)riazine. derivative, 2-hydroxy-benzophenone derivative, 1.3-
Bis(2'-hydroxy-benziyl)-benzene, esters of substituted benzoic acids, e.g. t% phenyl salicylates, acrylates, e.g. -α-cyano-β, β diphenyl acrylic acid ethyl ester or isooctyl ester, nickel compounds , such as the complexes 1:1 and 1:2 of 2,2'-thiobis-(4-tertiaryoctylphenol) and nickel, nickel dibutyldithiocarbamate, 2-hydroxy-4-methyl-
A nickel complex of phenyl-undecyl-ketone oxime, oxalic acid diamide, for example 4,4'-dioctyloxyoxanilide, metal deactivators such as oxanilide, phosphites such as triphenyl phosphite, 2- Salts of mercabutobenzimigsol, such as zinc salts, diphenylthiourea, etc.; as polyamide stabilizers, for example copper salts in viscosity with iodine and/or phosphorus compounds; as basic costabilizers; teeth,
For example, polyvinylpyrrolidone, polyurethane and alkali metal salts and alkaline earth metal salts of higher saturated or unsaturated fatty acids, for example calcium stearate, PVC stabilizers such as organotin compounds, barium or cadmium salts of fatty acids, nucleating As the agent, for example, 4-
Examples include tert-butylbenzoic acid.

The amounts of these additives in the compositions of the invention can vary within wide limits.

In the present invention, it is desirable to use an antioxidant, particularly a phenolic antioxidant, and the amount thereof is preferably about 0.01 to about 6% by weight based on the total composition.

Compositions of the invention are prepared in a variety of ways.

For example, after premixing any two components, they may be mixed with the remaining other components, or six components may be mixed at the same time. Further, additional amounts of additives such as antioxidants may be added at any of these stages as necessary.

More specifically, examples include mechanical mixing using an extruder, roll mill, Banbury mill, etc., and mixing the components in a solution or suspension state.

Further, as a method for preparing the composition of the present invention, in the coexistence of polyphenylene ether and ethylene-α-olefin copolymer, at least one or more compounds selected from unsaturated dicarboxylic acids and derivatives thereof and styrenic hydrocarbons are added. The composition of the present invention can also be prepared by polymerizing and blending other components as necessary, and is not particularly limited.

The composition of the present invention has improved impact resistance, a well-balanced reduction in heat distortion temperature and rigidity, and can be molded into various shapes by various conventionally known melt molding methods. Examples include methods such as injection molding, extrusion molding, compression molding, and foam molding, and are used in a wide range of applications including automobile parts, electrical appliances, and electrical parts.

Next, the present invention will be specifically explained using examples. In addition, in the method of the present invention, crystallinity and melt flow rate at 190°C (MFR (19,0-C)
) was measured by the following method.

Crystallinity was measured by X-ray diffraction at 23°C.

Melt flow rate CMFR (190'C):): A
STMD-1238-'-79 K conditions (190°C, 2
160g).

Example 1 Polyphenylene ether resin (Engineering Plastics Co., Ltd., (I) m-, 534, MFRCl, 57 g
/10 rnin, O condition), styrenated ethylene/propylene copolymer (propylene content 20 monoν%, MF
R (190°C) 0.5 g, '10 min', density 0.87g10n', crystallinity 13%, styrene content R
2.1 g/l 00 g copolymer) and styrene-ethylene/butylene-styrene block copolymer (manufactured by Shell Chemical Co., Ltd., Kraton G1652, styrene-containing N
ffi 29 wt%, density 11, o-91g/α3)
were mixed in the proportions shown in Table 1 to prepare a triblend. Furthermore, a single screw extruder (L/
D28.3Qmmφ) to prepare a melt blend (pellet form). Thereafter, injection molding was performed under the following conditions to create a subesimen for measuring physical properties.

Cylinder temperature: 290'C Injection pressure: 10okct/□cyn' Injection time = 10 seconds Mold temperature: 80'C Subsequently, physical properties were measured by the following method.

Moldability: JVIF'R was measured under ASTM D-1238-79.0 conditions.

Stiffness: Using a 1/8" thick test piece, ASTM D79
0-80, bending modulus F M (kg/an2)
, the bending yield strength PS (kg/cm2) was measured.

Izot impact strength: Measured according to ASTM D-2!56 using a 1/8" thick notched test piece.

Heat deformation temperature: load 18.6 kq/0ar2 condition"?
HD T (
0C).

Layered peeling: The injection molding test was bent and the layered peeling state was visually determined.

The results are shown in Table 1.

Comparative Examples 1 to 6 The physical properties of the polyphenylene ether resin shown in Table 1 alone were measured in the same manner as in Example 1. The results are shown in Table 1.

Examples 2 to 9, Comparative Examples 4 to 8 The polyphenylene, ether 'Mm resin, modified ethylene/a-olefin copolymer and styrenic hydrocarbon polymer block-olefin elastomer block copolymer shown in Table 1 were used. The same procedure as in Example 1 was carried out except as shown in Example 1. The results are shown in Table 1.

Claims (1)

[Claims] (1) (A) Polyphenylene ether resin (A1
) Composition of polyphenylene ether resin and styrene resin (A2) (B) Ethylene-α-olefin obtained by copolymerizing carbon 3 [5 to 18 α-olefins at a ratio of 70 to 7 mol%] A modified ethylene-α-olefin cofj polymer obtained by graft copolymerizing a graft monomer selected from styrenic hydrocarbons to part or all of the copolymer, wherein the proportion of the graft monomer is ethylene-〇-olefin copolymer. It is 0.3 to 50 parts by weight per 100 parts by weight of the polymer, and has a melt flow rate (MFR (19°C)
)) is 0.1 to 50 (0) Consisting of a styrene hydrocarbon polymer block-olefin elastomer block copolymer, (B) is 1 to 100 parts by weight per 100 parts by weight of (A) It is blended in the proportion of
A polyphenylene ether-based resin Ml characterized by containing (C) in a proportion of 1 to 100 parts by weight.
A product.