JPS6162550A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by adding specific amounts of a specific aromatic vinyl-(meth)acrylic alkyl ester copolymer and a graft copolymer containing a specific amount of (meth)acrylic alkyl ester, thus showing well-balanced improvement in properties including heat resistance. CONSTITUTION:(A) 5-95wt% of polyphenylene ether are combined with (B) 3-94wt% of a copolymer obtained by grafting monomers mainly consisting of aromatic vinyl compound and (meth)acrylic alkyl ester onto a rubber polymer, thus containing less than 20wt% of (meth)acrylic alkyl ester, (C) 3-60wt% of a thermoplastic resin obtained by mixing copolymers a, b, c, d and e of aromatic vinyl compound containing different amounts of (meth)acrylic alkyl ester so that the composition satisfies the equation and (D) 0-89wt% of a resin mainly consisting of an aromatic vinyl compound where the amount of the rubber is set to 2-50wt% in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a pyriphenylene ether thermoplastic resin composition having improved heat resistance, impact resistance, molded article surface gloss, and thermal stability.

[Prior art]

4 Liphenylene ether has excellent properties such as heat resistance, chemical properties, and chemical properties. Polyphenylene ether (poor impact resistance, poor processability, poor chemical resistance.

Discolors due to heat at high temperatures. Modified 4? is rarely used alone because it has drawbacks such as sulfurization at high temperatures, and is usually a composition of styrene and rubber-modified polystyrene. Liphenylene ether (used as a resin. Modified, 191) Phenylene ether resin has excellent heat resistance9 mechanical properties, electrical properties, processability, etc., so it is used in automobile parts.

Widely used in office equipment, parts for electrical appliances, etc.

Usually, rubber-modified polystyrene is obtained by dissolving rubbery polymer gold-styrene monomer and then mass-suspension A (combination).For this reason, the rubbery polymer used to advantageously control the solution viscosity and phase inversion. The amount of rubber-modified polystyrene is naturally limited and is usually used at around 10% by weight or less in rubber-modified polystyrene.Compositions with such rubber-modified polystyrene resins and polyphenylene ether resins have sufficient impact resistance. However, when removing the molded product from the special mold yJ), there were cases where the corners and thin-walled parts were cracked. Therefore, it has been attempted to mix a rubber-like elastic body into the composition in order to improve the overall impact resistance, but even in this case, the 1kt/10,000 impact resistance is not sufficient and there are problems such as easy discoloration due to heat and poor processability. It had drawbacks. Also, rubber modified polys f v :/,! :
Compositions with t IJ phenylene ether have the disadvantage that the surface gloss of the molded articles is poor.

Conventionally known modification methods have been used to improve impact resistance,
Heat discoloration resistance, processability, surface gloss of molded products, chemical resistance, etc. are not sufficient. As a method for completely improving this, as shown in Japanese Patent Publication No. 56-4585, modification of polyphenylene ether 1m, 1 fat by blending a rubber-modified styrenic resin obtained by graft polymerization of methyl methacrylate and styrene with a polystyrene resin. A method has been proposed, but according to that method, the surface gloss of the molded product can be improved.

Although chemical resistance is improved, impact resistance and processability are not sufficient. In particular, polyphenylene ether resin has a high softening temperature, so molding is performed at high temperatures, so impact resistance decreases significantly during high temperature molding (see below) (referred to as thermal stability).

[Problem that the invention seeks to solve]

The inventors of the present invention have conducted extensive studies on the composition of polyphenylene ether resin compositions that can be improved in all aspects of heat resistance, impact resistance, surface gloss of molded products, and thermal stability, and have surprisingly found that , a specific amount of an aromatic vinyl compound-(meth)acrylic acid alkyl ester compound copolymer polymerized so that the alkyl (meth)acrylic ester compound-containing compound in the copolymer has a specific composition distribution, and Aromatic vinyl compound grafted onto rubbery polymer
It is confirmed that the above improvement can be sufficiently achieved by blending a specific amount of the graft copolymer with 14 rifhenylene ether in a region where the content of the (meth)acrylic acid alkyl ester compound in the (meth)acrylic acid alkyl ester compound is small. The purpose of the present invention is to provide a novel polyphenylene ether resin composition that has excellent heat resistance, 1III' impact resistance, molded article surface gloss, and thermal stability.

[Problem K: Means to resolve M]

Polyphenylene ether (A) 5 to 95 ffli%, a graft copolymer obtained by graft polymerizing a rubbery polymer with an aromatic vinyl compound or a monomer whose main components are an aromatic vinyl compound and an alkyl (meth)acrylate ester. (B) 3-94 folds, aromatic vinyl compound and (meth)
In a composition consisting of a thermoplastic resin (C) completely copolymerized with an acrylic acid alkyl ester from 3 to 60 parts by weight, and a resin (D) mainly composed of an aromatic vinyl compound from 0 to 89 parts by weight, (a) Composition (b) The content of the rubbery polymer in the product is 2 to 50% by weight, and (b) the content of the alkyl (meth)acrylate in the grafted resinous polymer of the graft copolymer (B) is 20 weight coefficient or less, and (c) the above thermoplasticity (9
Copolymers a, b, c, d in which the fat (C) contains the following (meth)acrylic acid alkyl esters, respectively.
and composition ratio of e JI/b/c/d/e=1~90/1~
Consists of 90/1 to 9010 to 90/10 to 90 (weight ratio); Copolymer a 1 or more and less than 10 weight ratio Copolymer b
lO//20/F Copolymer c 20#40 Copolymer d40#60# Copolymer e It is characterized by having a weight of 60 or more.

chlorine, bromine or iodine, R is a hydrocarbon group, a hydrocarbon ox group, a halokenate hydrocarbon group having at least two carbon atoms between the halodane atom and the heptad enol nucleus, and a halogenated hydrocarbon A monovalent substituent selected from the okyne group, which is the same as R7fiR or a halodane atom (69, R2 and R3) ′″″″″″′1″8
"1°"', i) ;E, LA f"*Xf6.B,
ff1LR, none of R1, R2 and R3 have a tertiary carbon atom) A phenol compound of 1ff1 or more, oxidized under known conditions in the presence of a catalyst Among the above phenolic compounds, particularly preferred are In the formula R'
and R71, each of which is a monovalent substituent selected from a hydrocarbon group having carbon atoms a1 to 8; It is. ), and specific examples of the most preferred phenol compounds are 2.6-dimethylphenol and 2.6-dimethylphenol.

2-Methyl-6-ethylphenol, 2-)f-ru 6
-7 Lilphenol, 2-methyl-6-phenylphenol, 2.6-diphenylphenol.

2,6-Sibutylphenol, 2-methyl-6-propylphenol, 2,3.6-)limethylphenol, 2,3-trimethyl-6-ethylphenol.

2.3.6-) dimethylphenol, 2,3.6-
Examples include dolipropylphenol, 2,6-nomethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol. Most preferred? A specific example of liphenylene ether is 2,6-dimethylphenol. These are polyphenylene ether and polyphenylene ether obtained by copolymerization of 2,6-dimethylphenol and 2.3.6-) dimethylphenol. In particular, 2,3,6-) dimethylphenol and 2,6
-Copolymerized polyphenylene ether obtained from dimethylphenol is heat resistant.

Impact resistance, molded product surface gloss, processability, and solvent resistance.

Good thermal stability.

Used in this invention? Intrinsic viscosity of liphenylene ether [
η] (measured at 30°C in chloroform) is not particularly limited, but is preferably 0.2 to 1 dt/g, more preferably 0
．． 25 to 0.7 dt/l. The content of the present invention O1') phenylene ether in the total composition is from 5 to 94 degrees, preferably from 10 to 60 degrees. ,I? The amount of polyenylene ether is 51 catties -51r ≦ 1,000 yen σ)P 100 η-
900 Zhengyo buto 7h7↓ zepa noiri C1 not included,
If the weight exceeds 94 weight St-, no impact resistance improvement effect is observed.

In the present invention, the rubbery polymer contained in the graft copolymer (B) includes ethylene-α-olefin copolymer, ethylene-α-olefin-polyene terpolymer, polybutanoene, and styrene-butadiene random copolymer. Polymers and block copolymers.

Examples include citric rubber such as butadiene-isogrene copolymer, acrylic rubber, and the like.

The rubbery polymer may be an ethylene-α-olefin copolymer or an ethylene-α-olefin copolymer. The α-olefin used in the Liene terpolymer is a hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, butene-1, intene-1, hexene-11 heptene-1, Examples include 4-methylbutene-1,4-methyl-4-ethene-1, styrene, p-inglobylstyrene, and vinylcyclohexane, with particular preference given to &-i-no. It is pyrene. Moreover, as the polyene compound, 1.
4-<nta, kuen, 1. Ra-he = 1 廿notingso.

2-methyl-1,5-hexanoene, 3,3-methyl-1,5-hexadiene, 1,7-octadiene.

1.9-decatsuene, 6-methyl-1,5-hexadiene, 1,4-hexanoene, 7-methyl-1,6-octanoene, 9-methyl-1,9-undecane.

Isoprene, 1,3-pentanoef t L4,9-7
'Catriene, 4-vinyl-1-cyclohexane, cyclointatzene, 2-methyl-2,5-nor? lunadiene, 5-methylene-2-nordernene, 5-ethylidene-2-nordernene, 5-ingrohylidene-2-nordernene, 5-ingropenyl-2-norbornene, nonclopentadiene.

Examples include tricyclo<ntanoene.

The acrylic rubber may be a polymer obtained from one or more selected from (meth)acrylic acid alkyl esters having an alkyl group having 2 to 12 carbon atoms. , specifically ethyl, butyl, and hexyl (meth)acrylates.

Examples include esters such as octyl, 2-ethylhexyl, and lauryl. In some cases, monomers copolymerizable with acrylic acid alkyl esters can be used up. Acrylonitrile as these monomers.

Vinyltoluene, styrene, α-methylstyrene.

Ethylenically unsaturated monomers such as p-methylstyrene.

Conjugated tzene monomers such as butadiene, isoprene, 2,3-trimethylbutanoene, py4lylene, chloroprene, etc., as described above, I? There are diene compounds, etc. These monomers are 1
It can be used with a seeding speed of 21.1 or higher. (
The preferred ratio of monomers copolymerizable with meth)acrylic acid ester is 100 to 50% by weight of the former to 0% of the latter.
~50 weight (I'm sorry.

The above rubber components can be used alone or in two or more kinds.

Component (B) in the present invention is a resin polymer in which an aromatic vinyl compound or a resinous polymer consisting of an aromatic vinyl compound and an alkyl (meth)acrylic acid ester compound is grafted onto the above-mentioned rubbery composite; The rubbery polymer is present in the polyphenylene ether resin composition in an amount of 2 to 50% by weight. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, methylstyrene, nobromustyrene, p-tertiary-butylstyrene, p-
Examples include methylstyrene, ethylstyrene, vinylnaphthalene, etc., and these can be used alone or in combination of two or more. In addition, examples of (meth)acrylic acid alkyl ester compounds include methyl acrylate and ether acrylate 6-late.

Acrylic acids such as progyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, def-cycloacrylate, octadecyl acrylate, quenylacrylate, pennyl acrylate, etc. Alkyl ester, methyl methacrylate.

Ethyl methacrylate, butyl methacrylate.

Amyl methacrylate, hexyl methacrylate.

There are alkyl methacrylates and esters such as octyl methacrylate, 2-ethylhexyl metodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and pennor methacrylate, and these are used singly or in two or more types.

In addition, it is also possible to copolymerize other vinyl monomers that can be copolymerized with these (91 lipid polymer 30 weight or less, preferably 1 yen or less, more preferably 15 weight or less). The width is not more than 5 times JgJL%, particularly preferably not more than 5 times JgJL%.

Other copolymerizable vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylate, unsaturated acids such as acrylic acid and methacrylic acid, and unsaturated acids such as maleic anhydride, itaconic anhydride, and citraconic anhydride. There are acid anhydrides, and these vinyl monomers are used in combinations of one type and two or more types.

Grafted onto the rubbery polymer (the content of the metacoacrylic acid alkyl ester compound is 20% in the grafted resinous polymer ((B), excluding the rubbery polymer)
M' (i1% or less, preferably ljl.

11f (Pi-ftLJ lower, mf#2 size 1
/ w A -, t it I T
+? It does not contain a methacrylic branched alkyl ester compound.If the (meth)acrylic acid alkyl ester compound exceeds 20 f&=s, the thermal stability will deteriorate.

The content of the above-mentioned rubber 'P' polymer is 2 to 50% by weight, preferably 5% by weight in the polyphenylene ether resin composition of the present invention.
~40% by weight, more preferably 5 to 30 parts by weight, and impact resistance less than 2 parts by weight.

The surface gloss of the molded product is poor. Further, even if it exceeds 50 ef3't-, the effect of improving @1 impact resistance is small and the surface gloss of the molded product is poor, which is not preferable.

In the above graft copolymer (B), grafted (a
(The (meth)acrylic acid alkyl ester content in the lipid polymer and the rubbery polymer content in the polyphenylene ether resin composition -1 piece are determined as follows.

1. Dissolve all fat composition in methyl ethyl ketone and centrifuge 1.
Separation 4! ! Separate the soluble and insoluble components using The insoluble matter is the rubbery polymer and the resinous polymer grafted onto it (
That is, it corresponds to the graft copolymer (B)], while the soluble component corresponds to the non-grafted resinous polymer (that is, the components (A), (C), and A) of the present invention). Polymerization recipe of graft copolymer 9 Content of rubbery polymer in insoluble content based on polymerization conversion rate etc. 0 Grafted copolymer in insoluble content which can be determined by total calculation or analysis.
The content of (meth)acrylic acid alkyl ester in the E polymer and the content of (meth)acrylic acid alkyl ester in the non-grafted resinous polymer in the soluble portion can be determined by infrared spectrum analysis or It can be determined by elemental analysis.

Next, preferred embodiments and manufacturing methods of the graft copolymer (B) will be explained in detail.

The preferred content t of the rubbery polymer in the graft copolymer (B) varies depending on the graft polymerization method or the size of the rubbery polymer particles dispersed in the obtained graft copolymer. For example, graft polymerization methods include bulk polymerization, solution polymerization,
Suspension polymerization, bulk-core: When carrying out liquid polymerization or bulk-suspension polymerization, the particle size of the rubbery polymer is preferably 0.5 to 5 μm from the viewpoint of impact resistance, and from the viewpoint of the surface gloss of the molded product. A range of 0.5 to 2μ is preferable. In this case, the content of the rubbery polymer is preferably 3 to 20% by weight. On the other hand, when the graft polymerization method is carried out by emulsion polymerization, emulsion-suspension polymerization, etc., the particle size of the rubbery polymer is preferably 0.05 to 1μ, and in this case, the content of the rubbery polymer is 10 to 70% by weight,
Furthermore, it is preferably 20 to 60% by weight. In particular, from the viewpoint of impact resistance, it is preferable that the weight is 30 to 500 to 50%.〇The thermoplastic resin composition which has improved heat resistance, impact resistance, molded product surface gloss, etc. with a good balance of gold, which is the object of the present invention, is preferably In order to obtain this, the graft copolymer (B) is preferably produced by emulsion polymerization.

Emulsion polymerization is carried out using commonly used methods and conditions. As the emulsifier used, all known emulsifiers are used, but preferred emulsifiers are rosinate salts such as potassium rosinate and sodium rosinate, potassium oleate, and sodium oleate.

Fats such as potassium laurate, sodium laurate, sodium stearate, potassium stearate, etc.
sodium and mepotassium salts, lauryl sulfate)
Sulfuric ester salts of aliphatic alcohols such as IJum, alkylaryl sulfonic acids such as sodium dodecylbenzenesulfonate, and the like can all be used. As a polymerization initiator, organic hydro-2-oxides such as cumenohydroboroxide, noisozolopylbenzene hydroperoxide, mother ramethane hydroperoxide, etc., sugar-containing pyrophosphoric acid formulation, and sulfoxylate are used as polymerization initiators. , sugar-containing pyrophosphate formulation 7' Redox system initiator in combination with a reducing agent represented by a mixed formulation of sulfoxylate formulation - persulfates such as potassium persulfate and ammonium persulfate; azobisinobutyro nitrile,
Pennzoylno 9-oxide.

It is possible to use lauroirno-9-oxide or the like as an additive. Particularly preferred are cumene hydroba and -oxide from the viewpoint of molded product surface gloss and thermal stability.

Diisopropylbenzene hydroperoxide.

Organic hydroperoxides represented by paramenthane hydro-g-oxides, sugar-containing picric acid formulations, sulfoxylate formulations, sugar-containing birophosphoric acid formulations/sulfoxylate formulations, etc. It is a redox initiator in combination with a reducing agent. Preferred molecular weight modifiers are normal octyl mercaptan, normal dodecyl mercaptan, and tert-dodecyl mercaptan.

Melkagut ethanol, etc., various chills 4
and halodanized hydrocarbons such as chloroform and carbon tetrachloride can be used.

The amount of the resinous polymer grafted to the rubbery polymer in the present invention, that is, the grafting ratio (insoluble portion in the solvent methyl ethyl ketone)
It is preferable to rejuvenate impact resistance, heat resistance, molded product surface gloss, and thermal stability. It is in the range of 30% to 150% by weight, more preferably 50% to 120% by weight. Further, the thickness of the resin polymer grafted onto the surface of the rubbery polymer is preferably in the range of 100 to 200 mm from the viewpoint of the surface gloss of the molded product. The thickness of this resinous polymer is externally grafted resinous polymer't? Using the general method of iM sensing,
It can be measured from electron micrographs.

In the present invention, when a resin-forming component is graft-polymerized to a rubbery polymer by emulsion polymerization, the rubbery polymer used is in a latex state. As this latex, a rubbery polymer latex obtained by an emulsion polymerization method can be used, or a solid rubbery polymer obtained by another method can be used as a monomer and/or a solid rubbery polymer latex obtained by an emulsion polymerization method.
Alternatively, a rubbery polymer latex obtained by dissolving in an organic solvent and forming an emulsion may also be used. Preferred rubbery polymer latex butterfly used ■ Particle size 500X ~ 1
730^ is present at 70% by weight or more, and the content of r(toluene insoluble part, the same applies hereinafter) is 50% by weight or more, ■ Particle size of 1730X to 4400X is 70% by weight.
4 or more and the dull content is 60% by weight or more; (2) The polymer latex has 50 or more particles with a particle diameter of 4400 Å or more and the dull content is 70 to 20% by weight; (2) The polymer latex mentioned above; /■=5~70/95~30 weight t
A mixture of S, ■the above polymer latex■/■
= 95-515-95 Mgk% mixture, ■
Said polymer latex ■/■/■=10~60/85~
It is a mixture having a weight of 3015 to 60 kg. ■Also, when the rubbery polymer Latex 4'':r of ■ and ■ is used, there is no orientation cracking especially in the impact of a falling bell, and it shows very stable impact strength.Also, the rubbery polymer latex of ■ and ■ When using , the surface of the molded product is good and has good gloss.

The content of the graft copolymer CB) is 3 to 94% by weight, preferably 5 to 80% by weight, and more preferably 10 to 70% by weight, based on the fl:H polyphenylene ether resin composition. If the amount is too high, the heat resistance will be poor.

In the present invention, the thermoplastic resin (C) consists of an aromatic vinyl compound and an alkyl (meth)acrylate compound. As the aromatic vinyl compound and the (meth)acrylic acid alkyl ester compound used here, all of the above-mentioned aromatic vinyl compounds and (meth)acrylic acid alkyl ester compounds are used. It is also possible to copolymerize other vinyl monomers that can be copolymerized with these, and these monomers preferably have 30 or less carbon atoms, more preferably 15 tons or less, in the thermoplastic resin (C). The weight ratio is less than or equal to 5, particularly preferably 5 and 11 or less. As these other copolymerizable vinyl monomers, the above-described other copolymerizable vinyl monomers are used.

In addition, in the graft copolymer (B), when an aromatic vinyl compound and an alkyl (meth)acrylic acid ester compound are used as graft monomers, both copolymers that are not grafted to the rubber are used as the thermoplastic resin (C). Considered as an ingredient.

The thermoplastic resin (C) is characterized in that the content of the (meth)acrylic acid alkyl ester compound is composed of the following copolymers (,) to (,) having a specific composition distribution. That is, (a) the content of the (meth)acrylic acid alkyl ester compound is 1 to 90% by weight, preferably 1 to 50% by weight. 5-30 J
It is a matter of ij quantity. If it is less than 1% by weight, heat resistance, impact resistance,
The surface gloss of the molded product is poor. Moreover, if the weight exceeds 90, the impact resistance will be poor.

(b) The copolymer component having a composition in which the content of the (meth)acrylic acid alkyl ester compound is 10 to 20 mm is 1 to 90 [11 dφ, preferably 5 to 7 mm.
0 weight ja: s, more preferably f'i 10 to 60 weight -[
It is 11ch. If the width is less than 1 ton, the heat resistance and impact resistance will be poor, and if it exceeds 90 ton width, the impact resistance and solvent resistance will be poor. (C) The content of the (meth)acrylic acid alkyl ester compound is 20% by weight or more, and the copolymerization component of the composition is 1 to 90 weights, preferably 5 to 80 weights. , more preferably 10 to 70% by weight.

If it is less than 1 layer, the impact resistance and paintability will be poor, and if it exceeds 90 layers, the heat resistance, impact resistance, and solvent resistance will be poor.
) A copolymer component having a composition in which the (meth)acrylic acid alkyl ester compound content is 40 to 60% by weight, preferably 0 to 90% by weight, preferably 0 to 30% by weight,
More preferably, it is 0 to 20% by weight. 90 views)
Heat resistance, impact resistance, and molded product surface gloss exceed the lattice.

Poor thermal stability. (e) The copolymer component having a composition having a (meth)acrylic acid alkyl ester compound content of 60% by weight or more is preferably 0 to 90% by weight. If the weight exceeds 90, it has impact resistance and heat resistance.

Poor thermal stability, molded product surface gloss, and paintability. The average content of the (meth)acrylic acid alkyl ester compound in the thermoplastic resin (C) is 10 to 60, preferably 15 to 50, more preferably 15 to 4
It is particularly preferably 20 to 35 weight fc4. If the content of the (meth)acrylic acid alkyl ester compound is less than 10%, the surface gloss and impact resistance of the molded product will be poor.

In addition, when exceeding 60 weight SS, the surface gloss of the molded product, heat resistance,
Impact resistant.

Poor thermal stability.

These thermoplastic resins (C) account for 3 to 60% by weight, preferably 5 to 60% by weight, in the polyphenylene ether resin composition of the present invention.
It is 50% by weight, more preferably 5 to 30% by weight. 3
Less than % by weight, heat resistance.

Molded product surface gloss, impact resistance, and paintability are poor, 60 1
If it exceeds % by weight, impact resistance and heat resistance will be poor.

As mentioned above, the above thermoplastic resin (C) contains polymer components (a) to (o) that differ in (meth)acrylicty alkyl ester compound-containing [l], but this differs depending on the resin used. It can be obtained by polymerization while varying the monomer composition of the forming components.

As a method for measuring the composition distribution in the thermoplastic resin (C), for example, Polymer Journal Mol 6.4
6 e 532-536 (1974) (described later in Examples), it can be measured by changing the ratio of good solvent to poor solvent.

The thermoplastic resin (C) may be 2 as long as it does not exceed the scope of the present invention.
More than one species may be used in combination.

The aromatic vinyl resin CD) component used in the present invention is a polymer of an aromatic vinyl compound. Other vinyl monomers copolymerizable with the aromatic vinyl compound include the aforementioned acrylic acid alkyl esters, methacrylic acid alkyl esters, vinyl cyanide compounds,
[There are tetrahydric acid, etc. As these monomers, all the monomers mentioned above are used. Preferred aromatic vinyl resin (D)
Specific examples include styrene-acrylonitrile copolymer,
Styrene-maleic anhydride copolymer.

These include polystyrene, styrene-α-methylstyrene-acrytetranitri-methyl methacrylate copolymer, and the like. Particularly preferred is polystyrene.

The content of the aromatic vinyl resin (C) in the polyphenylene ether resin composition of the present invention is from 89 to 0 by weight,
Preferably 80 to 10 weight, more preferably 60 to 2
It's a lot of ON. If the weight exceeds 89, heat resistance, impact resistance, and paintability will be poor.

A method for producing a phenylene ether composition of the present invention will be explained.

Is the 4-refined nylene ether composition of the present invention included in the composition? It is only necessary that the liphenylene ether resin component (PPE) (A), the graft copolymer (B), the thermoplastic resin component (C), and the styrene resin component CD) each contain amounts within the range of the present invention. The manufacturing method for obtaining the composition is not particularly limited. The method is shown below.

(1) (B), (C)? Component (D) is produced by a generally known polymerization method, and these and P
A method of mixing with PE, (2) CB) and component (C) are produced by a known polymerization method (not polymerized separately but at the same time) and the polymer and υ
) into PPE; (3) components (B) and CD) are produced at once instead of being polymerized separately by a known polymerization method, and the polymer and (C) are prepared at the same time.
(4) A method in which components (C) and
B) is mixed with ppg K, (5) (B) F (C) and I) are produced by a known polymerization method (not polymerized separately but all at once) and mixed with ppF, etc. Can be mentioned.

When carrying out gold emulsion polymerization of aromatic vinyl, etc. in the presence of a rubbery polymer as a method for improving thermal stability, which is one of the objects of the present invention, after dissolving an antioxidant in the monomer before starting polymerization,
If the rubber polymer and the monomer in which the antioxidant is completely dissolved are stirred in the polymerization system at a temperature ranging from room temperature to 8oC and then the entire polymerization reaction is carried out, a composition with good thermal stability can be obtained. A polyphenylene ether resin composition containing a thermoplastic resin obtained by this method is also included within the scope of the present invention. Here, when bringing the rubbery polymer and the monomer into contact with each other, the amount of emulsifier is reduced as much as possible, and a small amount of a water-soluble organic solvent such as acetone is added to further stabilize the heat. It can improve the properties. The antioxidant used here is a commonly used and well-known antioxidant, and may be one having a vinyl bond or one having no vinyl bond, but preferably one having a vinyl bond. be.

The phenylene ether resin composition of the present invention can be obtained by mixing using a solution blender, mixed wire extruder, Banbury, kneader, or the like. Moreover, various molded products can be obtained from the polyphenylene ether resin composition by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.

When using the polyphenylene ether resin composition of the present invention, commonly used antioxidants, ultraviolet absorbers, and additives, etc. @Fuel agent, antistatic agent.

A blowing agent and glass fiber Apk can be blended.

Particularly preferred antioxidants are phosphorus-based antioxidants,
Also preferred is item 1 (the flame retardant is a phosphorus flame retardant represented by triphenyl phosphate, tri(nonylphenyl) phosphate, etc.).

Also, 4? of the present invention? Depending on the required performance, the refined nylene ether resin composition may be further combined with other known polymers, such as
Polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-glopyrene copolymer, EPDM
, styrene-butadiene block copolymer (combined), styrene-butadiene-styrene block copolymer and hydrogenated product, styrene-butadiene-styrene lanoartele block polymer.

and hydrogenated substances, 4ligropyrene, butanoene-acrylonitrile copolymer, polyvinyl chloride, polycar 11?
nate, PET, PBT, polyoxymethylene, 7I? Riamido, engineering d? xy resin, polyvinylidene fluoride 9,1? Risulfone, ethylene-vinyl acetate copolymer No. 9? Lysogren, natural rubber, chlorinated butyl rubber,
Chlorinated polyethylene l PPS 4a4+1h t,
I? It may be used by appropriately blending it with IJ ether ether ketone or the like.

Next, the present invention will be explained in more detail with reference to production examples and examples, but these are merely illustrative and do not limit the scope of the present invention. In addition, each side below (part and section indicate the anal part and weight%, respectively).

Production Example CD Phenylene ether (A) used in Examples and Comparative Examples was obtained by the following method.

Production of Polymer-A-1 (Polyphenylene Ether) An oxygen blowing device and a cooling coil are installed at the bottom of the reactor.

After sufficiently purging the inside of a stainless steel reaction vessel equipped with a stirrer with nitrogen, cupric bromide 53.6F and di-n-butylamine 1110.9. Furthermore, add 2,6-xylenol to 4 ol of toluene and 8. r5klPk'f6 was dissolved and added.

The polymer was heated for 90 minutes while stirring. During assembly, water was circulated through the cooling coil to maintain the internal temperature at 30°C. <rr
After finishing the stand, add 301f of toluene and add 40 ethylenenoamine.
'p At trisodium 430Ft-soluble in water 11+'
A 20% aqueous solution was added to stop the reaction. The polymer solution phase was removed by centrifugation. While vigorously stirring the polymer solution phase, methanol was gradually added to form a slurry. After being separated, the polymer was thoroughly washed with methanol, further separated in a furnace, and then dried to obtain Polymer A-1.

Polymer A-2 was obtained by performing polymerization in place of the phenolic compound 2.6-xylenol/2,3.6-drimethylphenol = 90/10 (mole ratio) used in the production method of Polymer A-1. Ta. (Copolymer type ppg) (II) Graft polymer C used in Examples and Comparative Examples
B) was obtained by the following method.

Copolymer) After sufficiently purging the interior of a stainless steel reaction vessel with a stirrer with total nitrogen, polybutadiene latex (JSR=ll-07
00 particle size 0.2-0.3μ) 4000g (Ii'; 1 form).

Disproportionated potassium rosin acid 130.9, potassium hydroxide 12g, styrene 2500.5', ion exchange water ・
After adding 14,000 Jt, the temperature was raised while circulating hot water at 70°C in the jacket. When the internal temperature reaches 50°C, add 20.0 g of sodium birophosphate to 950 g of ion exchange water. ! 9. Glucose 25,9. An aqueous solution containing 4I ferrous sulfate and cumene hydrogluoxide 25.
2Ji't" was added and the polymerization reaction was carried out for 2 hours. Then, an emulsion consisting of 3500 #styrene, 1701 #disproportionated potassium rononate, 18 I potassium hydroxide, 5009 ion-exchanged water, and 25.2 JFTh of cumenehypyrono-9-oxide was added for 3 hours. After addition of the emulsion, sodium pyrophosphate 6.7.5' and Pudoui Y5 were added continuously for a polymerization reaction.
8.3g, sulfuric acid η) 1 iron 0.13g, ion exchange water 31
7. ! i'd, aqueous pericardial fluid and cumene hydro-monooxide 0.71! The polymerization reaction was completed after 1 hour. After adding the antioxidant emulsion, it was coagulated with an aqueous sulfuric acid solution and then dried to obtain a polymer B-1i.

; 1 Polymer B-2 (styrene-butadiene copolymer was substituted with styrene-butanoene copolymer latex (particle size 0.07 to 0.09μ) instead of the polybutatsuene latex used in the production of polymer B-1. ) to form polymer B-
I got 2.

pK styrene-butanoene copolymer latex (JSR≠0561 particle size 0.5-0.7μ) instead of polybutanoene rubber latex used in the production of Polymer B-1
Polymer B-3 was obtained using

Polybutanoene latex (J
SR≠0700)/styrene-butanoene cot (combined latex (particle size 0.07 to 0.09 μ) = 5 o/
50 (:ii ffl ratio) Polymer B-4 was obtained by kongou, Polymer B-5 (t?liptadiene-styrene-methylene) After thoroughly replacing the inside of a stainless steel reaction vessel with a stirrer with nitrogen, 1680 g of methyl methacrylate was obtained. .

Styrene 1400F, disproportionated potassium rononate so,
p, potassium hydroxide II, ion exchange water 10, 300
After adding #, the mixture was thoroughly stirred, and the temperature was raised while circulating hot water at 70°C through the Noyakette. When the internal temperature reached approximately 50°C, an aqueous solution of 20 g of sodium rophosphate, 25.9 g of glucose, and 0.41 g of ferrous sulfate dissolved in 950 g of ion-exchanged water and cumene hydro/4-oxide 7,4, P was completely added and the first stage polymerization was carried out for 2 hours. Continue with styrene 1400. P, methyl methacrylate 60I, disproportionated potassium rosinate 60y, potassium hydroxide 1.2,9.
Ion exchange water 3000 yen! i. An emulsion containing 6.71 g of cumene hydro-9-oxide was continuously added over 2 hours to carry out a polymerization reaction. 1 of this second stage combination reaction
4 ribs per hour latte, couscous (JSR+0700)
/Styrene-butanoene copolymer latex (particle size 0.
A second reaction was carried out by adding 400 (solid content) of 50150 (07~0.09μ).Furthermore, 1 styrene
400.9, methyl methacrylate 60S, disproportionated potassium rosinate 40.9, potassium hydroxide 0.8! j
, ion exchange water 2000.9. A third stage polymerization reaction was carried out while continuously adding an emulsion containing 4.4 g of cumene hydro p-oxide over a period of t-2 hours. After that, 6.7 g of sodium pyrophosphate and 8.3.9 g of glucose were added.
Ferrous sulfate 0.13.9. After adding an aqueous solution consisting of ion-exchanged water 317I and cumene hydroglyoxide, a polymerization reaction was carried out for 1 hour.

All operations have been completed.

The polymer was recovered in the same manner as Polymer B-1 to obtain Polymer B-5.

Similarly, polymer B-6 was obtained by varying the styrene/methyl methacrylate ratio at each polymerization stage.

In Polymer B-5 and 13-6, the composition of the resin polymer (copolymer) that is not grafted to the rubber is as shown in the following table, and these can be considered as part of component (C). .

*The methyl methacrylate content in the non-grafted resin polymer was determined by IR (infrared analysis).

**The composition distribution of methyl methacrylate in a non-grafted resin polymer is determined by the weight of the polymer precipitated by adding acetone little by little to a homogeneous solution in which a fixed amount of thermoplastic resin is dissolved in methyl ethyl ketone, and the methyl methacrylate determined by IR. O determined by measuring methacrylate content After the interior of a stainless steel reaction vessel with a stirrer was sufficiently purged with nitrogen - Liptadiene latex (JSR4P0700)
/Styrene-butanoene copolymer latex (particle size 0.
07~0.09μ) = 50150t-4000!9 (solid content), styrene 1400. F, methyl methacrylate 600,9. Disproportionated potassium rosinate soI! After adding potassium hydroxide II and ion-exchanged water at 10,300F, the mixture was thoroughly stirred, and the temperature was raised while circulating hot water at 0°C through the salmon door. When the internal temperature reaches 50°C, add an aqueous solution prepared by dissolving 20g of sodium birophosphate, 25I of glucose, and 0.41C of ferrous sulfate in 950.91C of ion-exchanged water.
7.41 t of hydrogen oxide was added and polymerization was carried out for 1 hour. Subsequently, styrene 1400I, methyl methacrylate 600.9, disproportionated potassium rosin acid 6
09, potassium hydroxide 1.2, 9. Ion exchange water 300
0.9. Polymerization was carried out by continuously adding an emulsion containing 6.7 g of cumene hydro/mer oxide over a period of 1 hour. Furthermore, styrene 1400L methyl methacrylate 600.9, disproportionated potassium rosin acid 40#l water fi! Potassium dioxide 0.81 + ion exchange water 2000
,9. Cumene hydro/mother-oxide 4.4.9Th
Polymerization was carried out while continuously adding an emulsion containing the following over 1 hour. After that, sodium pyrophosphate 6.7,9.
Grape 1f, 't8.3.9. Ferrous sulfate 0.131!
was added to an aqueous solution consisting of 317 g of ion-exchanged water and 5.9 g of cumene hydroseoxide, and the polymerization reaction was completed for 1 hour.

The polymer was recovered in the same manner as Polymer B-1 to obtain Polymer B-7.

In a stainless steel reactor equipped with a paddle type stirrer,
Polybutanoene (JSR.

All polymers having the same methyl methacrylate composition distribution as Polymer B-5 were produced by solution polymerization using BRO2L)'e. The average rubber particle size in the polymer was 1 to 2μ.◎ In the printing of Polymer B-B, the stirring during transfer was strengthened,
Polymer B-9' having an average rubber particle size of 0.5 to 0.6μ
ff1(!J) The compositional distribution of methyl methacrylate content is the same as that of polymer 13-5.

In the production of polymer n-8, polymer B-1 was obtained by combining without using methyl methacrylate content.
0 futai [I ta.

The content of polymer B (methyl ethyl ketone insoluble portion) produced by the above polymerization method is shown below.

Polymer B which is a polymer containing the above methyl methacrylate
-5. Small a body B-6 and polymer B-7) were grafted with (η (methyl methacrylate content Fk in the fat polymer) and measured by the following method.

Contains @: Polymer B-52 Polymer B-6 and Polymer B-7 were each weighed II, dissolved in 25d methyl ethyl ketone by shaking for 24 hours, and then centrifuged at 23 OOO rpm to dissolve methyl ethyl ketone. It was separated into the molten part and the fushi part. After drying the methyl ethyl ketone soluble portion, 1? I looked at the absorption of IJ butanoene, but the absorption of polybutanoene is only one.

The insoluble part was dried and the weight fraction of the insoluble part was measured, and the methyl methacrylate content was determined from the infrared analysis results of the insoluble part, and the methyl methacrylate content in the grafted resin polymer was determined.

As a result, the content of methyl methacrylate in the grafted resin polymer is as follows.

Polymer B-5: 5.0 cm Polymer B-6: 30 cm Polymer B-7: 30 cm Cfl) Thermoplastic resin used in Examples and Comparative Examples (
C) 'The component was obtained as follows.

Production of polymer C-1 In the production of polymer B-5, polymerization was carried out without using a rubbery polymer, that is, polymerization was carried out by changing the styrene/methyl methacrylate ratio at each polymerization step, thereby producing f1 polymer c-
The following thermoplastic resin (C)'t- was obtained by changing the number of polymerization steps and changing the styrene/methyl methacrylate (tt) in each polymerization step in the same manner as in obtaining No. 1.

* Methyl methacrylate content in thermoplastic resin is I
It was determined from R (infrared analysis).

** The composition distribution of methyl methacrylate in a thermoplastic resin can be determined by adding acetone little by little to a homogeneous solution in which a certain amount of a thermoplastic resin is dissolved in methyl ethyl ketone, and determining the methyl methacrylate content by observing the precipitated polymer bands and IR. It was determined by measuring @.

[■] As the polystyrene resin (D) used in Examples and Comparative Examples, polystyrene was used as a toluene tS medium.
It was produced by thermal polymerization at 20-130°C.

Examples and Comparative Examples Seven of the various polymers were combined according to the composition ratios in Table 1,
After being extruded into 4-lets using a two-wheel kneading extruder at a temperature of 240 to 260°C, it is sufficiently dried, and then molded using an injection molding machine at a Schilling-1 grade of 280°C and a mold temperature of 50°C to achieve impact resistance and heat resistance. , molded product surface gloss.

A test piece for evaluating thermal stability was measured according to the test method described below under Molding 1, and the results are shown in 1N-1.

Evaluation method (1) Heat resistance According to ASTM D628, thickness 1/4" + 264p
The heat distortion temperature was measured with s i.

The thickness was measured according to ASTM D256 with a thickness of 1/4'' and a notch.

(3) Molded Product Surface Gloss Flat plates with a thickness of 2.4 were injection molded, and the molded product surface gloss was measured using a color difference meter manufactured by Suga Test Instruments.

After the various polyphenylene ether resin compositions were allowed to stay in the cylinder of an injection molding machine at a temperature of 280° C. for a total of 15 minutes, test pieces for measuring impact resistance were molded and measured with a thickness of 1/4 notch according to ASTM D256.

〔Effect of the invention〕

As described above, according to the present invention, a graft copolymer (
(Meta) in the grafted resin 1'1 polymer of B)
Heat resistance, by making the thermoplastic resin (C) from a polymer containing (meth)acrylic acid alkyl ester and having a specific composition distribution, with the content of acrylic acid alkyl ester being less than 20% by weight of gold. A polyphenylene ether resin composition with improved impact resistance, molded product surface gloss, and thermal stability in a well-balanced manner can be obtained.

Claims (1)

[Claims] 5 to 95% by weight of polyphenylene ether (A), graft polymerized with an aromatic vinyl compound or a monomer whose main components are an aromatic vinyl compound and an alkyl (meth)acrylate ester on a rubbery polymer. Graft copolymer (B
) 3 to 94% by weight, a thermoplastic resin formed by copolymerizing an aromatic vinyl compound and a (meth)acrylic acid alkyl ester (C) 3 to 60% by weight, and a resin mainly composed of an aromatic vinyl compound (D) In a composition consisting of 0 to 89% by weight, (a) the content of the rubbery polymer in the composition is 2 to 50% by weight, and (b) the resin material grafted with the graft copolymer (B). The (meth)acrylic acid alkyl ester content in the polymer is 20% by weight or less, and (c) the above thermoplastic resin (C) is each of the following (meth)
Copolymer a with acrylic acid alkyl ester content
, b, c, d and e composition ratio a/b/c/d/e=1~
Consists of 90/1 to 90/1 to 90/0 to 90/0 to 90 (weight ratio); Copolymer a 1% or more and less than 10% by weight Copolymer b 10〃20〃 Copolymer C 20 〃40〃 Copolymer d 40〃60〃 Copolymer e 60% by weight or more of a polyphenylene ether resin composition.