JPS6151051A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having well-balanced properties among resistance to heat, impact and solvents, processability and surface gloss of moldings, consisting of a polyphenylene ether, a thermoplastic resin and a styrene resin. CONSTITUTION:1-99mol% of a phenol compd. of formula I [wherein X is H, Cl, Br, I; R<1> is a hydrocarbon(oxy) group contg. no tertiary carbon atom, a halogenated hydrocarbon(oxy) group contg. at least two C atoms between the phenol nucleus and a halogen atom; R<2> is R<1> or halogen] is reacted with 99- 1mol% of a phenol compd. of formula II (wherein X' is X; R3, R4 are each R1; R5, R6 are each H, R1 provided that at least one of R5, R6 is alway a group other than H) to obtain a polyphenylene ether (A). 5-95wt% component A, 95- 5wt% thermoplastic resin (B) obtd. by polymerizing an arom. vinyl compd. in the presence of a rubbery polymer having a particle size of 0.05-0.8mum and 0- 85wt% styrene resin (C) are blended together.

Description

[Detailed Description of the Invention] [Field of the Invention] The present invention relates to polyphenylene ether resin compositions, and more specifically, the present invention relates to polyphenylene ether resin compositions, and more particularly, to heat resistance, impact resistance, impact resistance during high temperature molding, surface gloss of molded products, and processing. The present invention relates to a phenylene ether resin composition with improved properties and solvent resistance in a well-balanced manner.

[Prior art]

Polyphenylene ether resin has excellent heat resistance, mechanical and electrical properties, but has disadvantages such as poor impact resistance and processability, and thermal discoloration and dulling at high temperatures. Therefore, it is rarely used alone, and is usually used as a modified polyphenylene ether resin composed of a composition with rubber-modified polystyrene or the like. This modified polyphenylene ether resin has excellent heat resistance, mechanical/electrical properties, processability, etc., and is therefore widely used for parts for civil servants, office equipment, electrical appliance parts, etc.

However, rubber-modified polystyrene is usually obtained by dissolving a rubbery polymer containing polybutadiene as a main component in styrene monomer and then performing bulk-suspension polymerization.
In order to advantageously guide the phase transition in consideration of solution viscosity, the f! : It is necessary to limit υ, usually ko9
It is used in an amount equal to or less than the lot amount of polystyrene modified with polystyrene. However, a composition of such amounts of rubber-modified polystyrene and polyphenylene ether
The impact resistance was not sufficient, and when the molded product was removed from the mold, the corners and thin-walled parts sometimes cracked. Therefore, it has been attempted to mix a rubber-like elastic body into the composition for the purpose of improving the impact resistance, but in this case too, the impact resistance is not sufficient, and it also tends to discolor due to heat and has poor processability. It had disadvantages such as being inferior. Furthermore, since these modified polyphenylene ether resins have high heat resistance, very high temperatures are required when molded products are obtained by injection molding. The resin had the disadvantage that its strength decreased when it remained in an injection molding machine at high temperatures (hereinafter, impact resistance during high temperature molding is referred to as thermal stability). Compositions of rubber-modified polystyrene and polyphenylene ether also had drawbacks such as poor surface gloss of molded products and poor solvent resistance.

The present inventors have conducted intensive studies to obtain a polyphenylene ether resin composition that is excellent in not only heat resistance but also other properties such as impact resistance, thermal stability, molded product surface gloss, processability, and solvent resistance. Results 1. Surprisingly, the specific structure 2.
The present inventors have discovered that the above characteristics can be sufficiently imparted by blending polyphenylene ether obtained by copolymerizing various phenolic compounds with a specific styrene resin, and have thus arrived at the present invention.

[Purpose of the invention]

The object of the present invention is to provide a polyphenylene ether resin composition that has well-balanced improvements in heat resistance, impact resistance, thermal stability, molded article surface gloss, processability, and solvent resistance.

The above purpose is as follows: (A) Polyphenylene ether 5-95% by weight, ω
) Thermoplastic resin obtained by emulsion polymerization of aromatic vinyl compounds in the presence of rubbery polymer latex
A polyphenylene ether resin composition comprising (A)
The polyphenylene ether is a copolymer obtained by copolymerizing a phenol compound represented by the following general formula (a) and a phenol compound represented by the following general formula (b), and the thermoplastic polyphenylene ether of (B) This is achieved by the polyphenylene ether resin composition of the present invention, wherein the rubbery polymer has a particle size of 0.05 to 0.8 μm when dispersed in the resin.

A polyenylene ether resin composition characterized by.

General formula (a): General formula (b): (In general formulas (a) and (b), X and X' are hydrogen atoms, chlorine atoms, bromine atoms, or iodine atoms, respectively.
D, R, are hydrocarbon groups; hydrocarbon oxy groups; general formula (I
); and a halodanized hydrocarbon oxy group having at least two carbon atoms in the bond between the phenol nucleus and the rhodan atom; , R2 is one of the groups represented by R1 or a halogen atom, R3 and R4 are each one of the groups represented by R1, and R
5 and R6 are each one of the groups represented by R1 above.
one group or a hydrogen atom. However, R5 and 86 do not become hydrogen atoms at the same time, and Rlt R2r R3+
R4r Neither R5 nor R6 has a tertiary carbon atom. ) [Embodiment] The polyphenylene ether (g) used in the present invention is
A copolymer obtained by oxidative coupling polymerization of at least one phenol compound represented by the general formula (a) and at least 1m of the phenol compound represented by the general formula (b) in the presence of a known catalyst. It is a combination.

Among the phenolic compounds of general formula (a), the general formula (-'): R'1 (wherein R' and R'2 are each selected from a hydrocarbon group having 1 to 8 carbon atoms) is particularly preferable. (It is a monovalent group.) Preferred specific examples include 2,6-methylphenol,
2.6-diethylphenol, 2-)thyl-6-ethylphenol, 2-methyl-6-71Jruphenol, 2
-Methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-sibutylphenol, 2-methyl-6-f-ropylphenol and the like.

Particularly preferred among the phenol compounds of general formula (b) are general formula (b'): (wherein R1 and R'2 are each a monovalent group selected from hydrocarbon groups having 1 to 8 carbon atoms). RQ and RS are each a monovalent group selected from hydrocarbon groups having 1 to 8 carbon atoms or a hydrogen atom.However, Ra and R'6 cannot be hydrogen atoms at the same time.) As a preferred example, 2,3,6-trimethylphenyl
.

enol, 2,3-dimethyl-6-ethylphenol,
Examples thereof include 2,3.6-) diethylphenol, 2,3.6-doliprobylphenol, 2,6-dimethyl-3-ethylphenol, and 2,6-nomethyl-3-propylphenol.

The phenolic compound represented by the general formula (,) and the general formula (
The proportion of the phenolic compound indicated by b) is expressed as (in molar ratio) (
a)/(b)=1/99 to 99/1, preferably 5015 o to 99/1, more preferably 70/30 to 98/2. By using all the I-lifenylene ethers within these ranges, improvements in heat resistance, wI bonding resistance, surface gloss of molded products, processability, solvent resistance, and thermal stability can be particularly advantageously achieved. The intrinsic viscosity [η] (at 30°C in chloroform) of the polyphenylene ether (A) used in the present invention is not particularly limited, but is preferably 0.15 to 1 dl/I. More preferably, it is 0.2 to 0.5 dl171. The amount of polyphenylene ether blended in the polyphenylene ether resin composition of the present invention is 5 to 95 parts by weight, preferably 10 to 60 parts by weight. When the amount of polyphenylene ether is less than 5% by weight, no significant effect on improving heat resistance is observed, and when it exceeds 95% by weight, no effect on improving impact resistance and workability is observed.

The rubbery polymers used in the rubbery polymer latex used in the thermoplastic resin (B) include ethylene-α-olefin copolymer, ethylene-α-olefin-polyene terpolymer polybutadiene, and styrene-butadiene. Examples include random copolymers and block copolymers, diene rubbers such as acrylonide-butadiene copolymers, butadiene-isoprene copolymers, and non-zene rubbers such as acrylic rubbers.

The ethylene-α/olefin copolymer, ethylene-α
・Olefin-polyene ternary combination! α used for merging
Olefin is a 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, styrene, p-
Examples include inglobylstyrene and vinylcyclohexane, but propylene is particularly preferred. Further, the polyene compounds include 1,4-pentadiene, 1,5
-hexadiene, 2-methyl-1,5-hexadiene,
3,3-dimethyl-1,5-hexadiene, 1,7-octadiene, 1,9-deca diene, 6-methyl-1,
5-hexadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 9-'methyl-1,9-undecane, isoprene, 1,3--'! Octadiene 1
, 4.9-decatriene, 4-vinyl-1-cyclohexane, cyclopentadiene, 2-methyl-2,5-nor? lunadiene, 5-methylene-2-norbornene, 5-
Examples include ethylidene-2-norbornene, 5-impropylidene-2-norR runene, 5-impropenyl-2-norbornene, dicyclontadiene, tricyclopentadiene, and the like.

The acrylic rubber may be a polymer obtained from one or more monomers selected from (meth)acrylic acid alkyl esters having an alkyl group having 2 to 12 carbon atoms. is ethyl (meth)acrylate,
Examples include esters such as butyl, hexyl, octyl, 2-ethylhexyl, and lauryl. In some cases, monomers copolymerizable with acrylic acid alkyl esters are used. These copolymerizable monomers include ethylenically unsaturated monomers such as acrylonitrile, vinyltoluene, styrene, α-methylstyrene, p-methylstyrene, butadiene, isoprene, 2,3-dimethylbutadiene,
Examples include conjugated diene monomers such as birylene and chloroprene, and the aforementioned polyene compounds. These monomers can be used alone or in combination of two or more. The preferred amount of the alkyl ester of (meth)acrylic acid and the copolymerizable monomer is O to 50% by weight of the former.
50 weight section. The rubbery polymer is one type or two fi
It can be used with i and above. Particularly preferred dimeric polymers are polybutadiene and styrene-butadiene copolymers. The rubbery polymer is used in a latex state, and the rubbery polymer latex may be obtained by emulsion polymerization, or the rubbery polymer may be dissolved in a solvent or the like and then treated with a surfactant or the like. It may also be obtained by adding and re-emulsifying. The thermoplastic phase resin of CB) is obtained by emulsion polymerization of an aromatic vinyl compound in the presence of the rubbery polymer latex, and has superior thermal stability and surface gloss of molded products compared to those polymerized by other methods. . Furthermore, although the particle size of the sticky polymer used by the present inventors in polymerization is approximately the same as the particle size of the sticky polymer in the resulting thermoplastic resin or polyphenylene ether resin composition, molding may vary depending on its size. It was discovered that the surface gloss, solvent resistance, thermal stability, and impact resistance of the product changed significantly.

That is, in the polyphenylene resin composition of the present invention, the particle size of the rubbery polymer dispersed in the composition is 0.05.
It is necessary that the range is between μ and 0.8 μm, preferably 0.05 and 0.5 μm, and more preferably 0.05 μm.
~0.45 am. If it is less than 0.05 ttm, the impact resistance and surface gloss of the molded product will be poor. If it exceeds 0.8 μm, thermal stability, molded product surface gloss, and polymerization stability will deteriorate. The amount of polymer in the thermoplastic resin (B) is 5 to 8.
It is preferably 0 weight -IO:%, especially when it is 30 to 60 weight percent, the solvent resistance and thermal stability are good.

The preferred polymer latex used is ■particle size 500X.
- 1730X is present on a 70-weight plate, and the content of glue (toluene insoluble portion, the same applies hereinafter) is on a 50-weight plate, ■ Particle size is 1730X-4400X is 7
0 weight or more and the dull content is on a 60 weight plate, or 50 weight 4 with a particle size of 4400X or more
or more, and has a dull content of 70 to 20 weight.

■When using the rubbery polymer latex, it is especially effective!
'9rI'jA exhibits very stable gI impact strength without poor orientation cracking. In addition, when the rubbery polymer latex of (2) is used, the molded product has good surface gloss and paintability.

Aromatic vinyl compounds used in the present invention include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-tert-butylstyrene, and ethylstyrene. , vinylnaphthalene, etc. One meter or two or more of these can be used.

Depending on the use, other vinyl monomers that can be copolymerized with the aromatic vinyl compound may be copolymerized with a weight ratio of 10 or less, but preferably one that does not contain any monomer other than the aromatic vinyl monomer. It is. Other vinyl monomers that can be copolymerized with aromatic vinyl compounds include vinyl cyanide compounds, acrylic acid alkyl esters, methacrylic acid alkyl esters,
Examples include unsaturated acid anhydrides and unsaturated acids. These are 1
A species or two or more species can be used.

Examples of vinyl cyanide compounds include acrylonitrile 1 and methacrylate trile. Examples of acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, etc. @ Methacrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Examples include octyl methacrylate, 2-E, tylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate.

Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

Fugetsuwasan includes acrylic acid, methacrylic acid, etc.

When graft polymerizing an aromatic vinyl compound etc. in the presence of a rubbery polymer latex, all known emulsifiers can be used, but preferred emulsifiers include rosins such as potassium rosinate and sodium rosinate. acid salt,
Sodium and potassium salts of fatty acids such as potassium oleate, sodium oleate, potassium laurate, sodium laurate, sodium stearate, potassium stearate, sulfate ester salts of fatty alcohols such as sodium lauryl sulfate, and sodium dodecylbenzenesulfonate Any of the alkylaryl sulfonic acids such as the following can be used.

As a polymerization initiator, organic hydroperoxides such as cumeno hydroperoxide, diisopropylbenzene hydrono-9-oxide, and paramethane hydroperoxide, as well as sugar-containing birophosphoric acid formulations, sulfoxylate formulations, and sugar-containing formulations are used. Redox initiators in combination with reducing agents, such as pyrophosphate/sulfoxylate mixed formulations, persulfates such as potassium persulfate and ammonium persulfate, azobisisobutyronitrile, benzoyl Peroxide, lauroyl peroxide, etc. can be optionally used.

Particularly preferred from the viewpoint of surface gloss of the molded product are oxidizing agents of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxides, sugar-containing pyrophosphoric acid formulations, and sulfoxy It is a redox system initiator that can be used in combination with a reducing agent, such as a rate formulation or a mixed sugar-containing pyrophosphate/sulfoxylate formulation.

Preferred molecular weight regulators include mercaptans such as normal octyl mercaptan, normal dodecyl mercaptan, tertiary dodecyl mercaptan, and mercaptoethanol, various terpenes, and halodanized hydrocarbons such as chloroform and carbon tetrachloride.

The amount of resinous polymer grafted to the rubbery polymer in the thermoplastic resin (B) used in the present invention, that is, the grafting ratio (
The amount of the solvent (methyl ethyl ketone) is preferably in the range of 30 to 150 weight units, more preferably 50 to 120 weight units, in terms of impact resistance, heat resistance, molded product surface gloss, solvent resistance, and paintability.

Further, the thickness of the resinous polymer grafted onto the surface of the rubbery polymer is preferably in the range of 100 to 200X from the viewpoint of surface gloss of the molded product. The thickness of this resinous polymer is
Standard methods for observing externally grafted resinous polymers can be used to measure electron micrographs.

Further, the intrinsic viscosity of the methyl ethyl ketone soluble portion of the thermoplastic resin (B) (measured in toluene at 30°C) is preferably 0.3 to 1.5 dl/11, more preferably 0.
．． 3 to 1.0 coloring, particularly preferably 0.3 to 0.7°d
It is l/1/.

The amount of the thermoplastic resin (B) used in the polyphenylene resin composition is 95 to 5% by weight, preferably 90 to 10% by weight, and if the amount exceeds 95% by weight, the heat resistance will be improved. No significant effect was observed, and the resistance to kI was lower than 5 fk coefficients.
No improvement effect on impact resistance or workability was observed.

The styrenic resin (C) used in the present invention is different from the resin (B), and is a polymer of an aromatic vinyl compound or a monomer copolymerizable with an aromatic vinyl compound and other copolymerizable monomers. These aromatic vinyl compounds and other copolymerizable monomers include aromatic vinyl compounds and vinyl cyanide compounds in the resinous constituent components and other copolymerizable vinyl monomers. All of the specific compounds exemplified above can be used, and the styrenic resin can also contain rubbery polymers such as those exemplified above, if necessary.

Is polystyrene the preferred styrene resin? Lychlorstyrene, polyα-methylstyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-α/methylstyrene copolymer, styrene-α/methyl There are styrene-methyl methacrylate copolymers, styrene-α/methylstyrene-acrylonitrile-methyl methacrylate copolymers, and rubber modified products thereof, and these can be used alone or in combination of two or more.

Particularly preferred styrenic resins are +9 listyrene and styrene-acrylonitrile copolymer, and when using a styrene-acrylonitrile copolymer in which the acrylonitrile has a composition distribution as shown below, impact resistance and moldability are improved. A composition with good surface gloss, thermal stability, paintability, and heat resistance can be obtained.

Composition distribution (5) Polymer components with a composition in which the content of acrylonitrile is 1 weight range or more and less than 10 weight range is 1 to 50 weight 1, (B)
The content of acrylonitrile is 10% by weight or more and less than 20% by weight.
) 4 when the acrylonitrile content is 20% by weight or more
5 to 90% by weight of a polymer component with a composition of less than 0M, and 0 to 70% of a polymer component with a composition of 40% or more of acrylonitrile, and a copolymer. The acrylonitrile content in the copolymer is 10 to 40% by weight.The method for measuring the composition distribution in the above copolymer is, for example, P
olymer Journal Mo1.6 * A
6*532-536 (1974).

(The styrene resin c3 can be obtained by known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.

The polyphenylene ether resin composition of the present invention can be obtained by mixing using a solution blend, a kneading extruder, a Banbury, a kneader, or the like.

The yleU phenylene ether resin composition of the present invention can be used to obtain mild molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, etc. - When using the polyphenylene ether resin of the present invention, the polyphenylene ether resin composition of the present invention Known antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, foaming agents, lath ruts, etc. can be blended. Particularly preferred antioxidants are phosphorus-based antioxidants, and preferred flame retardants are triphenyl phosphate,
It is a flame retardant typified by tri(nonylphenyl)phosphate.

However, the polyphenylene ether resin composition of the present invention may be further combined with other known polymers such as polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene copolymer, NIL EPDMJ styrene-butadiene block copolymer, etc., depending on the required performance. Polymers, styrene-butadiene-styrene block copolymers and hydrogenated products, styrene-butadiene-styrene radial teleblock polymers and hydrogenated products, polypropylene, butadiene-acrylonitrile copolymers, polyvinyl chloride, polycargonates, PET, PBT, polyacetal, -Reamir1 Engineering H? It may be used in an appropriate blend with birch resin, polyvinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer, polyisoprene, natural rubber, chlorinated butyl rubber, chlorinated polyethylene, PPS resin, polyether ether ketone, etc.

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. Furthermore, on each side below, the parts and widths indicate parts by weight and weight, respectively.

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

After sufficiently purging the inside of the styrene reaction vessel equipped with an oxygen blowing device, a cooling coil, and a stirrer at the bottom of the reaction section with nitrogen, 53.6 g of cupric bromide and 1130 g of di-n-butylamine were added.
(li!) Furthermore, 8.75 kl of 2,6-xylenol was dissolved in 401 l of toluene and added.

After stirring to obtain a homogeneous solution, polymerization was carried out for 90 minutes while rapidly blowing oxygen into the reaction vessel. During polymerization, water was circulated through a cooling coil to maintain the internal temperature at 30°C. After the polymerization was completed, 301 tons of toluene was added, and 20 tons of disodium ethylenediaminetetraacetate was dissolved in water.
% 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 removed, and dried to obtain Polymer-A-1. 3
[η] measured in chloroform solution at 0°C is 0.37
It was d4/g.

Polymerization was carried out using 2,6-xylenol/2,3,6-drimethylphenol;90/]0 (molar ratio) instead of the 2,6-xylenol used in the production of Polymer A-1. A-2 was obtained. [η] measured in a chloroform solution at 30°C was 0.37 dt/g.

Production of Polymer A-3 In the production of Polymer A-2, polymerization was carried out in place of the phenolic compound used, total 2,6-xylenol/2,3.6-trimethylphenol = 85/) 5 (molar ratio). Polymer A-3'i was obtained. [η] measured in a chloroform solution at 30°C was 0.37 dt/9.

Production of Polymer A-4 The phenol compound used in the production of Polymer A-2 was replaced with 2,6-xylenol/2,3.6-trimethylphenol = 9515 (molar ratio) to produce Polymer A-4'. I got it. [η] measured in a chloroform solution at 30°C was 0.37 dt/9.

After sufficiently purging the interior of a stainless steel reaction vessel with a stirrer with gold nitrogen, styrene-butadiene copolymer rubber 5 ft. (JSR $0561 particle size 0.5-0.7 am)
000, p (solid content), disproportionated potassium rosinate 130
．． 9. Potassium hydroxide】211 Styrene 2500.9.
After adding to 14,000.9 ml of ion-exchanged water, the mixture was thoroughly stirred and heated while circulating 70'C of water in the jacket. When the internal temperature reaches 50℃, add 950.91C of ion exchange water.
Sodium pyrophosphate 2011 Glucose 2511 Ferrous sulfate 0.4! After adding cumene hydroperoxide 25.29 to an aqueous solution containing i and carrying out a polymerization reaction for 2 hours, styrene 3500, F, and disproportionated potassium rosinate]
7og, potassium hydroxide 18g, ion exchange water 5009
An emulsion containing 25.2 g of cumene hydroperoxide was added continuously over 3 hours, and one reaction was carried out.

After adding the emulsion, 6.7 g of sodium pyrophosphate, 8.3 g of glucose, and 0.131 g of ferrous sulfate were added. Ion exchange water 317
Aqueous solution consisting of 9 and cumene hydroperoxide 7
After the addition of 100 g, the polymerization reaction was completed.

After adding all of the antioxidant emulsion, it was coagulated with an aqueous calcium chloride solution and then dried to form a polymer B-1'? Obtained.

In the production of Polymer B-1, polybutadiene x :/(J
SR+0700 particle size 0.2 to 0.3 μm) 'e was used to obtain polymer n-2.

In the production of Polymer B-1, styrene-butadiene copolymer rubber latex (particle size 0.07 to 0.09 μm) was used instead of styrene-butadiene copolymer rubber latex.
Polymer B-3t- was obtained using t-.

In the production of Polymer B-1, a rubbery polymer (particle size 0.2 to 0.3 μtyt) consisting of n-butyl acrylate/butadiene = 80/20% was used in place of the styrene-butadiene copolymer latex. Polymer B-4 was obtained by
) 2.8 kllJ, 17.2 kg of styrene, ) 22 kj9 of luene, stirred for 50'CK until the rubber was completely dissolved, and tertiary dodecyl mercaptan 20
11 Dipenzoyl monooxide 4011 Tertiary-butyl peroxy-1-propyl cargoonate 40/
After adding I, dicumilno and monooxide 2 (1), the temperature was raised to 80°C for 3 hours, then the temperature was further raised to 100°C for 3 hours, and the temperature was further raised to 125°C to achieve a polymerization conversion of approximately 100°C. The reaction was carried out. The polymer was pelletized using a direct extruder to obtain Polymer B-5i. The average rubber particle size in the polymer was 1 to 2 μm.

In the production of Polymer B-5, stirring during transfer was strengthened to obtain Polymer B-6 having an average rubber particle size of 0.5 to 0.6 μm.

In the production of Polymer B-5, polymerization was carried out without using polybutadiene to obtain Polymer c-1.

The following styrene-acrylonitrile copolymer' was obtained by emulsion polymerization. Polymerization was carried out in three stages, with the first stage (charged styrene/acrylonitrile = 33.5/23.4 [:
The second stage (charged styrene/acrylonitrile = 19.010.84 [parts]) was batch polymerization, the third stage (charged styrene/acrylonitrile = 22.510.76 [parts]) was incremental polymerization. Increment polymerization was carried out, and the polymerization was finally carried out to a polymerization conversion rate of nearly 100%. Polymer C-2, obtained by recovering the polymer using an aqueous sulfuric acid solution and drying it, is a polymer in which acrylonitrile has a composition distribution.

Cyclohexane was added little by little to a homogeneous solution in which a certain amount of Polymer C-2 was dissolved in methyl ethyl ketone, and the precipitated polymer was separated at each stage and its acrylonitrile content was determined by nitrogen analysis.

All results are shown below.

Examples, comparative examples
(The above various polymers are mixed according to the composition ratios shown in Table 1, extruded into pellets at a temperature of 240℃ to 260℃ using a twin-screw kneading extruder, thoroughly dried, and then injected. 280℃, mold @ (50℃
Test pieces for measuring PR'MB resistance, heat resistance, molded product surface gloss, solvent resistance, and thermal stability were molded and measured according to the test method in W below. The results are shown in Table 1.

Evaluation method
■ Heat resistance Thickness according to ASTM Dfi48] /4', 264
Heat distortion temperature was measured in psi.
j ■ Impact resistance A flat plate with a thickness of 2.4 mm was injection molded and its DuPont impact strength was measured.

(2) Surface gloss of molded product Using the above test piece for measuring impact resistance, the surface gloss of the molded product was measured using a color difference meter manufactured by Suga Shikenki.

p Processability: Cylinder temperature 2 without using Shimadzu's advanced flow tester
The Q value (X 10-3crr13/sac) was measured at 60°C using a die 1ffi+IIφX2++l+IIL.

Solvent resistance A rod-shaped test piece with a thickness of 1/81' and a width of 1/2" and a depth of 0.
After applying a tensile stress of 60 kg/Crn2 to both ends of the notch of 385=, Nissin salad oil was attached to the notch part and the time until breakage was measured.

Φ Thermal stability Thickness of barley made by retaining various polyphenylene ether resins for 15 minutes in an injection molding machine cylinder temperature of 280°C 2.4
A test piece of the cabinet was molded, and the DuPont impact strength of the test piece was measured.

Procedural amendment April 4, 1985 Manabu Shiga, Commissioner of the Patent Office1, Indication of the case Japanese Patent Application No. 172506/19822, Title of the invention: Polyphenylene ether resin composition3, Person making the amendment Relationship to the case Patent Applicant name (A17) Japan Synthetic Rubber Co., Ltd. 4, Agent address 40 Mori Building, Toranomon 5-13-1, Minato-ku, Tokyo Detailed description of the invention Column 6 Details of the amendment (1) ms page 10, line 14 from the bottom, "...R1' and R4 are..."? It is assumed that "...R3 and R4 are...".

(21 Douban, same page, lines 13-12 from the bottom "..., R3'
And R4 is..."? "...R6 and R6 are..."
shall be.

(3) Full text on page 35 of the same j? I will make one correction in the attached sheet.

Claims (1)

[Scope of Claims] (A) 5 to 95% by weight of polyphenylene ether, (B)
95 to 5% by weight thermoplastic resin obtained by emulsion polymerization of an aromatic vinyl compound in the presence of rubbery polymer latex
, and (C) 0 to 85% by weight of a styrene resin, the polyphenylene ether resin composition comprising:
(A) Phenylene ether is a copolymer obtained by copolymerizing a phenol compound represented by the following general formula (a) and a phenol compound represented by the following general formula (b), and the polyphenylene ether resin composition The particle size of the rubbery polymer when dispersed in the material is 0.05 to 0.
．． A polyphenylene ether resin composition having a diameter of 8 μm. General formula (a): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (b): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In general formula (a) and general formula (b), X and X' are a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, respectively) R_1 is a hydrocarbon group; a hydrocarbon oxy group; the general formula (
I) is a monovalent group selected from a halogenated hydrocarbon group having at least two carbon atoms in the bond between the phenol nucleus and the halogen atom; and a halogenated hydrocarbon oxy group; R_2 is a monovalent group selected from One of the groups represented by R_1 or a halogen atom, and R_3 and R_
4 is each one of the groups represented by R_1, and R_5 and R_6 are each one of the groups represented by R_1 or a hydrogen atom. However, R
_5 and R_6 do not become hydrogen atoms at the same time, and R
None of _1, R_2, R_3, R_4, R_5 and R_6 have a tertiary carbon atom. )