JPH07242791A - Polyphenylene ether resin composition excellent in appearance and its production - Google Patents

Abstract

PURPOSE:To remarkably improve the appearance (hue) of a polyphenylene ether resin compsn. without detriment to its impact strength by forming a rubber-modified styrene resin under specified polymn. conditions in the presence of polyphenylene ether. CONSTITUTION:This compsn. comprises a rubber-modified styrene resin and polyphenylene ether, gives a molding having an index of yellowness (DELTAY1) according to JIS Z 8722 of 0-40, and is produced by the polymn. process wherein a polymer soln. (A) contg. an arom. vinyl monomer (e.g. styrene) and polyphenylene ether is mixed with a polymer soln. (B) contg. the arom. vinyl monomer, a rubberlike polymer (e.g. polybutadiene), and a polymn. initiator [e.g. tert-butyl peroxy(2-ethylhexanoate)] provided the soln. (A) is added to the soln. (B) before the phase reversal of the rubberlike polymer in the latter occurs.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene ether resin composition and a method for producing the same. More specifically, it relates to a polyphenylene ether resin composition having excellent appearance (color tone) and impact strength, and a method for producing the same.

[0002]

2. Description of the Related Art Polyphenylene ether resins are used in various fields such as automobile parts, home electric appliance parts and OA equipment parts because they have excellent heat resistance and impact resistance. In recent years, personal computers and facsimiles,
Office automation equipment such as word processors (office equipment, electronic information processing equipment)
With the widespread use of, the light-colored color tone is required as a housing material. However, in the case of manufacturing a housing by molding a polyphenylene ether resin, it is necessary to mold at a high temperature of 300 to 350 ° C. because of its excellent heat resistance. There is a problem in that a large number of radicals are formed to reduce the light resistance and the color tone.

On the other hand, by toning with a light-colored colorant, the above-mentioned problems can be improved to some extent, but they are not sufficient, and new problems such as economical efficiency and mechanical strength decrease occur. On the other hand, European Patent No. EP 226149 discloses that in a method for producing a resin composition of polyphenylene ether and rubber-modified polystyrene, polyphenylene ether is dissolved at a stage when a styrene monomer reaches a polymerization rate of 90% or more. Disclosed is a method for producing a resin composition by mixing the above solutions. The resin composition produced according to this publication has excellent color tone and appearance because it was produced at a relatively low temperature, but the rubber particles were destroyed due to the addition and mixing of polyphenylene ether after the rubber phase inversion. Impact strength is extremely low, limiting industrial use.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention is a polyphenylene ether resin composition which is free from the above-mentioned problems, that is, excellent in appearance (color tone) and impact strength, and its composition. It is intended to provide a manufacturing method.

[0005]

Means for Solving the Problems The inventors of the present invention have diligently studied a technique for improving the appearance (color tone) and impact strength of a polyphenylene ether-based resin, and as a result, have found that specific polymerization conditions in the presence of polyphenylene ether Then, it was surprisingly found that by polymerizing the rubber-modified styrenic resin, the appearance (color tone) is dramatically improved while maintaining the impact strength, and the present invention was reached.

That is, the present invention is a resin composition containing a rubber-modified styrene resin [component (A)] and polyphenylene ether [component (B)], and a molded article obtained from the resin composition. Is JIS-Z-8 which is an index of yellowness
A 722-defined ΔYI of 40 or less, a polyphenylene ether resin composition, and a polymer containing an aromatic vinyl monomer and polyphenylene ether.
The solution [(C) component] is a polymer solution [(D) containing an aromatic vinyl monomer, a rubbery polymer, and a polymerization initiator.
Component), the component (C) is added and mixed before the phase inversion of the rubbery polymer in the component (D), and a polyphenylene ether resin composition is produced. The present invention provides a method for producing a polyphenylene ether-based resin composition, which is characterized in that an organic solvent is added to the components (C) and (D).

The present invention will be described in detail below. The resin composition of the present invention is a rubber-modified styrene resin [(A) component].
And a polyphenylene ether [(B) component], wherein a molded article obtained from the resin composition has a Δ of JIS-Z-8722 standard, which is an index of yellowness.
YI is 40 or less. When ΔYI exceeds 40, not only the commercial value is deteriorated as an OA housing material requiring a light color tone but also the light resistance is deteriorated.

In order for ΔYI to be 40 or less, the melt extrusion temperature is preferably 180 ° C. or higher and not higher than 300 ° C., more preferably 180 ° C. or higher and not higher than 250 ° C. preferable. To that end, in the presence of polyphenylene ether, rubber-modified styrenic resin,
It can be achieved by polymerization preferably at 80 ° C. or higher and 200 ° C. or lower, and more preferably at 80 ° C. or higher and 150 ° C. or lower.

More specifically, a polymer solution [component (C)] containing an aromatic vinyl monomer, polyphenylene ether and, if necessary, an organic solvent is mixed with an aromatic vinyl monomer and a rubber substance. In a polymerization method in which a polymer, a polymerization initiator, and optionally an organic solvent are mixed in a polymer solution [(D) component], before the phase inversion of the rubbery polymer in the (D) component, The component (C) is added to and mixed with. When the component (C) is added and mixed after the phase inversion of the rubber-like polymer, the rubber particles are broken by the polyphenylene ether which is a hard resin, and the impact strength is remarkably lowered.

The rubber-modified styrenic resin used as the component (A) in the present invention is a polymer obtained by dispersing the rubber-like polymer in the form of particles in a matrix composed of a vinyl aromatic polymer and polyphenylene ether. In the presence of a rubber-like polymer, polyphenylene ether, an aromatic vinyl monomer as a main component, if necessary, a monomer mixture containing a vinyl monomer copolymerizable therewith, polymerization. It can be obtained by adding an initiator and, if necessary, an organic solvent and a chain transfer agent, and performing known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization.

Examples of such resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene). Resins containing polyphenylene ether such as propylene rubber-styrene copolymer) are known.

The rubbery polymer preferably has a glass transition temperature (Tg) of -30 ° C. or lower,
If the temperature exceeds 30 ° C, the impact resistance will decrease. Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene) and saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers, polyacrylics. Acrylic rubbers such as butyl acid and ethylene-propylene-diene monomer terpolymers (EPDM) can be mentioned, and diene rubbers are particularly preferable.

The aromatic vinyl monomer which is an essential component of the graft-polymerizable monomer mixture to be polymerized in the presence of the above rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or p-methylstyrene. -Chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like, and styrene is most preferable, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized.

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified styrene resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to reduce the melt viscosity during blending, an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used. Furthermore, when it is necessary to further increase the heat resistance of the resin composition, a monomer such as α-methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, or N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is 0 to 40% by weight.

The polymerization initiator of the present invention is t-butylperoxy (2-ethylhexanoate), t-butylperbenzoate, di-t-butylperoxide, benzoylperoxide, lauroylperoxide. , T
-Butylperacetate, t-butylperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, t-butylhydroperoxide, Cumene hydroperoxide, t-
Examples thereof include organic peroxides such as butyl peroxyisopropyl carbonate and azo compounds such as azobisisobutyronitrile.

The organic solvent of the present invention is benzene, toluene, xylene, ethylbenzene, cyclohexane, tetrahydrofuran or the like. The chain transfer agent of the present invention is butyl mercaptan, octyl mercaptan, t-
Alkyl mercaptans such as dodecyl mercaptan, α-
Examples include methylstyrene dimer, triethylamine, dimethylacetamide, dimethylformamide and the like.

The rubber particle size of the rubber-modified styrenic resin of the present invention is preferably 0.1 to 5.0 μm, and more preferably 0.2 to 5.0 μm.
3.0 μm is preferable. Within the above range, impact resistance is particularly improved. Reduced viscosity ηsp / c (0.5 g / dl, which is a measure of the molecular weight of the rubber-modified styrenic resin of the present invention,
Toluene solution, measured at 30 ° C) is 0.30 to 0.80d
It is preferably in the range of 1 / g, 0.40 to 0.6
It is more preferably in the range of 0 dl / g. As means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrene-based resin, adjustment of the amount of polymerization initiator, polymerization temperature, amount of chain transfer agent and the like can be mentioned.

The polyphenylene ether used as the component (B) in the present invention (hereinafter abbreviated as PPE).
Is a homopolymer and / or a copolymer composed of a bonding unit represented by the following formula.

[0019]

[Chemical 1]

However, R1, R2, R3, and R4 are each selected from the group consisting of hydrogen, hydrocarbons, and substituted hydrocarbon groups, and may be the same or different from each other. As a specific example of this PPE, poly (2,6-
Dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like are preferable, and among them, poly (2,6-dimethyl-1,4-phenylene ether). Is preferred. The method for producing such PPE is not particularly limited, and, for example, using a complex of cuprous salt and amine according to the method described in US Pat. No. 3,306,874 as a catalyst, for example, 2,6 xylenol is used. It can be easily produced by oxidative polymerization. In addition, US Pat.
061075, U.S. Pat. No. 3,257,357.
U.S. Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, and Japanese Patent Laid-Open No. 50-5119.
It can be easily manufactured by the method described in Japanese Patent Publication No. The reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the PPE used in the present invention is 0.20 to 0.70.
It is preferably in the range of dl / g, and 0.30 to 0.
More preferably, it is in the range of 60 dl / g. PPE
Examples of means for satisfying the above requirements regarding the reduced viscosity include the adjustment of the amount of catalyst during the production of the PPE.

The rubber-like polymer accounts for 100 parts by weight of the resin component composed of the rubber-modified styrene resin and polyphenylene ether of the present invention, preferably 1 to 50% by weight, particularly preferably 3 to 20% by weight, The graft-polymerizable monomer mixture is preferably 98 to 49% by weight, more preferably 94 to 67% by weight, and the polyphenylene ether is preferably 1 to 50% by weight, more preferably 3 to 30% by weight. In range. Within this range, the desired resin composition has a good balance between impact resistance and rigidity.

As the flame retardant (I), a halogen-based, phosphorus-based or inorganic flame-retardant can be added to the resin composition of the present invention. Examples of the halogen-based flame retardants include halogenated bisphenols, aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers and the like, preferably decabromo. Diphenyl oxide, tetrabromobisphenol A,
Tetrabromobisphenol A oligomer, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyloxide bisphenol condensate, halogen-containing phosphorus Examples thereof include acid esters and fluororesins.

Examples of the phosphorus-based flame retardants include organic phosphorus compounds, red phosphorus, inorganic phosphates and the like. The organic phosphorus compound of the present invention is, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinic acid salt, phosphoric acid ester, phosphorous acid ester and the like. More specifically, triphenyl phosphate,
Methyl neopentyl phosphite, Hentaerythritol diethyl diphosphite, Methyl neopentyl phosphonate, Phenyl neopentyl phosphate, Pentaerythritol diphenyl diphosphate, Dicyclopentyl Hypophosphite, Dineopentyl Hypophosphite, Phenylpyrocatechol Phosphite, ethylpyrocatechol phosphate, and dipyrocatechol hyposiphosphate.

Here, as the organic phosphorus compound, a hydroxyl group-containing aromatic phosphoric acid ester is particularly preferable, and an organic phosphorus compound mainly containing the hydroxyl group-containing aromatic phosphoric acid ester and containing no hydroxyl group can be contained. When the flame retardant (I) of the present invention contains an organic phosphorus compound containing no hydroxyl group, the quantitative ratio of the two is
The former is preferably 20 to 80% by weight and the latter is preferably 80 to 20% by weight.

The above-mentioned hydroxyl group-containing aromatic phosphate ester is one or more phenolic hydroxyl groups in tricresyl phosphate, triphenyl phosphate and condensed phosphate esters thereof. And a phosphoric acid ester containing, for example, the following compounds.

[0026]

[Chemical 2]

[0027]

[Chemical 3]

(However, Ar1, Ar2, Ar3, Ar4
, Ar5 and Ar6 are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group and a butylphenyl group, and at least one hydroxyl group is substituted with the above aromatic group in the phosphoric acid ester. ing. Further, n represents an integer of 0 to 3, and m represents 1
Represents the above integers. Among the hydroxyl group-containing aromatic phosphoric acid esters of the present invention, the following formula 4 diphenylresorcinyl phosphate or formula 5 diphenylhydroquinonyl phosphate is preferable, and its production method is, for example, Kohei
It is disclosed in Japanese Patent Laid-Open No. 1-223158, and
It is obtained by the reaction of phenol, hydroxyphenol, aluminum chloride and phosphorus oxychloride.

[0029]

[Chemical 4]

[0030]

[Chemical 5]

The red phosphorus is, in addition to general red phosphorus,
The surface of which has been previously coated with a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and hydroxide. On a metal hydroxide selected from titanium and a coating made of a thermosetting resin, on a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. A double-coated thermosetting resin coating can also be preferably used.

A typical example of the inorganic phosphate is ammonium polyphosphate. Further, as the inorganic flame retardant in the component (I) of the present invention, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, oxidation Examples thereof include hydrates of inorganic metal compounds such as hydrates of tin, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate and the like. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrotalcite have a good flame retarding effect and are economically advantageous.

The resin composition of the present invention may optionally contain one or more compounds selected from triazine skeleton-containing compounds, novolac resins, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers and fluororesins. A flame retardant aid (II) can be added. The triazine skeleton-containing compound is a component for further improving flame retardancy as a flame retardant aid for organic phosphorus compounds. Specific examples thereof include melamine, melam (Chemical formula 6),
Melem (chemical formula 7), melon (product of deammonification of 3 molecules of melem at 600 ° C. or higher), melamine cyanurate (chemical formula 8), melamine phosphate (chemical formula 9), succinoguanamine (chemical formula 10) ), Adipoguanamine, methylglutaloganamin, melamine resin (Chemical formula 11), BT resin (Chemical formula 12) and the like, and melamine cyanurate is particularly preferable from the viewpoint of volatile resistance.

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

The novolac resin is a component for suppressing dripping of fire species during combustion (drip resistance), and when it is used together with a hydroxyl group-containing aromatic phosphate ester, it has fluidity and heat resistance. It is also an improver. And
The resin is a thermoplastic resin obtained by condensing phenols and aldehydes in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid. Multiple Additions ”p.437-455 (Kyoritsu Shuppan Co., Ltd.)
It is described in. An example of production of novolac resin 13
Shown in.

[0042]

[Chemical 13]

The above-mentioned phenols include phenol, o-cresol, m-cresol, p-cresol and 2,5-
Dimethyl-, 3,5-dimethyl-, 2,3,5-trimethyl-, 3,4,5-trimethyl-, pt-butyl-, pn-octyl-, p-stearyl-, p-phenyl -, P- (2-phenylethyl)-, o-isopropyl-, p-isopropyl-, m-isopropyl-, p
-Methoxy- and p-phenoxyphenol, pyrocatechol, resorcinol, hydroquinone, salicylaldehyde, salicylic acid, p-hydroxybenzoic acid, methyl p-hydroxybenzoate, p-cyano-, and o -Cyanophenol, p-hydroxybenzenesulfonic acid, p-hydroxybenzenesulfonamide, cyclohexyl p-hydroxybenzenesulfonate, 4-
Hydroxyphenylphenylphosphinic acid, methyl 4
-Hydroxyphenylphenylphosphinate, 4-hydroxyphenylphosphonic acid, ethyl 4-hydroxyphenylphosphonate, diphenyl 4-hydroxyphenylphosphonate and the like.

The above-mentioned aldehydes are formaldehyde,
Acetaldehyde, n-propanal, n-butana-
, Isopropanal, isobutyraldehyde, 3-methyl-n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylacetaldehyde and the like.
The metal-containing compound is a metal oxide and / or a metal powder. The metal oxide is aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide. , A simple substance such as tungsten oxide or a composite thereof (alloy), and the metal powder is aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel,
Copper, tungsten, tin, antimony, etc. alone or
It is a complex of them.

The silicone resin is SiO2, RS
It is a silicone resin having a three-dimensional network structure formed by combining structural units of iO3 / 2, R2 SiO and R3 SiO1 / 2. Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituents. Here, a silicone resin containing a vinyl group is particularly preferable.

Such a silicone resin can be obtained by co-hydrolyzing and polymerizing the organohalosilane corresponding to the above structural unit. The silicone oil is a polydiorganosiloxane having a chemical bond unit represented by the chemical formula (14).

[0047]

[Chemical 14]

R in the above formula is C1-8 alkyl group, C
6 to 13 aryl groups, and one or more kinds of substituents selected from the vinyl-containing groups represented by Chemical formulas 15 and 16, in which it is preferable to contain a vinyl group in the molecule.

[0049]

[Chemical 15]

[0050]

[Chemical 16]

The viscosity of the silicone oil is 600 to
1,000,000 centipoise (25 ° C) is preferred,
More preferably, it is 90,000 to 150,000 centipoise (25 ° C). The above-mentioned silica is amorphous silicon dioxide, and in particular, a hydrocarbon-based compound-coated silica whose surface is treated with a hydrocarbon-based compound-based silane coupling agent is preferable, and a vinyl-based hydrocarbon-based compound coating is further preferable. Silica is preferred.

The silane coupling agent is vinyl such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane. Group-containing silanes, epoxy silanes such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N
An aminosilane such as phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit having a structure similar to that of the thermoplastic resin is particularly preferable, and for example, p-styryltrimethoxysilane is suitable for the styrene resin.

The treatment of the silane coupling agent on the silica surface is roughly classified into a wet method and a dry method. The wet method is a method in which silica is treated in a silane coupling agent solution and then dried.The dry method is to charge silica into a device capable of high-speed stirring such as a Henschel mixer and then stir it. Meanwhile, the silane coupling agent solution is slowly dropped, and then heat treatment is performed.

The aramid fibers are wholly aromatic polyamide fibers, and include polymetaphenylene isophthalamide,
Alternatively, it can be produced by dissolving polyparaphenylene terephthalamide in an amide-based polar solvent or sulfuric acid and performing solution spinning by a wet or dry method. The fluororesin is a component for further improving drip resistance, and is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene /
Hexafluoropropylene copolymer and the like can be mentioned. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination so long as the drip resistance is not impaired.

The method for producing these fluororesins is described in US Pat. No. 2,393,697 and US Pat.
No. 534,058, for example, tetrafluoroethylene is used in an aqueous medium with a radical initiator such as ammonium persulfate or potassium persulfate to give 7 to 70 kg /
Polymerization is carried out at a temperature of 0 to 200 ° C. under a pressure of cm ² , and then polytetrafluoroethylene powder is obtained from the suspension, dispersion or emulsion by coagulation or by precipitation.

Here, it is preferable to melt-knead at a temperature not lower than the melting point of the fluororesin. For example, in the case of polytetrafluoroethylene, it is preferable to melt in the temperature range of 300 to 350 ° C. It melts above the melting point under shearing force, resulting in highly fibrillation and oriented crystallization. And
It is possible to obtain a fluorine-based resin having a special branched high-order structure with respect to the trunk fiber. As a result, the thermoplastic resin is three-dimensionally entangled with the thermoplastic resin, and the melting of the molded body is suppressed. Further, in order to give a high shearing force, it is preferable to melt in a hard resin having a high melt viscosity such as polyphenylene-ter, rather than a rubber-modified resin (for example, rubber-modified polystyrene).

The method for producing a fluororesin having a special higher-order structure is as follows. A fluororesin, a thermoplastic resin and, if necessary, a dispersant are melt-kneaded at a melting point of the fluororesin or higher to prepare a master batch. A two-step process in which a thermoplastic resin or flame retardant is melt-kneaded after being prepared, or a side filler.
Using an extruder that can be heated, melt-knead the thermoplastic resin and the fluororesin and, if necessary, the dispersant at the melting point of the fluororesin or higher in the first stage, and lower the melting temperature in the latter stage. There is a one-step process method in which a flame retardant is fed and melt-kneaded.

The resin composition of the present invention may optionally contain a copolymer resin comprising an aromatic vinyl unit and an acrylic ester unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol. -, Or one or more kinds of fluidity improvers (III) selected from metal soaps can be blended. The aromatic vinyl unit of the copolymer resin is the aromatic vinyl unit shown in the description of the component (A), and the acrylate ester unit is an alkyl group having 1 to 8 carbon atoms such as methyl acrylate and butyl acrylate. It is an acrylic ester consisting of a group.

Here, the content of acrylic acid ester units in the copolymer resin is preferably 3 to 40% by weight, and further,
5-20% by weight is preferred. In addition, the solution viscosity, which is an index of the molecular weight of the copolymer resin (10% by weight of resin
The solution and the measurement temperature 25 ° C.) are preferably 2 to 10 cP (centipoise). When the solution viscosity is less than 2 cP, the impact strength decreases, while when it exceeds 10 cP, the effect of improving the fluidity decreases.

The aliphatic hydrocarbon-based processing aid is liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, fluorides, chlorides and the like. The higher fatty acids include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid and ferronic acid, and unsaturated fatty acids such as ricino-acid, lysine veridic acid and 9-oxy12 octadecenoic acid. Etc.

The higher fatty acid ester is a monovalent alcohol ester of a fatty acid such as methyl phenyl stearate or butyl phenyl stearate, and a monovalent alcohol ester of a polybasic acid such as a diphenyl stearyl phthalate diester. Further, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmi Tee
, Polyoxyethylene sorbitan monostearate,
Sorbitan esters such as polyoxyethylene sorbitan monooleate, stearic acid monoglyceride, oleic acid monoglyceride, capric acid monoglyceride,
Fatty acid ester of glycerin monomer such as behenic acid monoglyceride, polyglycerin stearate,
Polyglycerin oleic acid ester, polyglycerin fatty acid ester of polyglycerin such as lauric acid ester, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyalkylene ether such as polyoxyethylene monooleate Examples thereof include fatty acid esters having a ter unit and neopentylpolyol fatty acid esters such as neopentylpolyol distearic acid ester.

Examples of the higher fatty acid amides include saturated fatty acid monoamides such as phenylstearic acid amide, methylol stearic acid amide, and methylol behenic acid amide, coconut oil fatty acid diethanolamide, and lauric acid diethanoic acid.
Lamide and N, N′-2 substituted monoamides such as coconut oil fatty acid dietanoylamide and oleic acid dietanolamide, and further methylenebis (12-hydroxyphenyl) stearic acid amide, ethylenebisstearic acid amide, ethylenebis (12-Hydroxyphenyl) stearic acid amide, hexamethylenebis (12-
Saturated fatty acid bisamides such as hydroxyphenyl) stearic acid amide, and aromatic bisamides such as m-xylylenebis (12-hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohol is a monovalent alcohol such as stearyl alcohol or cetyl alcohol.
Polyalcohol such as ole, sorbitol and mannitol,
And polyoxyethylene dodecylamine, polyoxyethylene voctadecylamine, etc., and further, allyl ether having a polyalkylene ether unit such as polyoxyethylene allyl ether, and polyoxyethylene lauryl ether. -Ter, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether,
Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether
Polyoxyethylene alkylphenyl ethers such as ter, polyoxyethylene nonylphenyl ether, polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene Bisphenol A ether, polyoxyethylene polyoxypropylene glycol
It is a divalent alcohol having a polyalkylene ether unit such as ruthel.

The metal soap is a metal salt of higher fatty acid such as stearic acid such as barium, calcium, zinc, aluminum or magnesium. In order to further improve the impact strength of the resin composition of the present invention, (IV) styrene-based thermoplastic elastomer can be added, if necessary. The styrene-based thermoplastic elastomer
Is a block copolymer composed of an aromatic vinyl unit and a conjugated diene unit, or a block copolymer in which the conjugated diene unit portion is hydrogenated.

The aromatic vinyl monomer constituting the block copolymer is the aromatic vinyl monomer described in the explanation of the component (A), and styrene is the most preferable, but styrene is the main component and other aromatic vinyl monomers. Aromatic vinyl monomers may be copolymerized. Examples of the conjugated diene monomer forming the block copolymer include 1,3-butadiene and isoprene.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or its hydrogenated unit is represented by B. If SB, S
(BS) n, (where n is an integer of 1 to 3), S (BS
B) n, (where n is an integer of 1 to 2) linear-block copolymer, (SB) n X (where n is an integer of 3 to 6, X is silicon tetrachloride, tin tetrachloride, It is preferably a star-shaped block copolymer having a B portion as a bond center, which is represented by a coupling agent residue such as a polyepoxy compound. Among them, SB type 2 and SBS type 3
SBBS type 4 linear-block copolymers are preferred. If necessary for the resin composition of the present invention, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant,
One or more light resistance improvers (V) selected from halogen scavengers, light-shielding agents, metal deactivators, and quenchers can be added.

The above-mentioned ultraviolet absorber absorbs light energy and becomes a keto type molecule by intramolecular proton transfer (benzophenone, benzotriazole type), or cis-trans isomerization (cyanoacryle). -G type), released as heat energy,
It is a component to make it harmless. Specific examples are 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone), etc. 2-hydroxybenzophenones, 2- (2 '-Hydroxy-5'
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
t-butylphenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-butylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ',
5'-dicumylphenyl) benzotriazole, 2,
2- (2'-hydroxyphenyl) benzotriazoles such as 2'-methylenebis (4-t-octyl-6-benzotriazolyl) phenol, phenyl salicylyl
Resorcinol monobenzoate, 2,4-di-t
-Butylphenyl-3 ', 5'-di-t-butyl-4'
-Hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and other benzoates, 2-ethyl-2'-atoxyoxanilide,
Substituted oxanilides such as 2-ethoxy-4'-dodecyl oxanilide, and ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxy) And cyanoacrylates such as phenyl) acrylate.

The hindered amine light stabilizer is a component for decomposing hydroperoxide generated by light energy to generate stable N--O. Radicals, N--OR and N--OH for stabilization. Is. A specific example is
2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl -4-piperidyl benzoate, bis (2,2,6,6
-Tetramethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) ) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6)
-Pentamethyl-4-piperidyl) -1,2,3,4-
Butane tetracarboxylate, bis (1, 2, 2,
6,6-Pentamethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate
G., Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3 ', 5'-di-t-
Butyl-4-hydroxybenzyl) malonate, 1-
(2-Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4)
-Piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4)
-Piperidylamino) hexane / 2,4-dichloro-6
-T-octylamino-s-triazine polycondensate, 1,
6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate and the like.

The above-mentioned antioxidant stabilizes peroxide radicals such as hydroperoxy radicals produced by thermoforming or exposure to light, or produces hydroperoxide.
It is a component for decomposing peroxides such as oxides.
Specific examples thereof are hindered phenolic antioxidants and / or peroxide decomposers. The former serves as a radical chain inhibitor, and the latter decomposes the peroxide formed in the system into more stable alcohols to prevent autoxidation.

The hindered phenol type antioxidant is 2,6-di-tert-butyl-4-methylphenol-
Le, styrenate dephenol, n-octadecyl 3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenerubbis (4
-Methyl-6-tert-butylbutylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-
Di-charpentylphenyl) ethyl] -4,6-di-charpentylphenyl acrylate, 4,4'-
Butylidene bis (3-methyl-6-tert-butylbutylphenol), 4,4'-thiobis (3-methyl-6-tert-butylbutylphenol), alkylated bisphenol, tetrakis [methylene 3- (3,5-dither
Charbutyl-4-hydroxyphenyl) propione
To] methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,
4,8,10-tetraoxaspiro [5.5] undecane and the like.

The peroxide decomposer is trisnonylphenylphosphite, triphenylphosphite,
Organophosphorus peroxide decomposers such as tris (2,4-di-tert-butylphenyl) phosphite or dilauryl 3,3′-thiodipropionate, dimyristyl 3,
3'-thiodipropionate, distearyl 3,3'-
It is an organic sulfur-based peroxide decomposing agent such as thiodipropione, pentaerythrityl tetrakis (3-laurylthiopropionate), ditridecyl 3,3′-thiodipropionate, and 2-mercaptobenzimidazole.

The above-mentioned halogen scavenger is a component for scavenging free halogen produced during thermoforming or light exposure. Specific examples thereof are basic metal salts such as hydrotalcite, zeolite, magnesium oxide, calcium stearate, and zinc stearate, organic tin compounds, or organic epoxy compounds. The hydrotalcite is magnesium, calcium, zinc, aluminum,
It does not include water-containing basic carbonate such as bismuth or its crystal water, and includes natural products and synthetic products. Examples of natural products include those having a structure of Mg6 Al2 (OH) 16 CO3 .4H2 O. As a synthetic product, Mg0.
7 Al0.3 (OH) 2 (CO3) 0.15 ・ 0.54H2
O, Mg4.5 Al2 (OH) 13CO3 ・ 3.5H2O,
Mg4.2 Al2 (OH) 12.4 CO3, Zn6 Al2 (O
H) 16CO3 ・ 4 H2 O, Ca6 Al2 (OH) 16CO
3 ・ 4 H2 O, Mg14 Bi2 (OH) 29.6 ・ 4.2 H2
O etc. are mentioned.

The zeolite is Na2O.Al2O3.
A type 2 zeolite represented by 2SiO 2 .XH 2 O, or a metal-substituted zeolite containing at least one metal selected from metals of groups II and IV of the periodic table. And as the substitution metal, Mg, Ca, Z
n, Sr, Ba, Zr, Sn, etc., especially Ca, Z
n and Ba are preferable.

The organic epoxy compound is epoxidized soybean oil, tris (epoxypropyl) isocyanurate,
Hydroquinone diglycidyl ether, terephthalic acid diglycidyl ester, 4,4′-sulfobisphenol polyglycidyl ether, N-glycidyl phthalimide, or hydrogenated bisphenol A glycidyl ether,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-
Epoxy cyclohexyl spiro [5,5] -3,4-epoxy) cyclohexane-m-dioxane, bis (3,3
4-epoxycyclohexylmethyl) adipate, vinylcyclohexenedioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-
6-Methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadienebepoxide, di (3,4) ethylene glycol.
-Epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate)
A) and alicyclic epoxy compounds such as dioctyl epoxyhexahydrophthalate and di-2-ethylhexyl epoxyhexahydrophthalate.

The light-shielding agent is a component for preventing light from reaching the polymer bulk. Specific examples thereof include rutile type titanium oxide (TiO2), zinc oxide (ZnO), chromium oxide (Cr2 O3), cerium oxide (CeO2) and the like. The metal deactivator is a component for deactivating heavy metal ions in the resin with a chelate compound. Specific examples thereof include acid amine derivatives, benzotriazole, and derivatives thereof.

The quenching agent is a component for deactivating photoexcited functional groups such as hydroperoxide and carbonyl group in the polymer by energy transfer, and organic nickel and the like are known. In the resin composition of the present invention, the flame retardant (I) is 0 to 100 parts by weight of the resin component consisting of the rubber-modified styrene resin and polyphenylene ether.
40 parts by weight, 0 to 30 parts by weight of (II) flame retardant aid, (II
It is preferable to add 0 to 30 parts by weight of I) a fluidity improver, 0 to 10 parts by weight of (IV) styrene thermoplastic elastomer, and 0 to 30 parts by weight of (V) light resistance improver. Within the above range, flame retardancy, moldability (fluidity),
Excellent balance between impact resistance and heat resistance.

The resin composition of the present invention can be obtained by, for example, melt-kneading each of the above components with a commercially available single-screw extruder, a twin-screw extruder or the like. At that time, oxidation of hindered phenol or the like is carried out. Inhibitor, benzotriazole and hinder
UV absorbers such as doamine, tin-based heat stabilizers, other inorganic and halogen-based flame retardants, lubricants such as stearic acid and zinc stearate, fillers, reinforcing agents such as glass fibers, coloring agents such as dyes and pigments Etc. can be added as needed. The composition of the present invention thus obtained is, for example,
Thermal stability by injection molding machine or extrusion molding,
A molded product excellent in molding processability (fluidity), flame retardancy, heat resistance and impact resistance can be obtained.

[0078]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. The measurements in Examples and Comparative Examples were performed using the following methods or measuring machines.

(1) Weight average particle diameter of rubber The weight average particle diameter of the rubber-modified aromatic vinyl resin is determined by determining the particle diameter of the butadiene-based polymer in the transmission electron microscope photograph taken by the ultrathin section method of the resin composition. , Calculated by the following formula. Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene-based polymer particles whose particles are Di). (2) Reduced viscosity ηSP / C Rubber-modified aromatic vinyl resin 1g of methyl ethyl ketone
A mixed solvent of 8 ml and methanol 2 ml is added, shaken at 25 ° C. for 2 hours, and centrifuged at 5 ° C. and 18000 rpm for 30 minutes. The supernatant was taken out, the resin component was precipitated with methanol, and then dried.

0.1 g of the resin thus obtained was dissolved in toluene to give a solution having a concentration of 0.5 g / dl, and 10 ml of this solution was placed in a Canon-Fenske viscometer.
At 30 ° C., the number of seconds t1 during which the solution flowed was measured. On the other hand, the flowing seconds t0 of pure toluene was measured separately with the same viscometer,
It was calculated by the following mathematical formula. ηSP / C = (t1 / t0-1) / C (C: polymer concentration g / dl) On the other hand, regarding the reduced viscosity ηSP / c of the component (B) PPE, 0.1 g is dissolved in chloroform and the concentration 0.5 g /
A dl solution was prepared and measured in the same manner as above.

(3) Gel%, degree of swelling (SI) 20 times amount of toluene is added to the pellet Sg, and the pellet is dissolved at 25 ° C. with a shaker and then centrifuged at 5 ° C. and 20000 rpm for 1 hour. After removing the supernatant liquid by decantation, the weight is measured (W). Then, it is vacuum dried at 100 ° C. for 2 hours, and the weight of the residue is measured (D). Then, the gel% and the swelling degree (SI) are calculated by the following formulas.

Gel% = (D / S) × 100 Swelling degree (SI) = W / D (4) Izod impact strength It was measured at 23 ° C. by the method according to ASTM-D256. (V notch, 1/8 inch test piece) (5) Vicat softening temperature Measured by a method according to ASTM-D1525 and used as a scale of heat resistance.

(6) Melt flow rate (MFR) The melt flow rate was measured by a method in accordance with ASTM-D1238. It was determined from the extrusion amount (g / 10 minutes) per 10 minutes under the conditions of a load of 5 kg and a melting temperature of 200 ° C. (7) Yellowness ΔYI SM A color computer model SM-3 (manufactured by Suga Test Instruments Co., Ltd.) was used for measurement according to JIS-Z-8722.

(8) Observation of dispersion state of rubber particles Ultra thin slices of 0.1 mm square or less are prepared from a molded product of the resin composition, and the surface is cut with a diamond knife to finish. This sample was immersed in an osmumic acid aqueous solution at 80 ° C for 20
It was soaked for a minute and dyed. The test piece thus produced was observed with a transmission electron microscope for the dispersion state of rubber particles.

The following components were used as the components used in the examples and comparative examples. (A) Rubber-modified styrene resin (HIPS) polybutadiene {(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2/3) (manufactured by Nippon Zeon Co., Ltd., trade name Nipol 122OSL)}
Was dissolved in the following mixed solution to form a uniform solution. Polybutadiene 10.5% by weight Styrene 74.2% by weight Ethylbenzene 15.0% by weight α-Methylstyrene dimer 0.27% by weight 1,1-bis (t-butylperoxy) -3,3,5-trimethyl Cyclohexane 0.03% by weight

Next, the above mixed solution was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage had a stirring rate of 190 r.
pm, 126 ° C, second stage 50 rpm, 133 ° C, third
Stage is 20 rpm, 140 ° C, Fourth stage is 20 rpm, 15
Polymerization was carried out at 5 ° C. Subsequently, the polymerization liquid having a solid content of 73% was introduced into a devolatilization device to remove unreacted monomers and solvent,
A rubber-modified aromatic vinyl resin was obtained (referred to as HIPS). As a result of analyzing the obtained rubber-modified aromatic vinyl resin, the rubber content was 12.1% by weight, the weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl / g.
Met.

(B) Rubber-unmodified styrene resin [polystyrene (GPPS)] Commercially available polystyrene (weight average molecular weight 270,000, number average molecular weight 120,000) [(manufactured by Asahi Chemical Industry Co., Ltd.) (hereinafter, GPP
S))] was used. (C) Manufacture of polyphenylene ether (PPE) After the inside of a stainless steel reactor having an oxygen blowing port at the bottom of the reactor and having a cooling coil and stirring blades inside was thoroughly replaced with nitrogen, cupric bromide was used. 54.8 g, di-n-
Butylamine 1110 g, and toluene 20 liters,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into a reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 180 minutes while controlling the internal temperature to 30 ° C. After the polymerization was completed, the precipitated polymer was filtered off. A methanol / hydrochloric acid mixture was added to this to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and then dried to obtain powdery polyphenylene ether (referred to as PPE). Reduced viscosity ηSP is 0.55dl
/ G.

(D) Rubber polymer Commercially available polybutadiene [(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2 /
3) 5 wt% styrene solution viscosity 38 centipoise (hereinafter referred to as PB1)] was used. Commercially available polybutadiene [(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 33/49/1
8) 5 wt% styrene solution viscosity 25 centipoise (hereinafter referred to as PB2)] was used.

(V) Polymerization Initiator Commercially available organic peroxide t-butyl peroxyisopropyl carbonate [Perbutyl I (trade name: PO), manufactured by NOF CORPORATION) was used. . (F) Chain transfer agent Commercially available α-methylstyrene dimer (hereinafter, α-MSD
Is used).

(G) Organic solvent Commercially available ethylbenzene (hereinafter referred to as EB) was used.

[0091]

Example 1 A polymer solution prepared by dissolving 12 parts by weight of polyphenylene ether in 42.5 parts by weight of styrene at 80 ° C., and styrene / rubber polymer (PB1) / organic solvent (EB) / polymerization initiator. (PO) / chain transfer agent (α-MS
D) [25.9 / 3.6 / 16 / 0.03 / 0.1 (parts by weight)] and a polymer solution were added to a reaction vessel equipped with a stirrer, and stirred at 120 Polymerization was carried out at ° C for 2 hours and then at 140 ° C for 2 hours. The polymerization rate is 53.
It was 9%. Then, the obtained polymerization liquid was devolatilized in vacuum at 230 ° C. for 2 hours.

The resin thus obtained was molded into a 1/8 inch molded article at 200 ° C. using a compression molding machine. In Table 1 and FIG. 1, resin composition, gel%, swelling degree (S
I), the color tone (yellowness ΔYI) of the molded product, MFR, Izod impact strength, Vicat softening temperature, electron microscope photograph, and the result of rubber particle diameter measurement by an electron microscope are shown.

[0093]

Comparative Example 1 HIPS / GPPS / PPE 56/2
Mechanically mixed at a weight ratio of 2.3 / 21.7 and manufactured by Nakatani Machinery Co., Ltd. AS-20-2 Twin Screw Extruder (L / D
28) was used to extrude and pelletize under the following conditions. From the resin composition thus obtained, a test piece having a thickness of 1/8 inch was prepared by hot pressing, and the same evaluation as in Example 1 was repeated. The results are shown in Table 1.

(Extrusion conditions) Cylinder temperature 230-250-250 ° C Die temperature 250 ° C Rotation speed 60 rpm Discharge rate 1.1 Kg / hr Since the melting temperature of PPE is high, first, PPE and GPP are used.
A master batch was prepared with S and 300 ° C. in the above twin-screw extruder, and HIPS was extruded under the above conditions using the master batch.

[0095]

Examples 2 and 3 Comparative Example 2 In Example 1, polymerization was carried out under the composition and polymerization conditions shown in Table 1, and the same evaluation as in Example 1 was repeated. The results are shown in Table 1 and FIG. According to Table 1, when a molded body is produced by a usual extrusion blending method, P
The color tone of the molded product is extremely deteriorated because PE is heat-melted at 300 ° C. or higher. It can be seen that the color tone is excellent due to the heat history.

This is explained from the magnetic resonance spectroscopy (NMR) measurement results of PPE extracted from the compositions of Example 1 and Comparative Example 1. That is, as shown in Table 2, a large number of phenol units based on the head end and dislocation structure were detected by the usual extrusion blending method (Comparative Example 1), and it is presumed that this forms a quinone structure and is colored. The phenol unit based on the head end and dislocation structure is preferably in the range of 0.1 to 0.5 in 100 binding units of PPE.

Also in the above polymerization compounding method, large rubber particles are formed by adding the polymer solution of PPE before the phase inversion of the rubbery polymer, and high impact strength is exhibited (see FIG. 1). However, on the other hand, when the polymer solution of PPE is added after the phase inversion of the rubber-like polymer, it is found that the rubber particles are broken by the PPE which is a hard resin (see FIG. 2) and the impact strength is remarkably lowered.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

The present invention provides a polyphenylene ether resin composition excellent in appearance (color tone) and impact strength, and a method for producing the same. This composition is a household appliance part,
It is suitable for OA equipment parts, etc., and plays a large role in these industries.

[Brief description of drawings]

FIG. 1 is a schematic view of an electron micrograph of a molded body of Example 1.

2 is a schematic view of an electron micrograph of a molded body of Comparative Example 2. FIG.

Claims (3)

[Claims] 1. A rubber-modified styrene resin [component (A)]
And a polyphenylene ether [component (B)], wherein a molded product obtained from the resin composition has a Δ of JIS-Z-8722 standard, which is an index of yellowness.
YI is 0 or more and 40 or less, The polyphenylene ether resin fat composition characterized by the above-mentioned. 2. A polymer solution [component (C)] containing an aromatic vinyl monomer and polyphenylene ether is added to a polymer solution containing an aromatic vinyl monomer, a rubbery polymer, and a polymerization initiator. In the polymerization method of mixing with [(D) component], the (C) component is added and mixed before phase inversion of the rubbery polymer in the (D) component.
A method for producing the polyphenylene ether resin composition described. 3. The method for producing a polyphenylene ether resin composition according to claim 2, wherein an organic solvent is added to the components (C) and (D).