JP7409900B2 - Method for producing polyphenylene ether resin composition - Google Patents

Description

The present invention relates to a method for producing a polyphenylene ether resin composition.

The polyphenylene ether resin composition is made by adding a thermoplastic elastomer, a flame retardant, a heat stabilizer, a mold release agent, a lubricant, and an inorganic filler to the polyphenylene ether resin alone or to the polyphenylene ether resin and styrene resin, if necessary. It is made by blending additive components such as agents.

Polyphenylene ether resin compositions have various properties such as excellent mechanical properties, electrical properties, acid and alkali resistance, and heat resistance, as well as low specific gravity, low water absorption, and good dimensional stability. Because of this, it is widely used as a material for home appliances, office automation equipment, office machines, information equipment, automobiles, etc.

However, since polyphenylene ether resin compositions usually have a high melt viscosity, when melt-kneaded using an extruder or the like to form a resin composition (pellet), the melt-kneaded resin composition is exposed to high temperature conditions. Oxidative crosslinking of the polyphenylene ether resin is promoted by contacting it with oxygen below. Eventually, gelation and carbonization of the resin occur, and these foreign substances are mixed into the resin composition, which may cause deterioration in the appearance and toughness of the molded product.

In addition, when polyphenylene ether resin compositions are produced using an extruder, the resin composition adheres to the area around the circular discharge port (die nozzle) at the tip of the extruder through which the melted and kneaded resin composition is discharged. As production continues, deposits are exposed to heat and the outside air for a long time and grow into whiskers while oxidizing and crosslinking, which eventually attaches to the extruded resin and mixes into the resin composition. This may also cause deterioration in the appearance and toughness of the molded product.

Furthermore, since the grown resin does not leave the vicinity of the die nozzle, the resin (strand) that is continuously discharged from the die nozzle in the form of a string is collected and cut (pelletizing) by a cutting machine (pelletizer). Eventually, the flow of the strand becomes unstable, which may cause production problems such as strand breakage and poor strand take-up by the pelletizer.

Patent Document 1 describes that in a specific polyphenylene ether resin composition, by adjusting the oxygen concentration inside the first supply port hopper for supplying the raw material of the extruder to 1.0% by volume or less, the oxygen concentration generated inside the extruder barrel is A technique for reducing degraded products of polyphenylene ether resin has been disclosed.
Patent Document 2 states that when extruding a polyphenylene ether resin composition with an extruder, when the entire barrel length of the extruder is 100%, a length of 45 to 75% from the upstream is an unmelted mixing zone. discloses a technique for suppressing thermal deterioration of resin and improving impact resistance and heat aging resistance.

Japanese Patent Application Publication No. 2012-255046 Japanese Patent Application Publication No. 2008-274035

However, although the technique described in Patent Document 1 certainly reduces the degraded products of the polyphenylene ether resin produced in the extruder barrel, it is not necessarily sufficient to reduce the dirt around the die nozzle.
Furthermore, although the technology described in Patent Document 2 has been effective to some extent in reducing the generation of foreign matter in the extruder barrel and in suppressing the deterioration of the physical properties of the resin composition, it is still insufficient in terms of suppressing buildup during extrusion. Not enough.

Therefore, the present invention significantly suppresses the generation of degraded products of polyphenylene ether resin that normally occurs in the extruder barrel during extrusion and the generation of sludge around the die nozzle, improving extrusion productivity, and improves extrusion productivity. It is an object of the present invention to provide a manufacturing method capable of reducing the contamination of ether-derived foreign substances and obtaining a resin composition with good toughness.

The inventors of the present invention conducted extensive studies to solve the above problems, and found that by extruding a resin composition containing a certain amount or more of polyphenylene ether using an extruder using a specific extrusion method, it is possible to The generation of degraded products of the polyphenylene ether resin and the generation of slime around the die nozzle are significantly suppressed, improving extrusion productivity, and polyphenylene ether with good toughness and less contamination of foreign substances derived from polyphenylene ether. The present invention was completed by demonstrating that the based resin composition can be stably produced.

That is, the present invention is as follows.
[1]
A method for producing a resin composition using an extruder, the method comprising:
The resin composition contains 10% by mass or more of polyphenylene ether (A) based on the total amount of the resin composition (100% by mass),
The extruder has a solid conveyance zone, a melt kneading zone, and a melt conveyance zone, and the solid conveyance zone has a barrel C0 provided with a first supply port under a collecting hopper at the most upstream part . It is a shaft extruder,
When the barrel length of the entire extruder is 100%, 30 to 60% from the upstream side of the extruder is the solid conveyance zone, and the remaining 40 to 70% is the melt kneading zone and the melt conveyance zone. can be,
Among the barrels constituting the solid transport zone, when the length of the remaining barrels excluding barrel C0 (water-cooled) in which the first supply port is provided is taken as 100%, the set temperature of 75% or more of the barrels is within the range of 50 to 190°C,
The set temperature of the barrel constituting the melt kneading zone and the barrel constituting the melt conveyance zone is within the range of 250 to 320 ° C.,
The oxygen concentration in the collection hopper provided above the first supply port is 3 vol% or less,
A method for producing a resin composition.
[2]
Among the barrels constituting the solid transportation zone, when the length of the barrel excluding the barrel in which the first supply port is provided is taken as 100%, the set temperature of 100% of the barrels is within the range of 50 to 190 ° C. A method for producing a resin composition according to [1].
[3]
According to [1] or [2], the melting conveyance zone has a barrel provided with an opening, and a vent port having a nitrogen injection line and a gas vent is provided above the opening. A method for producing a resin composition.
[4]
The method for producing a resin composition according to any one of [1] to [3], wherein all of the extrusion raw materials are supplied from the first supply port.
[5]
The resin composition according to any one of [1] to [4], wherein the resin composition further contains 5 to 80% by mass of a styrene resin (B) based on the total amount of the resin composition (100% by mass). manufacturing method.
[6]
The resin composition further contains 0.1 to 25% by mass of a styrene thermoplastic elastomer (C) based on the total amount of the resin composition (100% by mass), according to any one of [1] to [5]. A method for producing a resin composition.
[7]
The resin composition according to any one of [1] to [6], wherein the resin composition further contains 0.001 to 3% by mass of an antioxidant (D) based on the total amount (100% by mass) of the resin composition. Method for producing the composition.
[8]
The method for producing a resin composition according to any one of [1] to [7], wherein the resin composition has a polyolefin resin component content of 5% by mass or less based on the total amount of the resin composition (100% by mass). .

According to the manufacturing method of the present invention, the generation of degraded polyphenylene ether resin that normally occurs in the extruder barrel during extrusion and the generation of sludge around the die nozzle are significantly suppressed, and extrusion productivity is improved. The contamination of foreign substances derived from polyphenylene ether is reduced, making it possible to stably obtain a resin composition with good toughness.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

The method for producing a polyphenylene ether resin composition according to the present embodiment is a method for producing a resin composition using an extruder, and the resin composition contains polyphenylene ether based on the total amount (100% by mass) of the resin composition. The extruder contains 10% by mass or more of ether (A), and the extruder has a solid conveyance zone, a melt kneading zone, and a melt conveyance zone, and the solid conveyance zone has a barrel provided with a first supply port. , is a twin-screw extruder, and when the barrel length of the entire extruder is taken as 100%, 30 to 60% from the upstream side of the extruder is a solid conveying zone, and the remaining 40 to 70% is a melt kneading zone and a melting zone. The set temperature of 75% or more of the barrels that constitute the solid transportation zone is 50 to 190°C, where the length of the barrels excluding the barrel where the first supply port is installed is taken as 100%. The set temperature of the barrel constituting the melt-kneading zone and the barrel constituting the melt conveyance zone is within the range of 250 to 320 °C, and the oxygen in the collecting hopper provided above the first supply port is within the range of 250 to 320 °C. The concentration is 3 vol% or less.

<<Resin composition>>
The resin composition according to the present embodiment contains polyphenylene ether (A) in an amount of 10% by mass or more based on the total amount (100% by mass) of the resin composition.

The polyphenylene ether-based resin composition according to the present embodiment is produced by using the manufacturing method according to the present embodiment described below, including component (A) of the present application, optionally components (B) to (D), and optionally components (B) to (D). Manufactured by melt-kneading other added ingredients.

The present inventors have discovered that by extruding the above-described resin composition using a specific extrusion method, the generation of oxidized cross-linked products of the polyphenylene ether resin generated in the extruder barrel during extrusion and the generation of slime around the die nozzle are significantly suppressed. It has been found that extrusion productivity is improved and contamination of foreign substances derived from polyphenylene ether is reduced. Each constituent component of the above resin composition will be explained in detail below.

・・・（１）〔ａ〕

・・・（１）〔ｂ〕
上記式（１）〔ａ〕、〔ｂ〕中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は、それぞれ独立して、炭素数１～４のアルキル基、炭素数６～１２のアリール基、並びにハロゲン原子及び水素原子からなる群から選ばれる一価の残基であることが好ましい。
但し、かかる場合、Ｒ５及びＲ６が同時に水素である場合を除く。
また、前記アルキル基のより好ましい炭素数は１～３であり、前記アリール基のより好ましい炭素数は６～８であり、前記一価の残基の中でもより好ましくは水素である。
なお、上記（１）の〔ａ〕及び〔ｂ〕における繰り返し単位の数については、ポリフェニレンエーテル（Ａ）の分子量分布により様々であるため、特に制限されることはない。 <Polyphenylene ether (A)>
The polyphenylene ether (A) is preferably a homopolymer or a copolymer whose repeating structural units are composed of [a] and/or [b] of general formula (1).

...(1) [a]

...(1) [b]
In the above formulas (1) [a] and [b], R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 4 carbon atoms, and 6 carbon atoms. Preferably, it is a monovalent residue selected from the group consisting of ~12 aryl groups, halogen atoms, and hydrogen atoms.
However, in such a case, the case where R5 and R6 are both hydrogen is excluded.
Further, the alkyl group preferably has 1 to 3 carbon atoms, the aryl group preferably has 6 to 8 carbon atoms, and among the monovalent residues, hydrogen is more preferable.
Note that the number of repeating units in [a] and [b] in (1) above is not particularly limited, since it varies depending on the molecular weight distribution of the polyphenylene ether (A).

Homopolymers of polyphenylene ether include, but are not limited to, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, etc. , poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1) ,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl -6-chloroethyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether, etc. can be mentioned.

In addition, copolymers of polyphenylene ether include, but are not limited to, copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and o-cresol, etc. and copolymers of 2,3,6-trimethylphenol and o-cresol, which mainly have a polyphenylene ether structure.

Among polyphenylene ethers, it is preferable to use poly(2,6-dimethyl-1,4-phenylene) ether.

The above-mentioned polyphenylene ether (A) may be used alone or in combination of two or more.

Moreover, the polyphenylene ether (A) may contain various phenylene ether units other than [a] and [b] in formula (1) as a partial structure.
Examples of such phenylene ether units include, but are not limited to, 2-(dialkylaminomethyl)-6-methylphenylene ether described in JP-A-01-297428 and JP-A-63-301222. units, 2-(N-alkyl-N-phenylaminomethyl)-6-methylphenylene ether units, and the like.

Moreover, polyphenylene ether (A) may contain structural units other than phenylene ether units in the main chain.
Examples of such structural units include units derived from diphenoquinone. However, the structural units other than phenylene ether units contained in the main chain are preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass, based on 100% by mass of polyphenylene ether (A). % by mass or less.

Furthermore, the polyphenylene ether (A) is a type selected from the group consisting of carboxylic acids, acid anhydrides, acid amides, imides, amines, orthoesters, hydroxy, and carboxylic acid ammonium salts. The polyphenylene ether may be functionalized by reacting (modifying) with a functionalizing agent including the above.

The reduced viscosity of the polyphenylene ether (A) used in this embodiment is preferably in the range of 0.25 to 0.60 dL/g, more preferably 0.30 to 0.55 dL/g, even more preferably It is in the range of 0.35 to 0.50 dL/g. From the viewpoint of sufficient mechanical properties, it is preferably 0.25 dL/g or more, and from the viewpoint of molding processability and brightness of the molded product, it is preferably 0.55 dL/g or less.
Note that the reduced viscosity in this embodiment is a value obtained by measurement using an Ubbelohde viscometer at 30° C. in a chloroform solvent at a concentration of 0.50 g/dL.

The ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw/Mn value) of the polyphenylene ether (A) used in this embodiment before heating processing by extrusion or the like (in polymer powder state) is preferably 1. 2 to 3.0, more preferably 1.5 to 2.5, even more preferably 1.8 to 2.3. The Mw/Mn value is preferably 1.2 or more from the viewpoint of moldability of the resin composition, and preferably 3.0 or less from the viewpoint of maintaining the mechanical properties of the resin composition, particularly tensile strength.
Note that the weight average molecular weight Mw and the number average molecular weight Mn are obtained from the polystyrene equivalent molecular weight measured by GPC (gel permeation chromatography).

In the polyphenylene ether resin composition of this embodiment, the content of polyphenylene ether (A) is 10% by mass or more based on the entire resin composition. The content is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. From the viewpoint of achieving sufficient effects by the manufacturing method of this embodiment, it is important to contain 10% by mass or more.

<Styrenic resin component (B)>
In the resin composition of this embodiment, a styrene resin (B) can be blended mainly for the purpose of improving molding fluidity.
In this embodiment, the styrene resin (B) is a homopolymer of a styrene compound, or a copolymer of a styrene compound and a compound copolymerizable with a styrene compound (excluding a conjugated diene compound). means. This component (B) does not include anything included in the category of component (C), which will be described later.
Specific examples of the styrene resin (B) include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene.

Compounds that can be copolymerized with styrene compounds include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. It will be done.

The styrenic resin (B) can be obtained by polymerizing a styrene compound or a styrene compound and a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.
Examples of the rubbery polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, hydrogenated products thereof, and ethylene-propylene copolymer rubbers.

In this embodiment, the styrene resin (B) is preferably polystyrene or high impact polystyrene reinforced with a rubbery polymer, and more preferably polystyrene.

The content of the styrene resin (B) in the resin composition used in this embodiment is preferably 5 to 80% by mass, more preferably 10 to 60% by mass based on 100% by mass of the resin composition. %, even more preferably 20 to 60% by weight, particularly preferably 25 to 45% by weight. A blending amount of 5% by mass or more is preferable from the viewpoint of imparting sufficient molding fluidity, and a blending of 80% by mass or less is preferable from the viewpoint of maintaining sufficient heat resistance.

<Styrenic thermoplastic elastomer (C)>
The styrenic thermoplastic elastomer (C) used in this embodiment is a block copolymer having a styrene block and a conjugated diene compound block.

From the viewpoint of thermal stability, the conjugated diene compound block is preferably hydrogenated at a hydrogenation rate of at least 50% or more. The hydrogenation rate is more preferably 80% or more, even more preferably 95% or more.

Examples of the conjugated diene compound block include, but are not limited to, polybutadiene, polyisoprene, poly(ethylene/butylene), poly(ethylene/propylene), and vinyl-polyisoprene. The conjugated diene compound blocks may be used alone or in combination of two or more.

The repeating units constituting the block copolymer may be arranged in either a linear type or a radial type. Further, the block structure constituted by the polystyrene block and the rubber intermediate block may be of type 2, type 3, or type 4. Among these, from the viewpoint of fully exhibiting the desired effects of this embodiment, a three-type linear type block copolymer constituted by a polystyrene-poly(ethylene/butylene)-polystyrene structure is preferred. Note that the conjugated diene compound block may contain butadiene units in an amount not exceeding 30% by mass.

Furthermore, in the composition of this embodiment, the styrene-based thermoplastic elastomer may be a functionalized styrene-based thermoplastic elastomer into which a functional group such as a carbonyl group or an amino group is introduced.

The amount of bound styrene in the styrenic thermoplastic elastomer (C) according to the present embodiment is selected from the range of 20 to 90% by mass, preferably 55 to 80% by mass, more preferably 60 to 70% by mass. be. From the viewpoint of miscibility with the component (A) and the component (B), the content is preferably 20% by mass or more, and from the viewpoint of imparting sufficient impact resistance, the content is preferably 90% by mass or less.

The number average molecular weight Mn of the styrenic thermoplastic elastomer (C) according to the present embodiment is preferably 30,000 to 500,000, more preferably 40,000 to 300,000, even more preferably 45,000 to The range is 250,000. From the viewpoint of imparting sufficient toughness to the molded product, the range is preferably from 30,000 to 500,000.
The Mw/Mn value of the component (C) determined from the weight average molecular weight Mw obtained from the polystyrene equivalent molecular weight and the number average molecular weight Mn is preferably 1.0 to 3.0, more preferably 1.0 to 2. 0, and even more preferably within the range of 1.0 to 1.5. From the viewpoint of mechanical properties, it is preferably within the range of 1.0 to 3.0.

The content of the styrene thermoplastic elastomer (C) according to the present embodiment is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass in 100% by mass of the resin composition. % by weight, even more preferably in the range from 1 to 20% by weight. From the viewpoint of improving toughness, the content is preferably 0.1% by mass or more, and from the viewpoint of the mechanical properties of the molded article, the content is preferably 25% by mass or less.

<Antioxidant (D)>
The resin composition according to this embodiment may further contain an antioxidant (D).

As the above-mentioned antioxidant (D), either a primary antioxidant that functions as a radical chain inhibitor or a secondary antioxidant that has the effect of decomposing peroxides can be used. That is, by using an antioxidant, it is possible to scavenge radicals that may be generated in the terminal methyl group or side chain methyl group when polyphenylene ether is exposed to high temperatures for a long time (primary antioxidant), or The radicals can decompose peroxides generated in terminal methyl groups or side chain methyl groups (secondary antioxidant), and therefore, oxidative crosslinking of polyphenylene ether can be prevented.

As the primary antioxidant, mainly hindered phenolic antioxidants can be used, and specific examples include 2,6-di-t-butyl-4-methylphenol, pentaerythritol tetrakis [3-(3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis(4- Methyl-6-t-butylphenol), 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy- 3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 4,4'-butylidenebis(3-methyl-6-t-butylphenol), alkylated bisphenol, tetrakis [Methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methyl) phenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxyspiro[5,5]undecane and the like.

As the secondary antioxidant, phosphorous antioxidants can mainly be used. Specific examples of phosphorous antioxidants include trisnonylphenyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and bis(2,4-di-t-butylphenyl). Pentaerythritol-di-phosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, 3,9-bis(2,6-di-tert-butyl-4 -methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane and the like.

Further, as other antioxidants, metal oxides such as zinc oxide and magnesium oxide, and metal sulfides such as zinc sulfide can be used in combination with the above antioxidants.

・・・（２） Among these, in order to improve the toughness of molded products and the mechanical properties after long-term high temperature exposure, phosphorus-based antioxidants, which are secondary antioxidants, are preferred, and phosphite-based antioxidants are more preferred, with the following chemical formula: A phosphite-based antioxidant having the structure (2) in its molecule is particularly preferred.

...(2)

The content of the antioxidant (D) is preferably 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, and more preferably 0.1 to 1% by mass, based on 100% by mass of the resin composition. % by weight is even more preferred, and 0.1 to 0.5% by weight is particularly more preferred. From the viewpoint of suppressing oxidative deterioration of the resin during extrusion processing, the addition amount is preferably 0.001% by mass or more, and from the viewpoint of maintaining the surface appearance of the molded product, the addition amount is preferably 3% by mass or less.

<Other ingredients>
When coloring the resin composition according to this embodiment, a coloring agent such as carbon black, titanium oxide, or other inorganic or organic known dyes or pigments is added to 100% by mass of the resin composition. The content is preferably within the range of .001 to 5% by mass. From the viewpoint of sufficient coloring, the content is preferably 0.001% by mass or more, and from the viewpoint of maintaining sufficient mechanical strength and appearance of the molded article, the content is preferably 5% by mass or less.

In the resin composition according to the present embodiment, the polyolefin resin component is preferably contained in an amount of 5% by mass or less in 100% by mass of the resin composition.
The polyolefin resin component includes polyolefin resins such as polyethylene and polypropylene, and polyolefin copolymers such as ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-ethyl acrylate copolymer, and ethylene-ethyl methacrylate copolymer. Examples include polymers.
The content of the polyolefin resin component in the resin composition according to the present embodiment is more preferably 3% by mass or less, and even more preferably 1% by mass or less. From the viewpoint of suppressing deterioration in physical properties and deterioration in appearance due to surface peeling of the molded article, the content is preferably 5% by mass or less.

The resin composition according to this embodiment preferably does not contain an inorganic filler as a reinforcing agent from the viewpoint of the toughness of the molded product and the appearance of the molded product. Inorganic fillers as reinforcing agents are generally used for reinforcing thermoplastic resins, and include, for example, glass fibers, carbon fibers, glass flakes, talc, mica, and the like. Here, "not containing an inorganic filler" means that the content of the inorganic filler in 100% by mass of the resin composition is 1% by mass or less. The content is preferably 0.5% by mass or less, more preferably 0.1% by mass or less.

In addition, an ultraviolet absorber, a mold release agent, a lubricant, and the like may be added to the resin composition according to the present embodiment, as necessary, to the extent that the effects of the present embodiment are not significantly reduced.

<<Production method of resin composition>>
The resin composition according to the present embodiment is produced by melt-kneading the component (A) of the present application, components (B) to (D) as necessary, and other components added as necessary. Manufactured by

The present inventors have discovered that by extruding the above resin composition using a specific extrusion method, the generation of degraded products of the polyphenylene ether resin generated in the extruder barrel during extrusion and the generation of slime around the die nozzle are significantly suppressed, and the extrusion We have found a manufacturing method that can stably mass-produce a polyphenylene ether-based resin composition that improves productivity, has less contamination of foreign substances derived from polyphenylene ether, and has good toughness.

The method for producing the resin composition will be described in detail below.

The polyphenylene ether resin composition of the present embodiment contains the component (A), the components (B) to (D) as necessary, and other components added as necessary in a solid state in a barrel. It is produced by melt-kneading using a twin-screw extruder having a conveyance zone, a melt-kneading zone, and a melt-conveyance zone.

At that time, when the barrel length of the entire extruder is taken as 100%, 30 to 60% from the upstream side of the extruder is the solid conveyance zone, and the remaining 40 to 70% is the melt kneading zone and the melt conveyance zone. Furthermore, among the barrels constituting the solids transport zone, the set temperature of 75% or more of the barrels is set at 50 to 190°C, assuming that the length of the barrel excluding the barrel where the first supply port is installed is 100%. The barrel temperature of the melt-kneading zone and the melt-conveying zone is set within the range of 250 to 320°C, and the oxygen concentration in the collection hopper provided above the first supply port is set to 3 vol. % or less and melt-kneading it.

In producing the resin composition, the twin-screw extruder used is a twin-screw extruder with a screw diameter of 40 to 90 mm, from the viewpoint of stably obtaining a large amount of a resin composition that can sufficiently exhibit the desired effects of the present embodiment. Preferably, a twin screw extruder is used.
As a preferred example, a TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels: 13 (including the lower barrel of the first supply port hopper), screw diameter: 58 mm, L/D = 53); kneading disk L: 2 pieces, When using a screw pattern with 12 kneading discs R and 4 kneading discs N, the barrel length of the entire extruder (including the barrel with a hopper installed at the first supply port) is 100%, the barrel length of the solid transport zone is 45%, the barrel length of the remaining melt kneading zone and melt transport zone is 55%, and the barrel set temperature of the solid transport zone (first supply port hopper (Excluding the lower barrel because it is water-cooled) 100 to 180°C, Barrel setting temperature of the melt kneading zone and melt conveyance zone 270 to 310°C, Oxygen concentration in the collecting hopper above the first supply port 0.3 to 2.0 vol% , a method of melt-kneading under conditions of a screw rotation speed of 350 to 600 rpm and an extrusion rate of 350 to 600 kg/h.

In producing the resin composition, the solid conveying zone in the barrel of a twin-screw extruder is defined as a zone in which the extruded raw material components are not completely melted, but are completely unmelted or unmelted components are present in the extruded raw material components. Refers to a zone that is conveyed in a semi-molten state only by a single-start and/or double-start right-handed feed screw element configuration.

The length of the solid conveying zone in the extruder is selected from a range of 30 to 60% of the barrel length of the entire extruder as 100%. It is preferably within the range of 35 to 60%, more preferably within the range of 40 to 55%, even more preferably within the range of 45 to 55%. From the viewpoint of sufficient suppression of thermal deterioration of the polyphenylene ether resin, it is required to be 30% or more, and from the viewpoint of sufficient melt-kneading and production stability of the extrusion raw material components, it is necessary to be 60% or less.

The melt-kneading zone in the barrel of a twin-screw extruder is a zone where completely unmolten or semi-molten extrusion raw material components sent from the solid conveyance zone are literally melt-kneaded. Refers to a zone consisting of a screw configuration including a plurality of kneading screw elements such as a kneading disk N and a kneading disk L.
The melt conveyance zone in the barrel of a twin-screw extruder is a zone in which the extruded raw material components sent from the melt-kneading zone are conveyed to the resin discharge port (die nozzle) of the extruder, and has a single thread and/or double thread right-hand thread. Refers to the zone in which the molten extrudate raw material components are conveyed only by the feeding screw element configuration.

The combined length of the melt kneading zone and the melt conveyance zone in the extruder is selected from a range of 70 to 40% of the barrel length of the entire extruder as 100%. It is preferably within the range of 60 to 40%, more preferably within the range of 57 to 40%, and even more preferably within the range of 57 to 45%. From the viewpoint of sufficient suppression of thermal deterioration of the polyphenylene ether resin, it is required to be 70% or less, and from the viewpoint of sufficient melting and kneading of the extrusion raw material components, it is necessary to be 40% or more.

The length of the melt-kneading zone in the extruder is preferably within a range of 15 to 40% when the barrel length of the entire extruder is taken as 100%. It is more preferably within the range of 20 to 40%, and even more preferably within the range of 22 to 35%. From the viewpoint of sufficient melt-kneading of the extruded resin component, it is preferably 15% or more, and from the viewpoint of suppressing thermal deterioration of the polyphenylene ether resin, it is preferably 40% or less.

The barrel set temperature of the solid conveyance zone in the extruder is 75% or more, when the barrel length excluding the barrel in which the first supply port is provided among the barrels constituting the solid conveyance zone is taken as 100%, Preferably 80% or more, more preferably 90% or more, and even more preferably 100% of the barrel temperature is selected from within the range of 50 to 190°C. The set temperature is preferably within the range of 70 to 190°C, more preferably within the range of 100 to 180°C, and even more preferably within the range of 130 to 170°C. From the viewpoint of production stability, the temperature needs to be 50°C or higher, and from the viewpoint of suppressing thermal deterioration of the polyphenylene ether resin, the temperature needs to be 190°C or lower.

The barrel temperature settings of the melt kneading zone and melt conveyance zone in the extruder are selected from within the range of 250 to 320°C. The temperature is preferably within the range of 260 to 320°C, more preferably within the range of 270 to 310°C. From the viewpoint of sufficient melt-kneading of the extruded resin component and production stability, the temperature must be 250°C or higher, and from the viewpoint of suppressing thermal deterioration of the polyphenylene ether resin and production stability, the temperature must be 320°C or lower. be.

The set temperature of the resin discharge part (die head) in the extruder is preferably within the range of 270 to 320°C. The temperature is more preferably within the range of 290 to 315°C, and even more preferably within the range of 300 to 310°C. From the viewpoint of production stability, the temperature is preferably 270°C or higher, and from the viewpoint of suppressing thermal deterioration of the polyphenylene ether resin, the temperature is preferably 320°C or lower.

When producing the resin composition used in this embodiment using a twin-screw extruder, it is important to note that gels and carbides produced by oxidative deterioration from the polyphenylene ether, which is the component (A), may be present in the extruded resin pellets. This is the point where the contamination of the molded product causes deterioration of the physical properties such as the surface appearance and toughness of the molded product.
Therefore, it is important to input the component (A) from the most upstream (top feed) raw material input port and to set the oxygen concentration inside the collecting hopper at the most upstream input port to 3 vol% or less. The oxygen concentration inside the collection hopper is preferably 2 vol% or less, more preferably 1 vol% or less, and even more preferably 0.5 vol% or less.

To adjust the oxygen concentration, replace the inside of the raw material storage hopper with sufficient nitrogen, seal the feed piping line from the raw material storage hopper to the extruder raw material input port to prevent air from entering or exiting, and then replace the nitrogen feed. This can be done by adjusting the amount and the opening degree of the gas vent.

In the production of the resin composition of this embodiment, all extruded raw materials are supplied from the first supply port (top feed) to sufficiently reduce the oxygen concentration inside the collecting hopper at the most upstream input port. It is preferable from this point of view, and also preferable from the perspective of suppressing oxidative deterioration of the component (A) and sufficiently exhibiting the effects required for the application of the present invention.

The oxygen concentration inside the collecting hopper is measured using an oxygen concentration meter, and by installing the oxygen concentration meter so that the sensor part is located in the middle of the collecting hopper, constant measurement is possible during extrusion. It is possible to do so.

In addition, when the molten resin extruded from the die nozzle of the extruder comes into contact with air, the molten resin adhering to the nozzle edge may progress to deteriorate due to oxidation crosslinking, which may be a contributing factor to the formation and growth of dirt. . As production progresses over a long period of time, nitrogen gas grows on the edges of the nozzle and may eventually get mixed into the resin, causing poor appearance and deterioration of physical properties. Therefore, nitrogen gas should not be sprayed onto the resin immediately after it comes out of the die nozzle. preferable. Nitrogen gas can be sprayed using a known dirt removal device by connecting a nitrogen gas line.

The amount of nitrogen gas sprayed to the die nozzle is preferably within the range of 1 to 50 L/min, more preferably within the range of 5 to 30 L/min, and even more preferably within the range of 10 to 25 L/min. From the viewpoint of sufficient contact between the resin and nitrogen gas, the flow rate is preferably 1 L/min or more, and from the viewpoint of consideration to the surrounding environment, the flow rate is preferably 50 L/min or less.

Normally, during extrusion, it is desirable to devolatilize under reduced pressure using a vacuum vent in order to remove residual volatile matter in the raw material components, but in this case, it is necessary to devolatilize the raw material under reduced pressure at the vacuum vent and the surrounding barrels. Outside air may be sucked in through the gap, accelerating the deterioration of the resin due to oxidative crosslinking of the molten resin. In that case, it may be preferable to extrude without devolatilizing under reduced pressure using a vacuum vent. If you remove the vacuum vent and plug the top of the barrel, the internal pressure of the barrel will increase due to the gas generated from the molten resin during extrusion, making the discharge of the molten resin from the die nozzle unstable and making it difficult to take off the strand during extrusion. Therefore, a vent port with a nitrogen injection line and a gas vent is installed at the opening at the top of the barrel, and nitrogen is injected from the nitrogen injection line into the vent port and sprayed onto the molten resin at the vent opening. Preferably, the gas component and nitrogen gas generated from the molten resin are extruded while being discharged from the gas venting section.

The flow rate of nitrogen gas injected into the vent port is preferably within the range of 1 to 50 L/min, more preferably within the range of 5 to 30 L/min, and even more preferably within the range of 10 to 25 L/min. . From the viewpoint of sufficient contact between the resin and nitrogen gas, the flow rate is preferably 1 L/min or more, and from the viewpoint of consideration to the surrounding environment, the flow rate is preferably 50 L/min or less.

In producing the resin composition of this embodiment, the screw rotation speed of the twin-screw extruder is preferably within the range of 250 to 700 rpm. The speed is more preferably within the range of 300 to 600 rpm, even more preferably within the range of 350 to 600 rpm, and even more preferably within the range of 400 to 500 rpm. The speed is preferably 250 rpm or more from the viewpoint of sufficient melt-kneading of the resin composition, and preferably 700 rpm or less from the viewpoint of suppressing thermal deterioration of the resin composition due to shear heat generation.

In producing the resin composition of this embodiment, the extrusion rate of the twin-screw extruder is preferably within the range of 250 to 700 kg/h. It is more preferably within the range of 300 to 600 kg/h, even more preferably within the range of 350 to 500 kg/h, and even more preferably within the range of 350 to 450 kg/h. From the viewpoint of sufficient mass productivity, it is preferably 250 kg/h or more, and from the viewpoint of production stability, it is preferably 700 kg/h or less.

[Molding]
The molded article made of the polyphenylene ether resin composition of this embodiment can be obtained by molding the resin composition obtained by the above-mentioned manufacturing method.
The method for molding the resin composition is not limited to the following, but suitable examples include injection molding, extrusion molding, vacuum molding, and pressure molding, with injection molding being more preferably used, particularly from the viewpoint of molded appearance. .

The molding temperature during molding of the resin composition is preferably within the range of the maximum barrel setting temperature of 250 to 340 °C, more preferably 270 to 330 °C, and even more preferably 280 to 320 °C. . From the viewpoint of sufficient molding processability, the molding temperature is preferably 250°C or higher, and from the viewpoint of suppressing thermal deterioration of the resin and maintaining physical properties, the molding temperature is preferably 340°C or lower.

The mold temperature during molding of the resin composition is preferably within the range of 40 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 120°C. From the viewpoint of maintaining sufficient appearance of the molded product, the mold temperature is preferably 40°C or higher, and from the viewpoint of molding stability, it is preferably 150°C or lower.

The preferred molded product in this embodiment is that the production method of this embodiment significantly suppresses the generation of degraded products of polyphenylene ether resin generated in the extruder barrel during extrusion and the generation of sludge around the die nozzle. As a result, extrusion productivity is improved, polyphenylene ether-based resin compositions with less contamination of polyphenylene ether-derived foreign substances and good toughness can be stably mass-produced. , automotive applications, various industrial products, etc.

Hereinafter, this embodiment will be described in more detail with reference to Examples and Comparative Examples, but this embodiment is not limited to these Examples.

Evaluation of physical properties, measurement methods, and raw materials used in Examples and Comparative Examples are shown below.

[Production stability]
1. Meyani The resin compositions of the following Examples and Comparative Examples were processed using a TEM58SS twin screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels: 12 (excluding the lower barrel of the first supply port hopper), screw diameter: 58 mm, L/D = 53). During production by melt-kneading under the extrusion conditions described below, it was confirmed whether sludge (melted resin adhered to the edge of the die nozzle and grew into needle-like shapes) was generated.
Those in which no buildup was visually observed after 2 hours of continuous operation were rated as "〇 (excellent)", and those in which buildup was visually observed within 2 hours of continuous operation were rated as "x" (poor). . As for the evaluation criteria, those with a rating of "○" are suitable for the manufacturing method of the present application.

2. Strand withdrawal stability In extrusion of the resin composition in the above "1. Meyani", those whose strands were stably withdrawn up to 2 hours of continuous operation were rated "〇 (excellent)", and strand breakage occurred during 2 hours of operation. Those in which the strand broke twice or less were judged as "△ (good)", and those in which strand breakage occurred three or more times during two hours of operation were judged as "x (poor)". As for the evaluation criteria, those with a rating of "○" are suitable for the manufacturing method of the present application.

[Evaluation of the physical properties]
3. Toughness (tensile strength, tensile elongation)
The pellets of the resin compositions of Examples and Comparative Examples obtained by extrusion using the above "1. Meyani" were dried for 2 hours in a hot air dryer at 100°C. The dried resin composition was molded using an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) equipped with an ISO physical property test piece mold at a cylinder temperature of 320°C, a mold temperature of 80°C, and an injection pressure of 50 MPa (gauge pressure). , an injection speed of 200 mm/sec, and an injection time/cooling time = 20 sec/20 sec were set to mold a dumbbell molded piece of ISO3167, multipurpose test piece A type. After leaving the obtained dumbbell molded pieces at 23°C for 24 hours, the tensile strength and tensile elongation (nominal tensile strain) were tested at 23°C for 5 pieces each at a tensile test speed of 5 mm/min in accordance with ISO527. The measurements were taken and the average value was determined. As evaluation criteria, it was determined that the higher the tensile strength, the better the mechanical strength, and the higher the tensile elongation, the better the toughness, the more oxidative deterioration of the resin composition was suppressed, and the less contamination of foreign substances.

4. Thermal stability (tensile strength retention after aging)
ISO dumbbell molded pieces of the resin compositions of Examples 1 to 12 and Comparative Examples 1 to 6 obtained by molding according to "3. Toughness (tensile strength, tensile elongation)" above were placed in a hot air oven set at 140°C. After aging for 1000 hours in a 23°C chamber, after standing at 23°C for 24 hours, the tensile strength of each 5 pieces was measured at 23°C at a tensile test speed of 5 mm/min in accordance with ISO527, and the average value was calculated. Then, when the tensile strength before aging was taken as 100%, the retention percentage of the tensile strength value after aging was calculated. It was determined that the higher the retention rate of tensile strength after aging, the more the oxidative deterioration of the resin composition inside the extruder barrel was suppressed and the less foreign matter was mixed in.

[raw materials]
<Polyphenylene ether (A)>
(A-1)
Poly(2,6-dimethyl-1,4-phenylene) ether with a reduced viscosity of 0.50 dL/g (0.5 g/dL chloroform solution, 30° C., measured with an Ubbelohde viscometer).
<Styrenic resin (B)>
(B-1)
General purpose polystyrene (trade name: Polystyrene 685 [registered trademark], manufactured by PSJ). Note that this is polystyrene that does not contain a rubber component, that is, polystyrene that is not reinforced with rubber.
<Styrenic thermoplastic elastomer (C)>
(C-1)
A three-type block copolymer with a bound styrene content of 62% by mass and a polystyrene block-poly(styrene-butadiene) random block-polystyrene block structure. Hydrogenation rate is 98%. Mn=48000, Mw=55000, Mw/Mn=1.146.
<Antioxidant (D)>
(D-1)
Phosphorous antioxidant (chemical name: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5 ]Undecane.Product name: ADEKA STAB PEP-36 [registered trademark], manufactured by ADEKA Corporation).
<Other ingredients>
(colorant)
Carbon black with an average primary particle size of 16 nm.
(Polyolefin resin component)
Ethylene-propylene copolymer (trade name: TAFMER P0680J [registered trademark], manufactured by Mitsui Chemicals).

[Example 1]
(A-1) 100% by mass was added to a TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13 (including the lower barrel of the first supply port hopper), screw diameter 58 mm, L/D = 53); kneading disk L: 2 pieces, kneading disk R: 12 pieces, and kneading disk N: 4 pieces. The barrel length of the solids transport zone (including the lower barrel of the first supply hopper) is 38.5%, and the barrel length of the remaining melt kneading zone and melt transport zone is 100%. The length is 61.5% (of which, the barrel length of the melt-kneading zone: 38.5%), and the barrel setting temperature of the solid conveyance zone (the lower barrel C0 of the first supply port hopper is excluded because it is water-cooled) C1 to C4 The melt kneading zone barrel set temperature C5 to C9 are all 290 °C. Of the melt conveyance zone barrel set temperatures C10 to C12, C10 is set to 290 °C, C11 is set to 300 °C, and C12 is set to 320 °C. Then, the die head was set at 320°C, nitrogen was blown into the die nozzle at a flow rate of 20 L/min, and a vent port with a nitrogen injection line and a gas vent was installed at the upper opening of the C11 barrel. During extrusion, nitrogen was blown from a nitrogen injection line at a flow rate of 20 L/min. Furthermore, the oxygen concentration in the collection hopper above the first supply port was set to 0.5 vol%, and a resin composition was obtained by melting and kneading at a screw rotation speed of 500 rpm and an extrusion rate of 400 kg/h. . The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 2]
70% by mass of (A-1) and 30% by mass of (B-1) were supplied from the most upstream part and extruded using the twin screw extruder described in Example 1 above. At that time, when the barrel length of the entire extruder (including the first supply port hopper bottom barrel) is taken as 100%, the barrel length of the solid conveyance zone (including the first supply port hopper bottom barrel) is 46. 2%, the barrel length of the remaining melt-kneading zone and melt-conveying zone is 53.8% (of which, the barrel length of the melt-kneading zone: 30.8%), and the barrel set temperature of the solid conveyance zone (first supply Barrel C0 (lower barrel of mouth hopper is excluded because it is water-cooled) C1 to C5 are all 180°C, melt kneading zone barrel setting temperature C6 to C9 are all 290°C, and melting conveyance zone barrel setting temperature C10 to C12 is 290°C. ℃, C11 was set to 300℃, C12 was set to 310℃, the die head was set to 310℃, nitrogen was not blown to the die nozzle, and the vent port was connected to the vent vacuum line to the upper opening of the C11 barrel. A resin composition was obtained by melt-kneading and extruding under the same conditions as in Example 1, except that a vent vacuum was set at 7.998 kPa (60 Torr). The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 3]
(A-1) 50% by mass, (B-1) 30% by mass, and (C-1) 20% by mass from the most upstream part using the twin screw extruder described in Example 1 above. It was fed and extruded. At that time, when the barrel length of the entire extruder (including the first supply port hopper bottom barrel) is taken as 100%, the barrel length of the solid conveyance zone (including the first supply port hopper bottom barrel) is 53. 8%, the barrel length of the remaining melt-kneading zone and melt-conveying zone is 46.2% (of which, the barrel length of the melt-kneading zone: 30.8%), and the barrel set temperature of the solid conveyance zone (first supply Barrel C0 below the mouth hopper is excluded because it is water-cooled) Among C1 to C6, C1 is set to 50°C, C2 to C4 to 100°C, C5 and C6 to 140°C, and the barrel setting temperature of the melt kneading zone is C7 to C10. All barrel temperatures C11 to C12 in the melting conveyance zone were set to 280°C, the die head was set to 300°C, nitrogen was not blown to the die nozzle, and a vent vacuum was applied to the upper opening of the C11 barrel. Except that a vent port with a line connected was installed, the vent vacuum was set to 7.998 kPa (60 Torr), and the oxygen concentration in the collection hopper above the first supply port was set to 1.0 vol%. A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 1. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 4]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 3, except that nitrogen was blown into the die nozzle at a flow rate of 20 L/min. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 5]
The above implementation was carried out except that a vent port with a nitrogen injection line and a gas vent was installed at the upper opening of the C11 barrel, and nitrogen was blown at a flow rate of 20 L/min from the nitrogen injection line during extrusion. A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 4. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 6]
(A-1) 30% by mass, (B-1) 50% by mass, and (C-1) 20% by mass to bring the oxygen concentration in the collection hopper above the first supply port to 1.5vol%. A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 3, except for the following settings. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 7]
(A-1) 15% by mass, (B-1) 65% by mass, and (C-1) 20% by mass, and the entire barrel length of the extruder (including the lower barrel of the first supply port hopper). When taken as 100%, the barrel length of the solid conveyance zone (including the first supply port hopper lower barrel) is 38.5%, and the barrel length of the remaining melt kneading zone and melt conveyance zone is 61.5% ( (The barrel length of the melt-kneading zone: 23.1%), and the barrel set temperature of the solid transport zone (the lower barrel C0 of the first supply port hopper is excluded because it is water-cooled), and of C1 to C4, C1 is 50℃ , C2 to C3 are set to 100°C, C4 is set to 130°C, barrel set temperatures C5 to C7 of the melt kneading zone are all set to 270°C, barrel set temperatures C8 to C12 of the melting conveyance zone are all set to 270°C, and the die head is The temperature was set at 280°C, nitrogen was not sprayed into the die nozzle, and a vent port with a vent vacuum line connected to the upper opening of the C11 barrel was installed to set the vent vacuum to 7.998 kPa (60 Torr). A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 6, except that the oxygen concentration in the collection hopper above the first supply port was set to 1.8 vol%. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 8]
(A-1) 50% by mass, (B-1) 29.5% by mass, (C-1) 20% by mass, and (D-1) 0.5% by mass in the barrel of the solid conveyance zone. Set temperature (excluding the lower barrel C0 of the first supply port hopper because it is water-cooled) set all C1 to C6 at 150°C, and set the oxygen concentration in the collection hopper above the first supply port to 2.7 vol%. A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 3 except for the following settings. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 9]
(A-1) 65% by mass, (B-1) 20% by mass, (C-1) 14% by mass, (D-1) 0.5% by mass, and carbon black 0.5% by mass. was supplied from the most upstream part and extruded using the twin screw extruder described in Example 1 above. At that time, when the barrel length of the entire extruder (including the first supply port hopper bottom barrel) is taken as 100%, the barrel length of the solid conveyance zone (including the first supply port hopper bottom barrel) is 46. 2%, the barrel length of the remaining melt-kneading zone and melt-conveying zone is 53.8% (of which, the barrel length of the melt-kneading zone: 38.5%), and the barrel set temperature of the solid conveyance zone (first supply (Excluding the lower barrel C0 of the mouth hopper because it is water-cooled) Among C1 to C5, set C1 to 120°C, C2 to C4 to 150°C, and C5 to 180°C, and set the barrel temperature C6 to C10 in the melt-kneading zone to all 280°C. Of the barrel set temperatures C11 to C12 in the melting conveyance zone, C11 was set to 280°C, C12 was set to 300°C, the die head was set to 310°C, nitrogen was not sprayed to the die nozzle, and C11 was A vent port with a vent vacuum line connected to the upper opening of the barrel was installed to set the vent vacuum level to 7.998 kPa (60 Torr) and the oxygen concentration in the collection hopper above the first supply port to 2.0 vol%. A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 1 except for the following settings. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 10]
(C-1) A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 9, except that 4% by mass of the 14% by mass was replaced with Tafmer P0680J, a polyolefin resin component. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 11]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 3, except that C6 was set at 230° C. in the barrel temperature of the solid conveyance zone. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 12]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 9, except that C5 was set at 250° C. among the barrel temperatures of the solid conveyance zone. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative example 1]
When the barrel length of the entire extruder (including the first supply port hopper bottom barrel) is taken as 100%, the barrel length of the solid conveyance zone (including the first supply port hopper bottom barrel) is 23.1%, The barrel length of the remaining melt-kneading zone and melt-conveying zone is set to 76.9% (of which, the barrel length of the melt-kneading zone: 38.5%), and the barrel set temperature of the solids conveying zone (below the first supply port hopper) is set to 76.9%. (Barrel C0 is excluded because it is water-cooled) Of C1 to C2, C1 is set to 120°C and C2 is set to 180°C. All barrel set temperatures C3 to C7 of the melt kneading zone are set to 280°C. Barrel set temperature of the melt conveyance zone is C8. A resin composition was obtained by melt-kneading and extruding under the same conditions as in Example 9, except that among C8 to C12, C8 to C11 were set to 280°C and C12 was set to 300°C. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative example 2]
Barrel set temperature of the solids transfer zone (first supply port hopper lower barrel C0 is excluded because it is water-cooled) Among C1 to C5, C1 is set to 230°C, C2 to C4 is set to 250°C, and C5 is set to 280°C. A resin composition was obtained by melt-kneading and extruding under the same conditions as in Example 9, except that the oxygen concentration in the collection hopper above the first supply port was set to 0.5 vol%. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative example 3]
When the barrel length of the entire extruder (including the first supply port hopper bottom barrel) is taken as 100%, the barrel length of the solid conveyance zone (including the first supply port hopper bottom barrel) is 61.5%, The barrel length of the remaining melt-kneading zone and melt-conveying zone is set to 38.5% (of which, the barrel length of the melt-kneading zone: 15.4%), and the barrel set temperature of the solids conveying zone (below the first supply port hopper) is set to 38.5%. Barrel C0 is excluded because it is water-cooled) Among C1 to C7, C1 to C3 are set to 120°C, C4 to C6 are set to 150°C, and C7 is set to 180°C. All barrel set temperatures C8 to C9 in the melt kneading zone are set. Of the barrel set temperatures C10 to C12 in the melting conveyance zone, set C10 and C11 to 280°C and C12 to 300°C, and set the oxygen concentration in the collecting hopper above the first supply port to 0.5 vol%. A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 9, except that the resin composition was set to be as follows. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative example 4]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 9, except that the oxygen concentration in the collection hopper above the first supply port was set to 4.5 vol%. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative example 5]
Nitrogen is blown into the die nozzle at a flow rate of 20 L/min, and a vent port with a nitrogen injection line and a gas vent is installed at the upper opening of the C11 barrel to maintain a flow rate of 20 L/min from the nitrogen injection line during extrusion. A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Comparative Example 2, except that nitrogen was blown therein. The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative example 6]
A resin composition was obtained by melt-kneading and extrusion under the same conditions as in Example 9, except that C4 and C5 of the barrel temperature of the solid conveyance zone were set at 250°C. The evaluation results of the obtained resin composition are shown in Table 1 below.

As shown in Table 1, the resin compositions of Examples 1 to 12 were all manufactured by the manufacturing method described in the claims of the present application, and no buildup was observed on the die nozzle during extrusion production for 2 hours. No strand breakage was observed, the strand take-up stability was good, and no strand breakage was observed.
In Example 4, nitrogen gas was sprayed to the part of the die nozzle where the resin was discharged from the hole, but the tensile elongation and tensile strength retention rate after aging were lower than in Example 3, which was not sprayed with nitrogen gas. A good trend was observed.
In Example 5, nitrogen gas was further blown into the vent port, but the tensile elongation and post-aging tensile strength retention tended to be even better than in Example 4.
In Example 8, in addition to the manufacturing method of the present application, by blending the antioxidant component (C) into the resin composition, oxidative deterioration of the resin during extrusion is further suppressed, and the tensile elongation and post-aging tensile strength are further reduced. A tendency for excellent strength retention was observed.
In Example 9, even when a colorant (carbon black) was blended into the resin composition, the production stability and resin performance were not affected by the present production method, and a resin composition with good performance was obtained.
In Example 10, even if the polyolefin resin component is blended within 5% by mass, the production stability and physical properties are not affected, but rather the tensile elongation and tensile strength retention after aging are A good trend was observed.
In both Examples 11 and 12, the barrel length and set temperature of the solid transport zone are within the claimed range of the present application, and the physical properties are also good. By setting the length of the barrel with a set temperature of 50 to 190°C to a range of 75 to less than 100%, the toughness and heat of the molded product can be improved compared to when the length is 100%. A tendency for stability to decrease slightly was observed.
On the other hand, in Comparative Examples 1 to 6, the resin compositions were produced by a manufacturing method that was outside the claimed range of the manufacturing method of the present application, so both production stability and physical properties were insufficient.
In Comparative Example 1, the length of the solid conveyance zone is short, and in Comparative Example 2, the barrel temperature setting of the solid conveyance zone is high, both of which are outside the scope of the claims of the present application. However, both production stability and physical properties were insufficient.
In Comparative Example 3, the length of the solid transport zone was too long and fell outside the scope of the claims of the present application, and unmelted substances were found in the resin composition, resulting in insufficient strand take-up stability and physical properties.
In Comparative Example 4, the oxygen concentration inside the collection hopper was high, which was outside the scope of the claimed production method, and the generation and growth of slime was observed during production, resulting in unsatisfactory production stability and physical properties.
In Comparative Example 5, like Comparative Example 2, the barrel temperature in the solid conveyance zone was high and was outside the scope of the claims of this application, and nitrogen was blown into the die nozzle and nitrogen was blown into the vent port, so the growth of Meyani was Although the strands were suppressed and the strand take-up was stable until the end, smearing was observed during production, and the physical properties were not sufficient.
In Comparative Example 6, since the set temperature of the solid conveyance zone was outside the claimed range of the present application, strand take-up was stable until the end, but smearing was observed during production. Moreover, the physical properties were also not sufficient.

The production method of the present invention significantly suppresses the generation of degraded polyphenylene ether resin generated in the extruder barrel during extrusion and the generation of dirt around the die nozzle, improving extrusion production stability, and Because there is little contamination, polyphenylene ether resin compositions with good toughness can be stably mass-produced, and the resulting resin compositions can be used in home appliance OA equipment parts, electrical and electronic equipment, automotive applications, various industrial products, etc. It is available in good condition.

Claims (8)

A method for producing a resin composition using an extruder, the method comprising:
The resin composition contains 10% by mass or more of polyphenylene ether (A) based on the total amount of the resin composition (100% by mass),
The extruder has a solid conveyance zone, a melt kneading zone, and a melt conveyance zone, and the solid conveyance zone has a barrel C0 provided with a first supply port under a collecting hopper at the most upstream part . It is a shaft extruder,
When the barrel length of the entire extruder is 100%, 30 to 60% from the upstream side of the extruder is the solid conveyance zone, and the remaining 40 to 70% is the melt kneading zone and the melt conveyance zone. can be,
Among the barrels constituting the solid transport zone, when the length of the remaining barrels excluding barrel C0 (water-cooled) in which the first supply port is provided is taken as 100%, the set temperature of 75% or more of the barrels is within the range of 50 to 190°C,
The set temperature of the barrel constituting the melt kneading zone and the barrel constituting the melt conveyance zone is within the range of 250 to 320 ° C.,
The oxygen concentration in the collection hopper provided above the first supply port is 3 vol% or less,
A method for producing a resin composition. Among the barrels constituting the solid transportation zone, when the length of the barrel excluding the barrel in which the first supply port is provided is taken as 100%, the set temperature of 100% of the barrels is within the range of 50 to 190 ° C. A method for producing the resin composition according to claim 1. The resin according to claim 1 or 2, wherein the melt conveyance zone has a barrel provided with an opening, and a vent port having a nitrogen injection line and a gas vent is provided above the opening. Method for producing the composition. The method for producing a resin composition according to any one of claims 1 to 3, wherein all of the extrusion raw materials are supplied from the first supply port. The resin composition according to any one of claims 1 to 4, wherein the resin composition further contains 5 to 80% by mass of a styrene resin (B) based on the total amount of the resin composition (100% by mass). manufacturing method. The resin composition further contains 0.1 to 25% by mass of a styrenic thermoplastic elastomer (C) based on the total amount of the resin composition (100% by mass), according to any one of claims 1 to 5. A method for producing a resin composition. The resin composition according to any one of claims 1 to 6, wherein the resin composition further contains 0.001 to 3% by mass of an antioxidant (D) based on the total amount of the resin composition (100% by mass). Method for producing the composition. The method for producing a resin composition according to any one of claims 1 to 7, wherein the resin composition has a polyolefin resin component content of 5% by mass or less based on the total amount of the resin composition (100% by mass). .