TW201215488A - Method for producing a polyphenylene ether-based resin composition - Google Patents

Abstract

The present invention provide a method to effectively produce resin compositions, which are excellent in color tones, no occurrence of scorches, and excellent in solution-resistance, from polyphenylene ester (PPE) and polystyrene (PS). It was according to a producing method for polyphenylene ester-based resin compositions characterized in that: When extrude forming after fuse kneading of PPE and PS to produce polyphenylene ester-based resin compositions, use PPE which contains 0.05 to 10 ppm of components originated from polymerization catalyst as copper element, use PS particles with average particle size 1 to 5 mm, appearance density 0.5 to 0.7 g/cm<SP>3</SP>, and supply to a twin screw extruder with length 10 to 80 in L/D, has more than one place for kneading zone, the total L/D of kneading zones is 3 to 18, and then heat, fuse, knead to obtain a polyphenylene ester-based resin composition having 0.015 to 0.6 mass% of ultrahigh molecular weight substance of polyphenylene ester-based resin with molecular weight more than 500,000, which formed in the resin composition.

Description

201215488 6. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for producing a polyphenylene ether-based resin composition, and in detail relates to a method of producing a color tone with high production efficiency and excellent solvent resistance. A method for producing a polyphenylene ether-based resin composition of a polyphenylene ether-based resin composition having little occurrence. [Prior Art] Although the polyphenylene ether-based resin is an engineering plastic excellent in heat resistance, electrical properties, and chemical resistance, on the other hand, it has a disadvantage that it is poor in fluidity and difficult to form by itself. Further, the product obtained by the polyphenylene ether resin from the polymerization apparatus is usually in the form of a powder, and is easily slipped on the surface of the screw of an extruder or the like, and the metering property becomes unstable, which is disadvantageous to moldability. Therefore, a material in which a polystyrene resin is blended has been developed for the purpose of improving the moldability, fluidity, and impact resistance of polyphenylene ether (see Patent Document 1), and is used as one of engineering plastics in many fields. . Further, in general, the shape of the raw material in the case of molding a thermoplastic resin is usually supplied by a resin block called small particles of nine particles. When the polystyrene resin is blended into a polyphenylene ether resin to obtain nine particles, a polyphenylene ether resin (usually powdery) and a polystyrene resin are supplied to an extruder and extruded to form a strand. The molten resin is cooled in a water tank or the like, and then granulated by a granulator to form nine particles. However, when a polystyrene-based resin is blended into a polyphenylene ether-based resin powder and supplied to an extruder and extruded, air is easily introduced along with the resin of the powder form -4-201215488, so that air is contained. On the one hand, the powder is unstable due to the easy sliding of the screw conveying surface of the extruder, and the residence time in the extruder becomes long, and the polyphenylene ether resin is easily oxidized and deteriorated. In order to prevent oxidative degradation, there is a method of adding an antioxidant to a raw material (see Patent Document 2). However, this method is insufficient in effect, and a method of supplying an inert gas such as nitrogen to an extruder is also performed ( Referring to Patent Document 3), the effect is insufficient only by simply supplying an inert gas. In particular, the polyphenylene ether-based resin has a high glass transition temperature (Tg: about 210 ° C), and has to increase the molding temperature, which is liable to cause discoloration due to thermal denaturation, even in the case of blending polystyrene resin. In the case, this discoloration problem is also a big problem. In addition, since the polystyrene-based resin has a low melting point and the solid transport portion in the extruder is faster than the polyphenylene ether-based resin, the polyphenylene ether-based resin powder tends to adhere thereto and is burned to become a foreign matter. It is also a big problem. Further, the polyphenylene ether-based resin or the resin composition of the polyphenylene ether-based resin and the polystyrene-based resin has a disadvantage of being inferior in solvent resistance, and is in contact with an organic solvent such as alcohol or hexane under stress. It is prone to cracking (poor crack resistance), so its use is limited. Further, the polyphenylene ether-based resin is usually used in the form of a powder which is taken out from the polymerization apparatus, and has a low apparent density in the form of a powder. When it is supplied to the extruder, air enters and is fed in the extruder. The feeding property of the machine portion (supply portion) is deteriorated and the feeding bottleneck is likely to occur, and in the kneading portion of the kneading -5 - ς 201215488 disk portion in the extruder, when the resin is melted, the air flows countercurrently to hinder the resin. The amount of extrusion is lowered by the conveyance, and there is a problem that the productivity is suddenly lowered. Under such circumstances, it has been strongly desired to develop a resin composed of a polyphenylene ether-based resin and a polystyrene-based resin to efficiently produce a resin which does not cause a decrease in color tone, is free from charring due to charring, and has improved solvent resistance. The method of things. [Prior Art Document] Patent Document 1: US Patent No. 3 3 8 3 4 3 5 Patent Document 2: Japanese Patent Publication No. 2003-246865 Patent Document 3: Japanese Patent Publication H06 (1 99 5 ) - 20 62 1 SUMMARY OF THE INVENTION [Invention] The object of the present invention is to provide a polyphenylene ether resin and a polystyrene resin which can be efficiently produced without causing a decrease in color tone and no cause. A method for producing a polyphenylene ether-based resin composition of a resin composition which is produced by burning and which is improved in solvent resistance. In order to achieve the above-mentioned problems, the inventors of the present invention have found that a polyphenylene ether-based resin containing a copper element derived from a polymerization catalyst containing 5 to 10 ppm of ruthenium is used as a polyphenylene ether resin. Using a resin particle having a specific average particle diameter and an apparent density as a polyphenylene styrene resin, supplying the same to a twin screw extruder having a specific screw configuration, and heating, dissolving, and kneading 'obtaining The resin composition of the ultrahigh molecular weight body of the polyphenylene-based resin can solve the above problems, and the present invention can be completed. -6-201215488 According to a first aspect of the invention, there is provided a method for producing a polyphenylene ether-based resin composition, characterized in that after the polyphenylene ether resin and the polystyrene resin are kneaded in a molten state, When the polyphenylene ether-based resin composition is produced by extrusion molding, the polyphenylene ether-based resin is a polyphenylene-based resin containing a copper element derived from a copper component of a polymerization catalyst in an amount of 0.05 to 10 ppm, and a polystyrene resin. Using particles having an average particle diameter of 1 to 5 mm and an apparent density of 0.5 to 0.7 g/cm 3 , the above two resins are supplied to a length of 10 to 80 in terms of L/D, at least one kneading zone, kneading zone A twin-screw extruder comprising a screw having a total L/D of 3 to 18, which is heated, melted, and kneaded to obtain polyphenylene having a molecular weight of 500,000 or more in an amount of 0.015 to 0.6% by mass in the resin composition. A polyphenylene ether resin composition of an ultrahigh molecular weight body of an ether resin. According to a second aspect of the invention, there is provided a method for producing a polyphenylene ether-based resin composition according to the first aspect of the invention, wherein a blend of 5 to 150 mass is blended with respect to 100 parts by mass of the polyphenylene ether-based resin composition. A portion of polystyrene resin. According to a third aspect of the present invention, there is provided a method for producing a polyphenylene ether-based resin composition according to the first or second aspect, wherein the polyphenylene ether-based resin is a terminal alkyl group with respect to 100 phenyl ether units. 0.15 to 1.5. According to a fourth aspect of the invention, there is provided a method for producing a polyphenylene ether-based resin composition according to any one of the first to third aspects, wherein the screw structure of the kneading zone of the above-mentioned Ji 201215488 press promotes kneading The element is disposed on the upstream side and the element having the boosting capability is disposed on the downstream side. According to a fifth aspect of the invention, there is provided a method for producing a polyphenylene ether-based resin composition according to any one of the first to fourth aspects, wherein the polyphenylene ether-based resin composition is extruded by an extruder After being stranded and moved in a cooling medium to be cooled, and then cut by a strand cutter to obtain nine particles, a guide roller formed with a groove is provided in the cooling medium, and The strand is wound in the groove of the guide roller and wound up, and the moving speed of the outer peripheral surface of the guide roller to which the strand is connected is assumed to be Vr (cm/min) on the assumption that the take-up speed is Vs (cm/sec). In the case of seconds, the winding speed 'the moving speed and the direction of rotation of the guide roller are set to satisfy the relationship of 〇.72Vr/Vs2 - 0.2. According to a sixth aspect of the present invention, there is provided a process for producing a polyphenylene ether-based resin composition according to the fifth aspect of the present invention, wherein the temperature of the strand is adjusted to 80 to 160 ° C by cooling, and This temperature range is pelletized. Furthermore, according to a seventh aspect of the present invention, there is provided a molded article obtained by molding a polyphenylene ether resin composition obtained by the production method according to any one of the first to sixth inventions. The method for producing a polyphenylene ether-based resin composition of the present invention can be efficiently produced by a polyphenylene ether-based resin and a polystyrene-based resin without causing a decrease in color tone, no foreign matter due to charring, and improved resistance. Solvent-based resin composition. -8 - 201215488 [Embodiment] The present invention will be described in detail below with reference to the embodiments and examples, but the present invention is not limited by the embodiments and examples shown below. It is arbitrarily changed and implemented within the scope of the gist of the invention. The method for producing a polyphenylene ether-based resin composition of the present invention is characterized in that, after the polyphenylene ether-based resin and the polystyrene-based resin are kneaded in a molten state, the mixture is extruded to produce a polyphenylene ether-based resin composition. The polyphenylene ether-based resin composition is a polyphenylene ether resin containing 0.05 to 1 ppm of a copper element derived from a polymerization catalyst, and the polystyrene resin is an average particle diameter of 1 to 5 mm, and an apparent density. For the particles of 0.5 to 0.7 g/cm 3 , the above two resins are supplied to a screw having a length L/D of from 1 Torr to 80, a kneading zone of at least one position, and a kneading zone total L/D of from 3 to 18. A super-high molecular weight polyphenylene having a polyphenylene ether resin having a molecular weight of 500,000 or more in an amount of 0.015 to 0.6% by mass in the resin composition by heating, melting, and kneading. An ether resin composition. Hereinafter, the present invention will be specifically described. (1) Polyphenylene ether-based resin The polyphenylene ether-based resin (hereinafter, also referred to as "PPE") used in the present invention has a structural unit represented by the following general formula (1) in the main chain. The polymer may be any individual polymer or copolymer. -9- 201215488 r^2

R Λ σ (1) (Formula, a; or a halogenated alkane; atom, oxy. · in: sub. In the base, ethyl, n- or heptyl preferred example to 10: 1 to the example of a hydrogen atom In the examples, 'Rl is the same or different, and is represented by a hydrogen atom, a halogen primary or a secondary alkyl group, an aryl group, an amine alkyl group, a haloalkyl group, an alkoxy group, an oxy group. R2 is the same or different It may be represented by a hydrogen atom, a halogen primary or secondary alkyl group, an aryl group, a haloalkyl group, an alkoxy group or a halogenated alkane, and two R1 are not simultaneously a hydrogen atom.) In the formula (1), 'R1 is In the case of a halogen atom, a chlorine atom or a bromine is preferred. When R1 is a primary alkyl group in the above formula (1), a preferred example is methyl, n-propyl, n-butyl, n-pentyl, isopentyl, 2-methylbutylhexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl, an alkyl group having 1 to 10 carbon atoms. When R1 is a secondary alkyl group, it is an alkyl group having 4 carbon atoms such as an isopropyl group, a second butyl group or a 1-ethylpropyl group. A preferred example of the case where R1 is an aryl group is a phenyl group; and an aminoalkyl group is preferably an alkylamino group having a carbon number of 5, such as a dimethylamino group, a diethylamino group or a dibutylamino group. A preferred example of the case where R2 is a haloalkyl group is a group formed by substituting one or more of the groups which are preferred examples of the alkyl group with a halogen atom. A preferred embodiment for the oxime oxy group is an alkoxy-10-201215488 group corresponding to the above-mentioned preferred examples of the alkyl group: an example of a haloalkoxy group is a halogen atom substituted for one of the alkoxy groups. More than one functional group formed by a hydrogen atom. R1 is preferably a hydrogen atom, a - or a secondary alkyl group, or an aryl group. A preferred example in the general formula (1) where R2 is a primary or secondary alkyl group, an aryl group, a halogen-based group, a hospitaloxy group, or a halogen-based oxy group is exemplified as the same one as in R1. In the present invention, R1 and R2 are preferably a hydrogen atom, a primary or secondary alkyl group, an aryl group, and R1 is more preferably an alkyl group or a phenyl group. Particularly preferably an alkyl group having 1 to 4 carbon atoms, and R2 is more preferred. It is a hydrogen atom. Further, the PPE in the present invention may include a structure represented by the general formula (1) in order to adjust the molecular weight, and to improve various properties such as melt viscosity or impact resistance within the range of the properties of the present invention. Repeating units other than. Preferred PPEs are poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dipropyl). _1,4-phenylene ether), poly(2-ethyl-6-methyl-1,4-phenylene ether), poly(2-methyl-6-propyl-1,4-phenylene ether), etc. A separate polymer of 2,6-dialkyl phenyl ether. Further, it is preferably a copolymer of 2,6-xylenol/2,3,6-trimethylphenol and a copolymer of 2,6-xylenol/2,3,6-triethylphenol' 2,6-two. 2,6-dialkylphenol / 2,3,6 - such as acetol / 2,3,6-trimethylphenol copolymer, 2,6-dipropionol / 2,3,6-trimethyl hydrazine copolymer Trialkylphenol copolymer. Further, it is also preferred to graft-polymerize a graft copolymer of styrene onto poly(2,6-dimethyl-1,4-phenylene ether) at 2,6-xylenol/2,3. A graft copolymer of styrene grafted onto a 6-trimethyl fluorene copolymer. -11- 201215488 The best among these PPEs are poly(2,6-dimethyl-1,4 and 2,6-xylenol/2,3,6-trimethylphenol random copolymers. PPE The molecular weight is preferably from 0.2 to 0.8 dl/g in chloroform at a viscosity of from 30 to < gt; C, more preferably from 〇·3 to 6.6 dl/g, and the ultimate viscosity is less than 0.2 dl/g. When the obtained resin group is used, the mechanical strength of the molded article tends to be lowered. Conversely, when it is @0.8 dl/g, the fluidity of the resin composition is deteriorated, and molding is difficult. PPE may be used in two or more types. In this case, the viscosity difference may be the desired ultimate viscosity. The PPE used in the present invention is preferably a polyphenylene having a number of terminal hydroxyl groups of 0.15 to 1.5 with respect to 1 unit. When the amount of terminal hydroxyl groups is less than 0.15, the compatibility of the vinyl resin is lowered, and when the obtained resin composition is finished, there is a case where the appearance is poor, and the color tone of the high temperature gas is deteriorated. 1. 5 times, it is easy to make the heat stable relative to 100 phenyl ether units, preferably the terminal hydroxyl group The number is 1.3. It is also considered that the presence of the terminal hydroxyl group contributes to the formation of the ultrahigh body described later. The unit having a terminal hydroxyl group, specifically, for example, 3,5-di- 4-hydroxyphenyl, 3,5- Diethyl-4-hydroxyphenyl, 3,5-dipropane 3 via the group, 3-methyl-5-ethyl-4-yl-phenyl, 3-methyl-yl-4-hydroxyphenyl, 2,3,5-trimethyl-4-hydroxyphenyl, etc. In the polyphenylene ether having a number of bases less than 0-15, due to the limitation with styrene-benzene. If the product is made larger than the work, it becomes the limit of the diphenyl ether monoether. Phase, and benzene are reduced in the molding environment. The compatibility of 0.2 to the molecular weight methyl-S - 4 - 5-propanyl hydroxy resin -12-201215488 is lowered, and the appearance of the molded article is poor or lamellar peeling, and the elongation at break or the surface punching strength is easy. reduce. Further, since the thermal stability in a high-temperature gas environment is also lowered, the color tone is easily deteriorated. A method of obtaining a PPE having a number of terminal hydroxyl groups of 0.15 or more is also disclosed in Japanese Patent Laid-Open Publication No. SHO 61-20576, for example, by a cuprous salt in the presence of oxygen in a solvent such as toluene or the like. The compound with an amine is a catalyst, and 2,6-dimethyl xylenol is subjected to oxidative polymerization, and a catalyst for forming a chelate compound with copper is added to the obtained polyphenylene ether solution to cause a catalyst. After the activity is lost, it is obtained by stirring the polyphenylene ether solution or the like in a gas atmosphere in which oxygen is prevented from entering. Further, a method of preparing the amount of terminal hydroxyl groups is known, and it is known that the conditions of the polymerization of the phenolic compound vary depending on the conditions of the reaction of the hydrazine after the polymerization is stopped, and the polyphenylene ether obtained by polymerization is generally added to carry out the oxime reaction. Then the hydroxyl concentration can be increased. In the present invention, 0.05 to 10 ppm of a copper element derived from a polymerizable catalyst component is present in the PPE. The component derived from the polymerization catalyst may be present by a catalyst which has been subjected to polymerization of PPE to some extent, or may be formed by adding a polymerization catalyst component to the PPE. Although the catalyst for oxidative polymerization of PPE is known to have a metal compound such as copper, manganese or cobalt, it is industrially used as a catalyst user when oxygen gas or air is used for oxidative polymerization. (1: 1 or 2 or more of copper salts such as Cu2S04, CuCl2, CuBr2, CuS04, Cul, etc.) -13- 201215488 Mono and diethylamine, mono- and di-propylamine, mono- and di-n-butylamine, propylamine, mono- and dibenzylamine, mono- and dicyclohexylamine, mono- and dimethylamine, methylpropylamine, butyl Dimethylamine, allylethylamine, fluolin, 'methyl-n-butylamine, ethyl isopropylamine, benzyl-methyl-octyl chlorobenzylamine 'methyl(phenylethyl)amine, benzylethylamine, One or more amines such as methylamine, N,N'-di-t-butylethylenediamine, bis(chlorophenylmethylamino-4-pentene, pyridine, picoline, 4-dipiperidine) In the method, a PPE resin having a component derived from the polymerization catalyst is kneaded in an extruded state as described in detail later, thereby purifying a high molecular weight body of PPE. The so-called ultra-high molecular weight body generally means a polymer having a molecular weight of several million or so, and in the present invention, it is confirmed that it is customary to use a polymer having a molecular weight of 500,000 or more. Therefore, the following The medium ultra-high molecular weight system indicates that the amount of the polyphenylene ether-based resin having a molecular weight of 500,000 or more is present in the resin composition, and it is preferable to achieve the above. In the conventional technology, external addition is performed. The polymer is used in PPE. For example, it is disclosed in Japanese Patent Publication, etc., and since the productivity is improved during extrusion molding, the slip property is good, and the appearance is good, the mixed polyethylene and the ultrahigh molecular weight poly 4 are added to the PPE. Ethylene fluoride, etc. plus I and di-diethanolamine, ethylmethylcyclohexylamine, hydrazine, octylamine, N-n-butyldiethylamine, 1-methylaminopyridine, in-machine In the case of melting and polystyrene, the molecular weight is determined by the amount of about 100,000 to the number, and the amount is determined to be 50,000 to I 0·015 to 0.6. 2 5 5 5 8 5 Surface of the product Ultra-high molecular weight is used. • 14- 201215488 However, it is also a fact that externally added such ultra-high molecular weight polyethylene and the like are formed into a block shape, and it is easy to form a defect called a fisheye or a surface defect called a convexity. The effect of the invention is found to be externally added to the PPE by the addition of the ultrahigh molecular weight body, and the ultrahigh molecular weight of the PPE can be formed by the PPE and the polystyrene resin composition. An ultrahigh molecular weight body (resin) which is difficult to form a raised eye and is well dispersed (widely dispersed body). The reason why the component derived from the polymerization catalyst exists in the PPE is for the formation of an ultrahigh molecular weight substance. The amount of the component derived from the polymerization catalyst in the PPE varies depending on the type of the catalyst, but the copper element (metal component) is up to 10 ppm. The polymerization catalyst system is as described above, and the remaining active PPE is combined with the catalyst. Or add later. As described above, the polymerization catalyst is generally copper chloride. Therefore, the copper element has the amount of the polymerization catalyst present or the amount of the component derived from the polymerization catalyst. When the amount of the polymerization catalyst is considered, the amount of the copper element is only the amount of the copper portion in the component. Although the amount of copper element varies depending on the amount of ultrahigh molecular weight formed, it is sufficient to always leave (or add) about 0.05 to 1 ppm of copper element and 'remain (add) 1 to 10 ppm of copper element as appropriate) There are many cases where the formation of ultrahigh molecular weight bodies is stable and the use is better. For the purpose of use, the final product can be appropriately selected. The shape of the shape is not a pinch or a fish-assisted amount of 0.05. The amount of demon ytw, Resin-15 - 201215488 The copper is applied by adjusting the amount of catalyst removal in the catalyst residue during polymerization of PPE, and adjusting the amount of deactivator which deactivates the catalyst. Modulation of the amount of the element, but due to excessive discoloration of the catalyst, it is necessary to pay attention to discoloration. In short, it is sufficient to add a predetermined amount of a copper compound (polymerization catalyst) to the catalyst-removed PPE. By containing 0.05 to 10 ppm of copper element in the polymerization catalyst and PPE and polystyrene resin in a molten state in an extruder, an ultrahigh molecular weight body having a molecular weight of 500,000 or more is obtained. The amount of the ultrahigh molecular weight (500,000 or more) varies to some extent depending on the amount of the polymerization catalyst, the kneading conditions, etc., but the total amount of the PPE and the polystyrene resin is usually 0.015 to 0.6% by mass. . Further, the copper element preferably has a range of from 0.1 to 9 ppm, more preferably from 0.2 to 8 ppm. Further, in the present invention, it is preferred that the number of terminal hydroxyl groups using PPE is 0.15 to 100 parts per 100 parts of the phenyl ether unit. A range of 1.5 polyphenyl hydrazines 'but the amount of terminal hydroxyl groups is also believed to be related to the formation of good ultrahigh molecular weight bodies. When the amount of terminal hydroxyl groups is less than 〇·15 with respect to 100 phenyl ether units, the surface appearance of the polystyrene resin composition with polyphenylene ether deteriorates, and if it is more than 1.5, the thermal stability decreases. . (2) Polystyrene-based resin and polystyrene-based resin (hereinafter sometimes abbreviated as PS resin) are exemplified by a polymer of a styrene monomer, a styrene monomer, and other copolymerizable monomers. A copolymer of a monomer, a styrene-based graft copolymer, or the like. -16- 201215488 The P s resin used in the present invention means a polymer or copolymer containing 50% by mass or more of a repeating unit derived from an aromatic vinyl compound, or the polymer is modified by rubber. By. The aromatic vinyl compound is exemplified by α-alkyl substituted styrene such as styrene or α-methylstyrene, p-methylstyrene, o-ethyl phenylethylene, vinyl toluene, o- or p-dichloro An alkyl group such as styrene or the like is substituted with styrene or the like. Examples of the monomer other than the aromatic vinyl compound are a vinyl cyanide compound such as acrylonitrile, methacrylonitrile or ethacrylonitrile; a methyl ester, an ethyl ester, a propyl ester or a n-butyl ester of acrylic acid and methacrylic acid; a (meth) acrylate compound such as n-amyl ester; maleimide, Ν-methyl maleimide, Ν-cyclohexyl maleimide, ν-phenyl cis a maleimide compound such as butylene diimine; an acrylamide compound such as acrylamide or hydrazine-methacrylamide; an unsaturated acid anhydride such as maleic anhydride or itaconic anhydride; Unsaturated acid such as acrylic acid or methacrylic acid; glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and methoxypolyethylene glycol Various vinyl compounds such as methacrylate. Specific examples of the P S resin are exemplified by polystyrene 'acrylonitrile-styrene resin (AS resin), methyl methacrylate-styrene resin (MS resin) and the like. The weight average molecular weight of the styrene resin is usually 50,000 or more, preferably 100,000 or more, more preferably 150,000 or more, and the upper limit is usually 500,000 or less, preferably 400,000 or less, more preferably 300, 〇〇. 〇The following. -17- 201215488 The styrene-based resin used in the present invention may be further modified with rubber as the above various polymers. The rubber is exemplified by polybutadiene, styrene-butadiene-thick copolymer, and polyiso Pentylene dilute, B storage _ propylene copolymer and so on. Specifically, the examples are rubber modified polystyrene (HIPS resin), acrylonitrile, butyl, dilute, S. saponin (ABS resin), methyl methacrylate, butyl acrylate, butadiene styrene resin. (MBS resin), a butadiene resin (AES resin) or the like in which the ABS resin is substituted with an ethylene-propylene copolymer. The styrene resin is preferably polystyrene or rubber modified polystyrene (HIPS resin) from the viewpoint of compatibility with PPE. In particular, when the impact resistance is necessary, it is more preferable to modify the polystyrene rubber. Description will be made regarding the use of powdered PPE and nine (granular) PS to carry out the invention. The PS resin is preferably a particle having an average particle diameter of 1 to 5 mm and an apparent density of 0.5 to 0.7 g/cm3. By mixing the PS resin particles in the powdery PPE and melt-kneading them, the generation of charred foreign matter can be suppressed. Although this reason is not clear, it can be considered as the following. That is, the glass transition temperature of the P S resin was 100 ° C, which was significantly lower than the glass transition temperature of the PPE of 210 ° C. Therefore, the ps resin is easily melted earlier in the solid transport region of the extruder than the powdered PPE (especially when the powdery PS is used as the PS resin). The molten PS resin becomes a binder, and the PPE is attached to the surface of the extruder wall or the screw of the solid conveying portion. The PPE is liable to cause a transfer reaction of a polymer chain due to heat and to carry out a crosslinking reaction. Thus, charred foreign matter is generated and mixed into the product. However, if! ^树 -18- 201215488 When the average particle size of the fat is lmm or more, ? Since the melting of the particles in the solid transporting region is slow, it also becomes less likely to cause adhesion to the wall of the cylinder or the surface of the screw. Therefore, it is less likely to generate charred foreign matter. Further, when the average particle diameter is increased to 5 mm or more, the feeding to the extruder becomes difficult. Although a feeder in the form of a screw (a dosing device) is usually provided before the extruder, if a large nine particles are used, the p S particles are caught between the screw and the wall of the feeder. Jammed to stop the screw of the feeder. Further, when the particle size of the PS particles is 5 mm or more, it becomes easy to classify with the PPE. When the apparent density of the PS resin is less than 〇5 g/cm3 or more than 〇7 g/cm3, it becomes easy to cause classification with the PPE resin. The PS resin particles are well-dissolved with PPE to improve the fluidity of PPE and prevent the ultra-high molecular weight substances produced in PPE from becoming agglomerates (condensed foreign matter), which is considered to be the ultra-high molecular weight formed in PPE. The important role of the state in which the object is dispersed in the PPE. In the present invention, the above PPE and PS resin are supplied to a twin-screw extruder, heated, melted, and kneaded. The twin-screw extruder used in the present invention is a kneading zone having at least one or more dispersive mixing property, and is generally provided by a raw material supply port and an exhaust port, and a jacketed drum; a plurality of screws for engraving a plurality of grooves on the surface and rotating in the same direction; and a die-casting mold for the device at the front end of the extruder, preferably in the form of mutual engagement or non-engagement between the screws A kneading portion composed of a plurality of kneading discs is provided; further, a conveying portion for conveying the kneaded material is provided. -19-201215488 Further, the average particle diameter in the present invention is as follows. That is, the particles are placed on a sieve having an opening size of i min, and the volume average specification of the particles measured by the laser diffraction type particle size distribution measuring device is less than 1 mm. In the present invention, a "laser diffraction scattering type particle size distribution measuring apparatus Laser Micron Sizer LMS-2000e" manufactured by Seishin Enterprise Co. Ltd. was used, and the measurement was carried out by a wet method (solvent: isopropyl alcohol). The particles of 1 mm or more were measured with a vernier caliper and the volume average particle diameter was determined. Then, the average particle diameter of the entire particles was determined from the particle diameter of less than 1 mm and the particle diameter of 1 mm or more. Further, the apparent density was determined by dividing the mass (g) by the apparent volume (cm3) (unit: g/cm3) by measuring the overall density of JISK5101 (the stationary method but not using the filter). The blending ratio of the PPE to the PS resin particles is preferably from 5 to 150 parts by mass based on 1 part by mass of the PPE. Although the PS resin is well-dissolved in the PPE, if the PS resin is too large (that is, when the PPE component is small), the heat resistance or mechanical strength of the molded article is insufficient. Conversely, if the amount is too large, the fluidity is lowered, and the thickness is thin. The molding of the product has become difficult. When the blending amount of the PS resin is less than 5 parts by mass, the color tone of the resin composition is deteriorated, and when it is more than 150 parts by mass, heat resistance or impact resistance is lowered. More preferably, the blending amount is from 10 to 120 parts by mass, particularly preferably from 15 to 90 parts by mass. (3) Melt kneading In the present invention, the above ppE and PS resins are supplied to a twin-screw extruder, heated, melted, and kneaded. -20- 201215488 In the twin-screw extruder, the twin-screw extrusion of the same direction rotation type can also impart sufficient shear stress while kneading the two resins well, and cannot be kneaded by a single screw extruder. The shear stress imparted at the same time. In terms of good mixing and dissolving of the resin, it is preferable to use a twin-screw extruder having a large shear stress. Although the types of twin-screw machines mainly have the same-direction rotary type and the opposite-direction rotation type, they are the same-direction rotary type twin-screws with large shear stress. Further, in order to knead, form a good ultrahigh molecular weight body, and uniformly disperse, a kneading zone in which the kneading disc is passed through the apparatus is provided. The twin-screw extruder used in the present invention is a kneading zone having at least one dispersion and strong mixing property, which is usually composed of a raw material supply port and a port, and a jacketed drum; disposed in the interior thereof and engraved on the surface a two-screw which is grooved in the same direction and rotated in the same direction; and a die-casting mold which is arranged at the pressing end, preferably in the form of mutually engaging or non-engaging in the middle of the screw to form a plurality of kneading discs The portion formed; further, the conveying zone for conveying the kneaded material. The whole screw of the twin-screw extruder used in the present invention (all: L/D is 10 to 80, and the total L/D of the kneading zone is 3 to 18. If the L/D of the screw is less than 10, then When degassing becomes difficult, if L/D is over, the residence time of the resin becomes long and deterioration of the resin is likely to occur. The so-called L/D of the present invention means that the unit has a length of no dimension, so that L represents length, The length of the screw, the length of the extruder, the meaning of the kneading length; D is the diameter of the cylinder. The other machine is the best machine for the best homogenization of the press. 80 thoughts. -2 - .201215488 The best twin-screw rotary extruder for use in the present invention, in which the ultrahigh molecular weight body is well formed by applying a strong shear force to knead the resin. After the ultra-high polymer, it tends to become agglomerates (blocks), but it is considered that the agglomerates are not formed by the shearing force, and the bulky body is formed. In order to obtain a good formation of an ultrahigh molecular weight body, the length of the kneading zone is 3 to 18 in terms of L/D. Originally, it is considered that the formation of the ultrahigh molecular weight body varies with the time of the shearing force or the application of the shearing force, but it is not easy to use the positive force. In the present invention, a strong rod extruder can be used, and The L/D of the kneading zone is defined. Further, even if the kneading zone is plural, if the L/D is less than 3, the kneading is insufficient, the PPE I phase is not sufficiently dissolved, and the formation of the ultrahigh molecular component is insufficient. In addition, the fever becomes remarkable, and on the one hand, the color tone deteriorates, and on the other hand, it is convex. In order to form an ultrahigh molecular weight body in a preferred amount and the inhibitor becomes "bump", heat and strong shearing force are necessary. The temperature tends to cause a shift reaction of the main chain, so that it is easy to enter the catalyst residue and promote crosslinking (or polymerization). The condensation of the PPE cross-linking body can also become the original g of the bulge, which requires strong shearing force. That is, the cross-linked body is condensed into a double-spiral kneading zone having a kneading region in which the PPE and the PS are formed in a strong ultrahigh molecular weight and dispersed state, and the shearing force is obtained by shearing the resin. When the total of the If and the PS resin is more than 18, it becomes easy to cause the I-made ultrahigh molecular weight PPE resin to be high; Also recognize 3. In order to suppress this: pre-stirring, suppression -22-201215488 condensation, and in the case of condensed (this has been done), it is desirable to destroy the condensate. In order to obtain such strong shearing forces, a twin-screw extruder of the same direction rotation type is preferred. Further, in order to satisfactorily knead the two resins with the strong shearing force, a screw structure (kneading zone) to be described later is also important. In the kneading zone, in order to uniformly knead the two resins, the raw material is subjected to shearing, distributing, diffusing, elongating flow, and the like by means of a screw and a drum. The length of the screw portion corresponding to the kneading zone is in the range of 3 to 8 in terms of L/d with respect to the entire length of the screw. If it is within this range, it can be divided into two or more. The screw for the twin-screw extruder is preferably constituted by a portion corresponding to each portion of the extruder. That is, it is preferably a portion (supply zone) formed by a feed screw that conveys the raw material resin from the feed port to the front end; and has a dispersive and highly mixed component for melting and kneading the two raw material resins sent from the supply zone. a portion (kneading zone for promoting the kneading element and the component having a pressure-up capability); and a portion (conveying zone) formed by a feed screw for conveying the material kneaded in the kneading zone to the front end of the extruder Composition. The screw structure of the kneading zone of the extruder is preferably such that the element for promoting kneading is disposed on the upstream side, and the element having the pressure increasing capability is disposed on the downstream side. Examples of the member for promoting kneading are (A) a forward feed kneading disc member, (B) a vertical kneading disc member, (C) a wide kneading disc member, and (D) a forward feed mixing screw member. -23-201215488 The kneading portion formed by the kneading disc is in a form of, for example, a kneading disc having an elliptical shape, a triangular shape, a quadrangular shape, or the like of a plurality of sheets, which is engaged between the two screws, or a form of not engaging. Regularly shifting and rearranging the direction. For example, if five elliptical-shaped kneading discs are used to explain the configuration of the disc as a forward feed, as shown in Fig. 1, each of the kneading discs of one of the screws is moved toward the feeding direction of the screw so as to be the second The elliptical-shaped kneading discs shown in the figure are evenly staggered at a twist angle of 0 (from the upstream side to the downstream side in the resin flow direction, clockwise) and the five sheets are rearranged so that the kneading discs of the other screws face the same direction. In the feed direction, the phase is shifted relative to the previous screw and the five sheets are rearranged. The (A) forward feeding kneading disc member has two or more side flaps ' and the side flap twist angle Θ is 10 to 75 degrees. By disposing the side flaps at a predetermined angle, a resin having a screw-like structure is sent toward the feeding direction while applying a strong shearing force to become a region where kneading is performed. The flank width La/D of the kneading disc member fed in the forward direction is 〇.〇8 to 0.4, which is generally referred to as R kneading. When the twist angle θ is less than 10 degrees or more than 75 degrees, the conveying ability is lowered. Further, the flank width l a / D is less than 〇 · 〇 8, or greater than 0.4, and the conveying capacity is insufficient. Further, in the present specification, the length l of the side width La/D kneading disk of each of the so-called kneading discs is divided by the screw diameter D' and divided by the number of side sheets. -24- 201215488 (B) The vertical kneading disc element has two or more flank wings and a side torsion angle Θ of 75 degrees to 1 〇 5 degrees. Since the flank is staggered by about 90 degrees, the force of the resin is weak but the kneading force is strong. The width La/D of the side flaps of the vertical kneading disc member is 0.08 to 0.4, and is generally referred to as N kneading. If it is less than 〇. 〇 8, the kneading becomes weak. If it is larger than 〇 · 4, the kneading is too strong, causing deterioration of the resin. (C) The wide kneading disc member has three or one flanks and a torsion angle Θ in the range of _10 degrees to +10 degrees, and the width La/D of the side flaps is 0.3 to 2. Often referred to as wide kneading. If La/D is less than 0 · 3, the kneading becomes weak, and if it is more than 2, the kneading is too strong to cause deterioration of the resin. Further, the (D) forward feed mixing screw element is a mixing screw of the forward screw of the convex portion (wing portion) of the ingot screw. 2 or 1 can be used, and the number of engravings is preferably 5 to 15 per screw. Further, a gear type mixing screw is included. The length L/D of the screw element is preferably from 0 to 3 to 2. When it is more than 2, a strong shearing force is generated to cause deterioration of the resin, and if it is less than 0.3, the shearing % is small, and the kneading of the resin is not sufficiently melted. On the downstream side of the above-mentioned "kneading-promoting element", it is desirable to provide "a component having a boosting capability". The "element having a boosting capability" is an element that acts to block the conveyed resin and simultaneously transport the transported resin toward the returning direction, and is made to block the resin by being disposed on the downstream side of the element for promoting kneading. Kneading effect. -25- 201215488 The aforementioned components with boosting capability are exemplified by (E) kneading disc member for reverse feeding, (F) screw member for reverse feeding, (G) mixing screw member for reverse feeding, and (H) sealing ring member. . (E) The reverse feed kneading disc member has two or more flank wings, and the torsion angle β of the flank is from 1 to 175 degrees. The width of the flanks, La/D, is 0.08 to 〇.4 ', which is commonly referred to as L-kneading. When the width La/D of the side flaps is less than 0.08 or more than 0.4, the pressure of the resin is weakened, and the kneading is insufficient. (F) The screw element for reverse feeding is referred to as an inverse screw, and the lead length in L/D is preferably 0.4 to 2. The lead length is the length of the screw when the screw is rotated 360 degrees, sometimes referred to as the pitch. If the lead is less than 0.4, the pressure rise is too high. If it is greater than 2, the pressure gradient drops and becomes insufficiently kneaded. A screw element length L/D of 0.3 to 2 is preferred because of a good boosting effect. (G) The reverse feed mixing screw element is a mixing screw of the counter screw of the convex portion (wing portion) of the ingot screw. 2 or 1 can be, the number of engraving is better for each! The number of screws is 5 to 15. Further, it includes a gear type mixing screw. The length L/D of the screw element of 0.3 to 2 is preferable because a good pressurizing effect is obtained. (Η) The seal ring element is a ring-shaped member that is connected to the barrel in order to narrow the gap between the screw and the barrel to block the flow of the resin to obtain a boosting effect. The seal ring member is a gap between the long diameter of the screw member and the barrel in terms of L/D of 0.004 to 0. and the screw length L/D = 0.3 to 2. Known as the seal ring. -26- 201215488 If the gap is less than 0.004, the pressure rises too high. If it is greater than 〇1, the pressure is not raised. When the screw element length L/D is more than 2, a strong shearing force is generated, causing deterioration of the resin. If it is less than 0.3, the shearing force is small, and the kneading of the resin is not sufficiently melted. The screw structure of the kneading zone is preferably one or more of one or more of the above (A), (B), (C) or (d), and the above (E), (F), (G) One or more of the combinations of (H) and one or more are used. Then preferably (A), (B), (C) or (D) is located on the upstream side of the kneading zone, and (E) '(F), (G) or (H) is located on the downstream side. The upstream side means the side close to the base of the screw, in other words, the side of the screw drive portion. Further, in the present invention, the number of the kneading discs constituting one kneading portion is preferably from 3 to 20 pieces, more preferably from 5 to 50 sheets. Then, it is made into one unit, and is preferably a unit of about 1 to 5 units, more preferably about 1 to 4 units, and particularly preferably 1 to 3 units, and is used as a kneading portion between the units. For example, a full-wing screw is delivered to the composition. When the number of the kneading discs of each of the kneading portions is less than the above range, the kneading effect tends to be small. On the other hand, when the number is larger than the above range, the heat generated by the shearing tends to become large and the appearance becomes an appearance. There is a tendency for the color to be easily deteriorated. The number of revolutions of the extruder is usually from 1 Torr to 1, 〇〇〇 rpm. If the number of rotations of the screw is less than 100 rpm, it is not preferable to perform sufficient kneading of the resin composition. Further, when the number of rotations of the screw is more than 1, at 〇〇〇 rpm, the shear heat is increased, and the color tone is deteriorated, the molecular weight is lowered, and the bulging is generated. -27- 201215488 (4) In the present invention, the ultrahigh molecular weight body is characterized by an ultrahigh molecular weight body of PPE in an amount of 〇·〇] in the resin composition, and is an ultrahigh molecular weight body. The formation of the main component is because the PPE polymerizes or crosslinks the high molecular weight body, but it is also considered that the molecular weight is increased as a result of the mutual condensation of the PPE molecules substituted by the amine alkyl group of the PPE. Fully identified, but formed into ultra-high molecular weight bodies. Further, it is considered that the PPE molecules are melt-kneaded in an extruder, and the PPE molecules are crosslinked with the ultrahigh molecular weight component before being dissolved in the polystyrene. The protrusions are formed under conditions in which ultrahigh molecular weight can be formed, and a range of preferred ultrahigh molecular weight is considered. By using the PPE with a terminal OH concentration of PPE of 0.15 to 1.5 PPE of 1 聚 polyphenylene, it is possible to form an ultrahigh molecular weight body for whatever reason, and form an ultrahigh molecular weight body. The high molecular weight body is more dispersible and causes the surface defects of the bumps and agglomerates. Then, the superelevation is necessary in order to exhibit chemical resistance. The ultra-high polymer is considered to form a high network in the polyphenylene ether resin and prevent the cracking of the drug. The amount of formation of the superabsorbent having a molecular weight of 500,000 or more was obtained as follows. After dissolving 20 mg of the nine particles in 20 ml of chloroform, a filter of 0.45 μm was filtered to remove the bulk resin, and 5 to 0.6 of the inventors recognized the formation of the super terminal group, etc., and formed It is easy to produce, and the ether unit is also considered to be formed. It is said that such a small amount is called a molecular polymerization polymer which is incorporated into a resin. The high molecular weight is mixed with a large solid mesh -28*201215488, etc., which cannot be used for the size of G P C. The solution passing through the filter was measured by the following g PC to determine the amount of the ultrahigh molecular weight body of 500,000 or more, and the amount of the polymer of 500,000 or more which was measured by the original nine particles was determined from the amount. The ratio of the amount to the mass of the original nine. Gel Permeation Chromatography (GPC) Device: HPLC8020 manufactured by Tosoh

Column: TSK G5 0 0 0HHR+ G3 000HHR Solvent: chloroform Detector: UV2 8 3 nm Pretreatment: 20 mg of the sample was dissolved in 20 ml of chloroform solvent, filtered through a 0.45 μm filter and measured. The column temperature is set to 40. . . Molecular weight calculation: Polystyrene conversion, calibration curve was prepared using standard polystyrene and measured. The molecular weight of the standard polystyrene used was 264, 364, 466, 568, 2800, 16700, 186000, and 1260000. The amount of the ultrahigh molecular weight body of the PPE in the resin composition is from 0.015 to 0.6% by mass, and when it is less than 0.015% by mass, the solvent resistance is lowered. Further, when it is more than 0.6% by mass, bulging is likely to occur. In the resin composition, the preferred amount of the ultrahigh molecular weight body is from 〇·〇2 to 0.4% by mass. (5) PS resin particles and bismuth-like PS resin are those having an average particle diameter (volume average particle diameter) of 1 to 5 mm and an apparent density of 0.5 to 77 g/cm 3 'the particles are in a general method - 29-201215488 The nine granules are preferably obtained by melt-kneading polystyrene by an extruder and extruding into a strand shape, and pelletizing by a pelletizer to obtain a length of about several mm. From the standpoint of balance with the PPE pellets, it is suitable to use PS resin particles having an average particle diameter of 1 to 5 mm and an apparent density of 0.5 to 0.7 g/cm3. In the method of the present invention, it is desirable to use a powder obtained by compressing a toluene having a toluene concentration of from 0.1 to 0.5% by mass at a temperature of Tg or less and curing it, and pulverizing the cured product as necessary. The granules having an average particle diameter (volume average particle diameter) of 0.1 to an apparent density of 0.35 to 0.7 g/cm 3 and a toluene concentration of 0.01 to 0.5% by mass are used as PPE. In the present specification, the term "particles" means a particle having a small particle diameter called fine particles, nine particles, or the like, and close to the density of the substance. Further, there is also a case where the fine particles of powder form are used. In addition, the "granular substance" means particles which are particles in shape, or which are compressed and solidified, and have a void ratio of more than nine particles in the particles. In the present specification, the term "molded article" means a so-called molded article or a molded article obtained by extrusion by a screw extruder or the like, and is cooled and solidified, regardless of its shape and size. Specifically, it is represented by a variety of forms such as a film or a nine-piece, and is applied to a film or a flat plate. In addition, in the present specification, although the "molded article" is referred to as "nine grains." or "composition material nine grains", the present invention is mainly used for the production of polyphenylene ether-based resins from -30 to 201215488. When the raw material for molding is nine, it is to be interpreted as a representative of the "molded article". Further, in the present invention, in the case of the PPE resin, it is preferred to use a PPE powder which is compressed at a temperature lower than Tg of the PPE to cure the cured product obtained by pulverization if necessary, and the average particle diameter is adjusted to 0.1 to 10 mm. The granules have an apparent density of 0.35 to 0.7 g/cm3. The compression of the PPE powder is preferably carried out at a temperature such as PPE not exceeding Tg, i.e., at a temperature below Tg. The preferred temperature may be up to Tg or less, more preferably from 0 to 200 °C, and may be pressurized when the PPE is less than Tg or more during compression. The method of compression can also be carried out by any method. Although it is also possible to carry out the usual die casting, a simple method is exemplified by passing the PPE powder through a rolling method in which a pair of pressure rollers are disposed opposite each other. The pressure roller may be a roller having a smooth surface, or may be embossed on the surface of the roller or having a hole or a recess. When a smooth roll or an embossing roll is used, the PPE powder may be in the form of a flat plate or a sheet, but it may be pulverized to have a desired particle size. Further, when a roller having a hole or a recess is provided, if the size of the hole or the recess is adjusted to a desired size, the granular material having a desired particle diameter can be directly obtained. The gap of the rolls is preferably about 1 to 3 mm. The number of rotations of the rolls is preferably about 2 to 20 rpm, and the pressure of the pressure rolls is preferably from about 5 to 20 MPa, more preferably from 2 to 15 MPa. It was confirmed that the hardness of the obtained pellet changes with the strength of the compression. -31 - 201215488 The shape of the cured product is a cured product of various shapes depending on the surface shape of the roll to be used, the structure, the presence or absence of pulverization, and the use of a device other than a roll. For example, a flat shape (circular, square, etc.), a columnar shape (column, square column, etc.), a spherical shape, a cylindrical shape, a sheet shape, a fragment shape, an indefinite shape, or the like, or a granular shape, a fragment shape, a nine-grain shape, Mixtures, etc., do not count their form. Further, it may be such a mixture, or may contain a powder or the like. In the present invention, it is preferred to use a pellet of PPE obtained by compressing and solidifying Tg or less as an average particle diameter of 0.1 to 10 mxn and an apparent density of 0.35 to 77 g/cm3. When the average particle diameter or apparent density of the cured product obtained by the above compression is larger than the above range, it is pulverized to adjust the particle diameter or apparent density. The shape of the granular material is spherical, flat (circular, square, etc.), columnar (column, square column, etc.), cylindrical, fragmented, indefinite shape, etc., cylindrical or granular, fragmented, Nine granules, mixtures of these, etc., regardless of their shape and morphology. If the average particle size of the PPE granules is less than 0.1 mm, the feeding of the air is caused by the difference in the feeding portion during the extrusion molding, and the feeding bottleneck is likely to occur. If it is larger than l 〇 mm, it is mixed with The difference in diameter of the PS resin particles is too large, and it is difficult to uniformly mix when it is supplied to the press machine, and it is also disadvantageous in operation. The preferred average particle size of the PPE granules is from 0.1 to 1 mm. Further, the apparent density of the granules is preferably from 0.35 to 77 g/cm3. If it is less than 0.35 g/cm3, a large amount of air is contained in the granules, that is, because it is too soft from -32 to 201215488, it is easily collapsed when placed in an extruder, and becomes powder with PPE. The situation in the body is not bad. When it is more than 0.7 g/cm3, it becomes too hard and the point of melting of the PS resin particles which are coexisting at the time of melting in the extruder becomes too slow, and it tends to be poorly dispersed or only the PS resin is melted to cause slippage on the surface of the screw. And the cause of poor extrusion. More preferably, the apparent density is from 0.37 to 0.68 g/cm3, particularly preferably from 0.39 to 0.66 g/cm3. Since the PPE usually has a density of about 1.1 g/cm3, in the present invention, the volume becomes high, i.e., it means that a certain degree of voids are formed in the particles. Further, the PPE pellets preferably have a compressive strength of 40 g to 4 kg. If the compressive strength is less than 40g, the feeding bottleneck is easily broken when the pellet screw is fed from the feeder to the extruder, and the feeding bottleneck is easily generated. If the compressive strength is 4 kg or more, the screw feeding from the pellet feeder is performed. When it comes to the extruder, it is easy to cause the particles to be caught between the screws or the inner wall to stop the screw. The preferred compression strength is from 500 g to 3 kg, more preferably from lkg to 3 kg. It is considered that by making the compressive strength of the PPE pellets in this range, the timing of melting of the PS resin particles to be coherent is improved. That is, a PPE having a high Tg (Tg is usually 210 ° C) is collapsed to some extent and becomes a hardened product which is easily compressed by using a PS resin having a lower melting point than PPE (Tg is usually 1 ° C). (When the melt-molding or the like is used to form particles (nine particles) having a small amount of voids, when the two are mixed and supplied to the extruder, the PPE particles are collapsed and the screw is transported forward to make the PS resin particles (nine) The granules are melted from their outer surface and mixed into the PPE. -33- 201215488 It is considered that the PPE having a difference in melting temperature (melting time point in the extruder) and the ps resin become a good compatibility state by making it into such a mixed state. Therefore, the PS resin is a particle (nine particles), and the PPE is a powder which is easily pulverized and compressed and solidified. Further, the PPE granules have a content of particles having a particle diameter of ΙΟΟΟμπ or more of 50% or more, 2) a content of particles having a particle diameter of 10 to ΙΟΟμηι of 3 to 40%, and 3) a particle diameter of ΙΟμιη or less. The content of the particles is preferably within 2%. By making it into such a particle size structure, the dispersibility of the powdery additive can be improved. That is, a powdery additive having an average particle diameter of about 10 to 100 μm is used, but if the powdery additive is directly added to the granules or the PS resin particles, the particle size is different. The classification is classified into particles (granular bodies) and powders in the hopper portion of the extruder, and it is not possible to perform uniform mixing, and it becomes a molded article in which a homogeneous composition cannot be obtained. However, by allowing the granules to have 3 to 40% by mass of particles having a particle diameter of 10 to 100 μm, the powdery additive is well mixed in the ruthenium of the particle size, and as a result, it becomes easy to uniformly in the entire composition. dispersion. Therefore, in the case where a powdery additive is added to the present composition, it is preferred to use a crucible having a particle size distribution as described above. (6) Additive In the present invention, other components may be added to the above-mentioned hydrazine and styrene resin as necessary. -34- 201215488 Other ingredients are flame retardant, weathering improver, foaming agent, slip agent, fluidity improver, impact improver, dye, pigment, tanning agent, stiffener, dispersant Wait. Among the additives, the flame retardant is a phosphorus-based flame retardant, preferably a phosphazene-based compound, a phosphate-based compound, or a condensed phosphate. The phosphazene compound is exemplified by a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound, and a crosslinked phenoxyphosphazene compound. Phosphate-based flame retardants are exemplified by triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethyltolyl phosphate, tris(isopropylphenyl)phosphate, diphenyltolyl phosphate , tributyl phosphate, and the like. Examples of condensed phosphate ester flame retardants are phenyl resorcinol polyphosphate, tolyl resorcinol polyphosphate, phenyl • tolyl resorcinol • polyphosphate, xylene • Resorcinol • Polyphosphate, phenyl – p-tert-butyl • m-benzoquinone phosphite, phenyl • cumene • resorcinol • polyphosphate • tolyl • xylyl • m-benzoic acid • polyphosphate, phenyl • cumene • diisopropyl phenyl • resorcinol • polyphosphate, etc. As a preferred example, phenyl • double Phenol • Polyphosphate tolyl • Bisphenol • Polyphosphate X Phenyl • Tolyl • Bisphenol • Polyphosphate, Xylylene • Bisphenol • Polyphosphate, Phenyl • Pair of T-Butyl • Double Phenol • Polyphosphate % Phenyl • Cumyl • Bisphenol polyphosphate tolyl • Xylyl • Bisphenol • Polyphosphate, Phenyl • • phenyl-propan-bis intoxicated dicumyl • • polyphosphates, etc. as preferred examples. -35- 201215488 A specific example of the phosphorus-based flame retardant can be preferably used, for example, "TPP" (triphenyl phosphate) of Daihachi Chemical Industry Co. Ltd., "Size 7 333" (resorcinol bis(diphenyl phosphate)), "CR741" (bisphenol A bis(diphenyl phosphate)), "PX200" (resorcinol bis(dimercaptophosphate)), ADEKA Corporation's "Adidastapp FP700" (ADKSTABFP700) (bisphenol A bis(diphenyl phosphate)) is a commercial product. Further, in the case of a tantalum or a hardener, an organic or inorganic tantalum, an organic or inorganic hardener, and the like are exemplified, and specific examples thereof include glass fiber, mica, talc, apatite, potassium titanate, and carbonic acid. Calcium, vermiculite, etc. The blending of the dip and the hardener is effective for improving rigidity, heat resistance, dimensional accuracy, and the like. The blending ratio of the dip and the hardener is preferably from 1 to 80 parts by mass, more preferably from 5 to 60 parts by mass, per 100 parts by mass of the total of the resin component. (7) Production of Resin Composition (Nine) Hereinafter, a preferred embodiment of the method for producing the resin composition (nine particles) of the present invention will be described. However, the present invention is of course not construed as being limited to the following embodiments. Pose. (i) the component derived from the polymerization catalyst contains 0.05 to 10 ppm of copper element, preferably PPE (preferably powder) having an adjusted toluene content to the above amount, preferably compressed and lightened by a light press or the like The slabs and lumps are obtained, and the solid compound is pulverized by a granulator or the like as needed to form PPE granules having a specified average particle diameter and apparent density, and a specific toluene content. -36- 201215488 (ii) Mixing PPE pellets with PS resin pellets having an average particle diameter of 1 to 5 mm and an apparent density of 0.5 to 0.7 g/cm3 by a mixer such as a drum, for example, by twin screw feeding The machine (feeder of raw materials) feeds the mixture to a twin-screw extruder, preferably a twin-screw co-rotating extruder. It is preferred to supply an inert gas from a raw material supply port (a hopper of the extruder). The inert gas is a gas inert to PPE such as nitrogen or argon, and nitrogen is usually used. The blending of the additive may be added by mixing the mixed PPE and PS, or by adding a side feeder to the extruder barrel. (iii) The extrusion screw in the cylinder of the twin-screw extruder is 1 〇 to 80 in length in L/D, and has at least one kneading zone, and the total L/D of the kneading zone is 3 to 18 The smooth conveyance of the resin raw material is carried out, followed by melt-kneading, and finally extruded into a strand shape by the discharge nozzle. The screw structure of the kneading zone is preferably such that the elements for promoting kneading (A) to (D) and the like are disposed on the upstream side, and the elements having the pressure-increasing ability such as (E) to (H) are disposed on the downstream side. . By such an arrangement, strong shearing, kneading, and formation of an ultrahigh molecular weight body are applied to the resin. Although the set temperature and time in the extruder may be arbitrarily selected depending on the resin composition or the type of the extruder, the kneading temperature (set temperature) is usually 200 to 3 50 ° C, preferably 220 to 320 ° C, The kneading time is preferably 3 minutes or less. When it is more than 350 °C or 3 minutes, it is difficult to prevent thermal deterioration of PPE or PS resin, and physical property deterioration and appearance are liable to occur. -37- 201215488 In the extruder, it is preferred to provide a reduced-pressure exhaust portion, since toluene or the like contained in the PPE granules often volatilizes from the exhaust portion toward the exhaust port, and causes accompanying airflow, It can attract and remove other volatile components well. Therefore, it is possible to suppress the condensation of the volatile component in the vicinity of the exhaust port, and it is possible to produce nine kinds of resin compositions having excellent quality by suppressing the incorporation of the deteriorated substances into the composition. The degree of vacuum in the exhaust portion of the extruder is preferably 20 x 10 3 Pa or less, more preferably 7 x 10 3 Pa or less. When the degree of vacuum is within this range, it is preferred to sufficiently remove volatile components such as toluene in the exhaust portion without adversely affecting the resin. (iv) The melt-kneaded composition is extruded into a string called a strand from a discharge nozzle provided at the front end of the kneading extruder. The shape of the die for discharging the nozzle is not particularly limited, and a known one is used. The diameter of the spout of the spout nozzle varies depending on the extrusion pressure and the size of the desired nine particles, but is usually about 2 to 10 mm. Figure 3 is a schematic view showing the steps from the discharge nozzle to the processing of the extruded strands into nine particles. Fig. 4 is a partial side elevational view showing one of the embodiments of the guide rolls used in the strand conveying step. The polyphenylene ether resin composition containing 0.05 to 1 ppm of copper element of the present invention generates a large amount of dirt. Although the reason is not clear, it is considered as follows. That is, because the polyphenylene ether ultra-high molecular weight system completed in extrusion has a molecular weight of several hundred thousand or more (based on 500,000 or more), it is compatible with polystyrene molecules or other polyphenyl-38-201215488 ether molecules. Low, it is easy to assemble the polyphenylene ether ultrahigh molecular weight bodies with each other. If the aggregate becomes too large, a coagulum is formed. The polyphenylene ether ultrahigh molecular weight aggregates form a large agglomerate in the compatibilized phase of polyphenylene ether and polystyrene and disturb the flow under shear flow. This flow disturbance is believed to promote the generation of fouling at the tip of the nozzle. Therefore, in the present invention, it is preferred to remove the dirt attached to the strands when the polyphenylene ether is extruded. This means can be achieved by using a guide roll as follows, although it is various and simple. The strands S are taken up by the take-up rolls 4, 4' and cut into nine pieces by the granulator 5, and are usually cooled on a conveying path before being supplied to the granulator 5. Specifically, as shown in Fig. 3, it is cooled by being transported to a cooling medium (usually water) W stored in the cooling bath 2. In order to reduce the deterioration of the resin, it is preferable that the time from the extrusion of the strand S by the discharge nozzle 1 until the entry into the cooling medium W is short. It is usually preferred to enter the cooling medium W within one second from the start of extrusion by the discharge nozzle 1. Therefore, it is preferable to convey the cooling medium W at a shortest distance from the discharge nozzle 1, and it is preferable to transport the cooling medium W for a long time. In order to realize a conveying path that satisfies these conditions, a guide roller such as 3, 3' is generally provided in the conveying path of the strand S. The diameter of the guide rolls 3, 3 is usually about 3 to 7 cm. (v) With such guide rolls 3, 3', dirt adhering to the surface of the strand S can be removed. -39- 201215488 Specifically, at least one of the guide rolls 3, 3' is rotated in the opposite direction b from the moving (conveying) direction a of the strand S to the moving speed of the strand S (winding speed) The slow circumferential speed is rotated in the same direction as the moving direction a of the strand S (or it may be maintained in a state of no rotation). The guide rolls 3, 3' generally have a cylindrical shape in which a direction intersecting the moving direction of the strands S is a rotating shaft, and in a state where the strands S are conveyed in a desired conveying path, the plurality of branches are parallel and are in a cylinder The surface supports the extruded strand S. In general, as shown in Fig. 4(a), the guide rolls 3, 3 are provided with a plurality of annular (ring-shaped) grooves 32 in the circumferential direction on the surface of the roll of the main shaft 31. The groove 32 receives and supports the moving strand S, preventing the strands S in the adjacent position from coming into contact with each other and being fused. Generally, the width of the groove 32 is slightly wider than the thickness of the strand S, so that the bottom of the groove 32 is curved to provide stable support. Also, the depth of the groove 32 is usually 2 mm to 10 mm. The diameter of the rolls 3, 3' is usually about 3 to 7 mm. Further, the pitch of the grooves 3 2 (the interval between the adjacent grooves 3 2) generally coincides with the interval of the strands S (the interval between the discharge nozzles 1 of the die). It also varies with the diameter of the strand S, but the pitch is 5mm to 20mm. The number of the grooves 32 may be more than the number of strands extruded. One or a plurality of guide rolls 3, 3' are disposed to move in the strands of the cooling tank 2. In the case of a plurality of branches, the strands are hung between the guide rolls 3, 3' and moved in the cooling bath 2 to be cooled. -40- 201215488 The guide rolls 3, 3' may be supported in a direction opposite to the moving direction a of the strand S or in the same direction as the moving direction a, and may or may not be rotatably supported. By moving the (transport) speed relative to the strand S, the movement (rotation) speed of the groove 32 of the guide rolls 3, 3' is relatively slow, by supporting the guide rolls 3, 3', with the groove 32 and The surface of the strand S contacts the surface of the strand S, and the dirt adhering to the surface of the strand S can be erased. Further, when a plurality of branch rolls are provided, at least one of the surfaces of the friction strands S may be provided. In the case where the guide rolls 3, 3' are rotated in the opposite direction b from the moving direction a of the strand S, the driving means may be provided on the guide rolls 3, 3'. In this case, since the resistance of the surface of the strand S and the groove 32 is excessively large and the movement of the strand S becomes unstable, the amount of rotation is determined within a range in which the movement of the strand S is stabilized. When the guide rolls 3, 3' are rotated in the same direction as the moving direction a, the driving means may not be provided. It is sufficient to cause a certain degree of resistance in the rotation of the guide rolls 3, 3' (at least by the frictional force of the moving strand S, not to the extent of the same circumferential speed as the strand S). Thereby, the guide rollers 3, 3' rotate with the movement of the strands S, and the resistance caused by the rotation of the strands S is slower than the moving speed of the strands S (slower circumferential speed), and the surface friction strands of the grooves 32 can be The surface of strip S. Although it is also possible to provide a driving device, unlike the case of reverse rotation, it is simpler to construct a resistance to rotation. Therefore, the strand S moves in the cooling medium W while being in contact with the surface of the guide rolls 3, 3', by the difference between the moving speed of the strand S and the rotational speed (circumferential speed) of the guide rolls 3, 3'. The surface of the groove 32 rubs against the surface of the strand S, -41 - 201215488 and removes dirt adhering to the surface of the strand S. Further, even if the grooveless guide roller ' rubs the strand with the surface of the guide roller, it has a certain degree of soil removal effect. This effect is not obtained when the guide rolls 3, 3 are rotated at the same peripheral speed as the moving speed of the strands S. When the moving speed of the strand s is slightly the same as the peripheral speed of the guide rolls 3, 3, it is considered that not only the surface of the strand S cannot be rubbed, but the surface of the groove 32 is attached to the strand and buried. In. The rotation speed (moving speed of the outer peripheral surface) Vr of the specific guide rolls 3, 3' is preferably 0.72 Vr/Vs $ - 〇 · 2 with respect to the speed Vs of the strands. The upper limit is more preferably 0.5 2 Vr/Vs, and the lower limit is more preferably Vr/Vs g 〇. Vs is the winding speed of the strand S, and Vr is obtained by the number of revolutions (the radius of the guide rolls 3, 3' and the groove depth) χ 2π χ 1 minute. When Vr/Vs is a positive number, the guide rolls 3, 3 are rotated in the same direction as the strand moving direction a, and if they are negative, the 'guide rolls 3, 3' are opposite to the strand moving direction a. The case of rotation. Although one or a plurality of guide rolls 3, 3' are provided in the cooling tank 2, when they are plural, all of the guide rolls 3, 3' do not have to be rotated as described above, and in the cooling medium 2, as described above The most recent guide roller (3 in Fig. 3) of the discharge nozzle 1 (die) has an effect on the removal of dirt. (vi) The strands S are conveyed from the crimping rolls 4, 4' to the granulator 5, and diced to form nine granules. The pelletizing is preferably performed at a strand temperature of 80 to 160 ° C, particularly in the range of 90 to 14 (TC). -42 - 201215488 Although the temperature is measured by a non-contact thermometer, However, it can be easily replaced by inserting a thermometer into nine bags or containers of nine bags that have been cut by a pelletizer. The nine-grain obtained by the method of the present invention can be used by general use. The molding method of the polyphenylene ether resin is molded by various molding methods such as injection molding, injection compression molding, hollow molding, extrusion molding, flat plate forming, thermoforming, rotational molding, laminated molding, and die casting molding, and is molded into It is used as a molded article in any shape. Examples of molded articles include electrical and electronic equipment, OA equipment, information terminals, and mechanical parts 'home appliances, vehicle parts, building components, various containers, leisure goods, and miscellaneous goods. Parts such as lighting and lighting equipment. Among these, 'especially suitable for use in electrical and electronic equipment, OA equipment, information terminals, home appliances, vehicle parts, lighting equipment, etc. EXAMPLES The following examples are shown to further illustrate the present invention, but the present invention is not construed as being limited to the following examples. [1. Measurement and evaluation methods] In the following examples and comparative examples, The measurement and evaluation methods are as follows: (1) The molecular weight is measured by the method described above. -43 - 201215488 (2) Hue (YI値) The measurement of the color tone of the nine particles obtained in the examples and the comparative examples. Dry nine pieces for 4 hours, using SH100 made by Sumitomo Heavy Industries Co., Ltd., with a cylinder temperature of 290 °C, a mold temperature of l〇〇°C, a molded product of length lOOmmx width lOOmmx and thickness of 2 mm, measured (Yellow index) (YI値) YI 値 was obtained by the color of J Color Meter S2000 manufactured by Nippon Denshoku Co., Ltd. Further, YI 値 was evaluated using the following three grades: 〇: YI値 is less than 40 △ : YI 値 4 0 or more to less than 5 0 X : YI 値 50 or more (3) Chemical resistance at 90 ° C for drying for 9 hours 4 hours using the system injection molding machine SH100, ISO mold type A (IS03 1 67, IS0294- 1 Apply a 0.5% twist (bend) on the surface of the test piece to isopropanol and positive After the mixture ratio of the weight ratio of the alkane was 1:1, the number of occurrences of cracks per one test piece was counted, and the number of chemicals was excellent. Further, the number of occurrences was counted and evaluated by the following three grades: Less than 30 △ : 30 or more to less than 40 0 X : 40 or more are set in 1 2 0 injection molding machine conditions, forming fixed color chromaticity meter r Spectr Sumitomo heavy machine production test piece at 2 3 ° C immersion in the night for less than 1 hour is less than estimated. -44- 201215488 (4) Types and quantities of terminal groups of PPE: JNM-A400 manufactured by Nippon Denshi Co., Ltd., CDC13 as solvent, tetramethyl decane as the reference, and the measurement mode is 13C-NMR completely Coupling mode, determination of 13c-magnetic resonance absorption spectrum 'by the method described in Macromolecules, 1990, Vol. 23, pp. 1318 to 1329, to find the type and number of hydroxyl ends (per 100 The number) (5) The ultimate viscosity of PPE: Dissolve 5.5g of polyphenylene ether in chloroform to a solution of l〇〇ml or more (concentration of 0.5g/dl or less), and use Ubbelohde type viscosity at 30 °C. The specific viscosity at different concentrations was determined, and the ultimate viscosity was calculated by extrapolating the specific viscosity to the concentration. (6) Copper element content rate After the polyphenylene ether resin was decomposed by nitric acid, the copper content in the residue was quantified by atomic absorption analysis to calculate the copper element content (ppm) in the polyphenylene ether resin. (7) Average particle size and particle size distribution (less than 1 mm) Laser diffraction scattering type manufactured by Sei Shin Enterprise Co. Ltd., which is a particle size analyzer for laser diffraction and scattering The particle size distribution measuring apparatus Laser Micron Sizer LMS-2000e" was measured by a wet method (isopropyl alcohol solvent). The volume average particle diameter is an average particle diameter (μηι). (8) Apparent density According to JIS Κ 5 101, it was measured by a standing method without using a filter. -45- 201215488 (9) Evaluation of charred foreign matter A flat plate of 0.3 mm was formed by die-casting 50 g of 50 g by hot die casting (260 °C). The die casting was visually observed and the amount of charred foreign matter was counted, and the following three grades were evaluated. 〇: One or less charred foreign matter △: Charred foreign matter 2 to 4 X: Charred foreign matter 5 or more (1 〇) Comprehensive evaluation Comprehensive evaluation is performed by the following 3 grades. 〇: Hue, solvent resistance, and charred foreign matter are all flaws. △: Δ, but no X in any of hue, solvent resistance, and charred foreign matter. X: X in any of hue, solvent resistance, and charred foreign matter. [Production Example of Polyphenylene Ether] (1) Production of Polyphenylene Ether (PPE-A) In a polymerization reactor equipped with an air blowing tube, a condenser was connected in series in two stages. The flow of the cold coal is temperature adjusted so that the temperature of the condenser is about Ot, and the toluene phase of the out of the tank is continuously returned to the polymerization vessel. Each lkg of monomer, 10 NL / min supply air to 22 〇g of copper dibromide, 4,00 〇g of dibutylamine, 98,000 g of toluene catalyst solution, while 23,5 〇〇g The 2,6-dimethylphenol was dissolved in toluene to a solution of 54,000 g, which was added to the polymerization at 40 ° C for 4 minutes. After the monomer was dropped for 130 minutes, the aqueous solution of sodium ethylenediaminetetraacetate (hereinafter referred to as sodium edTA4) was dissolved while stirring at 1.5 times the molar amount of the catalyst copper (the amount of the aqueous solution was relatively The reaction solution was stopped while the total amount of the polymerization reaction liquid was 〇·2 by weight. After the stirring is stopped, the aqueous solution which has been left to stand is discharged out of the system, and 5,500 g of pure water is added to the reaction liquid and stirred for 10 minutes, and left to stand for 1 minute, the separated aqueous layer is separated. Out of the system. Repeat the same operation further. In other words, the second aqueous solution of EDTA4 sodium (the amount of the aqueous solution is 0.2 times by weight based on the total amount of the polymerization reaction solution) of 0.5 times the molar amount of the catalyst copper used for the dissolution is added to the reaction liquid for the second time. Separation. Thereafter, 6,000 g of pure water was added to the reaction liquid in the same manner as above, and the mixture was stirred for 1 Torr, and allowed to stand for 1 〇 minutes, and then the separated aqueous layer was discharged outside the system. Approximately equal volume of methanol was added to the resulting reaction solution to precipitate the polyphenylene ether. The PPE precipitate was filtered, and the polyphenylene ether was further washed with an appropriate amount of methanol, and then dried at 14 (about TC for 1 hour) to obtain the following powdery polyphenylene ether (hereinafter referred to as "PPE-A" for short). PPE- The evaluation results of A are as follows. Ultimate viscosity: 〇.48 dl / g Terminal hydroxyl group: relative to 100 phenyl ether units 〇 · 26 average particle diameter: 90 μιη Copper element content: O.lppm Toluene concentration: l, 120 ppm Further, the toluene concentration was obtained by dissolving 2 g of the polyphenylene ether-based resin in chloroform, and then separating it with methanol, and analyzing the supernatant liquid to obtain a toluene concentration (%) by a gas chromatograph. -47 - 201215488 (2) The production of polyphenylene ether (ΡΡΕ-B) is carried out in the same manner as PPE-A except that the amount of sodium ED TA4 in the second time is the amount of catalyst used. The evaluation result of obtaining PPE-B PPE-B is as follows. The following is the ultimate viscosity: 〇.48 dl / g terminal hydroxyl group: relative to the phenyl ether unit is copper element content: p. 5 p P m toluene concentration: l, 2 〇〇 ppm (3) polyphenylene ether (PPE -C) The production was carried out in the same manner as PPE-A except that the amount of EDTA4 sodium in the second time was the amount of catalyst used. The evaluation results of PPE-C PPE-C are as follows. Limit viscosity: 48.48dl/g Terminal hydroxyl group: Relative to the phenyl ether unit, copper content: 1.2ppm Toluene concentration: 1,150ppm (4) Poly The production of phenyl ether (PPE-D) was carried out in the same manner as PPE-A except that the amount of EDTA4 sodium in the second time was the amount of catalyst used. The evaluation results of obtaining PPE-D PPE-D are as follows. Viscosity: 〇.48dl/g End hydroxyl group: Copper element content relative to 100 phenyl ether units: 5.2PPm Toluene concentration: l, 2 3 0PPm 0.3 times Mo 0.23 〇. 2 times 0.25 0.1 times to 0.22 -48 - 201215488 (5) The production of polyphenylene ether (PPE-E) was carried out in the same manner as PPE-A except that the second catalyst was not washed, and pp E - E was obtained. - The evaluation results of E are as follows. Limit viscosity: 〇.48 dl / g Terminal hydroxyl group: 0.27 copper element content per 1 phenyl ether unit Content: 1 1 · 4ρριη Toluene concentration: 1,420 ppm ( 6) Polyphenylene ether (PPE-F) is manufactured in addition to the second catalyst cleaning treatment (the amount of EDTA4 sodium is 0.5 of the catalyst used) After the same catalyst washing treatment was carried out, PPE-F was obtained in the same manner as PPE-A. The evaluation results of PPE-F are as follows. Ultimate viscosity: 〇.48 dl/g End hydroxyl group: relative The content of the phenyl ether unit is 0.21 copper. The content of the copper element is 〇.〇4ppm. Toluene concentration: 970ppm. (7) The production of polyphenylene ether (PPE-G) takes 70 minutes in addition to the solution of 54,000 g of toluene. After the dropwise addition, the polymerization was carried out at 4 ° C. After the monomer was dropped for 11 minutes, the aqueous solution of sodium EDTA 4 dissolved in a molar amount of 1.5 times with respect to the copper of the catalyst was stirred (the amount of the aqueous solution was relative to the polymerization reaction). The total amount of the liquid was 2. 2 times by weight), and it was produced in the same manner as PPE-C except that it was added to the reaction liquid and the reaction was stopped. -49- 201215488 The evaluation results of ΡΡΕ-G are as follows. Ultimate viscosity: 〇.48 dl/g End hydroxyl group: 〇〇·12 copper element content per one 〇〇1 element content: 1.2 ppm Toluene concentration: 1,120 ppm [Example 1] 80 parts by mass PPE-A and 20 parts by mass of A&amp;M styrene (A&amp;M styrene) polystyrene nine HT478 (hereinafter referred to as "PS-A". The average nine weight is 23 mg, and the average particle size is 3_3 mm (volume average particle diameter) and apparent density of 〇.62 g/cc) were mixed by a drum for 5 minutes. The mixture was transferred to a double-screw cassette weighing feeder CE-W-2 manufactured by Kubota Co., Ltd., and a twin-screw co-rotating extruder ΤΕΧ30α manufactured by Toshiba Machine Co., Ltd. was used: (L/D in length) It was counted as 52.5), fed at a rate of 20 kg/hour, and the mixture was melt-kneaded by an extruder. The number of screw rotations of the extruder was set to 300 rpm. The screw configuration is constituted by a screw having a kneading zone of RRRNNL. Here, R is an R kneading disc (the above (A)), N is an N kneading disc (the above (B)), and L is an L kneading disc (the above (E)). The length L of each kneading disc is set to L/D = 1. 〇, and the total length of the kneading zone is set to L/D = 6.0. The kneaded melt was extruded by using a die having a pore size of 4 mm and a 5-hole to form a strand, which was cooled by cooling the water tank, and pelletized by a granulator to obtain nine polystyrene-50-201215488 ether resin compositions. The extrusion was carried out for 1 hour, and nine samples were taken for evaluation after 30 minutes from the start of extrusion. Further, the dirt around the die nozzle (5 holes) generated at the time of extrusion for one hour was collected, and the measured weight was 19 mg. The strand was taken up at a speed of 18 m/min and placed on two rolls A and B in a cooling water tank, and cooled in a water tank. At this time, the rotational speed of the roller A in the circumferential direction was 5 m/min. The ratio of the circumferential speed of the roller to the speed of the strand was 0.28. The interval between the roll A and the roll B was adjusted, and the temperature of the strand entering the granulator was set to 1 1 2 ° C and diced. The cut surface is beautiful, and nine pieces of good shape are obtained. Only one of the nine adhering dirt was found out of 20 kg of the obtained nine particles. The nine pellets were dried at 120 ° C for 4 hours, and molded into a molding machine SH100 manufactured by Sumitomo Heavy Industries Co., Ltd., and molded into a molded article having a length of lOOmm x a width of 100 mm and a thickness of 2 mm at a cylinder temperature of 290 ° C and a mold temperature of 100 ° C. And measure the hue chromaticity (YI 値). YI値 is 32. The amount of formation of the ultrahigh molecular weight body (having a molecular weight of 500,000 or more) in the nine grains was 0.02% by mass. Further, in the chemical resistance test, the number of occurrences of cracks per one test piece was 27, and it was considered that the ultrahigh molecular weight component having a molecular weight of 500,000 or more formed a highly network structure and improved chemical resistance. The evaluation results are shown in Table 1. [Examples 2 to 4 and Comparative Examples 1 to 3] In the first embodiment, nine particles were produced in the same manner as in Example 1 except that the type of PPE and the type of PS resin were further described in Table 1. also

C -51 - 201215488 Yes, the PS-Β used in Comparative Example 3 was a freeze-pulverizer of PS-Α (average particle diameter 80 μm). The evaluation results are shown in Table 1. Table 1

EXAMPLES Comparative Example 1 2 3 4 1 2 3 PPE surface PPE-A PPE-B PPE-C PPE-D PPE-E PPE-F PPE-C Cu concentration ppm 0.1 0.5 1.2 5.2 11.4 0.04 1.2 PPE parts by weight 80 80 80 80 80 80 80 PS-A Parts by weight 20 20 20 20 20 20 PS-B Parts by weight 20 Tones YI 32 35 33 39 52 31 38 Ultra high molecular polymer % 0.02 0.04 0.09 0.31 0.63 0.01 0.12 Cracking count 27 23 18 17 13 41 22 Scorched foreign matter 0 0 0 1 4 0 6 Hue 〇〇〇〇X 〇〇 Solvent resistance 〇〇〇〇〇X 〇Charred foreign matter 〇〇〇〇Δ 〇X Comprehensive evaluation〇〇〇〇XXX

[Examples 5 to 15 and Comparative Examples 4 to 6] In the first embodiment, the screw configuration was changed to the screw configuration described in Table 2 below and carried out. In Table 2, the screw compositions A to Η are those satisfying the requirements of the present invention, and the I, J and single-screw extruders are those which are not satisfied with the requirements of the screw constituting the comparative example. The discharge amount was set to 30 kg/hr, and nine particles were obtained in the same manner as in Example 1 except that the type of the PPE was changed to Table 3. 201215488 Table 2 L/D Total Screw Composition Screw Composition A 4.0 RRNL Screw Composition B 6.0 RRRNNL Screw Composition c 6.0 RRRNNLs Screw Composition D 6.0 RRRNN Seal Ring Screw Na to E 5.0 RmRmRmLmLm Screw Composition F 8.0 RRRRNNNL Screw into G 12.0 ΚΚΝΙ^-- ΚΚΝΙ^--ΚΚΝ[ screw composition Η 6.0 RRRNNN screw composition I 20.0 ΚΚΝ]^--ΚΚΝί---ΚΚΝΙ^--ΚΚΜ^--ΚΚΝί screw constitutes J 2.0 RL single screw extruder field rubber machinery (shares) VS40-28 In the above Table 2, the code of the screw is as follows: R: R kneading disc (the above (A)) N: N kneading disc (the above (B)) L: L kneading disc (the aforementioned ( E))

Rm : forward thread scoring mixing screw (the aforementioned (D))

Ls: reverse threaded screw (previous (F)) -: ordinary conveying screw The length L of each kneading disc is all using a kneading screw of L/D = l_〇. The total length of the kneading zone is set to L/D = 6.〇. The evaluation results are shown in Table 3. -53- 201215488 Table 3 PPE Type Cu Concentration PPE PS-A Screw Composition Tone YI Ultra High Molecular Polymer Cracking Count Scorch Foreign Matter Number Tone Solvent Resistance Charred Foreign Matter Comprehensive Evaluation ppm Military Halo Parts by Weight % Example 5 PPE-A 0.1 80 20 B 32 0.02 27 0 〇〇〇〇 Example 6 PPE-A 0.1 80 20 F 34 0.05 22 0 〇〇〇〇 Example 7 PPE-A 0.1 80 20 I 28 0.016 39 0 〇△ 〇 Δ Example 8 PPE-D 5.2 80 20 A 37 0.12 23 0 〇〇〇〇 Example 9 PPE-D 5.2 80 20 B 39 0.31 17 0 〇〇〇〇 Example 10 PPE-D 5.2 80 20 C 41 0.29 21 0 Δ 〇〇〇 Example 11 PPE-D 5.2 80 20 D 40 0.27 16 0 Δ 〇〇〇 Example 12 PPE-D 5.2 80 20 E 38 0.33 20 0 〇〇〇〇 Example 13 PPE-D 5.2 80 20 F 42 0.36 14 1 Δ 〇〇 Δ Example 14 PPE-D 5.2 80 20 G 43 0.34 13 1 Δ 〇〇 Δ Example 15 PPE-D 5.2 80 20 Η 30 0.04 38 0 〇Δ 〇Δ Comparative Example 4 PPE- D 5.2 80 20 I 51 0.42 13 3 X 〇Δ X Comparative Example 5 PPE-D 5.2 80 20 J 33 0.01 40 0 〇X 〇X Single screw ratio Example 6 PPE-D 5.2 80 20 0.01 30 pressing lever 420 billion billion X X press

[Examples 16 to 20, Comparative Example 7] In Example 1, except that PPE-C was used instead of PPE-A, and the blending amount of PPE-C and PS-A was set to the amount described in Table 4, Example 1 In the same manner, nine tablets were obtained. The evaluation results are shown in Table 4. -54- 201215488 Table 4

EXAMPLES Comparative Example 16 17 18 19 20 7 PPE-C Parts by weight 100 100 100 100 100 100 PS-A Parts by weight 20 10 40 100 180 0 YI 33 42 23 14 11 59 Flexural strength MPa 111 117 104 102 88 123 Ultra high Molecular polymer% 0.09 0.12 0.04 0.02 0.01 0.29 Cracking number 18 17 21 28 53 5 Comprehensive evaluation 〇〇〇〇Δ X

[Examples 21 to 22] In the same manner as in Example 1, except that PPE_C and PPE_G described in Table 5 were used instead of PPE-A, nine particles were obtained. The evaluation results are shown in Table 5. Verify that it is affected by the amount of terminal OH groups in the PPE. Table 5 Example 21 Example 22 PPE type PPE-C PPE-G PPE Parts by weight 100 100 PS-A Parts by weight 20 20 YI 33 32 Surface appearance of the plate 〇Δ Ultrahigh molecular polymer% 0.09 0.04 Cracking count 18 23 Comprehensive Evaluation 〇 △ [Examples 23 to 26] In Example 1, 'except for the take-up speed (Vs) of the strand, the rotational speed of the roller A in the circumferential direction (V〇, Vs/Vr ratio, and the strand cut temperature) (Example 26 is a method of extending the cooling bath to change the cooling conditions), and the pellets were produced in the same manner as in Example 1 except for the temperature shown in Table 6. -55 - 201215488 The results are not shown in Table 6. In the comprehensive evaluation of 6 , 〇 indicates that the nine grains are in good condition and the nine particles adhering to the dirt are within 5/20 kg, △ indicates that the nine-state state is △ or the nine particles adhering to the dirt are five/20 kg or more. The so-called nine-grain state △ indicates that the cut-off surface is not sharp and has some cracks. Table 6 Example 1 23 24 25 26 PPE Heavy View 100 100 100 100 100 PS-A Parts by Weight 20 20 20 20 20 Vs Meters/minute 18 18 18 18 18 Vr meters / minute 5 10 0 18 5 Vs / Vr 0.28 0.56 0.00 1.00 0.28 Strip cutting temperature °C 112 113 113 113 76 The state of the nine particles 〇〇〇〇Δ The amount of dirt attached to the mold mg 19 21 22 25 23 The amount of nine particles attached to the dirt 20kg 1 2 0 6 2 Ultra-polymer Polymer% 0.09 0.1 0.06 0.08 0.12 Cracking branch 27 24 28 29 22 Comprehensive evaluation 〇〇〇. Δ Δ [Example 2 7 to 3 2 ] &lt;Example of compression granulation &gt; Using Furukawa Otsuka Iron and Steel Co., Ltd. C-102A mixer, feeder rotation speed of 40 rpm, roll gap 2 mm, roller rotation number of 6 rpm, application roller support pressure (1.5 to 18 MPa) to compress PPE-D, to obtain a flat compress. The pelletizer HB 189 manufactured by Furukawa Otsuka Steel Co., Ltd. crushed the obtained flat-shaped compressed product at 65 Orpm to obtain compressed granules "Com-Dl to D5". The conditions and characteristics are as follows. 7. 80 parts by mass of the compressed granules, and 20 parts by mass of the above - 8 persons (average nine weights of 2311 Å, average particle diameter of 3.31111 Å (volume average particle diameter), apparent density 〇 .62g/cc) mixed with a drum for 5 minutes -56- 201215488 Moved the mixture to Kubota Co., Ltd. The twin-screw type 匣-type feeder CE-W-2 is fed from a twin-screw co-rotating extruder ΤΕΧ30α (length is L/D 52.5) made by Toshiba Machine Co., Ltd. at a speed of 40 kg / hr. The mixture was melt-kneaded by an extruder. The number of screw rotations of the extruder was set to 3 0 0 r p m. The screw structure is constituted by a screw having a kneading zone of RRRNNL, wherein R is an R kneading disc (the above (A)), N is an N kneading disc (the aforementioned (B)), and L is an L kneading disc (the aforementioned ( E)). The length L of each kneading disc was set to L/D = 1.0, and the total length of the kneading zone was set to L/D = 6.0. The melt was extruded by using a die having a pore size of 4 mm and a diameter of 5 mm to form a strand, which was cooled by a cooling water tank, and granulated by a granulator to obtain nine polyphenylene ether resin compositions. The extrusion was carried out for 1 hour, and nine samples were taken for evaluation after 30 minutes from the start of extrusion. In Example 30 and Example 3 2, since the feeding bottleneck occurred within 1 minute from the start, the discharge amount was reduced to 30 kg / hour and extruded. The obtained evaluation was carried out in the same manner as in the previous examples. Further, the pellets were discharged from the initial stage 5 minutes after the start of extrusion, and nine pellets were discharged at the later stage before the last minute of extrusion (nine pellets in the latter stage), and the degree of "gradation" of polystyrene was compared. The classification means that when PPE particles and ps particles having different particle diameters are mixed, phase separation is caused by applying vibration to a hopper of the extruder or the like.

S -57- 201215488 The phenomenon of large particles (currently PS particles) staying above the hopper, resulting in the initial outflow (initial extrusion) of the resin component and the late elution (post-extrusion) resin The phenomenon of different ingredients. The grading degree of styrene was determined by using a DCS (differential scanning calorimeter: SEIKO Electronics Industrial Co., Ltd., SSC/520 0) and comparing the glass transition temperatures. The glass transition temperature of the initial outflow of the nine particles in Example 27 was 18 7.5 degrees. The glass transition temperature of the nine particles flowing out in the later period was 18 7.3 degrees. The difference between the glass transition temperature of the initial outflow and the glass transition temperature of the later elution is 〇·2 °C. The glass transition temperature of the polyphenylene ether/polystyrene resin composition is determined by the ratio of the amounts. The glass transition temperature of the polyphenylene ether is 210 ° C, and the glass transition temperature of the polystyrene is 1 ° C, which is about the weight average enthalpy. The glass transition temperature difference is used as the classification degree of the polystyrene resin. The so-called °·2 °C difference indicates that the polyphenylene ether and the polystyrene have almost no classification (from the initial outflow to the late elution and uniform mixing). The other examples also evaluated the degree of classification of polystyrene. Further, the grading evaluation in Table 7 and Δ are judged on the basis of the following criteria. 〇: △ T is within ± 1 °C △ : ΔΤ is ±3. (: to the range of ±1 °C, in Example 31, the screw was stopped once in the twin-screw type bellows type feeder CE-W-2. The reason was that the polyphenylene ether was compressed and granulated. Among them, coarse and hard particles are caught between the screw and the cylinder wall to stop it. -58- 201215488 Table 7 Example Unit 27 28 29 30 31 32 PPE-D PPE-D PPE-D PPE-D PPE- D PPE-D Roller support pressure and density compactor Roller support pressure MPa 10 4 3 1.5 18 Ungranulated in the state of the original fine powder. Density g/cc 0.92 0.83 0.8 0.78 1.01 Average particle size after crushing mm 1.6 1.4 1.2 1 1.7 Apparent density g/cc 0.50 0.47 0.42 0.39 0.56 Compressive strength kg 2.3 0.7 0.3 0.05 4.5 Compressed granulated product name Com-Dl Com-D2 Com-D3 Com-D4 Com-D5 Extruded PPE content 100 100 100 100 100 100 PS volume 20 20 20 20 20 20 With or without feeding bottleneck fnrr· Pick / 1 \\ No feeding error with feeder Μ J k No M ^ \ w Μ j \ w Discharge volume kg/hour after feeding bottleneck - - - 30 - 30 PS classification degree ΔΤ (°〇0.2 0.1 0.3 1.1 0.2 1.8 tone YI 36 35 35 41 35 42 ultra-high polymer Polymer% 0.27 0.28 0.26 0.32 0.25 0.34 Cracking branch 16 17 14 15 16 15 Productivity 〇〇〇Δ Δ Δ Grading evaluation 〇〇〇Δ 〇Δ Hue 〇〇〇Δ 〇Δ Solvent resistance 〇〇〇〇 〇〇Comprehensive evaluation 〇〇〇Δ Δ Δ [Industrial use possibility] According to the method for producing a polyphenylene ether resin composition of the present invention, a polyphenylene ether resin and a polystyrene resin raw material can be produced at a high level. Efficiently producing a resin composition (nine particles) with no color reduction, no foreign matter due to charring, and improved solvent resistance (nine particles), since it can obtain a good quality molded article from the obtained nine particles, it can be applied to electrical and electronic equipment. , OA machines, information terminal equipment, home appliances, vehicle parts, lighting equipment, etc., are widely used in the industry. -59- 201215488 [Simplified illustration] Figure 1 shows that it is better used in The kneading disc of the extruder used in the present invention constitutes an example of a drawing. Fig. 2 is an explanatory view of a kneading disc which is preferably used in the extruder used in the present invention. Fig. 3 is a general explanatory view of the steps from the strand extrusion step used in the present invention to the step of reaching the strand cutter. Fig. 4 (a) and (b) are partial side views showing one embodiment of the guide rolls used in the strand transporting step. [Description of main component symbols] S-strand W Cooling medium 1 Discharge nozzle 2 Cooling medium tank 3,3 ′ Guide roller 4,4 5 Conveying roller 5 Granulator 3 1 Spindle 32 Groove -60-

Claims (1)

201215488 VII. Patent application scope: 1. A method for producing a polyphenylene ether resin composition, characterized in that: a polyphenylene ether resin and a polystyrene resin are kneaded in a molten state and then extruded to produce a polyphenylene ether. In the case of the resin composition, the polyphenylene ether resin is a polyphenylene ether resin containing a copper element derived from a catalyst component of 0.05 to 10 Ppm, and the polystyrene resin is used in an average particle diameter of 1 to 5 mm. It is a particle of 〇5 to 0.7 g/cm3, and the two resins are supplied to a length of 10 to 80 in terms of L/D, to a kneading zone of one or more, and a total L/D of 3 to 18 in the kneading zone. The twin-screw extruder is constructed and heated, melted, and kneaded to obtain an ultrahigh molecular weight polyphenylene having a polyphenylene ether resin having a polyphenylene ether resin content of 500,000 or more in an amount of 0.015 to 0.6 mass% in the resin composition. Resin composition. 2. A process for producing a polyphenylene ether-based resin composition according to the first aspect of the invention, wherein a polyethylene-based resin is blended in an amount by mass based on 100 parts by mass of the polyphenylene ether-based resin. 3. The method for producing a polyphenylene ether-based resin composition according to the second or second aspect of the invention, wherein the polyphenylene ether-based resin is 0.15 to 1.5 units per one terminal of the phenyl ether. 4. The method for producing a polyphenylene ether-based transverse product according to any one of claims 1 to 3, wherein the screw structure of the kneading zone of the extruder disposes the element for promoting kneading on the upstream side, and The boosting element g is disposed on the downstream side. In the case of adding, the polymer is apparently reduced by a screw to obtain the amount of the ether system. The composition of the fat is -6 1- 201215488 5 . As claimed in any one of claims 1 to 4 A method for producing a polyphenylene ether-based resin composition, wherein a polyphenylene ether-based resin composition is extruded into a strand shape by an extruder, moved in a cooling medium, and cooled, and cut by a strand When the machine is cut to obtain nine particles, the grooved guide roller is placed in the cooling medium, and the strand is wound in a state of being connected to the groove of the guide roller, and at the same time, the winding speed is taken. When Vs (cm/sec) is set and the moving speed of the outer peripheral surface of the guide roller connected to the strand is Vr (cm/sec), the winding speed, the moving speed, and the rotation direction of the guide roller are set as Meet the relationship of 〇.72Vr/Vsg-0.2. 6. A method of producing a polyphenylene ether-based resin composition according to claim 5, wherein the temperature of the strand is adjusted to 80 ° C to 160 ° C by cooling, and pelletizing is carried out in the temperature range. A molded article obtained by molding a polyphenylene ether-based resin composition obtained by the production method according to any one of claims 1 to 6. -62-