KR101437255B1 - Process for production of polyphenylene ether resin molded article - Google Patents

Abstract

(PROBLEMS TO BE SOLVED BY THE INVENTION) Provided is a method for producing a pellet having good color tone and no deterioration in physical properties from a polyphenylene ether-based resin and a polystyrene-based resin material at a high production efficiency.
(Solution) In the process of kneading a polyphenylene ether-based resin and a polystyrene-based resin in a molten state and then extruding them to obtain a polyphenylene ether-based resin molding (pellet)
1) As a polyphenylene ether-based resin
Wherein the solid content of the polyphenylene ether resin in the toluene concentration of 0.01 to 0.5% by mass is solidified by compression at a temperature not higher than Tg to obtain an average particle size of 0.1 to 10 mm obtained by pulverizing the solidified product, 0.35 to 0.7 g / cm < 3 > and a toluene concentration of 0.01 to 0.5% by mass,
2) particles having an average particle size of 1 to 5 mm and an apparent density of 0.5 to 0.7 g / cm 3 were used as the polystyrene type resin,
Which is then fed to an extruder, and heated, melted and kneaded, and extruded, thereby producing a polyphenylene ether resin molded article.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a process for producing a polyphenylene ether-

More particularly, the present invention relates to a process for producing a polyphenylene ether-based resin molding which is capable of producing a polyphenylene ether resin-based molding having a good color tone at a high production efficiency .

The polyphenylene ether resin is an engineering plastic excellent in heat resistance, electrical properties, and chemical resistance, but on the other hand, it has drawbacks that molding is difficult because of poor fluidity. The polyphenylene ether-based resin is usually in the form of a powder, which is disadvantageous in terms of moldability. For this reason, a material blended with a polystyrene-based resin for the purpose of improving the moldability, flowability and impact resistance of polyphenylene ether has been developed (refer to Patent Document 1) and is used in many fields as one of engineering plastics.

On the other hand, in the form of a raw material for molding processing, it is provided as a resin mass of small particles called pellets. When a polystyrene type resin is blended with a polyphenylene ether type resin to form a pellet, a polyphenylene ether type resin which has a high glass transition temperature and is hardly melted is added to a polystyrene type resin and, if necessary, an additive, The mixture is melted and kneaded in an extruder and extruded from a die portion at the extruder end as a molten resin on a strand. After cooling rapidly in a water bath or the like, the strands are cut by a pelletizer to form pellets.

However, when the polyphenylene ether resin powder is blended with a polystyrene-based resin and fed to an extruder for extrusion molding, air tends to enter with the powdered resin, and such air-containing powder slips on the screw conveying surface of the extruder The transfer from the screw becomes unstable, or the residence time in the extruder becomes long, so that the polyphenylene ether resin is easily oxidized and deteriorated.

In order to prevent oxidation deterioration, there is usually a method of adding an antioxidant to a raw material (see Patent Document 2), but the effect is not sufficient by itself and a method of supplying an inert gas such as nitrogen gas to an extruder 3) is also carried out, but the effect is insufficient simply by supplying the inert gas.

Particularly, since the polyphenylene ether-based resin has a high glass transition temperature (Tg: about 210 캜), it is required to increase the molding temperature, so that the polyphenylene ether-based resin tends to cause discoloration due to heat deformation. Even when a polystyrene- The problem of discoloration is a big problem.

In the case of using a powder product as it is as a polyphenylene ether resin as it is taken out from the polymerization apparatus, the powder product has a low apparent density in the form of powder, and when air is supplied to the extruder, air enters the feeder And the feed neck is liable to occur. Further, when the resin is melted in a kneading portion in a kneading disk portion or the like in the extruder, the air flows backward and the resin is prevented from being conveyed, thereby lowering the amount of extrusion, thereby causing a problem that the productivity is reduced at once.

Under these circumstances, development of a method for efficiently producing composition pellets from a polyphenylene ether-based resin and a polystyrene-based resin without causing color tone deterioration has been strongly desired.

U.S. Patent No. 3383435 Japanese Patent Application Laid-Open No. 2003-246865 Japanese Patent Laid-Open Publication No. H06 (1995) -206216

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a polyphenylene ether resin molded article which can produce a polyphenylene ether resin-based molded product having a good color tone with high production efficiency, in view of the problems of the prior art.

In order to achieve the above object, in order to achieve the above object, the inventors of the present invention have analyzed in detail the phenomenon at the time of melt-kneading and, as a result of intensive studies, have found that a powdery product having a specific toluene concentration as a polyphenylene ether- Resin particles having a specific particle diameter and a specific apparent density and a specific toluene concentration obtained by crushing the solidified material as required and resin particles having a specific average particle diameter and apparent density as a polystyrene resin are used, And they are supplied to an extruder and heated, melted, kneaded and extruded to solve the above-mentioned problems, thereby completing the present invention.

As used herein, the term " particle " means a small-diameter particle called granule, pellet or the like and close to the density of the material. It may also mean minute particles of fine particles.

The term " granular material " means particles in the form of particles, but solidified by pressing the powder, and particles having a larger porosity in the particles than pellets or the like.

In the present specification, the term " molded product " means a so-called molded product or a molded product obtained by extruding from a screw extruder or the like, followed by cooling and solidification. Specifically, it is represented by strands and pellets, and means various forms depending on the application such as a film, a sheet, and a conventional body.

That is, according to the first invention of the present invention, in the process of kneading a polyphenylene ether-based resin and a polystyrene-based resin in a molten state, followed by extrusion molding to obtain a polyphenylene ether-

1) As the polyphenylene ether-based resin,

A solid of 0.01 to 0.5 mass% in a toluene concentration in a polyphenylene ether resin is compressed at a temperature not higher than the glass transition temperature Tg to solidify the solid, and the solidified product is pulverized as necessary to obtain an average particle size of 0.1 to 10 mm, A granular material having a density of 0.35 to 0.7 g / cm 3 and a toluene concentration of 0.01 to 0.5% by mass was used,

2) particles having an average particle size of 1 to 5 mm and an apparent density of 0.5 to 0.7 g / cm 3 were used as the polystyrene type resin,

Which is then fed to an extruder and heated, melted and kneaded and extruded.

According to the second invention of the present invention, in the first invention, the particulate material of the polyphenylene ether-based resin has a compressive strength of 40 g to 4 kg, Is provided.

According to a third aspect of the present invention, in the first or second aspect of the present invention, the particulate material of the polyphenylene ether-based resin contains 0.05 to 10 ppm of copper element A method for producing a resin molding is provided.

According to a fourth aspect of the present invention, there is provided a process for producing a polyphenylene ether-based resin molded article, characterized in that the copper element is derived from a polymerization catalyst of a polyphenylene ether-based resin in the third invention do.

According to a fifth aspect of the present invention, in any one of the first to fourth inventions, the polyphenylene ether-based resin particulate material and the polystyrene-based resin are melted and kneaded in an extruder to obtain a polymer having a molecular weight of 500,000 or more in an amount of 0.015 to 0.6 mass % Based on the total weight of the polyphenylene ether-based resin molded article.

According to a sixth aspect of the present invention, in any one of the first to fifth inventions, the polyphenylene ether-

The content of the granular material having a diameter of 1000 mu m or more is 50% or more,

The content of particles having a diameter of 10 to 100 占 퐉 in the granular material is 3 to 40%

And a content of particles having a diameter of 10 mu m or less of the granular material is 2% or less.

According to a seventh aspect of the present invention, in the sixth aspect, the polyphenylene ether resin particulate material containing 3 to 40% of particles having a particle diameter of 10 to 100 탆 has an average particle diameter of 10 to 100 By weight based on the total weight of the polyphenylene ether-based resin molded article.

According to an eighth aspect of the present invention, there is provided a process for producing a polyphenylene ether-based resin molded article, wherein the polystyrene-based resin particles are pellets in any one of the first to seventh inventions.

According to a ninth aspect of the present invention, in any one of the first to eighth aspects, the polystyrene type resin particle is used in an amount of 5 to 150 parts by mass based on 100 parts by mass of the polyphenylene ether type resin particulate material By weight based on the weight of the polyphenylene ether-based resin.

According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the polyphenylene ether-based resin is a polyphenylene ether-based resin having a number of terminal hydroxyl groups per 100 phenylene ether units of 0.15 to 1.5 A method for producing a phenol resin-based resin molding is provided.

According to an eleventh invention of the present invention, in any one of the first to the tenth inventions, the polyphenylene ether resin composition is extruded from a extruder into a strand, To obtain a pellet which is a molded product,

The guide roller is installed in the cooling medium,

The strands are brought into contact with the guide rollers,

When the take-in speed is Vs (cm / sec) and the moving speed of the outer circumferential surface of the guide roller contacting the strands is Vr (cm / sec)

And the rotation speed of the guide roller is determined so as to satisfy the relationship 0.7? Vr / Vs? -0.2.

According to a twelfth aspect of the present invention, in the eleventh aspect, the polyphenylene ether-based resin molded article is characterized in that the temperature of the strand is adjusted to 80 캜 to 160 캜 by cooling and cutting is performed in this temperature range Is provided.

According to a thirteenth aspect of the present invention, there is provided a polyphenylene ether-based resin molded article produced by any one of the methods of any one of the first to twelfth aspects, which comprises a polyphenylene ether-based resin containing 0.015 to 0.6% of an ultrahigh molecular weight polymer having a molecular weight of 500,000 or more A molding is provided.

According to the production method of the polyphenylene ether resin molded article of the present invention, the obtained pellets have good color tone, feedability to the extruder of the raw material is good, feed neck is not generated at the time of extrusion molding, Segregation), and the rubber stamp (extruded gum-like material during forming) formed during extrusion molding does not adhere well to the pellets, and the polyphenylene ether-based resin molding is subjected to high extrusion , It is possible to produce it with high production efficiency.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a general explanatory diagram of steps from a strand extrusion step to a strand cutter used in the present invention.
2 is a partial side view showing one embodiment of a guide roller used in a strand transporting step.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and the present invention may be arbitrarily changed without departing from the gist of the present invention .

The present invention relates to a method for producing a polyphenylene ether resin molded article by melt kneading a polyphenylene ether resin and a polystyrene resin and extrusion molding,

A granular material having a solidified average particle diameter of 0.1 to 10 mm, an apparent density of 0.35 to 0.7 g / cm 3 and a toluene concentration of 0.01 to 0.5% by mass is obtained by compressing the polyphenylene ether resin particle at a temperature not higher than Tg,

Particles having an average particle diameter of 1 to 5 mm and a bulk density of 0.5 to 0.7 g / cm 3 are used as the polystyrene-based resin.

In the present specification, the term " molded article " is sometimes referred to as " pellet " or " composition pellet ". This is because the present invention is mainly used for producing raw pellets for molding polyphenylene ether- It should be interpreted that the "molded article" is represented as a representative one.

Hereinafter, the present invention will be described in detail.

(1) Polyphenylene ether resin

The polyphenylene ether-based resin used in the present invention is a polymer having a structural unit represented by the following general formula (1) in its main chain, and may be either a homopolymer or a copolymer.

[Chemical Formula 1]

R ¹ represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, an alkoxy group or a haloalkoxy group, R ^{2 may be the same or different,} Represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, an alkoxy group or a haloalkoxy group, provided that when two R ^{1 s taken} together are a hydrogen atom However,

In the general formula (1), when R ¹ is a halogen atom, a chlorine atom or a bromine atom is preferable. In the general formula (1), when R ¹ is a primary alkyl group, preferred examples are a methyl group, an ethyl group, a n-propyl group, an n-butyl group, An alkyl group having 1 to 10 carbon atoms such as an n-hexyl group, a 2,3-dimethylbutyl group, a 2-, 3- or 4-methylpentyl group, or a heptyl group. Preferable examples of when R ¹ is a secondary alkyl group are alkyl groups having 4 to 10 carbon atoms, such as isopropyl, sec-butyl or 1-ethylpropyl. A preferred example of the case where R ¹ is an aryl group is a phenyl group, and a preferable example of the aminoalkyl group is an alkylamino group having an alkyl chain having 1 to 5 carbon atoms, such as a dimethylamino group, a diethylamino group and a dibutylamino group. As a preferable example of R ² being a haloalkyl group, preferred examples of the alkyl group include groups in which at least one hydrogen atom of each of the above-mentioned groups is substituted with a halogen atom. Preferable examples of the alkoxy group include an alkoxy group corresponding to each of the above-mentioned groups as a preferable example of the alkyl group, and examples of the haloalkoxy group include groups in which at least one hydrogen atom in the alkoxy group is substituted with a halogen atom have. As R ¹ , a hydrogen atom, a primary or secondary alkyl group or an aryl group is preferable.

In the general formula (1), preferred examples of when R ² is a primary or secondary alkyl group, an aryl group, a haloalkyl group, an alkoxy group or a haloalkoxy group include the same groups as those of R ¹ .

In the present invention, roneun R ¹ and R ^2, a hydrogen atom, a primary or secondary alkyl group, and aryl groups are preferred and, R ¹ is an alkyl group or a phenyl group more preferred, and an alkyl group having from 1 to 4 carbon atoms, particularly preferably, R ² is more preferably a hydrogen atom.

The polyphenylene ether-based resin in the present invention is preferably a polyphenylene ether-based resin represented by the general formula (1) in order to control the molecular weight or to improve various properties such as melt viscosity and impact strength, May include a repeating unit other than the structure showing the structure.

Preferred polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether) (2-ethyl-6-methyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), etc. Of homopolymers of 2,6-dialkylphenylene ether.

Further, a copolymer of 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3 , 6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer, and other 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers are also preferable . Further, a styrene graft copolymer obtained by graft-polymerizing styrene on poly (2,6-dimethyl-1,4-phenylene ether), a graft copolymer obtained by grafting styrene onto a 2,6-dimethylphenol / 2,3,6- A graft copolymer obtained by polymerization is also preferable.

Of these polyphenylene ether resins, poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer are particularly preferable.

The molecular weight of the polyphenylene ether resin is preferably 0.2 to 0.8 dl / g, more preferably 0.3 to 0.6 dl / g, as measured in chloroform at 30 캜. When the resin has an intrinsic viscosity of less than 0.2 dl / g, mechanical strength tends to be lowered when a molded article is produced using the obtained resin composition. On the contrary, when the amount of the resin is larger than 0.8 dl / g, the fluidity of the resin composition is deteriorated and molding processing becomes difficult. The polyphenylene ether resin may be used in combination of two or more kinds, and in that case, the polyphenylene ether resin may be mixed with the different intrinsic viscosity to obtain a desired intrinsic viscosity.

The polyphenylene ether resin used in the present invention is preferably polyphenylene ether in which the number of terminal hydroxyl groups is in the range of 0.15 to 1.5 per 100 phenylene ether units. If the amount of the terminal hydroxyl groups is less than 0.15 with respect to 100 phenylene ether units, compatibility with the styrene type resin is lowered, resulting in appearance defects when molded into a molded product, and the color tone is deteriorated in a high temperature atmosphere There are also cases. On the other hand, when the number exceeds 1.5, the thermal stability tends to deteriorate. More preferably, the number of terminal hydroxyl groups is 0.2 to 1.3 per 100 phenylene ether units.

Specific examples of the unit having a terminal hydroxyl group include a 3,5-dimethyl-4-hydroxyphenyl group, a 3,5-diethyl-4-hydroxyphenyl group, a 3,5- Methyl-5-ethyl-4-hydroxyphenyl group, 3-methyl-5-propyl-4-hydroxyphenyl group and 2,3,5-trimethyl-4-hydroxyphenyl group. In polyphenylene ethers having less than 0.15 hydroxyl groups on end, the compatibility with the styrene type resin is lowered, resulting in poor appearance and layer delamination of the molded article, and further, the elongation at break and the surface impact strength are likely to decrease . In addition, since the thermal stability in a high-temperature atmosphere is lowered, the color tone is liable to deteriorate.

A method of obtaining a polyphenylene ether resin having a number of terminal hydroxyl groups of 0.15 or more is described in Japanese Patent Publication No. 61-20576. For example, 2,6-dimethylzylenol is reacted with a cuprous salt Amine is oxidized and polymerized in the presence of oxygen in a solvent such as toluene as a catalyst and the compound is added to the resulting polyphenylene ether solution to form a chelate compound with copper, By stirring the polyphenylene ether solution under an atmosphere in which mixing of the polyphenylene ether solution is avoided.

It is known that the method for preparing the terminal hydroxyl group is known and varies depending on the conditions for polymerizing the phenolic compound and the quinone reaction after the polymerization is terminated. In general, the quinone compound is added to the polyphenylene ether obtained by polymerization To conduct quinone reaction to increase the concentration of hydroxyl groups.

2) Polystyrene resin

Examples of the polystyrene-based resin used in combination with the polyphenylene ether resin include a polymer of a styrene-based monomer, a copolymer of a styrene-based monomer and another copolymerizable monomer, and a styrene-based graft copolymer.

The polystyrene type resin used in the present invention means a polymer or copolymer containing 50 mass% or more of repeating units derived from an aromatic vinyl compound, or a polymer in which these polymers are rubber-modified.

Examples of the aromatic vinyl compound include styrene and alpha-alkyl substituted styrene such as alpha -methylstyrene, p-methylstyrene, o-ethylstyrene, vinyltoluene, o- or p-dichlorostyrene, have.

Examples of the monomer other than the aromatic vinyl compound include vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and ethacrylonitrile; vinyl cyanide compounds such as methyl, ethyl, propyl, n-butyl and n-hexyl of acrylic acid and methacrylic acid Maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, acrylamide compounds such as acrylamide and N-methylacrylamide, maleic anhydride compounds such as maleic anhydride , Unsaturated acid anhydrides such as itaconic anhydride, unsaturated acids such as acrylic acid and methacrylic acid, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, And various vinyl compounds such as methoxypolyethylene glycol methacrylate.

Specific examples of the polystyrene-based resin include polystyrene, acrylonitrile-styrene resin (AS resin), and methyl methacrylate-styrene resin (MS resin). The weight average molecular weight of the styrene type resin (B) 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 And more preferably not more than 300,000.

The styrene type resin used in the present invention may be one obtained by modifying the various polymers described above with rubber, and examples of the rubber include polybutadiene, styrene-butadiene copolymer, polyisoprene, and ethylene-propylene copolymer have. Specific examples of the rubber-modified polystyrene (HIPS resin), acrylonitrile-butadiene-styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin) (AES resin) and the like.

As the styrene-based resin, polystyrene and rubber-modified polystyrene (HIPS resin) are preferable from the viewpoint of compatibility with a polyphenylene ether-based resin. Particularly, when impact resistance is required, rubber-modified polystyrene is more preferable.

In the present specification, the styrene resin may be abbreviated as " PS ".

(3) Polyphenylene ether-based resin granules and polystyrene-based resin particles

In the process for producing the pellets of the present invention, it is preferable that the polyphenylene ether resin as the polyphenylene ether resin is solidified by compressing the dispersoid having a toluene concentration of 0.01 to 0.5% by mass at a temperature not higher than Tg, (Volume average particle diameter) of 0.1 to 10 mm, an apparent density of 0.35 to 0.7 g / cm 3, and a toluene concentration of 0.01 to 0.5% by mass.

On the other hand, as the polystyrene type resin, particles having an average particle diameter (volume average particle diameter) of 1 to 5 mm and an apparent density of 0.5 to 0.7 g / cm 3 are used. These particles were obtained by pelletizing by a conventional method, that is, by melt-kneading polystyrene with an extruder, extruding it into a strand shape, and cutting it to a length of about several millimeters by a pelletizer. As the polystyrene type resin particles, those having an average particle diameter of 1 to 5 mm and an apparent density of 0.5 to 0.7 g / cm 3 are preferably used in terms of balance with the polyphenylene ether type resin particulate material.

When a molded product (pellet) of a polyphenylene ether-based resin composition is produced by extrusion molding, if the concentration of toluene in a polyphenylene ether-based resin (hereinafter also referred to as PPE) is excessively high, The color tone becomes worse. The supply of the PPE raw material is carried out by supplying the PPE powder to the screw feeder in the resin supply portion of the extruder, but the powder of the PPE exhibits the appearance and behavior as wheat flour and the like, It is difficult to introduce it into the screw of the extruder. On the other hand, being a solid pellet of the PPE feedstock is liable to remain trapped between the feeder screws or the extruder cylinder inner wall, sometimes causing the feeder to stop. This phenomenon is the same even when the screw feeder is a single shaft or a double shaft.

In the present invention, by adjusting the toluene concentration of the PPE raw material in the range of 0.01 to 0.5 mass%, the bonding (fusion) between the powders of the PPE is enhanced and the poor solidification (passing through the solidified powder without solidification) can do.

The adjustment of the toluene concentration can be carried out by adding toluene to the PPE of the dispersion and adjusting the concentration of the toluene to 0.01 to 0.5% by mass. Specifically, it is possible to add the PPE dispersion and the required amount of toluene to the mixer and mix them. The PPE is usually produced by a polymerization reaction in a toluene solvent. After removing a solvent such as toluene or a low molecular weight through a washing step, the PPE is taken out from the polymerization apparatus as a powder, . However, the amount of toluene may be adjusted so that the concentration of toluene falls within the range specified in the present invention by controlling the degree of washing in the washing step.

In the present invention, the PPE powder having the toluene concentration is solidified by compression at a temperature not higher than the Tg of the PPE, and the resulting solidified product is pulverized as required to obtain a powder having an average particle diameter of 0.1 to 10 mm and an apparent density of 0.35 to 0.7 g / cm < 3 > and a concentration of toluene in the range of 0.01 to 0.5% by mass.

The compression of the PPE slurry is carried out at a temperature of not more than Tg so that the PPE does not have a temperature higher than Tg. The preferable temperature is not lower than 0 deg. C to less than Tg, more preferably about 0 to 200 deg. Any method of compression can be employed. As a simple method, a roll pressing method in which a PPE dispersed body is passed between a pair of press rolls opposed to each other can be mentioned. The pressing roll may be a roll having a smooth surface, or may be a roll having an embossed surface, a hole, a dent, or the like.

When a roll having a smooth surface or an embossing roll is used, the PPE powder is in the form of a plate or sheet, but it may be pulverized to a desired particle size. In the case of using a roller having a hole or an indentation, it is also possible to directly obtain a granular material having a desired particle size by adjusting the size of the hole or indentation to a desired size.

The gap between the rolls is preferably about 1 to 3 mm and the number of revolutions of the roll is preferably about 2 to 20 rpm. The supporting pressure of the pressing roll is preferably about 0.5 to 20 MPa, more preferably about 2 to 15 MPa. It was confirmed that the hardness of the granular material obtained varies depending on the strength of compression.

At this time, the hardness of the particulate material obtained varies depending on the concentration of toluene in the PPE powder, but when the toluene concentration is within the range of 0.01 to 0.5 mass%, the behavior of the PPE powder is stable and a granular material having no hardness unevenness is obtained.

Further, by providing a PPE granular material having a toluene concentration within a range of 0.01 to 0.5% by mass to the extrusion molding, the color tone of the polyphenylene resin molding after extrusion molding becomes good. The reason for this is not clear. However, when toluene is volatilized in the extruder, the components likely to be thermally degraded are removed by azeotropic distillation, or toluene is present in the gaseous phase to lower the oxygen concentration in the gaseous phase, And the possibility that the deterioration is suppressed. When the toluene concentration exceeds 0.5% by mass, the color tone deteriorates. The feed neck is liable to be generated, and the supply of the resin to the extruder becomes unstable.

As the shape of the solidified product, various forms of solidified product are obtained depending on the use of the apparatus other than the roller, such as the surface shape and structure of the roller used, the presence or absence of pulverization, and the like. For example, it may be in the form of a flat plate (circular, square, etc.), columnar (circumferential, circumferential, etc.), spherical, cylindrical, flake, chipped, indefinite, It does not matter. In addition, they may be mixed together, and powder or the like may be included.

In the present invention, as the particulate material of PPE obtained by compression and solidification at Tg or lower, an average particle diameter of 0.1 to 10 mm and an apparent density of 0.35 to 0.7 g / cm3 is used.

When the average particle diameter or apparent density of the solidified material obtained by the above-mentioned compression is larger than the above range, the particle size or the apparent density is adjusted by crushing.

Examples of the shape of the granular material include a spherical shape, a flat shape (circular, square, etc.), a columnar shape (columnar shape, a columnar shape, etc.), a cylindrical shape, a chipped shape, , Its shape, and its shape.

When the average particle diameter of the granular material is less than 0.1 mm, introduction into the feeding zone at the time of extrusion molding is bad, air is mixed, and the feed neck is easily generated. When the average particle diameter is more than 10 mm, the polystyrene- Is too large in diameter and is classified when it is supplied to the extruder, making it difficult to uniformly mix and there are many problems in handling. The preferred average particle diameter of the PPE particulate material is 0.1 to 10 mm.

The apparent density of the granular material is required to be 0.35 to 0.7 g / cm 3. When it is less than 0.35 / cm 3, the granular material contains a large amount of air, that is, it is too soft. Therefore, when it is put into an extruder, it easily collapses to be different from the case of using the powder of PPE. If it exceeds 0.7 g / cm < 3 >, the time of melting in the extruder becomes excessively slower than the melting point of the polystyrene type resin particles with which the coexisted polystyrene type resin particles are melted. Thus, only the dispersion failure or polystyrene type water is melted to cause slippage on the surface of the screw, ≪ / RTI > The preferable apparent density is 0.37 to 0.68 g / cm3, more preferably 0.39 to 0.66 g / cm3. Since the typical density of PPE is about 1.1 g / cm 3, it means that the volume is increased in the present invention, that is, a void is formed to some extent in the particle.

The PPE granular material preferably has a compressive strength of 40 g to 4 kg. If the compressive strength is less than 40 g, the granular material is broken when the feed material is screwed into the extruder from the feeder, and the feed neck is easily generated. When the compressive strength exceeds 4 kg, There is a tendency that the granular material is caught between the screw thread and the inner wall to stop the screw. The preferred compressive strength is 500 g to 3 kg, more preferably 1 kg to 3 kg.

By setting the compressive strength of the PPE granular material within this range, it is considered that the timing and balance of melting with the polystyrene type resin particles which are coexisting are improved.

That is, PPE (Tg: 210 占 폚) having a high Tg is used as a compacted solid which is liable to collapse to some degree, and a polystyrene type resin (Tg: 100 占 폚) When the PPE granular material is collapsed and fed to the screw, the polystyrene-based resin particles (pellets) are melted from the outer surface thereof when they are mixed and fed to the extruder by using particles (pellets) Mixed with PPE.

By such a mixing state, it is considered that PPE and PS having a difference in melting temperature (melting point in the extruder) are in a good commercial state.

Therefore, it is meaningful to make the polystyrene-based resin into particles (pellets) and to use PPE as a powder compacted solidified material which is relatively easily pulverized.

When the both resins are melt kneaded in an extruder, the polymerization catalyst is preferably present in PPE in an amount of 0.05 to 10 ppm as a copper element. The polymerization catalyst can be present by allowing the catalyst subjected to the polymerization of PPE to remain to a certain extent, but the polymerization catalyst may be added after the PPE.

Although it is known that the catalyst for oxidative polymerization of PPE is a metal compound such as copper, manganese, cobalt or the like, the catalyst which is actually industrially used is mainly an amine compound such as copper chloride and an alkylamine compound, a base such as pyridine , A so-called copper amine complex catalyst, a copper chloride / pyridine catalyst, and the like.

Generally, it is important to remove the polymerization catalyst by washing after the completion of the polymerization, or to inactivate the polymerization catalyst to lose its activity, in order to prevent discoloration and deterioration of the resin.

For this reason, although it is generally desired to avoid the presence of the polymerization catalyst as an active uppermost layer, it is meaningful to keep the polymerization catalyst in an active state in the present method. That is, a polymerization catalyst is present, and PPE and PS are kneaded in a molten state to produce a polymer having a high molecular weight (ultrahigh molecular weight) well.

The ultrahigh molecular weight polymer has a molecular weight of about 10 to 10 million. Normally, it is about 20 to 5 million.

Conventionally, this ultrahigh molecular weight polymer is externally added to PPE. For example, Japanese Patent Application Laid-Open No. 2009-255585 discloses a polypropylene resin which is excellent in productivity during extrusion molding, has good surface smoothness and good appearance, Etc. are mixed and used.

However, such ultrahigh molecular weight polyethylene or the like tends to become a lump when added externally, and it tends to be a surface defect called so-called fish eye, ruggedness, and the like.

It is an object of the present invention to provide a polyolefin resin composition which is excellent in dispersibility (dispersed state) in which PPE and PS are not easily added to PPE, Molecular weight polymer (resin) can be present.

The reason for the presence of the polymerization catalyst in the PPE is that it facilitates the production of an ultrahigh molecular weight polymer. The amount of the polymerization catalyst present in the PPE varies depending on the kind of the catalyst, but is 0.05 to 10 ppm as the copper element (metal component).

Although the polymerization catalyst has been described above, a part of the polymerization catalyst of PPE may be left as it is as it is, or it may be added later.

Although the polymerization catalyst has been described above, a copper chloride / base catalyst is generally used, and therefore the amount of the copper element has a meaning as the amount of the polymerization catalyst present, or the amount of the component derived from the polymerization catalyst. In the case where the amount of the copper element is understood as the amount of the polymerization catalyst present, the amount of the copper element only represents the amount of copper in the catalyst component.

The amount of the copper element may vary depending on the amount of the ultrahigh molecular weight polymer to be produced, but it is usually sufficient to leave (add) 0.05 to 1 ppm as the copper element. However, in some cases, a relatively large amount of 1 to 10 ppm is retained (added) as the copper element, so that the production of the ultrahigh molecular weight polymer is stable and may be preferable in use. It may be appropriately selected depending on the use of the resin, the intended product, and the like.

The amount of the copper element can be adjusted by adjusting the washing degree of the catalyst removal or adjusting the amount of the deflocculating agent for deactivating the catalyst in order to leave the catalyst at the time of polymerization of the PPE, The excessive residual portion of the material causes discoloration or the like, and therefore, it is necessary to pay sufficient attention.

For convenience, a predetermined amount of copper compound (polymerization catalyst) may be added to the PPE from which the catalyst has been removed.

0.05 to 10 ppm of a polymerization catalyst is present as a copper element, and PPE and PS are kneaded in a molten state in an extruder to produce an ultrahigh molecular weight polymer having a molecular weight of 100,000 or more.

Generally, a molecular weight of 100,000 to 10,000,000 or more is referred to as an ultrahigh molecular weight polymer. However, since an amount of an ultrahigh molecular weight polymer having a molecular weight of 500,000 or more is used as a standard of a person skilled in the art, And the amount of

Generally, the amount of the ultrahigh molecular weight polymer (with a reference of 500,000 or more) varies depending on the amount of the polymerization catalyst, the kneading conditions, and the like, but it is usually about 0.015 to 0.6 mass% with respect to the total amount of PPE and PS.

The preferable range of the copper element is 0.1 to 9 ppm, more preferably 0.2 to 8 ppm.

The present inventor believes that the production of ultrahigh molecular weight polymer is mainly attributable to the fact that PPE is polymerized (crosslinked) to give an ultrahigh molecular weight polymer. However, the present inventors believe that the cross-condensation between the PPE molecules via the amino- And the molecular weight is increased as a result of the above-mentioned method. Although the cause of the cause is not sufficient, an ultrahigh molecular weight polymer is produced.

Needless to say, the internally generated ultrahigh molecular weight polymer is good in dispersibility, and it is less likely to cause ruggedness and surface defects called agglomerates. Further, since the polymerization is carried out in an extruder, the entanglement property to the screw is improved and the extrusion efficiency is improved.

It is also conceivable that the terminal OH concentration of the PPE is 0.15 to 1.5 PPE per 100 polyphenylene ether units, thereby favorably producing an ultrahigh molecular weight polymer.

The production amount of the ultrahigh molecular weight polymer having a molecular weight of 500,000 or more was determined as follows.

20 mg of the pellets are dissolved in 20 ml of chloroform and then filtered with a filter having a mesh interval of 0.45 占 퐉 to remove large particles such as agglomerate resin and solid inclusion which are not caught by GPC. The solution having passed through the filter was measured by GPC as described below, and the amount of the ultrahigh molecular weight polymer of 500,000 or more was determined, and the ratio of the original pellet to the mass was determined.

Gel Permeation Chromatography (GPC)

Apparatus: HPLC8020 manufactured by TOSOH Corporation

Column: TSK G5000HHR + G3000HHR

Solvent: chloroform

Detector: UV 283 nm

Pretreatment: 20 mg of the sample was dissolved in 20 ml of a chloroform solvent, and the solution was then filtered through a 0.45 micron filter. The column temperature was 40 캜.

Calculation of molecular weight: Calculated in terms of polystyrene, standard polystyrene was used to prepare calibration curve.

The molecular weight of standard polystyrene was 264, 364, 466, 568, 2800, 16700, 186000, 1260000.

It is also conceivable that crosslinking of the PPE molecules progresses before the PPE is commercialized in the polystyrene and the ultrahigh molecular weight component is formed by making the solid PPE granule by raising the roll supporting pressure and melting and kneading the PPE granule in an extruder. It is believed that there is a range of ultrahigh molecular weight, which is prone to ruggedness under the conditions of ultrahigh molecular weight.

Further, the PPE particulate material preferably has the following characteristics: 1) the content of particles having a particle diameter of 1000 占 퐉 or more is 50% or more; 2) the content of particles having a particle diameter of 10 to 100 占 퐉 is 3 to 40%; and 3) Or less is preferably within 2%.

With such a particle size constitution, the dispersibility of the powder additive can be improved. That is, the powder additives are usually used in the form of particles having an average particle diameter of about 10 to 100 탆. When these powder additives are directly added to the PPE granules and PS particles, they are classified from the differences in particle diameters, (Granular body) and a disperse body, uniform mixing is not carried out, and a molded article having a homogeneous composition can not be obtained.

However, when 3 to 40 mass% of particles having a particle diameter of 10 to 100 占 퐉 are present as the PPE particulate material, the powder additive is mixed well with the PPE of the particle diameter, and as a result, the PPE particulate material is easily dispersed uniformly throughout the composition.

Therefore, when a powder additive is to be added to the present composition, it is preferable to use PPE having a particle diameter distribution as described above.

On the other hand, as the polystyrene-based resin to be mixed with the PPE granules, particles having an average particle diameter of 1 to 5 mm and an apparent density of 0.5 to 0.7 g / cm 3 are used. By mixing such polystyrene particles with the above PPE granules, they can be uniformly dispersed and mixed to be prevented from being unevenly distributed in classification at the time of molding.

The polystyrene type resin has a lower softening point than the polyphenylene ether type resin and has a lowered heat resistance. However, by introducing the particles having such a particle diameter and the apparent density into the extruder, good and uniform melt kneading is carried out, deterioration of the polystyrene type resin, It is considered that the effect of preventing discoloration is also exhibited. The polyphenylene ether-based resin and the polystyrene resin are compatible with each other in the whole composition, but the above-described ones are used in order to homogeneously mix the polyphenylene ether-based resin and the polystyrene resin. If the polystyrene type resin particle is out of the average particle diameter of 1 to 5 mm and the apparent density of 0.5 to 0.7 g / cm 3, a situation where feed neck is generated and can not be supplied easily occurs, and the color tone is deteriorated by heat generation. The preferable average particle diameter of the polystyrene-based resin pellets is 1 to 4 mm in consideration of the good dispersibility of the polyphenylene ether-based resin powder and the thermal behavior in the extruder.

As such polystyrene type resin particles, it is preferable to use pellets.

The average particle size in the present invention is defined as a volume average measured by a laser diffraction particle size distribution measuring apparatus. In the present invention, measurement was carried out using a wet method (solvent: isopropyl alcohol) using "Laser Micron Sizer LMS-2000e," a laser diffraction scattering type particle size distribution measuring apparatus manufactured by Seishin Enterprise Co. Ltd.

The apparent density is obtained by dividing the mass (g) by the apparent volume (cm 3) (in g / cm 3) from the bulk density measurement specified in JIS K5101 (stationary method, no short filter is used).

The mixing ratio of the polyphenylene ether-based resin particulate material to the styrene-based resin particle is preferably 5 to 150 parts by mass based on 100 parts by mass of the polyphenylene ether-based resin particulate material. If the amount of the polyphenylene ether-based resin component is small, heat resistance and mechanical strength of the molded article are insufficient. On the other hand, if the amount is too large, the fluidity is deteriorated and molding of the thin molded article becomes difficult. When the blending amount of the polystyrene type resin is less than 5 parts by mass, the color tone of the resin composition deteriorates, while when it exceeds 150 parts by mass, heat resistance and impact resistance are lowered. A more preferable blending amount is 10 to 120 parts by mass, particularly 15 to 90 parts by mass.

(4) Additives

In the present invention, other components may be added to the polyphenylene ether-based resin and the styrene-based resin, if necessary.

Examples of the other components include flame retardants, weatherability improvers, foaming agents, lubricants, flow improvers, impact resistance improvers, dyes, pigments, fillers, reinforcing materials and dispersants.

As the flame retarder, a phosphorus-based flame retardant, preferably a phosphazene-based compound, a phosphate-based compound, and a condensed phosphate ester are blended.

Examples of the phosphazene compound include a cyclic phenoxyphosphazene compound, a chained phenoxyphosphazene compound, and a crosslinked phenoxyphosphazene compound.

Examples of the phosphate flame retardant include triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, diphenylcresyl phosphate, tributyl phosphate and the like have.

Examples of the condensed phosphate ester flame retardant include phenylresorcinol polyphosphate, cresylresorcinol polyphosphate, phenyl cresylresorcinol polyphosphate, xylyl resorcinol polyphosphate, phenyl-p-tert -Butylphenyl-resorcin-polyphosphate, phenyl-isopropylphenyl-resorcinol-polyphosphate, cresyl-xylyl-resorcinol-polyphosphate, phenylisopropylphenyldiisopropylphenylresorcinphosphate, etc. As a preferable example.

In addition, it is also possible to use at least one selected from the group consisting of phenyl · bisphenol · polyphosphate, cresyl · bisphenol · polyphosphate, phenyl · cresyl · bisphenol · polyphosphate, xylyl · bisphenol · polyphosphate, phenyl -p-tert-butylphenyl · bisphenol · polyphosphate, Preferred examples include isopropylphenyl bisphenol polyphosphate, cresyl xylyl bisphenol polyphosphate, phenyl isopropylphenyl diisopropylphenyl bisphenol polyphosphate and the like.

Specific examples of phosphorus-based flame retardants include, for example, "TPP" (triphenylpostate), "CR733S" (resorcinol bis (diphenylphosphate)) of Daihachi Chemical Indusrty Co., ADK STAB FP700 " (ADK STAB FP700) from ADEKA Corporation, " CR741 " (bisphenol A bis (diphenylphosphate)) and PX200 (resorcinol bis (Bisphenol A bis (diphenylphosphate)) can be preferably used.

Examples of the filler and the reinforcing material include organic or inorganic fillers, organic or inorganic reinforcing materials and the like. Specific examples thereof include glass fibers, mica, talc, wollastonite, potassium titanate, calcium carbonate and silica. The combination of the filler and the reinforcing material is effective in improving rigidity, heat resistance, dimensional accuracy, and the like. The mixing ratio of the filler and the reinforcing material is preferably 1 to 80 parts by mass, and more preferably 5 to 60 parts by mass, based on 100 parts by mass of the total of the resin components.

(5) Production of resin pellets

Hereinafter, one embodiment of the method for producing the pellet of the present invention will be described, but the present invention is not limited to the following embodiments.

(i) A PPE particle having a toluene content adjusted to 0.01 to 0.5% by mass is compressed using a press roll or the like, and if necessary, ground with a granulater or the like to obtain a powder having a predetermined average particle diameter and apparent density, In addition, a specific toluene content of PPE granular material is used.

(ii) mixing the PPE granular material with polystyrene type resin particles having a predetermined average particle diameter and apparent density by a mixer such as a tumbler, and charging the mixture into a feeder of, for example, a biaxial screw type, From which it is fed to the extruder. It is preferable that inert gas is supplied from the raw material supply port. The inert gas is a gas inert to PPE such as nitrogen gas or argon gas, and usually nitrogen gas is used.

The additives may be added to the mixer, or may be added by installing a side feeder in the middle of the extruder barrel.

(iii) In the extruder cylinder, the screw is arranged so as to be freely rotatable, and smooth transportation of the resin raw material is carried out, followed by mixing and further melting, and finally, extruded from the discharge nozzle onto the strand. The set temperature and time in the extruder can be arbitrarily selected depending on the resin composition and the type of the extruder. Usually, the kneading temperature (set temperature) is 200 to 350 占 폚, preferably 220 to 320 占 폚, Or less. If it exceeds 350 占 폚 or more than 3 minutes, it is difficult to prevent thermal degradation of the polyphenylene ether-based resin or the styrene-based resin, and the physical properties and appearance are liable to be deteriorated.

It is preferable that a decompression vent is formed in the extruder, and the toluene contained in the PPE granule is always volatilized toward the exhaust port in the vent portion to generate the accompanying airflow, whereby other volatile components or the like are condensed or sublimed It is possible to produce pellets of a thermoplastic resin composition having excellent quality because the entanglement of the thermoplastic resin composition with the thermoplastic resin composition can be suppressed.

The degree of vacuum in the vent 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, toluene is sufficiently removed from the bent portion, which does not adversely affect the resin and the like, which is preferable.

(iv) The melt-kneaded composition is extruded from a discharge nozzle provided at the tip of a kneading extruder into a string called a strand. The shape of the die of the discharge nozzle is not particularly limited, and a known die is used. The diameter of the discharge port of the discharge nozzle may vary depending on the extrusion pressure and the dimensions of the desired pellet, but is usually about 2 to 10 mm.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram schematically showing a configuration related to a process up to processing of strands extruded from a discharge nozzle into pellets. FIG.

2 is a partial side view showing one embodiment of a guide roller used in the strand transporting step.

The strands S are taken by the drawing rollers 4 and 4 'and cut into pellets by the pelletizer 5. In the conveying path before being supplied to the pelletizer 5 It is usual to cool down. Specifically, as shown in Fig. 1, the water is cooled in a cooling medium (normally water) W which is stored in the cooling tank 2 and is conveyed. In order to reduce the deterioration of the resin, it is preferable that the time from when the strand S is extruded from the discharge nozzle 1 to when it enters the cooling medium W is short. Normally, it is preferable to enter the cooling medium 93 within 1 second after being extruded from the discharge nozzle 1. [

Therefore, it is preferable to convey the recording medium from the discharge nozzle 1 to the cooling medium W at the shortest distance. Also, it is preferable to transport the cooling medium W so that the cooling time is long. In order to realize a conveying path satisfying such conditions, guide rollers 3 and 3 'are generally formed in the conveying path of the strand S. [ The diameter of the guide rollers 3 and 3 'is usually about 3 to 7 cm.

(v) It is possible to remove the rubber stamp attached to the surface of the strand S by using the guide rollers 3 and 3 '.

Specifically, at least one of the guide rollers 3 and 3 'is rotated in the direction (b) opposite to the running (conveying) direction a of the strand S, or the traveling speed of the strand 5 (Or may be kept in a non-rotating state) in the same direction as the running direction a of the strand S at a main speed slower than that of the strand S.

The guide rollers 3 and 3 'have a cylindrical shape in which the rotation direction is generally a direction intersecting with the running direction of the strand S, and a plurality of strands S are extruded in parallel so that the strand S is conveyed in a desired conveying path. (S) on the cylindrical surface.

2 (a), on the circumferential roller surface of the main shaft 31 of the guide rollers 3 and 3 ', a plurality of annular (ring-shaped) grooves 32 are arranged in the circumferential direction . The grooves 32 receive and support the running strands S to prevent the strands S at the approaching positions from being contacted and fused.

It is preferable that the width of the groove 32 is slightly wider than the thickness of the strands S and the bottom of the groove 32 has an arc shape in order to stably support the groove 32. [ The depth of the normal groove 32 is usually 2 mm to 10 mm. The diameter of the rollers 3 and 3 'is usually about 3 to 7 cm.

The pitch of the grooves 32 (the spacing of the adjacent grooves 32) is normally set to the spacing of the strands S (the spacing of the discharge nozzles 1 of the die). Although the pitch varies depending on the diameter of the strand S, it is 5 mm to 20 mm. The number of grooves 32 may be equal to or greater than the number of strands to be extruded.

One or a plurality of guide rollers 3, 3 'are formed at the strand traveling position of the cooling bath 2. In the case of a plurality of cooling rollers 3 and 3 ', the cooler 2 running between the guide rollers 3 and 3' is run and cooled.

The guide rollers 3 and 3 'are rotatably supported in the same direction as the running direction a of the strand S in the reverse direction b or the running direction a and may be rotatably supported. By supporting the guide rollers 3 and 3 'so that the moving (rotating) speed of the grooves 32 of the guide rollers 3 and 3' is relatively slow relative to the running (conveying) speed of the strand S, The surface of the strand S is rubbed on the surface where the strands S come into contact with the strands S and the rubbers adhered to the surface of the strand S can be rubbed and removed. When a plurality of guide rollers are formed, the surface of the strand S may be rubbed in at least one of them.

In order to rotate the guide rollers 3 and 3 'in the direction (a) opposite to the running direction (a) of the strand S, a driving device may be formed on the guide rollers 3 and 3'. In this case, if the resistance between the strands S and the surfaces of the grooves 32 is excessively large, the running of the strands S may become unstable, so that the amount of rotation of the strands S is determined within a stable range.

When the guide rollers 3 and 3 'are rotated in the same direction as the running direction (a), a driving device may not be formed. It is sufficient to impart a certain degree of resistance to rotate the guide rollers 3 and 3 'at least to such a degree as not to rotate at the same main speed as the strand S due to the frictional force of the running strand S . The guide rollers 3 and 3 'rotate following the running of the strand S but are rotated later than the running speed of the strand S by the applied resistance, It is possible to rub the surface of the strand S at the surface of the strand S. Although it is possible to form the driving device, unlike the case of the reverse rotation, the configuration for giving resistance to rotation is simple.

As described above, the strand S is in contact with the surface of the guide rollers 3 and 3 'while traveling in the cooling medium W, and the traveling speed of the strand S and the rotation of the guide rollers 3 and 3' The surface of the strand S is rubbed at the surface of the groove 32 by the difference of the speed (the main speed), and the rubber stamp attached to the surface of the strand S is removed. Further, even if there is a groove-less guide roller, the strands are rubbed on the surface of the guide roller, so that there is some degree of gumming removal effect.

This effect is not obtained when the guide rollers 3 and 3 'are rotated at the same main speed as the running speed of the strand S. When the traveling speed of the strand S and the main speed of the guide rollers 3 and 3 'are substantially the same, not only the surface of the strand S is rubbed but also the surface of the groove 32 It is conceivable that the rubber stamp is attached to the strand or is buried.

The speed Vr of the rotation (peripheral speed of the outer peripheral surface) of the guide rollers 3 and 3 'is preferably 0.7? Vr / Vs? -0.2 with respect to the speed Vs of the strand. The upper limit is more preferably 0.5? Vr / Vs, and the lower limit is more preferably Vr / Vs? 0. Vs can be obtained at the pulling speed of the strand S and Vr is determined at the number of revolutions per minute (radius-groove depth of the guide rollers 3, 3 ') x 2 pi x 1 minute. When Vr / Vs is positive, the guide rollers 3 and 3 'rotate in the same direction as the strand running direction a, and when they are negative, the guide rollers 3 and 3' Is rotated in the strand traveling direction (a) and the reverse direction (b).

One or a plurality of guide rollers 3 and 3 'are formed in the cooling bath 2. In a plurality of guide rollers 3 and 3', all the guide rollers 3 and 3 'need not be rotated as described above, In the medium 2, it is effective for the rubber roller to remove the guide roller (3 in Fig. 1) closest to the discharge nozzle 1 (die).

(vi) The strands S are sent from the draw rollers 4 and 4 'to the pelletizer 5 and cut into pellets. The cutting is preferably performed when the strand temperature is in the range of 80 to 160 캜, particularly 90 to 140 캜.

This temperature can be measured by a noncontact type thermometer. The measurement can be conveniently carried out by piercing a pellet in a pouch or a container holding the pellet cut by the cutter.

The pellets obtained by the method of the present invention can be obtained by a molding method commonly used for polyphenylene ether resins such as injection molding, injection compression molding, blow molding, extrusion molding, sheet molding, thermoforming, rotational molding, Or the like, and is molded into an arbitrary shape to be used as a molded article.

Examples of the molded article include electric and electronic devices, OA devices, information terminal devices, machine parts, household appliances, automobile parts, building members, various containers, leisure goods, miscellaneous goods, lighting devices and the like. Among these, it is preferable to be used particularly in parts such as electric and electronic devices, OA devices, information terminal devices, household appliances, vehicle parts, and lighting devices.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[1. Measurement and evaluation method]

In the following Examples and Comparative Examples, the measurement and evaluation methods are as follows.

(1) Average Particle Diameter and Particle Size Distribution:

The measurement was carried out by a wet method (isopropyl alcohol solvent) using "Laser Micron Sizer LMS-2000e", a laser diffraction scattering type particle size distribution measuring apparatus manufactured by Seishin Enterprise Co. Ltd., a particle size analyzer of laser diffraction / scattering method Respectively. The volume average particle diameter was defined as an average particle diameter (占 퐉).

(2) Apparent density

In accordance with JIS K5101, the filter was not used in the static method and was measured.

(3) Toluene concentration:

2 g of a polyphenylene ether resin was dissolved in 10 ml of chloroform and then precipitated with methanol. The supernatant was analyzed by gas chromatography to obtain a toluene concentration (%).

(4) Hue:

The color tone of the pellets obtained in Examples and Comparative Examples was measured with a colorimeter "Spectro Color Meter S2000" manufactured by Nippon Sanso Co., Ltd. The hue YI value was determined.

(5) Compressive strength:

PPE particles with a particle size of 1 to 2 mm were placed on the balance, and the load at which fracture occurred was taken as the compressive strength, and an average value of 20 times of measurement was obtained.

(6) Intrinsic viscosity of PPE:

0.5 g of polyphenylene ether as a solution was dissolved in chloroform so as to have a concentration of not less than 100 ml (concentration not more than 0.5 g / dl), and the specific viscosity at 30 캜 was measured at different concentrations using a Uberoté type viscometer, Extreme viscosity is calculated by extrapolating the ratio of the viscosity to the concentration to zero.

(7) Kind and number of terminal groups of PPE:

¹³ C-NMR spectroscopy The absorption spectrum was measured with JNM-A400 manufactured by Nippon Denshi KK and using CDCl ₃ as a solvent and the tetramethylsilane as a standard. The measurement mode was measured as a ¹³ C-NMR complete decoupling mode, Macromolecules, 1990, Vol. 23, pp. 1318-1329, the kind and number (number per 100) of the hydroxyl group terminal were determined.

(8) Glass transition temperature (Tg) of PPE:

Using a DSC 220 U thermo analyzer manufactured by Seiko Instruments Inc., the temperature was raised from 25 ° C to 250 ° C at a rate of 20 ° C / min, and the glass transition temperature was determined from the pole point.

(Example 1)

(1) Production of polyphenylene ether (PPE-G)

In a 300 liter reactor equipped with a sparger and stirrer turbine blades and baffles for introducing oxygen-containing gas to the bottom of the reactor, and a reflux condenser attached to the bottom of a vent gas line at the top of the reactor for separating the condensate, 42.5 (DB), 1257.6 g of N, N-methyl-n-butylamine (BD), 102.4 (g) of copper oxide, 255.7 g of a 47% aqueous solution of hydrogen bromide, 495.8 g of N, g of N, N'-di-t-butylethylenediamine (Dt), 30.0 g of trioctylmethylammonium chloride (TOM) and about 83 kg of toluene. Then, nitrogen was introduced into the gaseous phase portion of the reactor, and the absolute pressure of the gaseous phase portion of the reactor was controlled to 0.108 MPa.

Subsequently, a gas obtained by diluting oxygen with nitrogen and having an absolute pressure of 0.108 MPa and an oxygen concentration of 70% was introduced from the sparger, and nitrogen was introduced into the gas phase portion of the reactor, including during polymerization, The control valve was controlled so that the absolute pressure of the gas phase portion of the reactor was maintained at 0.108 MPa. The introduction rate of the gas was 103.5 Nl / min. Immediately after the initiation of the introduction of the gas, the addition of 33,000 g of 2,6-dimethylphenol dissolved in 34,878 g of toluene was initiated at a rate of 30 minutes using the plunger pump at a rate that the entire amount was completely charged. The polymerization temperature was controlled by passing the heating medium through the jacket so as to maintain the temperature at 40 占 폚.

At about 140 minutes after the start of gas introduction, nitrogen was introduced into the reaction vessel, and 15,000 g of an aqueous solution containing 5% of sodium ethylenediaminetetraacetate (EDTA4 sodium) was added to the reaction solution and stirred. Thereafter, stirring was continued for 2 hours while controlling the temperature of the reaction solution to 70 캜 with heating medium.

After stirring was stopped, the aqueous solution separated by standing still was discharged out of the system, 7,500 g of pure water was further added to the reaction solution, stirred for 10 minutes, allowed to stand for 10 minutes, and then the separated aqueous layer was discharged out of the system.

Thereafter, almost isocratic methanol was added to the obtained reaction solution to precipitate polyphenylene ether. The precipitate of PPE was filtered, and the polyphenylene ether was washed with an appropriate amount of methanol four times and then dried at 140 ° C for about 2 hours to obtain a powdery polyphenylene ether (hereinafter abbreviated as "PPE-G" ).

The evaluation results of the obtained polyphenylene ether (PPE-G) are as follows.

Intrinsic viscosity: 0.48 dl / g

Terminal hydroxyl group content: For 100 phenylene ether units, 0.45

Average particle diameter: 90 占 퐉

Toluene concentration: 0.0083% (83 ppm)

Copper element content: 0.1 ppm

Apparent density: 0.34 g / cm < 3 >

Toluene was added to the PPE-G so that the toluene content in the powder was 1,000 ppm (0.1% by mass) (in this toluene, cupric bromide and dibutylamine were mixed in a ratio of 1: 10 by mass, 3.9 ppm, and added to the residual catalyst at the time of PPE production to 4.0 ppm with respect to PPE) and mixed with a three-hands mixer to obtain a polyphenylene ether resin (PPE-A).

PPE-A was compressed using a C-102A compactor manufactured by Furukawa Otsuka Steel Co. under the conditions of feeder rotation speed of 40 rpm, roll gap of 2 mm, roll rotation number of 6 rpm, roll support pressure of 7 MPa, ≪ / RTI >

The obtained plate-like compact was crushed at 650 rpm with a granulator HB189 manufactured by Furukawa Otsuka Steel Corporation to obtain a pressed granulated product "Com-A1". The toluene concentration of Com-A1 was 970 ppm. The apparent density was 0.50 g / cm 3.

The particle size distribution of ComA-1 was measured. The particle size distribution (wet method) was determined by a laser diffraction scattering type particle size distribution analyzer (LMS-2000e manufactured by Seishin Enterprise Co., Ltd.) for a particle size distribution of 1 mm or more using a mesh of 1 mm or more and for a size of 1 mm or less. The particle size distribution was as follows.

1 mm or more 73.1%

100 탆 to 1 탆 17.1%

10 mu m to 100 mu m 9.5%

10 μm or less 0.3%

                              Total 100.0%

The average particle diameter (volume average) was 1.5 mm.

(Preparation of pellets)

100 parts by mass of the compacted assembly Com-A1 and a polystyrene pellet HT478 (hereinafter referred to as "PS-A" manufactured by A & M Styrene Co., average pellet weight: 23 mg, Volume average particle diameter: 3.3 mm, apparent density: 0.62 g / cc) were mixed in a tumbler for 5 minutes.

The mixture was transferred to a twin screw type cassette weighing feeder CE-W-2 manufactured by Kubota Corporation and fed to a twin screw extruder TEM37BS manufactured by Toshiba Machine Co. at a feed rate of 60 kg / hr , And the mixture was melt-kneaded with an extruder. The number of screw rotations of the extruder was 400 rpm.

The kneaded melt was extruded using a die having a pore size of 4 mm and a diameter of 5 mm to form a strand shape. The kneaded melt was cooled in a cooling water bath and cut with a pelletizer to obtain a polyphenylene ether resin composition pellet. In the meantime, there was no extrusion of 1 hour, but the feed neck (the phenomenon in which the feed to the extruder was not sufficiently sent by the screw, and was deposited) was stable and the extrusion was stable. The pellets after 30 minutes of initiation of extrusion were used as evaluation pellets. The amount of the ultrahigh molecular weight polymer (molecular weight of 500,000 or more) in the pellets was 0.07% by mass.

The pellets were dried at 120 DEG C for 4 hours and molded into a sheet having a size of 100 mm in length x 100 mm in width x 100 mm in a cylinder temperature of 290 DEG C and a mold temperature of 100 DEG C using an injection molding machine SH100 manufactured by Sumitomo Heavy Industries Co., A molded article having a thickness of 2 mm was molded, and a color tone yellow index (YI value) was measured. The YI value was 34.

Further, the stick around the die nozzle (the 5th hole) generated during the extrusion for 1 hour was collected and the weight was measured to be 39 mg. The strands were cooled at a speed of 34 m / min in a water bath so as to cover two rolls A and B in the cooling water tank. At this time, the rotational speed of the roll A in the circumferential direction was 4 m / min. The ratio of the circumferential speed of the roll to the strand speed was 0.12. The distance between the rolls A and B was adjusted, and the strand temperature entering the pelletizer was cut to 117 캜. The cutting surface was clean, and a pellet of good shape was obtained. Only one pellet with a rubber stamp was found in 60 kg of the obtained pellets.

The obtained pellets were dried at 120 DEG C for 4 hours, and a test piece was produced using ISO Mold Type A using an injection molding machine SH100 manufactured by Sumitomo Heavy Industries, Ltd. (ISO3167, ISO294-1).

Test of chemical resistance: 0.5% of bending was applied to the surface of the test piece, and the number of cracks per one test piece was counted after immersing in a mixed solution of isopropanol and n-hexane at a weight ratio of 1: 1 at 23 캜 for 1 hour. The smaller the number, the better the chemical resistance.

The evaluation results are shown in Table 1.

It is considered that the ultrahigh molecular weight component having a molecular weight of 500,000 or more forms a highly entangled structure, and the chemical resistance is improved.

(Example 2)

Toluene (without addition of a catalyst component) was added to PPE-G in toluene so that the concentration of toluene in the powder was 1,000 ppm and mixed with a three-hands mixer to obtain a polyphenylene ether resin (PPE-B) composition ≪ / RTI > Pellets were prepared in the same manner as in Example 1 except that PPE-A was changed to PPE-B obtained in Example 1.

The obtained compression assembly was regarded as Com-B1. The evaluation results are shown in Table 1.

(Example 3)

In the same manner as in Example 1 except that a toluene solution (in which toluene was previously mixed with cupric bromide and dibutylamine in a weight ratio of 1 to 10 in such a manner that the content of toluene in the powder was 1,000 ppm (0.1 mass%) in PPE-G, Was added so as to be 1.9 ppm relative to PPE as an element, and added to the PPE in terms of PPE in combination with the remaining catalyst in the production of PPE). The resulting mixture was mixed with a three-hands mixer to obtain a polyphenylene ether resin. This PPE was called " PPE-C ".

Pellets were obtained in the same manner as in Example 1 except that PPE-C was used.

The obtained compression assembly was regarded as Com-C1. The evaluation results are shown in Table 1.

(Example 4)

In the same manner as in Example 1 except that a toluene solution (in which toluene was previously mixed with cupric bromide and dibutylamine in a weight ratio of 1 to 10 in such a manner that the content of toluene in the powder was 1,000 ppm (0.1 mass%) in PPE-G, Was added so as to be 7.9 ppm relative to PPE as an element, and 8.0 ppm of PPE was added to the residual catalyst in the production of PPE), and the mixture was mixed with a three-hands mixer to obtain a polyphenylene ether resin. This PPE was called " PPE-D ".

Pellets were obtained in the same manner as in Example 1 except that PPE-D was used.

The obtained compression assembly was designated as Com-D1. The evaluation results are shown in Table 1.

(Example 5)

A polyphenylene ether resin was obtained in the same manner as in Example 1 except that a toluene concentration of 500 ppm (0.05 mass%) and a copper element content of 4 ppm were used instead of PPE-A .

The obtained PPE was referred to as " PPE-E ".

Pellets were obtained in the same manner as in Example 1 except that PPE-E was used.

The obtained compression assembly was designated Com-E1. The evaluation results are shown in Table 1.

(Example 6)

A polyphenylene ether resin was obtained in the same manner as in Example 1, except that the toluene concentration was changed to 3,000 ppm (0.3 mass%) instead of PPE-A and the copper element content was 4 ppm. .

The obtained PPE was referred to as " PPE-F ".

Pellets were obtained in the same manner as in Example 1 except that PPE-F was used.

The obtained compression assembly was Com-F1. The evaluation results are shown in Table 1.

(Comparative Example 1)

A pellet was produced in the same manner as in Example 1, except that PPE-A was used instead of Com-A1 as it was (without compressing with a compactor and being powdered).

The results are shown in Table 1.

(Comparative Example 2)

Except that the polyphenylene ether resin (PPE-G) obtained in Example 1 was changed to a toluene concentration of 6,000 ppm (0.6 mass%) and a copper element content of 4 ppm instead of PPE-A , And Example 3, pellets were produced. The obtained compression assembly was defined as Com-G1.

The results are shown in Table 1.

(Comparative Example 3)

Pellets were prepared in the same manner as in Example 1 except that PPE-H was used instead of PPE-A. The obtained compression assembly was regarded as Com-H1.

The results are shown in Table 1.

In addition, the comprehensive evaluations? And? In Table 1 were judged based on the following criteria.

?: Discharge rate of 50 kg / hr or more, color tone YI of less than 40, and crack number of less than 40

X: The discharge amount was less than 50 kg / hr, or the color tone YI was 40 or more

(Examples 6 to 11)

Pellets were produced in the same manner as in Example 1 except that the supporting pressure of the compact roll was changed as shown in Table 2 below.

The results are shown in Table 2.

In Example 11, Com-A8 of the compression assembly was sandwiched between a screw and a wall of a twin-screw type cassette weighing feeder to stop the screw and to stop the feeder twice. The reason is that the assembly was too hard. Thus, the compression assembly has an appropriate hardness.

In Table 2,?,?, And X of the comprehensive evaluation were determined based on the following criteria.

?: Discharge rate of 50 kg / hr or more, color tone YI of less than 40, and crack number of less than 40

△: feeder abnormality or crack number of 40 or more

X: The discharge amount was less than 50 kg / hr, or the color tone YI was 40 or more

(Example 12)

100 parts by mass of the compression assembly Com-A1 of PPE-A, 20 parts by mass of polystyrene resin pellets PS-A, 0.5 parts by mass of zinc oxide powder (manufactured by Honjo Chemical Co., average particle diameter 0.6 占 퐉), talc And 20 parts by mass of "Talcan PKC" (trade name, manufactured by Hayashi-kasei Co., average particle diameter: 12 μm) were mixed in a blend tumbler in the same manner as in Example 1, and melt-kneaded in the same manner as in Example 1. Five minutes after the start of extrusion, the pellets of the fresh-flow pellet and the pellet of the last one minute before extrusion (sampled) were sampled to compare the degree of classification of polystyrene, zinc oxide, and talc.

The degree of classification of the polystyrene was determined by comparing the glass transition temperature of the pellets using DSC (differential scanning calorimeter: SSC / 5200 manufactured by SEICO Electronics industrial Co.). The glass transition temperature of the fresh-flow pellet was 189.3 degrees. The glass transition temperature of the wake was 189.1 degrees. The difference between the glass transition temperature of the supernatant and the glass transition temperature of the wake was 0.2 ° C. The glass transition temperature of the polyphenylene ether / polystyrene resin composition is determined by their ratio. The glass transition temperature of polyphenylene ether is 210 DEG C and the glass transition temperature of polystyrene is 100 DEG C, which is almost a weight average value. The glass transition temperature difference was defined as the degree of classification of the polystyrene resin. 0.2 ° C indicates that polyphenylene ether and polystyrene are almost not classified (mixed uniformly from the stream to the wake).

In addition, the zinc absorption intensity of the fresh-flow pellet / the zinc absorption intensity of the wake of the downstream pellet was classified as zinc oxide by comparing the absorption intensity of zinc with the fluorescent purity of the fresh-flow pellet and the downstream pellet.

Similarly, the value of the absorption intensity of the fluorescent pseudo-pellet silicon of the fluorescent X-ray / the absorption intensity of silicon of the wake pellet was regarded as the classification degree of the talc.

The classification ratio of zinc oxide was 1.02, and the classification ratio of talc was 1.03. From these results, it was found that classification hardly occurred.

The results are shown in Table 3.

(Example 13)

Except that the compression assembly Com-A1 of PPE-A (with a compactor roll pressure of 10 MPa) was changed to a compression assembly Com-A6 (with a compactor roll pressure of 3 MPa) in Example 11 In the same manner as in Example 11, pellets were produced. The particle size distribution of Com-A6 was as follows.

1 mm or more 61.7%

100 탆 to 1 탆 12.6%

10 mu m to 100 mu m 24.5%

10 μm or less 1.2%

                     Total 100.0%

The results are shown in Table 3.

(Example 14)

The procedure of Example 11 was repeated except that the compression assembly Com-A1 of PPE-A was changed to compression assembly Com-A7 (compactor roll pressure 1.5 MPa) having the following particle size distribution, . The particle size distribution of Com-A7 was as follows.

1 mm or more 53.7%

100 탆 to 1 탆 13.2%

10 mu m to 100 mu m 31.3%

10 μm or less 1.8%

                     Total 100.0%

The results are shown in Table 3.

(Example 15)

Same as Example 11, except that the compression assembly Com-A1 of PPE-A was changed to a compression assembly Com-A1X having the following particle size distribution obtained by cutting 100 μm or less from Com-A1 in Example 11 To prepare pellets.

1 mm or more 86.2%

100 μm to 1 mm 12.1%

10 mu m to 100 mu m 1.7%

10 μm or less 0.0%

                  Total 100.0%

The results are shown in Table 3.

(Comparative Example 4)

Pellets were prepared in the same manner as in Example 11 except that the compression assembly Com-A1 of PPE-A was changed to PPE-A. The particle size distribution of PPE-A was as follows.

1 mm or more 2.1%

100 mu m to 1 mm 35.3%

10 mu m to 100 mu m 56.2%

10 μm or less 6.4%

                   Total 100.0%

The results are shown in Table 3.

(Comparative Example 5)

Pellets were prepared in the same manner as in Example 11, except that the polystyrene PS-A was changed to PS-B (PS-B having an average particle diameter of 80 탆) of PS-A.

The results are shown in Table 3.

In addition, the classification evaluations?,?, And? In Table 3 were determined based on the following criteria.

∘: ΔT is within ± 1 ° C and the classification ratio of additive is within 1.1

Δ: ΔT is in the range of ± 3 ° C. to ± 1 ° C., or the classification ratio of the additive is in the range of 1.2 to 1.1

X: A range where ΔT is ± 3 ° C. or more, or the classification ratio of the additive exceeds 1.2

(Examples 16 to 19 and Comparative Example 6)

The procedure of Example 1 was repeated except that the ratio of PPE-A to PS-A was changed to that shown in Table 4 below.

The results are shown in Table 4.

The flexural strength was measured in accordance with ISO 178 using an injection molding machine SH100 manufactured by Sumitomo Heavy Industries, Ltd., and ISO test specimens were molded according to ISO 3167 at a cylinder temperature of 290 캜 and a mold temperature of 100 캜.

In addition, the comprehensive evaluations?,?, And? In Table 4 were judged based on the following criteria.

?: YI value less than 40, bending strength not less than 100 MPa

?: YI value of less than 40, bending strength of less than 100 MPa, or cracks of 40 or more

X: YI value of 40 or more

(Example 20)

[(1) Production of polyphenylene ether (PPE-I)

The condenser was connected in two stages in a polymerization reactor equipped with an air inlet tube. The temperature of the condenser was adjusted by flowing a refrigerant so that the temperature of the condenser was about 0 ° C, and the toluene phase of the liquid from the can was continuously returned to the polymerization reactor. 23,500 g of 2,6-dimethylphenol was dissolved in 59,400 g of toluene while 220 g of cupric bromide, 4,000 g of dibutylamine and 98,000 g of toluene were fed with air at a rate of 10 NL / min per 1 kg of monomer The solution was added dropwise over 60 minutes and polymerization was carried out at 40 占 폚.

After 120 minutes of monomer dropping, the reaction was stopped by adding an aqueous solution of EDTA tetra sodium to the catalyst copper in an amount 1.5 times the molar amount (the amount of aqueous solution was 0.2 times by mass with respect to the total amount of the polymerization reaction solution) while stirring.

After the stirring was stopped, the separated aqueous solution was discharged to the outside of the system. Further, 5,500 g of pure water was added to the reaction solution and stirred for 10 minutes. After standing for 10 minutes, the separated aqueous layer was discharged to the outside of the system. The same operation was repeated. That is, secondly, an aqueous solution of EDTA 4 sodium dissolved in a 0.5-fold molar amount of catalytic copper (the amount of aqueous solution was 0.2 mass times as much as the total amount of the polymerization reaction solution) was added to the reaction solution while stirring.

Thereafter, 6000 g of pure water was added to the reaction solution and stirred for 10 minutes. After standing for 10 minutes, the separated aqueous layer was discharged outside the system. Methanol was added to the reaction solution so that polyphenylene ether was precipitated. The precipitate of PPE was filtered, and further polyphenylene ether was washed four times with an appropriate amount of methanol, followed by rapid drying at 140 ° C for 2 hours to obtain the following powdery polyphenylene ether (hereinafter abbreviated as "PPE-HI" ) Was obtained.

Intrinsic viscosity: 0.48 dl / g

Terminal Hydroxyl Content: For 100 phenylene ether units, 0.12

Average particle diameter: 85 占 퐉

Toluene concentration: 95 ppm

Copper element content: 0.3 ppm

Apparent density: 0.34 g / cm < 3 >

In the same manner as in Example 1, toluene was added to PPE-I so that the toluene content in the powder was 1,000 ppm (0.1 mass%) and the copper element content was 4 ppm, and the mixture was mixed with a three-hands mixer , And a compression assembly "Com-I1" was obtained in the same manner as in Example 1. Com-I1 had an average particle diameter of 1.6 mm, an apparent density of 0.50, a compressive strength of 2.2 kg, and a toluene concentration of 960 ppm.

In addition,

1 mm or more 69.7%

100 탆 to 1 mm 18.5%

10 mu m to 100 mu m 11.2%

10 μm or less 0.6%

                   Total 100.0%

Respectively.

In the same manner as in Example 1, pellets were produced. The results are summarized in Table 5 and in Example 1. [

In addition, the number of terminal hydroxyl groups of PPE-A in Example 1 was 0.45 / 100. In Example 20 in which the number of terminal hydroxyl groups was less than 0.15 / 100, the appearance of the plate surface was slightly fogged in light. And the compatibility with polystyrene is slightly lowered.

In the evaluation of appearance of the plate surface in Table 5, " Good " indicates " Good "

(Examples 21 to 24)

Pellets were produced in the same manner as in Example 1, except that the pulling speed (Vs) of the strand and the moving speed (Vr) of the outer circumferential surface of the guide roller were changed as shown in Table 6 in Example 1.

Extrusion from the extrusion nozzle was carried out for 2 hours, and the sticks adhered to the nozzle were collected and weighed. In addition, the number of pellets (number of pellets / 60 kg) to which the rubber stamp was attached was measured in the pellets obtained from extrusion for 2 hours.

The results are shown in Table 6.

In addition, the comprehensive evaluations? And? In Table 6 were judged based on the following criteria.

○: Good pellet condition, less than 5 pellets with rubberized pellets / less than 60 kg

[Delta]: When the pellet state is not so good or when the pellets with rubberized pellets are 5 pellets / 60 kg or more

Industrial availability

INDUSTRIAL APPLICABILITY According to the method for producing a polyphenylene ether resin composition pellet of the present invention, it is possible to produce pellets having good color tone and no deterioration in physical properties from polyphenylene ether resin powder and polystyrene resin raw material with high production efficiency, The obtained pellets can be used in a wide range of fields such as electrical and electronic equipment, office automation equipment, information terminal equipment, household appliances, automobile parts, lighting equipment, and the like.

S: Strand
1: Discharge nozzle
2: cooling medium tank
3, 3 ': guide roller
4, 4 ': conveying roller
5: Pelletizer
32: Home

Claims (13)

In the case of kneading a polyphenylene ether-based resin and a polystyrene-based resin in a molten state and then extruding them to obtain a polyphenylene ether-based resin molded article,
1) As the polyphenylene ether-based resin,
Wherein the polyphenylene ether resin is solidified by compressing the polyphenylene ether resin with a toluene concentration of 0.01 to 0.5% by mass at a temperature not higher than the glass transition temperature Tg, and the solidified material is pulverized to obtain an average particle diameter of 0.1 to 10 mm, 0.7 g / cm < 3 > and a toluene concentration of 0.01 to 0.5% by mass,
2) particles having an average particle size of 1 to 5 mm and an apparent density of 0.5 to 0.7 g / cm 3 were used as the polystyrene type resin,
And the mixture is fed to an extruder and heated, melted and kneaded and extruded. The method according to claim 1,
Wherein the granular material of the polyphenylene ether-based resin has a compressive strength of 40 g to 4 kg. 3. The method according to claim 1 or 2,
Wherein the particulate material of the polyphenylene ether-based resin contains 0.05 to 10 ppm as a copper element. The method of claim 3,
Wherein the copper element is derived from a polymerization catalyst of a polyphenylene ether-based resin. 3. The method according to claim 1 or 2,
Wherein the polyphenylene ether resin particulate material and the polystyrene resin are melted and kneaded in an extruder to produce 0.015 to 0.6 mass% of a polymer having a molecular weight of 500,000 or more. 3. The method according to claim 1 or 2,
The polyphenylene ether-based resin particulate material,
The content of the granular material having a diameter of 1000 mu m or more is 50% or more,
The content of particles having a diameter of 10 to 100 占 퐉 in the granular material is 3 to 40%
Wherein the content of particles having a diameter of 10 mu m or less is 2% or less. The method according to claim 6,
Characterized by adding a powdery additive having an average particle diameter of 10 to 100 占 퐉 to a polyphenylene ether resin particulate material containing 3 to 40% of particles having a particle diameter of 10 to 100 占 퐉 (2). 3. The method according to claim 1 or 2,
Wherein the polystyrene-based resin particles are pellets. 3. The method according to claim 1 or 2,
Wherein the polystyrene-based resin particles are used in an amount of 5 to 150 parts by mass based on 100 parts by mass of the polyphenylene ether-based resin particulate material. 3. The method according to claim 1 or 2,
Wherein the polyphenylene ether-based resin has a number of terminal hydroxyl groups per 100 phenylene ether units of 0.15 to 1.5. 3. The method according to claim 1 or 2,
A polyphenylene ether resin composition is extruded from an extruder into a strand, and the polyphenylene ether resin composition is run in a cooling medium and cooled, and cut by a strand cutter to obtain a pellet as a molded product,
The guide roller is installed in the cooling medium,
The strands are brought into contact with the guide rollers,
When the take-in speed is Vs (cm / sec) and the moving speed of the outer circumferential surface of the guide roller contacting the strands is Vr (cm / sec)
0.7? Vr / Vs? -0.2, the pulling speed, the moving speed and the rotating direction of the guide roller are determined. 12. The method of claim 11,
Wherein the temperature of the strand is adjusted to 80 占 폚 to 160 占 폚 by cooling, and cutting is performed in this temperature range. A polyphenylene ether-based resin molded article produced by the method according to claim 1 or 2, wherein the polyphenylene ether-based resin molded article contains 0.015 to 0.6% of an ultrahigh molecular weight polymer having a molecular weight of 500,000 or more.

Images