JP2005298798A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition containing a polyphenylene ether and a polyester resin and having good compatibility and excellent mechanical strengths and appearance. <P>SOLUTION: This thermoplastic resin composition is produced by compounding (C) 100 pts. wt. of a resin composition composed of (A) 10-60 wt.% polyphenylene ether having ≥0.3 mol of the terminal group of formula (1) based on 100 mol of the phenylene ether units, an intrinsic viscosity of 0.3-0.6 dl/g and a copper content of ≤0.2 ppm and (B) 40-90 wt.% thermoplastic polyester resin with (D) 0.1-10 pts. wt. of a solubilizing agent and (E) 1-30 pts. wt. of an impact strength modifier. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition. More specifically, it contains polyphenylene ether and polyester resin, has good compatibility, excellent solvent resistance, heat resistance rigidity, dimensional stability at the time of moisture absorption, mechanical strength and appearance, electrical / electronic / OA equipment members, The present invention relates to a thermoplastic resin composition useful as a material for automobile members and the like.

  Polyphenylene ether is a thermoplastic resin having excellent heat resistance, dimensional stability, low hygroscopicity, and mechanical strength, but has a drawback that it has poor solvent resistance and melt fluidity and is inferior in moldability. On the other hand, the polyester resin is excellent in molding processability, solvent resistance and mechanical strength, and is widely used as a member for automobiles and electrical / electronic / OA equipment members. However, polyester resins have the disadvantages of high molding shrinkage and linear expansion coefficient, and large reduction in rigidity at high temperatures. For this reason, if a thermoplastic resin composition having both the excellent characteristics of polyphenylene ether and polyester resin and compensating for the disadvantages of both can be obtained, it will be possible to provide an excellent resin material in a wide range of fields of use. It can be said that the value is very large.

  Conventionally, many compositions obtained by simply melt-mixing polyphenylene ether and polyester resin are known (for example, Patent Document 1, Patent Document 2, and Patent Document 3). However, polyphenylene ether and polyester resin have poor compatibility, and in such a simple melt-mixing system, the composition is unlikely to be in a uniform and fine mixed form. As a result, a satisfactory improvement effect is not seen in the impact resistance, heat rigidity, dimensional stability and solvent resistance of the obtained composition, and the appearance of the molded product is deteriorated.

  It is known that when a block copolymer of polyphenylene ether and polyester resin is added to a composition of polyphenylene ether and polyester resin, the compatibility is improved. It is also known that when triphenyl phosphite and an amino compound are used, a direct esterification reaction between a phenolic hydroxyl group and a carboxylic acid occurs. Therefore, it is known to add a phosphorus compound (including a phosphorous acid compound) to a composition comprising polyphenylene ether and a polyester resin for the purpose of flame retardancy (for example, Patent Document 4). However, here, flame retardancy is aimed at, and a composition having good physical properties by improving compatibility has not been obtained. In Patent Document 5, a block copolymer composed of a polyphenylene ether and a polyester resin is produced using a phosphorous acid compound exemplified by triphenyl phosphite and the like, and the compatibility between the polyphenylene ether and the polyester resin is improved. However, in this method, in order to promote the reaction, it is essential to remove the phosphite compound decomposed by the reaction or side reaction or the unreacted phosphite compound. The physical properties such as mechanical strength of the material are not satisfactory.

  Patent Document 6 discloses that the compatibility of polyphenylene ether and polyester resin is improved by using a specific phosphite compound and a compound having a boiling point of 35 ° C. or more and 300 ° C. or less at normal pressure, such as mechanical strength. Although it is described that the physical properties are remarkably improved, the compounds having a boiling point of 35 ° C. or more and 300 ° C. or less at normal pressure used here are dangerous substances such as xylene and toluene, and these compounds are used. This manufacturing method has a drawback that a large-scale device (such as an explosion-proof facility) is required.

Japanese Patent Publication No. 51-21664 JP-A-49-75662 JP 59-159847 A US Pat. No. 4,672,086 US Pat. No. 5,124,411 JP-A-7-3132

  An object of the present invention is to provide a thermoplastic resin composition containing polyphenylene ether and a polyester resin, having good compatibility, having the advantages of both resins, and having excellent mechanical strength and appearance of a molded product to be obtained. is there.

As a result of intensive studies to solve the above problems, the present inventors have used a polyphenylene ether having a specific end group at a specific ratio and a small copper content, and further blending a compatibilizing agent. The inventors have found that the compatibility between the polyphenylene ether and the polyester resin can be remarkably improved, and as a result, all the above problems can be solved, and the present invention has been completed.
That is, the gist of the present invention is that there are 0.3 or more terminal groups represented by the following general formula (1) with respect to 100 phenylene ether units represented by the following general formula (2), and the intrinsic viscosity is 0. A resin composition comprising 10 to 60% by weight of polyphenylene ether (A) having a copper content of 0.2 ppm or less and 3 to 0.6 dl / g and 40 to 90% by weight of the thermoplastic polyester resin (B). (C) A thermoplastic resin composition obtained by blending 0.1 to 10 parts by weight of a compatibilizer (D) and 1 to 30 parts by weight of an impact resistance improver (E) with respect to 100 parts by weight, and molding obtained therefrom It exists in goods.

(In the formula, two R ^{1 s} each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and two R ^{2 s} each independently represent a hydrogen atom or 1 to 3 carbon atoms. (However, two R ^{1 s} are not hydrogen atoms.)

(In the formula, two R ^{3 s} each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Represents a group, but two R ³ are not hydrogen atoms.)

  In the resin composition of the present invention, the compatibility between the polyphenylene ether and the polyester resin is remarkably improved by using a polyphenylene ether having a specific terminal group, and the solvent resistance, heat resistance rigidity, dimensional stability at the time of moisture absorption, In addition, as a resin material having excellent mechanical strength and appearance of a molded product, it is useful as a material for electrical / electronic / OA equipment members and automobile members.

  Hereinafter, the present invention will be described in detail. The polyphenylene ether (A) used in the thermoplastic resin composition of the present invention is a polymer having a phenylene ether unit represented by the general formula (2) in the main chain, and may be a homopolymer or a copolymer. May be.

  Specific examples of the homopolymer include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2,6-phenylene). 2,6 such as dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether -Dialkyl phenylene ether polymers are mentioned, and examples of the copolymer include various 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers. Examples of the polyphenylene ether (A) used in the present invention include poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer. Is preferred.

  The terminal group represented by the general formula (1) included in the polyphenylene ether (A) used in the resin composition of the present invention is specifically a 3,5-dimethyl-4-hydroxyphenyl group, 3 , 5-Diethyl-4-hydroxyphenyl group, 3,5-dipropyl-4-hydroxyphenyl group, 3-methyl-5-ethyl-4-hydroxyphenyl group, 3-methyl-5-propyl-4-hydroxyphenyl group 2,3,5-trimethyl-4-hydroxyphenyl group and the like.

  The production method of the polyphenylene ether (A) used in the resin composition of the present invention is not particularly limited. For example, as shown in Japanese Patent Publication No. 61-20576, 2,6-xylenol (raw material monomer) Can be easily produced by oxidative polymerization in the presence of a cuprous salt and an amine compound, and the specific production method is shown in the production examples described later.

In the polyphenylene ether (A) used in the present invention, the number of terminal groups represented by the general formula (1) is 0.3 or more with respect to 100 phenylene ether units represented by the general formula (2). It is necessary to be. When polyphenylene ether having a number of end groups represented by the general formula (1) of less than 0.3 is used, compatibility with the polyester resin (B) is lowered, resulting in poor appearance of the molded product and delamination. In addition, mechanical strength such as impact strength also decreases.
A method for obtaining the polyphenylene ether of the present invention in which the number of terminal groups represented by the general formula (1) is 0.3 or more is also described in the above Japanese Patent Publication No. 61-20576, but is particularly limited. It is not a thing. For example, 2,6-dimethylxylenol is subjected to an oxidative polymerization reaction in the presence of oxygen in a solvent such as toluene using a cuprous salt and amine compound as a catalyst, and the resulting polyphenylene ether solution is mixed with a chelate compound with copper. After deactivating the catalyst by a method such as adding a compound that forms, the polyphenylene ether solution can be obtained by stirring in an atmosphere that avoids mixing of oxygen. The temperature of the solution being stirred is preferably maintained at 50 ° C. or higher, preferably about 70 ° C. The number of terminal groups represented by the general formula (1) is preferably 0.4 to 2, more preferably 0.5 to 1. with respect to 100 phenylene ether units represented by the general formula (2). Five. If the number of end groups exceeds 2, the strength and thermal stability tend to be lowered.

  The polyphenylene ether (A) used in the present invention has an intrinsic viscosity of 0.3 to 0.6 dl / g. When the intrinsic viscosity is less than 0.3 dl / g, the surface impact strength of the resin composition is insufficient, and when it exceeds 0.6 dl / g, the moldability is insufficient and the appearance of the molded product may be poor. In the present specification, the intrinsic viscosity of the polyphenylene ether (A) means the intrinsic viscosity when measured at 30 ° C. in chloroform. Thus, the polyphenylene ether (A) having a predetermined intrinsic viscosity can be obtained by adjusting the catalyst amount and appropriately adjusting the reaction time. The intrinsic viscosity is preferably 0.35 to 0.55 dl / g.

The polyphenylene ether (A) used in the present invention has a copper content of 0.2 ppm or less based on the weight of the polyphenylene ether. The copper content is attributed to the residual catalyst.
When the copper content of polyphenylene ether exceeds 0.2 ppm, the thermal stability when the resin composition of the present invention is produced and molded, and the thermal stability when the molded product is used in a high-temperature atmosphere are deteriorated. The appearance of the product may be poor and the mechanical strength may be reduced. Thus, in order to make the copper content of the polyphenylene ether (A) 0.2 ppm or less, it is important to effectively remove the copper salt used as a catalyst for the oxidative polymerization reaction from the solution. The removal method is not particularly limited. For example, an aqueous solution of sodium ethylenediaminetetraacetate that forms a chelate compound with copper is added to a polyphenylene ether solution obtained by an oxidative polymerization reaction, and after stirring sufficiently, the aqueous layer is formed. By separating, copper can be separated efficiently. Generally, the copper content of polyphenylene ether can be effectively reduced by repeating this operation. After adding a non-solvent such as methanol to the polyphenylene ether solution with this operation insufficient, the copper content of the polyphenylene ether is reduced even if the polyphenylene ether separated as a solid is thoroughly washed with methanol, water, etc. It is difficult to let The copper content of the polyphenylene ether is preferably 0.15 ppm or less.

  The thermoplastic polyester resin (B) used in the present invention can be any thermoplastic polyester resin, but is preferably a polyester resin obtained from terephthalic acid or an ester-forming derivative thereof and an alkylene diol as main raw materials. More preferably, it is polybutylene terephthalate containing terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol as main raw materials. The main raw material means that terephthalic acid or an ester-forming derivative thereof accounts for 50 mol% or more of all dicarboxylic acid components, and 1,4-butanediol accounts for 50 mol% or more of all diol components. Terephthalic acid or an ester-forming derivative thereof preferably accounts for 80 mol% or more of the total dicarboxylic acid component, and more preferably accounts for 95 mol% or more. More preferably, 1,4-butanediol occupies 80 mol% or more of the total diol component, and more preferably 95 mol% or more.

  In the present invention, the dicarboxylic acid component other than terephthalic acid is not particularly limited, and examples thereof include phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, and 4,4′-benzophenone. Aromatic dicarboxylic acids such as dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3- Cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. These ester-forming derivatives can be mentioned.

  In the present invention, the diol component other than 1,4-butanediol is not particularly limited. For example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, polytetramethylene ether glycol, 1,5 -Aliphatic diols such as pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1 , Aromatic compounds such as cycloaliphatic diols such as 4-cyclohexanedimethylol, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone Geo It is possible to increase the Le.

  Furthermore, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, hydroxycarboxylic acid such as p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol Monofunctional components such as stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, A trifunctional or higher polyfunctional component such as pentaerythritol can be used as a copolymerization component.

  The intrinsic viscosity of polybutylene terephthalate preferably used in the present invention is 1.0 to 1.5 dl / g measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1). It is preferable. When the intrinsic viscosity exceeds 1.5 dl / g, the melt viscosity becomes high, the fluidity is deteriorated, and the moldability may be deteriorated. Two or more types of polybutylene terephthalate having different intrinsic viscosities may be used in combination to adjust the intrinsic viscosity within the above range.

  There is no limitation on the method for producing polybutylene terephthalate used in the present invention, and any of continuous polymerization method and batch polymerization method may be used, and those produced by known methods and catalysts can be used. It is preferably polybutylene terephthalate obtained by continuously polymerizing a dicarboxylic acid component having a main component and a diol component having 1,4-butanediol as a main component.

  The compatibilizing agent (D) used in the present invention is a substance that improves the dispersibility of polyphenylene ether in a thermoplastic polyester resin. For example, a carboxyl group, a carboxylic acid ester group, an acid amide group, an imide group, Examples thereof include compounds having one or more acid anhydride groups, epoxy groups, oxazolinyl groups, amino groups or hydroxyl groups, polycarbonate resins, and phosphite triester compounds. A particularly preferred compatibilizer (D) is a phosphorous acid triester compound represented by the following general formula (3).

(In the formula, n represents 1 or 2, Ar represents an aryl group or substituted aryl group having 6 to 30 carbon atoms, and when n is 2, Ar may be the same or different. Represents an alkylene group or an arylene group having 2 to 18 carbon atoms, and represents an alkanetetrayl group having 4 to 18 carbon atoms when n is 2.

In the general formula (3), specific examples of Ar include a phenyl group, 2-, 3- or 4-methylphenyl group, 2,4- or 2,6-dimethylphenyl group, 2,3,6-trimethylphenyl. Group, 2-, 3- or 4-ethylphenyl group, 2,4- or 2,6-diethylphenyl group, 2,3,6-triethylphenyl group, 2-, 3- or 4-tert-butylphenyl group 2,4- or 2,6-di-tert-butylphenyl group, 2,6-di-tert-butyl-4-methylphenyl group, 2,6-di-tert-butyl-4-ethylphenyl group, Examples include octylphenyl group, isooctylphenyl group, 2-, 3- or 4-nonylphenyl group, 2,4-dinonylphenyl group, biphenyl group, naphthyl group and the like.
Specific examples of R in formula (3) include 1,2-phenylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group and the like when n is 1. When is 2, a tetrayl group represented by the following general formula (5) derived from pentaerythritol is exemplified.

  (In the formula, each Q independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

  Specific examples of the phosphorous acid triester compound represented by the general formula (3) include (phenyl) (1,3-propanediol) phosphite, (4-methylphenyl) (1,3-propanediol) phosphine. Phyto, (2,6-dimethylphenyl) (1,3-propanediol) phosphite, (4-tert-butylphenyl) (1,3-propanediol) phosphite, (2,4-di-tert-butyl) Phenyl) (1,3-propanediol) phosphite, (2,6-di-tert-butylphenyl) (1,3-propanediol) phosphite, (2,6-di-tert-butyl-4-methyl) Phenyl) (1,3-propanediol) phosphite, (phenyl) (1,2-ethanediol) phosphite, (4-methylphenyl) (1 2-ethanediol) phosphite, (2,6-dimethylphenyl) (1,2-ethanediol) phosphite, (4-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,4 -Di-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert) -Butyl-4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) (1,4-butanediol) phosphite, etc., diphenylpentaerythritol Diphosphite, bis (2-methylphenyl) pentaerythritol diphosphite, bis (3-methylphenyl) pentaeri Ritol diphosphite, bis (4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, bis (2,3,6-trimethylphenyl) pentaerythritol diphosphite, bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (3-tert-butylphenyl) pentaerythritol diphosphite, bis (4- tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butylphenyl) pentaerythritol diphosphite Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis ( Nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, dinaphthylpentaerythritol diphosphite, and the like.

Among these, more preferable phosphorous acid triester compounds include bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite or a mixture thereof. In addition, in the composition of this invention, the phosphorus compound produced by decomposition | disassembly (hydrolysis, thermal decomposition, etc.) of phosphorous acid triester may be included.
In particular, a phosphite triester compound preferable as a compatibilizing agent used in the present invention is 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) represented by the following formula (6): ) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane {also known as bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite}. .

  The compounding amount of the compatibilizing agent (D) in the composition of the present invention is 100 parts by weight of a resin composition (C) comprising 10 to 60% by weight of polyphenylene ether (A) and 40 to 90% by weight of a polyester resin (B). Is 0.1 to 10 parts by weight. In addition, the preferable compounding quantity in the case of using a phosphorous acid triester type compound as a compatibilizing agent (D) is 0.1-3 weight part with respect to 100 weight part of resin compositions (C). If the blending amount of the phosphorous triester compound is less than 0.1 parts by weight, the effect of improving the compatibility is small, and if it exceeds 3 parts by weight, the hydrolysis resistance of the resin composition may be lowered.

  The impact resistance improver (E) used in the present invention is not particularly limited as long as it has the effect of improving the impact resistance of the resin. Preferably, the styrene-butadiene block copolymer and its butadiene portion are used. Hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, ethylene-propylene copolymer rubber, ethylene-propylene- Diene copolymer rubbers, and those α, β-unsaturated carboxylic anhydride modified products, modified products with glycidyl esters or unsaturated glycidyl ethers, or copolymers comprising an unsaturated epoxy compound and ethylene, Or the addition of a copolymer comprising an unsaturated epoxy compound and an ethylenically unsaturated compound, It is effective for improving the strength of the composition. The impact resistance improver (E) may be used alone or in combination of two or more. The compounding amount of the impact resistance improver (E) in the composition of the present invention is 10 wt% of the polyphenylene ether (A) and 100 wt% of the resin composition (C) consisting of 40 wt% to 90 wt% of the polyester resin (B). The amount is 3 to 30 parts by weight, preferably 5 to 25 parts by weight per part. When the blending amount of the impact resistance improver (E) is less than 3 parts by weight, the effect of improving the impact strength is small, and when it exceeds 30 parts by weight, the heat resistance rigidity is lowered.

  The resin composition of the present invention can further contain a phosphate ester (F). The phosphate ester further improves the compatibility between the polyphenylene ether and the polyester resin. The phosphate ester compound (F) used is not particularly limited, but is preferably a triphenyl phosphate compound represented by the following general formula (4).

(In the formula, two R ^{5 s} each independently represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms).

  Specific examples of the triphenyl phosphate compound represented by the general formula (4) include triphenyl phosphate, tris (2,4-di-t-butylphenyl) phosphate, and tris (2-t-butyl-4). -Methylphenyl) phosphate, tris (2-t-butylphenyl) phosphate, tris [2- (1,1-dimethylpropyl) phenyl] phosphate, tris [2,4- (1,1-dimethylpropyl) phenyl] phosphate Etc. are preferred.

  The compounding quantity of the phosphate ester compound (F) in this invention composition is resin composition (C) 100 weight consisting of polyphenylene ether (A) 10-60 weight% and polyester resin (B) 40-90 weight%. 15 parts by weight or less based on parts. If the amount of the phosphate ester compound (F) exceeds 15 parts by weight, the load deflection temperature and mechanical strength may be lowered.

  In addition to the above components (A) to (F), other components can be further added to the thermoplastic resin composition of the present invention as necessary. Examples of components other than (A) to (F) include, for example, flame retardants, weather resistance improvers, foaming agents, lubricants, nucleating agents, fluidity improvers, impact resistance improvers, dyes, pigments, and fillers. Agents, reinforcing agents, dispersants and the like. Examples of fillers and reinforcing agents include organic fillers, inorganic fillers, organic reinforcing agents, inorganic reinforcing agents and the like. Specific examples include glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate. And silica. The blending of the filler and the reinforcing agent is effective for improving rigidity, heat resistance, dimensional accuracy, and the like. The blending ratio of the filler and the reinforcing agent is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight with respect to 100 parts by weight as a total of the component (A) and the component (B).

  The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and any method can be adopted. Preferably, the method is by melt kneading, and kneading generally used for thermoplastic resins. The method is applicable. As an example of a manufacturing method, it is uniform with a Henschel mixer, a ribbon blender, a V-type blender, etc. together with the above components (A) to (F) and other components other than (A) to (F) as necessary. After mixing, the mixture can be kneaded with a single-screw or multi-screw kneading extruder, roll, Banbury mixer, Laboplast mill (Brabender) or the like. Each component may be fed to the kneader in a lump or sequentially, and two or more components selected from each component including other components other than (A) to (F) are mixed in advance. May be used. The kneading temperature can be appropriately selected depending on the type of the kneader and the blending ratio of the resin, but is usually in the range of 150 to 350 ° C.

  The thermoplastic resin composition of the present invention is a molding method generally used for thermoplastic resins, that is, injection molding, injection compression molding, hollow molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding. It can shape | mold by various molding methods, such as.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following examples, unless the summary is exceeded. Moreover, the measuring method of the physical property value of the resin and the evaluation method of the resin composition in the following examples are as follows.
<Physical properties of polyphenylene ether>
(1) Intrinsic viscosity: Polyphenylene ether is dissolved in chloroform, solutions with different concentrations of 0.5 g / dl or less are prepared, and specific viscosities at different concentrations are measured at 30 ° C. using an Ubbelohde viscometer. The ratio between the specific viscosity and the concentration was calculated, and the ratio when the concentration was extrapolated to 0 was calculated as the intrinsic viscosity.
(2) Types and number of end groups: JNM-A400 manufactured by JEOL Ltd., CDCl ₃ as a solvent, tetramethylsilane as a reference, measurement mode as ¹³ C-NMR complete decoupling mode, polyphenylene ether The ¹³ C-nuclear magnetic resonance absorption spectrum of the resin is measured. From the obtained spectrum, the type and number of hydroxyl terminals were determined by the method described in Macromolecules, 1990, 23, 1318-1329.
(3) Copper content: After decomposing polyphenylene ether with nitric acid, the copper in the residue was quantified by atomic absorption analysis, and the copper content in the polyphenylene ether was calculated.

<Evaluation method of thermoplastic resin composition>
Molding condition of test piece: After drying the pellets of the thermoplastic resin composition obtained in the examples or comparative examples at 100 ° C for 5 hours, the mold temperature is 70 ° C using an SG125 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. At a cylinder set temperature of 260 to 290 ° C., an injection pressure of 98 MPa, and a molding cycle of 40 seconds, a tensile test piece, a bending test piece, a Charpy impact test piece, and a load deflection temperature test piece used in the test method shown below are molded and tested. went.
(1) Tensile strength, elongation at break: According to ISO 527.
(2) Flexural strength, flexural modulus: according to ISO178.
(3) Notched Charpy impact strength: Conforms to ISO179.
(4) Load deflection temperature: According to ISO75. However, the load is 0.45 MPa.
(5) Compatibility: The fracture surface of the test piece after the tensile strength evaluation in the above (1) is visually observed. From the state of delamination, the one having good compatibility is ◯, the one slightly inferior is Δ, the one inferior is × Evaluation based on the criteria.

The materials used in the following examples are as follows.
(A) Polyphenylene ether-I (PPE-I): produced in Production Example 1.
(B) Polyphenylene ether-II (PPE-II): produced in Production Example 2.
(C) Polyphenylene ether-III (PPE-III): produced in Production Example 3.
(D) Polybutylene terephthalate (PBT): inherently measured at 30 ° C. using a mixed solvent of “Novadour (registered trademark) 5040ZS”, phenol / tetrachloroethane (weight ratio 1/1), manufactured by Mitsubishi Engineering Plastics The viscosity is 1.40.
(E) Impact resistance improver: manufactured by Kuraray Co., Ltd., hydrogenated styrene-butadiene block copolymer, trade name “Septon 8006”.
(F) Phosphorous acid triester (PEP): bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, manufactured by Asahi Denka Kogyo Co., Ltd., trade name “MARK PEP-36 "
(G) Phosphate ester (TPP): Triphenyl phosphate, manufactured by Daihachi Chemical Co., Ltd.

Production Example 1
A 10-liter jacket equipped with a sparger for introducing oxygen-containing gas at the bottom of the reactor, a stirring turbine blade and baffle, and a reflux condenser with a decanter for separating condensate attached to the bottom of the vent gas line at the top of the reactor. An autoclave reactor equipped with 1.4172 g cuprous oxide, 8.5243 g 47% aqueous hydrogen bromide, 16.5277 g N, N-di-n-butylamine, 41.9196 g N, N-dimethyl- n-Butylamine, 3.4139 g of N, N′-di-t-butylethylenediamine, 1.00 g of trioctylmethylammonium chloride and 2770.3 g of toluene were added to prepare an initial charging solution. Next, nitrogen was introduced into the reactor gas phase, and the absolute pressure in the reactor gas phase was controlled to 0.108 MPa.

  Subsequently, a gas made by diluting oxygen with nitrogen and having an absolute pressure of 0.108 MPa and an oxygen concentration of 70% was introduced from a sparger, and thereafter nitrogen was introduced into the reactor gas phase part including during polymerization. During the introduction, the control valve was controlled so that the absolute pressure in the gas phase of the reactor was maintained at 0.108 MPa with nitrogen and the above gas. The gas introduction rate was 3.45 NL / min. Immediately after starting the introduction of the gas, a solution in which 1100 g of 2,6-dimethylphenol was dissolved in 1056.9 g of toluene was added at a speed at which the entire amount was charged in 30 minutes using a plunger pump. Started. The polymerization temperature was adjusted by passing a heating medium through the jacket so as to maintain 40 ° C. About 120 minutes after the start of gas introduction, nitrogen was introduced instead of the oxygen-containing gas, and 500 g of a 5% aqueous solution of sodium ethylenediaminetetraacetate (4 sodium EDTA) was added to the reactor and stirred.

  Thereafter, stirring was continued for 2 hours while controlling with a heat medium so that the temperature of the reaction solution became 70 ° C. After the stirring was stopped, the aqueous solution separated by standing was discharged out of the system, and 250 g of pure water was further added to the reaction solution, stirred for 10 minutes, and allowed to stand for 10 minutes, and then the separated aqueous layer was discharged out of the system. . An approximately equal volume of methanol was added to the reaction solution from which the aqueous layer was separated to precipitate polyphenylene ether. The precipitate was collected by filtration, further washed with an appropriate amount of methanol, and then strongly dried at about 140 ° C. for 1 hour to obtain powdered polyphenylene ether.

The evaluation results of the obtained polyphenylene ether-I (hereinafter sometimes abbreviated as PPE-I) are shown below.
Intrinsic viscosity: 0.40 dl / g
Number of end groups: 0.64 per 100 phenylene ether units Copper content: 0.1 ppm

Production Example 2
Produced in the same manner as the above polyphenylene ether-I, but only using 0.3 g of trioctylmethylammonium chloride and starting to introduce nitrogen instead of oxygen-containing gas in about 135 minutes after starting gas introduction. Was changed to obtain a powdery polyphenylene ether.

The evaluation results of the obtained polyphenylene ether-II (hereinafter sometimes abbreviated as PPE-II) are shown below.
Intrinsic viscosity: 0.40 dl / g
Number of end groups: 0.61 per 100 phenylene ether units Copper content: 0.59 ppm

Production Example 3
Two stages of condensers were connected in series to a polymerization reactor equipped with an air blowing tube. The temperature of the condenser was adjusted so that the condenser temperature was about 0 ° C., and the temperature was adjusted so that the toluene phase of the bottoms was continuously returned to the polymerization reactor. A solution prepared by dissolving 2,350 g of 2,6-dimethylphenol (monomer) in 5400 g of toluene while supplying air at a rate of 10 NL / min per kg of monomer into a catalyst solution of 22 g of cupric bromide, 400 g of dibutylamine and 9800 g of toluene. The solution was added dropwise over 60 minutes and polymerization was carried out at 40 ° C. 100 minutes after dropping the monomer, an aqueous solution in which EDTA4 sodium was dissolved in a 1.5-fold molar amount with respect to the catalyst copper (the amount of the aqueous solution was 0.2 weight times the total amount of the polymerization reaction solution) was added to the reaction solution while stirring to stop the reaction. .

After the stirring was stopped, the aqueous layer was discharged out of the system by standing and separated. Further, 550 g of pure water was added to the reaction solution, stirred for 10 minutes, and allowed to stand for 10 minutes. Discharged. Further, the same operation was repeated. That is, in the second time, an aqueous solution in which EDTA tetrasodium was dissolved in a molar amount of 0.5 times the amount of catalyst copper (the amount of the aqueous solution was 0.2 times by weight with respect to the total amount of the polymerization reaction solution) was added to the reaction solution while stirring and left to stand. Thereafter, the aqueous layer was discharged out of the system in the same manner as described above, 600 g of pure water was 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.
An approximately equal volume of methanol was added to the resulting reaction solution to precipitate polyphenylene ether. The precipitate was collected by filtration, washed with polyphenylene ether with an appropriate amount of methanol, and then strongly dried at about 140 ° C. for 1 hour to obtain powdered polyphenylene ether.

The evaluation results of the obtained polyphenylene ether-III (hereinafter sometimes abbreviated as PPE-III) are shown below.
Intrinsic viscosity: 0.40 dl / g
Number of terminal groups: 0.23 for 100 phenylene ether units Copper content: 0.11 ppm

[Examples 1 to 3 and Comparative Examples 1 to 6]
In accordance with the blending ratio shown in Tables 1 to 3, each component was sufficiently mixed with a tumbler, and then set using a twin screw extruder with a vacuum vent (manufactured by Nippon Steel Works, trade name “TEX44”) at a set temperature of 230. The mixture was kneaded under the conditions of ° C., screw rotation speed 230 rpm, and discharge rate 100 kg / hour to obtain pellets. The pellet was injection molded under the above conditions to form a test piece, and an evaluation test of the test piece was performed. The results are shown in Tables 1 to 3.

Since the thermoplastic resin composition of the present invention is excellent in compatibility, and has excellent mechanical strength and appearance of molded products, it can be used as a molding material in a wide range of fields including electric / electronic / OA equipment members and automotive parts. Can be used.

Claims (6)

For 100 phenylene ether units represented by the following general formula (2), it has 0.3 or more terminal groups represented by the following general formula (1), and the intrinsic viscosity is 0.3 to 0.6 dl / g. And 100 parts by weight of a resin composition (C) comprising 10 to 60% by weight of a polyphenylene ether (A) having a copper content of 0.2 ppm or less and 40 to 90% by weight of a thermoplastic polyester resin (B). A thermoplastic resin composition comprising 0.1 to 10 parts by weight of a compatibilizer (D) and 1 to 30 parts by weight of an impact modifier (E),

(In the formula, two R ^{1 s} each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and two R ^{2 s} each independently represent a hydrogen atom or 1 to 3 carbon atoms. Wherein two R ^{1 s} are not hydrogen atoms.),

(In the formula, two R ^{3 s} each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and two R ^{4 s} each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Represents a group, but two R ³ are not hydrogen atoms.)   The thermoplastic resin composition according to claim 1, further comprising 15 parts by weight or less of a phosphate ester (F) per 100 parts by weight of the resin composition (C).   The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic polyester resin (B) is polybutylene terephthalate. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the compatibilizer (D) is a phosphorous acid triester compound represented by the following general formula (3):

(In the formula, n represents 1 or 2, Ar represents an aryl group or substituted aryl group having 6 to 30 carbon atoms, and when n is 2, Ar may be the same or different. Represents an alkylene group or an arylene group having 2 to 18 carbon atoms, and represents an alkanetetrayl group having 4 to 18 carbon atoms when n is 2. The thermoplastic resin composition according to any one of claims 2 to 4, wherein the phosphate ester (F) is a triphenyl phosphate compound represented by the following general formula (4):

(In the formula, two R ^{5 s} each independently represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms). A molded product formed by molding the thermoplastic resin composition according to claim 1.