WO2013069782A1 - Method for producing thermoplastic resin composition, and molded article - Google Patents

Abstract

A method for producing a thermoplastic resin composition includes: using a melt-kneading extrusion machine provided with a nozzle, a cylinder, and a screw positioned within the cylinder; obtaining a mixture by supplying (A) a thermoplastic resin, (B) alumina fine particles, and (C) a fibrous filler material to the cylinder via the supply port in the cylinder, and melt-kneading the components (A, B, C); extruding the mixture via the nozzle of the melt-kneading extrusion machine to the exterior thereof; and cooling the mixture at a cooling rate of 35°C or less per second. Also, a molded article is obtained by molding the thermoplastic resin composition obtained using this production method.

Description

Method for producing thermoplastic resin composition and molded body

The present invention relates to a molded article excellent in thermal conductivity and a method for producing a thermoplastic resin composition for obtaining the molded article.
This application claims priority based on Japanese Patent Application No. 2011-247742 filed in Japan on November 11, 2011, the contents of which are incorporated herein by reference.

In recent years, in the field of electric / electronic components, there is a concern about heat generation in the components as the size and performance thereof increase. If heat dissipation measures against such heat generation are insufficient, the performance of electric / electronic parts is degraded due to the accumulation of heat. Therefore, it is desired that members used for electric / electronic components have high thermal conductivity (high thermal conductivity).
Until now, metal materials have been mainly used for parts that require high thermal conductivity, but metal materials are difficult in terms of lightness and moldability in order to adapt to the miniaturization of parts. Alternatives to resin materials are progressing.
However, resin materials generally have low thermal conductivity, and it is difficult to increase the thermal conductivity of the resin material itself. For this reason, it is usually considered to produce a resin composition with high thermal conductivity by filling a resin material with a filler of a high thermal conductivity material such as copper, aluminum, aluminum oxide, etc. to produce an electrical / electronic component therefrom. (For example, see Patent Documents 1 to 3).

JP-A-62-100577 Japanese Patent Laid-Open No. 4-178421 JP-A-5-86246

On the other hand, a molded body having a relatively complicated shape such as used for electric / electronic parts is generally manufactured by injection molding. However, in injection molding, the thermal conductivity in the resin flow direction can be improved relatively easily, but it is very difficult to improve the thermal conductivity in the thickness direction of the molded product perpendicular to the flow direction. There was a problem that it was difficult. Furthermore, in order to impart thermal conductivity to the resin, the filler has to be highly filled, so that there is a problem that the strength of the molded body is lowered.

The present invention has been made in view of the above circumstances, and has a molded body excellent in electrical conductivity and strength in the thickness direction, having excellent electrical insulation as an electrical / electronic component, and the molded body It is an object of the present invention to provide a method for producing a thermoplastic resin composition for obtaining the above.

In order to solve the above problems, the present invention has the following aspects.

The first aspect of the present invention is:
[1] Using a melt-kneading extruder provided with a nozzle, a cylinder and a screw installed in the cylinder, from the supply port provided in the cylinder, the following component (A), the following component (B) and the following component ( C) is supplied to the cylinder to melt and knead the component (A), the component (B) and the component (C) to obtain a kneaded product, and the kneaded product is fed from the nozzle to the melt kneading extruder. The present invention relates to a method for producing a thermoplastic resin composition, comprising extruding to the outside and cooling the kneaded product at a cooling rate of 35 ° C./second or less.
Component (A) Thermoplastic resin Component (B) Alumina fine particle Component (C) Fibrous filler

[2] The method for producing a thermoplastic resin composition according to [1], wherein the component (B) has a BET specific surface area of 1.0 to 5.0 m ² / g.

[3] The method for producing a thermoplastic resin composition according to [1] or [2], wherein the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is bimodal.

[4] The particle size distribution obtained by laser diffraction scattering measurement of the component (B) is maximum in the range of the volume average particle size of 1 to 5 μm and in the range of the volume average particle size of 0.1 to 1 μm, respectively. The method for producing a thermoplastic resin composition according to any one of [1] to [3], which is bimodal having a value.

[5] The component (C) is at least one substance selected from the group consisting of carbon fiber, glass fiber, wollastonite whisker, aluminum borate whisker, and potassium titanate whisker. The manufacturing method of the thermoplastic resin composition as described in any one.

[6] The method for producing a thermoplastic resin composition according to any one of [1] to [5], wherein the component (A) is a liquid crystal polyester.

[7] The liquid crystalline polyester comprises a repeating unit derived from at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, hydroquinone and 4,4 ′ A repeating unit derived from at least one aromatic diol selected from the group consisting of -dihydroxybiphenyl, and at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid A total of 30 to 80 mol% of the repeating units derived from the aromatic hydroxycarboxylic acid, based on the total amount of all the repeating units constituting the liquid crystal polyester. 10 to 35 mol% in total of repeating units derived from the aromatic dicarboxylic acid The method for producing a thermoplastic resin composition according to [6] having 10 to 35 mol% in total of repeating units derived from.

[8] The total supply amount of the components (B) and (C) is 100 parts by mass or more with respect to 100 parts by mass of the component (A). A method for producing a thermoplastic resin composition.

The second aspect of the present invention is:
[9] relates to a molded article obtained by molding the thermoplastic resin composition obtained by the production method according to any one of [1] to [8].

[10] The molded article according to [9], wherein the volume resistivity value at 23 ° C. is 1 × 10 ¹⁰ Ωm or more.

[11] The molded article according to [9] or [10], which is for electric / electronic parts.

[12] The electrical / electronic component is at least one component selected from the group consisting of a sealing material for electronic elements, an insulator, a reflector for display device, a housing for storing electronic elements, and a surface-mounted component. ] The molded object of description.

A third aspect of the present invention uses a melt kneading extruder provided with a cylinder and a screw installed in the cylinder, and from the supply port provided in the cylinder, the following components (A), (B) and ( C) is supplied to the cylinder and melt-kneaded to produce a thermoplastic resin composition, in which the kneaded product extruded from the nozzle of the melt-kneading extruder is cooled at a cooling rate of 35 ° C / Provided is a method for producing a thermoplastic resin composition characterized by cooling in seconds or less.
(A) Thermoplastic resin (B) Alumina fine particles (C) Fibrous filler In the method for producing a thermoplastic resin composition according to the third aspect of the present invention, the BET specific surface area of the component (B) is 1.0. It is preferably ˜5.0 m ² / g.
In the method for producing a thermoplastic resin composition according to the third aspect of the present invention, the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is preferably bimodal.
In the method for producing the thermoplastic resin composition of the third aspect of the present invention, the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is in the range of 1-5 μm in volume average particle size, and the volume Bimodality having maximum values in the average particle size range of 0.1 to 1 μm is preferable.
In the method for producing a thermoplastic resin composition according to the third aspect of the present invention, the component (C) is made of the group consisting of carbon fiber, glass fiber, wollastonite whisker, aluminum borate whisker, and potassium titanate whisker. It is preferably one or more selected.
In the method for producing a thermoplastic resin composition of the third aspect of the present invention, the component (A) is preferably a liquid crystal polyester.
In the method for producing a thermoplastic resin composition of the third aspect of the present invention, the liquid crystal polyester is a repeating product derived from an aromatic hydroxycarboxylic acid of p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid. One or more aromatic dicarboxylic acids selected from the group consisting of a unit, a repeating unit derived from an aromatic diol of hydroquinone and / or 4,4′-dihydroxybiphenyl, and terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid A total of 30 to 80 mol% of the repeating units derived from the aromatic hydroxycarboxylic acid with respect to the total amount of all repeating units constituting the liquid crystal polyester. 10 to 35 mol% of repeating units derived from the above, and repeating units derived from the aromatic dicarboxylic acid It is preferable to have 10 to 35 mol% of units in total.
In the method for producing the thermoplastic resin composition of the third aspect of the present invention, the total supply amount of the components (B) and (C) is 100 parts by mass or more with respect to 100 parts by mass of the component (A). Preferably there is.
Moreover, the 4th aspect of this invention provides the molded object formed by shape | molding the thermoplastic resin composition obtained by the said manufacturing method.
The molded body of the fourth aspect of the present invention preferably has a volume resistivity value at 23 ° C. of 1 × 10 ¹⁰ Ωm or more.
The molded body of the fourth aspect of the present invention is preferably for electric / electronic parts.
In the molded body according to the fourth aspect of the present invention, the electrical / electronic component is composed of a group consisting of an electronic element sealing material, an insulator, a display device reflector, a housing for electronic element storage, and a surface mount component. It is preferably one or more selected.

ADVANTAGE OF THE INVENTION According to this invention, the molded object which has the electrical insulation suitable as an electrical / electronic component, and was excellent in the thermal conductivity of thickness direction, and intensity | strength, and the thermoplastic resin composition for obtaining this molded object Can be provided.

It is a schematic diagram which shows the outline | summary (an example) of the bimodal particle size distribution calculated | required by the laser diffraction scattering measurement. It is a schematic diagram which shows the outline | summary (other example) of the bimodal particle size distribution calculated | required by the laser diffraction scattering measurement.

<Method for producing thermoplastic resin composition>
The method for producing a thermoplastic resin composition according to the first aspect of the present invention uses a melt-kneading extruder provided with a nozzle, a cylinder, and a screw installed in the cylinder, from a supply port provided in the cylinder. The following component (A), the following component (B) and the following component (C) are supplied to the cylinder, and the component (A), the component (B) and the component (C) are melt-kneaded to obtain a kneaded product. Obtaining, extruding the kneaded material from the nozzle to the outside of the melt-kneading extruder, and cooling the kneaded material at a cooling rate of 35 ° C./second or less.
Component (A) Thermoplastic Resin Component (B) Alumina Fine Particles Component (C) Fibrous Filler According to the present invention, the cooling rate of the extruded kneaded product is set to 35 ° C./second or less, which is lower than before. Thus, a thermoplastic resin composition capable of producing a molded article excellent in electrical insulation, thermal conductivity in the thickness direction, and strength can be obtained. In the following description, unless otherwise specified, “thermal conductivity” means “thermal conductivity in the thickness direction of the molded body”. The “thickness direction” means a direction perpendicular to the MD direction and the TD direction of the molded product (molded plate). “MD direction” means the injection direction of the molded product (molded plate), and “TD direction” means the width direction of the molded product (molded plate) perpendicular to the injection direction.

The method for producing a thermoplastic resin composition according to the third aspect of the present invention uses a melt-kneading extruder provided with a cylinder and a screw installed in the cylinder, and from the supply port provided in the cylinder, the following A method for producing a thermoplastic resin composition by supplying components (A), (B) and (C) to the cylinder and melt-kneading them, and is extruded from the nozzle of the melt-kneading extruder. The kneaded product is cooled at a cooling rate of 35 ° C./second or less.
(A) Thermoplastic resin (B) Alumina fine particles (C) Fibrous filler According to the present invention, the cooling rate of the extruded kneaded product is set to 35 ° C./sec or less, which is lower than the conventional one, so A thermoplastic resin composition capable of producing a molded article having excellent properties, thermal conductivity in the thickness direction, and strength is obtained. In the following description, unless otherwise specified, “thermal conductivity” means “thermal conductivity in the thickness direction of the molded body”.

The thermoplastic resin (component (A)) is preferably one that can be molded at a molding temperature of 200 to 450 ° C. Examples thereof include polyolefin, polystyrene, polyamide, halogenated vinyl resin, polyacetal, saturated polyester, polycarbonate, poly Examples thereof include aryl sulfone, polyaryl ketone, polyphenylene ether, polyphenylene sulfide, polyaryl ether ketone, polyether sulfone, polyphenylene sulfide sulfone, polyarylate, polyamide, liquid crystal polyester, and fluororesin.
A thermoplastic resin may be used individually by 1 type, and may use 2 or more types together as a polymer alloy.

The thermoplastic resin is preferably liquid crystal polyester, polyethersulfone, polyarylate, polyphenylene sulfide, polyamide 4/6 or polyamide 6T, and more preferably polyphenylene sulfide or liquid crystal polyester because of excellent heat resistance and electrical insulation. . And since it is excellent also in the thin-wall moldability in addition to the point which is excellent in heat resistance and electrical insulation, liquid crystalline polyester is especially preferable. As described above, when the liquid crystalline polyester having excellent thin-wall moldability is used as the thermoplastic resin, the moldability at the time of molding a relatively complicated shape of electric / electronic parts becomes particularly good.

Hereinafter, polyphenylene sulfide and liquid crystal polyester will be described.
Polyphenylene sulfide is typically a resin mainly containing a repeating unit represented by the following formula (10). Such polyphenylene sulfide can be produced by a reaction of a halogen-substituted aromatic compound and an alkali sulfide disclosed in “US Pat. No. 2,513,188” and “Japanese Examined Patent Publication No. 44-27671”, “US Pat. No. 3,274,165”. A method of performing a condensation reaction in the presence of an alkali catalyst or a copper salt of a thiophenol disclosed in the specification, or an aromatic compound disclosed in Japanese Patent Publication No. 46-27255 Examples include a method of performing a condensation reaction with sulfur chloride under a Lewis acid catalyst. Moreover, you may use the commercially available polyphenylene sulfide (for example, polyphenylene sulfide by Dainippon Ink & Chemicals, Inc.) which can be obtained easily.

The liquid crystalline polyester is a liquid crystalline polyester that exhibits liquid crystallinity in a molten state, and is preferably melted at a temperature of 450 ° C. or lower. The liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide. Here, the “liquid crystal polyester amide” has an ester bond (—O—CO—) and an amide bond (—NH—CO—) in the polymer skeleton. “Liquid crystal polyester ether” has an ester bond and an ether bond (—O—) in the polymer skeleton. The “liquid crystal polyester carbonate” has an ester bond and a carbonate bond (—O—CO—O—) in the polymer skeleton. The “liquid crystal polyester imide” has an ester bond and an imide structure represented by the following chemical formula in a polymer skeleton.

The liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer. Here, the “fully aromatic liquid crystal polyester” is, for example, a polyester called a thermotropic liquid crystal polymer,
(1) Composed of a combination of aromatic dicarboxylic acid, aromatic diol and aromatic hydroxycarboxylic acid (2) Consisting of different types of aromatic hydroxycarboxylic acid (3) Combination of aromatic dicarboxylic acid and aromatic diol The thing which consists of etc. is mentioned. In addition, instead of these aromatic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids, their ester-forming derivatives may be used as raw materials. “Aromatic” is a group of cyclic unsaturated organic compounds represented by benzene.

As a typical example of liquid crystal polyester,
(I) An aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine are polymerized (polycondensed). thing,
(II) a polymer obtained by polymerizing plural kinds of aromatic hydroxycarboxylic acids,
(III) A polymer obtained by polymerizing an aromatic dicarboxylic acid and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine and an aromatic diamine,
(IV) What polymerizes polyester, such as a polyethylene terephthalate, and aromatic hydroxycarboxylic acid is mentioned. Here, the “aromatic hydroxycarboxylic acid” is a compound represented by the following general formula (a). The aromatic dicarboxylic acid is a compound represented by the following general formula (b). The aromatic diol is a compound represented by the following general formula (c). The aromatic hydroxyamine is a compound represented by the following general formula (d). An aromatic diamine is a compound represented by the following general formula (e).
(A) HO—Ar ¹⁰ —COOH
(B) HOOC-Ar ²⁰ -COOH
(C) HO—Ar ³⁰ —OH
(D) NH ₂ —Ar ⁴⁰ —OH
(E) NH ₂ —Ar ⁵⁰ —NH ₂
(However, Ar ¹⁰ , Ar ²⁰ , Ar ³⁰ , Ar ⁴⁰ and Ar ⁵⁰ in the formula are the same or different and each represents a divalent aromatic group.)
Examples of the divalent aromatic group include a phenylene group, a naphthylene group, and a biphenylylene group.
Here, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine, and the aromatic diamine are each independently replaced with a part or all of the polymerizable derivative. Also good.

Examples of polymerizable derivatives of a compound having a carboxyl group such as aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group (ester), carboxyl Examples include those obtained by converting a group into a haloformyl group (acid halide), and those obtained by converting a carboxyl group into an acyloxycarbonyl group (acid anhydride).
Examples of polymerizable derivatives of hydroxyl group-containing compounds such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating hydroxyl groups and converting them to acyloxyl groups (acylated products) ).
Examples of polymerizable derivatives of amino group-containing compounds such as aromatic hydroxyamines and aromatic diamines include those obtained by acylating an amino group and converting it to an acylamino group (acylated product).

The liquid crystalline polyester preferably has a repeating unit represented by the following general formula (1) (hereinafter sometimes referred to as “repeating unit (1)”). The repeating unit (1) and the following general formula (2) ) (Hereinafter sometimes referred to as “repeat unit (2)”) and a repeat unit represented by the following general formula (3) (hereinafter referred to as “repeat unit (3)”). More preferably).

(1) —O—Ar ¹ —CO—
(2) —CO—Ar ² —CO—
(3) —X—Ar ³ —Y—
(In the formula, Ar ¹ is a phenylene group, a naphthylene group or a biphenylylene group; Ar ² and Ar ³ are each independently a phenylene group, a naphthylene group, a biphenylylene group or a group represented by the following general formula (4): Yes; X and Y are each independently an oxygen atom or imino group; one or more hydrogen atoms in Ar ¹ , Ar ² and Ar ³ are each independently substituted with a halogen atom, an alkyl group or an aryl group May be.)
(4) —Ar ⁴ —Z—Ar ⁵ —
(In the formula, Ar ⁴ and Ar ⁵ are each independently a phenylene group or a naphthylene group; Z is an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group.)

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
For example, the alkyl group preferably has 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group Group, 2-ethylhexyl group, n-octyl group, n-nonyl group and n-decyl group.
For example, the aryl group preferably has 6 to 20 carbon atoms. Specific examples include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group. When one or more hydrogen atoms in Ar ¹ , Ar ^2, and Ar ³ are substituted with these groups, the number is as follows for each group represented by Ar ¹ , Ar ^2, or Ar ³ , respectively. Independently, it is preferably 2 or less, more preferably 1.

As an example of the alkylidene group, the number of carbon atoms is preferably 1 to 10. Specific examples include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group, and a 2-ethylhexylidene group. *

The repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid. As the repeating unit (1), Ar ¹ is a 1,4-phenylene group (repeating unit derived from p-hydroxybenzoic acid), and Ar ¹ is a 2,6-naphthylene group (6-hydroxy Preferred is a repeating unit derived from -2-naphthoic acid.

The repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid. As the repeating unit (2), Ar ² is a 1,4-phenylene group (repeating unit derived from terephthalic acid), Ar ² is a 1,3-phenylene group (repeating unit derived from isophthalic acid) ), Ar ² is a 2,6-naphthylene group (repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar ² is a diphenyl ether-4,4′-diyl group (diphenyl) Preferred is a repeating unit derived from ether-4,4′-dicarboxylic acid).

The repeating unit (3) is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxylamine or aromatic diamine. As the repeating unit (3), Ar ³ is a 1,4-phenylene group (a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine), and Ar ³ is a 4,4′-biphenylylene group. (Repeating units derived from 4,4′-dihydroxybiphenyl, 4-amino-4′-hydroxybiphenyl or 4,4′-diaminobiphenyl) are preferred.

The content of the repeating unit (1) is the total amount of all repeating units constituting the liquid crystal polyester (the substance of each repeating unit is obtained by dividing the mass of each repeating unit constituting the liquid crystal polyester by the formula weight of each repeating unit). The equivalent amount (mole) is obtained and the total of these is preferably 30 mol% or more, more preferably 30 to 80 mol%, still more preferably 40 to 70 mol%, particularly preferably 45 to 65 mol%. Mol%.
The content of the repeating unit (2) is preferably 35 mol% or less, more preferably 10 to 35 mol%, still more preferably 15 to 30 mol%, based on the total amount of all repeating units constituting the liquid crystal polyester. Particularly preferred is 17.5 to 27.5 mol%.
The content of the repeating unit (3) is preferably 35 mol% or less, more preferably 10 to 35 mol%, still more preferably 15 to 30 mol%, based on the total amount of all repeating units constituting the liquid crystal polyester. Particularly preferred is 17.5 to 27.5 mol%.
The higher the content of the repeating unit (1), the easier it is to improve the melt flowability, heat resistance, strength and rigidity of the liquid crystalline polyester. However, if the content is too large, the melting temperature and melt viscosity tend to increase, and the temperature required for molding. Tends to be high.

The ratio between the content of the repeating unit (2) and the content of the repeating unit (3) is expressed as [content of repeating unit (2)] / [content of repeating unit (3)] (mol / mol). The ratio is preferably 0.9 / 1 to 1 / 0.9, more preferably 0.95 / 1 to 1 / 0.95, and still more preferably 0.98 / 1 to 1 / 0.98.

The liquid crystal polyester may have two or more repeating units (1) to (3) independently. The liquid crystal polyester may have a repeating unit other than the repeating units (1) to (3), but the content thereof is preferably 10 with respect to the total amount of all repeating units constituting the liquid crystal polyester. The mol% or less, more preferably 5 mol% or less.

The liquid crystal polyester preferably has, as the repeating unit (3), X and Y each having an oxygen atom, that is, a repeating unit derived from a predetermined aromatic diol. As the repeating unit (3), More preferably, X and Y each have only an oxygen atom. By doing in this way, liquid crystalline polyester tends to become low in melt viscosity.

The liquid crystalline polyester comprises a repeating unit derived from at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid as the repeating unit (1), and a repeating unit ( 2) as a repeating unit derived from one or more aromatic dicarboxylic acids selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and as repeating unit (3) hydroquinone and 4,4′-dihydroxy It is preferable to have a repeating unit derived from at least one aromatic diol selected from the group consisting of biphenyl, and it is more preferable to have only these repeating units. Specifically, as repeating unit (1), Ar ¹ is a 1,4-phenylene group (repeating unit derived from p-hydroxybenzoic acid); as repeating unit (2), Ar ² is 1,4 A group having a phenylene group (repeating unit derived from terephthalic acid) and a group in which Ar ² is a 1,3-phenylene group (repeating unit derived from isophthalic acid); Ar ³ is 4 as the repeating unit (3) , 4′-biphenylylene groups (repeating units derived from 4,4′-dihydroxybiphenyl) are more preferred.

The liquid crystal polyester is preferably produced by melt polymerizing raw material monomers corresponding to the repeating units constituting the liquid crystal polyester and solid-phase polymerizing the obtained polymer (prepolymer). Thereby, high molecular weight liquid crystal polyester having high heat resistance, strength and rigidity can be produced with good operability. Melt polymerization may be carried out in the presence of a catalyst. Examples of the catalyst in this case include metals such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide. And nitrogen-containing heterocyclic compounds such as 4- (dimethylamino) pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.

The liquid crystal polyester has a flow initiation temperature of preferably 270 ° C. or higher, more preferably 270 ° C. to 400 ° C., and further preferably 280 ° C. to 380 ° C. As the flow start temperature is higher, the heat resistance, strength, and rigidity are more likely to be improved. However, if the flow start temperature is too high, the melting temperature and the melt viscosity are likely to be high, and the temperature required for molding is likely to be high.
As described above, when solid phase polymerization is performed in the production of liquid crystal polyester, the flow start temperature of liquid crystal polyester can be set to 270 ° C. or higher in a relatively short time.

The flow start temperature is also called flow temperature or flow temperature, and the temperature is raised at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm ² ) using a capillary rheometer while liquid crystal polyester is used. Is a temperature showing a viscosity of 4800 Pa · s (48000 poise) when extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm, and is a measure of the molecular weight of the liquid crystalline polyester (Naide Koide, “ “Liquid Crystal Polymers—Synthesis / Molding / Application—”, see CMC Corporation, June 5, 1987, p.

The alumina fine particles (component (B)) are preferably fine particles made of α-alumina, and the content of aluminum oxide (Al ₂ O ₃ ) is 95% by mass or more based on the total mass of the alumina fine particles, Those having a volume average particle size of 0.1 to 50 μm are particularly suitable.
The higher the content of aluminum oxide, the better the resulting molded product has better electrical insulation and thermal conductivity. Therefore, the content is preferably 99% by mass or more, more preferably 99.5% by mass or more. preferable.
The volume average particle size of the alumina fine particles is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, and particularly preferably 0.1 to 10 μm. Here, the “volume average particle diameter” of the alumina fine particles is measured using a microtrack particle size analyzer (for example, HRA manufactured by Nikkiso Co., Ltd.), and the alumina fine particles are 2% by mass aqueous sodium hexametaphosphate. After being sufficiently dispersed using an ultrasonic cleaning device, the laser beam is irradiated and the diffraction (scattering) is measured (particle size distribution measurement by laser diffraction scattering measurement).

As long as the alumina fine particles satisfy the aluminum oxide content as described above, the shape may be any of spherical, polyhedral and crushed particles.
However, the alumina fine particles preferably have a BET specific surface area of 1.0 to 5.0 m ² / g, and the alumina fine particles are crushed particles in that the specific surface area tends to be relatively large. Particularly preferred. When the BET specific surface area of the alumina fine particles is in the range of 1.0 to 5.0 m ² / g, when the thermoplastic resin composition obtained by the production method according to the present invention is melt-molded to obtain a molded body The damage of the mold used for molding can be further reduced, and the resulting molded product is more excellent in thermal conductivity. From the viewpoint of further excellent such effects, the BET specific surface area of the alumina fine particles is more preferably 1.0 to 3.0 m ² / g, and particularly preferably 1.0 to 2.5 m ² / g. preferable. In order to obtain such alumina fine particles, commercially available alumina fine particles as described later may be selected from those having a BET specific surface area of 1.0 to 5.0 m ² / g, Alumina particles having an appropriate volume average particle size (for example, about 40 to 70 μm) are prepared, crushed by various known means, and the specific surface area is increased, so that the BET specific surface area is 1.0 to 5 An alumina fine particle of 0.0 m ² / g may be prepared. Examples of the crushing means at this time include a method using a pulverizer such as a jet mill, a micron mill, a ball mill, a vibration mill, and a media mill.

Examples of the method for measuring the BET specific surface area of alumina fine particles include the following nitrogen adsorption method. First, after the alumina fine particles are vacuum degassed at 120 ° C. for 8 hours, the adsorption isotherm by nitrogen is measured using a constant volume method. By using this adsorption isotherm, the specific surface area is calculated by the BET single point method. As an apparatus used at this time, for example, “BELSORP-mini” manufactured by Nippon BEL Co., Ltd. may be mentioned.

Commercially available products may be used as the alumina fine particles. Examples of commercially available products of alumina fine particles include alumina fine particles manufactured by Sumitomo Chemical Co., Ltd., Showa Denko Co., Ltd., and Nippon Light Metal Co., Ltd. Among these commercially available products, the BET specific surface area is preferably 1.0 to 5.0 m ² / g, more preferably 1.0 to 3.0 m ² / g as described above, and the volume average particle size is preferably May be selected from 0.1 to 50 μm.

The alumina fine particles preferably have a bimodal particle size distribution determined by laser diffraction scattering measurement. In order to satisfy the preferable volume average particle size as described above, the particle size distribution has a volume average particle size of 1 It is more preferable to have bimodality having local maximum values in the range of ˜5 μm and the volume average particle size in the range of 0.1 to 1 μm. By using alumina fine particles having such a bimodal particle size distribution, the resulting molded body is more highly filled with alumina fine particles and becomes more excellent in thermal conductivity.
Alumina fine particles having such a bimodal particle size distribution are commercially available. Also, alumina fine particles having a bimodal particle size distribution can be obtained by mixing two types of alumina fine particles having different particle sizes. Here, “bimodal” means that the particle size distribution has two maximum values.
“Maximum value” means the maximum value of intensity in one mountain-shaped waveform in a particle size distribution diagram (horizontal axis: particle size, vertical axis: intensity at the particle size) representing the distribution of the abundance ratio of particles. .

Here, the “bimodality” will be described with reference to the drawings. 1 and 2 are schematic views showing an outline of a bimodal particle distribution obtained by laser diffraction scattering measurement. In the schematic diagram, the horizontal axis represents the particle size, and the right side represents the larger particle size. The vertical axis represents the strength at the particle size. FIG. 1 shows a typical bimodal particle size distribution, and the particle size distribution has two maximum values (a first maximum value and a second maximum value). In addition, as shown in FIG. 2, the bimodal particle size distribution is also used when the particle size distribution is such that the first maximum value appears like a shoulder peak with respect to the peak having the second maximum value. And In these bimodal particle size distributions, the first maximum value is in the range of the volume average particle size of 0.1 to 1 μm, and the second maximum value is in the range of the volume average particle size of 1 to 5 μm. A certain alumina fine particle is more preferable.

The fibrous filler (component (C)) may be an inorganic filler or an organic filler.
Examples of the fibrous inorganic filler include glass fibers; carbon fibers such as pan-based carbon fibers and pitch-based carbon fibers; ceramic fibers such as silica fibers, alumina fibers and silica-alumina fibers; and metal fibers such as stainless fibers. It is done. In addition, whiskers such as potassium titanate whisker, barium titanate whisker, wollastonite whisker, aluminum borate whisker, silicon nitride whisker, and silicon carbide whisker are also included.
Examples of the fibrous organic filler include polyester fibers and aramid fibers.
Among these, the fibrous filler is preferably carbon fiber, glass fiber, wollastonite whisker, aluminum borate whisker and potassium titanate whisker, and more preferably carbon fiber and glass fiber.
A fibrous filler may be used individually by 1 type, and may use 2 or more types together.

The fibrous filler preferably has a number average fiber diameter of 1 to 15 μm and a number average aspect ratio (number average fiber length / number average fiber diameter) of 10 or more. By using a long fibrous filler having such a number average aspect ratio, the mechanical strength of the molded body is further improved. The number average aspect ratio of the fibrous filler is more preferably 50 or more, and preferably 500 or less, more preferably 400 or less. The number average fiber diameter and the number average fiber length of the fibrous filler can be measured by observing the fibrous filler with an electron microscope.

As the fibrous filler, for example, a commercially available product may be used as it is, or the surface is a coupling agent (silane coupling agent) in order to improve the dispersibility with respect to the thermoplastic resin and the adhesion to the thermoplastic resin. , Titanium coupling agents, etc.) or surface treated with a surfactant or the like may be used.

Examples of the silane coupling agent include methacryl silane, vinyl silane, epoxy silane, amino silane, and the like. Examples of the titanium coupling agent include titanic acid.
Examples of the surfactant include higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid salts and the like.

In the present invention, other than the thermoplastic resin, the alumina fine particles, and the fibrous filler (components (A) to (C)) as long as they do not interfere with the effects of the present invention as necessary during melt-kneading. Components may be supplied (blended), and the thermoplastic resin composition may contain these other components.
Examples of the other components include fillers and additives other than the alumina fine particles and the fibrous filler.

Examples of the filler other than the alumina fine particles and the fibrous filler include talc, glass flakes, silica particles, calcium carbonate and the like, and among these, talc is preferable.
Examples of the additives include mold release improvers such as fluororesins; colorants such as dyes and pigments; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; .

In the present invention, it is preferable that the supply amount of the alumina fine particles is larger than the supply amount of the fibrous filler by mass comparison. When the ratio of the supply amount of the alumina fine particles to the supply amount of the thermoplastic resin composition is W _B (mass%) and the ratio of the supply amount of the fibrous filler is W _C (mass%), W _B / more preferably the value of W _C is 2 or more, particularly preferably 3 or more. Specifically, the value of W _B / W _C is preferably 2 to 100, and more preferably 3 to 50.
Further, the total supply amount of the alumina fine particles and the fibrous filler is preferably 100 parts by mass or more and more preferably 150 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin supply. Specifically, the total supply amount of the alumina fine particles and the fibrous filler is preferably 100 to 500 parts by mass, and 150 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin supply. Is more preferable.

The thermoplastic resin composition is preferably obtained by extrusion melting and kneading the thermoplastic resin, alumina fine particles and fibrous filler (components (A) to (C)), and obtained by extrusion melting and kneading into pellets. .

A typical melt-kneading extruder used for extrusion melt-kneading includes a nozzle that is a small hole for extruding a heated melt, includes a cylinder having heating means, and supplies the raw material to be melt-kneaded to the cylinder A single-screw melt kneading extruder provided with a supply port for pushing out the heated melt is preferably provided in the cylinder, and one screw is rotationally driven in the cylinder. Alternatively, a twin-screw melt kneading extruder in which two screws are rotationally driven in different directions or in the same direction in the cylinder may be used, but a biaxial melt kneading extruder is preferable.

In the melt-kneading extruder, the ratio (L / D) of the effective length (L) of the screw to the diameter (D) of the screw is preferably 20 or more (where L and D are the same scale unit). By doing in this way, a thermoplastic resin, an alumina fine particle, and a fibrous filler are disperse | distributed more uniformly. Here, “the effective length of the screw” means the length in the axial direction of the screw, and “the diameter of the screw” means the nominal outer diameter of the screw.

In the present invention, the kneaded product (thermoplastic resin composition) extruded from the nozzle of the melt-kneading extruder to the outside of the extruder is cooled at a cooling rate of 35 ° C./second or less. By doing in this way, the molded object obtained from the thermoplastic resin composition will have the outstanding heat conductivity and mechanical strength.

The said cooling rate can be adjusted with the cooling method of the kneaded material extruded from the melt-kneading extruder, and the extrusion amount of a kneaded material, for example.
The cooling rate is, for example, the temperature a (° C.) of the kneaded product immediately after being extruded from the nozzle of the melt-kneading extruder, and the time after the kneaded product is extruded from the nozzle (after measuring the temperature a (° C.)). This is obtained by measuring the temperature b (° C.) of the kneaded material after elapse of t (seconds) and dividing the difference between the temperature a and the temperature b by the time t ((ab) / t). The temperature of the kneaded product can be easily measured using, for example, an infrared radiation thermometer. By setting the time t to 3 to 10 seconds, for example, the cooling rate can be measured with higher accuracy.

In the present invention, the kneaded product extruded from the nozzle has a cooling rate of 35 ° C./second during cooling until it is heated again, such as until it is subjected to production of a molded body as a thermoplastic resin composition. What is necessary is as follows. Usually, since the kneaded material immediately after being extruded from the nozzle is hot, when cooling by adding some forced cooling operation to this, for example, the cooling rate during this cooling operation is 35 ° C./second or less. This cooling operation may be continued until at least the cooling rate does not exceed 35 ° C./second in a state where heat is naturally radiated. If the forced cooling operation is not performed on the kneaded material immediately after being extruded, the cooling rate is generally considered not to exceed 35 ° C./sec. Is.

In the present invention, when the kneaded product extruded from the nozzle using a cutting machine is cut into a pellet or the like, the temperature b is preferably set to the temperature of the kneaded product immediately before the entrance of the cutting machine. In this case, the time t is a time until the extruded kneaded material reaches the entrance of the cutting machine from the nozzle.

The forced cooling of the kneaded product is preferably performed by air cooling, water cooling, or the like. For example, if a strand cooling take-up device is used, the cooling rate of the kneaded product can be adjusted relatively easily by adjusting the conditions for spraying cooling shower water and blowing air. Examples of such a strand cooling and taking device include those manufactured by Isuzu Chemical Industries and Tanaka.
For example, the cooling rate during water cooling can be 35 ° C./second or less, and the cooling rate during air cooling can be 30 ° C./second or less.

The extrusion rate of the kneaded product is preferably 5 to 300 kg / hour, more preferably 10 to 100 kg / hour. By setting it as such a range, the cooling rate of a kneaded material can be adjusted more easily.

<Molded body>
The molded body according to the second aspect of the present invention is characterized by molding the thermoplastic resin composition obtained by the production method according to the first aspect of the present invention.
Such a molded article is excellent in electrical insulation, thermal conductivity and strength by using the thermoplastic resin composition.

The molded body according to the fourth aspect of the present invention is formed by molding a thermoplastic resin composition obtained by the production method according to the third aspect of the present invention.
Such a molded article is excellent in electrical insulation, thermal conductivity and strength by using the thermoplastic resin composition.

As the molding method of the thermoplastic resin composition, a suitable one can be appropriately selected depending on the shape of the target molded body, and among these, a melt molding method such as an injection molding method or an extrusion injection molding method is preferable, and an injection molding method is more preferable. preferable. The injection molding method has an advantage that it is easy to mold a molded body having a complicated shape having a thin portion. The molded body according to the present invention obtained by the injection molding method is useful as a part that requires heat conductivity, such as an electric / electronic part.

Injection molding is performed by melting the thermoplastic resin composition using an injection molding machine (for example, “Hydraulic Horizontal Molding Machine PS40E5ASE Model” manufactured by Nissei Plastic Industry Co., Ltd.) It can be performed by heating to a temperature and injecting it into a mold having the desired cavity shape. The temperature at which the thermoplastic resin composition is heated and melted for injection is [Tp ′ + 10] ° C. or more and [Tp ′ + 50] ° C. or less based on the flow start temperature Tp ′ ° C. of the thermoplastic resin composition used. It is preferable to do. The temperature of the mold is preferably selected from the range of room temperature (for example, 23 ° C.) to 180 ° C. from the viewpoint of the cooling rate and productivity of the thermoplastic resin composition.

For example, the molded body can have a volume resistivity of 1 × 10 ¹⁰ Ωm or more at 23 ° C. Here, the “volume specific resistance value” is a value measured according to “ASTM D257”.
In addition, the molded body can have a thermal conductivity of preferably 0.92 W / (m · K) or more and a bending strength of preferably 98 MPa or more, for example. Here, “thermal conductivity” is a value obtained from the product of thermal diffusivity, specific heat and specific gravity, and “bending strength” is a value measured according to “ASTM D790”.

The molded body can be applied to various uses, but is particularly suitable as an electric / electronic component because it is excellent in electrical insulation, thermal conductivity and mechanical strength. Among these, the molded body is at least one selected from the group consisting of a sealing material for electronic elements, an insulator, a reflector for display device, a casing for storing electronic elements, a motor insulator for automobiles and industrial machines, and a surface mount component. It is preferable to use as a component. Further, as the surface mount component, a connector is suitable. In such electric / electronic parts, heat is generated by the operation of the electric / electronic equipment provided with these parts, and if the heat dissipation of these parts is insufficient, malfunctions occur and the reliability of the equipment decreases. Easy to do. On the other hand, the molded body according to the present invention has a characteristic advantageous for heat dissipation in that the thermal conductivity becomes relatively isotropic as described above. Therefore, when the molded body according to the present invention is used as the electrical / electronic component, even if these components have a relatively complicated shape, the molded body according to the present invention efficiently dissipates heat due to the isotropic thermal conductivity. Realize stable operation of electrical and electronic equipment equipped with

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples. In addition, the flow start temperature of liquid crystalline polyester was measured with the following method.

(Measurement of flow start temperature of liquid crystal polyester)
Using a flow tester (manufactured by Shimadzu Corp., CFT-500 type), about 2 g of liquid crystal polyester was filled into a cylinder equipped with a die having a nozzle having an inner diameter of 1 mm and a length of 10 mm, and 9.8 MPa (100 kg / cm ^2). The liquid crystal polyester was melted while being heated at a rate of 4 ° C./min under a load of 4), extruded from a nozzle, and a temperature showing a viscosity of 4800 Pa · s (48000 poise) was measured.

The alumina fine particles and fibrous filler used in this example are as follows.
(Alumina fine particles)
Fine low soda alumina AL-45-2 (manufactured by Showa Denko KK): volume average particle size 1.4 μm (in the particle size distribution, the volume average particle size is in the range of 1.0 to 2.0 μm and the volume average particle size It was bimodal, each having a maximum value in the range of 0.2 to 0.4 μm.), BET specific surface area 1.8 m ² / g
(Fibrous filler)
DIALEAD K223HE (Mitsubishi Chemical Corporation): Carbon fiber Chopped glass fiber CS03JAPX-1 (Asahi Fiber Glass Co., Ltd.): Glass fiber (plate-like inorganic filler)
Talc X-50 (Nihon Talc): Talc

<Manufacture of liquid crystal polyester>
[Production Example 1]
To a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 994.5 g (7.2 mol) of p-hydroxybenzoic acid, 446.9 g of 4,4′-dihydroxybiphenyl ( 2.4 mol), 299.0 g (1.8 mol) of terephthalic acid, 99.7 g (0.6 mol) of isophthalic acid, and 1347.6 g (13.2 mol) of acetic anhydride. After substituting with nitrogen gas, the temperature was raised to 150 ° C. over 30 minutes with stirring under a nitrogen gas stream, and this temperature (150 ° C.) was maintained and refluxed for 1 hour.
Next, while distilling off the by-product acetic acid and unreacted acetic anhydride to be distilled off, the temperature was raised to 320 ° C. over 2 hours and 50 minutes. Got.
The obtained prepolymer was cooled to room temperature, pulverized with a coarse pulverizer, then heated in a nitrogen gas atmosphere from room temperature to 250 ° C. over 1 hour, raised from 250 ° C. to 285 ° C. over 5 hours, Solid-state polymerization was performed by holding at 285 ° C. for 3 hours. After the completion of the solid phase polymerization, the flow initiation temperature of the obtained liquid crystal polyester was 327 ° C.

<Production of Liquid Crystalline Polyester Composition and Molded Body>
[Example 1]
(Production of liquid crystal polyester composition)
The liquid crystal polyester obtained in Production Example 1 and the alumina fine particles and the fibrous filler were mixed in the same direction biaxial melt kneading extruder ("PCM-30HS" manufactured by Ikekai Tekko Co., Ltd.) in the ratio shown in Table 1. Then, after supplying from the supply port provided in this cylinder and then melt-kneading at 330 ° C., as shown in Table 1, the kneaded product is extruded in a strand form from the nozzle of the extruder and cooled, and then a strand cutter is used. The pellet-like liquid crystal polyester composition was obtained by cutting and granulating. At this time, the strand-like kneaded material was cooled by air cooling by blowing air using a strand cooling take-up device (manufactured by Isuzu Chemical Industries Ltd.). The cooling rate is the time t from the nozzle to the strand cutter, which is the difference between the temperature a of the kneaded product immediately after being extruded from the nozzle of the extruder and the temperature b of the kneaded product immediately before the strand cutter entrance. The value was divided.

(Manufacture of molded products)
Using an injection molding machine (“PS40E5ASE type” manufactured by Nissei Plastic Industry Co., Ltd.), the liquid crystal polyester composition obtained above was injected under the conditions of a cylinder temperature of 350 ° C., a mold temperature of 130 ° C., and an injection rate of 30 cm ³ / s. It shape | molded and obtained two types of molded objects (shaped body (1) and (2)) of the shape shown below.
Molded body (1): 64 mm × 64 mm × 1 mm
Molded body (2): 126 mm × 12 mm × 6 mm

[Example 2, Comparative Examples 1 and 2]
A liquid crystal polyester composition and a molded body were produced in the same manner as in Example 1 except that the production conditions were as shown in Table 1. The strand-shaped kneaded product was water-cooled by spraying cooling shower water.

<Evaluation of molded body>
With respect to the molded bodies obtained in each of the above Examples and Comparative Examples, the thermal conductivity (W / (m · K)), bending strength (MPa) and volume resistivity (Ωm) in the thickness direction were determined by the following methods. Measured and evaluated for thermal conductivity, strength and insulation in the thickness direction. The results are shown in Table 1.

(Measurement of thermal conductivity in the thickness direction)
A central part of the molded body (1) was cut out to obtain a sample for thermal conductivity evaluation. The thermal diffusivity of this sample was measured using a laser flash method thermal constant measuring device (“TC-7000” manufactured by ULVAC-RIKO Inc.). Further, the specific heat of this sample was measured using DSC ("DSC7" manufactured by PERKIN ELMER), and the specific gravity of this sample was measured using an automatic specific gravity measuring device ("ASG-320K" manufactured by Kanto Major). . The thermal conductivity was determined from the product of thermal diffusivity, specific heat and specific gravity ([thermal conductivity] = [thermal diffusivity] × [specific heat] × [specific gravity]).

(Measurement of bending strength)
The molding (2) was measured according to “ASTM D790”.

(Measurement of volume solid resistance)
The molded body (1) was measured at 23 ° C. by volume resistivity measurement in accordance with “ASTM D257” (using “Digital Super Insulation / Micro Ammeter DSM-8104” manufactured by Toa DK Corporation).

As is clear from the above results, the molded products of Examples 1 and 2 in which the kneaded product extruded from the nozzle of the extruder was cooled at a cooling rate of 20 to 22 ° C./second were all thermal conductivity in the thickness direction. It was excellent in strength and insulation. On the other hand, the molded product of Comparative Example 1 in which the kneaded product extruded from the nozzle of the extruder was cooled at a cooling rate of 42 ° C./second was inferior in thermal conductivity in the thickness direction. In addition, the molded product of Comparative Example 2 in which the kneaded product was cooled at a cooling rate of 38 ° C./second was inferior in thermal conductivity and strength in the thickness direction.

The present invention can be used for manufacturing electrical / electronic components that require high heat dissipation.

Claims (12)

1. Using a melt-kneading extruder equipped with a nozzle, a cylinder and a screw installed in the cylinder, the following component (A), the following component (B) and the following component (C) are supplied from a supply port provided in the cylinder. Supplying the cylinder and melt-kneading the component (A), the component (B) and the component (C) to obtain a kneaded product,
   A method for producing a thermoplastic resin composition, comprising: extruding the kneaded material from the nozzle to the outside of the melt-kneading extruder; and cooling the kneaded material at a cooling rate of 35 ° C./second or less.
   Component (A) Thermoplastic resin Component (B) Alumina fine particle Component (C) Fibrous filler
2. The method for producing a thermoplastic resin composition according to claim 1, wherein the component (B) has a BET specific surface area of 1.0 to 5.0 m ² / g.
3. The method for producing a thermoplastic resin composition according to claim 1 or 2, wherein the particle size distribution obtained by laser diffraction scattering measurement of the component (B) is bimodal.
4. The particle size distribution obtained by laser diffraction scattering measurement of the component (B) is
   Within a volume average particle size range of 1-5 μm,
   A volume average particle size in the range of 0.1 to 1 μm;
   The method for producing a thermoplastic resin composition according to any one of claims 1 to 3, wherein each of the two has a maximal value.
5. The component (C) is at least one substance selected from the group consisting of carbon fiber, glass fiber, wollastonite whisker, aluminum borate whisker and potassium titanate whisker. The manufacturing method of the thermoplastic resin composition of description.
6. The method for producing a thermoplastic resin composition according to any one of claims 1 to 5, wherein the component (A) is a liquid crystal polyester.
7. The liquid crystal polyester is
   repeating units derived from at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid;
   Repeating units derived from at least one aromatic diol selected from the group consisting of hydroquinone and 4,4′-dihydroxybiphenyl;
   Repeating units derived from at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid;
   Have
   The total number of repeating units derived from the aromatic hydroxycarboxylic acid is 30 to 80 mol%, and the total number of repeating units derived from the aromatic diol is 10 to 35, based on the total amount of all repeating units constituting the liquid crystal polyester. The method for producing a thermoplastic resin composition according to claim 6, wherein the thermoplastic resin composition has a total of 10 to 35 mol% of repeating units derived from the aromatic dicarboxylic acid.
8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein a total supply amount of the components (B) and (C) is 100 parts by mass or more with respect to 100 parts by mass of the component (A). Manufacturing method.
9. A molded product obtained by molding the thermoplastic resin composition obtained by the production method according to any one of claims 1 to 8.
10. The molded product according to claim 9, wherein the volume resistivity value at 23 ° C. is 1 × 10 ¹⁰ Ωm or more.
11. The molded article according to claim 9 or 10, which is for electric / electronic parts.
12. The electrical / electronic component is at least one component selected from the group consisting of a sealing material for electronic elements, an insulator, a reflector for a display device, a housing for storing electronic elements, and a surface mounting component. Molded body.

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