JP2014152270A - High thermal conductive thermoplastic resin composition, and production method of high thermal conductive thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in thermal conductivity, maintaining such high thermal conductivity without blending a large amount of a high thermal conductive inorganic compound, and capable of being injection molded even when a general purpose mold for injection molding is used.SOLUTION: A thermoplastic resin composition mainly includes a thermoplastic resin of which a main chain has a repeating unit structure represented by general formula (1), where Aris a trivalent aromatic residue obtained by removing three carboxyl groups from an aromatic tricarboxylic acid, Sp is a bivalent straight substituent which may have a branch having 2 to 20 carbon atoms in the main chain, Aris a substituent selected from the group consisting of an aromatic group, a condensed aromatic group, a heterocyclic group, an alicyclic group and a cycloaliphatic and heterocyclic group, and an inorganic filler.

Description

  The present invention relates to a heat-dissipating material excellent in thermal conductivity, and relates to a thermoplastic resin composition that can be injection-molded, and a method for producing a thermoplastic resin that constitutes the thermoplastic resin composition.

  When a thermoplastic resin composition is used in various applications such as PC and display housings, electronic device materials, and interior and exterior of automobiles, the heat generated due to the low thermal conductivity of plastics compared to inorganic materials such as metal materials. Difficult to escape may be a problem. In order to solve such problems, attempts have been widely made to obtain a high thermal conductive resin composition by blending a large amount of a high thermal conductive inorganic substance in a thermoplastic resin. As the high thermal conductivity inorganic compound, a high thermal conductivity inorganic material such as graphite, carbon fiber, alumina, boron nitride or the like is usually 30% by volume (hereinafter referred to as “Vol%”) or more, and further, as high as 50 Vol% or more. It is necessary to mix | blend with resin by content.

  However, even if a large amount of the high thermal conductivity inorganic substance is blended, the thermal conductivity of the resin composition is limited because the thermal conductivity of the resin alone is low. Therefore, improvement of the thermal conductivity of the resin alone is required.

  Regarding thermoplastic resins with excellent thermal conductivity of resin alone, there are almost no research reports on thermoplastic resins that have high thermal conductivity due to the resin molded by injection molding without special molding processes such as stretching and magnetic field orientation. There is no patent document 1 as a few report examples. However, although the thermoplastic resin described in Patent Document 1 can obtain a molded article exhibiting high thermal conductivity by molding by injection molding, the heat resistance is insufficient.

  Non-Patent Documents 1 to 4 describe polyesterimides exhibiting a liquid crystal phase, but Non-Patent Documents 1 to 4 describe (i) thermal conductivity of polyesterimide and (ii) inorganic to polyesterimide. There is no description at all about blending other blends such as fillers into a resin composition.

International Publication Number WO2010 / 050202 Pamphlet (Publication May 6, 2010)

Macromolecules, Vol. 21, P551 (1988) Polymer, Vol. 28, P1772 (1987) Mol. Cryst. Liq. Cryst. Inc. Nonlin. Opt. , Vol. 157, P13 (1988) Polymer, Vol. 35, P5577 (1994)

  The present invention is a thermoplastic resin composition having excellent thermal conductivity, and maintains the high thermal conductivity of the thermoplastic resin composition without blending a large amount of high thermal conductivity inorganic compound, and the thermoplastic resin composition However, it is an object to provide a thermoplastic resin composition that can be injection-molded even with a general-purpose injection mold, and a method for producing a thermoplastic resin constituting the thermoplastic resin composition.

  As a result of intensive investigations, the present inventors have found that a thermoplastic resin having a specific molecular structure has high thermal conductivity, and further excellent thermal conductivity even in a thermoplastic resin composition containing an inorganic filler. The present invention has been found out. That is, the present invention includes the following <1> to <9>.

<1>
The structure of the repeating unit of the main chain is mainly represented by the general formula (1)

(In the formula, Ar ¹ is a trivalent aromatic residue excluding three carboxyl groups of an aromatic tricarboxylic acid, and Sp is a divalent linear substitution which may contain a branch having 2 to 20 main chain atoms. A group, Ar ² represents a substituent selected from the group consisting of an aromatic group, a condensed aromatic group, a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group),
A thermoplastic resin composition comprising an inorganic filler.

<2>
The thermoplastic resin composition according to <1>, wherein a portion corresponding to Sp of the thermoplastic resin is a linear aliphatic hydrocarbon chain or an aliphatic ether chain.

<3>
The thermoplastic resin composition according to <1> or <2>, wherein the number of main chain atoms in a portion corresponding to Sp of the thermoplastic resin is an even number.

<4>
The thermoplastic resin composition according to any one of <1> to <3>, wherein the reduced viscosity of the thermoplastic resin is 0.15 to 2.0 (dL / g).

<5>
The thermoplastic resin composition according to any one of <1> to <4>, wherein the inorganic filler is an inorganic compound having a thermal conductivity of 1 W / (m · K) or more.

<6>
The inorganic filler is at least one inorganic compound selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, beryllium oxide, and diamond. The thermoplastic resin composition according to any one of <1> to <5>.

<7>
The inorganic filler is one or more inorganic compounds selected from the group consisting of graphite, conductive metal powder, soft magnetic ferrite, carbon fiber, conductive metal fiber, and zinc oxide, <1 The thermoplastic resin composition according to any one of> to <5>.

<8>
The thermoplastic resin composition according to any one of <1> to <6>, wherein the volume ratio of the thermoplastic resin to the inorganic filler is 90:10 to 30:70.

<9>
<1>-<8> The molded object containing the thermoplastic resin composition in any one of.

<10>
The structure of the repeating unit of the main chain is mainly represented by the general formula (1)

(In the formula, Ar ¹ is a trivalent aromatic residue excluding three carboxyl groups of an aromatic tricarboxylic acid, and Sp is a divalent linear substitution which may contain a branch having 2 to 20 main chain atoms. Group, Ar ² represents a substituent selected from the group consisting of an aromatic group, a condensed aromatic group, a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group). A method,
(i) represented by general formula (2)

(Wherein Ar ¹ represents a trivalent aromatic residue excluding three carboxyl groups of the aromatic tricarboxylic acid) tribasic acid anhydride,
Formula _{(3): H 2 N-} Sp-NH 2 (3)
And a diamine represented by general formula (4): HO—Ar ² —OH (4)
An imidization step in which a diol represented by the formula (2) is charged into a reactor and an imide group is generated by a reaction between the tribasic acid anhydride represented by the general formula (2) and the diamine represented by the general formula (3);
(ii) an acylation step of acylating the hydroxyl group of the diol represented by the general formula (4) by adding a lower fatty acid anhydride;
(iii) A method for producing a thermoplastic resin, comprising a step of increasing the molecular weight while distilling off lower fatty acids.

<11>
A tribasic acid anhydride represented by the general formula (2), a diamine represented by the general formula (3), and a diol represented by the general formula (4) are charged into a reactor at the same time. The manufacturing method of the thermoplastic resin as described in 10>.

  The thermoplastic resin composition of the present invention is excellent in thermal conductivity, maintains the high thermal conductivity of the thermoplastic resin composition without blending a large amount of a high thermal conductive inorganic compound, and the thermoplastic resin composition. Can be injection-molded even with general-purpose injection molds.

  Furthermore, this invention also provides the manufacturing method which synthesize | combines the thermoplastic resin which comprises the thermoplastic resin composition of this invention simply.

  Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention. Moreover, all the well-known literatures described in this specification are used as reference in this specification. In the present specification, “to” indicating a range indicates “above or below” unless otherwise specified. For example, “A to B” means “A or more and B or less”.

  The thermoplastic resin composition of the present invention is characterized by containing a thermoplastic resin and an inorganic filler described below. In the following description, the thermoplastic resin and the inorganic filler constituting the thermoplastic resin composition of the present invention will be referred to as “the thermoplastic resin of the present invention” and “the inorganic filler of the present invention”, respectively.

<1. Thermoplastic resin of the present invention>
Here, “thermoplastic” in this specification means a property of plasticizing by heating. Although this invention is not specifically limited, For example, it can be determined whether a certain sample is thermoplastic by the resin softening at the time of a heating.

  The thermoplastic resin of the present invention has the property that molecules are regularly aligned by a repeated structure of bent portions and rigid portions to form a periodic higher order structure of about 20 to 60 nm. And this regular periodic high-order structure greatly contributes to transferring heat efficiently. The presence or absence of this periodic higher order structure and the period of the higher order structure can be confirmed by small angle X-ray scattering measurement.

  The thermoplastic resin of the present invention may have a property of forming a liquid crystal phase due to a repeating structure of a bent portion and a rigid portion. The “liquid crystal phase” means a phase state that flows like a liquid while maintaining the molecular alignment state. When the resin is molded at the temperature of the liquid crystal phase, a molded body can be obtained without disturbing the periodic higher-order structure that contributes to thermal conductivity. From the viewpoint of obtaining a molded article having high thermal conductivity, the thermoplastic resin of the present invention preferably forms a liquid crystal phase. Whether the thermoplastic resin can form a liquid crystal phase can be confirmed by differential scanning calorimetry (DSC) and observation with a polarizing microscope. Although it varies depending on the type of liquid crystal, with regard to the thermoplastic resin of the present invention, in DSC, two endothermic peaks corresponding to the transition from the crystal phase to the liquid crystal phase and the transition from the liquid crystal phase to the isotropic phase are observed. Thus, it can be determined that the thermoplastic resin forms a liquid crystal phase. In general, a resin is sandwiched between two glass plates, heated and observed under a polarizing microscope under crossed Nicols, and the optical structure characteristic of the liquid crystal phase can be observed in a molten state, so that the thermoplastic resin can be in a liquid crystal phase. Can be determined.

  In the thermoplastic resin of the present invention, the structure of the repeating unit of the main chain is mainly represented by the general formula (1).

(In the formula, Ar ¹ is a trivalent aromatic residue excluding three carboxyl groups of an aromatic tricarboxylic acid, and Sp is a divalent linear substitution which may contain a branch having 2 to 20 main chain atoms. Group Ar ² represents a substituent selected from the group consisting of an aromatic group, a condensed aromatic group, a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group).

  In the present specification, “mainly” means that the repeating structure of the general formula (1) is 50% or more of the whole molecular chain, preferably 70% or more, more preferably 90%. It means that it is above, more preferably it means 95% or more.

The portion corresponding to Ar ^{1 of the} thermoplastic resin is a trivalent aromatic ring residue excluding three carboxyl groups of the aromatic tricarboxylic acid. The portion corresponding to Ar ^{1 of the} thermoplastic resin is a trivalent benzene ring residue in which 60% or more is obtained by removing three carboxyl groups from trimellitic acid, and the remainder is trivalent based on other aromatic tricarboxylic acids. The aromatic residue is preferably. The ratio of the trivalent benzene ring residue obtained by removing three carboxyl groups from trimellitic acid is more preferably 80% or more, still more preferably 90% or more, and particularly preferably 100%.

As a specific example of a portion corresponding to Ar ^{1 of the} thermoplastic resin,

Any trivalent aromatic residue represented by

  The portion corresponding to Sp of the thermoplastic resin of the present invention is a divalent linear substituent which may include a branch having 2 to 20 main chain atoms, preferably a linear aliphatic hydrocarbon chain or It is an aliphatic ether chain, more preferably a linear aliphatic hydrocarbon chain. Further, the linear substituent in the portion corresponding to Sp of the thermoplastic resin of the present invention may be saturated or unsaturated, but is preferably saturated. When an unsaturated bond is included, sufficient flexibility may not be expressed, and thermal conductivity may be reduced.

  Moreover, the number of main chain atoms of the linear substituent of the part corresponding to Sp of the thermoplastic resin of this invention is 2-20, Preferably it is 4-16, More preferably, it is 4-12. When the number of main chain atoms is 21 or more, the crystallinity may decrease and the thermal conductivity may decrease. Moreover, it is preferable that the number of main chain atoms of the linear substituent of the part corresponding to Sp of the thermoplastic resin of this invention is an even number. In the case of an odd number, the crystallinity may decrease and the thermal conductivity may decrease. Moreover, it is preferable that the linear substituent of the part corresponding to Sp of the thermoplastic resin of this invention does not contain a branch. When including a branch, crystallinity may fall and thermal conductivity may be reduced.

  Moreover, the part corresponding to Sp of the thermoplastic resin of the present invention may contain two or more different linear substituents in the repeating unit. By including two or more different linear substituents, variations in liquid crystal phase transition temperature and melting point can be increased.

Further, the portion corresponding to Ar ^{2 of the} thermoplastic resin of the present invention represents a substituent selected from the group consisting of an aromatic group, a condensed aromatic group, a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group. Preferable specific examples of the portion corresponding to Ar ² include

(Wherein R ^{1 to} R ⁸ each independently represents hydrogen, a lower alkyl group, a lower alkoxy group, F, Cl, Br, I, CN, or NO ₂ , and X represents —CH ₂ —, —C _{(CH 3) 2 -, -} O -, - S -, - CH 2 -CH 2 -, - C = C -, - C≡C -, - CO -, - CO-O -, - CO-NH- , -CH = N-, -CH = N-N = CH-, -N = N- and N (O) = N- represents a divalent substituent selected from the group consisting of:
Any of the groups represented by

(In the formula, each of R ^{1 to} R ⁸ independently represents hydrogen, a lower alkyl group, a lower alkoxy group, F, Cl, Br, I, CN, or NO _2. )
More preferably,

(In the formula, each of R ^{1 to} R ⁸ independently represents hydrogen, a lower alkyl group, a lower alkoxy group, F, Cl, Br, I, CN, or NO _2. )
And particularly preferably

One of them.

The portion corresponding to Ar ^{2 of the} thermoplastic resin of the present invention may contain two or more different substituents in the repeating unit. By including two or more different substituents, variations in liquid crystal phase transition temperature and melting point can be increased.

The reduced viscosity as an index representing the molecular weight of the thermoplastic resin of the present invention is a 1: 1 (volume ratio) mixed solvent of 4-chlorophenol and tetrachloroethane so that the thermoplastic resin has a concentration of 0.5 g / dL. It was dissolved in the solution and the fall time was measured at 25 ° C. using an Ubbelohde viscometer. The reduced viscosity η _sp / c is expressed as follows: when the solvent fall time is t ₀ , the sample solution fall time is t, and the sample concentration is c.

It is represented by

  The reduced viscosity of the thermoplastic resin of the present invention is preferably 0.15 to 2.0 (dL / g). Considering the upper limit, the reduced viscosity of the thermoplastic resin of the present invention is more preferably 0.15 to 1.7 (dL / g), and preferably 0.15 to 1.5 (dL / g). Is more preferable. Considering the lower limit, the reduced viscosity of the thermoplastic resin of the present invention is more preferably 0.20 to 2.0 (dL / g), and 0.25 to 2.0 (dL / g). Is more preferable. Furthermore, when considering the upper limit and the lower limit, the reduced viscosity of the thermoplastic resin of the present invention is more preferably 0.20 to 1.7 (dL / g), and more preferably 0.25 to 1.5 (dL / g). More preferably, When the reduced viscosity is less than 0.15 (dL / g), the strength may decrease. When the reduced viscosity is greater than 2.0 (dL / g), the thermal conductivity is low even if the resin has the same primary structure. It may be significantly reduced.

  The end structure of the thermoplastic resin of the present invention is not particularly limited, but from the viewpoint of obtaining a resin suitable for injection molding, the end is sealed with a hydroxyl group, a carboxyl group, an ester group, an acyl group, an alkoxy group, an amide group, or the like. It is preferable that it is stopped, and it is more preferable that it is sealed with a carboxyl group, an ester group or an amide group from the viewpoint of ease of synthesis. When the terminal has a highly reactive functional group such as an epoxy group or a maleimide group, the resin becomes thermosetting and the injection moldability may be impaired.

  In the present invention, a low molecular weight compound may be used to seal the molecular chain end. The low molecular weight compound used refers to a compound that may optionally contain at least one structure selected from aromatics, condensed aromatics, alicyclic rings, alicyclic heterocyclic rings, or chain structures having a molecular weight of 400 or less. When the molecular weight is 401 or more, the end-capping reaction to the main chain polymer may decrease. The low molecular compound of the present invention needs to have at least one reactive group capable of reacting with a hydroxy group, a carboxyl group and / or an amino group, which is a functional group at the terminal of the polymer to be sealed, to seal the functional group. The reactive group is aldehyde, hydroxy, carboxyl, amine, imino, glycidyl ether, glycidyl ester, allyl-substituted methyl, isocyanate, acetoxy and the like. Preferred are hydroxy, carboxyl, amino and their esters and glycidyl groups. There are no particular limitations on the low molecular weight compound used to seal the molecular chain end as long as the above conditions are satisfied, but from the viewpoints of reactivity and stability of the sealing end, the following formulas (A) to Any compound represented by (C) is exemplified.

(Wherein Y represents a functional group selected from aldehyde, hydroxy, carboxyl, amino, imino, glycidyl ether, glycidyl ester, methyl, isocyanate, acetoxy, carboxyalkyl ester (alkyl 1 to 4 carbon atoms), and carboxyphenyl ester. shown, Z is alkyl having 1 to 20 carbon _{atoms, -Cl, -Br, -OCH 3,} -CN, -NO 2, -NH 2, vinyl, ethynyl, acrylate, phenyl, benzyl, alkyl urea, alkyl esters, Mareimino A substituent selected from m, m is an integer of 0-4, and n is an integer of 0-2.)
Preferable examples of the formula (A) include a C1-C20 primary to tertiary alcohol and an aliphatic monocarboxylic acid having 1-20 carbon atoms.

  Preferred examples of formula (B) are phenol, p-propylphenol, pt-butylphenol, cresol, xylenol, p-maleminophenol, chlorophenol and their acetoxylated compounds, benzoic acid, p-chlorobenzoic acid. P-methylbenzoic acid and their methyl esters, phenyl glycidyl ether, and the like.

  Preferred examples of formula (C) are p-phenylphenol, p-acetoxyphenylbenzene, p-phenylbenzoic acid, methyl p-phenylbenzoate and the like.

  The thermoplastic resin of the present invention may be copolymerized with other monomers to such an extent that the effect is not lost. For example, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids or caprolactams, caprolactones, aliphatic dicarboxylic acids, aliphatic diols, aliphatic diamines, Examples of the monomer include alicyclic dicarboxylic acid, and alicyclic diol, aromatic mercaptocarboxylic acid, aromatic dithiol, and aromatic mercaptophenol.

  Specific examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy -7-naphthoic acid, 2-hydroxy-3-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid and their Examples thereof include alkyl, alkoxy, and halogen-substituted products.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl, 4,4 ″ -dicarboxyterphenyl, bis (4-carboxyphenyl) ether, bis (4-carboxyphenoxy) butane, bis (4-carboxyphenyl) ethane, bis (3- Carboxyphenyl) ether, bis (3-carboxyphenyl) ethane, and the like, alkyl, alkoxy or halogen substituted products thereof.

  Specific examples of the aromatic diol include, for example, hydroquinone, resorcin, catechol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4 ′. -Dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenol ether, bis (4-hydroxyphenyl) ethane, 2,2'-dihydroxybinaphthyl, etc., and alkyl, alkoxy or halogen substituted products thereof Is mentioned.

  Specific examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide and 2,2'-diaminobinaphthyl and their alkyls , Alkoxy or halogen-substituted products.

  Specific examples of the aromatic diamine and aromatic aminocarboxylic acid include 1,4-phenylenediamine, 1,3-phenylenediamine, N-methyl-1,4-phenylenediamine, and N, N′-dimethyl-1,4. -Phenylenediamine, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminobiphenyl sulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminobiphenoxyethane 4,4′-diaminobiphenylmethane (methylenedianiline), 4,4′-diaminobiphenyl ether (oxydianiline), 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid and And 7-amino-2-naphthoic acid and alkyl, alkoxy or halogen substituted products thereof. That.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid Etc.

  Specific examples of the aliphatic diamine include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1,8-octanediamine, 1,9- Nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, and the like can be given.

  Specific examples of the alicyclic dicarboxylic acid, aliphatic diol and alicyclic diol include hexahydroterephthalic acid, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, and trans-1,4-cyclohexane. Dimethanol, cis-1,4-cyclohexanedimethanol, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexanedimethanol, ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neo Linear chain such as pentyl glycol Or the like branched chain aliphatic diols, as well as reactive derivatives thereof.

  Specific examples of aromatic mercaptocarboxylic acid, aromatic dithiol and aromatic mercaptophenol include 4-mercaptobenzoic acid, 2-mercapto-6-naphthoic acid, 2-mercapto-7-naphthoic acid, benzene-1,4- Dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, 2,7-naphthalene-dithiol, 4-mercaptophenol, 3-mercaptophenol, 6-mercapto-2-hydroxynaphthalene, 7-mercapto-2 -Hydroxynaphthalene and the like, as well as reactive derivatives thereof.

  Examples of the terminal structure analysis method include NMR, IR, and MALDI-TOFMS.

The thermoplastic resin of the present invention may have a point (T _m ) for transition from a solid phase to a liquid crystal phase and a point (Ti) for transition from a liquid crystal phase to an isotropic phase. From the viewpoint that it can be used without also not melt during soldering, it is preferred that the _{T m} is 250 to 350 ° C., more preferably from two hundred and sixty to three hundred and forty ° C., more preferably from 270-330 ° C.. When the melting point is less than 250 ° C., it is not preferable for use in electronic parts in terms of heat resistance. Moreover, when it is 350 degreeC or more, resin decomposition may occur remarkably at the time of shaping | molding. If using a thermoplastic resin such T _m, it can be injection molded be a general-purpose mold easily obtain thermoplastic resin composition.

  Since the thermoplastic resin of the present invention has a very high symmetry and a structure in which the rigid portion is bonded at the bent portion, the thermoplastic resin of the present invention has a high molecular orientation, and the formed higher order structure is dense. Become. For this reason, it is preferable that the thermoplastic resin of this invention has the outstanding heat conductivity, and the heat conductivity is 0.4 W / (m * K) or more. When the thermal conductivity is 0.4 W / (m · K) or more, a high thermal conductivity inorganic compound is blended with a thermoplastic resin to produce a thermoplastic resin composition having the same thermal conductivity. The compounding quantity of a compound can be reduced more. Further, the thermal conductivity of the thermoplastic resin of the present invention is more preferably 0.5 W / (m · K) or more. On the other hand, the upper limit of the thermal conductivity of the thermoplastic resin composition of the present invention is not particularly limited, and is preferably as high as possible, but has a melting point capable of injection molding, such as magnetic field, voltage application, rubbing, stretching, etc. during molding. If no physical treatment is applied, it is generally 30 W / (m · K) or less, and further 10 W / (m · K) or less.

<2. Production method of thermoplastic resin of the present invention>
The thermoplastic resin of the present invention is
(i) represented by general formula (2)

(Wherein Ar ¹ represents a trivalent aromatic residue excluding three carboxyl groups of the aromatic tricarboxylic acid) tribasic acid anhydride,
Formula _{(3): H 2 N-} Sp-NH 2 (3)
And a diamine represented by general formula (4): HO—Ar ² —OH (4)
A diol represented by the formula:
(ii) an acylation step of acylating the hydroxyl group of the diol represented by the general formula (4) by adding a lower fatty acid anhydride;
(iii) A tribasic acid represented by the general formula (2) is preferably produced by a production method including a high molecular weight process in which a lower fatty acid is distilled off to increase the molecular weight. It is more preferable that an anhydride, a diamine represented by the general formula (3), and a diol represented by the general formula (4) are simultaneously charged into the reactor. The manufacturing method described above may be a method including at least the steps (i) to (iii), but may be a manufacturing method including only the steps (i) to (iii).

  In the above production method, the tribasic acid anhydride represented by the general formula (2), the diamine represented by the general formula (3), and the diol represented by the general formula (4) are simultaneously charged into the reactor, A tribasic acid anhydride represented by the general formula (2) and a diamine represented by the general formula (3) are heated to 180 to 230 ° C in an inert gas atmosphere such as nitrogen in the absence of a solvent. To form an imide group ((i) imidization step). Thereafter, a lower fatty acid anhydride such as acetic anhydride is charged into the reactor and heated to effect acylation of the diol represented by the general formula (4) ((ii) acylation step). Thereafter, the temperature is gradually raised, and the reaction is usually carried out at a temperature of 220 to 340 ° C., preferably 250 to 330 ° C., more preferably 270 to 330 ° C. under normal pressure or reduced pressure for 0.5 to 5 hours (( iii) High molecular weight process). When the reaction temperature in the polymerizing step is lower than 220 ° C., the reaction proceeds slowly, and when it is higher than 330 ° C., side reactions such as decomposition tend to occur.

  When the polymerizing step is performed under reduced pressure, the degree of reduced pressure is preferably increased stepwise. When the pressure is rapidly reduced to a high degree of vacuum, the monomer component volatilizes, and a resin having a desired composition or molecular weight may not be obtained. The ultimate vacuum is preferably 40 Torr or less, more preferably 30 Torr or less, further preferably 20 Torr or less, and particularly preferably 10 Torr or less. When the degree of vacuum is higher than 40 Torr, deoxidation does not proceed sufficiently and a low molecular weight resin may be obtained.

  In the polymerizing step, a multi-stage reaction temperature may be adopted, and in some cases, the reaction product can be withdrawn in a molten state and recovered as soon as the temperature rises or reaches the maximum temperature. The obtained thermoplastic resin may be used as it is, or unreacted raw materials may be removed, or solid phase polymerization may be performed in order to improve physical properties. When solid phase polymerization is performed, the obtained thermoplastic resin is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and inert such as nitrogen at 100 to 350 ° C. in a solid state. The treatment is preferably performed in a gas atmosphere or under reduced pressure for 1 to 30 hours. If the particle size of the polymer particles is larger than 3 mm, the treatment is not sufficient, and problems with physical properties are caused, which is not preferable. It is preferable to select the treatment temperature and the rate of temperature increase during solid phase polymerization so that the thermoplastic resin particles do not cause fusion. In the method for producing a thermoplastic resin of the present invention, the imidization step and the acylation step may be performed in separate reactors.

  When the thermoplastic resin of the present invention is produced by the above production method, a resin end-capped with a carboxyl group or an ester group is obtained, but when obtaining a resin having other terminal structure, the end is sealed. A low molecular weight compound for stopping the reaction may be added at the start of the reaction or during the reaction.

  The thermoplastic resin of the present invention may be manufactured by any known method other than the above manufacturing method. From the viewpoint that the control of the structure is simple, the general formula (6)

A compound represented by
General formula (4)
HO—Ar ² —OH (4)
It may be produced by a production method in which a diol represented by the formula is reacted with a lower fatty acid anhydride.

You may use a catalyst for manufacture of the thermoplastic resin of this invention. As the catalyst, conventionally known polyester polymerization catalysts can be used, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, oxidation. Examples thereof include metal salt catalysts such as magnesium and organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole. The amount of the catalyst added is usually 0.1 × 10 ^{−2 to} 100 × 10 ⁻² wt%, preferably 0.5 × 10 ⁻² to 50 × 10 ^{−2, based on} the total weight of the thermoplastic resin. % By weight, more preferably 1 × 10 ⁻² to 10 × 10 ⁻² % by weight is employed.

  As the lower fatty acid anhydride used for the production of the thermoplastic resin in the present invention, an acid anhydride of a lower fatty acid having 2 to 5 carbon atoms such as acetic anhydride, propionic anhydride, acetic anhydride monochloroacetic acid, dichloroacetic anhydride, Trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, etc. Acetic anhydride, propionic anhydride, and trichloroacetic anhydride are particularly preferably used. The amount of the lower fatty acid anhydride used in the acylation step is 1.01-1.50 times equivalent to the total of hydroxyl groups of the diol represented by the general formula (3) used, preferably 1 0.02 to 1.2 equivalents.

  In addition, the manufacturing method of a thermoplastic resin composition is comprised by adding the process of adding the inorganic filler mentioned later and other well-known fillers to a thermoplastic resin after the manufacturing method of the thermoplastic resin of this invention. be able to. Therefore, it can be said that this invention includes the manufacturing method of such a thermoplastic resin composition.

<3. Thermoplastic resin composition of the present invention>
By adding an inorganic filler to the thermoplastic resin of the present invention to obtain a thermoplastic resin composition, the thermal conductivity can be further increased. The thermal conductivity of the thermoplastic resin composition of the present invention is preferably 0.4 W / (m · K) or more, more preferably 1.0 W / (m · K) or more, and even more preferably 5.0 W / (M · K) or more, particularly preferably 10 W / (m · K) or more. When the thermal conductivity is less than 0.4 W / (m · K), it is difficult to efficiently transmit the heat generated from the electronic component to the outside. The upper limit of the thermal conductivity of the thermoplastic resin composition of the present invention is not particularly limited, and is preferably as high as possible. Generally, it is 100 W / (m · K) or less, and further 80 W / (m · K) or less. It is preferable that Since the thermoplastic resin of the present invention has excellent thermal conductivity, it becomes possible to easily obtain a high thermal conductivity thermoplastic resin composition having a thermal conductivity in the above range.

  The amount of the inorganic filler used in the thermoplastic resin composition of the present invention is preferably 90:10 to 30:70, more preferably 80:20 to 40:60, by volume ratio of the thermoplastic resin and the inorganic filler. And particularly preferably 70:30 to 50:50. If the volume ratio of the thermoplastic resin to the inorganic filler is 100: 0 to 90:10, satisfactory thermal conductivity may not be obtained. Further, when the volume ratio of the thermoplastic resin to the inorganic filler is 30:70 to 0: 100, the mechanical properties may be lowered. Since the thermoplastic resin composition of the present invention has excellent thermal conductivity, even when the amount of the inorganic filler used is 90:10 to 70:30 in a small volume ratio of the thermoplastic resin and the inorganic filler, The plastic resin composition has excellent thermal conductivity, and at the same time, the density can be lowered because the amount of the inorganic filler used is small. The excellent thermal conductivity and low density are advantageous when used as a heat-dissipating / heat-transfer resin material in various situations such as in the electric / electronic industry and automobile fields.

  As the inorganic filler of the present invention, known fillers can be widely used. The thermal conductivity of the inorganic filler alone is preferably 1 W / (m · K) or more, more preferably 10 W / (m · K) or more, most preferably 20 W / (m · K) or more, particularly preferably 30 W. / (M · K) or more is used. The upper limit of the thermal conductivity of the inorganic filler alone is not particularly limited, and it is preferably as high as possible. Generally, it is 3000 W / (m · K) or less, more preferably 2500 W / (m · K) or less. Preferably used.

  When the thermoplastic resin composition of the present invention is used for applications where electrical insulation is not particularly required, a metal compound or a conductive carbon compound is preferably used as the inorganic filler. Among these, since it is excellent in thermal conductivity, conductive carbon materials such as graphite and carbon fibers, conductive metal powders obtained by atomizing various metals, conductive metal fibers obtained by processing various metals into fibers, soft magnetic ferrite Inorganic fillers such as various ferrites such as zinc oxide and metal oxides such as zinc oxide can be preferably used.

In the case where the thermoplastic resin composition of the present invention is used particularly for applications requiring electrical insulation, a compound exhibiting electrical insulation is preferably used as the inorganic filler. Specifically, the electrical insulating property indicates a material having an electrical resistivity of 1 Ω · cm or more. However, it is preferable to use those having 10 Ω · cm or more, more preferably 10 ⁵ Ω · cm or more, further preferably 10 ¹⁰ Ω · cm or more, and most preferably 10 ¹³ Ω · cm or more. There is no particular restriction on the upper limit of the electrical resistivity, generally less 10 ¹⁸ Ω · cm. It is preferable that the electrical insulation of the molded product obtained from the high thermal conductivity thermoplastic resin composition of the present invention is also in the above range.

  Among the inorganic fillers of the present invention, specific examples of the compound exhibiting electrical insulation include metal oxides such as aluminum oxide, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide, boron nitride, and nitride. Examples thereof include metal nitrides such as aluminum and silicon nitride, metal carbides such as silicon carbide, metal carbonates such as magnesium carbonate, insulating carbon materials such as diamond, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. These can be used alone or in combination.

  Various shapes can be applied to the shape of the inorganic filler of the present invention. For example, particles, fine particles, nanoparticles, aggregated particles, tubes, nanotubes, wires, rods, needles, plates, irregular shapes, rugby balls, hexahedrons, large particles and fine particles are combined Various shapes such as converted composite particles and liquids can be mentioned. These inorganic fillers may be natural products or synthesized ones. In the case of a natural product, there are no particular limitations on the production area and the like, which can be selected as appropriate. These inorganic fillers may be used alone or in combination of two or more different shapes, average particle diameters, types, surface treatment agents and the like.

  These inorganic fillers may have been subjected to surface treatment with various surface treatment agents such as a silane treatment agent in order to enhance the adhesion at the interface between the resin and the inorganic compound or to facilitate workability. . It does not specifically limit as a surface treating agent, For example, conventionally well-known things, such as a silane coupling agent and a titanate coupling agent, can be used. Among them, an epoxy group-containing silane coupling agent such as epoxy silane, an amino group-containing silane coupling agent such as aminosilane, polyoxyethylene silane, and the like are preferable because they hardly reduce the physical properties of the resin. The surface treatment method of the inorganic compound is not particularly limited, and a normal treatment method can be used.

  In addition to the inorganic fillers described above, known fillers can be widely used in the thermoplastic resin composition of the present invention depending on the purpose. Since the thermal conductivity of the resin alone is high, the resin composition has a high thermal conductivity even if the thermal conductivity of the known filler is relatively low, less than 10 W / (m · K). Examples of fillers other than inorganic fillers include diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder silica, quartz powder, crystalline silica, kaolin, talc, antimony trioxide, fine powder mica, and molybdenum disulfide. Inorganic fibers such as rock wool, ceramic fibers and asbestos, and glass fillers such as glass fibers, glass powder, glass cloth, and fused silica. By using these fillers, for example, it is possible to improve characteristics preferable for applying a thermoplastic resin composition such as thermal conductivity, mechanical strength, or abrasion resistance. Further, if necessary, organic fillers such as paper, pulp, wood, synthetic fiber such as polyamide fiber, aramid fiber and boron fiber, and resin powder such as polyolefin powder can be used in combination.

  The thermoplastic resin composition of the present invention includes an epoxy resin, a polyolefin resin, a bismaleimide resin, a polyimide resin, a polyether resin, a phenol resin, a silicone resin, a polycarbonate resin, and a polyamide as long as the effects of the present invention are not lost. Any known resin such as a resin, a polyester resin, a fluorine resin, an acrylic resin, a melamine resin, a urea resin, or a urethane resin may be contained. Specific examples of preferred resins include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, liquid crystal polymer, nylon 6, nylon 6,6 and the like. The usage-amount of these resin is the range of 0-10000 weight part with respect to 100 weight part of thermoplastic resins of this invention contained in the resin composition of this invention.

  In the thermoplastic resin composition of the present invention, as an additive other than the above resin and filler, any other component, for example, a reinforcing agent, a thickener, a release agent, a coupling agent, a difficulty agent, or the like, depending on the purpose. A flame retardant, a flame retardant, a pigment, a colorant, other auxiliary agents, and the like can be added as long as the effects of the present invention are not lost. The amount of these additives used is preferably in the range of 0 to 20 parts by weight in total with respect to 100 parts by weight of the thermoplastic resin contained in the thermoplastic resin composition of the present invention.

  It does not specifically limit as a compounding method of the various compound with respect to the thermoplastic resin composition of this invention. For example, it can be produced by drying the above-described components, additives and the like and then melt-kneading them in a melt-kneader such as a single-screw or twin-screw extruder. Moreover, when a compounding component is a liquid, it can also manufacture by adding to a melt-kneader on the way using a liquid supply pump etc.

  The thermoplastic resin composition of the present invention can be widely used in various applications such as electronic materials, magnetic materials, catalyst materials, structural materials, optical materials, medical materials, automobile materials, and building materials. The thermoplastic resin composition of the present invention has excellent properties such as particularly excellent moldability and high thermal conductivity, and is therefore very useful as a resin material for heat dissipation and heat transfer.

  The thermoplastic resin composition of the present invention can be suitably used for injection molded products such as home appliances, OA equipment parts, AV equipment parts, automobile interior and exterior parts, and the like. In particular, it can be suitably used as an exterior material in home appliances and office automation equipment that generate a lot of heat. Furthermore, in an electronic device having a heat source inside but difficult to be forcibly cooled by a fan or the like, it is suitably used as an exterior material for these devices in order to dissipate the heat generated inside to the outside. Among these, preferable devices include portable computers such as notebook computers, PDAs, cellular phones, smartphones, portable game machines, portable music players, portable TV / video devices, portable video cameras, and other small or portable electronic devices. It is very useful as a resin for housings, housings, and exterior materials. Also, resin for battery peripherals in automobiles, trains, etc., resin for power semiconductors requiring high heat resistance, resin for electronic circuit boards, resin for portable battery of home appliances, resin for power distribution parts such as circuit breakers, motors, etc. It can also be used very effectively as a stopping material.

  The thermoplastic resin composition of the present invention can be made higher in thermal conductivity than a well-known resin and has good molding processability. It has useful properties.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  Next, although the thermoplastic resin and composition of the present invention will be described in more detail with reference to examples and comparative examples, the present invention is not limited to such examples. Unless otherwise specified, the reagents listed below were used without purification from Wako Pure Chemical Industries.

[reagent]
(1) Inorganic filler / magnesium oxide: RF-50-SC manufactured by Ube Material Co., Ltd., thermal conductivity 40 W / m · K alone with magnesium oxide, volume average particle diameter 50 μm, electrical insulation, volume resistivity 10 ¹⁴ Ω · cm.
Boron nitride (PT110 manufactured by Momentive Performance Materials, thermal conductivity 60 W / m · K alone with boron nitride, volume average particle diameter 45 μm, electrical insulation, volume resistivity 10 ¹⁴ Ω · cm).
・ Glass fiber (T187H / PL, manufactured by Nippon Electric Glass Co., Ltd., thermal conductivity of glass fiber alone: 1.0 W / (m · K), fiber diameter: 13 μm, number average fiber length: 3.0 mm, electrical insulation, volume specific Resistance 10 ¹⁵ Ω · cm).

(2) Additives / Phosphorus antioxidants: ADEKA Corporation ADK STAB PEP-36.
-Phenol stabilizer: AO-60 manufactured by ADEKA Corporation.
-Brominated flame retardant: SAYTEX BT-93W manufactured by Albemarle.
Flame retardant aid: Nippon Seiko Co., Ltd. sodium antimonate SA-A.

[Method]
(1) Reduced viscosity: The thermoplastic resin of the present invention is dissolved in a 1: 1 (volume ratio) mixed solvent of 4-chlorophenol (Tokyo Chemical Industry) and tetrachloroethane so as to have a concentration of 0.5 g / dL. The drop time was measured at 25 ° C. using an Ubbelohde viscometer with an automatic viscosity measuring device (Seikasha: VMC-352). The reduced viscosity η _sp / c is expressed as follows: when the solvent fall time is t ₀ , the sample solution fall time is t, and the sample concentration is c.

It is represented by

(2) Thermophysical property measurement: In differential scanning calorimetry (DSC measurement), the temperature is raised and lowered at a rate of 10 ° C / min. The transition point (T _m ) from the solid phase to the liquid crystal phase was determined from the peak top of the endothermic peak.

  (3) Unless otherwise specified, molded product production: A plate-shaped molded product having a width of 10 mm, a length of 40 mm, and a thickness of 1 mm was produced by injection molding. The injection flow direction was the length direction of the plate.

(4) Thermal conductivity: Unless otherwise specified, it was evaluated by the following method. A spray for absorbing laser light (Black Guard Spray FC-153 manufactured by Fine Chemical Japan Co., Ltd.) is applied to the surface of the molded body and dried, and then perpendicular to the flow direction in the plane with a Xe flash analyzer (LFA447 Nanoflash manufactured by NETZSCH). The thermal diffusivity in a certain direction (hereinafter referred to as “TD direction”) was measured. The density of the molded body was measured by an underwater substitution method, the specific heat was measured by a DSC method, and the thermal conductivity was calculated by the following formula (6).
Thermal conductivity = thermal diffusivity x density x specific heat (6)
[Synthesis Example 1]
A closed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirring rod was charged with trimellitic anhydride (2712 g) and 1,10-decanediamine (1219 g), and N, N-dimethylformamide ( 1.5 L) as a solvent and refluxed for 1 hour under normal pressure and nitrogen atmosphere. Subsequently, acetic anhydride (1517 g) was added, and the mixture was further refluxed for 1 hour. After completion of the reaction, the reactor contents were discharged toward a large amount of ice water. The precipitated white solid was filtered, washed with water and methanol, and then dried in a vacuum oven at 120 ° C. under reduced pressure for 10 hours to give a white solid N, N-decane-α, ω-diylbistrimellitic imide (general The portion corresponding to Sp in the formula (5) was (CH ₂ ) ₁₀ ).

[Example 1]
N, N-decane-α, ω-diylbistrimellitic imide (120 g), 4,4′-dihydroxybiphenyl, acetic anhydride was added to a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirring rod. , And sodium acetate at a molar ratio of 1: 1: 2.2: 10 ⁻³ and reacted at 145 ° C. for 40 minutes under normal pressure and nitrogen atmosphere. The temperature was raised to 310 ° C at a rate of ° C / min. Subsequently, the reaction was carried out under a reduced pressure of 10 Torr while maintaining the temperature, and after 15 minutes from the start of the reduced pressure, the pressure was returned to normal pressure with nitrogen gas, and the produced thermoplastic resin was taken out. Table 2 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ), and thermal conductivity of the resin alone.

  In addition, the synthesized thermoplastic resin and magnesium oxide, which is an inorganic filler, are mixed at a volume ratio of 70:30, and a phosphorus-based antioxidant (ADEKA STAB PEP-36 manufactured by ADEKA Corporation) is heated. 0.2 part by weight was added to 100 parts by weight of the plastic resin. This mixture was melt-kneaded using a Technobel Co., Ltd. 15 mm co-rotating fully meshed twin screw extruder KZW15-45MG to obtain a thermoplastic resin composition. The obtained pellets of the thermoplastic resin composition were molded using an injection molding machine, and the thermal conductivity was measured. Table 1 shows the thermal conductivity of the thermoplastic resin composition.

[Example 2]
Polymerization was carried out in the same manner as in Example 1, except that the molar ratio of N, N-decane-α, ω-diylbistrimeritimide and 4,4′-dihydroxybiphenyl was 1: 1.14. Sealed thermoplastic resins having different molecular weights were synthesized.

Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 1 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 3]
Polymerization was conducted in the same manner as in Example 1 except that the molar ratio of N, N-decane-α, ω-diylbistrimellitic imide and 4,4′-dihydroxybiphenyl was changed to 1.09: 1. Sealed thermoplastic resins having different molecular weights were synthesized. Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 1 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 4]
The thermoplastic resin obtained in Example 1 was finely pulverized, charged into a closed reactor, and subjected to solid state polymerization at 260 ° C. and 10 Torr for 7 hours. Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 1 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 5]
Polymerization was conducted in the same manner as in Example 2 except that 4,4′-dihydroxybiphenyl was hydroquinone and the maximum polymerization temperature was 290 ° C., and thermoplastic resins having different molecular structures were synthesized. Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 1 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 6]
Stearic acid was used as the end capping agent, and N, N-decane-α, ω-diylbistrimellitic imide, hydroquinone, stearic acid, acetic anhydride, and sodium acetate were mixed at a molar ratio of 1: 1. Polymerization was conducted in the same manner except that the ratio was 14: 0.28: 2.7: 10 ⁻³ , and a thermoplastic resin end-capped with stearic acid ester was synthesized. Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 1 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 7]
Polymerization was conducted in the same manner as in Example 2 except that 4,4′-dihydroxybiphenyl was changed to 2,6-naphthalenediol and the maximum polymerization temperature was set to 290 ° C., thereby synthesizing thermoplastic resins having different molecular structures. Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 1 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 8]
In a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirring rod, moles of trimellitic anhydride (836 g), 1,10-decanediamine, 4,4′-dihydroxybiphenyl, and sodium acetate The mixture was charged at a ratio of 2: 1: 1: 10 ⁻³ , heated to 230 ° C. under normal pressure and nitrogen atmosphere, and reacted for 10 minutes under a reduced pressure of 10 Torr, and the generated water was distilled off. After cooling once, acetic anhydride (680 g) was charged and reacted at 145 ° C. for 40 minutes, and then heated to 310 ° C. at 3 ° C./min while acetic acid was distilled off. Subsequently, the reaction was carried out under a reduced pressure of 10 Torr while maintaining the temperature, and after 15 minutes from the start of the reduced pressure, the pressure was returned to normal pressure with nitrogen gas, and the produced thermoplastic resin was taken out. Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 2 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 9]
In the raw material of Example 8, the molar ratio of trimellitic anhydride, 1,10-decanediamine, 1,6-hexamethylenediamine, 4,4′-dihydroxybiphenyl, and sodium acetate was 2: 0.9: 0. . 1: 1: 10 ^{−3 The} same synthesis was carried out except that the thermoplastic resin having a different molecular structure was obtained. Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 2 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 10]
The raw material of Example 8 was trimellitic anhydride, 2,2 ′-(ethylenedioxy) bis (ethylamine) (manufactured by Sigma-Aldrich), 4,4′-dihydroxybiphenyl, and sodium acetate in a molar ratio of 2 A thermoplastic resin having a different molecular structure was obtained in the same manner except that the ratio was 1: 1: 1: 10 ⁻³ . Using the obtained thermoplastic resin, a thermoplastic resin composition was obtained in the same manner as in Example 1. Table 2 shows the molecular structure, reduced viscosity, liquid crystal phase transition temperature (T _m ) of the obtained thermoplastic resin, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Example 11]
Volume ratio (thermoplastic resin 50, magnesium oxide 20, boron nitride 25, glass fiber 5, bromine flame retardant 4.5, difficulty shown below for the thermoplastic resin, inorganic filler, and various additives synthesized in Example 6 The mixture was added at 0.75), and 0.2 parts by weight of a phosphorus-based antioxidant was added to 100 parts by weight of the resin. This mixture was melt-kneaded using a Technobel Co., Ltd. 15 mm co-rotating fully meshed twin screw extruder KZW15-45MG to obtain a thermoplastic resin composition. The pellets of the obtained thermoplastic resin composition were molded into a disk-shaped sample having a thickness of 1 mm × 25 mmφ using an injection molding machine, and the thermal conductivity was measured. The thermal conductivity in the thickness direction was 3.3 W / (m · K), and the thermal conductivity in the in-plane direction was 7.8 W / (m · K).

[Comparative Example 1]
Using a commercially available polybutylene terephthalate resin (Novaduran 5008L manufactured by Mitsubishi Engineering Plastics Co., Ltd.), polybutylene terephthalate resin and magnesium oxide as an inorganic filler are mixed in a volume ratio of 70:30, and phenol is added thereto. 0.2 parts by weight of a system stabilizer and a phosphorus-based antioxidant were added to 100 parts by weight of the resin.

  This mixture was melt-kneaded using a Technobel Co., Ltd. 15 mm co-rotating fully meshed twin screw extruder KZW15-45MG to obtain a thermoplastic resin composition. The obtained pellets of the thermoplastic resin composition were molded using an injection molding machine, and the thermal conductivity was measured. Table 2 shows the melting point, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Comparative Example 2]
A thermoplastic resin composition was obtained in the same manner except that the polybutylene terephthalate resin in Comparative Example 1 was a polyphenylene sulfide resin (FZ2100 manufactured by DIC Corporation). The obtained pellets of the thermoplastic resin composition were molded using an injection molding machine, and the thermal conductivity was measured. Table 2 shows the melting point, the thermal conductivity of the thermoplastic resin alone, and the thermal conductivity of the thermoplastic resin composition.

[Comparative Example 3]
A thermoplastic resin composition was obtained in the same manner except that the polybutylene terephthalate resin in Comparative Example 1 was nylon 9T resin (Genare N1000A manufactured by Kuraray Co., Ltd.). The obtained pellets of the thermoplastic resin composition were molded using an injection molding machine, and the thermal conductivity was measured. Table 2 shows the melting point, the thermal conductivity of the resin alone, and the thermal conductivity of the thermoplastic resin composition.

In Table 2, the numbers in parentheses at T _m [° C.] indicate melting points.

  From Tables 1 and 2, it was found that all examples formed a liquid crystal phase and had higher thermal conductivity than the commercially available thermoplastic resins alone and the thermoplastic resin compositions shown in the comparative examples.

  The thermoplastic resin composition of the present invention is excellent in thermal conductivity and maintains high thermal conductivity even when a large amount of high thermal conductivity inorganic compound is not blended. For this reason, the thermoplastic resin composition of the present invention can be injection-molded with a general-purpose injection mold.

  For this reason, the thermoplastic resin composition of the present invention is industrially useful because it can be used as a heat countermeasure material in various situations such as in the electric / electronic industry field and the automobile field.

Claims (11)

The structure of the repeating unit of the main chain is mainly represented by the general formula (1)

(In the formula, Ar ¹ is a trivalent aromatic residue excluding three carboxyl groups of an aromatic tricarboxylic acid, and Sp is a divalent linear substitution which may contain a branch having 2 to 20 main chain atoms. A group, Ar ² represents a substituent selected from the group consisting of an aromatic group, a condensed aromatic group, a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group),
A thermoplastic resin composition comprising an inorganic filler.   The thermoplastic resin composition according to claim 1, wherein a portion corresponding to Sp of the thermoplastic resin is a linear aliphatic hydrocarbon chain or an aliphatic ether chain.   The thermoplastic resin composition according to claim 1 or 2, wherein the number of main chain atoms in a portion corresponding to Sp of the thermoplastic resin is an even number.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the reduced viscosity of the thermoplastic resin is 0.15 to 2.0 (dL / g).   The thermoplastic resin composition according to claim 1, wherein the inorganic filler has a thermal conductivity of 1 W / (m · K) or more.   The inorganic filler is at least one inorganic compound selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, beryllium oxide, and diamond. The thermoplastic resin composition according to any one of claims 1 to 5, wherein   The inorganic filler is one or more inorganic compounds selected from the group consisting of graphite, conductive metal powder, soft magnetic ferrite, carbon fiber, conductive metal fiber, and zinc oxide. The thermoplastic resin composition of any one of -5.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the volume ratio of the thermoplastic resin to the inorganic filler is 90:10 to 30:70.   The molded object containing the thermoplastic resin composition of any one of Claims 1-8. The structure of the repeating unit of the main chain is mainly represented by the general formula (1)

(In the formula, Ar ¹ is a trivalent aromatic residue excluding three carboxyl groups of an aromatic tricarboxylic acid, and Sp is a divalent linear substitution which may contain a branch having 2 to 20 main chain atoms. Group, Ar ² represents a substituent selected from the group consisting of an aromatic group, a condensed aromatic group, a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group). A method,
(i) represented by general formula (2)

(Wherein Ar ¹ represents a trivalent aromatic residue excluding three carboxyl groups of the aromatic tricarboxylic acid) tribasic acid anhydride,
General formula (3)
_{H 2 N-Sp-NH 2} (3)
A diamine represented by the general formula (4)
HO—Ar ² —OH (4)
Is charged into a reactor,
An imidization step for generating an imide group by a reaction between the tribasic acid anhydride represented by the general formula (2) and the diamine represented by the general formula (3);
(ii) an acylation step of acylating the hydroxyl group of the diol represented by the general formula (4) by adding a lower fatty acid anhydride;
(iii) A method for producing a thermoplastic resin, comprising a step of increasing the molecular weight while distilling off lower fatty acids. The tribasic acid anhydride represented by the general formula (2), the diamine represented by the general formula (3), and the diol represented by the general formula (4) are simultaneously charged into the reactor. Item 11. A method for producing a thermoplastic resin according to Item 10.