JP2011084714A - High thermal conductive thermoplastic resin composition for extrusion molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin material for extrusion molding being excellent in thermal conductivity and indicating sufficient appearance without appearance failure such as floating of a filler on a molded article at extrusion molding. <P>SOLUTION: A high thermal conductive thermoplastic resin composition for extrusion molding contains at least a high thermal conductive thermoplastic resin with a specific structure comprising repetition of a unit composed of a mesogen group and a spacer and having the thermal conductivity in a single resin of 0.45 W/(mK) or more. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a novel high heat conductive thermoplastic resin material for extrusion molding, which is excellent in heat conductivity. Specifically, the resin alone exhibits high thermal conductivity even without the addition of thermal conductive fillers, etc., and the addition of a small amount of thermal conductive fillers demonstrates innovative high thermal conductivity compared to previously known materials. The present invention relates to a highly heat conductive resin composition for extrusion molding, which is made of a resin that exhibits good moldability even in extrusion molding such as sheeting, film processing, and profile extrusion.

  When a thermoplastic resin composition is used in various applications such as personal computers and display housings, electronic device materials, automotive interiors and exteriors, plastic is generated because it has lower thermal conductivity than inorganic materials such as metal materials. Difficult to escape heat can 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, it is necessary to blend a high thermal conductivity inorganic material such as graphite, carbon fiber, alumina, boron nitride, etc. into the resin with a high content of usually 30% by volume or more, and further 50% by volume or more. There is. However, even if a large amount of the inorganic substance is blended, the thermal conductivity of the resin alone is low, so that the thermal conductivity of the resin composition has a limit.

  In addition, a thermoplastic resin composition highly filled with such a filler can obtain a molded body having a relatively good appearance by a molding method such as injection molding that is poured into a mold at a high pressure, whereas a sheet is obtained. When molding is performed by an extrusion molding method such as plasticization, film processing, or profile extrusion, the filler is raised on the surface of the molded body, which makes it difficult to obtain a molded body having a good appearance.

Due to such problems, there has been a strong demand for improving the thermal conductivity of the resin alone.
As a thermosetting resin excellent in thermal conductivity of a single resin, for example, an epoxy resin described in Patent Document 1 or Patent Document 2 or a bismaleimide resin described in Patent Document 3 has been reported. However, since these resins exhibit thermosetting properties, a molding method such as extrusion molding cannot be applied, and the molecular structure is complicated and the production is difficult. The epoxy resin described in Patent Document 2 is relatively simple to synthesize, but has insufficient thermal conductivity.

  On the other hand, for thermoplastic resins, there are research examples that give high thermal conductivity in a specific direction by adopting special molding methods such as stretching and magnetic field orientation at the time of injection molding, but without using special molding methods. There have been no reports on resins that can obtain high thermal conductivity by ordinary extrusion molding.

International Publication Number WO2002 / 094905 International Publication Number WO2006 / 120993 JP 2007-2224060 A

The present invention provides a high thermal conductive resin material for extrusion molding, in which a single resin is excellent in thermal conductivity, easy to manufacture, and a high thermal conductive molded article having a good appearance can be obtained even if molded by an extrusion molding method. The purpose is to do.

The present inventor has a thermoplastic resin having a specific structure and excellent thermal conductivity as a single resin, and a composition thereof, which shows a good molded product appearance and thermal conductivity even when molded by an extrusion molding method. As a result, they have reached the present invention. That is, the present invention has the following configuration.

1). Heat whose main chain is mainly composed of repeating units represented by the following general formula (1), mainly composed of a chain structure, and has a thermal conductivity of 0.45 W / (m · K) or more in the resin resin alone A highly heat-conductive thermoplastic resin composition for extrusion molding containing a plastic resin.
-M-Sp- (1)
(In the formula, M represents a mesogenic group, and Sp represents a spacer.)

2). The high thermal conductive resin composition for extrusion molding according to 1), wherein the general formula (1) is composed of repeating units represented by the following general formula (2).
^{-A 1 -x-A 2 -y-} R-z- (2)
(In the formula, A ¹ and A ² each independently represent a substituent selected from an aromatic group, a condensed aromatic group, an alicyclic group, and an alicyclic heterocyclic group. X, y, and z are each independently a direct _{bond, -CH 2 -, - C (} CH 3) 2 -, - O -, - S -, - CH 2 -CH 2 -, - C = C -, - C≡C -, - CO 2 selected from the group of-, -CO-O-, -CO-NH-, -CH = N-, -CH = N-N = CH-, -N = N- or -N (O) = N-. R represents a divalent substituent which may contain a branch having 2 to 20 main chain atoms.)

3). The portion corresponding to -A ¹ -x-A ² -is a mesogenic group represented by the following general formula (3), and the high heat conductive thermoplastic resin composition for extrusion molding according to 2) .

  4). The high thermal conductivity thermoplastic resin composition for extrusion molding according to any one of 2) and 3), wherein a portion corresponding to R of the thermoplastic resin is a linear aliphatic hydrocarbon chain.

  5). 2. The high thermal conductive thermoplastic resin composition for extrusion molding according to any one of 2) to 4), wherein the number of carbon atoms in the R molecular chain of the thermoplastic resin is an even number.

6). R of the thermoplastic resin is at least one selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ —, and the number average molecular weight is 3000 to 40000 2) -5) The high heat conductive thermoplastic resin composition for extrusion molding as described in any one of the above.

  7). A high thermal conductive resin material for extrusion molding using the thermoplastic resin according to 2), wherein -yRz- of the thermoplastic resin is -O-CO-R-CO-O-.

  8). The high thermal conductive resin thermoplastic composition for extrusion molding according to any one of 1) to 7), which contains an inorganic filler (B).

  9). The high thermal conductive resin thermoplastic composition for extrusion molding according to 8), wherein the inorganic filler (B) is an inorganic compound having a single body thermal conductivity of 12 W / m · K or more.

  10). 8. The high heat conductive resin thermoplastic composition for extrusion molding according to 8) or 9), wherein the inorganic filler (B) is an electrically insulating high heat conductive inorganic compound.

  11). The high heat conductive resin thermoplastic composition for extrusion molding according to 8) or 9), wherein the inorganic filler (B) is a conductive high heat conductive inorganic compound.

Since the thermoplastic thermoplastic resin composition of the present invention exhibits high thermal conductivity, a thermoplastic resin composition having high thermal conductivity can be obtained by adding only a small amount of a high thermal conductive inorganic filler, and thus extrusion molding is performed. In particular, a molded product having both a good molded product appearance and high thermal conductivity can be easily obtained.

FIG. 1 shows the shape of the entrance and exit of a die outlet and a sizing die.

The resin used in the highly heat-conductive thermoplastic resin composition for extrusion molding according to the present invention is characterized in that the main chain mainly consists of repeating units of the unit represented by the following general formula (1) and mainly has a chain structure. It is what.
-M-Sp- (1)
(In the formula, M represents a mesogenic group, and Sp represents a spacer.)
The thermoplasticity referred to in the present invention is a property of plasticizing by heating.
The term “mainly” as used in the present invention means that the amount of the general formula (1) contained in the main chain of the molecular chain is 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol%, based on all structural units. % Or more, and most preferably essentially 100 mol%. When it is less than 50 mol%, the crystallinity of the resin is lowered, and the thermal conductivity may be lowered.
The resin of the present invention has extremely high symmetry and has a structure in which a rigid straight chain is bound by a bent chain, so that the orientation of the molecule is high, the formed higher order structure is dense, and has excellent thermal conductivity.

  The thermal conductivity of the resin used in the high thermal conductivity thermoplastic resin composition for extrusion molding of the present invention is 0.45 W / (m · K) or more, preferably 0.6 W / (m · K) or more. Preferably 0.8 W / (m · K) or more, more preferably 1.0 W / (m · K) or more, more preferably 1.2 W / (m · K) or more, particularly preferably 1.3 W / ( m · K) or more. The upper limit of the thermal conductivity is not particularly limited and is preferably as high as possible. Generally, values of 30 W / (m · K) or less, and further 10 W / (m · K) or less can be exemplified.

The mesogenic group contained in the resin used in the high heat conductive thermoplastic resin composition for extrusion molding of the present invention means a rigid and highly oriented substituent. Preferred mesogenic groups include the following general formula -A ¹ -x-A ^2-
(A ¹ and A ² each independently represent a substituent selected from an aromatic group, a condensed aromatic group, an alicyclic group, and an alicyclic heterocyclic group. X is a connector, a direct bond,- _{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— or —N (O) ═N— are each a divalent substituent. ) Is represented. A ¹ and A ² are each independently a hydrocarbon group having 6 to 12 carbon atoms having a benzene ring, a hydrocarbon group having 10 to 20 carbon atoms having a naphthalene ring, and 12 to 24 carbon atoms having a biphenyl structure. Hydrocarbon group having 3 or more benzene rings, a hydrocarbon group having 12 to 36 carbon atoms, a hydrocarbon group having 12 to 36 carbon atoms having a condensed aromatic group, and an alicyclic heterocyclic group having 4 to 36 carbon atoms It is preferable that it is selected from.

Specific examples of A ¹ and A ² include phenylene, biphenylene, naphthylene, anthracenylene, cyclohexyl, pyridyl, pyrimidyl, thiophenylene, and the like. These may be unsubstituted or may be a derivative having a substituent such as an aliphatic hydrocarbon group, a halogen group, a cyano group, or a nitro group.

Among these, when the number of atoms in the main chain of x corresponding to the bond is an even number, the molecular width of the mesogen group is small, the degree of freedom of rotation of the bond is small, and the crystallization rate tends to be high. It is preferable because the thermal conductivity is easily improved. That is, a direct bond, —CH ₂ —CH ₂ —, —C═C—, —C≡C—, —CO—O—, —CO—NH—, —CH═N—, —CH═N—N═CH A divalent substituent selected from the group of-, -N = N- or -N (O) = N- is preferred.

  Specific examples of mesogenic groups include biphenyl, terphenyl, quarterphenyl, stilbene, diphenyl ether, 1,2-diphenylethylene, diphenylacetylene, benzophenone, phenylbenzoate, phenylbenzamide, azobenzene, 2-naphthoate, phenyl-2-naphthoate, and Examples thereof include a divalent group having a structure in which two hydrogen atoms are removed from these derivatives. Of these, direct bonding is preferred, and specific examples include biphenyl, terphenyl, and quarterphenyl.

  More preferably, it is a mesogenic group represented by the following general formula (3). This mesogenic group is rigid and highly oriented due to its structure, and is easily available or synthesized.

  The highly heat-conductive thermoplastic resin for extrusion molding of the present invention can be made into a composition by itself or using various blends. The mesogenic group contained in the high thermal conductive thermoplastic resin for extrusion used in the composition is preferably one that does not contain a crosslinkable substituent.

  The spacer of the general formula (1) according to the present invention means a flexible molecular chain and includes a bonding group with a mesogenic group. The number of main chain atoms of the spacer is preferably 4 to 28, more preferably 6 to 24, and still more preferably 8 to 20. When the number of main chain atoms of the spacer is in this range, the molecular structure of the thermoplastic resin is sufficiently flexible, and the crystallinity is high and the thermal conductivity is preferable. The type of atoms constituting the main chain of the spacer is not particularly limited, and any type can be used. However, it is preferably at least one atom selected from C, H, O, S, and N.

As a preferable spacer, the following general formula -yRz-
(Y and z are each independently a direct bond, —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— or —N (O) ═N -Represents a divalent substituent selected from the group of-R. R represents a divalent substituent which may contain a branch having 2 to 20 main chain atoms, and may be a branch. It is done. Here, R has a chain saturated hydrocarbon group having 2 to 20 carbon atoms, a saturated hydrocarbon group having 2 to 20 carbon atoms including 1 to 3 cyclic structures, and 1 to 5 unsaturated groups. A hydrocarbon group having 2 to 20 carbon atoms, a hydrocarbon group having 2 to 20 carbon atoms having 1 to 3 aromatic rings, and a polyether group having 2 to 20 carbon atoms having 1 to 5 oxygen atoms Those selected from are preferred.

  Specific examples of the spacer include an aliphatic hydrocarbon chain and a polyether chain. Since the crystallinity of the thermoplastic resin is increased and the thermal conductivity tends to be high, R is preferably a linear aliphatic hydrocarbon chain that does not include a branch. R may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain because the high heat conductive thermoplastic resin for extrusion molding of the present invention has appropriate flexibility. In the total R, the unit exceeding 50% by weight is preferably a saturated aliphatic hydrocarbon chain, and most preferably it does not contain an unsaturated bond.

  R preferably has 2 to 20 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 6 to 16 carbon atoms. Further, when the mesogenic groups are connected in a straight line, the crystallinity is unlikely to decrease, and the thermal conductivity can be secured. Therefore, R is preferably a straight-chain saturated aliphatic hydrocarbon having these carbon numbers, and the number of carbons is even. It is preferable that In the case of an even number, since the mesogenic groups are arranged more regularly, the thermal conductivity tends to be high.

In particular, R is at least one selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ — from the viewpoint that a resin having excellent thermal conductivity can be obtained. Is preferred. y and z are groups for bonding the substituent R to the mesogenic group. Among the spacers having such a group, the general formula (4) is —CO—O—R—O—CO— or —O—CO—R—CO— from the viewpoint that a resin having excellent thermal conductivity can be obtained. Those having a structure of O- are preferable, and -O-CO-R-CO-O- is particularly preferable.

The number average molecular weight of the resin used in the composition of the present invention is polystyrene as a standard, and the thermoplastic resin used in the present invention is 0.25 in a 1: 2 (Vol ratio) mixed solvent of p-chlorophenol and o-dichlorobenzene. It can measure at 80 degreeC by GPC using the solution prepared by melt | dissolving so that it might become a weight% density | concentration. The number average molecular weight of the thermoplastic resin of the present invention is preferably 3000 to 40000, more preferably 3000 to 30000, and particularly preferably 3000 to 20000 in view of the upper limit. On the other hand, considering the lower limit, it is preferably 3000 to 40000, more preferably 5000 to 40000, and particularly preferably 7000 to 40000. Furthermore, when an upper limit and a lower limit are considered, it is more preferable that it is 5000-30000, and it is most preferable that it is 7000-20000. When the number average molecular weight is less than 3000 or greater than 40000, even if the resin has the same primary structure, the thermal conductivity may be 0.45 W / (m · K) or less.
The liquid crystalline thermoplastic resin used as the organic heat conductive additive of the present invention preferably contains lamellar crystals. In the liquid crystalline thermoplastic resin of the present invention, the amount of lamellar crystals can be used as an index of crystallinity. The more lamellar crystals, the higher the crystallinity.
The lamellar crystal referred to in the present invention corresponds to a plate-like crystal in which long chain molecules are folded and arranged in parallel. Whether or not such crystals exist in the resin can be easily determined by observation with a transmission electron microscope (TEM) or X-ray diffraction.

The ratio of lamellar crystals forming the continuous phase can be calculated by directly observing a sample stained with RuO ₄ with a transmission electron microscope (TEM). As a specific method, as a sample for TEM observation, a part of a molded sample having a thickness of 6 mm × 20 mmφ was cut out, stained with RuO _4, and then an ultrathin section having a thickness of 0.1 μm prepared by a microtome was used. It shall be. The prepared slice is observed with a TEM at an accelerating voltage of 100 kV, and a lamellar crystal region can be determined from the obtained 40,000-fold scale photograph (20 cm × 25 cm). The boundary of the region can be determined by using the lamellar crystal region as a region where periodic contrast exists. Since the lamella crystals are similarly distributed in the depth direction, the ratio of the lamella crystals is calculated as a ratio of the lamella crystal region to the entire area of the photograph. Moreover, in order for resin itself to have high thermal conductivity, it is preferable that the ratio of a lamellar crystal is 10 Vol% or more. The ratio of lamellar crystals is more preferably 20 Vol% or more, further preferably 30 Vol% or more, and particularly preferably 40 Vol% or more.
The liquid crystalline thermoplastic resin of the present invention preferably contains crystals. In the present invention, the degree of crystallinity can be determined by the following calculation formula from the ratio of lamellar crystals in the liquid crystalline thermoplastic resin.
Crystallinity (%) = ratio of lamellar crystals (Vol%) x 0.7
In order for the resin itself to have high thermal conductivity, the crystallinity of the liquid crystalline thermoplastic resin is preferably 7% or more. The degree of crystallinity is more preferably 14% or more, further preferably 21% or more, and particularly preferably 28% or more.

In order for the liquid crystalline thermoplastic resin of the present invention to exhibit high thermal conductivity, the density of the resin itself is preferably 1.1 g / cm ³ or more, more preferably 1.13 g / cm ³ or more. It is preferably 1.16 g / cm ³ or more. A high resin density means that the content of lamellar crystals is high, that is, the degree of crystallinity is high.

  The liquid crystalline thermoplastic resin used in the present invention preferably has an isotropic high thermal conductivity. As a method for measuring whether or not the thermal conductivity is isotropic, for example, a sample in which a thermoplastic resin is made into a disk shape having a thickness of 1 mm × 25.4 mmφ, the thickness direction by the Xe flash method, A method of separately measuring the thermal conductivity in the plane direction is mentioned. The thermal conductivity of the thermoplastic resin according to the present invention is isotropically high, and the thermal conductivity in the thickness direction and the plane direction measured by the above measurement method is 0.3 W / (m · K) or more. is there.

  The thermoplastic resin used in the composition of the present invention may be produced by any known method. From the viewpoint that the control of the structure is simple, a method of reacting a compound having a reactive functional group at both ends of the mesogenic group with a compound having a reactive functional group at both ends of the substituent R is preferable. . As such a reactive functional group, known groups such as a hydroxyl group, a carboxyl group, an alkoxy group, an amino group, a vinyl group, an epoxy group, and a cyano group can be used, and the conditions for reacting these are not particularly limited.

  From the viewpoint of ease of synthesis, a reaction with a hydroxyl group and a carboxyl group is preferred. Specifically, a compound having a hydroxyl group at both ends of the mesogenic group and a compound having a carboxyl group at both ends of the substituent R, or a compound having a carboxyl group at both ends of the mesogenic group and a hydroxyl group at both ends of the substituent R The manufacturing method which makes the compound which has it react is mentioned.

  As an example of a method for producing a thermoplastic resin comprising a compound having a hydroxyl group at both ends of a mesogenic group and a compound having a carboxyl group at both ends of the substituent R, a mesogenic group having a hydroxyl group at both ends may be converted to a lower group such as acetic anhydride. A method in which a fatty acid is individually or collectively converted into an acetate ester and then subjected to a deacetic acid polycondensation reaction with a compound having a carboxyl group at both ends of the substituent R in another reaction tank or the same reaction tank. Can be mentioned. The polycondensation reaction is preferably carried out in the substantial absence of a solvent. The reaction temperature is preferably 200 to 350 ° C, more preferably 230 to 330 ° C, particularly preferably 250 to 300 ° C. Moreover, it is preferable to carry out for 0.5 to 5 hours by presence of inert gas, such as nitrogen, under a normal pressure or pressure reduction. If the reaction temperature is too low, the reaction proceeds slowly, and if it is too high, side reactions such as decomposition tend to occur.

  A multi-stage reaction temperature may be employed. In some cases, the reaction product can be withdrawn in a molten state and recovered as soon as the temperature rises or when the maximum temperature is reached. The obtained thermoplastic resin may be used as it is, or it may be subjected to solid phase polymerization in order to remove unreacted raw materials or improve physical properties.

  In the case of performing solid phase polymerization, the obtained thermoplastic resin is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and an inert gas such as nitrogen at 250 to 350 ° C. in a solid state. The treatment is preferably performed under an atmosphere or under reduced pressure for 1 to 20 hours. If the particle size of the polymer particles is 3 mm or more, 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.

  Examples of the acid anhydride of the lower fatty acid used in the production of the resin of the present invention include acid anhydrides of lower fatty acids having 2 to 5 carbon atoms such as acetic anhydride, propionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroanhydride. Acetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, etc. , Propionic anhydride and trichloroacetic anhydride are particularly preferably used.

  The amount of the lower fatty acid anhydride used is preferably 1.01 to 1.50 times equivalent, more preferably 1.02 to 1.2 times equivalent to the total of the hydroxyl groups of the mesogenic groups used. As for other production methods in which a compound having a carboxyl group at both ends of a mesogenic group and a compound having a hydroxyl group at both ends of the substituent R are reacted, for example, as described in JP-A-2-258864, 4,4′- A method of melt polymerization of dimethyl biphenyldicarboxylate and an aliphatic diol is mentioned.

  The terminal structure of the resin of the present invention is not particularly limited, but from the viewpoint that a resin suitable for extrusion molding can be obtained, the terminal is sealed with a hydroxyl group, a carboxyl group, an ester group, an acyl group, an alkoxy group, or the like. Preferably it is. 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.

  The resin of the present invention may be copolymerized with another monomer to such an extent that the effect is not lost. For example, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, aromatic diamine, aromatic aminocarboxylic acid or caprolactam, caprolactone, aliphatic dicarboxylic acid, aliphatic diamine, aliphatic diol, Examples include alicyclic dicarboxylic acids, alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols, and aromatic mercaptophenols.

  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 and 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, 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, and the like, and alkyl, alkoxy or halogen substituted products thereof. .

  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, 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 7-amino-2-naphthoic acid and alkyl, alkoxy or halogen substituted products thereof It is below.

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 Such as pentyl glycol Such Jo or branched chain aliphatic diols, as well as reactive derivatives thereof.

  Specific examples of the 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.

  The thermal conductivity of the high thermal conductivity thermoplastic resin composition for extrusion molding of the present invention is preferably 0.4 W / (m · K) or more, more preferably 1.0 W / (m · K) or more, and still more preferably. Is 5.0 W / (m · K) or more, particularly preferably 10 W / (m · K) or more. By containing the inorganic filler (B) in the thermoplastic resin (A), higher thermal conductivity can be obtained. If the thermal conductivity is low, it is difficult to efficiently transmit the heat generated from the electronic component to the outside. The upper limit of the thermal conductivity is not particularly limited, and is preferably as high as possible. Generally, a thermal conductivity of 100 W / (m · K) or less, further 80 W / (m · K) or less is used. Since the thermoplastic resin (A) has excellent thermal conductivity, it is possible to easily obtain a high thermal conductivity thermoplastic resin composition having a thermal conductivity in the above range.

  Since the thermoplastic resin (A) of the present invention has excellent thermal conductivity, it has excellent thermal conductivity without using the inorganic filler (B), but heat is obtained by using the inorganic filler (B). The conductivity can be further improved.

  In the high thermal conductive resin composition for extrusion molding of the present invention, when the inorganic filler (B) is used, the amount used is preferably 99: by volume ratio of the thermoplastic resin (A) and the inorganic filler (B). It is 1-20: 80, Preferably it is 90: 10-30: 70, More preferably, it is 80: 20-40: 60, Especially preferably, it is 70: 30-50: 50. When the volume ratio of (A) and (B) is within these ranges, the balance between thermal conductivity and mechanical properties is favorable, which is preferable.

  Moreover, even when the volume ratio of the thermoplastic resin (A) and the inorganic filler (B) is as small as 90:10 to 70:30, the high thermal conductivity thermoplastic resin composition has excellent thermal conductivity, At the same time, since the amount of the inorganic filler (B) used is small, the appearance of the molded product becomes good during extrusion molding, and the density of the molded product can be lowered. The excellent thermal conductivity and appearance of the molded product and the low density are advantageous when used as a resin material for heat dissipation and heat transfer in various situations such as in the electric / electronic industry field and the automobile field.

  As the inorganic filler (B), known fillers can be widely used. The thermal conductivity of the inorganic filler (B) alone is not particularly limited, but is preferably 0.5 W / m · K or more, more preferably 1 W / m · K or more. From the viewpoint that the resulting composition is excellent in thermal conductivity, it is particularly preferable that the composition is a highly thermally conductive inorganic compound having a single thermal conductivity of 10 W / m · K or more.

  The thermal conductivity of the high thermal conductivity inorganic compound alone is preferably 12 W / m · K or more, more preferably 15 W / m · K or more, most preferably 20 W / m · K or more, particularly preferably 30 W / m · K. The above is used. The upper limit of the thermal conductivity of the high thermal conductivity inorganic compound alone is not particularly limited, and it is preferably as high as possible, but is generally 3000 W / m · K or less, more preferably 2500 W / m · K or less. Used.

  In the case where the molded body is used in applications where electrical insulation is not particularly required, a metal-based compound, a conductive carbon compound, or the like can be used as the conductive highly thermally conductive inorganic compound. Examples of the conductive carbon compound include graphite and carbon fiber because of excellent thermal conductivity. As the metal compound, highly heat conductive inorganic compounds such as conductive metal powders, conductive metal fibers, ferrites, and metal oxides can be preferably used. As conductive metal powder, conductive metal powder obtained by atomizing various metals, as conductive metal fiber, conductive metal fiber obtained by processing various metals into fibers, as ferrite, various ferrites such as soft magnetic ferrite, metal Examples of the oxide include highly thermally conductive inorganic compounds such as metal oxides such as zinc oxide.

  Among these, one or more conductive high thermal conductive inorganic compounds selected from the group consisting of graphite, conductive metal powder, soft magnetic ferrite, carbon fiber, conductive metal fiber, and zinc oxide are preferable.

When the molded body is used for applications requiring electrical insulation, a compound exhibiting electrical insulation is preferably used as the highly thermally conductive inorganic compound. Specifically, the electrical insulating property indicates an electrical resistivity of 1 Ω · cm or more, preferably 10 Ω · cm or more, more preferably 10 ⁵ Ω · cm or more, and further preferably 10 ¹⁰ Ω · cm or more. It is preferable to use a material having a size of cm or more, 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 high thermal conductive inorganic compounds, examples of the electrically insulating high thermal conductive inorganic compounds exhibiting electrical insulation include metal oxides, metal nitrides, metal carbides, metal carbonates, insulating carbon materials, and metal hydroxides. can do. Examples of the metal oxide include aluminum oxide, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride.

  Examples of the metal carbide include silicon carbide, examples of the metal carbonate include magnesium carbonate, examples of the insulating carbon material include diamond, and examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.

  Among them, one or more electrically insulating high heat conductive inorganic substances 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 Compounds are preferred. These can be used alone or in combination.

  Various shapes can be applied to the shape of the high thermal conductive inorganic compound. 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 a composite particle shape, a liquid, etc. can be exemplified. These high thermal conductivity inorganic compounds 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 high thermal conductive inorganic compounds may be used alone or in combination of two or more different shapes, average particle diameters, types, surface treatment agents, and the like.

  These highly heat-conductive inorganic compounds may be those that have been surface-treated with a surface 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 the resin composition of the present invention, known inorganic fillers can be widely used depending on the purpose in addition to the above-described highly thermally conductive inorganic compound. Since the thermal conductivity of the single resin is high, even if the thermal conductivity of the inorganic compound is relatively low at less than 10 W / mK, the resin composition can exhibit high thermal conductivity.

  Examples of inorganic fillers other than the high thermal conductivity inorganic compound include diatomaceous earth powder; basic magnesium silicate; calcined clay; fine powder silica; quartz powder; crystalline silica; kaolin; talc; antimony trioxide; Examples thereof include molybdenum sulfide; rock wool; ceramic fiber; inorganic fiber such as asbestos; and glass fillers such as glass fiber, glass powder, glass cloth, and fused silica.

  By using these fillers, for example, it is possible to improve favorable characteristics in applying a resin composition such as thermal conductivity, mechanical strength, or abrasion resistance. Further, if necessary, organic fillers such as paper, pulp, wood, synthetic fibers such as polyamide fiber, aramid fiber, and boron fiber; resin powder such as polyolefin powder; can be used in combination.

  In the high thermal conductivity thermoplastic resin composition for extrusion molding of the present invention, an epoxy resin, a polyolefin resin, a bismaleimide resin, a polyimide resin, a polyether resin, a phenol resin, a silicone are used as long as the effects of the present invention are not lost. Any known resin such as resin, polycarbonate resin, polyamide resin, polyester resin, fluorine resin, acrylic resin, melamine resin, urea resin, 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. When these resins are used in combination, the amount used is preferably from 0 to 10,000 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A) usually contained in the resin composition.

  The highly heat-conductive resin material for extrusion molding of the present invention includes any other component depending on the purpose, for example, a reinforcing agent, a thickener, a release agent, a coupling, as an additive other than the resin and filler. Agents, flame retardants, flame retardants, pigments, colorants, other auxiliaries 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.

  The method for producing the composition of the present invention is not particularly limited. 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 composition of the present invention can be suitably used as a highly heat-conductive extruded product because of its excellent thermal conductivity and appearance of a molded product, and extrusion molding is suitable as a molding method.

  Examples of usage forms include various forms such as a resin film, a resin molded product, a resin foam, a paint and a coating agent. As the molding method, for example, injection molding, extrusion molding, vacuum molding, press molding, calendar molding, blow molding, or the like can be used. Since the highly heat-conductive thermoplastic resin composition obtained in the present invention is excellent in moldability, it is possible to use an extrusion machine that is widely used at present, and to convert a long product having a deformed shape into a sheet or film shape. Even continuous molding is easy to mold.

  The high thermal conductivity thermoplastic resin composition for extrusion molding of the present invention is widely used for various applications such as electronic materials, magnetic materials, catalyst materials, structural materials, optical materials, medical materials, automotive materials, building materials, etc. Is possible. In particular, since it has excellent properties such as excellent appearance of molded products and high thermal conductivity, it is very useful as a resin material for heat dissipation and heat transfer.

  The highly heat-conductive thermoplastic resin composition for extrusion molding of the present invention can be suitably used for injection-molded products such as home appliances, OA equipment parts, AV equipment parts, automotive interior / 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, small or portable electronic devices such as portable computers such as notebook computers, PDAs, cellular phones, portable game machines, portable music players, portable TV / video devices, portable video cameras, etc. are preferable among these. It is very useful as a resin for housings, housings, and exterior materials. It can also be used very effectively as a resin for battery peripherals in automobiles, trains, etc., a resin for portable batteries in home appliances, a resin for power distribution parts such as breakers, and a sealing material for motors.

  The high heat conductive thermoplastic resin composition for extrusion molding of the present invention has a good molding processability because the amount of the high heat conductive inorganic substance can be reduced as compared with a conventionally well-known composition. It has characteristics useful as a component such as a substrate in an application or a housing.

Next, the composition of the present invention and the molded product thereof will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to such examples. Unless otherwise specified, the reagents listed below were manufactured by Wako Pure Chemical Industries, Ltd.

[Production Example 1]
4,4′-Dihydroxybiphenyl, tetradecanedioic acid, and acetic anhydride were charged into a closed reactor at a molar ratio of 1: 1.05: 2.1, respectively. A time acetylation reaction was carried out, and polycondensation was carried out by heating to 265 ° C. at a temperature rising rate of 1 ° C./min. When the acetic acid distillate amount reached 90% of the theoretical acetic acid production amount, while maintaining the temperature, the pressure was reduced to 1.0 torr over about 20 minutes, and melt polymerization was carried out to a high molecular weight. One hour after the start of decompression, the pressure was returned to normal pressure with an inert gas, and the produced polymer (thermoplastic resin (A)) was taken out. The obtained polymer is the thermoplastic resin of the present invention.

  The obtained polymer was dissolved in a 1: 2 (Vol ratio) mixed solvent of p-chlorophenol and o-dichlorobenzene so as to have a concentration of 0.25% by weight, and high-temperature GPC (manufactured by Waters, Inc .; 150- CPC), GPC measurement was performed using polystyrene as a standard substance under the conditions of INJECTOR COMP: 80 ° C., COLUMN COMP: 80 ° C., PUMP / SOLVENT COMP: 60 ° C., and Injection Volume: 200 μl. As a result, the number average molecular weight was 8,500, and the weight average molecular weight was 18,800.

  In addition, two cylindrical test pieces of 30 mmφ × 3.0 mm thickness were press-molded at 240 ° C., and the thermal conductivity was measured with a 4φ sensor using a hot disk method thermal conductivity measuring device manufactured by Kyoto Electronics Industry. As a result of measurement, the thermal conductivity was 1.36 W / mK.

[Evaluation methods]
Thermal conductivity: Two plate columnar test pieces of 30 mm square x 3.0 mm thickness were cut out from the obtained extrusion-molded product, and the thermal conductivity was measured with a 4φ sensor using a hot disk method thermal conductivity measuring device manufactured by Kyoto Electronics Industry. It was measured.

  Appearance of molded product: Appearance defects such as irregularities and filler floating on the surface of the obtained extrusion-molded product were visually observed and evaluated according to the following criteria. A: Appearance is very good, B: Appearance is good, B: Appearance is partially good but almost good, B: Appearance is poor.

[Example 1]
After adding 0.2 parts by weight of AO-60 (manufactured by ADEKA) as a phenolic stabilizer to 100 parts by weight of the thermoplastic resin (A) synthesized in Production Example 1, and mixing with a Henschel mixer, It was fed from a hopper provided in the vicinity of the screw root of a 45 mm same-direction meshing twin screw extruder TEX44 manufactured by Nippon Steel. The set temperature was 200 ° C. in the vicinity of the supply port, and the set temperature was sequentially increased, and the extruder screw tip temperature was set to 220 ° C.

Under these conditions, a highly heat-conductive thermoplastic resin composition for extrusion molding was obtained. The obtained composition was dried at 140 ° C. for 4 hours and then subjected to extrusion molding using a 40 mm single-screw extruder 10VSE-40-28V manufactured by Osaka Seiki. Molding conditions are set at a cylinder temperature of 220 ° C and a die temperature of 210 ° C, and after passing through a sizing die (set temperature of 90 ° C) placed at a location 5 cm away from the die, it is taken out and extruded. When the processing was carried out, the extrusion moldability was good. The shape of the entrance and exit of the die outlet and the sizing die is shown in FIG.
As a result of evaluating the thermal conductivity of the obtained molded product, the thermal conductivity was 1.36 W / mK, and the molded product appearance was ◎.

[Example 2]
Boron nitride powder (PT110 manufactured by Momentive Performance Materials, Inc., single unit thermal conductivity 60 W / m · K) with respect to 100 parts by weight of the thermoplastic resin (A) synthesized in Production Example 1 , Volume average particle diameter 45 μm, electrical insulation, volume resistivity 10 ¹⁴ Ω · cm) (h-BN) 50 parts by weight, phenolic stabilizer AO-60 (manufactured by ADEKA Corporation) 0.2 After adding a weight part and mixing with a Henschel mixer, it injected | thrown-in from the hopper provided in the screw base vicinity of 45 mm same direction meshing type twin screw extruder TEX44 made from Nippon Steel Works.

  The set temperature was 200 ° C. in the vicinity of the supply port, and the set temperature was sequentially increased, and the extruder screw tip temperature was set to 250 ° C. Under these conditions, a highly heat-conductive thermoplastic resin composition for extrusion molding was obtained. The obtained composition was extruded in the same manner as in Example 1. As a result, the extrudability was good, the thermal conductivity of the molded product was 5.61 W / mK, and the appearance of the molded product was ◯.

[Comparative Example 1]
Evaluation was performed in the same manner as in Example 1 except that polyethylene terephthalate (Bell Polyester Products Belpet EFG-70) was used as the thermoplastic resin, and the extruder screw tip temperature and die temperature were set to 270 ° C. As a result, it was difficult to obtain a uniform molded body because the extrusion molding was severely drawn down during extrusion molding. As a result of selecting and evaluating the comparatively maintained shape from the obtained molded products, the thermal conductivity was 0.21 W / mK and the molded product appearance was Δ.

[Comparative Example 2]
Evaluation was performed in the same manner as in Example 2 except that polyethylene terephthalate (Bell Polyester Products Belpet EFG-70) was used as the thermoplastic resin and the extruder screw tip temperature and parison temperature were set to 270 ° C. It was. Some drawdown occurred during extrusion molding, and the moldability was not good. As a result of evaluating the molded product, the thermal conductivity was 1.05 W / mK, the molded product appearance was ◯, and the thermal conductivity was significantly lower than that of Example 2.

[Comparative Example 3]
Evaluation was performed in the same manner as in Comparative Example 2 except that 100 parts by weight of the boron nitride powder as the inorganic filler (B) was used and the extruder screw tip temperature and the die temperature were set to 290 ° C. Extrudability was greatly reduced, such as the molded body being deformed and cracked during extrusion molding, and the appearance of fillers was severe and the surface appearance was not smooth. As a result of evaluating the molded product, it was found that the thermal conductivity was 3.10 W / mK, the molded product appearance was x, and the molded product appearance was remarkably reduced when trying to obtain high thermal conductivity.

[Example 3]
For 100 parts by weight of the thermoplastic resin (A) synthesized in Production Example 1, natural scaly graphite powder as an inorganic filler (B) (BF-250A manufactured by Chuetsu Graphite Co., Ltd., thermal conductivity 1200 W / alone) m · K, volume average particle diameter 250.0 μm, conductivity) (GC) 50 parts by weight, phenol stabilizer AO-60 (manufactured by ADEKA) 0.2 part by weight, Henschel mixer Then, the mixture was fed from a hopper provided in the vicinity of the screw root of a 45 mm same-direction meshing twin screw extruder TEX44 manufactured by Nippon Steel Works.

  The set temperature was 200 ° C. in the vicinity of the supply port, and the set temperature was sequentially increased, and the extruder screw tip temperature was set to 250 ° C. Under these conditions, a highly heat conductive resin composition for extrusion molding was obtained. The obtained composition was extruded in the same manner as in Example 1. As a result, the extrusion moldability was good, the thermal conductivity of the molded product was 40.1 W / mK, and the appearance of the molded product was ◯.

  As described above, since the high thermal conductivity thermoplastic resin composition for extrusion molding of the present invention uses a thermoplastic resin having excellent thermal conductivity, high heat conductivity can be obtained without blending a large amount of high thermal conductivity inorganic filler. A resin composition exhibiting conductivity is obtained. Therefore, when the resin composition is extruded, there is little filler floating on the surface of the molded product, and an extruded product with a good appearance can be obtained. Such a composition can be used as a heat-dissipating / heat-transfer resin material in various situations such as in the electric / electronic industrial field and the automobile field, and is industrially useful.

Claims (11)

Thermoplastic whose main chain is mainly composed of repeating units represented by the following general formula (1), mainly has a chain structure, and the thermal conductivity of the resin itself is 0.45 W / (m · K) or more. A high thermal conductive thermoplastic resin composition for extrusion molding containing a resin.
-M-Sp- (1)
(In the formula, M represents a mesogenic group, and Sp represents a spacer.) The high thermal conductive resin material for extrusion molding according to claim 1, wherein the general formula (1) is composed of repeating units represented by the following general formula (2).
^{-A 1 -x-A 2 -y-} R-z- (2)
(In the formula, A ¹ and A ² each independently represent a substituent selected from an aromatic group, a condensed aromatic group, an alicyclic group, and an alicyclic heterocyclic group. X, y, and z are each independently a direct _{bond, -CH 2 -, - C (} CH 3) 2 -, - O -, - S -, - CH 2 -CH 2 -, - C = C -, - C≡C -, - CO 2 selected from the group of-, -CO-O-, -CO-NH-, -CH = N-, -CH = N-N = CH-, -N = N- or -N (O) = N-. R represents a divalent substituent which may contain a branch having 2 to 20 main chain atoms.) -A 1 ^-x-A 2 ^- wherein the portion corresponding to is a mesogenic group represented by the following general formula (3), extrusion molding highly thermally conductive thermoplastic resin composition according to claim 2 object.

The high thermal conductive thermoplastic resin composition for extrusion molding according to any one of claims 2 and 3, wherein a portion corresponding to R of the thermoplastic resin is a linear aliphatic hydrocarbon chain. The high thermal conductivity thermoplastic resin composition for extrusion molding according to any one of claims 2 to 4, wherein the number of carbon atoms in the R molecular chain of the thermoplastic resin is an even number. R of the thermoplastic resin is at least one selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ —, and the number average molecular weight is 3000 to 40000. The high thermal conductive thermoplastic resin composition for extrusion molding according to any one of 2 to 5. The high thermal conductive resin material for extrusion molding using the thermoplastic resin according to claim 2, wherein -yRz- of the thermoplastic resin is -O-CO-R-CO-O-. The high thermal conductive resin thermoplastic composition for extrusion molding according to any one of claims 1 to 7, comprising an inorganic filler (B). The high thermal conductive resin thermoplastic composition for extrusion molding according to claim 8, wherein the inorganic filler (B) is an inorganic compound having a single thermal conductivity of 12 W / m · K or more. The high thermal conductive resin thermoplastic composition for extrusion molding according to claim 8 or 9, wherein the inorganic filler (B) is an electrically insulating high thermal conductive inorganic compound. The high thermal conductive resin thermoplastic composition for extrusion molding according to claim 8 or 9, wherein the inorganic filler (B) is a conductive high thermal conductive inorganic compound.

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