JP5860664B2 - High thermal conductivity thermoplastic resin composition - Google Patents

Description

The present invention relates to a heat radiation material excellent in thermal conductivity, and relates to a thermoplastic resin composition that can be injection-molded.

  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. For that purpose, it is necessary to mix highly heat-conductive inorganic substances such as graphite, carbon fiber, alumina, boron nitride and the like in the resin with a high content of usually 30 Vol% or more, and further 50 Vol% or more. 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. Therefore, improvement in the thermal conductivity of the resin alone has been demanded.

  As for the thermoplastic resin with excellent thermal conductivity of the resin itself, there are almost no research reports on thermoplastic resins in which the resin itself molded by injection molding has high thermal conductivity without special molding processes such as stretching and magnetic field orientation. There is no patent document 1 as a few examples. As described in Patent Document 1, the inventors of the present invention have found a thermoplastic resin exhibiting high thermal conductivity with a single resin.

  On the other hand, a method for improving properties such as mechanical strength, moist heat resistance, hydrolysis resistance, and surface properties by blending a thermoplastic polyester resin with a compound having an epoxy group, an oxazoline group, a carbodiimide group, etc. is widely known. Patent Documents 2 to 6 are given as examples. However, in Patent Documents 2 to 5, there is no description of blending a high thermal conductivity inorganic filler, and in Patent Document 6, a low thermal conductivity polyester resin is used, so a high thermal conductivity inorganic filler is blended. The resulting resin composition also has a problem of low thermal conductivity.

International Publication Number WO2010 / 050202 Japanese Patent Laid-Open No. 3-14863 JP-A-3-2259 JP 2007-153992 A JP-A-4-50258 JP 2007-262295 A

  Although the thermoplastic resin described in Patent Document 1 can obtain a molded article exhibiting excellent thermal conductivity by injection molding, an improvement in bending strength when an inorganic filler is blended has been demanded. In order to obtain higher bending strength, it is conceivable to use a higher molecular weight thermoplastic resin. However, in the thermoplastic resin described in Patent Document 1, a higher molecular weight resin has a higher thermal conductivity than a single resin. Has become a problem, and there has been a demand for both excellent thermal conductivity and high bending strength.

  Then, an object of this invention is to provide the thermoplastic resin composition which shows the outstanding heat conductivity and has high bending strength.

  As a result of intensive studies, the present inventors have two or more reactive functional groups in one molecule when an inorganic filler is filled into a polycondensate having a specific molecular structure having high thermal conductivity. It has been found that by containing a molecular chain extender, the obtained resin composition not only exhibits high bending strength, but also maintains high thermal conductivity, leading to the present invention. That is, the present invention includes the following 1) to 16).

1)
The structure of the main chain is general formula (1)

(Wherein X represents a divalent substituent selected from the group of O and CO)
Unit (A) having a biphenyl group represented by 25 to 60 mol%,
General formula (2)
-YR-Y- (2)
(In the formula, R represents a divalent linear substituent which may contain a branch having 2 to 20 main chain atoms. Y represents a divalent substituent selected from the group of O and CO.)
Unit (B) represented by 25 to 60 mol%,
General formula (3)
-Z ¹ -MZ ^2- (3)
(In the formula, Z ¹ and Z ² represent a divalent substituent selected from the group of O, NH, CO, S and NHCO. M represents an aromatic group having a main chain folding effect, a condensed aromatic group, A substituent selected from a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group is shown.)
Unit (C) represented by 0 to 25 mol% (however, the total of units (A), (B), and (C) is 100 mol%), and at least 60 mol% of the end of the molecular chain is carboxyl. A thermoplastic resin (i) having a thermal conductivity of 0.4 W / (m · K) or more and a molecular chain extender (ii) having two or more reactive functional groups in one molecule. A thermoplastic resin composition characterized by comprising:

2)
The thermoplastic resin composition according to 1), comprising the thermoplastic resin (i), the molecular chain extender (ii), and an inorganic filler (iii).

3)
The thermoplastic resin composition according to 1) or 2), wherein X in the general formula (1) is O and Y in the general formula (2) is CO.

4)
The thermoplastic resin composition according to any one of 1) to 3), wherein a portion corresponding to R of the thermoplastic resin is a linear aliphatic hydrocarbon chain.

5)
The thermoplastic resin composition according to any one of 1) to 4), wherein the number of main chain atoms in a portion corresponding to R 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 1) to 5) The thermoplastic resin composition as described.

7)
The thermoplastic resin composition according to any one of 1) to 6), wherein M of the thermoplastic resin is any one of the structures shown below.

8)
The thermoplastic resin composition according to any one of 1) to 7), wherein the number average molecular weight of the thermoplastic resin is 3000 to 40000.

9)
The ratio of lamellar crystals in the thermoplastic resin is 10 Vol% or more, The thermoplastic resin according to any one of 1) to 8).

10)
The thermoplastic resin composition according to any one of 1) to 9), wherein the content of the molecular chain extender is 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 11)
The thermoplastic resin composition according to any one of 1) to 10), wherein the reactive functional group of the molecular chain extender is at least one selected from an epoxy group, an oxazoline group, an oxazine group, and a carbodiimide group. object.

12)
The thermoplastic resin composition according to any one of 1) to 11), wherein the inorganic filler is an inorganic compound having a single member thermal conductivity of 1 W / (m · K) or more. .

13)
The inorganic filler is at least one electrically insulating high heat 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. It is a conductive inorganic compound, The thermoplastic resin composition as described in any one of 1) -12) characterized by the above-mentioned.

14)
The inorganic filler is 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. The thermoplastic resin composition according to any one of 1) to 13).

15)
A resin material for heat dissipation and heat transfer, comprising the thermoplastic resin composition according to any one of 1) to 14).

  16) A molded article containing the thermoplastic resin composition according to any one of 1) to 15).

  The thermoplastic resin composition of the present invention has excellent thermal conductivity and high bending strength.

  The thermoplastic resin in the present invention has a main chain structure of the general formula (1)

(Wherein X represents a divalent substituent selected from the group of O and CO)
Unit (A) having a biphenyl group represented by 25 to 60 mol%,
General formula (2)
-YR-Y- (2)
(In the formula, R represents a divalent linear substituent which may contain a branch having 2 to 20 main chain atoms. Y represents a divalent substituent selected from the group of O and CO.)
Unit (B) represented by 25 to 60 mol%,
General formula (3)
-Z ¹ -MZ ^2- (3)
(In the formula, Z ¹ and Z ² represent a divalent substituent selected from the group of O, NH, CO, S and NHCO. M represents an aromatic group having a main chain folding effect, a condensed aromatic group, A substituent selected from a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group is shown.)
Unit (C) represented by 0 to 25 mol% (however, the total of units (A), (B), and (C) is 100 mol%), and at least 60 mol% of the end of the molecular chain is carboxyl. The thermal conductivity of a single resin is 0.4 W / (m · K) or more.

  The thermoplasticity referred to in the present invention is a property of being plasticized by heating, and the thermoplastic resin of the present invention is preferably such that the unit (A) is 30 to 55 mol% and the unit (B) is 30. It is -55 mol%, and is a thermoplastic resin whose unit (C) is 0-20 mol%. More preferably, it is a thermoplastic resin in which the unit (A) is 30 to 48%, the unit (B) is 45 to 55 mol%, and the unit (C) is 0 to 15 mol%. When the unit (C) is 26 mol% or more, the thermal conductivity may decrease.

  The ratio of the carboxyl group with respect to all the terminals of the molecular chain of the thermoplastic resin of this invention is 60 mol% or more, Preferably it is 70 mol% or more, More preferably, it is 80 mol% or more. When it is less than 60 mol%, when an inorganic filler is blended, the thermal conductivity of the resin composition may be lower than that of a resin having a terminal carboxyl group of 60 mol% or more. For example, when the ratio of the carboxyl group with respect to all terminals of the molecular chain of the thermoplastic resin is 50 mol%, it may be difficult to improve the thermal conductivity of the resin composition when a filler is blended. This is presumed to be caused by a large thermal resistance at the contact interface between the resin and the filler. The present inventors can reduce the thermal resistance at the contact interface between the resin and the thermally conductive filler by making a carboxyl group that binds or has affinity with the thermally conductive filler at the end of the molecular chain of the resin. As a result of repeated thoughts and intensive studies, it has been found that a thermoplastic resin having a specific molecular structure and having a carboxyl group at 60 mol% or more of the molecular chain ends can overcome the above-mentioned problems.

The thermal conductivity of the thermoplastic resin of the present invention is 0.4 W / (m · K) or more, preferably 0.6 W / (m · K) or more, more preferably 0.8 W / (m · K). ) Or more, and particularly preferably 1.0 W / (m · K) or more. The upper limit of the thermal conductivity is not particularly limited and is preferably as high as possible, but generally 30 W / (m · K) or less unless physical treatment such as magnetic field, voltage application, rubbing, and stretching is performed during molding. Further, it becomes 10 W / (m · K) or less.
General formula (1)

(Wherein X represents a divalent substituent selected from the group of O and CO)
X in the inside is preferably O from the viewpoint of obtaining a resin having excellent thermal conductivity.
General formula (2)
-YR-Y- (2)
(In the formula, R represents a divalent linear substituent which may contain a branch having 2 to 20 main chain atoms. Y represents a divalent substituent selected from the group of O and CO.)
Y in the inside is preferably CO from the viewpoint that a resin having excellent thermal conductivity can be obtained.

R in the general formula (2) represents a divalent linear substituent which may include a branch having 2 to 20 main chain atoms, and is a linear aliphatic hydrocarbon chain not including a branch. preferable. When branching is included, the crystallinity may be reduced, and the thermal conductivity may be reduced. R may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain. When the unsaturated bond is included, sufficient flexibility cannot be obtained, and the thermal conductivity may be lowered. R is preferably a straight chain saturated aliphatic hydrocarbon chain having 2 to 20 carbon atoms, more preferably a straight chain saturated aliphatic hydrocarbon chain having 4 to 18 carbon atoms, particularly 8 to 8 carbon atoms. Preferably, it is a 14 straight chain saturated aliphatic hydrocarbon chain. The number of main chain atoms of R is preferably an even number. In the case of an odd number, the crystallinity may decrease and the thermal conductivity may decrease. In particular, R is preferably 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. .
General formula (3)
-Z ¹ -MZ ^2- (3)
(In the formula, Z ¹ and Z ² represent a divalent substituent selected from the group of O, NH, CO, S and NHCO. M represents an aromatic group having a main chain folding effect, a condensed aromatic group, A substituent selected from a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group is shown.)
The main chain folding effect referred to here means the effect of bending the polymer main chain so as to fold, and the angle between the bonds forming the main chain is 150 degrees or less, preferably 120 degrees or less, more preferably It is 60 degrees or less. Specific examples of M in the general formula (3) include groups represented by the following.

From the viewpoint of obtaining a resin having excellent thermal conductivity, specific examples of M in the general formula (3) include groups represented by the following.

Further, from the viewpoint of obtaining a resin having excellent thermal conductivity, a group represented by the following is more preferable.

^Z 1, ^{Z 2} in formula (3) is O, NH, CO, S, from the viewpoint represents a divalent substituent selected from the group consisting of NHCO, thermal conductivity and excellent resin is obtained, ^{Z 1} , Z ² is preferably any one of O, NH, and CO, and more preferably, both Z ¹ and Z ² are O.
The thermoplastic resin in the present invention exhibits liquid crystallinity and has a liquid crystal phase transition temperature and an isotropic phase transition temperature. When the thermoplastic resin of the present invention is injection molded, when the resin is heated to a temperature between the liquid crystal phase transition temperature and the isotropic phase transition temperature and injected in a liquid crystal state, high thermal conductivity is exhibited. The liquid crystal phase transition temperature and the isotropic phase transition temperature referred to here are the low-temperature side and the high-temperature side, respectively, of two peaks observed in the temperature rising process in differential scanning calorimetry (DSC).

  The number average molecular weight of the thermoplastic resin in the present invention is polystyrene as a standard, and the thermoplastic resin in the present invention is dissolved in a mixed solvent of p-chlorophenol and toluene in a volume ratio of 3: 8 to a concentration of 2.5% by weight. It is the value measured at 80 ° C. by GPC using the prepared solution. The number average molecular weight of the thermoplastic resin in the present invention is preferably 3000 to 40000, more preferably 5000 to 30000, and still more preferably 7000 to 20000. When the number average molecular weight is less than 3000 or greater than 40000, the thermal conductivity may be less than 0.4 W / (m · K) even if the resin has the same primary structure. The thermoplastic resin according to the present invention may be produced by any known method. From the viewpoint that the control of the structure is simple, a compound having a reactive functional group at both ends of the biphenyl group, a compound having a reactive functional group at both ends of the linear substituent R, and the main chain folding effect A method in which a substituent M having a hydrogen atom is reacted with a compound having two reactive functional groups is preferred. As such a reactive functional group, known ones such as a hydroxyl group, a carboxyl group, an ester group, an amino group, a thiol group, and an isocyanate group can be used, and the conditions for reacting them are not particularly limited.

  From the viewpoint of easy synthesis, a combination of a compound having a reactive functional group at both ends of the biphenyl group and a compound having a reactive functional group at both ends of the linear substituent R is Both a compound having a hydroxyl group at the end, a compound having a carboxyl group at both ends of the linear substituent R, or a compound having a carboxyl group or an ester group at both ends of the biphenyl group, and both of the linear substituent R A combination of compounds having a hydroxyl group at the terminal is preferred. In addition, for a compound having two reactive functional groups in the substituent M having a main chain folding effect, the substituent M having a main chain folding effect has at least one of a hydroxyl group, a carboxyl group, an ester group, and an amino group. It is preferable to have one.

  A thermoplastic resin comprising a compound having a hydroxyl group at both ends of a biphenyl group, a compound having a carboxyl group at both ends of a linear substituent R, and a compound having a hydroxyl group at a substituent M having a main chain folding effect As an example of the production method, the hydroxyl group of the compound is individually or collectively converted into a lower fatty acid ester using a lower fatty acid such as acetic anhydride, and then substituted with a straight chain in another reaction vessel or the same reaction vessel. Examples include a method in which a compound having a carboxyl group at both ends of the group R is subjected to a delowering fatty acid polycondensation reaction. The polycondensation reaction is carried out at a temperature of usually 220 to 330 ° C., preferably 240 to 310 ° C. in the presence of substantially no solvent, in the presence of an inert gas such as nitrogen, at normal pressure or reduced pressure, and at a pressure of 0. 5 to 5 hours. When the reaction temperature 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 making it react under reduced pressure, it is preferable to raise a pressure reduction degree in steps. When the pressure is rapidly reduced to a high degree of vacuum, the monomer having the linear substituent R and the monomer having the main chain folding effect volatilize, 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. 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 unreacted raw materials may be removed, or solid phase polymerization may be performed in order to increase 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.

  Examples of the acid anhydride of the lower fatty acid used in the production of the thermoplastic resin in 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, 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 is 1.01 to 1.5 times equivalent, preferably 1.02 to 1.2 times equivalent to the total of hydroxyl groups and amino groups of the monomers used. When the amount is less than 1.01 equivalent, the lower fatty acid anhydride may volatilize, whereby the hydroxyl group and amino group may not completely react with the lower fatty acid anhydride, and a low molecular weight resin may be obtained. is there. In addition, a compound having a carboxyl group or an ester group at both ends of the biphenyl group, a compound having a hydroxyl group at both ends of the substituent R, and a compound having a carboxyl group or an ester group at the substituent M having a main chain folding effect As a method for producing a thermoplastic resin comprising, for example, a method of melt polymerization of dimethyl 4,4′-biphenyldicarboxylate and an aliphatic diol as described in JP-A-2-258864 is mentioned. 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 and the like. Mention may be made of organic compound catalysts such as metal salt catalysts, N, N-dimethylaminopyridine, N-methylimidazole and the like.

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 wt% is used.

  In this invention, it is preferable that the ratio of the lamellar crystal in a thermoplastic resin is 10 Vol% or more. The ratio of lamellar crystals is preferably 20 Vol% or more, more preferably 30 Vol% or more, and particularly preferably 40 Vol% or more.

  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. There exists a tendency for the heat conductivity of a thermoplastic resin and a resin composition to become high, so that the ratio of a lamellar crystal is high. Whether or not lamellar crystals are present in the resin can be easily determined by observation with a transmission electron microscope (TEM) or X-ray diffraction.

The ratio of lamellar crystals can be calculated by directly observing a sample stained with RuO ₄ with a transmission electron microscope (TEM). As a specific method, a specimen for TEM observation was prepared by cutting out a part of a molded cylindrical sample having a thickness of 6 mm × 20 mmφ, staining with RuO ₄ , and then forming a 0.1 μm-thick ultrathin slice with a microtome. Shall be used. The prepared slice is observed with a TEM at an acceleration voltage of 100 kV, and a lamella crystal region can be determined from the obtained 40,000-fold scale photograph (18 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 can be calculated as a ratio of the lamella crystal region to the entire area of the photograph. The molecular chain extender used in the present invention has two or more reactive functional groups in one molecule, and the reactive functional group having at least one selected from an epoxy group, an oxazoline group, an oxazine group, and a carbodiimide group. Preferably it is a seed. If the number of reactive functional groups contained in one molecule is less than 2, a resin composition having a sufficiently high bending strength cannot be obtained.

The molecular chain extender having an epoxy group is not necessarily limited, but biphenol diglycidyl ether, bisphenol A diglycidyl ether and the like, glycidyl ethers synthesized by reaction of phenols with epichlorohydrin, and the like, novolac resins Type epoxy resin synthesized from chlorohydrin and epichlorohydrin, polyvalent aliphatic, alicyclic, glycidyl ether compound synthesized by reaction of aromatic alcohol with epichlorohydrin, aliphatic or alicyclic having multiple unsaturated groups Epoxy compounds epoxidized with acetic acid and peracetic acid, polyvalent aliphatic, alicyclic, glycidylamine compounds synthesized by reaction of aromatic amines with epichlorohydrin, compounds with multiple nitrogen-containing heterocycles and epichlorohydrin Etc. Epoxy compounds synthesized by reaction, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, glycidyl esters such as glycidyl methacrylate, p-hydroxybenzoic acid glycidyl From glycidyl esters and ethers synthesized from hydroxycarboxylic acids such as esters and ethers and epichlorohydrin, epoxidized polybutadiene and unsaturated monomers having an epoxy group such as glycidyl methacrylate and other unsaturated monomers such as ethylene Epoxy group-containing copolymers, glycidylamines synthesized from aminobenzenes such as tetraglycidyldiaminodiphenylmethane and epichlorohydrin, and the like. That.
From the viewpoint of obtaining a resin composition with high bending strength, the epoxy equivalent of the molecular chain extender having an epoxy group is preferably 3000 or less, more preferably 2000 or less, and further preferably 1000 or less. Preferably, it is 500 or less, and most preferably 300 or less. The epoxy equivalent referred to here is the number of grams of a compound containing 1 g equivalent of an epoxy group.

  Specific examples of the molecular chain extender having an epoxy group include ethylene glycol diglycidyl ether, propylene glycol glycidyl ether, tetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Polyalkylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polybutanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyneopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, etc. Glycidyl ether, resorcin diglycidyl ether, erythlit polyglycidyl ether Trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, hydroquinone diglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, sorbitol polyglycidyl ether, bisphenol S diglycidyl ether, diglycidyl aniline, Examples include tetraglycidyl-4,4′-diaminodiphenylmethane, triglycidyl tris (2-hydroxyethyl) isocyanate, and the like.

Among these, 4,4′-biphenyldiyl bis (glycidyl ether), 3,3 ′, 5,5′-tetramethyl-4,4′-bis (glycidyloxy) -1, 1′-biphenyl, bisphenol A diglycidyl ether is preferably used.
Examples of the molecular chain extender having an oxazoline group include 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4,4- Dimethyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4,4-diethyl-2-oxazoline), 2,2′-bis (4- Propyl-2-oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-bis (4-hexyl-2-oxazoline), 2,2′-bis (4-phenyl-) 2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2'-butylenebis (2-oxazoline), 2,2 ' Hexamethylene bis (2-oxazoline), 2,2′-octamethylene bis (2-oxazoline), 2,2′-decamethylene bis (2-oxazoline), 2,2′-ethylene bis (4-methyl-2) -Oxazoline), 2,2'-ethylenebis (4,4-dimethyl-2-oxazoline), N, N'-ethylenebis (2-carbamoyl-2-oxazoline), N, N'-propylenebis (2- Carbamoyl-2-oxazoline), N, N′-butylenebis (2-carbamoyl-2-oxazoline), N, N′-hexamethylenebis (2-carbamoyl-2-oxazoline), N, N′-octamethylenebis ( 2-carbamoyl-2-oxazoline), N, N′-decamethylenebis (2-carbamoyl-2-oxazoline), N, N′-phenylenebis (2-cal Moyl-2-oxazoline), N, N′-ethylenebis (2-carbamoyl-4-methyl-2-oxazoline), N, N′-butylenebis (2-carbamoyl-4,4-dimethyl-2-oxazoline), N, N′-dimethyl-N, N′-ethylenebis (2-carbamoyl-2-oxazoline), N, N′-dimethyl-N, N′-butylenebis (2-carbamoyl-2-oxazoline), 2,2 '-O-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylene Bis (4-methyl-2-oxazoline), 2,2′-m-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2′-p-phenylenebis (4-methyl-2-oxazo) Emissions), 2,2'-p-phenylene bis (4,4-dimethyl-2-oxazoline), and a bis oxazoline compounds such as.

Among these, it is particularly preferable to use 2,2′-bis (2-oxazoline).
Examples of the molecular chain extender having an oxazine group include 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-bis (4-methyl-5,6-dihydro-). 4H-1,3-oxazine), 2,2′-bis (4-ethyl-5,6-dihydro-4H-1,3-oxazine), 2,2′-bis (4,4-dimethyl-5, 6-dihydro-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-ethylenebis (5,6-dihydro-4H-1) , 3-oxazine), 2,2′-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-butylenebis (5,6-dihydro-4H-1,3-oxazine) 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxadi ), N, N′-ethylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), N, N′-propylenebis (2-carbamoyl-5,6-dihydro-4H-1) , 3-oxazine), N, N′-butylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), N, N′-hexamethylenebis (2-carbamoyl-5,6-dihydro) -4H-1,3-oxazine), N, N'-octamethylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), N, N'-decamethylenebis ((2- Carbamoyl-5,6-dihydro-4H-1,3-oxazine), N, N′-phenylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), N, N′-ethylene Bis (2-carba Moyl-4-methyl-5,6-dihydro-4H-1,3-oxazine), N, N′-ethylenebis (2-carbamoyl-4,4-dimethyl-5,6-dihydro-4H-1,3 -Oxazine), N, N'-dimethyl-N, N'-ethylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), N, N'-dimethyl-N, N'- Butylenebis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), 2,2′-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2 ′ Bisoxazine compounds such as -p-phenylenebis (5,6-dihydro-4H-1,3-oxazine) and 2,2'-naphthylenebis (5,6-dihydro-4H-1,3-oxazine) It is done.

  Of these, 2,2'-bis (5,6-dihydro-4H-1,3-oxazine) is particularly preferred.

Examples of the molecular chain extender having a carbodiimide group include p-phenylenebisdicyclohexylcarbodiimide, p-phenylenebis-o-tolylcarbodiimide, p-phenylenebis (di-p-chlorophenylcarbodiimide), hexamethylenebis (dicyclohexylcarbodiimide), Dicarbomide compounds such as ethylenebis (dicyclohexylcarbodiimide), ethylenebis (diphenylcarbodiimide), poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly ( Tolylcarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (naphthylenecarbodiimide), poly (1,6-hexamethylenecarbodi) Imide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (1,3-diisopropylphenylenecarbodiimide) , Poly (1-methyl-3,5-diisopropylphenylenecarbodiimide), poly (1,3,5-triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), and the like.
Among these, poly (4,4′-diphenylmethanecarbodiimide), poly (tolylcarbodiimide), poly (p-phenylenecarbodiimide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (triisopropylphenylenecarbodiimide) Is preferably used.
These molecular chain extenders may be used alone or in combination of two or more.

  Content of the molecular chain extender used by this invention is 0.1-10 weight part with respect to 100 weight part of thermoplastic resins, Preferably it is 1-8 weight part, More preferably, it is 2-5. Parts by weight. When the content is less than 0.1 parts by weight, the bending strength may not be sufficiently improved. When the content is more than 10 parts by weight, the thermal conductivity may decrease due to the decrease in crystallinity accompanying the increase in molecular weight.

  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 further 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 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 used in the present invention has excellent thermal conductivity, it is possible to easily obtain a highly thermally conductive 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. 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 of the present invention has excellent thermal conductivity, the resin composition can be used even when the amount of the inorganic filler used is as small as 90:10 to 70:30 in the volume ratio of the thermoplastic resin to the inorganic filler. Has excellent thermal conductivity, and at the same time, the density can be lowered due to the small amount of inorganic filler used. 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.

  A wide variety of known fillers can be used as the inorganic filler. The thermal conductivity of the inorganic filler alone is preferably 1 W / (m · K) or more, more preferably 10 W / (m · K) or more, further preferably 20 W / (m · K) or more, particularly preferably 30 W / The thing more than (m * K) 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 resin composition is used for applications that do not require electrical insulation, a metal compound, a conductive carbon compound, or the like 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 suitably used.

When the resin composition is used for applications requiring electrical insulation, a compound showing electrical insulation is suitably used as the inorganic filler. 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 one having a thickness 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 inorganic fillers, specific examples of compounds that exhibit electrical insulation include metal oxides such as aluminum oxide, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide, boron nitride, aluminum nitride, and nitride. Examples thereof include metal nitrides such as silicon, 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 of the inorganic filler can be applied. 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 the thermoplastic resin composition of the present invention, known fillers can be widely used in addition to the inorganic fillers according to the purpose. Since the thermal conductivity of the single resin is high, the resin composition has a high thermal conductivity even if the thermal conductivity of the known filler is relatively low as 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, molybdenum disulfide, Examples thereof include 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 favorable characteristics in applying a resin composition such as thermal conductivity, mechanical strength, or abrasion resistance. Furthermore, if necessary, organic fillers such as paper, pulp, wood, polyamide fiber, aramid fiber, boron fiber and other synthetic fibers, polyolefin powder and the like 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 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. The amount of these resins used is in the range of 0 to 10,000 parts by weight with respect to 100 parts by weight of the thermoplastic resin of the present invention usually contained in the resin composition.

  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.

It does not specifically limit as a manufacturing method of 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. In particular, it has excellent properties such as excellent moldability and high thermal conductivity, so it is 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, 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 casings, 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 and the like.

  The thermoplastic resin composition of the present invention can be made higher in thermal conductivity than resin and resin compositions well known in the art, and has good molding processability. It has characteristics useful for a housing.

Next, although the manufacture example, an Example, and a comparative example are given and demonstrated further in detail about the thermoplastic resin composition of this invention, this invention is not restrict | limited only to this Example. Unless otherwise specified, the reagents listed below were used without purification from Wako Pure Chemical Industries.
The molecular chain extender used is shown below.
Molecular chain extender (B-1): 3,3 ′, 5,5′-tetramethyl-4,4′-bis (glycidyloxy) -1, 1′-biphenyl (YX4000H manufactured by Mitsubishi Chemical Corporation)
Molecular chain extender (B-2): 2,2′-bis (2-oxazoline) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Molecular chain extender (B-3): 2,2′-bis (5,6-dihydro-4H-1,3-oxazine)
Molecular chain extender (B-4): poly (4,4′-methylenebiscyclohexylcarbodiimide) (Carbodilite LA-1 manufactured by Nisshinbo Co., Ltd.)
[Evaluation method]
Number average molecular weight: A sample was prepared by dissolving the thermoplastic resin used in the present invention in a mixed solvent of p-chlorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene in a volume ratio of 3: 8 to a concentration of 2.5 wt%. . The standard material was polystyrene, and a similar sample solution was prepared. The measurement was performed using a high temperature GPC (350 HT-GPC System manufactured by Viscotek) under conditions of a column temperature of 80 ° C. and a flow rate of 1.00 mL / min. A differential refractometer (RI) was used as a detector.

Test piece molding: The obtained pellet-shaped resin composition was dried at 120 ° C. for 4 hours using a hot air dryer, and then a disk-shaped sample having a thickness of 1 mm × 25 mmφ and 127 mm × 12.7 mm using an injection molding machine. X A test piece having a thickness of 3.2 mm was molded. At this time, the cylinder temperature was set to 220 to 240 ° C. and the mold temperature was set to 120 to 150 ° C., and injection was performed in a liquid crystal state.
Thermal conductivity: Using a disk-shaped sample having a thickness of 1 mm × 25 mmφ, the thermal conductivity in the in-plane direction in the room temperature atmosphere was measured with a laser flash method thermal conductivity measuring device (LFA447 manufactured by NETZSCH).

Bending strength: The bending strength was measured according to ASTM D790 with a test piece of 127 mm × 12.7 mm × thickness of 3.2 mm. Quantification of terminal carboxyl groups: Using 1H-NMR (400 MHz, deuterated chloroform: trifluoroacetic acid = 2: 1 measured in a Vol specific solvent), the ratio of carboxyl group terminals is measured from the integral value of the characteristic signal of each terminal group. did. Table 1 shows chemical shift values of typical signals used for the measurement.
Percentage of lamella crystals: Cut out sections for observation from injection-molded samples with a thickness of 6 mm × 20 mmφ, stained with RuO ₄ , and then converted 0.1 μm-thick ultrathin sections prepared with a microtome into TEM at an acceleration voltage of 100 kV. And observed. From the 40,000-fold scale photograph obtained by this TEM observation, the ratio of the lamellar crystal region was calculated as the ratio of the lamellar crystal region to the entire area of the photo.

[Production Example 1]
In a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring rod, 4,4′-dihydroxybiphenyl, dodecanedioic acid, and acetic anhydride were each in a molar ratio of 1.0: 1.1: 2. .1 was charged, and sodium acetate was used as a catalyst to react at 145 ° C. under normal pressure and nitrogen atmosphere to obtain a uniform solution, and then the temperature was raised to 250 ° C. at 2 ° C./min while acetic acid was distilled off. And stirred at 250 ° C. for 1 hour. Subsequently, while maintaining the temperature, the pressure was reduced to 10 Torr over about 40 minutes, and then the reduced pressure state was maintained. Three hours after the start of pressure reduction, the pressure was returned to normal pressure with nitrogen gas, and the produced polymer was taken out. The number average molecular weight of the obtained resin was 9100, the thermal conductivity of the resin alone was 0.9 W / (m · K), the terminal carboxyl group was 99% or more, and the ratio of lamellar crystals was 80 Vol%. Let the obtained resin be (A-1).

[Production Example 2]
In a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stir bar, 4,4′-dihydroxybiphenyl, sebacic acid, catechol, and acetic anhydride were each in a molar ratio of 0.9: 1.1: The mixture was charged at a ratio of 0.1: 2.1, and sodium acetate was used as a catalyst to react at 145 ° C. under atmospheric pressure and nitrogen atmosphere to obtain a uniform solution. Then, while acetic acid was distilled off at 2 ° C./min. The temperature was raised to 240 ° C., and the mixture was stirred at 240 ° C. for 30 minutes. Furthermore, it heated up to 260 degreeC at 1 degreeC / min, and stirred at 260 degreeC for 1 hour. Subsequently, while maintaining the temperature, the pressure was reduced to 10 Torr over about 40 minutes, and then the reduced pressure state was maintained. Three hours after the start of pressure reduction, the pressure was returned to normal pressure with nitrogen gas, and the produced polymer was taken out. The number average molecular weight of the obtained resin was 7700, the thermal conductivity of the resin alone was 0.9 W / (m · K), the terminal carboxyl group was 99% or more, and the ratio of lamellar crystals was 70 Vol%. Let the obtained resin be (A-2).

[Production Example 3]
In a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirring rod, 4,4′-dihydroxybiphenyl, dodecanedioic acid, and acetic anhydride were each in a molar ratio of 1.0: 1.04: 2. .05 was added, and 1-methylimidazole was used as a catalyst to react at 145 ° C. under normal pressure and nitrogen atmosphere to obtain a uniform solution, and then acetic acid was distilled off to 260 ° C. at 1 ° C./min. The temperature was raised, and the mixture was stirred at 260 ° C. for 2 hours. Subsequently, while maintaining the temperature, the pressure was reduced to 30 Torr over about 20 minutes, and then the reduced pressure state was maintained. Two hours after the start of decompression, the pressure was returned to normal pressure with nitrogen gas, and the produced polymer was taken out. The number average molecular weight of the obtained resin was 7100, the thermal conductivity of the resin alone was 1.1 W / (m · K), and the terminal carboxyl group was 66%. Let the obtained resin be (A-3).

[Example 1]
The resin (A-1) obtained in Production Example 1 was dried at 120 ° C. for 4 hours using a hot air dryer, and boron nitride powder (PT110 manufactured by Momentive Performance Materials Co., Ltd. as a single substance) was used as the inorganic filler. Thermal conductivity 60 W / (m · K), 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.) 1.0 W / (m · K), fiber diameter 13 μm, number average fiber length 3.0 mm, electrical insulation, volume resistivity 10 ¹⁵ Ω · cm), resin (A-1), boron nitride powder, glass fiber The mixture was prepared so that the volume ratio was 50:30:20. To this, 2 parts by weight of the molecular chain extender (B-1) with respect to 100 parts by weight of the resin, a phenol-based stabilizer (AO-60 manufactured by ADEKA Corporation) and a phosphorus-based antioxidant (Adeka Stab PEP manufactured by ADEKA Corporation) -36) was added in an amount of 0.2 parts by weight per 100 parts by weight of the resin.

  This mixture is melt-kneaded with a 15 mm co-rotating fully meshed twin screw extruder KZW15-45MG manufactured by Technobel Co., Ltd. as shown in Table 2, and is discharged from the die head portion. Was cooled with water to obtain a resin composition. The discharge amount was set to 20 g / min, and the screw rotation speed was set to 150 rpm. The thermoplastic resin in the twin screw extruder sequentially flows from C1 to C6 and is discharged from the die head portion. The obtained resin composition was molded using an injection molding machine, and the thermal conductivity and bending strength in the in-plane direction were measured. Table 3 shows values of thermal conductivity and bending strength in the in-plane direction.

[Examples 2-7, Comparative Examples 1-3]
A resin composition was obtained in the same manner as in Example 1 except that the amounts of the resin, the molecular chain extender, and the molecular chain extender were changed as shown in Table 3. The obtained resin composition was molded using an injection molding machine, and the thermal conductivity and bending strength in the in-plane direction were measured. Table 3 shows values of thermal conductivity and bending strength in the in-plane direction.

  From Table 3, it can be seen that Comparative Examples 1 to 3 have high thermal conductivity but insufficient bending strength, while Examples 1 to 7 achieve both high thermal conductivity and high bending strength.

  The thermoplastic resin composition of the present invention exhibits excellent thermal conductivity and high bending strength. Such a thermoplastic resin composition can be used as a resin material for heat dissipation and heat transfer in various situations such as in the electric / electronic industry and automobile fields, and is industrially useful.

Claims (15)

The structure of the main chain is general formula (1)

(Wherein X represents a divalent substituent selected from the group of O and CO)
Unit (A) having a biphenyl group represented by 25 to 60 mol%,
General formula (2)
-YR-Y- (2)
(In the formula, R represents a divalent linear substituent which may contain a branch having 2 to 20 main chain atoms. Y represents a divalent substituent selected from the group of O and CO.)
Unit (B) represented by 25 to 60 mol%,
General formula (3)
-Z ¹ -MZ ^2- (3)
(In the formula, Z ¹ and Z ² represent a divalent substituent selected from the group of O, NH, CO, S and NHCO. M represents an aromatic group having a main chain folding effect, a condensed aromatic group, A substituent selected from a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group is shown.)
Unit (C) represented by 0 to 25 mol% (however, the total of units (A), (B), and (C) is 100 mol%), and at least 60 mol% of the end of the molecular chain is carboxyl. A thermoplastic resin (i) having a thermal conductivity of 0.4 W / (m · K) or more, which is a resin base,
A molecular chain extender (ii) having two or more reactive functional groups in one molecule , and
Containing an inorganic filler (iii),
The thermoplastic resin composition, wherein the content of the molecular chain extender is 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The structure of the main chain is general formula (1)

(Wherein X represents a divalent substituent selected from the group of O and CO)
Unit (A) having a biphenyl group represented by 25 to 60 mol%,
General formula (2)
-YR-Y- (2)
(In the formula, R represents a divalent linear substituent which may contain a branch having 2 to 20 main chain atoms. Y represents a divalent substituent selected from the group of O and CO.)
Unit (B) represented by 25 to 60 mol%,
General formula (3)
-Z ¹ -MZ ^2- (3)
(In the formula, Z ¹ and Z ² represent a divalent substituent selected from the group of O, NH, CO, S and NHCO. M represents an aromatic group having a main chain folding effect, a condensed aromatic group, A substituent selected from a heterocyclic group, an alicyclic group, and an alicyclic heterocyclic group is shown.)
Unit (C) represented by 0 to 25 mol% (however, unit (C) exceeds 0 mol%, and the total of units (A), (B) and (C) is 100 mol%), Thermoplastic resin (i) in which 60 mol% or more of molecular chain terminals are carboxyl groups, and the thermal conductivity of the resin itself is 0.4 W / (m · K) or more,
A molecular chain extender (ii) having two or more reactive functional groups in one molecule , and
Containing an inorganic filler (iii),
The thermoplastic resin composition, wherein the content of the molecular chain extender is 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin.   The thermoplastic resin composition according to claim 1 or 2, wherein X in the general formula (1) is O and Y in the general formula (2) is CO.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein a portion corresponding to R of the thermoplastic resin is a linear aliphatic hydrocarbon chain.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein the number of main chain atoms in a portion corresponding to R of the thermoplastic resin is an even number. 6. The thermoplastic resin according to claim 1, wherein R of the thermoplastic resin is at least one selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ —. The thermoplastic resin composition as described. The thermoplastic resin composition according to any one of claims 1 to 6, wherein M of the thermoplastic resin is any one of the structures shown below.

  The thermoplastic resin composition as described in any one of Claims 1-7 whose number average molecular weights of the said thermoplastic resin are 3000-40000. The thermoplastic resin composition according to any one of claims 1 to 8, wherein a ratio of lamellar crystals in the thermoplastic resin is 10 Vol% or more. The thermoplastic resin composition according to any one of claims 1 to 9 , wherein the reactive functional group of the molecular chain extender is at least one selected from an epoxy group, an oxazoline group, an oxazine group, and a carbodiimide group. object. 11. The thermoplastic resin composition according to claim 1 , wherein the inorganic filler is an inorganic compound having a thermal conductivity of 1 W / (m · K) or more as a simple substance. . The inorganic filler is at least one electrically insulating high heat 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. It is a conductive inorganic compound, The thermoplastic resin composition as described in any one of Claims 1-11 characterized by the above-mentioned. The inorganic filler is 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. The thermoplastic resin composition according to any one of claims 1 to 12 . A resin material for heat dissipation and heat transfer, comprising the thermoplastic resin composition according to any one of claims 1 to 13 . The molded object containing the thermoplastic resin composition as described in any one of Claims 1-14 .