JP2015183033A - High-thermal-conductivity resin composition and resin material for heat release/heat transfer and heat conductive film containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in heat conductivity and light and is improved in brittleness and a resin material for heat release/heat transfer and a heat conductive film containing it.SOLUTION: A resin composition comprises 70 vol.% or more of a resin which consists of 40-60 mol% of units (A) having a biphenyl group, 5-40 mol% of linear units (B) and 0-40 mol% of linear units (C) and has a number average molecular weight of 10,000 or higher and less than 30 vol.%, relative to the total amount of the resin composition, of an inorganic filler having a thermal conductivity of 1 W/(m K) or higher and an average particle size of 10 μm or smaller. A resin material for heat release/heat transfer and a heat conductive film containing the resin composition are also provided.

Description

The present invention relates to a resin composition having excellent thermal conductivity, light weight and improved brittleness, and a heat radiation / heat transfer resin material and a heat conductive film containing the resin composition.

  When resin compositions are used in various applications such as personal computers and display housings, electronic device materials, and interior and exterior of automobiles, plastics have low thermal conductivity compared to inorganic materials such as metal materials, so the generated heat is released. Difficult things 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 into the 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, when a large amount of inorganic material is blended, the specific gravity increases, resulting in disadvantages such as being hard and brittle. Therefore, improvement in the thermal conductivity of the resin alone has been demanded.

  As a thermosetting resin excellent in the thermal conductivity of a single resin, for example, an epoxy resin described in Patent Document 1 has been reported. The resin has a certain degree of thermal conductivity, but has a complicated molecular structure and is difficult to produce. 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, the thermal liquid crystal polyester described in Patent Document 3 is aligned by at least one external field selected from a flow field, a shear field, a magnetic field, and an electric field, so that the thermal liquid crystal polyester is heated in the alignment direction of the thermal liquid crystal polyester. There is a resin molded body with high conductivity. The resin molded body has high thermal conductivity in the uniaxial direction but low thermal conductivity in the other biaxial directions. In order to obtain a desired thermal conductivity, a magnetic flux density of at least 3 Tesla or more is required in the case of a magnetic field. Is difficult to manufacture.

  As a thermoplastic resin excellent in thermal conductivity of a single resin, Patent Documents 4 to 6 and Non-Patent Document 1 describe alternating polycondensates of mesogenic groups and bent chains. In particular, Non-Patent Document 1 describes that the resin functions isotropically as a 1 W / (m · K) matrix by blending 30 vol% or more of magnesium oxide having an average particle size of 50 μm with the resin. However, since it does not function as such at a blending amount of less than 30 vol%, a further increase in thermal conductivity has been demanded with a blending amount of less than 30 vol% that can improve the reduction in specific gravity and brittleness of the resin composition.

International Publication Number WO2002 / 094905 International Publication Number WO2006 / 120993 JP 2008-150525 A International Publication Number WO2010 / 050202 International Publication Number WO2011 / 132389 International Publication Number WO2011 / 132390

Journal of Applied Polymer Science, vol 131, P39896 (2014)

  An object of the present invention is to provide a resin composition having excellent thermal conductivity, light weight and improved brittleness, a heat radiation / heat transfer resin material containing the resin composition, and a heat conductive film.

As a result of intensive studies, the present inventors have determined that a resin having a specific structure and molecular weight has an inorganic filler having a thermal conductivity of 1 W / (m · K) or more and an average particle size of 10 μm or less as a resin composition. The present inventors have found that a resin composition contained in an amount of less than 30 vol% with respect to the whole product has a low specific gravity and high thermal conductivity, and can further improve brittleness. That is, the present invention includes the following 1) to 10).
1) The structure of the main chain is general formula (1)

40 to 60 mol% of a unit (A) having a biphenyl group represented by
General formula (2)
—CO—R ₁ —CO— (2)
(In the formula, R ₁ represents a divalent linear substituent which may contain a branch having 2 to 18 main chain atoms.)
5 to 50 mol% of the unit (B) represented by
General formula (3)
_-CO-R 2 -CO- (3)
(In the formula, R ₂ may include a branch having 4 to 20 main chain atoms, and represents a divalent linear substituent having a larger number of main chain atoms than R _1. )
The unit (C) is represented by 0 to 45 mol% (however, the total of the units (A), (B), and (C) is 100 mol%), and the number average molecular weight is 10,000 or more. And a resin comprising an inorganic filler having a thermal conductivity of 1 W / (m · K) or more and an average particle size of 10 μm or less in an amount of less than 30 vol% with respect to the entire resin composition Composition.
2) The resin composition according to ₁ ), wherein the portions corresponding to R ₁ and R ₂ of the resin are linear saturated aliphatic hydrocarbon chains.
3) The resin composition according to any one of 1) and 2), wherein the number of main chain atoms in the portion corresponding to R ₁ and R ₂ of the resin is an even number.
4) The resin composition according to any one of 1) to 3), wherein the number of main chain atoms m and n corresponding to R ₁ and R ₂ of the resin satisfies the following general formula (4).
nm−4 (4)

5) The resin composition according to any one of 1) to 4), wherein a content of the resin with respect to the resin composition is 50 vol% or more. 6) The inorganic filler is at least one electrically insulating high thermal conductive inorganic compound selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, aluminum hydroxide, and magnesium hydroxide. The resin composition according to any one of 1) to 5).
7) The inorganic filler is at least one conductive highly thermally conductive inorganic compound selected from the group consisting of graphite, carbon nanotubes, conductive metal powder, soft magnetic ferrite, carbon fiber, conductive metal fiber, and zinc oxide. The resin composition according to any one of 1) to 5), wherein:

8) The resin composition according to 6) or 7), wherein the inorganic filler has an aspect ratio of 5 or less.
9) A heat dissipation / heat transfer resin material containing the resin composition according to any one of 1) to 8).
10) A heat conductive film containing the resin composition according to any one of 1) to 8).

  According to the present invention, the resin composition has excellent thermal conductivity, and can achieve a lower specific gravity and improved brittleness.

Photo showing anisotropic domains of micron order with molecular chains oriented Angle of plate sample for evaluation of brittleness

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

40 to 60 mol% of a unit (A) having a biphenyl group represented by
General formula (2)
—CO—R ₁ —CO— (2)
(In the formula, R ₁ represents a divalent linear substituent which may contain a branch having 2 to 18 main chain atoms.)
5 to 50 mol% of the unit (B) represented by
General formula (3)
_-CO-R 2 -CO- (3)
(In the formula, R ₂ may include a branch having 4 to 20 main chain atoms, and represents a divalent linear substituent having a larger number of main chain atoms than R _1. )
The unit (C) is represented by 0 to 45 mol% (however, the total of the units (A), (B) and (C) is 100 mol%), and the number average molecular weight is 10,000 or more. The resin comprising the characteristic resin and an inorganic filler having a thermal conductivity of 1 W / (m · K) or more and an average particle size of 10 μm or less is contained in an amount of less than 30 vol% with respect to the entire resin composition. It is characterized by that.

  The molar ratio (B) / (C) of units (B) and (C) for copolymerization of the resin of the present invention is preferably 8/1 to 1/8, more preferably 6/1 to 1/4. More preferably, it is 4/1 to 1/2, and most preferably 3/1 to 1/1. When the molar ratio is largely biased to one unit of 8/1 or 1/8, the crystallinity of the resin increases, which makes it brittle, and it may be difficult to ensure flexibility during thin-wall molding. Moreover, it is preferable to make the copolymerization ratio of the unit (B) having a small number of main chain atoms larger than that of the unit (C) because the transition temperature to the isotropic phase of the resin becomes high and the heat resistance of the resin can be increased.

  Furthermore, in the resin of the present invention, the molar ratio of units (A), (B) and (C), that is, unit (A): unit (B): unit (C) in the molar ratio is usually 40-60: Although it is 5-50: 0-45, Preferably it is 45-55: 20-45: 5-30, More preferably, it is 48-52: 25-40: 10-25. It is preferable that (A) :( B) + (C) is closer to 50:50 because the molecular weight is easily improved during polymerization.

The resin of the present invention preferably exhibits a smectic liquid crystal phase when heated. The resin showing a liquid crystal phase is a general term for those showing a liquid crystal phase from a certain temperature when the resin is heated. Typical types of liquid crystal are nematic liquid crystal and smectic liquid crystal. In the nematic liquid crystal, the constituent molecules have an orientation order, but do not have a three-dimensional positional order. On the other hand, the smectic liquid crystal has a layer structure in which molecules are arranged in parallel with the molecular axis, and the center of gravity of the portions connected in parallel is on the same plane. It is known that smectic liquid crystals exhibit a peculiar pattern such as a short-toned structure, a mosaic structure, a fan-shaped structure or the like in a microscopic observation under orthogonal polarization. As the thermophysical properties of smectic liquid crystal molecules or resins, generally, in the temperature rising process, the transition point from the solid phase to the smectic liquid crystal phase (hereinafter T _S ) and the transition point from the smectic liquid crystal phase to the isotropic phase (hereinafter T _i). ). Depending materials also indicate transition to a nematic liquid crystal phase (hereinafter T _N) from the smectic liquid crystal phase at a lower than T _i temperature. These phase transition points can be confirmed as the peak top of the endothermic peak in the temperature rising process of differential scanning calorimetry (DSC) measurement.

  The magnitude relationship between the liquid crystallinity of the resin can be judged by the phase transition enthalpy (ΔH) of the endothermic peak from the liquid crystal phase to the isotropic phase in the temperature rising process of DSC measurement. The greater the ΔH, the higher the liquid crystallinity. The resin of the present invention tends to have a high degree of liquid crystallinity, and can form anisotropic domains of micron order with molecular chains oriented as shown in FIG. The following can be considered as factors that cause the resin composition of the present invention to have isotropic high thermal conductivity even in a region where the blending amount of the inorganic filler is small. When the average particle diameter of the inorganic filler is larger than 10 μm, when the amount of the inorganic filler is small, the interparticle distance becomes long, and a plurality of domains formed by the resin exist between the particles. At this time, since each anisotropic domain faces a random direction, the efficiency of the heat conduction path between the particles becomes poor. On the other hand, when the average particle diameter of the inorganic filler, which is a feature of the present invention, is 10 μm or less, the interparticle distance is inevitably shortened even if the blending amount of the inorganic filler is small. Therefore, the anisotropic domain of micron order formed by the resin is accommodated between the inorganic filler particles, and can function as a good heat conduction path between the particles. Therefore, in the region where the blending amount of the inorganic filler is less than 30 vol%, it is considered that the thermal conductivity of the resin composition is higher when the particle size is 10 μm or less than when the large particle size is used.

  The number average molecular weight of the resin in the present invention is prepared by dissolving polystyrene in a mixed solvent of p-chlorophenol and toluene in a volume ratio of 3: 8 so that the concentration is 0.25% by weight with polystyrene as a standard. It is the value measured at 80 ° C. by GPC using the solution. The number average molecular weight of the resin in the present invention is preferably 10,000 or more, more preferably 15,000 or more, and further preferably 20,000 or more. When the number average molecular weight is less than 10,000, the mechanical properties of the molded article are lowered. The upper limit of the number average molecular weight is not particularly limited because it varies depending on the intended use of the resin composition, but if it is greater than 100,000, the moldability may be lowered.

  The resin composition of the present invention contains an inorganic filler having a thermal conductivity of 1 W / (m · K) or more and an average particle size of 10 μm or less of less than 30 vol%. The average particle diameter of the inorganic filler is 10 μm or less from the viewpoint of high thermal conductivity, preferably 8 μm or less, more preferably 6 μm or less, and further preferably 4 μm from the viewpoint of moldability into a film. Or less, most preferably 3 μm or less. The amount of the inorganic filler used is preferably 25 vol% or less, more preferably 20 vol% or less, still more preferably 15 vol% or less, and most preferably 10 vol% or less. If it is 30 vol% or more, it becomes hard and brittle. While the resin composition of the present invention is excellent in thermal conductivity, the specific gravity of the composition can be lowered because the amount of the inorganic filler used is small. Further, when an insulating inorganic filler is used, the insulation reliability is excellent. Having the characteristics as described above is advantageous when used as a heat dissipation / heat transfer resin material and a heat conduction film in various situations such as in the electric / electronic industry field and the automobile field.

  Although the terminal structure of the resin of the present invention is not particularly limited, it is a curable resin having solder reflow resistance in order to enhance compatibility with other resins or using a compound having other polyfunctional reactive groups as a curing agent. For this purpose, the terminal of the resin can be a carboxyl group. In this case, the ratio of the carboxyl group with respect to all terminals of the molecular chain is 60 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and most preferably 90 mol% or more. On the other hand, in order to increase the hydrolysis resistance and long-term heat resistance of the resin, and to prevent adverse effects such as deterioration of other resins when other resins are mixed, the ends are sealed with monofunctional low molecular weight compounds. Can be stopped. At this time, the sealing ratio with respect to all ends of the molecular chain is 60% or more, preferably 70% or more, more preferably 80% or more, and most preferably 90% or more.

The terminal blocking rate of the resin can be determined by the following formula (5) by measuring the number of terminal functional groups sealed and unblocked in the resin. The number of each terminal group is preferably determined from the integral value of the characteristic signal corresponding to each terminal group by ¹ H-NMR in terms of accuracy and simplicity. Terminal sealing rate (%) = [number of sealed terminal functional groups] / ([number of sealed terminal functional groups] + [number of unsealed terminal functional groups]). . . (5)

  The terminal blocking agent is preferably a monoamine having 1 to 20 carbon atoms or an aliphatic monocarboxylic acid, more preferably an aliphatic monocarboxylic acid having 1 to 20 carbon atoms, from the viewpoint of increasing the thermal conductivity of the resin. 10-20 aliphatic monocarboxylic acids are more preferred. Specific examples of aliphatic monocarboxylic acids include fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Group monocarboxylic acids, and any mixtures thereof. Among these, myristic acid, palmitic acid, and stearic acid are preferable from the viewpoint of particularly improving the thermal conductivity of the resin. Specific examples of monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and any of these A mixture etc. can be mentioned. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, and cyclohexylamine are preferable from the viewpoints of reactivity, high boiling point, stability of the capped end, and price. The thermal conductivity of the resin simple substance of the present invention is preferably 0.4 W / (m · K) or more, more preferably 0.5 W / (m · K) or more as a physical property value of the isotropic molded body. Yes, particularly preferably 0.7 W / (m · K) or more, and most preferably 0.8 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.

  The thermal conductivity of the single resin here is a value obtained by directly measuring the single resin with a thermal conductivity measuring device. Alternatively, the thermal conductivity of a resin composition containing an inorganic filler having an isotropic property shown in the present invention is directly measured, and the value obtained by calculating the thermal conductivity of the resin matrix from the following Bruggeman's theoretical formula It is good also as thermal conductivity of.

1−V = {(λ _c −λ _f ) / (λ _m −λ _f )} × (λ _m / λ _c ) ^1/3 (6)
Where V is the volume content of the inorganic filler (0 ≦ V ≦ 1), λ _c is the thermal conductivity of the resin composition, λ _f is the thermal conductivity of the inorganic filler, and λ _m is the thermal conductivity of the resin alone. It is. Therefore, if V, λ _c , and λ _f are known, λ _m can be calculated.

As a method for measuring whether or not the thermal conductivity is isotropic, for example, a resin and a resin composition are molded into a plate shape having a thickness of 1 mm, and a laser flash method thermal conductivity measuring apparatus (LFA447 manufactured by NETZSCH) is used. A method of separately measuring the thermal conductivity in the thickness direction and the plane direction in the air at room temperature can be considered. If these thermal conductivities are approximately equal, the compact is isotropic.
General formula (2)
—CO—R ₁ —CO— (2)
R ₁ therein represents a divalent linear substituent which may include a branch having 2 to 18 main chain atoms. Here, the number of main chain atoms is the number of atoms in the main chain skeleton. For example, when —R ₁ — is — (CH ₂ ) ₈ —, the number of main chain atoms is 8 as the number of carbon atoms. Since the thermal conductivity is high, it is preferably a straight-chain substituent that does not contain a branch, and more preferably a straight-chain aliphatic hydrocarbon chain that does not contain a branch. R ₁ 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 ₁ is preferably a straight-chain saturated aliphatic hydrocarbon chain having 2 to 18 carbon atoms, more preferably a straight-chain saturated aliphatic hydrocarbon chain having 4 to 16 carbon atoms, particularly 8 carbon atoms. It is preferably a -14 linear saturated aliphatic hydrocarbon chain. The number of main chain atoms of R ₁ is preferably an even number. In the case of an odd number, the microscopic molecular orientation may be lowered, and the thermal conductivity may be lowered. In particular, R ₁ is _one selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ — from the viewpoint that a resin having excellent heat resistance and thermal conductivity can be obtained. It is preferable.
General formula (3)
_-CO-R 2 -CO- (3)
R ₂ therein may contain a branch having 4 to 20 main chain atoms, and represents a divalent linear substituent having a larger number of main chain atoms than R ₁ , and has a high thermal conductivity. It is preferably a linear substituent not containing a branch, and more preferably a linear aliphatic hydrocarbon chain not containing a branch. R ₂ 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 ₂ is preferably a linear saturated aliphatic hydrocarbon chain having 4 to 20 carbon atoms, more preferably a linear saturated aliphatic hydrocarbon chain having 8 to 18 carbon atoms, particularly 10 carbon atoms. It is preferably a -18 linear saturated aliphatic hydrocarbon chain. The number of main chain atoms of R ₁ is preferably an even number. In the case of an odd number, the microscopic molecular orientation may be lowered, and the thermal conductivity may be lowered. The greater the difference in the number of main chain atoms between R ₁ and R _2, the lower the crystallinity, increasing the processability of thin wall molding and the flexibility of the molded body. In particular, from the viewpoint of obtaining a resin having low crystallinity and excellent flexibility, it is preferable that the number of main chain atoms m and n corresponding to R ₁ and R ₂ satisfy the following general formula (4).
nm−4 (4)
Specific examples of R ₂ satisfying the general formula (4) are selected from — (CH ₂ ) ₁₀ —, — (CH ₂ ) ₁₂ —, and — (CH ₂ ) ₁₈ — from the viewpoint of chemical stability and availability. It is preferable that it is 1 type.

  Moreover, since heat conductivity becomes high, it is preferable that content with respect to the resin composition of the said resin is 50 vol% or more, It is more preferable that it is 60 vol% or more, It is further more preferable that it is 70 vol% or more. On the other hand, if the resin of the present invention is contained in the above range, the resin composition has an epoxy resin, a polyolefin resin, a bismaleimide resin, a polyimide resin, and a polyether as long as the effects of the present invention are not lost. Any known resin such as resin, polyphenylene sulfide resin, phenol resin, silicone resin, polycarbonate resin, polyamide resin, polyester resin, fluorine resin, acrylic resin, melamine resin, urea resin, urethane resin may be contained. Specific examples of preferable resins include epoxy resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, liquid crystal polymer, polyphenylene sulfide, nylon 6, nylon 6,6 and the like. In addition, the resin composition of the present invention may contain an epoxy compound, an acid anhydride compound, and an amine compound for the purpose of increasing the adhesive strength with a metal. 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 diol, aliphatic diamine, Examples include alicyclic dicarboxylic acids, and 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, pyrocatechol, 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, etc., and alkyl, alkoxy or halogen substituted products thereof Is mentioned.

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

  Specific examples of the aromatic diamine and aromatic aminocarboxylic acid include 1,4-phenylenediamine, 1,3-phenylenediamine, N-methyl-1,4-phenylenediamine, 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 resin according to the present invention may be produced by any known method. From the viewpoint of easy control of the structure, 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 substituents R ₁ and R ₂ are reacted. And a method of manufacturing the same is preferable. As such a reactive functional group, known groups such as a hydroxyl group, a carboxyl group, and an ester group can be used, and the conditions for reacting them are not particularly limited.

From the viewpoint of simple synthesis, for 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 substituents R ₁ and R ₂ , A combination of a compound having a hydroxyl group at both ends of the biphenyl group and a compound having a carboxyl group at both ends of the linear substituents R ₁ and R ₂ is preferable.

As an example of a method for producing a resin comprising a compound having a hydroxyl group at both ends of a biphenyl group and a compound having a carboxyl group at both ends of the linear substituents R ₁ and R ₂ , the hydroxyl group of the compound is converted to acetic anhydride or the like. A compound having a carboxyl group at both ends of the linear substituents R ₁ and R _{2 in} a separate reaction tank or the same reaction tank after individually or collectively making a lower fatty acid ester using a lower fatty acid And 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 substituents R ₁ and R ₂ volatilizes, and a resin having a desired composition or molecular weight may not be obtained. The ultimate vacuum is preferably 40 Torr or less, more preferably 30 Torr or less, further preferably 20 Torr or less, and particularly preferably 10 Torr or less. When the degree of vacuum is higher than 40 Torr, deoxidation does not proceed sufficiently, and the polymerization time may become longer. 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 resin may be used as it is, or unreacted raw materials can be removed, or solid phase polymerization can be performed in order to increase physical properties. In the case of performing solid phase polymerization, the obtained resin is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and in an inert gas atmosphere such as nitrogen at 100 to 350 ° C. in a solid state. It is preferable to process for 1 to 30 hours under or under reduced pressure. If the particle diameter of the resin particles is larger than 3 mm, the treatment is not sufficient and problems in physical properties occur, which is not preferable. It is preferable to select the treatment temperature and the temperature increase rate during solid-phase polymerization so that the resin particles do not cause fusion.

  Examples of the acid anhydride of the lower fatty acid used in the production of the 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, 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 1.01 to 1.5 times equivalent, preferably 1.02 to 1.2 times equivalent to the total of functional groups such as hydroxyl groups of the monomers used. When the amount is less than 1.01 equivalent, the lower fatty acid anhydride may volatilize, so that the functional group such as a hydroxyl group may not completely react with the lower fatty acid anhydride, and a low molecular weight resin can be obtained. There is. You may use a catalyst for manufacture of 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 wt%, based on the total weight of the resin. More preferably, 1 × 10 ⁻² to 10 × 10 ⁻² wt% is used.

  In this invention, it is preferable that the ratio of the lamellar structure in resin is 10 Vol% or more. The ratio of the lamella structure is preferably 30 Vol% or more, more preferably 50 Vol% or more, and particularly preferably 70 Vol% or more.

  The lamellar structure referred to in the present invention corresponds to a plate-like structure in which chain molecules are arranged in parallel. There exists a tendency for the heat conductivity of resin and a resin composition to become high, so that the ratio of a lamella structure is high. Whether or not a lamella structure exists in the resin can be easily determined by observation with a scanning electron microscope (SEM), observation with a transmission electron microscope (TEM), or X-ray diffraction.

The ratio of the lamella structure 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 the region of the lamellar structure can be determined from the obtained 40,000 times scale photograph (18 cm × 25 cm). The boundary of the region can be determined by setting the lamellar structure region as a region where periodic contrast exists. Since the lamella structure is similarly distributed in the depth direction, the ratio of the lamella structure can be calculated as the ratio of the lamella structure region to the entire area of the photograph.

  The thermal conductivity of the resin composition of the present invention is preferably 0.8 W / (m · K) or more, more preferably 1.0 W / (m · K) or more, and further preferably 1.5 W / (m. K) or more, particularly preferably 2.0 W / (m · K) or more, most preferably 2.5 W / (m · K) or more. When the thermal conductivity is less than 0.8 W / (m · K), it is difficult to efficiently transmit the heat generated from the electronic component to the outside. Since the resin used in the present invention has excellent thermal conductivity, it is possible to easily obtain a high thermal conductive resin composition having a thermal conductivity in the above range.

  Known inorganic fillers can be widely used as the inorganic filler. The thermal conductivity of the inorganic filler alone is 1 W / (m · K) or more, more preferably 10 W / (m · K) or more, further preferably 20 W / (m · K) or more, and particularly preferably 30 W / (M · K) or more, most preferably 50 W / (m · K) or more is used. The upper limit of the thermal conductivity of the inorganic filler alone is not particularly limited, and it is preferably as high as possible. Generally, it is 3000 W / (m · K) or less, more preferably 2500 W / (m · K) or less. Preferably used.

  Various shapes can be applied to the inorganic filler. 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.

  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, because of its excellent thermal conductivity, conductive carbon materials such as graphite, carbon nanotubes, and carbon fibers, conductive metal powders obtained by atomizing various metals, conductive metal fibers obtained by processing various metals into fibers, Inorganic fillers such as various ferrites such as soft magnetic ferrite 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 preferably 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 body obtained from the high thermal conductive 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, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. These can be used alone or in combination.

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

  In addition to the inorganic fillers described above, known fillers can be widely used in the resin composition of the present invention depending on 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, less than 1 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. Further, 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. In the resin composition of the present invention, as an additive other than other resins and fillers, any other component depending on the purpose, for example, a reinforcing agent, a thickener, a release agent, a coupling agent, a flame retardant Further, 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 100 parts by weight with respect to 100 parts by weight of the resin. In particular, the addition of a flame retardant is preferable because it imparts flame retardancy to the resin composition. The flame retardancy of the resin composition is equivalent to V-0 in the UL-94 standard, which can be a condition adopted in electric / electronic devices that handle large currents.

  As a usage-amount of a flame retardant, it is more preferable that it is 7-80 weight part with respect to 100 weight part of resin, It is more preferable that it is 10-60 weight part, It is further more preferable that it is 12-40 weight part. Various flame retardants are known, and examples thereof include, but are not limited to, those described in “Technology and Application of Polymer Flame Retardation” (P149-221) issued by CMC Chemical. It is not done. Among these flame retardants, phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants can be preferably used.

  Examples of phosphorus flame retardants include phosphate esters, halogen-containing phosphate esters, condensed phosphate esters, polyphosphates, and red phosphorus. These phosphorus flame retardants may be used alone or in combination of two or more. Specific examples of the halogen flame retardant include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, deca Brominated diphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, brominated crosslinked aromatic polymer, particularly brominated polystyrene and brominated polyphenylene ether are preferred. These halogen flame retardants may be used alone or in combination of two or more. In addition, the halogen element content of these halogen flame retardants is preferably 15 to 87%.

  Specific examples of the inorganic flame retardant include aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, tin oxide, zinc oxide, iron oxide, magnesium hydroxide, calcium hydroxide, zinc borate, Examples include kaolin clay and calcium carbonate. These inorganic compounds may be treated with a silane coupler, a titanium coupler, or the like, or may be used alone or in combination of two or more.

  It does not specifically limit as a manufacturing method of the 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. Further, after dissolving the resin in a solvent and stirring and mixing the inorganic filler in the solution, the solvent can be removed by drying. The resin composition of the present invention can be molded by various resin molding methods such as injection molding, extrusion molding, press molding and blow molding.

The resin composition of the present invention can also improve the thermal conductivity in the thickness direction by orienting the resin molecular chains in the thickness direction of the molded body by the shear flow field during molding. In order to orient the molecular chain in the thickness direction by the shear flow field, it is preferable to place the resin in a smectic liquid crystal state and place it in the shear flow field. In order to use the shear flow field, an injection molding method can be mentioned as a simple method. The injection molding is a molding method in which a mold is attached to an injection molding machine, a resin composition melt-plasticized by the molding machine is injected into the mold at a high speed, and the resin composition is cooled and solidified to be taken out. Specifically, the resin is heated to a smectic liquid crystal state and injected into a mold. Here, in order to highly orient the molecular chain, the mold temperature is preferably T _m −100 ° C. or higher, more preferably T _m −80 ° C. or higher, and T _m −50 ° C. or higher. More preferably. In order to orient the resin molecular chain in the thickness direction, the number average molecular weight of the resin is preferably 10,000 to 40,000, more preferably 12,000 to 30,000, and even more preferably 15,000 to 20,000.

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

  Furthermore, since the thin molded article which consists of the resin composition of this invention has a softness | flexibility, it is suitable for the use of a heat conductive film. Here, the heat conductive film can be called a heat conductive sheet or a heat conductive film depending on the film thickness. The thickness of the heat conductive film of the present invention is preferably 500 μm or less. When the film thickness is larger than 500 μm, the heat resistance of the heat conducting film increases, and the heat dissipation effect of the heating element may be insufficient. For the purpose of reducing the thermal resistance, the thickness of the heat conductive film is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. The lower limit of the film thickness is not particularly limited, but is usually 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more when there is a purpose such as ensuring the dielectric breakdown strength of the film.

  The heat conductive film of the present invention is preferably electrically insulating. The dielectric breakdown strength at that time is preferably 10 kV / mm or more, more preferably 15 kV / mm or more, and further preferably 20 kV / mm or more. Most preferably, it is 25 kV / mm or more. If it is less than 10 kV / mm, it may be impossible to use in an electric / electronic device that handles a large current.

  The insulating film of the present invention can be combined with other base materials. Examples of the base material include insulating base materials such as kraft paper, glass cloth, glass non-woven fabric, aramid paper, mica sheet, etc. Non-insulating base materials such as cloth can be used. The heat conductive film of the present invention has high heat conductivity in the thickness direction. Moreover, since the resin composition which comprises a heat conductive film does not require a large amount of heat conductive inorganic fillers for the purpose of high heat conductivity, it has low specific gravity and good moldability. Such heat conductive films are particularly heat conductive among electrical and electronic devices such as light emitting diodes (LEDs), generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, and chargers. It can be suitably used as an insulating paper and as an insulating layer for ensuring insulation between a metal substrate and a conductive foil for forming a wiring pattern. Further, the electronic circuit board configured as described above has high heat dissipation performance, and can contribute to further miniaturization and higher performance of the electric / electronic device.

  Next, although the manufacture example, an Example, and a comparative example are given and the resin composition of this invention is demonstrated in detail, 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.

[Evaluation method]
Number average molecular weight: The resin used in the present invention was dissolved in a 3: 8 mixed solvent of p-chlorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene in a volume ratio of 3: 8 to prepare a sample. 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.
Phase transition temperature / resin crystallinity and liquid crystallinity evaluation: In differential scanning calorimetry (DSC measurement), the temperature is raised and lowered at a rate of 10 ° C./min. The transition point (T _s ) from the solid phase to the liquid crystal phase and the transition point (T _i ) from the liquid crystal phase to the isotropic phase were determined from the peak top of the endothermic peak when the temperature was increased.
Test piece molding: The resin or the resin composition was dried at 120 ° C. for 4 hours using a hot air dryer, and then a plate-like sample having a length of 80 mm × width of 10 mm × thickness of 0.8 mm was molded by a press molding machine. At this time, the press temperature was set to 10 ° C. higher than the isotropic phase transition point (T _i ) of the resin.
Thermal conductivity: Using a disk-shaped sample having a thickness of 1 mm × 25 mmφ, the thermal conductivity in the thickness direction in the air at room temperature was measured with a laser flash method thermal conductivity measuring device (LFA447 manufactured by NETZSCH).
Specific gravity: Specific gravity was measured by the Archimedes method using a disk-shaped sample having a thickness of 1 mm × 25 mmφ.
Evaluation of brittleness: When a plate-like sample having a length of 80 mm, a width of 10 mm, and a thickness of 0.8 mm is bent to 90 degrees or less at the angle shown in FIG. , When breaking at 120 degrees. [Materials used]

<Resin>
[Production Example 1]
4,4′-dihydroxybiphenyl, sebacic acid, and tetradecanedioic acid were charged into a sealed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring rod in a ratio of 48:39:13 mol%, respectively. 2.1 equivalents of acetic anhydride and a catalytic amount of sodium acetate to 4,4′-dihydroxybiphenyl were added. After making it react at 145 degreeC by a normal pressure and nitrogen atmosphere, it heated up to 260 degreeC at 2 degrees C / min, distilling off acetic acid, and stirred at 260 degreeC for 1 hour. Subsequently, while maintaining the temperature, the pressure was reduced to 10 Torr over about 60 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 14,000, the thermal conductivity of the resin alone 0.46W / (m · K), T s is 121 ° C., _{T i} was 251 ° C.. Let the obtained resin be (A-1).

[Production Example 2]
A resin was obtained in the same manner as in Production Example 1 except that 4,4′-dihydroxybiphenyl, tetradecanedioic acid, and eicosanedioic acid were charged as raw materials at a ratio of 48:26:26 mol%, respectively. The number average molecular weight of the obtained resin 16,000, the thermal conductivity of the resin alone 0.43W / (m · K), T s is 110 ° C., _{T i} was 201 ° C.. 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, 50: 37.5: 12.5 mol% of 4,4′-dihydroxybiphenyl, sebacic acid, and tetradecanedioic acid were respectively added. Charged in proportions, 2.1 equivalents of acetic anhydride and a catalytic amount of 1-methylimidazole were added to 4,4′-dihydroxybiphenyl. After making it react at 145 degreeC by a normal pressure and nitrogen atmosphere, it heated up to 260 degreeC at 2 degrees C / min, distilling off acetic acid, and stirred at 260 degreeC for 1 hour. Subsequently, while maintaining the temperature, the pressure was reduced to 10 Torr over about 60 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 73,000, the thermal conductivity of the resin alone 0.45W / (m · K), T s is 121 ° C., _{T i} was 253 ° C.. Let the obtained resin be (A-3).

[Production Example 4]
A resin was obtained in the same manner as in Production Example 1 except that the stirring time at 260 ° C. was 2 hours and the resin was taken out without reducing the pressure. The number average molecular weight of the obtained resin 8,000, the thermal conductivity of the resin alone 0.52W / (m · K), T s is 121 ° C., _{T i} was 251 ° C.. Let the obtained resin be (A-4).

[Production Example 5]
In a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring rod, 50: 37.5: 12.5 mol% of 4,4′-dihydroxybiphenyl, sebacic acid, and dodecanedioic acid were used. Charged in proportions, 2.1 equivalents of acetic anhydride and a catalytic amount of 1-methylimidazole were added to 4,4′-dihydroxybiphenyl. After making it react at 145 degreeC by a normal pressure and nitrogen atmosphere, it heated up to 260 degreeC at 2 degrees C / min, distilling off acetic acid, and stirred at 260 degreeC for 1 hour. Subsequently, while maintaining the temperature, the pressure was reduced to 10 Torr over about 60 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 56,000, the thermal conductivity of the resin alone 0.45W / (m · K), T s is 190 ° C., _{T i} was 272 ° C.. Let the obtained resin be (A-5).

[Production Example 6]
A closed reactor equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirring rod was charged with 4,4′-dihydroxybiphenyl and dodecanedioic acid at a ratio of 50:50 mol%, respectively. 2.1 equivalents of acetic anhydride and a catalytic amount of 1-methylimidazole were added to dihydroxybiphenyl. After reacting at 145 ° C. under normal pressure and nitrogen atmosphere, a uniform solution was obtained, and the temperature was raised to 270 ° C. at 2 ° C./min while acetic acid was distilled off, followed by stirring at 270 ° C. for 1 hour. Subsequently, while maintaining the temperature, the pressure was reduced to 10 Torr over about 60 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 60,000, the thermal conductivity of the resin alone 0.42W / (m · K), T s is 203 ° C., _{T i} was 253 ° C.. Let the obtained resin be (A-6).
(A-7) Polybutylene terephthalate (Mitsubishi Engineering Plastics, Novaduran 5008L)

<Inorganic filler>
(B-1) Alumina powder (DAW03, manufactured by Denki Kagaku Co., Ltd., thermal conductivity 30 W / (m · K) alone, volume average particle diameter 3 μm, electrical insulation)
(B-2) Alumina powder (AS-50 manufactured by Showa Denko KK, single body thermal conductivity 30 W / (m · K), volume average particle diameter 9 μm, electrical insulation)
(B-3) Alumina powder (AS-40 manufactured by Showa Denko KK, single body thermal conductivity 30 W / (m · K), volume average particle diameter 12 μm, electrical insulation)
(B-4) Aluminum nitride powder (H grade manufactured by Tokuyama Corporation, thermal conductivity of 170 W / (m · K) alone, volume average particle diameter of 1 μm, electrical insulation)
(B-5) Aluminum powder (aluminum powder for filler manufactured by Toyo Aluminum Co., Ltd., thermal conductivity 200 W / (m · K) alone, volume average particle diameter 9 μm, conductivity)

[Example 1]
The resin (A-1) is dried at 120 ° C. for 4 hours using a hot air dryer, and mixed with the inorganic filler (B-1) at a ratio of 90:10 vol% in a twin screw extruder to obtain a resin composition. Got. The resin composition dried at 120 ° C. for 4 hours using a hot air dryer was molded into each shape using a press molding machine, and the thermal conductivity in the thickness direction, thin-wall formability and flexibility were evaluated. The evaluation results are shown in Table 2.

[Examples 2-7, Comparative Examples 1-3]
A resin composition was obtained in the same manner as in Example 1 except that the amount of the inorganic filler was changed as shown in Table 2. The amount of the resin is a value obtained by subtracting the amount of the inorganic filler shown in Table 2 from 100 vol%. The obtained resin composition was molded into each shape using a press molding machine, and the thermal conductivity in the thickness direction, thin moldability and flexibility were evaluated. The evaluation results are shown in Table 2.

[Example 8]
The resin composition obtained in Example 1 was extruded from a T-die having a clearance adjusted to 300 μm and taken out to obtain a heat conductive film having a thickness of 100 μm. At that time, a more flexible film was obtained without causing T-die wear or the like.

  From the comparison between Example 1 and Comparative Example 1, it can be seen that the thermal conductivity of the resin composition is higher when the average particle size of the inorganic filler is 10 μm or less. In addition, the comparison with Comparative Example 4 shows that the heat conductivity of the resin composition can be greatly improved because the resin having a specific structure of the present invention functions as a good heat conduction path between the inorganic filler particles. It can be seen that when 30 vol% of the inorganic filler is blended as in Comparative Example 2, the thermal conductivity increases, but it becomes brittle. On the other hand, when the number average molecular weight of the resin is 10,000 or less as in Comparative Example 4, the resin becomes brittle. From the comparison between Example 7 and Comparative Example 4, it can be seen that a high thermal conductivity can be obtained even if other resins are blended if the resin composition is blended with 50 vol% or more of the resin having the specific structure of the present invention. Further, as in Example 8, the resin composition of the present invention can be processed into a film by a T-die.

  The resin composition of the present invention exhibits excellent thermal conductivity, and has low specific gravity and improved brittleness. Such a resin composition can be used as a heat-dissipating / heat-transfer resin material, particularly as a heat-conducting film, and is industrially useful in various situations such as in the electric / electronic industry and automobile fields.

Claims (10)

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

40 to 60 mol% of a unit (A) having a biphenyl group represented by
General formula (2)
—CO—R ₁ —CO— (2)
(In the formula, R ₁ represents a divalent linear substituent which may contain a branch having 2 to 18 main chain atoms.)
5 to 50 mol% of the unit (B) represented by
General formula (3)
_-CO-R 2 -CO- (3)
(In the formula, R ₂ may include a branch having 4 to 20 main chain atoms, and represents a divalent linear substituent having a larger number of main chain atoms than R _1. )
The unit (C) is represented by 0 to 45 mol% (however, the total of the units (A), (B), and (C) is 100 mol%), and the number average molecular weight is 10,000 or more. And a resin comprising an inorganic filler having a thermal conductivity of 1 W / (m · K) or more and an average particle size of 10 μm or less in an amount of less than 30 vol% with respect to the entire resin composition Composition. The resin composition according to claim 1, wherein a portion corresponding to R ₁ and R ₂ of the resin is a linear saturated aliphatic hydrocarbon chain. 3. The resin composition according to claim 1, wherein the number of main chain atoms in a portion corresponding to R ₁ and R ₂ of the resin is an even number. The resin composition according to any one of claims 1 to 3, wherein the number of main chain atoms m and n corresponding to R ₁ and R ₂ of the resin satisfies the following general formula (4).
nm−4 (4) Content with respect to the resin composition of the said resin is 50 vol% or more, The resin composition as described in any one of Claims 1-4. The inorganic filler is one or more electrically insulating high thermal conductive inorganic compounds selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, and diamond. The resin composition according to any one of claims 1 to 5, wherein The inorganic filler is at least one conductive highly thermally conductive inorganic compound selected from the group consisting of graphite, carbon nanotubes, conductive metal powder, soft magnetic ferrite, carbon fiber, conductive metal fiber, and zinc oxide. The resin composition according to any one of claims 1 to 5, which is characterized. The resin composition according to claim 6 or 7, wherein an aspect ratio of the inorganic filler is 5 or less. A resin material for heat dissipation / heat transfer containing the resin composition according to any one of claims 1 to 8. The heat conductive film containing the resin composition as described in any one of Claims 1-8.