JP5689612B2 - High thermal conductive curable resin and curable resin composition - Google Patents

Description

The present invention relates to a novel highly thermally conductive curable resin and a curable resin composition excellent in thermal conductivity. Specifically, the present invention relates to a highly thermally conductive curable resin and a curable resin composition excellent in thermal conductivity, heat resistance, and moldability.

  In recent years, downsizing of electrical equipment has been rapidly progressed, and characteristics required for insulating materials have become considerably high. In particular, the amount of heat generated from a high-density conductor is increasing with downsizing, and how to dissipate heat is an important issue. On the other hand, thermosetting resins are widely used as insulating materials for various electric devices from the viewpoints of high insulation performance, ease of molding, heat resistance, and the like. However, in general, the thermal conductivity of the thermosetting resin is low, which is a major factor preventing the heat dissipation.

  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 thermosetting resin. As the high thermal conductivity inorganic compound, it is necessary to blend a high thermal conductivity inorganic material such as graphite, carbon fiber, alumina, boron nitride, etc. into the resin with a high content of usually 30% by volume or more, and further 50% by volume or more. There is. However, when such a highly heat-conductive inorganic compound is mixed with a thermosetting resin, the viscosity of the resin before molding is remarkably increased, so that it is difficult to produce a fine structure and its workability is extremely high. bad. In addition, it is actually difficult to uniformly disperse a large amount of high thermal conductive inorganic compound in the resin.

That is, a resin material that achieves a high thermal conductivity has long been desired. If the thermal conductivity of the resin material is high, a molded body having a high thermal conductivity can be obtained without blending a large amount of the high thermal conductivity inorganic compound. If there are few compounding quantities of a highly heat conductive inorganic compound, shaping | molding of a resin composition will become easy.
By the way, as a thermosetting resin excellent in thermal conductivity of a single resin, for example, an epoxy resin described in Patent Document 1 or Patent Document 2 or a bismaleimide resin described in Patent Document 3 has been reported. However, these resins have the disadvantage that the molecular structure is complicated and the production is difficult.

International Publication Number WO2002 / 094905 International Publication Number WO2006 / 120993

  In view of the above circumstances, an object of the present invention is to provide a highly heat-conductive curable resin and a curable resin composition having greatly increased thermal conductivity. The curable resin or curable resin composition of the present invention is preferably a thermosetting resin or a thermosetting resin composition.

The present inventor has found that a resin having a specific polyester structure and having a crosslinkable functional group at its terminal exhibits excellent thermal conductivity as a single resin, and has led to the present invention. That is, the present invention has the following configuration.
1) A curable resin in which the main chain is a polyester mainly composed of repeating units represented by the following general formula (1) or (2) and has a crosslinkable functional group at 50 mol% or more of the terminals.
-M-OCO-R-COO- (1)
-M-COO-R-OCO- (2)
(In the formula, M represents a mesogenic group, and R represents a divalent substituent which may include a branch having 2 to 20 main chain atoms.)
2) The curable resin according to 1), wherein the crosslinkable functional group is selected from the group consisting of a maleimide group, an acryl group, a methacryl group, and an allyl group.
3) The curable resin according to 1) or 2), wherein the curable resin has a number average molecular weight of 3000 to 40000.
4) M in the general formula (1) and (2) -A ¹ -x-A ² - is a unit represented by the 1) to 3) The curable resin according to.
(A ¹ and A ² each independently represent a substituent selected from an aromatic group, a condensed aromatic group, an alicyclic group, and an alicyclic heterocyclic group. X each independently represents a direct bond, − _{CH 2 -, - C (CH} 3) 2 -, - O -, - S -, - CH 2 -CH 2 -, - C = C -, - C≡C -, - CO -, - CO-O- , —CO—NH—, —CH═N—, —CH═N—N═CH—, —N═N— or —N (O) ═N— are each a divalent substituent. )
5) The curable resin according to 1) to 3), wherein M in the general formulas (1) and (2) is a mesogenic group represented by the following general formula (3).

6) The curable resin according to any one of 1) to 5), wherein R in the general formulas (1) and (2) is a linear aliphatic hydrocarbon chain.
7) Curable resin in any one of 1) -6) whose carbon number of the molecular chain of R of said general formula (1) and (2) is an even number.
8) R in the general formula (1) and (2) _{- (CH 2) 8 -,} - (CH 2) 10 -, and - (CH _{2) 12} - is at least one selected from 1) -7) Curable resin in any one.
9) The curable resin according to any one of 1) to 8), wherein the thermal conductivity of the resin alone is 0.45 W / (m · K) or more.
10) A curable resin composition containing the curable resin according to any one of 1) to 9) above and an inorganic filler.
11) The curable resin composition according to 10), wherein the inorganic filler is an inorganic compound having a thermal conductivity of 12 W / m · K or more.
12) The curable resin composition according to 10) or 11), wherein the inorganic filler is an electrically insulating high thermal conductive inorganic compound.
13) The curable resin composition according to 10) or 11), wherein the inorganic filler is a conductive highly thermally conductive inorganic compound.
14) The curable resin composition according to any one of 1) to 13), which contains another curable resin.

Since the high thermal conductivity curable resin of the present invention exhibits high thermal conductivity with a single resin, it exhibits high thermal conductivity without particularly blending a high thermal conductivity inorganic filler, and has good moldability and high thermal conductivity. It is possible to easily obtain a molding material having both.

The resin used for the highly thermally conductive curable resin of the present invention has a polyester structure in which the main chain is mainly composed of repeating units of the units represented by the following general formula (1) or (2).
-M-OCO-R-COO- (1)
-M-COO-R-OCO- (2)
(In the formula, M represents a mesogenic group, and R represents a divalent substituent which may include a branch having 2 to 20 main chain atoms.)

  The curable resin in the present invention refers to a resin that is cured by a crosslinking reaction. The curable resin of the present invention is preferably a thermosetting resin that forms a crosslinked structure by heating. Moreover, the crosslinkable functional group in this invention means the functional group which participates in the said crosslinking reaction. That is, as long as it is not involved in the crosslinking reaction, even a group generally called a functional group does not fall under the crosslinkable functional group in the present invention.

  The term “mainly” as used in the present invention means that the amount of the general formula (1) or (2) contained in the main chain of the molecular chain is 50 mol% or more, preferably 70 mol% or more, with respect to all the structural units. More preferably, it is 90 mol% or more, and most preferably 95 mol%. When it is less than 50 mol%, the crystallinity of the resin is lowered, and the thermal conductivity may be lowered.

The resin of the present invention has extremely high symmetry and has a structure in which a rigid straight chain is bound by a bent chain, so that the orientation of the molecule is high, the formed higher order structure is dense, and has excellent thermal conductivity.
In the present invention, a crosslinkable functional group is preferably introduced at 50 mol% or more of the terminal of the high thermal conductive curable resin, more preferably 60 mol% or more, and further preferably 70 mol% or more. If it is less than 50 mol%, a crosslinked structure cannot be formed, and the heat resistance may be insufficient. Specific examples of the crosslinkable functional group include a maleimide group, an acryl group, a methacryl group, and an allyl group.

In obtaining the introduction ratio of the crosslinkable functional group to the terminal, it is preferable from the viewpoint of accuracy and simplicity to obtain from the integral value of the characteristic signal corresponding to each terminal group by 1H-NMR. For example, for a resin into which a maleimide group (characteristic signal is equivalent to two protons) is introduced, if the acetyl group and the carboxyl group can be terminal, if the characteristic signal for distinguishing the carboxyl group is a methylene proton at the α-position of the carboxyl group, It can be calculated by equation (4).
[Integral value of maleimide group / 2] / [(Integrated value of carboxyl group α-position proton / 2) + (Integrated value of acetyl group / 3) + (Integrated value of maleimide group / 2)] × 100 = [To end Introduction rate of crosslinkable functional group (%)] . . . (4)

  The thermal conductivity of the single resin referred to in the present invention is the thermal conductivity of a cured product obtained by curing the curable resin alone or by reacting with another curing agent, such as other inorganic fillers. This is the thermal conductivity of the cured product when it does not contain anything that affects the thermal conductivity of the resin composition. The thermal conductivity of the resin itself varies depending on its thermal history and crystallinity, but is usually 0.45 W / (m · K) or more, preferably 0.6 W / (m · K) or more, more preferably Is 0.8 W / (m · K) or more, more 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. Generally, values of 30 W / (m · K) or less, and further 10 W / (m · K) or less can be exemplified. In the case of a resin with advanced crystallization, high thermal conductivity is often exhibited.

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

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

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

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

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

R contained in the highly thermally conductive curable resin of the present invention means a flexible molecular chain.
Here, R has a chain saturated hydrocarbon group having 2 to 20 carbon atoms, a saturated hydrocarbon group having 2 to 20 carbon atoms including 1 to 3 cyclic structures, and 1 to 5 unsaturated groups. A hydrocarbon group having 2 to 20 carbon atoms, a hydrocarbon group having 2 to 20 carbon atoms having 1 to 3 aromatic rings, and a polyether group having 2 to 20 carbon atoms having 1 to 5 oxygen atoms Those selected from are preferred.

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

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

In particular, R is at least one selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ — from the viewpoint that a resin having excellent thermal conductivity can be obtained. Is preferred. The group for bonding the substituent R to the mesogenic group is —O—CO—R—CO—O— or —CO—O—R—O—CO— from the viewpoint of obtaining a resin having excellent thermal conductivity. Those having a structure are preferred, and —O—CO—R—CO—O— is particularly preferred.

  The number average molecular weight of the resin used in the composition of the present invention is polystyrene as a standard, and the curable resin used in the present invention is 0.25 in a 1: 2 (Vol ratio) mixed solvent of p-chlorophenol and o-dichlorobenzene. It can measure at 80 degreeC by GPC using the solution prepared by melt | dissolving so that it might become a weight% density | concentration. The number average molecular weight of the curable resin of the present invention is preferably 3000 to 40000, more preferably 3000 to 30000, and particularly preferably 3000 to 20000 in view of the upper limit. On the other hand, considering the lower limit, it is preferably 3000 to 40000, more preferably 5000 to 40000, and particularly preferably 7000 to 40000. Furthermore, when an upper limit and a lower limit are considered, it is more preferable that it is 5000-30000, and it is most preferable that it is 7000-20000. When the number average molecular weight is less than 3000 or greater than 40000, even if the resin has the same primary structure, the thermal conductivity may be 0.45 W / (m · K) or less.

  Moreover, it is preferable that the highly heat conductive curable resin of this invention contains a lamellar crystal. In the high thermal conductive curable resin of the present invention, the amount of lamellar crystals can be used as an index of crystallinity. The more lamellar crystals, the higher the crystallinity.

  The lamellar crystal referred to in the present invention corresponds to a plate-like crystal in which long chain molecules are folded and arranged in parallel. Whether or not such crystals exist in the resin can be easily determined by observation with a transmission electron microscope (TEM) or X-ray diffraction.

The ratio of lamellar crystals forming the continuous phase can be calculated by directly observing a sample stained with RuO ₄ with a transmission electron microscope (TEM). As a specific method, as a sample for TEM observation, a part of a molded sample having a thickness of 6 mm × 20 mmφ is cut out, stained with RuO _4, and then an ultrathin section having a thickness of 0.1 μm prepared by a microtome is used. It shall be. 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 (20 cm × 25 cm). The boundary of the region can be determined by using the lamellar crystal region as a region where periodic contrast exists. Since the lamella crystals are similarly distributed in the depth direction, the ratio of the lamella crystals is calculated as a ratio of the lamella crystal region to the entire area of the photograph. Moreover, in order for resin itself to have high thermal conductivity, it is preferable that the ratio of a lamellar crystal is 10 Vol% or more. The ratio of lamellar crystals is more preferably 20 Vol% or more, further preferably 30 Vol% or more, and particularly preferably 40 Vol% or more.

Moreover, it is preferable that the highly heat conductive curable resin of this invention contains a crystal | crystallization. In the present invention, the degree of crystallinity can be obtained from the ratio of lamellar crystals in the high thermal conductive curable resin by the following formula.
Crystallinity (%) = ratio of lamellar crystals (Vol%) x 0.7
In order for the resin itself to have high thermal conductivity, the crystallinity of the high thermal conductivity curable resin is preferably 7% or more. The degree of crystallinity is more preferably 14% or more, further preferably 21% or more, and particularly preferably 28% or more.

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

  Moreover, it is preferable that the high thermal conductivity curable resin used in the present invention has an isotropic thermal conductivity. As a method for measuring whether or not the thermal conductivity is isotropic, for example, a sample having a thermal effect resin in a disk shape having a thickness of 1 mm × 25.4 mmφ is measured in the thickness direction by the Xe flash method. And a method of separately measuring the thermal conductivity in the plane direction. The thermal conductivity of the curable resin according to the present invention is isotropically high, and the thermal conductivity in the thickness direction and the plane direction measured by the above measurement method is 0.3 W / (m · K) or more. is there.

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

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

  The method for introducing a crosslinkable functional group at the end is not limited, but there is a method in which a compound having a crosslinkable functional group and a hydroxyl group or a carboxyl group is added during the synthesis of the polyester structure and introduced at the end of the polyester structure. It is preferable from the point of simplicity.

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

  A multi-stage reaction temperature may be employed. In some cases, the reaction product can be withdrawn in a molten state and recovered as soon as the temperature rises or when the maximum temperature is reached. The obtained resin may be used as it is, or it may be subjected to solid phase polymerization in order to remove unreacted raw materials or 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 remains in a solid state at 250 to 350 ° C. in an inert gas atmosphere such as nitrogen. Alternatively, the treatment is preferably performed under reduced pressure for 1 to 20 hours. If the particle size of the polymer particles is 3 mm or more, the treatment is not sufficient, and problems with physical properties are caused, which is not preferable. It is preferable to select the treatment temperature and the 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 of the present invention include acid anhydrides of lower fatty acids having 2 to 5 carbon atoms such as acetic anhydride, propionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroanhydride. Acetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, etc. , Propionic anhydride and trichloroacetic anhydride are particularly preferably used.

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

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

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

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

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

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

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

Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid Etc.
Specific examples of the aliphatic diamine include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1,8-octanediamine, 1,9- Nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, and the like can be given.

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

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

  The thermal conductivity of the high thermal conductive curable 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. It is 0 W / (m · K) or more, particularly preferably 10 W / (m · K) or more. By containing an inorganic filler in the curable resin, it is possible to achieve higher thermal conductivity. If the thermal conductivity is low, it is difficult to efficiently transmit the heat generated from the electronic component to the outside. The upper limit of the thermal conductivity is not particularly limited, and is preferably as high as possible. Generally, a thermal conductivity of 100 W / (m · K) or less, further 80 W / (m · K) or less is used. Since the curable resin has excellent thermal conductivity, it is possible to easily obtain a highly thermally conductive curable resin composition having a thermal conductivity in the above range.

  The curable resin of the present invention is cured by, for example, thermosetting reaction, photocuring reaction, electron beam curing reaction, other radical curing reaction, or moisture curing reaction. Among these, it is preferable that it is hardened | cured by thermosetting reaction.

  Examples of the crosslinkable functional group in the curable resin of the present invention include a group having a polymerizable carbon-carbon double bond, an epoxy group, a hydroxyl group, an amino group, an isocyanate group, and a crosslinkable silyl group. it can. As a specific crosslinkable functional group, a maleimide group, an acrylic group, a methacryl group or an allyl group is preferable. The crosslinkable functional group may be present in the main chain of the polymer, but is preferably present only at the end of the polymer.

  Since the curable resin of the present invention has excellent thermal conductivity, it has excellent thermal conductivity without using an inorganic filler, but the thermal conductivity can be further improved by using an inorganic filler. .

  In the high thermal conductive resin composition of the present invention, when an inorganic filler is used, the amount used is preferably 99: 1 to 20:80, preferably 90: by volume ratio of the curable resin and the inorganic filler. It is 10-30: 70, More preferably, it is 80: 20-40: 60, Most preferably, it is 70: 30-50: 50. When the volume ratio is in these ranges, the balance between thermal conductivity and mechanical properties is favorable, which is preferable.

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

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

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

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

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

When the molded body is used for applications requiring electrical insulation, a compound exhibiting electrical insulation is preferably used as the highly thermally conductive inorganic compound. Specifically, the electrical insulating property indicates an electrical resistivity of 1 Ω · cm or more, preferably 10 Ω · cm or more, more preferably 10 ⁵ Ω · cm or more, and further preferably 10 ¹⁰ Ω · cm or more. It is preferable to use a material having a thickness of cm or more, most preferably 10 ¹³ Ω · cm or more. The upper limit of the electrical resistivity is not particularly limited, but is generally 10 ¹⁸ Ω · cm or less. It is preferable that the electrical insulation of the molded product obtained from the high thermal conductivity thermoplastic resin composition of the present invention is also in the above range.

  Among the high thermal conductive inorganic compounds, examples of the electrically insulating high thermal conductive inorganic compounds exhibiting electrical insulation include metal oxides, metal nitrides, metal carbides, metal carbonates, insulating carbon materials, and metal hydroxides. can do. Examples of the metal oxide include aluminum oxide, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride.

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

  Among them, one or more electrically insulating high heat conductive inorganic substances selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, beryllium oxide, and diamond Compounds are preferred. These can be used alone or in combination.

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

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

  In the resin composition of the present invention, known inorganic fillers can be widely used depending on the purpose in addition to the above-described highly thermally conductive inorganic compound. Since the thermal conductivity of the single resin is high, even if the thermal conductivity of the inorganic compound is relatively low at less than 10 W / mK, the resin composition can exhibit high thermal conductivity.

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

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

  In the high thermal conductive curable resin of the present invention, epoxy resin, polyolefin resin, bismaleimide resin, polyimide resin, polyether resin, phenol resin, silicone resin, polycarbonate resin, as long as the effects of the present invention are not lost. Any known resin such as polyamide resin, polyester resin, fluororesin, acrylic resin, melamine resin, urea resin, urethane resin may be contained. Specific examples of preferred resins include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, liquid crystal polymer, nylon 6, nylon 6,6 and the like. When these resins are used in combination, the amount used is preferably from 0 to 10,000 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A) usually contained in the resin composition.

  In the high thermal conductive resin material of the present invention, as an additive other than the above resin and filler, any other components such as a reinforcing agent, a thickener, a release agent, a coupling agent, a difficult agent, and the like, depending on purposes. A flame retardant, a crystal nucleating agent, a stabilizer, 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 60 parts by weight in total with respect to 100 parts by weight of the thermoplastic resin.

  The method for producing the composition of the present invention is not particularly limited.

  The molding method of the highly heat-conductive curable resin and the composition of the present invention is not limited, and can be produced in a desired shape by a known resin molding method, that is, transfer molding, injection molding, casting, or the like.

  The highly heat-conductive curable resin and composition of the present invention can also be produced in the form of a laminate by applying or impregnating a desired base material, laminating and curing. In this case, although the base material used is not specifically limited, As a preferable example, a glass cloth, a glass nonwoven fabric, carbon fiber, a synthetic fiber cloth, a synthetic fiber nonwoven fabric, paper etc. can be mentioned. The bismaleimide cured product according to the present invention is excellent in adhesiveness with a base material and can be practiced without using an ordinary adhesive, but within the range that does not impair the effects of the present invention depending on the purpose. An adhesive such as a coupling agent or various surface treatment agents may be applied to the substrate surface in advance. In producing the heat dissipation material of the present invention, the method of applying or impregnating on a desired substrate is not particularly limited, for example, application using a spin coater, application using a spray coater, application using a bar coater, Spraying, dipping, printing, etc. can be mentioned. The amount to be applied is not particularly limited. For example, the final film thickness after curing is 0. It is applied so as to be 1 μm to 100 μm, more generally 1 to 50 μm. After coating and impregnation, a prepreg is produced through a drying process. About drying conditions, it determines suitably by the boiling point of the solvent to be used. The prepreg thus obtained is produced by laminating one or a plurality of laminated prepregs by heating and pressing. In manufacturing a laminated plate-shaped heat dissipation material, a conductive layer or an insulating layer can be overlaid on one or both surfaces of the outermost layer. Examples of preferred conductive layers include copper foil, copper plate, aluminum foil, aluminum plate, iron foil, iron plate, stainless steel foil, stainless steel plate, gold foil, gold plate, silver foil, silver plate and the like. Examples of the insulating layer include a ceramic substrate and a resin sheet. Moreover, it is good also as a laminated board for multilayer printed wiring boards using an inner layer core material.

  The highly heat-conductive curable resin and composition of the present invention are used for circuit board materials, sealing materials such as resistors, inductors and capacitors, or cases for electronic components, ICs, sealing materials for power transistor elements, lighting devices, etc. Sealing materials and base substrate materials for light-emitting elements such as light bulbs, LEDs and semiconductor lasers used, casings for notebook computers and mobile phones, automotive parts such as lamp reflectors, insulating case materials and casings for motor cores, etc. It is extremely effective for sliding parts such as motor parts and bearing members, cooling parts such as heat radiating fins and heat sinks and heat pipes, heat exchanger parts, and O A and communication equipment such as copier roller members.

  The highly heat-conductive curable resin of the present invention has a good moldability because it can reduce the amount of the highly heat-conductive inorganic material compared to the conventionally well-known curable resins, such as a substrate in the above applications. It has characteristics useful as a part.

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

[Evaluation method]
Number average molecular weight: A sample was prepared by dissolving the curable resin of the present invention in a 1: 2 Vol ratio mixed solvent of p-chlorophenol and o-dichlorobenzene to a concentration of 0.25% by weight. The standard material was polystyrene, and a similar sample solution was prepared. Measurement was carried out under the conditions of INJECTOR COMP: 80 ° C., COLUMN COMP: 80 ° C., PUMP / SOLVENT COMP: 60 ° C., and Injection Volume: 200 μl using a high-temperature GPC (manufactured by Waters, Inc .; 150-CV).
Terminal functional group introduction rate: 1H-NMR (400 MHz, deuterated chloroform: deuterated trifluoroacetic acid = 2: 1 (Vol ratio) measured in a solvent) and crosslinking from the integral value of the characteristic signal of each terminal group The ratio of the functional functional group terminal was measured. Tables 1 and 2 show chemical shift values of typical signals for the types of crosslinkable functional groups and the types of terminal groups used in the measurement.

Thermal conductivity: A 1-inch φ × 1 mm-thick test piece was prepared with a heat press machine (mini test press manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a laser light absorbing spray (black guard spray made by Fine Chemical Japan) was applied to the test piece surface. FC-153) was applied and dried, and then the thermal diffusivity in the thickness direction was measured using an Xe flash analyzer LFA447 Nanoflash manufactured by NETZSCH. The thermal conductivity was calculated from the specific heat and density from the measured thermal diffusivity.
[Thermal conductivity] = [thermal diffusivity] x [specific heat] x [density]
Specific heat: measured by DSC method.
Density: measured by an underwater substitution method.

[Example 1]
4,4′-dihydroxybiphenyl, sebacic acid, acetic anhydride, and N- (4-acetoxyphenyl) -maleimide in a molar ratio of 1: 1.05: 2.1: 0.05, respectively, in a closed reactor. The mixture was charged and subjected to acetylation reaction at 150 ° C. in a nitrogen gas atmosphere under normal pressure, followed by polycondensation by heating to 280 ° C. at a temperature increase rate of 1 ° C./min. When the acetic acid distillate amount reached 90% of the theoretical acetic acid production amount, while maintaining the temperature, the pressure was reduced to 10 torr over about 20 minutes to carry out melt polymerization to a high molecular weight. One hour after the start of pressure reduction, the pressure was returned to normal pressure with an inert gas, and the produced resin was taken out. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight. The obtained resin was pulverized into particles having a particle size of 0.5 mm or less, and 1 part by weight of Park Mill D (manufactured by NOF Corporation) was uniformly mixed with 100 parts by weight of the resin. For 4 hours. Table 4 shows the thermal conductivity of the resin.

[Example 2]
A resin was obtained by polymerizing in the same manner except that sebacic acid in Example 1 was changed to dodecanoic acid. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight. The obtained resin was pulverized into particles having a particle size of 0.5 mm or less, and 1 part by weight of Park Mill D (manufactured by NOF Corporation) was uniformly mixed with 100 parts by weight of the resin. For 4 hours. Table 4 shows the thermal conductivity of the resin.

[Example 3]
4,4′-dihydroxybiphenyl, tetradecanoic acid, acetic anhydride, and N- (4-hydroxyphenyl) -acrylamide in a molar ratio of 1: 1.05: 2.2: 0.05, respectively. Then, acetylation reaction was performed at 150 ° C. in a nitrogen gas atmosphere under normal pressure, and polycondensation was performed by heating to 280 ° C. at a temperature increase rate of 1 ° C./min. When the acetic acid distillate amount reached 90% of the theoretical acetic acid production amount, while maintaining the temperature, the pressure was reduced to 10 torr over about 20 minutes to carry out melt polymerization to a high molecular weight. One hour after the start of pressure reduction, the pressure was returned to normal pressure with an inert gas, and the produced resin was taken out. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight. The obtained resin was pulverized into particles having a particle size of 0.5 mm or less, and 1 part by weight of Park Mill D (manufactured by NOF Corporation) was uniformly mixed with 100 parts by weight of the resin. For 4 hours. Table 4 shows the thermal conductivity of the resin.

[Comparative Example 1]
The thermal conductivity was measured in the same manner except that m-phenylene bismaleimide (Daiwa Kasei Kogyo Co., Ltd.), which is a known bismaleimide, was used instead of the resin synthesized in Example 1. The results are shown in Table 4.

[Comparative Example 2]
Regarding the raw material of Example 3, 4,4′-dihydroxybiphenyl, tetradecanoic acid, acetic anhydride, and N- (4-hydroxyphenyl) -acrylamide were each in a molar ratio of 1: 1: 2.2: 0.01. Resin was polymerized in the same manner except that it was charged, and molding and thermal conductivity were measured. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight and the thermal conductivity of the molded product.

[Example 4]
A polymerization reactor was charged with dimethyl 4,4′-biphenyldicarboxylate, 1,10-decanediol and N- (methyl 4-benzoate) -methacrylamide at a molar ratio of 1: 1.05: 0.05, and the catalyst TBT (tetrabutyl titanate) was added at 5 × 10 ⁻⁴ mol per 1 mol of the structural unit of the polyester, and the ester exchange reaction was carried out at a temperature of 280 ° C. to distill methanol, followed by 280 ° C. under a reduced pressure of 10 torr. The polycondensation reaction was carried out for 1.5 hours. After that, the pressure was returned to normal pressure with an inert gas, and the produced resin was taken out. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight. The obtained resin was pulverized into particles having a particle size of 0.5 mm or less, and 1 part by weight of Nyper BW (manufactured by NOF Corporation) was uniformly mixed with 100 parts by weight of the resin. For 4 hours. Table 4 shows the thermal conductivity of the resin.

[Example 5]
Polymerization was carried out in the same manner except that 1,10-decanediol in Example 4 was changed to triethylene glycol. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight. The obtained resin was pulverized into particles having a particle size of 0.5 mm or less, and 1 part by weight of Nyper BW (manufactured by NOF Corporation) was uniformly mixed with 100 parts by weight of the resin. For 4 hours. Table 4 shows the thermal conductivity of the resin.

[Example 6]
A resin was obtained in the same manner as in Example 4 except that N- (methyl 4-benzoate) -methacrylamide was changed to methyl 4-allyloxybenzoate. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight. The obtained resin was pulverized into particles having a particle size of 0.5 mm or less, 3 parts by weight of CR500 (manufactured by Kaneka Corp.) as a silane addition type curing agent and 100% by weight of Pt as a platinum curing catalyst with respect to 100 parts by weight of the resin. -VTSC-3.0IPA (manufactured by OMG Precious Metals Japan) was mixed uniformly and thermally cured at 160 degrees for 2 hours with a hot press machine. Table 4 shows the thermal conductivity of the resin.

[Example 7]
The resin was obtained in the same manner as in Example 1 except that 4,4′-dihydroxybiphenyl was changed to 4,4′-diacetoxyazoxybenzene and acetic anhydride was not used during the polymerization. Table 3 shows the molecular structure and terminal functional group introduction rate of the obtained resin, and Table 4 shows the number average molecular weight. The obtained resin was pulverized into particles having a particle size of 0.5 mm or less, and 1 part by weight of Park Mill D (manufactured by NOF Corporation) was uniformly mixed with 100 parts by weight of the resin. For 4 hours. Table 4 shows the thermal conductivity of the resin.

[Example 8]
Boron nitride powder (PT110 manufactured by Momentive Performance Materials, single unit thermal conductivity 60 W / (m · K), volume average particle diameter 45 μm, electrical insulation as the pulverized resin and inorganic filler obtained in Example 2 , Volume resistivity 10 ¹⁴ Ω · cm) (h-BN) is mixed at a ratio of 50:50 Vol%, and 1 part by weight of Park Mill D (manufactured by NOF Corporation) is uniformly mixed with 100 parts by weight of the resin. I prepared what I did. It was heated and cured at 210 ° C. for 4 hours with a hot press. Table 5 shows the thermal conductivity of the composition.

[Example 9]
The pulverized resin obtained in Example 2, m-phenylene bismaleimide (Daiwa Kasei Kogyo Co., Ltd.), which is a known bismaleimide, and boron nitride powder (PT110 manufactured by Momentive Performance Materials, Inc.) alone as an inorganic filler The thermal conductivity of 60 W / (m · K), volume average particle diameter 45 μm, electrical insulation, volume resistivity 10 ¹⁴ Ω · cm) (h-BN) are mixed at a ratio of 25:25:50 Vol%, What prepared Park Mill D (made by NOF Corporation) uniformly 1 weight part with respect to 100 weight part of resin was prepared. It was heated and cured at 210 ° C. for 4 hours with a hot press. Table 5 shows the thermal conductivity of the composition.

[Comparative Example 3]
XMAP (RC100C manufactured by Kaneka Corporation), which is a commercially available acrylic thermosetting resin having an acrylic group at both ends, and boron nitride powder (PT110 manufactured by Momentive Performance Materials Co., Ltd., thermal conductivity of 60 W as a simple substance) / (M · K), volume average particle diameter 45 μm, electrical insulation, volume resistivity 10 ¹⁴ Ω · cm) (h-BN) is mixed at a ratio of 50:50 Vol%, and nipper is added to 100 parts by weight of resin. What mixed 1 weight part of BWD (made by NOF Corporation) uniformly was prepared. It was cured by heating at 150 ° C. for 30 minutes with a hot press. Table 5 shows the thermal conductivity of the composition.

  As described above, since the high thermal conductivity thermosetting resin and composition of the present invention are excellent in thermal conductivity, even if no high thermal conductivity inorganic filler is particularly blended, high thermal conductivity is exhibited and blended in large quantities. In this case, the thermal conductivity is greatly improved. Such a composition can be used as a heat-dissipating / heat-transfer resin material in various situations such as in the electric / electronic industrial field and the automobile field, and is industrially useful.

Claims (9)

The main chain is a polyester containing 90 mol% or more of repeating units of the units represented by the following general formula (1) or (2) with respect to all constituent units of the main chain, and the crosslinkable functional group is present at 50 mol% or more of the terminals. The crosslinkable functional group is a maleimide group, an acryl group, a methacryl group or an allyl group,
A curable resin having a number average molecular weight of 3000 to 40000.
-M-OCO-R-COO- (1)
-M-COO-R-OCO- (2)
(A pre-Symbol R is an aliphatic linear hydrocarbon chain of the main chain atoms 2-20 in formula (1) and (2), the general formula (1) and M is -A ¹ (2) It is a mesogenic group which is a unit represented by -x-A ^2- .)
(A ¹ and A ² each independently represent a substituent selected from an aromatic group, a condensed aromatic group, an alicyclic group, and an alicyclic heterocyclic group. X each independently represents a direct bond, − CH ₂ —CH ₂ —, —C═C—, —C≡C—, —CO—O—, —CO—NH—, —CH═N—, —CH═N—N═CH—, —N═ A divalent substituent selected from the group of N- and -N (O) = N-. The main chain is a polyester containing 90 mol% or more of repeating units of the units represented by the following general formula (1) or (2) with respect to all constituent units of the main chain, and the crosslinkable functional group is present at 50 mol% or more of the terminals. The crosslinkable functional group is a maleimide group, an acryl group, a methacryl group or an allyl group,
A curable resin having a number average molecular weight of 3000 to 40000.
-M-OCO-R-COO- (1)
-M-COO-R-OCO- (2)
(Before following general formula (1) and (2) R is an aliphatic linear hydrocarbon chain of the main chain atoms 2-20 of the general formula (1) and M is the following general formula (2) (It is a mesogenic group represented by (3) .)

The curable resin according to claim 1 or 2 , wherein the R molecular chain of the general formulas (1) and (2) has an even number of carbon atoms. Formula (1) and the R of _{(2) - (CH 2)} 8 -, - (CH 2) 10 -, and - (CH _{2) 12} - is at least one selected from, in claim 3 The curable resin described. The curable resin according to any one of claims 1 to 4 , wherein the thermal conductivity of the resin alone is 0.45 W / (m · K) or more. Containing the curable resin according to any one of claims 1 to 5 and an inorganic filler,
The curable resin composition, wherein the inorganic filler is an inorganic compound having a single body thermal conductivity of 1 W / m · K or more. The curable resin composition according to claim 6 , wherein the inorganic filler is an inorganic compound having a single body thermal conductivity of 12 W / m · K or more. The curable resin composition according to claim 6 or 7 , wherein the inorganic filler is an electrically insulating high thermal conductive inorganic compound. The curable resin composition according to claim 6 or 7 , wherein the inorganic filler is an electrically conductive highly thermally conductive inorganic compound.