WO2015083523A1 - 高熱伝導性樹脂組成物、それを含有する放熱・伝熱用樹脂材料および熱伝導膜 - Google Patents
高熱伝導性樹脂組成物、それを含有する放熱・伝熱用樹脂材料および熱伝導膜 Download PDFInfo
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C08K3/38—Boron-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
Definitions
- the present invention relates to a resin composition that is excellent in thermal conductivity and can be processed into a thin and flexible molded body, and a heat dissipation / heat transfer resin material and a heat conductive film containing the same.
- an epoxy resin described in Patent Document 1 has been reported as a thermosetting resin having excellent thermal conductivity of a single resin.
- 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.
- Patent Document 3 discloses that the thermal liquid crystalline polyester is aligned in the alignment direction of the thermal liquid crystalline polyester by aligning the thermal liquid crystalline polyester with at least one external field selected from a flow field, a shear field, a magnetic field, and an electric field.
- a resin molded body having high thermal conductivity is described.
- the resin molded body has high thermal conductivity in the uniaxial direction but low thermal conductivity in the other biaxial directions.
- a magnetic flux density of at least 3 Tesla or more is required in the case of a magnetic field. Is difficult to manufacture.
- Patent Documents 4 to 6 describe alternating polycondensates of mesogenic groups and bent chains as thermoplastic resins having excellent thermal conductivity of a single resin. These polyesters were known to have high crystallinity and high thermal conductivity due to their mesogenic groups and their ordered molecular structure, but on the other hand they were hard and brittle, especially thin-walled. There has been a demand for improvement in molding processability to a film-like molded body.
- Non-Patent Document 1 investigates the phase transition temperature and crystallinity of a random copolymer polyester of biphenol which is a mesogenic group and two types of aliphatic dicarboxylic acids.
- An object of the present invention is to provide a resin composition that is excellent in thermal conductivity and can be processed into a thin and flexible molded body, a heat-dissipating / heat-transfer resin material containing the resin composition, and a thermal conductive film.
- a liquid crystalline resin having a specific structure obtained by random copolymerization of two types of biphenol and a divalent linear unit has a low crystallinity, but the heat of the resin itself is low.
- a resin composition containing an inorganic filler having high conductivity and further having a thermal conductivity of 1 W / (m ⁇ K) or higher has high thermal conductivity, and can be processed into a thin and flexible molded body.
- the headline, the present invention has been reached. That is, the present invention includes the following 1) to 9).
- Unit (C) 5 to 40 mol% (provided that the total of units (A), (B), and (C) is 100 mol%), and the thermal conductivity of the resin alone
- a resin composition comprising: a resin having a thermal conductivity of not less than 0.4 W / (m ⁇ K) and an inorganic filler having a thermal conductivity of not less than 1 W / (m ⁇ K).
- the inorganic filler is one or more electrically insulating high heat conductive inorganic materials selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, and diamond.
- the inorganic filler is at least one conductive high thermal 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:
- the resin composition of the present invention has excellent thermal conductivity and can be processed into a thin and flexible molded body.
- the resin composition of the present invention has a main chain structure represented by the following general formula (1)
- Unit (C) 5 to 40 mol% (provided that the total of units (A), (B), and (C) is 100 mol%), and the thermal conductivity of the resin alone Is characterized by containing a resin having a thermal conductivity of not less than 0.4 W / (m ⁇ K) and an inorganic filler having a thermal conductivity of not less than 1 W / (m ⁇ K).
- the resin composition of the present invention has a main chain structure represented by the following general formula (1):
- the following general formula (2) -CO-R 1 -CO- (2) (In the formula, R 1 represents a main chain atoms 2 to 18, including a branch indicating also be a divalent straight chain substituent.) Represented by the unit (B) 5 ⁇ 40 mol%, and the following general Formula (3) —CO—R 2 —CO— (3) (In the formula, R 2 represents a divalent linear substituent having 4 to 20 main chain atoms which may contain a branch and has a larger number of main chain atoms than R 1.
- Unit (C) represented by 5 to 40 mol% (provided that the total of units (A), (B), and (C) is 100 mol%), and the thermal conductivity of the resin alone May contain a resin having a thermal conductivity of not less than 0.4 W / (m ⁇ K) and an inorganic filler having a thermal conductivity of not less than 1 W / (m ⁇ K).
- the molar ratio (B) / (C) of the copolymerized units (B) and (C) of the present invention is preferably 8/1 to 1/8, more preferably 6/1 to 1 /. 4, more preferably 4/1 to 1/2, and most preferably 3/1 to 1/1.
- a molar ratio of 8/1 to 1/8 is preferable from the viewpoint that the increase in crystallinity of the resin is suppressed, thereby making the resin difficult to become brittle and ensuring the flexibility of thin-wall molding.
- 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.
- 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.
- the constituent molecules In the nematic liquid crystal, the constituent molecules have an orientation order, but do not have a three-dimensional positional order.
- 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.
- thermophysical properties of smectic liquid crystal molecules or resins in general, 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). ).
- T S the transition point from the solid phase to the smectic liquid crystal phase
- T i the transition point from the smectic liquid crystal phase to the isotropic phase
- T N nematic liquid crystal phase
- the magnitude relationship of the crystallinity of the resin can be judged by the phase transition enthalpy ( ⁇ H) of the endothermic peak from the solid phase to the liquid crystal phase in the temperature rising process of DSC measurement.
- the resin of the present invention is copolymerized with units (B) and (C) having different numbers of main chain atoms. It has been found that the thermal conductivity is drastically improved when a thermal conductive inorganic filler is blended. This is because the decrease in liquid crystallinity is slight even by copolymerization, and it can form an anisotropic domain of micron order with molecular chains oriented, and this domain serves as a good heat conduction path between inorganic fillers. This is thought to be functional.
- the terminal structure of the resin of the present invention is not particularly limited, but it is intended to increase the compatibility with other resins, or is a curability having solder reflow resistance using a compound having another polyfunctional reactive group as a curing agent.
- the terminal of the resin can be a carboxyl group.
- 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.
- the end can be sealed with a monofunctional low-molecular compound in order to improve the hydrolysis resistance and long-term heat resistance of the resin.
- 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 end-capping 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 enhancing the thermal conductivity of the resin.
- aliphatic monocarboxylic acids More preferred are 10-20 aliphatic monocarboxylic acids.
- 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 myristic acid, palmitic acid, and stearic acid are more preferable from the viewpoint of particularly enhancing the thermal conductivity of the resin.
- 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.
- aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, and cyclohexylamine are more preferable from the viewpoints of reactivity, high boiling point, stability of the capped end and price.
- the thermal conductivity of the single resin of the resin of the present invention is 0.4 W / (m ⁇ K) or more, preferably 0.5 W / (m ⁇ K) or more as a physical property value of the isotropic molded body. More preferably 0.6 W / (m ⁇ K) or more, 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.
- the thermal conductivity of a resin composition containing 40 vol% or less of an inorganic filler having an isotropic property is directly measured, and the thermal conductivity of the resin matrix is calculated from the following formula (6) (Bruggeman's theoretical formula). The obtained value may be used as the thermal conductivity of the resin alone.
- V is the volume content of the inorganic filler (0 ⁇ V ⁇ 1)
- ⁇ c is the thermal conductivity of the resin composition
- ⁇ f is the thermal conductivity of the inorganic filler
- ⁇ m is the thermal conductivity of the resin alone. It is. Therefore, if V, ⁇ c , and ⁇ f are known, ⁇ m can be calculated.
- a resin and a resin composition are formed into a disk shape having a thickness of 1 mm ⁇ 25 mm ⁇ , and a laser flash method thermal conductivity measuring device (manufactured by NETZSCH) is used.
- NETZSCH laser flash method thermal conductivity measuring device
- a method of separately measuring the thermal conductivity in the thickness direction and the surface direction in the room temperature atmosphere by LFA447) is conceivable. If these thermal conductivities are approximately equal, the compact is isotropic.
- R 1 represents a divalent linear substituent having 2 to 18 main chain atoms which may contain a branch.
- the number of main chain atoms is the number of atoms in the main chain skeleton.
- R 1 is preferably a linear substituent containing no branch, and more preferably a linear aliphatic hydrocarbon chain containing no branch.
- R 1 may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain.
- 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. When the number of main chain atoms of R 1 is an even number, the microscopic molecular orientation does not deteriorate, and a resin having high thermal conductivity can be easily obtained.
- 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. Preferably there is.
- R 2 therein may contain a branched chain 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 high thermal conductivity. Therefore, 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 2 may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain. When R 2 does not contain an unsaturated bond, the resin can obtain sufficient flexibility, and a resin having high thermal conductivity can be easily obtained.
- 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. When the number of main chain atoms of R 1 is an even number, the microscopic molecular orientation does not deteriorate, and a resin having high thermal conductivity can be easily obtained.
- the number of main chain atoms m and n corresponding to R 1 and R 2 in other words, the number of main chain atoms m corresponding to R 1 And the number n of main chain atoms in the portion corresponding to R 2 preferably satisfies the following general formula (4).
- R 2 satisfying the general formula (4) include — (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 chosen.
- the resin of the present invention may be copolymerized with other monomers to such an extent that the effect is not lost.
- aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, aromatic diamine, aromatic aminocarboxylic acid, caprolactams, caprolactone, aliphatic dicarboxylic acid, aliphatic diol, aliphatic diamine examples thereof include alicyclic dicarboxylic acids, alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols, and aromatic mercaptophenols.
- aromatic hydroxycarboxylic acid examples 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.
- aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl, 4,4 ′′ -dicarboxyterphenyl, bis (4-carboxyphenyl) ether, bis (4-carboxyphenoxy) butane, bis (4-carboxyphenyl) ethane, bis (3- Carboxyphenyl) ether, bis (3-carboxyphenyl) ethane, and the like, and alkyl, alkoxy or halogen substituted products thereof.
- aromatic diol examples include 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.
- aromatic hydroxyamine examples 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, 2,2'-diaminobinaphthyl and their alkyls , Alkoxy or halogen-substituted products.
- 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'-diaminobiphenylsulfone, 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, Examples include 7-amino-2-naphthoic acid and alkyl, alkoxy or halogen substituted products
- aliphatic dicarboxylic acid examples 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.
- aliphatic diamine examples 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 mentioned.
- alicyclic dicarboxylic acid examples include hexahydroterephthalic acid, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, and trans-1,4-cyclohexane.
- 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 number average molecular weight of the resin in the present invention is based on polystyrene, and the resin in the present invention is dissolved in a mixed solvent of p-chlorophenol and toluene in a volume ratio of 3: 8 so as to have a concentration of 0.25% by weight. It is the value measured at 80 ° C. by GPC using the prepared solution.
- the number average molecular weight of the resin in the present invention is preferably 3000 to 70000, more preferably 4000 to 60000, and still more preferably 5000 to 50000. When the number average molecular weight is 3000 or more, it is preferable from the viewpoint that the resin having the same primary structure tends to have a thermal conductivity of 0.4 W / (m ⁇ K) or more.
- 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.
- 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.
- the hydroxyl group of the compound is converted to acetic anhydride or the like.
- the polycondensation reaction is carried out at a temperature of usually 220 to 330 ° C., preferably 240 to 310 ° C.
- reaction temperature is 220 ° C. or higher, it is preferable from the viewpoint that the reaction proceeds quickly, and when it is 330 ° C. or lower, it is preferable from the viewpoint that side reactions such as decomposition hardly occur.
- 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.
- the degree of vacuum is 40 Torr or less, it is preferable because the deoxidation proceeds sufficiently and the polymerization time is shortened.
- 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.
- the obtained resin is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and an inert gas atmosphere such as nitrogen at 100 to 350 ° C. in a solid state. It is preferable to perform the treatment for 1 to 30 hours under or under reduced pressure. By setting the particle size of the resin particles to 3 mm or less, sufficient treatment is performed, and problems with physical properties are less likely to occur. 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, anhydrous Examples include trichloroacetic acid, anhydrous monobromoacetic acid, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, etc.
- Acetic acid, 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.
- 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.
- 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.
- metal salt catalysts organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
- the amount of the catalyst added is usually 0.1 ⁇ 10 ⁇ 2 to 100 ⁇ 10 ⁇ 2 wt%, preferably 0.5 ⁇ 10 ⁇ 2 to 50 ⁇ 10 ⁇ 2 wt%, based on the total weight of the resin. More preferably, 1 ⁇ 10 ⁇ 2 to 10 ⁇ 10 ⁇ 2 wt% is used.
- the ratio of the lamellar structure in the resin is preferably 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 lamella structure referred to in the present invention corresponds to a plate-like structure in which chain molecules are formed 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 the 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.
- SEM scanning electron microscope
- TEM transmission electron microscope
- X-ray diffraction 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).
- TEM transmission electron microscope
- a specimen for TEM observation was prepared by cutting out a part of a molded cylindrical sample having a thickness of 6 mm ⁇ 20 mm ⁇ , staining with RuO 4 , and then forming a 0.1 ⁇ m-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 0.4 W / (m ⁇ K) or more, more preferably 1.0 W / (m ⁇ K) or more, and further preferably 2.0 W / (m. K) or more, particularly preferably 5.0 W / (m ⁇ K) or more, most preferably 10 W / (m ⁇ K) or more.
- 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 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.
- the resin composition of the present invention contains an inorganic filler having a thermal conductivity of 1 W / (m ⁇ K) or more.
- the amount of the inorganic filler used is preferably 95: 5 to 20:80, more preferably 90:10 to 30:70, and still more preferably 80:20 to 40 by volume ratio of the resin and the inorganic filler. 40:60, most preferably 70:30 to 40:60.
- the volume ratio of the resin and the inorganic filler (the resin / inorganic filler) to 20/80 or more, the moldability of the resulting resin composition is unlikely to be lowered.
- the resin used in the present invention has excellent thermal conductivity, the resin composition is used even when the amount of the inorganic filler used is as small as 95: 5 to 70:30 in the volume ratio of the resin to the inorganic filler.
- the product has excellent thermal conductivity, and at the same time, the density can be lowered due to the small amount of inorganic filler used.
- the excellent thermal conductivity and low density are advantageous when used as a heat-dissipating / heat-transfer resin material in various situations such as in the electric / electronic industry and automobile fields.
- the thermal conductivity of the inorganic filler alone is preferably 1 W / (m ⁇ K) or more, more preferably 10 W / (m ⁇ K) or more, further preferably 20 W / (m ⁇ K) or more, particularly preferably 30 W / (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.
- ⁇ As for the shape of the inorganic filler various shapes can be applied. For example, particles, fine particles, nanoparticles, aggregated particles, tubes, nanotubes, wires, rods, needles, plates, irregular shapes, rugby balls, hexahedrons, large particles and fine particles are combined Various shapes such as converted composite particles and liquids can be mentioned.
- These inorganic fillers may be natural products or synthesized ones. In the case of a natural product, there are no particular limitations on the production area and the like, which can be selected as appropriate. These inorganic fillers may be used alone or in combination of two or more different shapes, average particle diameters, types, surface treatment agents, and the like.
- the average particle diameter of the inorganic filler is preferably in the range of 0.1 ⁇ m to 300 ⁇ m, more preferably 1 ⁇ m to 150 ⁇ m, and particularly preferably 10 ⁇ m to 60 ⁇ m.
- the average particle size is 0.1 ⁇ m or more, it is preferable because the thermal conductivity of the insulating film tends to be a sufficient value.
- the average particle size is 300 ⁇ m or less, the molding processability of the obtained resin composition is deteriorated. Since it becomes difficult to do, it is preferable. If it is the average particle diameter of this range, 2 or more types of inorganic fillers may be mixed and 2 or more types of inorganic fillers of different average particle diameters may be mixed.
- a metal compound, a conductive carbon compound, or the like is suitably used as the inorganic filler.
- 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.
- the electrical insulating property indicates an electrical resistivity of 1 ⁇ ⁇ cm or more, preferably 10 ⁇ ⁇ cm or more, more preferably 10 5 ⁇ ⁇ cm or more, and further preferably 10 10 ⁇ ⁇ cm or more. It is preferable to use a material having a size of cm or more, most preferably 10 13 ⁇ ⁇ cm or more. There is no particular restriction on the upper limit of the electrical resistivity, generally less 10 18 ⁇ ⁇ 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.
- 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.
- metal oxides such as aluminum oxide, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide
- boron nitride aluminum nitride
- nitride examples thereof include metal nitrides such as silicon, metal carbides such as silicon carbide, metal carbonates such as magnesium carbonate, insulating carbon materials such as diamond, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. These can be used alone or in combination.
- 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.
- a surface treating agent For example, conventionally well-known things, such as a silane coupling agent and a titanate coupling agent, can be used.
- 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.
- 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 10 W / (m ⁇ K).
- 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,
- inorganic fibers such as rock wool, ceramic fibers, and asbestos
- glass fillers such as glass fibers, glass powder, glass cloth, and fused silica.
- epoxy resin epoxy resin, polyolefin resin, bismaleimide resin, polyimide resin, polyether resin, phenol resin, silicone resin, polycarbonate resin, polyamide resin, as long as the effects of the present invention are not lost.
- Any known resin such as a polyester resin, a fluororesin, an acrylic resin, a melamine resin, a urea resin, or a urethane resin may be contained.
- Specific examples of preferred resins include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, liquid crystal polymer, nylon 6, nylon 6,6 and the like.
- the amount of these resins used is usually in the range of 0 to 10,000 parts by weight with respect to 100 parts by weight of the resin in the resin composition of the present invention contained in the resin composition.
- 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.
- any other component depending on the purpose for example, a reinforcing agent, a thickener, a release agent, a coupling agent, a flame retardant, Flameproofing agents, 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.
- the resin in “with respect to 100 parts by weight of the resin” means all resins contained in the resin composition of the present invention.
- the addition of a flame retardant is preferable because it imparts flame retardancy to the resin composition.
- the flame retardancy of the resin composition corresponding to V-0 in the UL-94 standard can be a condition adopted in electric / electronic devices that handle large currents.
- the amount of flame retardant used is preferably 7 to 80 parts by weight, more preferably 10 to 60 parts by weight, and further preferably 12 to 40 parts by weight with respect to 100 parts by weight of the resin.
- the resin in “with respect to 100 parts by weight of the resin” means all resins contained in the resin composition of the present invention.
- Various flame retardants are known, including, for example, various ones described in “Technology and Application of Polymer Flame Retardation” (P149-221) issued by CMC Chemical Co., Ltd. It is not done. Among these flame retardants, phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants can be preferably used.
- phosphorus-based flame retardants examples 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.
- halogen flame retardant examples 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.
- the halogen element content of these halogen flame retardants is preferably 15 to 87%.
- 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.
- the method for producing the resin composition of the present invention is not particularly limited. For example, it can be produced by drying the above-described components, additives and the like and then melt-kneading them in a melt-kneader such as a single-screw or twin-screw extruder. Moreover, when a compounding component is a liquid, it can also manufacture by adding to a melt-kneader on the way using a liquid supply pump etc. 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 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 at the time of molding.
- 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.
- the resin is heated to a smectic liquid crystal state and injected into a mold.
- 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.
- T m is the melting temperature of the resin.
- the number average molecular weight of the resin is preferably 3000 to 40000, more preferably 4000 to 30000, and further preferably 5000 to 20000.
- 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.
- 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.
- it can be suitably used as an exterior material in home appliances and office automation equipment that generate a lot of heat.
- 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.
- 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.
- 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.
- 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 ⁇ m or less. By setting the film thickness to 500 ⁇ m or less, it is preferable because the thermal resistance of the heat conductive film can be reduced and the heat dissipation effect of the heating element can be sufficiently exhibited.
- the thickness of the heat conductive film is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 100 ⁇ m or less.
- the lower limit of the film thickness is not particularly limited, but is usually 10 ⁇ m or more, preferably 30 ⁇ m or more, more preferably 50 ⁇ m 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.
- the dielectric breakdown strength is 10 kV / mm or more, it is preferable from the viewpoint of enabling use in electric / electronic devices that handle a large current.
- the insulating film of the present invention can be combined with other base materials.
- 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.
- LEDs light emitting diodes
- 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.
- 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 in the range of 50 ° C. to 300 ° C. at a second rate of 10 ° C./min. from the peak top of an endothermic peak during heating, it was determined transition point from the solid phase to a liquid crystal phase (T s) and the transition point to the isotropic phase from the liquid crystal phase (T i).
- DSC measurement differential scanning calorimetry
- phase transition enthalpies ( ⁇ H s and ⁇ H i , J / g) were determined from the peak areas of T s and T i , respectively, and used as indexes of resin crystallinity and liquid crystallinity, respectively.
- Test piece molding A resin or a resin composition was dried at 120 ° C. for 4 hours using a hot air dryer, and then a disk-shaped sample having a thickness of 1 mm ⁇ 25 mm ⁇ and a film having a thickness of 80 mm ⁇ 80 mm ⁇ 150 ⁇ m in a press molding machine. Samples were molded. At this time, the press temperature was set to 10 ° C. higher than the isotropic phase transition point (T i ) of the resin.
- T i isotropic phase transition point
- Thermal conductivity Using a disk-shaped sample having a thickness of 1 mm ⁇ 25 mm ⁇ , the thermal conductivity in the thickness direction in the air at room temperature was measured with a laser flash method thermal conductivity measurement device (LFA447 manufactured by NETZSCH).
- Thin wall formability evaluation When a film sample having a size of 80 mm ⁇ 80 mm ⁇ thickness 150 ⁇ m can be molded without cracking, it was evaluated as “ ⁇ ”, and when cracking occurred, it was marked as “X”.
- Flexibility evaluation 80 mm ⁇ 80 mm ⁇ 150 ⁇ m thickness of the film-like sample shown in FIG. 1 is bent at 90 degrees, bent at 120 degrees, broken at 90 degrees, ⁇ , broken at 120 degrees When it did, it was set as x.
- the obtained resin is referred to as (A-1).
- 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..
- the ⁇ H s is 3.3J / g, ⁇ H i was 54J / g.
- the obtained resin is referred to as (A-2).
- the obtained resin is referred to as (A-3).
- the obtained resin is referred to as (A-4).
- the obtained resin is referred to as (A-5).
- a commercially available polycarbonate resin (Taflon A2200, manufactured by Idemitsu Kosan Co., Ltd.) was designated as (A-7).
- B-1 Alumina powder (DAW03 manufactured by Denki Kagaku Co., Ltd., thermal conductivity of 30 W / (m ⁇ K) alone, volume average particle diameter of 3 ⁇ m, electrical insulation)
- B-2 Alumina powder (AS-50 manufactured by Showa Denko KK, thermal conductivity 30 W / (m ⁇ K) alone, volume average particle diameter 9 ⁇ m, electrical insulation)
- B-3 Magnesium oxide powder (RF-50-SC manufactured by Ube Materials Co., Ltd., single body thermal conductivity 42 W / (m ⁇ K), volume average particle diameter 50 ⁇ m, electrical insulation)
- B-4 Aluminum nitride powder (H grade manufactured by Tokuyama Corporation, single body thermal conductivity 170 W / (m ⁇ K), volume average particle diameter 1 ⁇ m, electrical insulation)
- B-5 Aggregated boron nitride powder (SGPS manufactured by Denki Kagaku Co., Ltd., thermal conductivity 60 W / (m ⁇ K) alone
- Resin (A-1) was dried at 120 ° C. for 4 hours using a hot air dryer and dissolved in N-methylpyrrolidone (NMP) at 170 ° C. To this was added the inorganic filler (B-1) so that the volume ratio of the resin (A-1) and the inorganic filler (B-1) was 90:10, and the mixture was stirred for 10 minutes. The obtained varnish was added to stirred toluene to precipitate a resin, and the solid content was filtered and washed with methanol three times. 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 to 7, Comparative Examples 1 to 3 A resin composition was obtained in the same manner as in Example 1 except that the types of resin and inorganic filler used and the amount of inorganic filler used were 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.
- Resin (A-1) was dried at 120 ° C. for 4 hours using a hot air dryer and dissolved in N-methylpyrrolidone (NMP) at 170 ° C. To this was added the inorganic filler (B-1) so that the volume ratio of the resin (A-1) and the inorganic filler (B-2) was 50:50, and the mixture was stirred for 10 minutes. Further, 6 parts by weight of epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX4000) and a catalytic amount of triphenylphosphine were added to 100 parts by weight of the resin, followed by stirring for 1 minute. The resulting varnish was thinly dispensed onto a stainless steel plate and dried at 120 ° C.
- NMP N-methylpyrrolidone
- the obtained resin composition powder was molded into a film sample having a size of 80 mm ⁇ 80 mm ⁇ thickness 150 ⁇ m using a press molding machine, the thermal conductivity in the thickness direction was 3.0 W / (m ⁇ K), Both formability and flexibility were good. Further, after the solder reflow test at 260 ° C. for 3 minutes, the appearance of the molded body was not changed.
- Comparative Example 1 has high crystallinity due to the high order of the molecular structure, and the thermal conductivity of the resin composition is significantly higher than that of Comparative Example 3, but it cannot be molded into a thin wall. Recognize.
- Comparative Example 2 the thin-wall moldability becomes ⁇ by greatly increasing the molecular weight of the resin, but the flexibility is insufficient.
- Example 1 although the crystallinity of the resin used is relatively low, a high thermal conductivity is maintained in order to maintain high liquid crystallinity, and a resin composition having both thin moldability and flexibility can be obtained. .
- Example 2 it can be seen that as the blending amount of the inorganic filler is increased, the thermal conductivity is greatly improved, and a resin composition having both thin moldability and flexibility can be obtained in resins having various molecular structures. .
- the resin composition of the present invention has an effect of increasing thermal conductivity 3 to 4 times as compared with the case of using a general-purpose resin.
- Example 8 an epoxy resin and an effect catalyst were added to the resin composition of the present invention and cured by reacting the carboxyl group at the end of the resin of the present invention with the epoxy group of the epoxy resin, thus having solder reflow resistance. A heat conducting film is obtained.
- Comparative Example 7 shows that the thermal conductivity of the resin composition of Example 8 is high with the same amount of inorganic filler.
- the resin composition of the present invention exhibits excellent thermal conductivity and has both thin moldability and flexibility.
- 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.
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Abstract
Description
下記一般式(2)
-CO-R1-CO- (2)
(式中、R1は主鎖原子数2~18の、分岐を含んでもよい2価の直鎖状置換基を示す。)で表されるユニット(B)5~40モル%、および
下記一般式(3)
-CO-R2-CO- (3)
(式中、R2は主鎖原子数4~20の、分岐を含んでもよく、R1より主鎖原子数の数が多い2価の直鎖状置換基を示す。)
で表されるユニット(C)5~40モル%(ただしユニット(A)、(B)、および(C)の合計を100モル%とする)を含むことを特徴とし、樹脂単体の熱伝導率が0.4W/(m・K)以上である樹脂と、1W/(m・K)以上の熱伝導率を有する無機充填材とを含有することを特徴とする樹脂組成物。
n-m≧4 (4)
5)前記樹脂の数平均分子量が3000~70000である、1)~4)のいずれか一項に記載の樹脂組成物。
下記一般式(2)
-CO-R1-CO- (2)
(式中、R1は主鎖原子数2~18の、分岐を含んでもよい2価の直鎖状置換基を示す。)で表されるユニット(B)5~40モル%、および
下記一般式(3)
-CO-R2-CO- (3)
(式中、R2は主鎖原子数4~20の、分岐を含んでもよく、R1より主鎖原子数の数が多い2価の直鎖状置換基を示す。)
で表されるユニット(C)5~40モル%(ただしユニット(A)、(B)、および(C)の合計を100モル%とする)を含むことを特徴とし、樹脂単体の熱伝導率が0.4W/(m・K)以上である樹脂と、1W/(m・K)以上の熱伝導率を有する無機充填材とを含有することを特徴とする。
下記一般式(2)
-CO-R1-CO- (2)
(式中、R1は主鎖原子数2~18の、分岐を含んでもよい2価の直鎖状置換基を示す。)で表されるユニット(B)5~40モル%、および
下記一般式(3)
-CO-R2-CO- (3)
(式中、R2は主鎖原子数4~20の、分岐を含んでもよく、R1より主鎖原子数の数が多い2価の直鎖状置換基を示す。)
で表されるユニット(C)5~40モル%(ただしユニット(A)、(B)、および(C)の合計を100モル%とする)からなることを特徴とし、樹脂単体の熱伝導率が0.4W/(m・K)以上である樹脂と、1W/(m・K)以上の熱伝導率を有する無機充填材とを含有するものであってもよい。
末端封止剤としては、樹脂の熱伝導性を高める観点から炭素数1~20のモノアミン、または脂肪族モノカルボン酸が好ましく、炭素数1~20の脂肪族モノカルボン酸がより好ましく、炭素数10~20の脂肪族モノカルボン酸がさらに好ましい。脂肪族モノカルボン酸の具体例としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、ラウリン酸、トリデカン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ピバリン酸、イソ酪酸等の脂肪族モノカルボン酸、およびこれらの任意の混合物などを挙げることができる。これらのなかでも、樹脂の熱伝導性を特に高める点から、ミリスチン酸、パルミチン酸、ステアリン酸がより好ましい。モノアミンの具体例としては、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ステアリルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン等の脂肪族モノアミン、およびこれらの任意の混合物などを挙げることができる。これらのなかでも、反応性、高沸点、封止末端の安定性および価格などの点から、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ステアリルアミン、シクロヘキシルアミンがより好ましい。
1-V={(λc-λf)/(λm-λf)}×(λm/λc)1/3 (6)
ここでVは無機充填材の体積含有量(0≦V≦1)、λcは樹脂組成物の熱伝導率、λfは無機充填材の熱伝導率、λmは樹脂単体の熱伝導率である。従って、V、λc、およびλfがわかればλmが計算できる。
-CO-R1-CO- (2)
中のR1は、主鎖原子数2~18の、分岐を含んでもよい2価の直鎖状置換基を表す。ここで主鎖原子数とは主鎖骨格の原子の数であり、例えば-R1-が-(CH2)8-である場合、主鎖原子数は炭素原子の数として8となる。熱伝導率が高くなることから、R1は分岐を含まない直鎖状置換基であることが好ましく、さらには分岐を含まない直鎖の脂肪族炭化水素鎖であることが好ましい。また、R1は飽和でも不飽和でもよいが、飽和脂肪族炭化水素鎖であることが好ましい。R1が不飽和結合を含まない場合には、樹脂は十分な屈曲性を得ることができ、高い熱伝導率を有する樹脂が得られ易くなる。R1は炭素数2~18の直鎖の飽和脂肪族炭化水素鎖であることが好ましく、炭素数4~16の直鎖の飽和脂肪族炭化水素鎖であることがより好ましく、特に炭素数8~14の直鎖の飽和脂肪族炭化水素鎖であることが好ましい。R1の主鎖原子数は偶数であることが好ましい。R1の主鎖原子数が偶数の場合には、微視的な分子の配向性が低下せず、高い熱伝導率を有する樹脂を得られ易くなる。特に耐熱性および熱伝導性の優れる樹脂が得られるという観点から、R1は-(CH2)8-、-(CH2)10-、および-(CH2)12-から選ばれる1種であることが好ましい。
-CO-R2-CO- (3)
中のR2は、主鎖原子数4~20の、分岐を含んでもよく、R1より主鎖原子数の数が多い2価の直鎖状置換基を表し、熱伝導率が高くなることから分岐を含まない直鎖状置換基であることが好ましく、さらには分岐を含まない直鎖の脂肪族炭化水素鎖であることが好ましい。また、R2は飽和でも不飽和でもよいが、飽和脂肪族炭化水素鎖であることが好ましい。R2が不飽和結合を含まない場合には、樹脂は十分な屈曲性を得ることができ、高い熱伝導率を有する樹脂が得られ易くなる。R2は炭素数4~20の直鎖の飽和脂肪族炭化水素鎖であることが好ましく、炭素数8~18の直鎖の飽和脂肪族炭化水素鎖であることがより好ましく、特に炭素数10~18の直鎖の飽和脂肪族炭化水素鎖であることが好ましい。R1の主鎖原子数は偶数であることが好ましい。R1の主鎖原子数が偶数の場合には、微視的な分子の配向性が低下せず、高い熱伝導率を有する樹脂を得られ易くなる。
n-m≧4 (4)
一般式(4)を満たすR2の具体的なものとして化学的安定性、入手性の観点から-(CH2)10-、-(CH2)12-、および-(CH2)18-から選ばれる1種であることが好ましい。
数平均分子量:本発明に用いる樹脂をp-クロロフェノール(東京化成工業製)とトルエンの体積比3:8混合溶媒に0.25重量%濃度となるように溶解して試料を調製した。標準物質はポリスチレンとし、同様の試料溶液を調製した。高温GPC(Viscotek社製 350 HT-GPC System)にてカラム温度:80℃、流速1.00mL/minの条件で測定した。検出器としては、示差屈折計(RI)を使用した。
<樹脂>
[製造例1]
還流冷却器、温度計、窒素導入管及び攪拌棒を備え付けた密閉型反応器に、4,4’-ジヒドロキシビフェニル、セバシン酸、テトラデカン二酸をそれぞれ48:39:13モル%の割合で仕込み、4,4’-ジヒドロキシビフェニルに対し2.1当量の無水酢酸および触媒量の酢酸ナトリウムを加えた。常圧、窒素雰囲気下で145℃にて反応させ均一な溶液を得た後、酢酸を留去しながら2℃/minで260℃まで昇温し、260℃で1時間撹拌した。引き続きその温度を保ったまま、約60分かけて10Torrまで減圧した後、減圧状態を維持した。減圧開始から2時間後、窒素ガスで常圧に戻し、生成したポリマーを取り出した。得られた樹脂の数平均分子量は14,000、樹脂単体の熱伝導率は0.46W/(m・K)、末端カルボキシル基は99%以上、Tsは121℃、Tiは251℃であった。またΔHsは3.8J/g、ΔHiは48J/gであった。得られた樹脂を(A-1)とする。
原料として4,4’-ジヒドロキシビフェニル、テトラデカン二酸、エイコサン二酸をそれぞれ48:26:26モル%の割合で仕込んだ以外は製造例1と同様にして樹脂を得た。得られた樹脂の数平均分子量は16,000、樹脂単体の熱伝導率は0.43W/(m・K)、Tsは110℃、Tiは201℃であった。またΔHsは3.3J/g、ΔHiは54J/gであった。得られた樹脂を(A-2)とする。
還流冷却器、温度計、窒素導入管及び攪拌棒を備え付けた密閉型反応器に、4,4’-ジヒドロキシビフェニル、セバシン酸、テトラデカン二酸をそれぞれ50:37.5:12.5モル%の割合で仕込み、4,4’-ジヒドロキシビフェニルに対し2.1当量の無水酢酸および触媒量の1-メチルイミダゾールを加えた。常圧、窒素雰囲気下で145℃にて反応させ均一な溶液を得た後、酢酸を留去しながら2℃/minで260℃まで昇温し、260℃で1時間撹拌した。引き続きその温度を保ったまま、約60分かけて10Torrまで減圧した後、減圧状態を維持した。減圧開始から2時間後、窒素ガスで常圧に戻し、生成したポリマーを取り出した。得られた樹脂の数平均分子量は73,000、樹脂単体の熱伝導率は0.45W/(m・K)、Tsは121℃、Tiは253℃であった。またΔHsは3.7J/g、ΔHiは49J/gであった。得られた樹脂を(A-3)とする。
還流冷却器、温度計、窒素導入管及び攪拌棒を備え付けた密閉型反応器に、4,4’-ジヒドロキシビフェニル、セバシン酸、ドデカン二酸をそれぞれ50:37.5:12.5モル%の割合で仕込み、4,4’-ジヒドロキシビフェニルに対し2.1当量の無水酢酸および触媒量の1-メチルイミダゾールを加えた。常圧、窒素雰囲気下で145℃にて反応させ均一な溶液を得た後、酢酸を留去しながら2℃/minで260℃まで昇温し、260℃で1時間撹拌した。引き続きその温度を保ったまま、約60分かけて10Torrまで減圧した後、減圧状態を維持した。減圧開始から2時間後、窒素ガスで常圧に戻し、生成したポリマーを取り出した。得られた樹脂の数平均分子量は56,000、樹脂単体の熱伝導率は0.45W/(m・K)、Tsは190℃、Tiは272℃であった。またΔHsは17J/g、ΔHiは48J/gであった。得られた樹脂を(A-4)とする。
還流冷却器、温度計、窒素導入管及び攪拌棒を備え付けた密閉型反応器に、4,4’-ジヒドロキシビフェニルおよびドデカン二酸をそれぞれ48:52モル%の割合で仕込み、4,4’-ジヒドロキシビフェニルに対し2.1当量の無水酢酸および触媒量の1-メチルイミダゾールを加えた。常圧、窒素雰囲気下で145℃にて反応させ均一な溶液を得た後、酢酸を留去しながら2℃/minで270℃まで昇温し、270℃で1時間撹拌した。引き続きその温度を保ったまま、約60分かけて10Torrまで減圧した後、減圧状態を維持した。減圧開始から2時間後、窒素ガスで常圧に戻し、生成したポリマーを取り出した。得られた樹脂の数平均分子量は11,000、樹脂単体の熱伝導率は0.52W/(m・K)、Tsは203℃、Tiは253℃であった。またΔHsは24J/g、ΔHiは47J/gであった。得られた樹脂を(A-5)とする。
製造例5の4,4’-ジヒドロキシビフェニルおよびドデカン二酸の仕込み比率をそれぞれ50:50モル%の割合で仕込んだ以外は同様にして樹脂を得た。得られた樹脂の数平均分子量は60,000、樹脂単体の熱伝導率は0.42W/(m・K)、Tsは203℃、Tiは253℃であった。またΔHsは29J/g、ΔHiは55J/gであった。得られた樹脂を(A-6)とする。
(B-1)アルミナ粉末(電気化学社製DAW03、単体での熱伝導率30W/(m・K)、体積平均粒子径3μm、電気絶縁性)
(B-2)アルミナ粉末(昭和電工社製AS-50、単体での熱伝導率30W/(m・K)、体積平均粒子径9μm、電気絶縁性)
(B-3)酸化マグネシウム粉末(宇部マテリアルズ社製RF-50-SC、単体での熱伝導率42W/(m・K)、体積平均粒子径50μm、電気絶縁性)
(B-4)窒化アルミニウム粉末(トクヤマ社製Hグレード、単体での熱伝導率170W/(m・K)、体積平均粒子径1μm、電気絶縁性)
(B-5)凝集窒化ホウ素粉末(電気化学社製SGPS、単体での熱伝導率60W/(m・K)、体積平均粒子径12μm、電気絶縁性)
(B-6)球状黒鉛粉末(中越黒鉛社製CGC-100、単体での熱伝導率100W/(m・K)以上、体積平均粒子径90μm、導電性)。
樹脂(A-1)を、熱風乾燥機を用いて120℃で4時間乾燥し、N-メチルピロリドン(NMP)に170℃で溶解した。これに無機充填材(B-1)を樹脂(A-1)と無機充填材(B-1)の体積比率が90:10となるよう添加し、10分撹拌した。得られたワニスを撹拌したトルエン中に添加し、樹脂を析出させ、固形分をろ過してメタノールで3回洗浄したものを取り出した。熱風乾燥機を用いて120℃で4時間乾燥した樹脂組成物を、プレス成形機を用いて各形状に成形し、厚み方向の熱伝導率および薄肉成形性と柔軟性の評価を実施した。評価結果を表2に示す。
使用する樹脂および無機充填剤の種類、並びに使用する無機充填材の量を表2に示すように変えた以外は実施例1と同様にして、樹脂組成物を得た。樹脂の量は100vol%から表2の無機充填材の量を差し引いた値である。得られた樹脂組成物を、プレス成形機を用いて各形状に成形し、厚み方向の熱伝導率および薄肉成形性と柔軟性の評価を実施した。評価結果を表2に示す。
樹脂(A-1)を、熱風乾燥機を用いて120℃で4時間乾燥し、N-メチルピロリドン(NMP)に170℃で溶解した。これに無機充填材(B-1)を樹脂(A-1)と無機充填材(B-2)の体積比率が50:50となるよう添加し10分撹拌した。さらにエポキシ樹脂(三菱化学社製、YX4000)を樹脂100重量部に対して6重量部、トリフェニルホスフィンを触媒量添加し1分撹拌した。得られたワニスをステンレス板上に薄く払出し、熱風乾燥機を用いて120℃で4時間乾燥して樹脂組成物粉末を得た。得られた樹脂組成物粉末を、プレス成形機を用いて80mm×80mm×厚み150μmの膜状サンプルに成形したところ、厚み方向の熱伝導率は3.0W/(m・K)であり、薄肉成形性と柔軟性はともに○であった。また260℃、3分のハンダリフロー試験後、成形体外観に変化がなかった。
Claims (9)
- 主鎖の構造が下記一般式(1)
下記一般式(2)
-CO-R1-CO- (2)
(式中、R1は主鎖原子数2~18の、分岐を含んでもよい2価の直鎖状置換基を示す。)で表されるユニット(B)5~40モル%、および
下記一般式(3)
-CO-R2-CO- (3)
(式中、R2は主鎖原子数4~20の、分岐を含んでもよく、R1より主鎖原子数の数が多い2価の直鎖状置換基を示す。)
で表されるユニット(C)5~40モル%(ただしユニット(A)、(B)、および(C)の合計を100モル%とする)を含むことを特徴とし、樹脂単体の熱伝導率が0.4W/(m・K)以上である樹脂と、1W/(m・K)以上の熱伝導率を有する無機充填材とを含有することを特徴とする樹脂組成物。 - 前記樹脂のR1およびR2に相当する部分が直鎖の飽和脂肪族炭化水素鎖である、請求項1に記載の樹脂組成物。
- 前記樹脂のR1およびR2に相当する部分の主鎖原子数が偶数である、請求項1または2のいずれかに記載の樹脂組成物。
- 前記樹脂のR1およびR2に相当する部分の主鎖原子数mおよびnが下記一般式(4)を満たす、請求項1~3のいずれか一項に記載の樹脂組成物。
n-m≧4 (4) - 前記樹脂の数平均分子量が3000~70000である、請求項1~4のいずれか一項に記載の樹脂組成物。
- 前記無機充填材が、窒化ホウ素、窒化アルミニウム、窒化ケイ素、酸化アルミニウム、酸化マグネシウム、水酸化アルミニウム、水酸化マグネシウム、およびダイヤモンドからなる群より選ばれる1種以上の電気絶縁性高熱伝導性無機化合物であることを特徴とする、請求項1~5のいずれか一項に記載の樹脂組成物。
- 前記無機充填材が、グラファイト、カーボンナノチューブ、導電性金属粉、軟磁性フェライト、炭素繊維、導電性金属繊維、および酸化亜鉛からなる群より選ばれる1種以上の導電性高熱伝導性無機化合物であることを特徴とする、請求項1~5のいずれか一項に記載の樹脂組成物。
- 請求項1~7のいずれか一項に記載の樹脂組成物を含有する放熱・伝熱用樹脂材料。
- 請求項1~7のいずれか一項に記載の樹脂組成物を含有する熱伝導膜。
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CN105814137B (zh) | 2018-03-16 |
EP3078710A4 (en) | 2017-07-19 |
US20160304762A1 (en) | 2016-10-20 |
EP3078710A1 (en) | 2016-10-12 |
CN105814137A (zh) | 2016-07-27 |
US9809735B2 (en) | 2017-11-07 |
JPWO2015083523A1 (ja) | 2017-03-16 |
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