JP4390720B2 - Thermally conductive composition and thermally conductive film - Google Patents

Description

The present invention relates to a heat conductive composition containing an organic polymer and a heat conductive inorganic filler, and a film formed using the composition.

In recent years, with the improvement in performance of electronic equipment, semiconductor elements used for these devices tend to have higher power consumption. Therefore, it is required to efficiently dissipate heat generated from electronic components.

Conventionally, in order to efficiently dissipate heat from a semiconductor package or semiconductor element, a heat dissipating mechanism such as bonding a heat spreader to the semiconductor element via a highly heat conductive adhesive sheet or the like is provided in the semiconductor package, or the semiconductor A heat sink such as a heat sink or a heat radiating fin is pressure-bonded via a package and a resin sheet having thermal conductivity.

As such a highly heat conductive composition interposed between a semiconductor package or a semiconductor element and a heat radiator, a material such as silicone rubber or acrylic resin blended with a heat conductive inorganic filler is used. ing. (For example, see Patent Document 1 and Patent Document 2.)
However, there is a concern that silicone rubber will cause defects in the contact parts of electronic components due to the generation of low molecular weight siloxane, and acrylic resin has low heat resistance and moisture resistance. There was room for contrivance to have high reliability even in the use of the period.

As a method for solving these problems, a heat conductive film forming liquid containing an emulsion of electrodepositable particles selected from polyimide polymer, epoxy polymer, fluorine polymer, and the like and heat conductive fine particles is proposed. Has been. (For example, refer to Patent Document 3.)
However, since this liquid for forming a heat conductive film is an emulsion, its moisture resistance is low, and when it is formed into a thin film, the electric insulation tends to be deteriorated. Further, since attention has not been paid to achievement of heat resistance and moisture resistance, no disclosure of a fluorinated aromatic polymer capable of obtaining a heat-resistant and moisture-resistant film as a fluorinated polymer has been made.

Also disclosed is a heat-resistant and heat-conductive packing made by filling a polyether ether ketone resin having excellent heat resistance with a heat-conductive filler as a heat radiator used to release heat of the heat-generating electronic component to the outside. Yes. (For example, refer to Patent Document 4.) However, there is room for improvement to further improve the electrical insulation, moisture absorption, and the like of the packing, and to make the packing more suitable as a heat radiator that releases heat from the heat-generating electronic component. .

JP 54-61253 A specification Japanese Patent Laid-Open No. 58-40703 Japanese Patent Application Laid-Open No. 2002-161244 Japanese Patent Laid-Open No. 7-157469

Therefore, in the present invention, the thermal conductivity composition is excellent in dispersibility between the organic polymer and the thermally conductive inorganic filler, exhibits a high thermal conductivity when formed into a film, and further has excellent heat resistance, moisture resistance, and the like. The issue is to provide goods.

In order to solve the above-described problems, the thermally conductive composition according to the present invention is characterized by containing an inorganic filler having a thermal conductivity of 20 W / m · K or more together with a fluorinated aromatic polymer. By using a fluorinated aromatic polymer as the organic polymer, the fluorinated aromatic polymer is excellent in dispersibility of the thermally conductive inorganic filler, and therefore, a film having high thermal conductivity can be obtained.

Moreover, since the intensity | strength of the film obtained from the said heat conductive composition improves that the shape of the said heat conductive inorganic filler is spherical or scale-like particle | grains is a preferable embodiment.

Furthermore, the present invention includes a film using the above-described heat conductive composition.

Since the heat conductive composition of this invention consists of the above-mentioned structure, it is excellent in the dispersibility of an organic polymer and a heat conductive inorganic filler, and can mix | blend this inorganic filler highly. Therefore, the film obtained from the heat conductive composition of the present invention has high heat conductivity. Furthermore, since the fluorinated aromatic polymer has high heat resistance and moisture resistance, the film obtained from the heat conductive composition of the present invention has both high heat resistance and moisture resistance as a thin film, and as a long-term insulating material. It becomes a reliable material.

As a result of intensive studies on a thermally conductive composition in which a thermally conductive inorganic filler is dispersed in an organic polymer, the present inventors have obtained a fluorinated aromatic polymer, which is an essential composition of a fluorinated aromatic polymer. It has been found that a composition containing an inorganic filler having a thermal conductivity of 20 W / m · K or more together with a group polymer becomes a composition exhibiting high thermal conductivity. In addition, the film obtained from the thermally conductive composition exhibits high thermal conductivity, and further, since the fluorinated aromatic polymer has high heat resistance and moisture resistance, it has high heat resistance and moisture resistance. I came up with the idea that the above-mentioned problem can be solved brilliantly.

The thermally conductive composition of the present invention contains a fluorinated aromatic polymer and an inorganic filler having a thermal conductivity of 20 W / m · K or more. In the heat conductive composition of this invention, as long as the effect mentioned above is exhibited, each content of a fluorinated aromatic polymer and an inorganic filler, and both content ratio are not restrict | limited.

The present invention is also a composition essentially comprising a fluorinated aromatic polymer, and 30 mass of an inorganic filler having a thermal conductivity of 20 W / m · K or more with respect to 100 mass parts of the fluorinated aromatic polymer. It is also a composition containing at least parts. When the fluorinated aromatic polymer and the inorganic filler having a thermal conductivity of 20 W / m · K or more are contained in such a ratio, the resulting composition has thermal conductivity, heat resistance, and It becomes a composition excellent in various properties such as moisture resistance, and can be used in various forms such as a film. Such a film is also one aspect of the present invention.
As long as the ratio of the content of the fluorinated aromatic polymer and the inorganic filler is as described above, the content of each component in the composition is not particularly limited.

In the composition, the content ratio of the fluorinated aromatic polymer and the inorganic filler is 30 parts by mass or more of the inorganic filler with respect to 100 parts by mass of the fluorinated aromatic polymer. If content of this inorganic filler is less than 30 mass parts, there exists a possibility that the heat conductivity of the film which consists of this composition may become low. The minimum with more preferable content of this inorganic filler is 40 mass parts or more with respect to 100 mass parts of a fluorinated aromatic polymer, and 50 mass parts or more is the most preferable. Moreover, the upper limit with preferable content of an inorganic filler is 2,000 mass parts or less with respect to 100 mass parts of a fluorinated aromatic polymer, and it is still more preferable that it is 1,500 mass parts or less.

Thermal conductivity with respect to 100 parts by mass of the fluorinated aromatic polymer of the present invention and an inorganic filler having a thermal conductivity of 20 W / m · K or more, and 100 parts by mass of the fluorinated aromatic polymer A composition containing 30 parts by mass or more of an inorganic filler having a weight of 20 W / m · K or more (hereinafter, both are referred to as the composition of the present invention) contains a fluorinated aromatic polymer as an organic polymer. is there. Since the fluorinated aromatic polymer generally has a glass transition temperature higher than that of a fluorinated aliphatic polymer having a glass transition temperature of 130 ° C. or lower, the composition of the present invention contains a fluorinated aromatic polymer. This results in excellent heat resistance compared to a composition containing a fluorinated aliphatic polymer or the like. In addition, since the fluorinated aromatic polymer is superior in volume resistivity and water absorption compared to an aromatic polymer having no fluorine group, the composition of the present invention is an aromatic polymer having no fluorine group. It becomes a composition excellent in insulation and hygroscopicity compared with the thing containing this.

The fluorinated aromatic polymer in the present invention preferably has a glass transition temperature of 150 ° C. or higher. If the glass transition temperature is less than 150 ° C., the heat resistance of the film obtained from the composition of the present invention may be lowered. The glass transition temperature of the fluorinated aromatic polymer is more preferably in the range of 150 ° C to 400 ° C, and most preferably in the range of 170 ° C to 300 ° C. The glass transition temperature can be measured, for example, using DSC (trade name “DSC6200” manufactured by Seiko Denshi Kogyo Co., Ltd.) under a nitrogen atmosphere and a temperature increase rate of 20 ° C./min.

The surface resistance value of the fluorinated aromatic polymer of the present invention is preferably 1.0 × 10 ¹⁵ Ω / cm ² or more. If the surface resistance value is less than 1.0 × 10 ¹⁵ Ω / cm ² , the electrical insulation of the film obtained from the composition of the present invention may be lowered. The surface resistance value of the fluorinated aromatic polymer is more preferably in the range of 1.0 × 10 ¹⁷ Ω / cm ² or more. The surface resistance value can be measured under the condition of a measurement voltage of 500 V using, for example, a resistance value measurement device (manufactured by Hewlett Packard, trade name “High Resistance Meter 4329A & Resistivity Cell 16008A”).

The average molecular weight of the fluorinated aromatic polymer of the present invention is preferably in the range of 5,000 to 500,000 in terms of number average molecular weight (Mn). If the number average molecular weight is less than 5,000, the heat resistance of the film obtained from the composition of the present invention may be lowered, and if the number average molecular weight exceeds 500,000, the viscosity of the composition becomes high and workability is improved. May decrease. The number average molecular weight (Mn) is more preferably in the range of 10,000 to 200,000, and most preferably in the range of 10,000 to 100,000. The number average molecular weight is, for example, G-5000HXL + GMHXL-L as a column, tetrahydrofuran (THF) as a developing solvent, using a gel permeation chromatograph analyzer (GPC) (trade name “HLC-8120GPC” manufactured by Tosoh Corporation), Using standard polystyrene as a standard, measurement can be performed under conditions of a flow rate of 1 mL / min.

The fluorinated aromatic polymer of the present invention has at least one selected from the group consisting of an aromatic ring having at least one fluorine group and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. Examples include a polymer composed of a repeating unit containing one bond, specifically, for example, a polyimide having a fluorine atom, polyether, polyetherimide, polyetherketone, polyethersulfone, polyamide ether, polyamide, Examples thereof include polyether nitrile and polyester.
The composition of the present invention may contain one of these fluorinated aromatic polymers, or may contain two or more.

The fluorinated aromatic polymer of the present invention is preferably a polymer having an aromatic ring having at least one fluorine group and a repeating unit containing an ether bond as essential sites among the above-described ones. A polyaryl ether having a fluorine atom containing a repeating unit represented by the general formula (1) or (2) is more preferable. If the fluorinated aromatic polymer has such a structure, it is considered that the interaction with the inorganic filler is moderately suppressed, and a phenomenon that hinders the preparation of the composition of the present invention, for example, a significant increase. Viscosity, gelation, loss of fluidity, aggregation and the like are reduced. Therefore, a composition in which more inorganic fillers are blended can be created, and not only can exhibit higher thermal conductivity as a thermally conductive sheet, but also can reduce the viscosity, The heat conductive sheet can be easily formed. The repeating units represented by the general formula (1) or (2) may be the same or different, and may be in any form such as a block form or a random form.

In the general formula (1), R ¹ represents a divalent organic chain having an aromatic ring having ¹ to 150 carbon atoms. Z represents a divalent chain or a direct bond. x and y are integers of 0 or more, satisfy x + y = 1 to 8, and represent the number of fluorine atoms that are the same or different and are bonded to the aromatic ring. n represents the degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.
In the general formula (2), R ² is an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylamino group having 1 to 12 carbon atoms, and carbon. An alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms is represented. R ³ represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms bonded to the aromatic ring and is 1 or 2. n represents the degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.

In the general formula (1), x + y is preferably in the range of 2-8, and more preferably in the range of 4-8. In addition, the position where the ether structure portion (—O—R ¹ —O—) is bonded to the aromatic ring is preferably bonded to the para position with respect to Z.

In the above general formulas (1) and (2), R ¹ and R ³ are divalent organic chains, but any one of the following structural formula groups (3) or a combination thereof: A chain is preferred.

(Wherein Y ^{1 to} Y ⁴ are the same or different and each represents a hydrogen group or a substituent, and the substituent is a halogen atom, an optionally substituted alkyl group, an alkoxy group, an alkylamino group, Represents an alkylthio group, an aryl group, an aryloxy group, an arylamino group, or an arylthio group.)
More preferable specific examples of R ¹ and R ³ include organic chains represented by the following structural formula group (4).

In the general formula (1), Z represents a divalent chain or a direct bond. The divalent chain is preferably, for example, a chain represented by the following structural formula group (5) (structural formulas (5-1) to (5-13)).

(In the formula, X is a divalent organic chain having 1 to 50 carbon atoms.)
Examples of X include an organic chain represented by the structural formula group (4), and among them, a diphenyl ether chain, a bisphenol A chain, a bisphenol F chain, and a fluorene chain are preferable.

In R ² in the general formula (2), as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group Neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group and the like are preferable.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group. , Dodecyloxy group, furfuryloxy group, allyloxy group and the like are preferable.
As the alkylamino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, propylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group and the like are preferable.
As the alkylthio group, methylthio group, ethylthio group, propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, iso-propylthio group and the like are preferable.

As the aryl group, phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, A biphenylyl group, a benzhydryl group, a trityl group, a pyrenyl group, and the like are preferable.
Examples of the aryloxy group include groups derived from a phenoxy group, a benzyloxy group, hydroxybenzoic acid and esters thereof (for example, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester, and phenyl ester). A naphthoxy group, o-, m- or p-methylphenoxy group, o-, m- or p-phenylphenoxy group, phenylethynylphenoxy group, a group derived from cresotinic acid and esters thereof, and the like are preferable.
The arylamino group includes an anilino group, o-, m- or p-toluidino group, 1,2- or 1,3-xylidino group, o-, m- or p-methoxyanilino group, anthranilic acid and its Groups derived from esters are preferred.
The arylthio group is preferably a phenylthio group, a phenylmethanethio group, an o-, m- or p-tolylthio group, a group derived from thiosalicylic acid and esters thereof, and the like.
Of these, R ² is preferably an alkoxy group, aryloxy group, arylthio group or arylamino group which may have a substituent. However, R ² may or may not contain a double bond or a triple bond.

Examples of the substituent for R ² in the general formula (2) include an alkyl group having 1 to 12 carbon atoms as described above; a halogen atom such as fluorine, chlorine, bromine and iodine; a cyano group, a nitro group, and a carboxyester group. Etc. are suitable. Moreover, hydrogen of these substituents may or may not be halogenated. Among these, preferably, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and a carboxy ester, which may or may not be halogenated. It is a group.

As a method for synthesizing the fluorinated aromatic polymer of the present invention, a general polymerization reaction may be used, and examples thereof include condensation polymerization, addition polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. What is necessary is just to set reaction conditions, such as reaction temperature and reaction time in the case of the said polymerization reaction, suitably. Moreover, it is preferable to perform the said polymerization reaction in nitrogen atmosphere.

For example, when synthesizing a polyaryl ether having a fluorine atom containing a repeating unit represented by the general formula (1), Z is (5-6) in the structural formula group (5). Furthermore, when obtaining a polyaryl ether having a fluorine atom in which X is a diphenyl ether chain, 4,4′-bis (2,3,4,5,6-pentafluoro in an organic solvent in the presence of a basic compound. And a method of heating benzoyl) diphenyl ether (hereinafter referred to as “BPDE”) and a divalent phenol compound.
In addition, when Z is (5-11) in the above structural formula group (5) and X is a polyaryl ether having a fluorine atom which is a diphenyl ether chain, the presence of a basic compound in an organic solvent Below, a method of heating 4,4′-bis (2,3,4,5,6-pentafluorobenzoyloxy) diphenyl ether (hereinafter referred to as “BPDES”) and a divalent phenol compound may be mentioned.

For example, when synthesizing a polyaryl ether having a fluorine atom containing a repeating unit represented by the general formula (2), when R ² is a phenoxy group, in an organic solvent in the presence of a basic compound, Examples thereof include a method of heating 4-phenoxy-2,3,5,6-tetrafluorobenzonitrile (hereinafter referred to as “PTFBN”) and a divalent phenol compound.
The method for producing BPDE is not particularly limited, and can be obtained by the method described in JP-A-2001-64226, for example.
The method for producing BPDES is not particularly limited, and can be obtained, for example, by reacting pentafluorobenzoyl chloride with 4,4′-dihydroxydiphenyl ether.
Although the manufacturing method of PTFBN is not particularly limited, for example, it can be obtained by the method described in JP-A No. 2002-12661.

The reaction temperature in the above synthesis method is preferably in the range of 0 ° C to 150 ° C, and more preferably in the range of 10 ° C to 120 ° C.

Examples of the organic solvent used in the above synthesis method include nitriles such as acetonitrile and benzonitrile; ketones such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and cyclohexanone; chloroform, methylene chloride, four Halogenated hydrocarbons such as carbon chloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; hydrocarbons such as pentane, hexane, cyclohexane and heptane; diethyl ether and isopropyl ether , Tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether, tert-butyl ether, and other ethers; methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate Esters such as isopropyl acetate; N- methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), can be used dimethylacetamide (DMAc) and the like. These may be used alone or in combination of two or more. Among these, acetonitrile, acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and dimethylacetamide (DMAc) are preferable. . These solvents may be used alone or in combination of two or more.

Examples of the basic compound used in the above synthesis method include potassium carbonate, lithium carbonate, potassium hydroxide, triethylamine and the like. These basic compounds may be used alone or in combination of two or more.

In the above synthesis method, examples of the divalent phenol compound include 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (hereinafter referred to as “6FBA”). ), Bisphenol A (hereinafter referred to as “BA”), 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter referred to as “HF”), bisphenol F, hydroquinone, resorcinol and the like.

The amount of the divalent phenol compound used is preferably in the range of 0.8 to 1.2 mol, more preferably in the range of 0.9 to 1.1 mol, with respect to 1 mol of the fluorinated aromatic compound. .

In the above synthesis method, after completion of the reaction, the solvent is removed from the reaction solution, and the distillate is washed as necessary to obtain a fluorinated aromatic polymer. It can also be obtained by adding the reaction solution to a solvent with low solubility of the fluorinated aromatic polymer to precipitate the polymer and separating the precipitate by filtration.

The thermally conductive inorganic filler in the present invention is an inorganic filler having a thermal conductivity of 20 W / m · K or more. When the thermal conductivity of the inorganic filler is less than 20 W / m · K, the thermal conductivity of the film obtained from the composition is low. The thermal conductivity of the inorganic filler is obtained by preparing a plate-like molded article by cooling or molding the inorganic filler after sintering or melting, and measuring the thermal conductivity by a hot disk method (manufactured by Kyoto Electronics Industry Co., Ltd.) It can be determined by measuring using product number TPA-501). The thermal conductivity is more preferably 30 W / m · K or more.

As the thermally conductive inorganic filler in the present invention, inorganic oxides, inorganic nitrides, and the like are preferable because of excellent dispersibility with the fluorinated aromatic polymer.

Examples of the inorganic oxide and inorganic nitride include zinc oxide, aluminum oxide, magnesium oxide, beryllium oxide, calcium oxide, zirconium oxide, aluminum nitride, boron nitride, and silicon nitride. Among these, aluminum oxide, magnesium oxide, aluminum nitride, and boron nitride are preferable. By using these compounds as the inorganic filler, the effects of the present invention are sufficiently exhibited. These inorganic fillers may be used alone or in combination of two or more.

Examples of the shape of the thermally conductive inorganic filler in the present invention include a spherical shape, a fibrous shape, a scale shape, a conical shape, a crushed shape, a planar shape, and an indefinite shape. Among these, spherical or scale-like particles are preferable.

The average particle size of the inorganic filler is appropriately selected in consideration of the thickness of the film, but is preferably in the range of 0.01 to 100 μm, and preferably in the range of 0.1 to 50 μm. More preferably, the range of 0.5 to 30 μm is most preferable. The specific surface area per volume of the inorganic filler is ^preferably in the range of 0.1m ² / g~20m 2 / ^g, more preferably in the range of ^{0.5m 2 / g~18m 2 / g,} 0 .7m the range of ² / ^{g~15m 2} / g being most preferred.

The composition of the present invention preferably contains a solvent for the purpose of improving film formability and adjusting the viscosity.

Examples of the solvent include aromatic solvents such as toluene, xylene, nitrobenzene, and benzonitrile, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and isobutyl ketone, ethyl acetate, isopropyl acetate, and acetic acid. Examples include ester solvents such as butyl, ethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, methanol, ethanol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and acetonitrile. These solvents may be used alone or as a mixture of two or more for the purpose of adjusting the stability, drying property and film properties of the composition.

The amount of the solvent is preferably in the range of 1% by mass to 80% by mass in the composition. When the blending amount of the solvent is less than 1% by mass, the viscosity of the composition is not sufficiently reduced and the film formability may be lowered. Moreover, when it exceeds 80 mass%, there exists a possibility that a solvent may remain in the obtained film and thermal conductivity may fall. The blending amount of the solvent is more preferably in the range of 2% by mass to 75% by mass, and most preferably in the range of 3% by mass to 70% by mass.

The composition of the present invention may contain other compounds and auxiliary materials as necessary. Examples of the other compounds and auxiliary materials include polyamide resins, polyamideimide resins, epoxy resins, phenol resins, fluororesins, acrylic resins, polycarbonate resins, polyester resins and the like, silica, aluminum hydroxide, glass, graphite and the like. Fillers, silane coupling agents, titanate coupling agents, flame retardants, antioxidants, plasticizers, leveling agents, repellency inhibitors, dispersants and the like.

In the composition of the present invention, the compounding amount of the above-mentioned other compounds and auxiliary materials may be in a range that does not impair the effects of the invention, and the total amount of the fluorinated aromatic polymer and the inorganic filler in the composition is 100 mass. The amount is preferably within the range of 0.001 to 500 parts by mass with respect to parts.

Examples of a method for forming a film obtained using the composition of the present invention include casting, dipping coating, spin coating, roll coating, spray coating, bar coating of the composition on a film, a substrate, an element, a metal foil or the like. After coating by a method such as coating, screen printing, flexographic printing or the like to form a coating film, the solvent is dried to form a thin layer.
The film obtained using the composition of the present invention may be peeled off from the film or substrate and used alone or may be used without peeling. Further, in order to increase the strength of the film, a cloth-like reinforcing material such as a plastic film, a metal foil, a glass cloth, a cloth made of polymer fibers, or a metal mesh may be used on or inside the film.

The thickness of the film obtained using the composition of the present invention is preferably in the range of 0.1 μm to 0.5 mm. If the thickness of the film is less than 0.1 μm, the handleability of the film may be deteriorated, and if it exceeds 0.5 mm, the heat dissipation characteristics may be deteriorated when used for heat dissipation applications of semiconductor elements.

The thermal conductivity of the film of the present invention is preferably in the range of 0.5 W / m · K or more. When the thermal conductivity is less than 0.5 W / m · K, the heat dissipation characteristics may be deteriorated when used for heat dissipation of semiconductor elements. The thermal conductivity of the film is more preferably in the range of 1.0 to 30 W / m · K, and most preferably in the range of 3.0 to 10 W / m · K. The thermal conductivity is measured by, for example, a hot disk method thermophysical property measuring apparatus (trade name “TPA-501” manufactured by Kyoto Electronics Industry Co., Ltd.) or a rapid thermal conductivity meter (trade name “QTM-500” manufactured by Kyoto Electronics Industry Co., Ltd.). Can be measured.

As the heat resistance characteristics of the film of the present invention, the weight loss rate up to 300 ° C. in a thermal analyzer (TG-DTA analysis) is preferably 1.0% by mass or less. Moreover, as a moisture absorption characteristic, it is preferable that the moisture absorption rate in a pressure cooker test (PCT test, 135 degreeC, 3 atmospheres, 2 hours) is 0.3 mass% or less. The TG-DTA analysis is performed, for example, using a thermal analyzer (TG-DTA) (manufactured by Shimadzu Corporation, trade name “Shimadzu differential thermo-thermogravimetric measuring device”) at a heating rate of 10 ° C./min in a nitrogen atmosphere. This can be done by measuring the weight loss from room temperature to 300 ° C. In addition, the PCT test, for example, using a pressure cooker (trade name “PC-242HS pressure cooker” manufactured by HIRAYAMA Co., Ltd.) using a pressure cooker, 135 ° C., 3 atmospheres, 2 hours, This can be done by measuring the moisture absorption rate.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. Unless otherwise specified, “%” indicates “mass%” and “part” indicates “mass part”.

Synthesis example 1
In a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirrer, 16.74 parts of BPDE (4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether), 6FBA (2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane) 10.14 parts, potassium carbonate 4.34 parts, and N-methyl-2- 90 parts of pyrrolidone was charged. The mixture was heated to 60 ° C. and reacted for 5 hours. After completion of the reaction, the reaction solution was poured into a 1% aqueous acetic acid solution with vigorous stirring with a blender. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated aromatic polymer (1). The polymer had a glass transition temperature (Tg) of 193 ° C., a number average molecular weight (Mn) of 72,370, and a surface resistance value of 1.0 × 10 ¹⁸ Ω / cm ² or more.

Synthesis example 2
A reactor similar to Synthesis Example 1 was charged with 16.74 parts of BPDE, 10.5 parts of HF (9,9-bis (4-hydroxyphenyl) fluorene), 4.34 parts of potassium carbonate, and 90 parts of dimethylacetamide. . The mixture was warmed to 80 ° C. and reacted for 8 hours. After completion of the reaction, a fluorinated aromatic polymer (2) was obtained in the same manner as in Synthesis Example 1. The glass transition temperature (Tg) of the polymer was 242 ° C., the number average molecular weight (Mn) was 70,770, and the surface resistance value was 1.0 × 10 ¹⁸ Ω / cm ² or more.

Synthesis example 3
In the same reactor as in Synthesis Example 1, 16.74 parts of BPDE, 5.88 parts of BA (bisphenol A), 4.34 parts of potassium carbonate, and 90 parts of dimethylacetamide were charged. The mixture was warmed to 80 ° C. and reacted for 10 hours. After completion of the reaction, a fluorinated aromatic polymer (3) was obtained in the same manner as in Synthesis Example 1. The polymer had a glass transition temperature (Tg) of 180 ° C., a number average molecular weight (Mn) of 62,750, and a surface resistance value of 1.0 × 10 ¹⁸ Ω / cm ² or more.

Synthesis example 4
A reactor equipped with a thermometer, a gas introduction tube, and a stirrer was charged with 5.00 parts of 4,4′-dihydroxydiphenyl ether, 5.01 parts of triethylamine, and 100 parts of dichloromethane, and maintained at 10 ° C. using a water bath. did. Pentafluorobenzoyl chloride 11.41 parts and 20 parts of dichloromethane were charged into a dropping funnel and slowly dropped into the reactor.
After completion of dropping, the water bath was removed and the reaction was allowed to proceed at room temperature for 3 hours. After throwing it into water, the solid was recovered and recrystallized from methanol to obtain BPDES (4,4′-bis (2,3,4,5,6-pentafluorobenzoyloxy) diphenyl ether).
A reactor similar to Synthesis Example 1 was charged with 3.000 parts of BPDES, 1.70 parts of 6FBA, 3.51 parts of potassium carbonate, 10 parts of molecular sieve, and 100 parts of methyl ethyl ketone. The mixture was warmed to 75 ° C. and reacted for 5 hours. After completion of the reaction, a fluorinated aromatic polymer (4) was obtained in the same manner as in Synthesis Example 1. The glass transition temperature (Tg) of the polymer was 185 ° C., the number average molecular weight (Mn) was 58,700, and the surface resistance value was 1.0 × 10 ¹⁸ Ω / cm ² or more.

Synthesis example 5
In the same reactor as in Synthesis Example 1, 13.36 parts of PTFBN (4-phenoxy-2,3,5,6-tetrafluorobenzonitrile), 16.81 parts of 6FBA, 34.55 parts of potassium carbonate, molecular sieve 10 Parts and 100 parts of methyl ethyl ketone were charged. The mixture was warmed to 75 ° C. and reacted for 4 hours. After completion of the reaction, a fluorinated aromatic polymer (5) was obtained in the same manner as in Synthesis Example 1. The polymer had a glass transition temperature (Tg) of 156 ° C., a number average molecular weight (Mn) of 54,040, and a surface resistance value of 1.0 × 10 ¹⁷ Ω / cm ² or more.

Examples 1-11, Comparative Examples 1-3
As the composition of the present invention, the fluorinated aromatic polymer, the organic solvent, the dispersant, and the thermally conductive inorganic filler are blended in the order shown in Table 1 and mixed uniformly by the chemistor, A composition was obtained. Moreover, it mixed similarly by the compounding quantity described in Table 2 as a comparative composition, and obtained the composition.

Next, after applying the above composition on a PET film using a bar coater, after drying at room temperature for 30 minutes and further drying in an oven at 150 ° C. to remove the PET film, the thickness is 50 μm. A film of the present invention and a comparative film were obtained. The obtained film of the present invention and the comparative film were evaluated by the methods shown below. The results are shown in Tables 3 and 4.

Evaluation Method (1) Film Formability The film state of each film obtained was confirmed visually.
Good: Uniform film
Evil: Non-uniformity such as inadequate viscosity of the composition or inability to form a film due to poor dispersion of inorganic filler, molded film is fragile, or aggregates are observed in the film Membrane

(2) Thermal conductivity The thermal conductivity of each of the obtained films was measured by a hot disk method thermophysical property measuring apparatus (TPA-501) manufactured by Kyoto Electronics Industry Co., Ltd.

(3) Heat resistance characteristics The weight loss rate up to 300 ° C. was measured for each obtained film with a thermal analyzer (TG-DTA analysis).

(4) Hygroscopic properties Each film obtained was subjected to a pressure cooker test (135 ° C., 3 atm, 2 hours), and the moisture absorption rate of the film after the test was measured.

PGMAc: propylene glycol monomethyl ether acetate alumina AS-50: trade name, manufactured by Showa Denko KK, spherical alumina, thermal conductivity 36 W / m · K, average particle diameter 11.5 μm, specific surface area 2.2 m ² / g
Boron nitride GP: trade name, manufactured by Denki Kagaku Kogyo Co., Ltd., scaly boron nitride, thermal conductivity 63 W / m · K, average particle diameter 8 μm, specific surface area 8 m ² / g
Boron nitride HGP: trade name, manufactured by Denki Kagaku Kogyo Co., Ltd., scaly boron nitride, thermal conductivity 63 W / m · K, average particle diameter 5 μm, specific surface area 11 m ² / g
BYK W9010: Product name, manufactured by Big Chemie Japan

Iupifine ST: Trade name, polyimide varnish, solid concentration 18.5%, YD-127 manufactured by Ube Industries, Ltd .: Trade name, manufactured by Tohto Kasei Co., Ltd., bisphenol A type epoxy resin MT-500: Trade name, manufactured by Shin Nippon Chemical Co., Ltd. , Methyltetrahydrophthalic anhydride

As is apparent from Table 3, the films obtained from the compositions of Examples 1 to 11 are excellent in dispersibility of the thermally conductive inorganic filler with the organic polymer and have good film formability. , Has high thermal conductivity. In addition, it exhibits ideal performance as a heat dissipation material for electronic parts, such as high heat resistance and low hygroscopicity.

On the other hand, as shown in Table 4, with the polyimide of Comparative Example 1, although a certain thermal conductivity is obtained, a somewhat larger heat loss rate is seen in the heat resistance characteristics, and the moisture absorption rate is also large. Moreover, in the epoxy resins of Comparative Examples 2 and 3, it is difficult to add a high amount of the inorganic filler, and since the resin itself has low heat resistance and high hygroscopicity, the performance as a heat conductive film is also low.

The film obtained from the composition of the present invention exhibits high thermal conductivity, and further has high heat resistance and moisture resistance. Therefore, it is effectively used as a heat dissipation material from heat-generating electronic components such as semiconductor elements. be able to.

Claims (10)

A composition comprising a fluorinated aromatic polymer as an essential component,
The composition contains an inorganic filler having a thermal conductivity of 20 W / m · K or more together with a fluorinated aromatic polymer ,
The fluorinated aromatic polymer is a polyaryl ether having a fluorine atom containing a repeating unit represented by the following general formula (1) or (2):
The thermally conductive composition, wherein the inorganic filler is spherical or scaly particles .

(In the general formula (1), R ¹ represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. Z represents a divalent chain or a direct bond. X and y are It is an integer of 0 or more and represents the number of fluorine atoms that satisfy x + y = 1 to 8 and are the same or different and are bonded to the aromatic ring, and n represents the degree of polymerization.
In the general formula (2), R ² is an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylamino group having 1 to 12 carbon atoms, and carbon. An alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms is represented. R ³ represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms bonded to the aromatic ring and is 1 or 2. n represents the degree of polymerization. ) 2. The thermoconductive composition according to claim 1, wherein the divalent chain that Z can represent is a chain represented by any one of the following structural formulas (5-1) to (5-13). object.

(In the formula, X is a divalent organic chain having 1 to 50 carbon atoms.) R ¹ And R ³ The divalent organic chain represented by the formula (1) is any one of the following structural formula groups (3), or a combination thereof: 3. Thermally conductive composition.

(Where Y ¹ ~ Y ⁴ Are the same or different and each represents a hydrogen group or a substituent, and the substituent is a halogen atom, an optionally substituted alkyl group, an alkoxy group, an alkylamino group, an alkylthio group, an aryl group, an aryloxy group. Represents a group, an arylamino group, or an arylthio group. ) The number average molecular weight of the said fluorinated aromatic polymer exists in the range of 10,000-200000, The thermoelectric composition in any one of Claims 1-5 characterized by the above-mentioned. The thermoconductive composition according to claim 1, wherein the inorganic filler is an inorganic oxide and / or an inorganic nitride. 6. The thermoconductive composition according to claim 1, wherein an average particle size of the inorganic filler is in a range of 0.01 to 30 μm. Wherein the heat conductive composition, thermally conductive according to any one of claims 1 to 6, with respect to the 100 parts by mass of the fluorinated aromatic polymer, characterized by containing the inorganic filler at least 30 parts by weight Sex composition. Films characterized by using a thermally conductive composition according to any one of claims 1-7. The film according to claim 8 , wherein the thermal conductivity is 0.5 W / m · K or more. The film according to claim 8 or 9, wherein the film is obtained by drying the thermoconductive composition at room temperature to 150 ° C.