JP2017057340A - Polyimide resin composition and glue film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of providing a thermal conductive glue film having excellent adhesiveness, high thermal conductivity and good electrical insulation properties by dispersing an inorganic filler having specific particle diameter at a certain ratio.SOLUTION: There is provided the resin composition that contains a phenolic hydroxyl group-containing aromatic polyimide resin (A) having a specific structure, an epoxy resin (B) and a thermal conductive inorganic filler (C). In the resin composition, content of the inorganic filler C) in the resin composition is 45 to 64 vol.% at 25°C and the inorganic filler (C) contains an aggregate (c1) consisting of boron nitride and having an average particle diameter (D50) of 50 to 100 μm, alumina (c2) having an average particle diameter (D50) of 30 to 50 μm, alumina (c3) having an average particle diameter (D50) of 1 to 10 μm and one or two or more kind of inorganic filler (c4) selected from a group consisting of boron nitride, alumina and aluminum nitride each having an average particle diameter (D50) of 0.1 to 3 μm.SELECTED DRAWING: None

Description

  The present invention relates to an electronic material such as a power module and a composition containing a polyimide resin used for an electronic component, a thermally conductive adhesive film using the composition, and an electronic component.

  In recent years, semiconductor integrated circuits have been used in various electronic devices. Among them, in a device that requires a large amount of power, a power module in which power elements such as high-power diodes, transistors, and ICs are mounted is used. The power module is required to have sufficient heat dissipation for radiating heat generated from the power element and high electrical insulation (electric reliability) at high temperatures.

In order to provide sufficient heat dissipation, various heat conductive adhesive films are used for the purpose of bonding the power module and the heat sink. These thermal conductive adhesive films have high thermal conductivity metals, alloys, compounds such as silver, copper, gold, and aluminum, or electrical insulation such as aluminum oxide, silicon nitride, and silicon carbide to increase thermal conductivity. Thermally conductive fillers in the form of granular materials and fibers such as conductive ceramics, carbon black, graphite, and diamond are blended. Among them, an electrically insulating heat conductive adhesive film filled with boron nitride, aluminum oxide, aluminum nitride, silica or the like having excellent heat conductivity and electrical insulation has been widely put into practical use.

  Many resin compositions comprising a heat-resistant resin such as polyimide and a heat-conductive inorganic filler have been proposed to obtain the above-mentioned heat-conductive adhesive film. In particular, since a resin composition comprising a ring-closed polyimide containing an ether bond in the skeleton and a thermally conductive inorganic filler can be designed to have a low glass transition temperature, a low temperature of about 170 to 200 ° C. when used as a film. It is known that it can be adhered to an adherend and can be suitably used as a heat conductive adhesive film (Patent Document 1).

  In recent years, silicon carbide power semiconductors that can be smaller, lower power consumption, and more efficient than silicon semiconductors, and that have excellent switching characteristics and high operating characteristics under high-temperature environments are expected as next-generation low-loss power devices. Has been. When a silicon carbide power module is used as a silicon carbide power module, the temperature range in which the peripheral member is used rises to around 200 ° C.

  However, since the glass transition temperature of the film after adhesion lamination is less than 200 ° C., Patent Document 1 cannot be used as a heat conductive adhesive film for bonding a silicon carbide power module.

  On the other hand, a resin composition comprising a phenolic hydroxyl group-containing aromatic polyamide resin and a thermally conductive inorganic filler can be adhered to an adherend at a low temperature of about 170 to 200 ° C. when used as a film. And since the glass transition temperature of the film after adhesion lamination exceeds 200 degreeC, there exists a possibility of application with respect to a silicon carbide type power module (patent document 2). However, with the recent increase in required characteristics, the resin composition has become insufficient in electrical insulation and thermal conductivity.

  On the other hand, a resin composition of an aromatic polyimide resin and an epoxy resin containing an ether bond in the skeleton and containing a phenolic hydroxyl group is known (Patent Document 3). The resin composition in which the above-described thermally conductive inorganic filler is further blended with the resin composition can be adhered to an adherend at a low temperature of about 170 to 200 ° C. when formed into a film, and the film after adhesive lamination Since its glass transition temperature exceeds 200 ° C., application to a silicon carbide power module is expected.

  Further, with the recent increase in required characteristics, various heat conductive inorganic fillers have been studied (Patent Document 4), but no resin composition having both sufficient heat conductivity and adhesiveness has been found. .

WO2011 / 001698 WO2011 / 114665 gazette JP 2011-124175 A JP, 2014-214213, A

  The present invention relates to a thermally conductive inorganic filler containing an aromatic bond resin containing an ether bond in a skeleton and containing a phenolic hydroxyl group, an epoxy resin, and aluminum nitride having a specific range of particle sizes in a certain ratio. It is an object of the present invention to provide a resin composition that exhibits high adhesiveness, sufficient thermal conductivity, and good electrical insulation when formed into a heat conductive adhesive film.

As a result of intensive studies by the present inventors, a resin composition containing an aromatic polyimide resin (A) having a phenolic hydroxyl group, an epoxy resin (B) and a thermally conductive inorganic filler (C), the specific amount Agglomerates (c1) having a specific average particle size, the alumina (c2) having a specific average particle size, the inorganic filler (C) comprising boron nitride And (c3), and a resin composition containing a specific amount of one or more inorganic fillers (c4) selected from the group consisting of boron nitride, alumina and aluminum nitride having a specific average particle size. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention
(1) The following formula (1)

（式中、ｍ及びｎは平均値であり、０．００５＜ｎ／（ｍ＋ｎ）＜０．１４、かつ０＜ｍ＋ｎ＜２００の関係を満たす正数である。Ｒ_１は下記式（２）

(In the formula, m and n are average values, and are positive numbers satisfying the relationship of 0.005 <n / (m + n) <0.14 and 0 <m + n <200. R ₁ is the following formula (2)

で表される４価の芳香族基を表し、Ｒ_２は下記式（３）

Represents a tetravalent aromatic group represented by the formula: R ₂ represents the following formula (3):

で表される２価の芳香族基を表し、Ｒ_３は下記式（４）

R ₃ represents a divalent aromatic group represented by the following formula (4):

1 type or 2 or more types of bivalent aromatic groups chosen from the group represented by these are represented. )
A resin composition containing a phenolic hydroxyl group-containing aromatic polyimide resin (A), an epoxy resin (B) and a heat conductive inorganic filler (C) having a repeating unit represented by In the resin composition, the content of the inorganic filler (C) is 45 to 64% by volume, and the inorganic filler (C) has an average particle diameter (D50) made of boron nitride of 50 to 100 μm. Agglomerates (c1), alumina (c2) having an average particle size (D50) of 30 to 50 μm, alumina (c3) having an average particle size (D50) of 1 to 10 μm, and an average particle size (D50) of 0.1 to A resin composition containing one or more inorganic fillers (c4) selected from the group consisting of 3 μm boron nitride, alumina, and aluminum nitride;
(2) The resin composition according to item (1), wherein the melt viscosity at 150 ° C. of the epoxy resin (B) measured by a cone plate method is 0.04 Pa · s or less,
(3) The content of the aggregate (c1) made of boron nitride in the thermally conductive inorganic filler (C) is 40 to 60% by volume, and the content of alumina (c2) is 20 to 40% by volume. The content of alumina (c3) is 5 to 20% by volume and the content of one or more inorganic fillers (c4) selected from the group consisting of boron nitride, alumina and aluminum nitride is 1 to 15% by volume. The resin composition according to the above item (1) or (2),
(4) A thermally conductive adhesive film comprising the resin composition according to any one of (1) to (3) above,
(5) A laminate comprising the thermally conductive adhesive film according to the preceding item (4) and copper foil or stainless foil,
(6) A laminate of the heat conductive adhesive film and the heat sink described in (4) above,
(7) It is related with the electronic component which uses the heat conductive adhesive film as described in the preceding clause (4) as a structural component.

The film obtained by using the resin composition of the present invention can be adhered to an adherend at a low temperature of about 170 to 200 ° C. Furthermore, since the film has high adhesive strength and there are few differences in the characteristics of the front and back surfaces of the film, the adhesive strength at high temperatures can be maintained. In addition, since it exhibits high thermal conductivity and good electrical insulation, it can be suitably used for silicon carbide power modules.

  The phenolic hydroxyl group-containing aromatic polyimide resin (A) (hereinafter also simply referred to as “polyimide resin (A)”) contained in the resin composition of the present invention is usually represented by the following formula (5).

で表されるテトラカルボン酸二無水物と、下記式（６）

And a tetracarboxylic dianhydride represented by the following formula (6)

で表されるジアミン化合物および下記式（７）

And a diamine compound represented by the following formula (7):

It can be obtained by subjecting the polyamic acid obtained by addition reaction with one or more diaminodiphenol compounds selected from the group represented by These series of reactions are preferably performed in one pot.
By going through the above-mentioned steps, the following formula (1)

（式中、ｍ及びｎは平均値であり、０．００５＜ｎ／（ｍ＋ｎ）＜０．１４、かつ０＜ｍ＋ｎ＜２００の関係を満たす正数である。Ｒ_１は下記式（２）

(In the formula, m and n are average values, and are positive numbers satisfying the relationship of 0.005 <n / (m + n) <0.14 and 0 <m + n <200. R ₁ is the following formula (2)

で表される４価の芳香族基を表し、Ｒ_２は下記式（３）

Represents a tetravalent aromatic group represented by the formula: R ₂ represents the following formula (3):

で表される２価の芳香族基を表し、Ｒ_３は下記式（４）

R ₃ represents a divalent aromatic group represented by the following formula (4):

1 type or 2 or more types of bivalent aromatic groups chosen from the group represented by these are represented. The phenolic hydroxyl group-containing aromatic polyimide resin (A) having a repeating unit represented by

The molar ratio of the diamine compound represented by formula (6) and the diaminodiphenol compound selected from the group represented by formula (7) used in the above step is the ratio of m to n in formula (1). It becomes. The values of m and n need to satisfy the relationship of 0.005 <n / (m + n) <0.14 and 0 <m + n <200. When the values of m and n satisfy the above relationship, the hydroxyl equivalent of the phenolic hydroxyl group derived from the aromatic group R ₃ that the polyimide resin (A) has in one molecule and the molecular weight of the polyimide resin (A) are the present invention. It is an appropriate value to exert the effect of. More preferably, the values of m and n satisfy the relationship of 0.01 <n / (m + n) <0.06 and 0 <m + n <200, 0.015 <n / (m + n) <0.04, It is further preferable to satisfy the relationship of 0 <m + n <200. When the values of m and n satisfy the above relationship, the glass transition temperature of the film after bonding exceeds 200 ° C., high adhesive strength with the adherend is obtained, and good electrical insulation is exhibited.

  The average molecular weight of the polyimide resin (A) is preferably 1,000 to 70,000 in terms of number average molecular weight and 5,000 to 500,000 in terms of weight average molecular weight. When the average molecular weight is within this range, the required mechanical strength is exhibited when the heat conductive adhesive film is obtained, and the necessary adhesiveness is obtained when the heat conductive adhesive film is obtained.

  The molecular weight of the polyimide resin (A) is the R value (= (number of moles of diamine compound) which is the ratio of the sum of the number of moles of the diamine compound and diaminodiphenol compound used in the reaction to the number of moles of tetracarboxylic dianhydride. It can be controlled by adjusting (number of moles of diaminodiphenol compound) / number of moles of tetracarboxylic dianhydride). As the R value is closer to 1.00, the average molecular weight of the polyimide resin (A) increases. The R value is preferably 0.80 to 1.20, more preferably 0.9 to 1.1.

  When the R value is less than 1.00, the end of the polyimide resin (A) is an acid anhydride, and when it is higher, the end is an amine or aminophenol, but the end of the polyimide resin (A) is limited to any structure. Is not to be done.

  In addition, in order to adjust heat resistance and a curing characteristic, the substituent which a polyimide resin (A) has at the terminal can be chemically modified. For example, an addition reaction product of an acid anhydride polyimide resin (A) and glycidol, or a polycondensate of an amine or aminophenol polyimide resin (A) and 4-ethynylphthalic anhydride is This is a preferred embodiment of the invention.

  The addition reaction and dehydration ring closure reaction in obtaining the polyimide resin (A) are carried out by a solvent capable of dissolving the polyamic acid and the polyimide resin (A), which are synthetic intermediates, such as N-methyl-2-pyrrolidone, N, N- It is preferably carried out in a solvent containing one or more selected from dimethylacetamide or γ-butyrolactone.

The addition reaction between the tetracarboxylic dianhydride, the diamine compound and the diaminophenol compound is usually carried out at 10 to 100 ° C, preferably 40 to 90 ° C.
In the dehydration ring closure reaction, a small amount of a relatively low boiling nonpolar solvent such as toluene, xylene, hexane, cyclohexane or heptane is used as a dehydrating agent, and water produced as a by-product during the reaction is removed from the reaction system. preferable. It is also preferable to add a small amount of a basic organic compound selected from pyridine, N, N-dimethyl-4-aminopyridine, and triethylamine as a catalyst. The reaction temperature during the dehydration ring closure reaction is usually 150 to 220 ° C., preferably 160 to 200, and the reaction time is usually 2 to 15 hours, preferably 5 to 10 hours. The addition amount of the dehydrating agent is usually 5 to 20% by mass with respect to the reaction solution, and the addition amount of the catalyst is usually 0.1 to 5% by mass with respect to the reaction solution.

The polyimide resin (A) is obtained as a form dissolved in a solvent after the dehydration ring-closing reaction, that is, as a varnish of the polyimide resin (A). As one embodiment of the present invention, there is a method in which a poor solvent such as water or alcohol is added to the obtained varnish of the polyimide resin (A) to precipitate the polyimide resin (A), which is purified and used. As another embodiment, the varnish of the polyimide resin (A) obtained after the dehydration ring-closing reaction can be used as it is without purification, and this embodiment is more preferable from the viewpoint of operability.
The content of the polyimide resin (A) in the resin composition of the present invention is such that the total volume of the polyimide resin (A) in the resin composition and the epoxy resin (B) described later at 25 ° C. is usually 36 to 55 volumes. %.

  The resin composition of the present invention contains an epoxy resin (B). The epoxy resin (B) serves as a crosslinking agent for the polyimide resin (A), and is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. Can be used. Examples of the epoxy resin (B) include bisphenol A type epoxy resins and epoxy resins obtained by reacting bisphenol A type epoxy resins with diphenols, bisphenol F type epoxy resins bisphenol F type epoxy resins and diphenols. Examples include epoxy resins, biphenol skeleton epoxy resins, alkylbiphenol skeleton epoxy resins, and the like, which are reacted to increase the molecular weight, and specific examples thereof include novolak type epoxy resins (for example, N-660 (manufactured by DIC Corporation), YDCN-700-5 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.)), dicyclopentadiene-phenol condensed epoxy resin (For example, XD-1000 (manufactured by Nippon Kayaku Co., Ltd.) , Xylylene skeleton-containing phenol novolac type epoxy resin (for example, NC-2000 (manufactured by Nippon Kayaku Co., Ltd.)), biphenyl skeleton-containing novolak type epoxy resin (for example, NC-3000 (manufactured by Nippon Kayaku Co., Ltd.)), Naphthalene type epoxy resin (for example, HP-4710 (manufactured by DIC Corporation)) alicyclic epoxy resin (for example, Celoxide 2021P (manufactured by Daicel Corporation)), bisphenol A type epoxy resin (for example, JER828 (Mitsubishi Chemical Corporation) )), EP4100 (manufactured by ADEKA Corporation), 850-S (manufactured by DIC Corporation), RE-310S (manufactured by Nippon Kayaku Co., Ltd.), Rikaresin BEO-60E (manufactured by Shin Nippon Rika Co., Ltd.) Bisphenol F type epoxy resin (for example, YDF-870GS (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), YDF- 170C (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), RE-303S (manufactured by Nippon Kayaku Co., Ltd.)), RE-602S (manufactured by Nippon Kayaku Co., Ltd.), biphenol skeleton epoxy resin or alkylbiphenol skeleton epoxy resin ( Examples thereof include YX-4000 (manufactured by Mitsubishi Chemical Corporation), YL6121H (manufactured by Mitsubishi Chemical Corporation), etc. Two or more of these epoxy resins may be used in combination.

Among these epoxy resins, an epoxy resin having a melt viscosity of 0.04 Pa · s or less is preferably used as the epoxy resin (B). By using an epoxy resin having a melt viscosity of 0.04 Pa · s or less, excellent characteristics such as good electrical insulation, high thermal conductivity, and high adhesion at low temperatures are exhibited. Melt viscosity is 0.04 Pa. Specific examples of epoxy resins below s include bisphenol A type epoxy resin to YL6121H and bisphenol F type epoxy resin to RE-602S in the specific examples of the epoxy resin (B).
In addition, the melt viscosity said here means the melt viscosity in 150 degreeC measured by the cone plate method according to JISK-7117-2.

  The content of the epoxy resin (B) in the resin composition of the present invention is such that the total volume of the polyimide resin (A) in the resin composition at 25 ° C. and the epoxy resin (B) described later is usually 36 to 55 volumes. %, Preferably 38 to 50% by volume. Moreover, the compounding ratio of the epoxy resin (B) with respect to the polyimide resin (A) is an epoxy group that the epoxy resin (B) has in its structure with respect to 1 equivalent of active hydrogen that the polyimide resin (A) has in its structure. Is usually 0.7 to 1.3 equivalents, preferably 0.8 to 20 equivalents. In addition, when using the epoxy resin (B) of the quantity with which an epoxy group becomes excess with respect to the hydroxyl group of a polyimide resin (A), it is a preferable aspect to use together the epoxy hardening | curing agent mentioned later to the resin composition of this invention. one of.

The resin composition of the present invention has an aggregate (c1) having an average particle diameter (D50) of 50 to 100 μm, alumina (c2) having an average particle diameter (D50) of 30 to 50 μm, and an average particle diameter (D50) of 1 to Thermally conductive inorganic filler (C) containing 10 μm alumina (c3) and inorganic filler (c4) having an average particle size (D50) of 0.1 to 3 μm (hereinafter simply referred to as “inorganic filler (C)”) Contain). The resin composition of the present invention exhibits excellent adhesion, high thermal conductivity, and good electrical insulation by using specific amounts of aggregates and inorganic fillers having different average particle diameters (D50) and materials. To do.
The aggregate (c1) is generally an aggregate composed of scaly boron nitride microcrystals. As the microcrystals, those having an average crystal grain size of 2 μm or less and those having a crystal major axis of 10 μm or less are known. The aggregate (c1) of the present invention has these microcrystals aggregated. It means a relatively large secondary aggregate particle to be formed.

  The average particle diameter (D50) of the aggregate (c1) is usually 50 to 100 μm, preferably 60 to 95 μm. When the average particle diameter is less than 50 μm, sufficient thermal conductivity cannot be shown, and when the average particle diameter (D50) is greater than 100 μm, a large amount of voids are generated in the film, and sufficient insulation is obtained. Can't get. Therefore, when using boron nitride of large secondary agglomerated particles as a raw material, the size of the secondary agglomerated particles of boron nitride dispersed in the resin composition of the present invention is appropriately pulverized so as to be in the above range. It is preferable to adjust. The particle diameter of boron nitride may be adjusted in advance by stirring and mixing, or secondary particles may be adjusted together with mixing when stirring or kneading with other raw materials.

  The average particle diameter (D50) of alumina (c2) is usually 30 to 50 μm, preferably 35 to 45 μm. By using alumina (c2) having an average particle diameter (D50) in the above range, sufficient adhesiveness and sufficient thermal conductivity can be obtained. When the average particle diameter (D50) of alumina (c2) is less than 30 μm, sufficient thermal conductivity cannot be exhibited, and when the average particle diameter (D50) is greater than 50 μm, the inorganic filler settles and the resin The stability of the composition is reduced. Therefore, sufficient adhesiveness and sufficient thermal conductivity cannot be exhibited.

  The average particle diameter (D50) of alumina (c3) is usually 1 to 10 μm, preferably 3 to 8 μm. By using alumina (c3) having an average particle diameter (D50) in the above range, sufficient adhesiveness and sufficient thermal conductivity can be obtained. When the average particle diameter (D50) of alumina (c3) is less than 1 μm, sufficient thermal conductivity cannot be exhibited, and when the average particle diameter (D50) is greater than 10 μm, the inorganic filler is precipitated and the resin The stability of the composition is reduced. Therefore, sufficient adhesiveness and sufficient thermal conductivity cannot be exhibited.

  The inorganic filler (c4) comprises one or more inorganic fillers selected from the group consisting of boron nitride, alumina, and aluminum nitride. The average particle size of the inorganic filler (c4) is usually 0.1 to 3 μm, preferably 0.5 to 2 μm. When the average particle diameter (D50) is less than 0.1 μm, sufficient thermal conductivity cannot be exhibited, and when the average particle diameter is greater than 3 μm, the filling property of the inorganic filler is reduced and sufficient adhesion and Sufficient electrical insulation cannot be obtained.

  The content of the inorganic filler (C) in the resin composition of the present invention is such that the volume of the inorganic filler (C) in the resin composition at 25 ° C. is usually 45 to 64% by volume, preferably 50 to 60% by volume. By setting the content of the inorganic filler (C) in the resin composition of the present invention in the above range, the resin composition of the present invention exhibits sufficient adhesiveness, and the cured product of the resin composition is Sufficient thermal conductivity is developed.

The content of the aggregate (c1) in the inorganic filler (C) is not particularly limited, but is preferably 40 to 60% by volume, more preferably 45 to 55% by volume, and the inorganic filler. The content of alumina (c2) in (C) is not particularly limited, but is preferably 20 to 40% by volume, more preferably 25 to 35% by volume, and the inorganic filler (C). The content of (c3) is not particularly limited, but is preferably 5 to 20% by volume, more preferably 8 to 15% by volume. Furthermore, the content of the inorganic filler (c4) in the inorganic filler (C) is not particularly limited, but is preferably 1 to 15% by volume, and more preferably 4 to 10% by volume.
By setting the content of the components (c1) to (c4) in the inorganic filler (C) within the above-mentioned preferable range, the resin composition of the present invention further exhibits sufficient adhesiveness, and the resin composition is bonded. When used as a sheet, the voids in the adhesive sheet are reduced to exhibit further sufficient electrical insulation, and the cured product of the resin composition further exhibits sufficient thermal conductivity.

  In the resin composition of the present invention, additives for developing various physical properties can be blended in addition to the components described above. For example, blending an epoxy resin curing agent and a curing accelerator is one of the preferred embodiments of the present invention.

Specific examples of epoxy resin curing agents include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophorone diamine, dicyandiamide, a polyamide resin synthesized from linolenic acid and ethylene diamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, polyphenol compounds such as phenol novolac, triphenyl methane and modified products thereof, imidazole, BF 3 _- amine complex, but such guanidine derivatives is not limited thereto, be appropriately selected according to the aspect It can be.

  When blending an epoxy resin curing agent, it depends on the curing agent used together, so it cannot be said unconditionally, but the curing agent is preferably 500 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the total amount of epoxy resin. It is as follows. If it is more than this, the heat resistance of the thermally conductive adhesive film is lowered, which is not preferable.

  Specific examples of the curing accelerator that can be used in the present invention include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole, tertiary amines such as 2- (dimethylaminomethyl) phenol and 1,8-diaza-bicyclo (5,4,0) undecene-7 , Phosphines such as triphenylphosphine, and metal compounds such as tin octylate, but are not limited thereto. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the epoxy resin.

  In the resin composition of this invention, you may use together heat conductive inorganic fillers other than the said (c1)-(c4) component. The thermally conductive inorganic filler that can be used in combination preferably has a thermal conductivity of 1 W / m · k or more, more preferably 5 W / m · k or more. Specific examples of thermally conductive inorganic fillers that can be used in combination include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, aluminum borate whisker, silicon nitride, and crystalline silica. , Amorphous silica and silicon carbide. The average particle diameter of the thermally conductive inorganic filler that can be used in combination is not particularly limited.

If necessary, additives such as a coupling agent, an organic solvent and an ion scavenger may be added to the resin composition of the present invention. The coupling agent to be used is not particularly limited, but a silane coupling agent is preferable, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- Examples include ureidopropyltriethoxysilane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane. What is necessary is just to select the usage-amount of these coupling agents according to the use of a resin composition, the kind of coupling agent, etc., and it is 5 mass parts or less normally in 100 mass parts of resin compositions of this invention.

  The ion scavenger that can be used in the resin composition of the present invention is not particularly limited. For example, a triazine thiol compound or 2,2′-methylene-bis known as a copper damage inhibitor for preventing copper from being ionized and dissolved out. Examples include bisphenol-based reducing agents such as-(4-methyl-6-tert-butylphenol), zirconium-based compounds as inorganic ion adsorbents, antimony bismuth-based compounds, magnesium aluminum-based compounds, and hydrotalcite. By adding these ion scavengers, ionic impurities are adsorbed and the electrical reliability at the time of moisture absorption can be improved. The amount of the ion scavenger used is usually 5% by mass or less in the resin composition of the present invention in view of its effect, heat resistance, cost and the like.

The resin composition of the present invention can also be used as a varnish dissolved in an organic solvent. Examples of the organic solvent that can be used include lactones such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and the like. Amide solvents, sulfones such as tetramethylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether, acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, cyclopentanone and cyclohexanone, and aromatic solvents such as toluene and xylene And the like.

The varnish can be produced by a crusher, three rolls, a bead mill, a planetary, or a combination of these when considering the dispersion of the thermally conductive inorganic filler. In addition, it is possible to reduce the time required for mixing by mixing the heat conductive inorganic filler and the low molecular weight component in advance and then mixing the high molecular weight component. Moreover, when mixing each component, it is preferable to remove the bubble contained in the inside from the obtained varnish by vacuum deaeration.
After apply | coating the said varnish to a base material, the resin composition of this invention can be made into the heat conductive adhesive film of this invention by drying an organic solvent and forming into a film.

  As a base material that can be used for film formation, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polyester film, a fluorine film, a copper foil, a stainless steel foil, or the like is preferably used. When the base material is peeled after drying, the surface of the base material may be subjected to a release treatment with silicone or the like. Specifically, the varnish of the resin composition of the present invention is applied to the surface of the substrate with a comma coater, die coater, etc., and the solvent in the coating is volatilized to such an extent that the curing reaction does not proceed with hot air or an infrared heater. Then, a film made of the resin composition of the present invention can be obtained by peeling from the substrate. In addition, when using the base material used here as a to-be-adhered body of the resin composition of this invention, it is not necessary to peel a base material after volatilizing a solvent.

  The thickness of the heat conductive adhesive film of this invention is 50-500 micrometers normally, Preferably it is 75-250 micrometers. If the thickness of the film is too thin, the thermally conductive inorganic filler protrudes, resulting in a decrease in electrical insulation, and a significant decrease in adhesion strength with the adherend. If the thickness of the film is too thick, When the environmental test is performed on the adherend with the adherend, the remaining solvent increases, and problems such as floating and swelling and a decrease in the electrical reliability test occur.

  Although the use of the heat conductive adhesive film of this invention is not specifically limited, From the effects, such as the adhesiveness, high heat conductivity, electrical insulation, and heat resistance which it has, an electric circuit, metal foil or a circuit board, and a heat sink are adhere | attached. Therefore, it is preferably used. The material of the metal foil is not particularly limited, but copper foil or stainless steel foil is preferable from the viewpoint of versatility.

The heat sink here is a plate laminated on the surface on which the electronic component is mounted for the purpose of promoting heat dissipation from the electronic component mounted on the electric circuit, and usually a metal plate or the like is used. The Examples of the material of the heat sink include metals such as copper, aluminum, stainless steel, nickel, iron, gold, silver, molybdenum, and tungsten, composites of metal and glass, and alloys, among which copper having high thermal conductivity. Aluminum, gold, silver, iron, and alloys using these are preferable. Although there is no restriction | limiting in particular in the thickness of a heat sink, it is 0.1-5 mm normally from the point of workability. By applying the resin composition of the present invention to these heat radiating plates and metal foils or laminating the above adhesive film, the heat radiating plate with adhesive and the metal foil with adhesive of the present invention can be obtained.

  A laminate in which a heat sink is stacked on an electric circuit can be prepared by processing a metal foil portion of a metal foil with a heat sink. The electronic component is mounted on the electric circuit by solder connection or the like, and becomes the electronic component of the present invention.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by mass” and “%” means “% by mass”.

Synthesis example 1
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 30.79 parts (0.105 mol) and ABPS (3,3′-diamino-4,4′-dihydroxydiphenylsulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.30) 0.467 parts (0.0017 mol) was added, and 164.00 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, followed by stirring at 70 ° C. for 30 minutes. Thereafter, ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22), 32.54 parts (0.105 mol) as tetracarboxylic dianhydride, and 1.66 parts of pyridine as a catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, thereby obtaining the following formula (8):

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 20,000, and the weight average molecular weight is 100,000. The value of m in the formula (8) calculated from the molar ratio was 49.22, and the value of n was 0.78.

Synthesis example 2
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 30.79 parts (0.105 mol) and ABPS (3,3′-diamino-4,4′-dihydroxydiphenylsulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.30) 0.467 parts (0.0017 mol) was added, N-methylpyrrolidone 162.50 parts was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Then, as tetracarboxylic dianhydride, ODPA (4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 31.92 parts (0.103 mol), and 1.66 parts pyridine as a catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, thereby obtaining the following formula (8):

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 14,000, and the weight average molecular weight is 58,000. The value of m in the formula (8) calculated from the molar ratio was 24.61, and the value of n was 0.39.

Synthesis example 3
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 30.31 parts (0.104 mol) and ABPS (3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.30) 0.935 parts (0.032 mol) was added, and 164.00 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, followed by stirring at 70 ° C. for 30 minutes. Then, as tetracarboxylic dianhydride, ODPA (4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 31.92 parts (0.103 mol), and 1.66 parts pyridine as a catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, thereby obtaining the following formula (8):

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 12,000, and the weight average molecular weight is 54,000. The value of m in the formula (8) calculated from the molar ratio was 24.22, and the value of n was 0.78.

Synthesis example 4
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 28.36 parts (0.097 mol) and ABPS (3,3′-diamino-4,4′-dihydroxydiphenylsulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.30) 2.803 parts (0.010 mol) was added, and 164.00 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, followed by stirring at 70 ° C. for 30 minutes. Then, as tetracarboxylic dianhydride, ODPA (4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 31.92 parts (0.103 mol), and 1.66 parts pyridine as a catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm.
Following formula (8)

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 15,000, and the weight average molecular weight is 57,000. The value of m in the formula (8) calculated from the molar ratio was 22.66, and the value of n was 2.34.

Synthesis example 5
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 30.54 parts (0.104 mol) and BAFA (2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, Nippon Kayaku Co., Ltd. Produced, molecular weight 366.26) 0.814 parts (0.0022 mol) was added, N-methylpyrrolidone 159.00 parts was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, as tetracarboxylic dianhydride, ODPA (4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 31.15 parts (0.100 mol), and 1.66 parts pyridine as a catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, whereby the following formula (9)

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) determined in terms of polystyrene based on the measurement result of gel permeation chromatography is 15,000, and the weight average molecular weight is 60,000. The value of m in the formula (8) calculated from the molar ratio was 24.48, and the value of n was 0.52.

Synthesis Example 6
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33), 30.70 parts (0.105 mol) and HAB (3,3′-diaminobiphenyl-4,4′-diol, Nippon Kayaku Co., Ltd., molecular weight 216 .24) 0.481 parts (0.0022 mol) was added, 161.00 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Thereafter, ODPA (4,4'-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 31.32 parts (0.101 mol) as tetracarboxylic dianhydride, 1.66 parts pyridine as catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, whereby the following formula (10)

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 12,000, and the weight average molecular weight is 53,000. The value of m in the formula (8) calculated from the molar ratio was 24.48, and the value of n was 0.52.

Synthesis example 7
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33), 31.27 parts (0.107 mol) was added, and 162.50 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, followed by stirring at 70 ° C. for 30 minutes. did. Then, as tetracarboxylic dianhydride, ODPA (4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 31.90 parts (0.103 mol), and 1.66 parts pyridine as a catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, whereby the following formula (11)

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 10,000, the weight average molecular weight is 53,000, and each component used in the synthesis reaction The value of m in the formula (11) calculated from the molar ratio was 25.00.

Synthesis Example 8
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 26.06 parts (0.089 mol) and ABPS (3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.30) 5.097 parts (0.0182 mol) was added, 162.50 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, and the mixture was stirred at 70 ° C. for 30 minutes. Then, as tetracarboxylic dianhydride, ODPA (4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22), 32.01 parts (0.103 mol), and 1.67 parts of pyridine as a catalyst. And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, thereby obtaining the following formula (8):

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 14,000, and the weight average molecular weight is 56,000. The value of m in the formula (8) calculated from the molar ratio was 20.76, and the value of n was 4.24.

Synthesis Example 9
APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Benzene, manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 15.64 parts (0.054 mol) and ABPS (3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.30) 15.00 parts (0.054 mol) was added, and 161.10 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, followed by stirring at 70 ° C. for 30 minutes. Then, as tetracarboxylic dianhydride, ODPA (4,4'-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 31.92 parts (0.103 mol), and 1.67 parts pyridine as a catalyst And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, thereby obtaining the following formula (8):

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 16,000, and the weight average molecular weight is 58,000. The value of m in formula (8) calculated from the molar ratio was 12.50, and the value of n was 12.50.

Synthesis Example 10
ABPS (3,3′-diamino-4,4′-dihydroxydiphenyl) as a diamine compound was added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirring device. Sulfone, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.30), 30.07 parts (0.107 moles) was added, and 160.01 parts of N-methylpyrrolidone was added as a solvent while flowing dry nitrogen, and at 70 ° C. for 30 minutes. Stir. Then, as tetracarboxylic dianhydride, ODPA (4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22), 32.01 parts (0.103 mol), and 1.67 parts of pyridine as a catalyst. And 28.49 parts of toluene was added as a dehydrating agent, and the temperature in the reactor was raised to 180 ° C. While removing water generated by the imidization reaction using a Dean-Stark apparatus, a heat ring-closing reaction was performed at 180 ° C. for 3 hours, followed by further heating for 4 hours to remove pyridine and toluene. After completion of the reaction, the reaction solution cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 μm, thereby obtaining the following formula (8):

200 parts of a polyimide resin varnish containing 28% of a polyimide resin (A) having a repeating unit represented by the formula: The number average molecular weight of the polyimide resin (A) obtained in terms of polystyrene based on the measurement result of gel permeation chromatography is 30,000, and the weight average molecular weight is 65,000. The value of m in the formula (8) calculated from the molar ratio was 0.00, and the value of n was 25.00.

Example 1
To 107 parts of the polyimide resin varnish obtained in Synthesis Example 1, 16 parts of RE-602S (bisphenol F type epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 188 g / eq) as an epoxy resin (B), epoxy resin cured 13 parts of GPH-65 (biphenylphenol condensation type novolak resin, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent: 200 g / eq) as an agent, and 0 of 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ) as a curing accelerator .3 parts and 33 parts of N-methylpyrrolidone as a solvent were added, respectively, and stirred at 30 ° C. for 2 hours to obtain a mixed solution (solid content concentration 35% by mass). 16.7 parts of boron nitride (manufactured by 3M: Agglomerates 100, average particle size 90 μm) as an inorganic filler (C) and 50 parts of the mixed solution (solid content: 17.5 parts), alumina (electrochemical) Industrial Co., Ltd .: DAW-45, average particle size 41.2 μm) 27.3 parts, Alumina (Denki Kagaku Kogyo Co., Ltd .: DAW-05, average particle size 5.3 μm) 10.5 parts and boron nitride (Mitsui Chemicals Co., Ltd. product: MBN-010T, average particle diameter 1 micrometer) 2.0 parts was added, and it knead | mixed with the three rolls, and obtained the varnish (1) of the resin composition of this invention.

Example 2
The resin composition varnish (2) of the present invention was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 2. .

Example 3
A varnish (3) of the resin composition of the present invention was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 3. .

Example 4
A varnish (4) of the resin composition of the present invention was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 4. .

Example 5
A varnish (5) of the resin composition of the present invention was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 5. .

Example 6
A varnish (6) of the resin composition of the present invention was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 6. .

Example 7
Varnish (7) of the resin composition of the present invention in the same procedure as in Example 1 except that RE-602S was changed to YX4000 (alkyl biphenol skeleton epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186 g / eq). Got.

Example 8
The amount of RE-602S used was changed from 16 parts to 30 parts, 13 parts of GPH-65 were changed to 1.8 parts of DICY (dicyandiamide, Nippon Carbide Industries, Ltd., active hydrogen equivalent 21 g / eq), N- A varnish (8) of the resin composition of the present invention was obtained in the same procedure as in Example 1 except that the amount of methylpyrrolidone used was changed from 33 parts to 38.5 parts.

Example 9
Boron nitride (3M: Agglomerates 100, average particle size 90 μm) 26.5 parts, alumina (Denki Kagaku Kogyo Co., Ltd .: DAW-45, average particle size 41.2 μm) 15.1 parts of inorganic filler (C) 5.9 parts of alumina (Denki Kagaku Kogyo Co., Ltd .: DAW-05, average particle size 5.3 μm) and 2.0 parts of boron nitride (Mitsui Chemicals Co., Ltd .: MBN-010T, average particle size 1 μm) A varnish (9) of the resin composition of the present invention was obtained in the same procedure as in Example 8 except that.

Comparative Example 1
A comparative resin composition varnish (10) was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 7. .

Comparative Example 2
A comparative resin composition varnish (11) was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 8. .

Comparative Example 3
A comparative resin composition varnish (12) was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 9. .

Comparative Example 4
A comparative resin composition varnish (13) was obtained in the same procedure as in Example 1 except that the polyimide resin varnish obtained in Synthesis Example 1 was changed to the polyimide resin varnish obtained in Synthesis Example 10. .

Comparative Example 5
A varnish (resin composition for comparison) in the same procedure as in Example 1 except that RE-602S was changed to NC-3000 (bisphenol F type epoxy resin, Nippon Kayaku Co., Ltd., epoxy equivalent 275 g / eq). 14) was obtained.

Comparative Example 6
Boron nitride (made by 3M: Agglomerates 100, average particle size 90 μm) 15.5 parts, alumina (manufactured by Denki Kagaku Kogyo Co., Ltd .: DAW-45, average particle size 41.2 μm) 28.7 parts of inorganic filler (C) , 11.2 parts of alumina (Denki Kagaku Kogyo Co., Ltd .: DAW-05, average particle size 5.3 μm) and 2.0 parts of boron nitride (Mitsui Chemicals Co., Ltd .: MBN-010T, average particle size 1 μm) A varnish (15) of a comparative resin composition was obtained in the same procedure as in Example 8 except that.

Comparative Example 7
Inorganic filler (C) is boron nitride (3M: Agglomerates 100, average particle size 90 μm) 30.5 parts, alumina (Denki Kagaku Kogyo Co., Ltd .: DAW-45, average particle size 41.2 μm) 9.8 parts And 4.2 parts of alumina (Denki Kagaku Kogyo Co., Ltd .: DAW-05, average particle size 5.3 μm) and 2.0 parts of boron nitride (Mitsui Chemicals Co., Ltd .: MBN-010T, average particle size 1 μm) A varnish (16) of a comparative resin composition was obtained in the same procedure as in Example 8 except that.

Comparative Example 8
Changed inorganic filler (C) to 32.5 parts of boron nitride (3M: Agglomerates 100, average particle size 90 μm) and 2.0 parts of boron nitride (Mitsui Chemicals, Inc .: MBN-010T, average particle size 1 μm) A varnish (17) of a comparative resin composition was obtained in the same procedure as in Example 8 except that.

Examples 10-18
The varnishes (1) to (9) of the resin composition of the present invention obtained in Examples 1 to 9 were each applied on a PET film so that the thickness after drying was 200 μm, and dried at 130 ° C. for 10 minutes. To remove the solvent. The obtained film was peeled from the PET film to obtain the heat conductive adhesive films (1) to (9) of the present invention. In addition, the surface of the obtained film on the PET film side was defined as C surface, and the air side was defined as A surface.

Comparative Examples 9-16
The comparative resin compositions varnishes (10) to (17) obtained in Comparative Examples 1 to 8 were applied on a PET film so that the thickness after drying was 200 μm, and dried at 130 ° C. for 10 minutes. To remove the solvent. The obtained film was peeled from the PET film to obtain comparative heat conductive adhesive films (10) to (17). In addition, the surface of the obtained film on the PET film side was defined as C surface, and the air side was defined as A surface.

The adhesiveness, thermal conductivity, and electrical insulation of the thermally conductive adhesive films obtained in Examples 10 to 18 and Comparative Examples 9 to 16 were measured as follows. The measurement results are shown in Table 1.

(Melt viscosity of epoxy resin)
Based on JIS K7117-2, it measured at 150 degreeC by the cone plate method.
Measuring machine: Cone plate (ICI) high temperature viscometer
(Made by RESEARCH EQUIIPMENT (LONDON) LTD.)
Corn No. : 3 (measurement range 0 to 2.00 Pa · s)
Sample amount: 0.155 ± 0.01 g
It measured based on JIS K-7117-2. The measurement results are shown in Table 1.

(Heat conduction)
Three heat conductive adhesive films of Examples 10 to 18 and Comparative Examples 9 to 16 were each stacked, and a heat conductive test sample was obtained by thermocompression bonding at 180 ° C. and 3 MPa for 60 minutes using a hot plate press. Obtained. The obtained sample was measured for thermal diffusivity using a laser flash method thermal diffusivity measuring apparatus (manufactured by Netch, LFA447). Specific gravity was measured by Archimedes method, specific heat was measured by DSC method, and thermal conductivity was calculated by thermal diffusivity x specific gravity x specific heat. The results are shown in Table 1.

(Adhesiveness (peel strength after lamination with copper foil))
The heat conductive adhesive films of Examples 10 to 18 and Comparative Examples 9 to 16 were each made of two electrolytic copper foils (CF-T9B-HTE, manufactured by Fukuda Metal Foil Powder Industries) with a thickness of 18 μm, and the rough surfaces were heat conductive adhesive films. Both sides were sanded on the side, and were subjected to thermocompression bonding at 180 ° C. and 3 MPa for 60 minutes using a hot plate press to obtain a sample for adhesion test. About these samples, using a tensile tester (AGS-X, manufactured by Shimadzu Corporation), a test piece having a width of 1 cm was set in accordance with JIS C6481, a peeling speed was set to 50 mm / min, and 90 ° (plus or minus) The film was peeled in the direction of 5 °), and the adhesion between the C surface side and the A surface side was measured. The results are shown in Table 1.

(Adhesiveness (shear strength after lamination with a copper plate)) The heat conductive adhesive films of Examples 10 to 18 and Comparative Examples 9 to 16 were each two copper plates having a thickness of 2 mm on the side of the heat conductive adhesive film. Sanding was performed, and heat press bonding was performed for 60 minutes at 180 ° C. and 6 MPa using a hot plate press to obtain a sample for adhesion test. These samples are peeled off using a Tensilon tester (AG-X plus, manufactured by Shimadzu Corporation) in accordance with JIS C6850 with the peeling speed set to 50 mm / min, and the adhesion at room temperature and 180 ° C. It was measured. The results are shown in Table 1.

(Electrical insulation)
The heat conductive adhesive films of Examples 10 to 18 and Comparative Examples 9 to 16 were each heat-pressed for 60 minutes under the conditions of 180 ° C. and 3 MPa using a hot plate press to obtain samples for electrical insulation test. The obtained cured film was measured for electrical insulation by using a dielectric breakdown tester (manufactured by Yasuda Seiki Seisakusho) and measuring the pressure increase rate at 100 V / sec and 10 mA. The results are shown in Table 1.

The film obtained by using the resin composition of the present invention can be adhered to an adherend at a low temperature of about 170 to 200 ° C. Furthermore, since the film has high adhesive strength and there are few differences in the characteristics of the front and back surfaces of the film, the adhesive strength at high temperatures can be maintained. In addition, since it exhibits high thermal conductivity and good electrical insulation, it can be suitably used for silicon carbide power modules.

Claims (7)

Following formula (1)

(In the formula, m and n are average values, and are positive numbers satisfying the relationship of 0.005 <n / (m + n) <0.14 and 0 <m + n <200. R ₁ is the following formula (2)

Represents a tetravalent aromatic group represented by the formula: R ₂ represents the following formula (3):

R ₃ represents a divalent aromatic group represented by the following formula (4):

1 type or 2 or more types of bivalent aromatic groups chosen from the group represented by these are represented. )
A resin composition containing a phenolic hydroxyl group-containing aromatic polyimide resin (A), an epoxy resin (B) and a heat conductive inorganic filler (C) having a repeating unit represented by In the resin composition, the content of the inorganic filler (C) is 45 to 64% by volume, and the inorganic filler (C) has an average particle diameter (D50) made of boron nitride of 50 to 100 μm. Agglomerates (c1), alumina (c2) having an average particle size (D50) of 30 to 50 μm, alumina (c3) having an average particle size (D50) of 1 to 10 μm, and an average particle size (D50) of 0.1 to A resin composition comprising one or more inorganic fillers (c4) selected from the group consisting of 3 μm boron nitride, alumina, and aluminum nitride.   The resin composition according to claim 1, wherein the melt viscosity at 150 ° C of the epoxy resin (B) measured by a cone plate method is 0.04 Pa · s or less. The content of the aggregate (c1) composed of boron nitride in the thermally conductive inorganic filler (C) is 40 to 60% by volume, the content of alumina (c2) is 20 to 40% by volume, and alumina ( The content of c3) is 5 to 20% by volume, and the content of one or more inorganic fillers (c4) selected from the group consisting of boron nitride, alumina, and aluminum nitride is 1 to 15% by volume. The resin composition according to claim 1 or 2. The heat conductive adhesive film which consists of a resin composition as described in any one of Claims 1 thru | or 3. The laminate which consists of a heat conductive adhesive film of Claim 4, and copper foil or stainless steel foil. The laminate of the heat conductive adhesive film of Claim 4, and a heat sink. The electronic component which uses the heat conductive adhesive film of Claim 4 as a structural component.