WO2020115914A1 - Resin composition, resin sheet, metal substrate, power semiconductor device, and production method for metal substrate - Google Patents

Abstract

A resin composition which comprises a polymer having an anaerobic curable functional group at a side chain terminal end, and which is used under an anaerobic condition in which a supply of oxygen is suppressed.

Description

Resin composition, resin sheet, metal substrate, power semiconductor device, and method for manufacturing metal substrate

The present invention relates to a resin composition, a resin sheet, a metal substrate, a power semiconductor device, and a method for manufacturing a metal substrate.

As a component of an electronic device and an electric device, a laminated body in which a resin layer for insulation or the like is arranged between a pair of members is used for various purposes (see, for example, Patent Document 1). Such a laminate has been manufactured by attaching both members via a resin sheet.

Japanese Patent No. 5431595

While the cured product of the resin sheet described in Patent Document 1 has high thermal conductivity, it is necessary to apply heat of 100° C. or higher when the resin sheet is cured and manufactured, and thus a heating device or the like for curing the resin sheet is used. Will be needed. Further, even when it is assumed that a resin sheet or the like that is cured by light, moisture or the like is supposed to be cured, a device, equipment, etc. for curing the resin sheet are required separately. Therefore, it is desirable to use a resin sheet that can be cured under room temperature conditions or conditions close to room temperature without requiring any special device or equipment. Furthermore, in the case of a resin sheet that is cured by heat, light, moisture, etc., it is intended before attaching to an adherend, such as during preparation of an A-stage sheet obtained by drying a resin composition or during preparation of a semi-cured B-stage sheet. There is room for improvement in pot life because curing may proceed.

One form of the present invention has been made in view of the above, can be cured under room temperature conditions or conditions close to room temperature, a resin composition and a resin sheet excellent in pot life, and using this resin sheet An object is to provide a metal substrate, a power semiconductor device, and a method for manufacturing a metal substrate.

The present inventors have accomplished the present invention as a result of extensive studies to solve the above problems. That is, the present invention includes the following aspects.
<1> A resin composition containing a multimer having an anaerobic curable functional group in its side chain and used under anaerobic conditions in which oxygen supply is suppressed.
<2> The resin composition according to <1>, wherein the multimer has the anaerobic curable functional group at a side chain terminal.
<3> The resin composition according to <1> or <2>, further including an inorganic filler.
<4> The resin composition according to <3>, wherein the content of the inorganic filler is 40% by volume to 90% by volume based on the total solid content.

<5> A resin sheet which is a sheet-shaped molded product of the resin composition according to any one of <1> to <4>.
<6> The two main surfaces are respectively adhered to an adherend, and at least one main surface is used by being adhered to a surface of the adherend containing at least one of metal and metal ions. Resin sheet.
<7> The resin sheet according to <5> or <6>, wherein at least one of the two main surfaces is used by being bonded to a metal-containing layer containing at least one of a metal and a metal ion.
<8> The resin sheet according to any one of <5> to <7>, wherein the resin sheet has a thickness of 30 μm to 400 μm.
<9> The resin sheet according to any one of <5> to <8>, which is cured at a temperature of 5° C. to 70° C.

<10> A metal support, a cured product of the resin sheet according to any one of <5> to <9> disposed on the metal support, and a metal foil disposed on the cured product. And a metal substrate including.

<11> A semiconductor module in which a metal plate, a solder layer, and a semiconductor chip are laminated in this order, a heat dissipation member containing metal, and <5>, which is arranged between the metal plate and the heat dissipation member of the semiconductor module. A cured product of the resin sheet according to any one of <9>, and a power semiconductor device.

<12> A step of laminating a metal support, the resin sheet according to any one of <5> to <9>, and a metal foil in this order, and anaerobic control of oxygen supply to the resin sheet. A method of manufacturing a metal substrate, comprising:
<13> The method for producing a metal substrate according to <12>, wherein in the curing step, the resin sheet is cured at a temperature of 5°C to 70°C.

According to one embodiment of the present invention, a resin composition and a resin sheet that can be cured under room temperature conditions or conditions close to room temperature and have an excellent pot life, and a metal substrate, a power semiconductor device and a metal using the resin sheet. A method for manufacturing a substrate can be provided.

It is a schematic sectional drawing which shows an example of a structure of the power semiconductor device of this indication. It is a schematic sectional drawing which shows an example of a structure of the power semiconductor device of this indication.

Hereinafter, modes for carrying out the resin composition, the resin sheet, the metal substrate, the power semiconductor device, and the method for manufacturing the metal substrate of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present disclosure, the term “process” includes not only a process independent of other processes but also the process even if the process is not clearly distinguishable from the other processes as long as the purpose of the process is achieved. ..
In the present disclosure, the numerical range indicated by using "to" includes the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may include a plurality of types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of types of particles present in the composition unless otherwise specified.
In the present disclosure, the term “layer” may include not only the case where the layer is formed over the entire area when the area where the layer is present is observed, but also the case where the layer is formed only in a part of the area. included.
In the present disclosure, the term “laminate” refers to stacking layers, two or more layers may be combined and two or more layers may be removable.
In the present disclosure, “(meth)acrylic” means acrylic or methacrylic, “(meth)acryloyl” means acryloyl or methacryloyl, and “(meth)acrylate” means acrylate or methacrylate.

<Resin composition>
The resin composition of the present disclosure includes a multimer having an anaerobic curable functional group in its side chain, and is used under anaerobic conditions in which oxygen supply is suppressed. For example, the above resin composition is used to obtain a cured product obtained by curing under anaerobic conditions, and more specifically, a resin sheet that is a sheet-shaped molded product of this resin composition is anaerobic. It is used to obtain a cured product that is cured under the conditions. The above-mentioned resin composition can be cured under room temperature conditions or conditions close to room temperature, and is cured under anaerobic conditions, so that unintentional curing hardly occurs and the pot life is excellent. Furthermore, by using a resin sheet obtained by molding the above-mentioned resin composition into a sheet for adhesion to an adherend, when the resin sheet is adhered to the adherend and then cured, a heating device, a light irradiation device, etc. No special equipment is required, and it is possible to simplify manufacturing equipment and effectively use existing equipment.

Further, the resin composition of the present disclosure includes a multimer having an anaerobic curable functional group in the side chain. This makes it possible to increase the strength of the resin composition before and after curing, and when the resin composition containing a monomer having an anaerobic curable functional group and not containing the above-described polymer is cured. In comparison, the generation of volatile components can be suppressed.

In the present disclosure, the anaerobic conditions in which the supply of oxygen is suppressed means that a molded product of a resin composition such as a resin sheet formed by molding the resin composition into a sheet from the outside (hereinafter, "resin sheet"). It is also referred to as “etc.”) in which the oxygen is not supplied to the resin sheet or the like from the outside.
The environment where it is difficult to supply oxygen to the resin sheet or the like from the outside means that the two main surfaces of the resin sheet or the like are in contact with members each having an oxygen permeability of 0.5 mL/(m ² ·24 h·atm) or less. Means that. For example, when the two main surfaces of a resin sheet or the like are respectively brought into contact with a metal member, the oxygen permeability of the two metal members may be 0.5 mL/(m ² ·24h·atm) or less, When the two main surfaces are brought into contact with the metal member and the resin member, respectively, the oxygen permeability of the metal member and the resin member may be 0.5 mL/(m ² ·24 h·atm) or less.
The oxygen permeability of the member can be measured under the conditions of a temperature of 23° C. and a relative humidity of 65% using an oxygen permeability measuring device (for example, MOCON, OX-TRAN).

(Multimer)
The resin composition of the present disclosure includes a multimer having an anaerobic curable functional group in its side chain (hereinafter, also referred to as “specific multimer”). The anaerobic curable functional group may be any functional group capable of initiating a curing reaction under anaerobic conditions, and at least one of the two main surfaces of the resin sheet or the like under anaerobic conditions is a metal or a metal ion. It is preferably a functional group that initiates a curing reaction under the condition of being in contact with at least one.

As the anaerobic curable functional group, (meth)acryloyl group, vinyl group, allyl group and the like can be mentioned. The multimer preferably has two or more anaerobic curable functional groups in one molecule. The multimer may or may not have an anaerobic curable functional group in the main chain.

The specific multimer preferably has an anaerobic curable functional group at the side chain terminal from the viewpoint of strength when the resin composition is used as a cured product. In addition, the specific multimer may have an anaerobic curable functional group at the main chain terminal, or may have each at the main chain terminal and the side chain terminal.

The main chain of the specific multimer includes olefins such as ethylene and propylene, styrene, vinyl chloride, vinylidene chloride, acrylonitrile, vinylcarbazole, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, It may have a structure in which a monomer such as a monofunctional (meth)acrylic compound having a polyalkylene structure such as (meth)acrylate or methacrylate is homopolymerized or copolymerized.

The specific multimer may include, for example, a multimer represented by the following general formula (I).

In the general formula (I), R ^4's each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. A group in which one hydrogen atom is replaced with an anaerobic curable functional group is shown. R ^5's each independently represent a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom, a hydroxy group, or a group in which one hydrogen atom of a hydroxyalkyl group having 1 to 4 carbon atoms is substituted with an anaerobic curable functional group. m is 1 to 8, v is 0 or 1, and n is 2 to 20.
The group in which one hydrogen atom of the hydroxyalkyl group having 1 to 4 carbon atoms is substituted with the anaerobic curable functional group is preferably a group in which the hydrogen atom of the hydroxy group is substituted with the anaerobic curable functional group.

The specific multimer includes, for example, a multimer having a reactive functional group such as a hydroxy group, an amino group, a carboxy group, an isocyanate group, a thiol group, an epoxy group in a side chain, and a reactive functional group contained in the multimer. It may be a reaction product of a monomer having a reactive functional group and an anaerobic curable functional group that react. This reaction product has a structure in which the reactive functional group in the multimer reacts with the reactive functional group in the monomer, and has an anaerobic curable functional group in the side chain.
Further, the reaction product obtained by reacting the monomer having an anaerobic curable functional group at the terminal with the multimer having the reactive functional group in the side chain has the anaerobic curable functional group at the side chain terminal.

Further, the specific multimer has an anaerobic curable functional group at the main chain terminal, and has a side chain having a reactive functional group such as a hydroxy group, an amino group, a carboxy group, an isocyanate group, a thiol group, and an epoxy group. And a monomer having a reactive functional group that reacts with the reactive functional group contained in the multimer and a monomer having an anaerobic curable functional group. This reaction product has a structure in which the reactive functional group in the multimer reacts with the reactive functional group in the monomer, and has an anaerobic curable functional group at the side chain and main chain terminal.
Furthermore, the reaction product obtained by reacting a monomer having an anaerobic curable functional group at the terminal with a polymer having an anaerobic curable functional group at the main chain terminal and having the above-mentioned reactive functional group in the side chain It has an anaerobic curable functional group at the main chain end and side chain end.

As an example, the specific multimer may be a reaction product of a multimer having a hydroxy group in a side chain and a monomer having an isocyanate group and an anaerobic curable functional group. This reaction product has a urethane bond formed by the reaction of a hydroxy group and an isocyanate group, and has an anaerobic curable functional group in its side chain.

For example, the specific multimer may have the following structure (I) in the side chain.

In the structure (I), R ¹ and R ² each independently represent a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom or a methyl group, and * represents a bonding site. ..

In the structure (I), R ¹ and R ² are each independently a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n -Pentylene group, isopentylene group, neopentylene group, tert-pentylene group and the like.
In structure (I), * is preferably bonded to a carbon atom in the main chain.

The weight average molecular weight (Mw) of the specific multimer is preferably 5,000 to 800,000, more preferably 10,000 to 500,000.
In the present disclosure, the weight average molecular weight refers to a value measured by gel permeation chromatography (GPC).

The content of the specific multimer in the resin composition is not particularly limited. The content of the specific multimer is preferably 5% by mass to 40% by mass, more preferably 7% by mass to 36% by mass, and further preferably 9% by mass to 32% by mass.

The resin composition of the present disclosure, together with a specific multimer, a monomer having an anaerobic curable functional group, a multimer having no anaerobic curable functional group in its side chain and having an anaerobic curable functional group in its main chain. Etc. (hereinafter, also referred to as “other compound”) may be included.

Other examples of the compound include monofunctional (meth)acrylic compounds and polyfunctional (meth)acrylic compounds. Other compounds may be used alone or in combination of two or more.

Specific examples of the monofunctional (meth)acrylic compound include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth). ) Acrylate, isononyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc., alkyl (meth)acrylate having 1 to 18 carbon atoms in the alkyl group; benzyl (meth) ) Acrylate, (meth)acrylate compounds having an aromatic ring such as phenoxyethyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as butoxyethyl (meth)acrylate; amino such as N,N-dimethylaminoethyl (meth)acrylate Alkyl (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monobutyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, hexaethylene glycol monomethyl ether (meth)acrylate, octaethylene glycol monomethyl ether Polyalkylene glycols such as (meth)acrylate, nonaethylene glycol monomethyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, heptapropylene glycol monomethyl ether (meth)acrylate and tetraethylene glycol monoethyl ether (meth)acrylate Monoalkyl ether (meth)acrylate; polyalkylene glycol monoaryl ether (meth)acrylate such as hexaethylene glycol monophenyl ether (meth)acrylate; cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth) (Meth)acrylate compounds having an alicyclic ring such as acrylates and methylene oxide-added cyclodecatriene (meth)acrylates; (meth)acrylate compounds having a heterocycle such as (meth)acryloylmorpholine and tetrahydrofurfuryl (meth)acrylate; hepta Fluorinated alkyl (meth)acrylates such as decafluorodecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth) (Meth)acrylate compound having a hydroxyl group such as acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, octapropylene glycol mono(meth)acrylate; glycidyl( (Meth)acrylate compound having a glycidyl group such as (meth)acrylate; 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate having a isocyanate group-containing (meth)acrylate Compounds: polyethylene glycol mono(meth)acrylates such as tetraethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, octapropylene glycol mono(meth)acrylate; (meth)acrylamide, N,N-dimethyl( (Meth)acrylamide compounds such as (meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylamide; And so on.

Specific examples of the polyfunctional (meth)acrylic compound include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and ethoxy. Bisphenol A-type di(meth)acrylate, propoxylated bisphenol A-type di(meth)acrylate, propoxylated ethoxylated bisphenol A-type di(meth)acrylate, and other alkylene glycol di(meth)acrylates; polyethylene glycol di(meth)acrylate , Polyalkylene glycol di(meth)acrylates such as polypropylene glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri( Tri(meth)acrylate compounds such as (meth)acrylate; tetra(meth)acrylate compounds such as ethylene oxide-added pentaerythritol tetra(meth)acrylate, trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate; Be done.

The content of other compounds in the resin composition may be 10% by mass or less, 5% by mass or less, or 3% by mass or less. Further, the resin composition may not contain any other compound, and may contain 1% by mass or more.

(Inorganic filler)
The resin composition of the present disclosure preferably contains an inorganic filler. The inorganic filler may be non-conductive or conductive. The use of the non-conductive inorganic filler tends to suppress the decrease in insulation. Further, the thermal conductivity tends to be further improved by using the conductive inorganic filler.

Specific examples of the non-conductive inorganic filler include aluminum oxide (alumina), magnesium oxide, aluminum nitride, boron nitride, silicon nitride, silica (silicon dioxide), silicon oxide, aluminum hydroxide, barium sulfate and the like. .. Examples of the conductive inorganic filler include gold, silver, nickel, copper, graphite and the like. Among them, graphite is preferable from the viewpoint of suppressing the curing of the resin composition before adhering to the adherend. Among them, from the viewpoint of thermal conductivity, the inorganic filler is at least one selected from the group consisting of aluminum oxide (alumina), boron nitride, magnesium oxide, aluminum nitride, silica (silicon oxide) and graphite. It is more preferably at least one selected from the group consisting of boron nitride and aluminum oxide (alumina).
These inorganic fillers may be used alone or in combination of two or more.

As the inorganic filler, it is preferable to use a mixture of two or more kinds having different volume average particle diameters. As a result, the small-particle-diameter inorganic filler is packed in the voids of the large-particle-diameter inorganic filler, so that the inorganic-filler is packed more densely than when using only the single-particle-diameter inorganic filler. It becomes possible to exhibit higher thermal conductivity.
Specifically, when aluminum oxide is used as the inorganic filler, 60% by volume to 75% by volume of aluminum oxide having a volume average particle diameter of 16 μm to 20 μm and an average volume average particle diameter of 2 μm to 4 μm are oxidized in the inorganic filler. By mixing aluminum in an amount of 10% to 20% by volume and aluminum oxide having a volume average particle size of 0.3 μm to 0.5 μm in a range of 10% to 20% by volume, more dense packing can be achieved. Become.
Further, when boron nitride and aluminum oxide are used together as the inorganic filler, boron nitride having a volume average particle diameter of 20 μm to 100 μm is oxidized in the inorganic filler having a volume average particle diameter of 2 μm to 4 μm. Higher thermal conductivity can be achieved by mixing 5% by volume to 20% by volume of aluminum and 5% by volume to 20% by volume of aluminum oxide having a volume average particle size of 0.3 μm to 0.5 μm. ..

The volume average particle diameter (D50) of the inorganic filler can be measured using a laser diffraction method. For example, the inorganic filler in the resin composition is extracted and measured using a laser diffraction/scattering particle size distribution analyzer (for example, Beckman Coulter, Inc., trade name: LS230). Specifically, using an organic solvent, nitric acid, aqua regia, etc., the inorganic filler component is extracted from the resin composition and sufficiently dispersed with an ultrasonic disperser or the like, and the weight cumulative particle size distribution curve of this dispersion liquid is calculated. taking measurement.
The volume average particle diameter (D50) refers to a particle diameter at which the cumulative value becomes 50% from the smaller diameter side in the volume cumulative particle size distribution curve obtained by the above measurement.

When the resin composition contains an inorganic filler, the content of the inorganic filler is not particularly limited. Among them, the content of the inorganic filler in the resin composition is preferably 40% by volume or more, more preferably more than 40% by volume, and more preferably 50% by volume from the viewpoint of thermal conductivity. It is more preferably more than 90% by volume and particularly preferably 55% by volume to 80% by volume.
When the content of the inorganic filler is 40% by volume or more, it tends to be possible to achieve higher thermal conductivity. On the other hand, when the content of the inorganic filler is 90% by volume or less, it tends to be possible to suppress deterioration in flexibility and insulation of the cured product of the resin sheet.

The content of the inorganic filler in the resin composition is preferably 40% by mass to 95% by mass, more preferably 50% by mass to 95% by mass, and 60% by mass to 95% by mass based on the total solid content. The content is more preferably mass%, particularly preferably 65 mass% to 95 mass%, and even more preferably 65 mass% to 93 mass%.

(Polymerization initiator)
The resin composition of the present disclosure may contain a polymerization initiator. By including the polymerization initiator, the metal ion and the polymerization initiator react with each other to generate a radical, and the generated radical reacts with the anaerobic curable functional group to suitably proceed the curing reaction.

The polymerization initiator may be an organic peroxide. Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; 1 ,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n -Butyl-4,4-bis(t-butylperoxy)valerate, peroxyketals such as 2,2-bis(t-butylperoxy)butane; t-butyl hydroperoxide, cumene hydroperoxide, diisopropyl Hydroperoxides such as benzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide; di t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α′-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t -Butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 and other dialkyl peroxides; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, deca Diacyl peroxides such as noyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. Kinds; diisopropyl peroxydicarbonate, di2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis-(4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2 -Peroxydicarbonates such as ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, diallyl peroxydicarbonate; t-butyl peroxydiamine Cetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5 -Di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctoate, t-hexylperoxyneodecanoate, t-hexylperoxypivalate, Peroxy esters such as t-butyl peroxy neohexanoate, t-hexyl peroxy neohexanoate, cumyl peroxy neohexanoate; acetylcyclohexyl sulfonyl peroxide, t-butyl peroxy allyl carbonate, etc. Be done.
These organic peroxides may be used alone or in combination of two or more.

When the resin composition contains a polymerization initiator, the content of the polymerization initiator in the resin composition is 0.01 parts by mass with respect to 100 parts by mass of the specific multimer in terms of storage stability and curability. It is preferably from 10 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass.

(Polymerization accelerator)
The resin composition of the present disclosure contains a polymerization accelerator. The polymerization accelerator is not particularly limited, and examples thereof include a hydrazine compound, an amine compound, a mercaptan compound, and a transition metal-containing compound.
These polymerization accelerators may be used alone or in combination of two or more.

The hydrazine compound is not particularly limited, 1-acetyl-2-phenylhydrazine, 1-acetyl-2(p-tolyl)hydrazine, 1-benzoyl-2-phenylhydrazine, 1-(1′,1′, 1'-trifluoro)acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazine, 1-formyl-2-phenylhydrazine, 1-acetyl-2-(p-bromophenyl)hydrazine, 1-acetyl-2 Examples include -(p-nitrophenyl)hydrazine, 1-acetyl-2-(2'-phenylethylhydrazine), ethylcarbazate, p-nitrophenylhydrazine, p-trisulfonylhydrazide and the like.

The amine compound is not particularly limited, and is a heterocyclic secondary amine such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone, 1,2,3,4-tetrahydroquinaldine; quinoline, methylquinoline. , Quinaldine, quinoxalinephenazine and other heterocyclic tertiary amines; N,N-dimethyl-para-toluidine, N,N-dimethyl-anisidine, N,N-dimethylaniline and other aromatic tertiary amines; 1,2 Examples include azole compounds such as 1,4-triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, and 3-mercaptobenzotrizole.

The mercaptan compound is not particularly limited, and examples thereof include linear mercaptans such as n-dodecyl mercaptan, ethyl mercaptan, and butyl mercaptan.

Examples of transition metal-containing compounds include metal chelate complex salts. The metal chelate complex salt is not particularly limited, pentadione iron, pentadione cobalt, pentadione copper, propylenediamine copper, ethylenediamine copper, iron naphthate, nickel naphthate, cobalt naphthate, copper naphthate, copper octate, iron hexoate, iron propionate. , Vanadium acetylacetone and the like.

When the resin composition contains a polymerization accelerator, the content of the polymerization accelerator in the resin composition is 0.05 parts by mass with respect to 100 parts by mass of the specific polymer in terms of storage stability and curing accelerating property. It is preferably from 5 to 5 parts by mass, more preferably from 0.1 to 3 parts by mass.

(Silane coupling agent)
The resin composition may contain at least one silane coupling agent. The silane coupling agent plays a role of forming a covalent bond between the surface of the inorganic filler and the resin that surrounds it (corresponding to a binder agent), improves the thermal conductivity, and prevents moisture from penetrating to insulate the insulation. It can be considered to play a role of improving sex.

The type of silane coupling agent is not particularly limited, and a commercially available one may be used. In the present disclosure, it is preferable to use a silane coupling agent having an acryloyl group, an epoxy group, an amino group, a mercapto group, a ureido group or a hydroxyl group at the terminal.

Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxy Examples include silane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane. it can. Further, a silane coupling agent oligomer represented by trade name: SC-6000KS2 (Hitachi Chemical Techno Service Co., Ltd.) and the like can also be mentioned. These silane coupling agents may be used alone or in combination of two or more.

When the resin composition contains a silane coupling agent, the content of the silane coupling agent in the resin composition is not particularly limited. The content of the silane coupling agent is preferably 0.01% by mass to 0.2% by mass, more preferably 0.03% by mass to 0.1% by mass.

(Other ingredients)
The resin composition may contain other components in addition to the above components, if necessary. The resin composition of the present disclosure may be a varnish-shaped resin composition prepared by adding an organic solvent such as methyl ethyl ketone or cyclohexanone.

<Resin sheet>
The resin sheet of the present disclosure is a sheet-shaped molded product of the resin composition of the present disclosure described above. For example, the above-mentioned resin sheet is used to obtain a cured product after being cured under anaerobic conditions in which the supply of oxygen is suppressed.

Under anaerobic conditions in which the supply of oxygen is suppressed, the two main surfaces of the resin sheet may be in contact with a member having an oxygen permeability of 0.5 mL/(m ² ·24 h·atm) or less, respectively. ^{.3mL / (m 2 · 24h ·} atm) may be in contact with at a member or less, may be in contact with ^{0.1mL / (m 2 · 24h ·} atm) or less is member.

The member that comes into contact with the resin sheet may be an adherend that is adhered to the resin sheet.

Further, the resin sheet of the present disclosure has two main surfaces bonded to an adherend, and at least one main surface bonded to a surface of the adherend containing at least one of metal and metal ions. Is preferred, and it is more preferred that the two main surfaces are used by being adhered to the surface of the adherend containing at least one of metal and metal ions. At least one main surface of the resin sheet is covered under anaerobic conditions in which the supply of oxygen is suppressed, for example, under the condition that the two main surfaces of the resin sheet are in contact with the adherend and the supply of oxygen is suppressed. By adhering to the surface of the adherend containing at least one of the metal and the metal ion, the polymerization reaction of the specific multimer contained in the resin sheet suitably proceeds, and the resin sheet can be suitably cured.

In the resin sheet of the present disclosure, at least one of the two main surfaces may be used by being bonded to a metal-containing layer containing at least one of a metal and metal ions, and the two main surfaces may be bonded to the metal-containing layer. It may be used. Incidentally, another layer may be laminated on the surface of the metal-containing layer that is not bonded to the resin sheet, and this other layer may or may not include at least one of a metal and a metal ion. You don't have to.

Examples of metals include iron, aluminum, zinc, titanium, chromium, manganese, cobalt, nickel, tin, lead, copper, silver and gold, and examples of metal ions include these ions. The metal may be an alloy such as stainless steel.

The thickness of the resin sheet is not particularly limited and can be appropriately selected according to the purpose. For example, the thickness of the resin sheet may be 30 μm to 400 μm, or may be 50 μm to 300 μm from the viewpoint of high thermal conductivity, insulation and curability. In the present disclosure, the thickness of the resin sheet or the like can be measured by a known method, and is the number average value of the values measured at 5 points.

The resin sheet may be cured at a temperature of 5°C to 70°C, preferably 10°C to 40°C.

The use of the resin sheet of the present disclosure is not particularly limited. For example, a semiconductor device can be given. Among semiconductor devices, it is preferably used for parts having a particularly high heat generation density.

The method for producing the resin sheet of the present disclosure is not particularly limited. For example, a resin composition in which a varnish-shaped resin composition prepared by adding an organic solvent such as methyl ethyl ketone or cyclohexanone (hereinafter, also referred to as “resin varnish”) on a resin support is applied by a dispenser or the like. After forming the layer of the product, it can be produced by removing at least a part of the organic solvent from the layer of the resin composition by drying.

The drying method is not particularly limited as long as at least a part of the organic solvent contained in the resin varnish can be removed, and from the commonly used drying methods, the type of the organic solvent contained in the resin varnish, the content may be appropriately selected depending on the content. You can

<Metal substrate>
The metal substrate of the present disclosure includes a metal support, a cured product of the resin sheet of the present disclosure disposed on the metal support, and a metal foil disposed on the cured product. The metal substrate of the present disclosure can be manufactured by curing a resin sheet under room temperature conditions or conditions close to room temperature.

The material, thickness, etc. of the metal support can be appropriately selected according to the purpose. Specifically, a metal such as aluminum or iron can be used and the thickness can be set to 0.5 mm to 5 mm.

The metal foil in the metal substrate is not particularly limited, and examples thereof include gold foil, copper foil, aluminum foil, and the like, and generally copper foil is used.
The thickness of the metal foil is, for example, 1 μm to 200 μm, and is preferably 120 μm or less from the viewpoint of flexibility.
As the metal foil, nickel, nickel-phosphorus alloy, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as an intermediate layer, and a copper foil layer is provided on both surfaces of the foil to form a composite foil having a three-layer structure. Examples include a composite foil having a two-layer structure in which an aluminum foil and a copper foil are combined. In the three-layer composite foil in which copper layers are provided on both surfaces of the intermediate layer, it is preferable that one copper layer has a thickness of 0.5 μm to 15 μm and the other copper layer has a thickness of 10 μm to 300 μm.

<Metal Substrate Manufacturing Method>
The method for producing a metal substrate of the present disclosure includes a step of laminating a metal support, a resin sheet of the present disclosure, and a metal foil in this order, and curing the resin sheet under anaerobic conditions in which oxygen supply is suppressed. And a step of

In the above-mentioned laminating step, a resin sheet is formed by placing the resin composition on the metal support or the metal foil and drying the resin sheet or disposing the resin sheet, and further, the metal foil or the metal support is placed on the resin sheet. By disposing, the metal support, the resin sheet of the present disclosure, and the metal foil may be laminated in this order.

In the curing step described above, the two main surfaces of the resin sheet may be in an anaerobic condition in which the supply of oxygen to the resin sheet is suppressed by contacting the metal support and the metal foil. As a result, when the resin sheet is cured, there is no need for a device, an operation, or the like for setting an anaerobic condition.

In the above curing step, the resin sheet may be cured at a temperature of 5°C to 70°C, preferably 10°C to 40°C.

In the curing step described above, the resin sheet may be cured while being pressurized, for example, 0.05 MPa to 20 MPa may be pressurized, preferably 0.2 MPa to 15 MPa.

<Power semiconductor device>
The power semiconductor device of the present disclosure includes a semiconductor module in which a metal plate, a solder layer, and a semiconductor chip are laminated in this order, a heat dissipation member containing a metal, and the present disclosure disposed between the metal plate and the heat dissipation member of the semiconductor module. And a cured product of the resin sheet.
In the power semiconductor device, only the semiconductor module portion may be sealed with a sealing material or the like, or the entire power semiconductor module may be molded with a molding resin or the like. Hereinafter, an example of the power semiconductor device will be described with reference to the drawings.

FIG. 1 is a schematic sectional view showing an example of the configuration of a power semiconductor device. In FIG. 1, a cured product 102 of a resin sheet is arranged between a metal plate 106 in a semiconductor module in which a metal plate 106, a solder layer 110, and a semiconductor chip 108 are laminated in this order, and a heat dissipation base substrate 104. Is sealed with a sealing material 114. The heat dissipation base substrate 104 can be configured by using copper or aluminum having thermal conductivity.
Further, FIG. 2 is a schematic sectional view showing another example of the configuration of the power semiconductor device. In FIG. 2, a cured product 102 of a resin sheet is arranged between a metal plate 106 in a semiconductor module in which a metal plate 106, a solder layer 110, and a semiconductor chip 108 are laminated in this order, and a heat dissipation base substrate 104. The heat dissipation base substrate 104 is molded with the mold resin 112.

As described above, the cured product of the resin sheet of the present disclosure can be used as a heat dissipation adhesive layer between a semiconductor module and a heat dissipation base substrate as shown in FIG. Further, even when the entire power semiconductor device is molded as shown in FIG. 2, it can be used as a heat dissipation material between the heat dissipation base substrate and the metal plate.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

The materials used for the synthesis of polymer A and polymer B and their abbreviations are shown below.
(monomer)
・Ethyl acrylate (Ethyl acrylate, Fujifilm Wako Pure Chemical Industries, Ltd.)
・Butyl acrylate (n-butyl acrylate, Fujifilm Wako Pure Chemical Industries, Ltd.)
・2-Hydroxyethyl acrylate (NOF CORPORATION)
・2-Isocyanatoethyl methacrylate (MOI) (2-methacryloyloxyethyl isocyanate, Showa Denko KK)
(Polymerization initiator)
・Azobisisobutyronitrile (Fujifilm Wako Pure Chemical Industries, Ltd.)
(catalyst)
・Dibutyltin dilaurate (Fujifilm Wako Pure Chemical Industries, Ltd.)
(solvent)
・Methyl ethyl ketone (Fujifilm Wako Pure Chemical Industries, Ltd.)
・Isopropanol (Fujifilm Wako Pure Chemical Industries, Ltd.)

[Synthesis of acrylic resin]
As described below, the acrylic resin used in the examples was synthesized by a known solution polymerization method.

(Synthesis example of acrylic intermediate A)
A 500 mL flask composed of a stirrer, a thermometer, a nitrogen gas introduction pipe, a discharge pipe and a heating jacket was used as a reactor, and 45.0 g of ethyl acrylate as a monomer, 94.5 g of butyl acrylate, and 2-hydroxyethyl acrylate 10. 5 g and 177.3 g of methyl ethyl ketone as a solvent were mixed and added to the reactor, and the mixture was stirred at room temperature (25° C.) at a stirring rotation speed of 250 rpm, and nitrogen was flowed at 100 mL/min for 1 hour. Thereafter, the temperature was raised to 65° C. over 30 minutes, and after the temperature was completed, a solution prepared by dissolving 0.38 g of azobisisobutyronitrile in 6 g of methyl ethyl ketone was added to the reactor to start the reaction. After that, the mixture was stirred at a reactor internal temperature of 65° C. and reacted for 5 hours. Then, a solution prepared by dissolving 0.08 g of azobisisobutyronitrile in 1.5 g of methyl ethyl ketone was added to the reactor, heated to 80° C. over 15 minutes, and further reacted for 2 hours. Then, the solvent was removed and dried to obtain an acrylic intermediate A.

(Synthesis example of acrylic intermediate B)
A 500 mL flask composed of a stirrer, a thermometer, a nitrogen gas introduction pipe, a discharge pipe, and a heating jacket was used as a reactor, and 41.1 g of ethyl acrylate as a monomer, 86.4 g of butyl acrylate, and 2-hydroxyethyl acrylate 15. 0 g and 164.6 g of isopropanol as a solvent were mixed and added to the reactor, and the mixture was stirred at room temperature (25° C.) at a stirring rotation speed of 250 times/min, and nitrogen was flowed at 100 mL/min for 1 hour. Then, the temperature was raised to 70° C. over 30 minutes, and after the temperature was completed, a solution prepared by dissolving 0.38 g of azobisisobutyronitrile in 3 g of methyl ethyl ketone was added to the reactor to start the reaction. After that, the mixture was stirred at a reactor temperature of 70° C. and reacted for 5 hours. Then, a solution prepared by dissolving 0.08 g of azobisisobutyronitrile in 1.5 g of methyl ethyl ketone was added to the reactor, heated to 80° C. over 15 minutes, and further reacted for 2 hours. Then, the solvent was removed and dried to obtain an acrylic intermediate B.

(Synthesis method of MOI modified acrylic resin)
(Multimer A)
Using a 100-mL eggplant-shaped flask as a reactor, 30 g of acrylic intermediate A, 2 g of MOI, and 0.002 g of dibutyltin dilaurate were mixed, and the mixture was stirred at 75° C. for 1 hour at a rotation speed of 400 times/minute to obtain an acrylic intermediate polymer. MOI-modified to obtain MOI-modified acrylic resin A (multimer A). The weight average molecular weight (Mw) of MOI modified acrylic resin A was 200,000. The multimer A has a urethane bond formed by the reaction of the hydroxy group derived from 2-hydroxyethyl acrylate in the acrylic intermediate A with the isocyanate group in MOI, and has (meth)acryloyl at the side chain end. It is a multimer having a group.
(Multimer B)
Using a 100-mL eggplant-shaped flask as a reactor, 30 g of acrylic intermediate B, 4 g of MOI, and 0.002 g of dibutyltin dilaurate were mixed, and the mixture was stirred at 75° C. for 1 hour at a stirring rotation number of 400 times/minute to obtain an acrylic intermediate polymer. MOI modified to obtain MOI modified acrylic resin B (multimer B). The weight average molecular weight (Mw) of MOI modified acrylic resin B was 20000. The multimer B has a urethane bond formed by the reaction between the hydroxy group derived from 2-hydroxyethyl acrylate in the acrylic intermediate B and the isocyanate group in the MOI, and has (meth)acryloyl at the side chain terminal. It is a multimer having a group.

The materials used for the preparation of the resin composition and the resin sheet and their abbreviations are shown below.
(Specific multimers)
・Polymer A (weight average molecular weight 200,000)
・Polymer B (weight average molecular weight 20000)

・Polymerization initiator: Cumene hydroperoxide (Tokyo Chemical Industry Co., Ltd.)
・Polymerization accelerator: Cobalt naphthenate (Tokyo Chemical Industry Co., Ltd.)

(Other curable compounds and curing agents)
-Resin A: YL6121H (Mitsubishi Chemical Corporation, epoxy equivalent: 172 g/eq)
-Curing agent A: MEHC-7403H [highly heat-resistant and flame-retardant phenolic resin, Meiwa Kasei Co., Ltd., hydroxyl equivalent: 136 g/eq]
-Curing agent B: QC11 (manufactured by Mitsubishi Chemical Corporation, amine value: 420 KOHmg/g)
-Curing accelerator A: TPP (triphenylphosphine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

(Inorganic filler)
Inorganic filler 1: AA-18 (alumina particles, Sumitomo Chemical Co., Ltd., D50: 18 μm)
Inorganic filler 2: AA-3 (alumina particles, Sumitomo Chemical Co., Ltd., D50: 3 μm)
Inorganic filler 3: AA-04 (alumina particles, Sumitomo Chemical Co., Ltd., D50: 0.4 μm)
Inorganic filler 4: HP-40 (boron nitride particles, Mizushima Iron & Iron Co., Ltd., D50: 40 μm)

(Additive)
-KBM-573: 3-phenylaminopropyltrimethoxysilane [silane coupling agent, Shin-Etsu Chemical Co., Ltd., trade name]

(solvent)
・Methyl ethyl ketone (Fujifilm Wako Pure Chemical Industries, Ltd.)

(Support)
・PET film [Teijin Film Solutions Co., Ltd., trade name: A31, thickness 50 μm, oxygen permeability 100 mL/(m ² ·24 h·atm) or less]

・Copper foil [Furukawa Electric Co., Ltd., thickness: 105 μm, GTS grade, oxygen permeability 0.5 mL/(m ² ·24 h·atm) or less]

<Example 1>
(Preparation of resin composition)
9.76% by mass of the polymer A, 0.1% by mass of the polymerization initiator, 0.01% by mass of the polymerization accelerator, 50.34% by mass of the inorganic filler 1, and 2 of the inorganic filler 2. 18.30% by mass, 7.63% by mass of the inorganic filler 3, 0.08% by mass of the additive, and 13.78% by mass of the solvent are mixed to prepare a varnish-like resin composition. did.
The density of the inorganic filler 1 is 3.98 g/cm ³ , the density of the inorganic filler 2 is 3.98 g/cm ³ , the density of the inorganic filler 3 is 3.98 g/cm ³ , the polymer A, the polymerization initiator, and When the density of the polymerization accelerator was 1.2 g/cm ^{3 and} the ratio of the inorganic filler to the total volume of the total solid content of the resin composition was calculated, it was 70% by volume.

(Preparation of B stage sheet)
Using this varnish, a PET film was applied using an applicator so that the thickness after drying was 200 μm, and then dried at 70° C. for 10 minutes. After that, a copper foil is placed on the opposite side of the PET film, and pressure is applied (press temperature: room temperature, press pressure: 2 MPa, pressurization time: 2 minutes) with a press machine, and a PET film and a B stage sheet with copper foil are applied. Got

(Curing of resin sheet)
Peel off the PET film from the PET film and B stage sheet with copper foil, place the copper foil on the surface from which the PET film was peeled off, and press-bond with a press machine (press temperature: room temperature, press pressure: 2 MPa, pressurizing time: 12 hours). By doing so, a cured resin sheet was obtained.

(B stage sheet curability)
To evaluate the curability of the B stage sheet, the above varnish-shaped resin composition was applied onto a PET film using an applicator so that the thickness after drying was 200 μm, and then dried at 70° C. for 10 minutes. A sample before being B-staged was prepared.
Furthermore, the PET film was peeled off from the PET film and the B stage sheet with the copper foil, and after the B stage, a sample was prepared.
Using a differential scanning calorimeter (manufactured by Perkin Elmer, model number DSC8500), the sample before and after the B stage was heated from 20°C to 300°C at 10°C/min, and the calorific value was measured.
The curing rate A was calculated by the following formula.
Curing rate A (%) = (heat generation amount of sample after B stage conversion/heat generation amount of sample before B stage conversion) x 100
<Evaluation of curability>
The curability was evaluated based on the following criteria.
A: Curing rate 50% or more B: Curing rate less than 50%

(PET film peelability)
The ratio of the resin sheet attached to the PET film (resin transfer rate) when the PET film was peeled off from the PET film and the B-stage sheet with copper foil was calculated based on the following formula.
Resin transfer rate (%)=(mass of resin sheet attached to PET film/mass of resin sheet before peeling)×100
<Evaluation of peelability>
The peelability was evaluated based on the following criteria.
A: Resin transfer rate of less than 5% B: Resin transfer rate of 5% or more

(Curing confirmation)
For confirmation of curing, a sample before being B-staged was prepared in the same manner as the curability of the B-stage sheet described above.
Further, the above-mentioned cured resin sheet was used as a sample after curing.
Using a differential scanning calorimeter (manufactured by Perkin Elmer, model number DSC8500), the pre-B-stage sample and the post-curing sample were heated from 20° C. to 300° C. at 10° C./min, and the calorific value was measured.
The curing rate B was calculated by the following formula.
Curing rate B (%)=(calorific value of sample after curing/calorific value of sample before B stage conversion)×100
<Evaluation of curability>
The curability was evaluated based on the following criteria.
A: Curing rate less than 20% B: Curing rate 20% or more

(Measurement of thermal conductivity)
The copper foil of the cured resin sheet was removed by etching to obtain a resin sheet for evaluating thermal conductivity. The obtained resin sheet was cut into a length of 10 mm and a width of 10 mm to obtain a sample. After blackening the sample with graphite spray, the thermal diffusivity was evaluated by the xenon flash method (trade name: LFA447 nanoflash of NETZSCH). The thermal conductivity of the cured resin sheet was obtained from the product of this value, the density measured by the Archimedes method, and the specific heat measured by DSC (differential scanning calorimeter; product name of Perkin Elmer: DSC Pyris1). .. The results are shown in Table 1.

<Example 2>
(Preparation of resin composition)
9.76% by mass of the polymer B, 0.1% by mass of the polymerization initiator, 0.01% by mass of the polymerization accelerator, 50.34% by mass of the inorganic filler 1, and 2 of the inorganic filler. 18.30% by mass, 7.63% by mass of the inorganic filler 3, 0.08% by mass of the additive, and 13.78% by mass of the solvent are mixed to prepare a varnish-like resin composition. did.
The density of the inorganic filler 1 is 3.98 g/cm ³ , the density of the inorganic filler 2 is 3.98 g/cm ³ , the density of the inorganic filler 3 is 3.98 g/cm ³ , the polymer A, the polymerization initiator, and When the density of the polymerization accelerator was 1.2 g/cm ^{3 and} the ratio of the inorganic filler to the total volume of the total solid content of the resin composition was calculated, it was 70% by volume.

<Example 3>
(Preparation of resin composition)
Polymer A 15.00 mass %, polymerization initiator 0.15 mass %, polymerization accelerator 0.01 mass %, inorganic filler 4 33.34 mass %, inorganic filler 2 7.54% by mass, 7.54% by mass of the inorganic filler 3, 0.05% by mass of the additive, and 36.37% by mass of the solvent are mixed to prepare a varnish-like resin composition. did.
The density of the inorganic filler 4 is 2.20 g/cm ³ , the density of the inorganic filler 2 is 3.98 g/cm ³ , the density of the inorganic filler 3 is 3.98 g/cm ³ , the polymer A, the polymerization initiator, and When the density of the polymerization accelerator was 1.2 g/cm ^{3 and} the ratio of the inorganic filler to the total volume of the total solid content of the resin composition was calculated, it was 60% by volume.

<Comparative Example 1>
(Preparation of resin composition)
The resin A is 5.53% by mass, the curing agent A is 4.30% by mass, the curing accelerator is 0.2% by mass, the inorganic filler 1 is 50.24% by mass, and the inorganic filler 2 is 18%. A varnish-like resin composition was prepared by mixing 0.27% by mass, 7.61% by mass of the inorganic filler 3, 0.08% by mass of the additive, and 13.77% by mass of the solvent. ..
The density of the inorganic filler 1 is 3.98 g/cm ³ , the density of the inorganic filler 2 is 3.98 g/cm ³ , the density of the inorganic filler 3 is 3.98 g/cm ³ , the polymer A, the polymerization initiator, and When the density of the polymerization accelerator was 1.2 g/cm ^{3 and} the ratio of the inorganic filler to the total volume of the total solid content of the resin composition was calculated, it was 70% by volume.

<Comparative example 2>
(Preparation of resin composition)
6.57% by mass of the resin A, 3.29% by mass of the curing agent B, 50.34% by mass of the inorganic filler 1, 18.30% by mass of the inorganic filler 2 and 3 of the inorganic filler 3. 7.63% by mass, 0.08% by mass of the additive, and 13.79% by mass of the solvent were mixed to prepare a varnish-shaped resin composition.
The density of the inorganic filler 1 is 3.98 g/cm ³ , the density of the inorganic filler 2 is 3.98 g/cm ³ , the density of the inorganic filler 3 is 3.98 g/cm ³ , the polymer A, the polymerization initiator, and When the density of the polymerization accelerator was 1.2 g/cm ^{3 and} the ratio of the inorganic filler to the total volume of the total solid content of the resin composition was calculated, it was 70% by volume.

<Comparative example 3>
(Preparation of resin composition)
Butyl acrylate 6.15% by mass, ethyl acrylate 2.93% by mass, 2-hydroxyethyl acrylate 0.68% by mass, polymerization initiator 0.10% by mass, and polymerization accelerator 0.01% by mass, 50.34% by mass of the inorganic filler 1, 18.30% by mass of the inorganic filler 2, 7.63% by mass of the inorganic filler 3, and 0.08% by mass of the additive. And 13.78 mass% of a solvent were mixed to prepare a varnish-like resin composition.
The density of the inorganic filler 1 is 3.98 g/cm ³ , the density of the inorganic filler 2 is 3.98 g/cm ³ , the density of the inorganic filler 3 is 3.98 g/cm ³ , and butyl acrylate and ethyl acrylate. The ratio of the inorganic filler to the total volume of the total solid content of the resin composition was calculated by setting the densities of the 2-hydroxyethyl acrylate, the polymerization initiator and the polymerization accelerator to be 1.2 g/cm ³ and found to be 70% by volume. there were.

Regarding Examples 2 and 3 and Comparative Examples 1 to 3, under the same conditions as in Example 1, the curability of the B stage sheet, the PET film peeling property, the confirmation of curing, and the measurement of the thermal conductivity were performed.
The results are shown in Table 1. In addition, "-" in Table 1 means that there is no data.

In Examples 1 to 3, regarding the curability of the B stage, it is presumed that the value of the curing rate A increased because the curing of the resin sheet proceeded without the heat treatment. Furthermore, in Examples 1 to 3, the curing progressed sufficiently even without heat treatment, so it is presumed that the value of the curing rate B became low.
From the above, it was found that in Examples 1 to 3, the resin sheet could be cured under room temperature conditions. Furthermore, since it is cured under anaerobic conditions, unintentional curing is unlikely to occur and the pot life is presumed to be excellent.

In Comparative Example 1, regarding the curability of the B stage, it is presumed that the value of the curing rate A increased because the curing of the resin sheet proceeded without heat treatment. However, in Comparative Example 1, it is presumed that the value of the curing rate B became high because the curing did not proceed sufficiently when the same operation as in Example 1 in which the curing was performed without the heat treatment was performed.
In Comparative Example 2, regarding the curability of the B-stage sheet, the varnish-shaped resin composition was applied to a PET film and then cured when dried, and the value of the curing rate A was low.
From the above, in Comparative Examples 1 and 2, it was found that unintended curing of the resin sheet proceeded before being attached to the adherend, and the pot life was poor.

Further, in Comparative Example 3, since the monomer having the anaerobic curable functional group was used, the resin was likely to remain on the PET film, and the PET film releasability was insufficient.

All documents, patent applications, and technical standards mentioned herein are to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference, Incorporated herein by reference.

102: cured product of resin sheet, 104: heat dissipation base substrate, 106: metal plate, 108: semiconductor chip, 110: solder layer, 112: mold resin, 114: sealing material

Claims (13)

1. Including a multimer having an anaerobic curable functional group in the side chain,
   A resin composition used under anaerobic conditions in which supply of oxygen is suppressed.
2. The resin composition according to claim 1, wherein the multimer has the anaerobic curable functional group at a side chain end.
3. The resin composition according to claim 1 or 2, further comprising an inorganic filler.
4. The resin composition according to claim 3, wherein the content of the inorganic filler is 40% by volume to 90% by volume based on the total solid content.
5. A resin sheet which is a sheet-shaped molded product of the resin composition according to any one of claims 1 to 4.
6. The resin sheet according to claim 5, wherein the two main surfaces are used by being adhered to an adherend, respectively, and at least one main surface is used by being adhered to a surface containing at least one of metal and metal ions of the adherend.
7. The resin sheet according to claim 5 or 6, wherein at least one of the two main surfaces is used by being bonded to a metal-containing layer containing at least one of a metal and a metal ion.
8. The resin sheet according to any one of claims 5 to 7, wherein the resin sheet has a thickness of 30 µm to 400 µm.
9. The resin sheet according to any one of claims 5 to 8, which is cured at a temperature of 5°C to 70°C.
10. A metal support, a cured product of the resin sheet according to any one of claims 5 to 9 disposed on the metal support, and a metal foil disposed on the cured product. Metal substrate.
11. 10. A semiconductor module in which a metal plate, a solder layer, and a semiconductor chip are laminated in this order, a heat dissipation member containing metal, and the semiconductor module is arranged between the metal plate and the heat dissipation member of the semiconductor module. A cured product of the resin sheet according to claim 1.
12. A step of laminating a metal support, the resin sheet according to any one of claims 5 to 9 and a metal foil in this order;
    Curing the resin sheet under anaerobic conditions in which the supply of oxygen is suppressed,
    A method of manufacturing a metal substrate including:
13. The method for manufacturing a metal substrate according to claim 12, wherein in the curing step, the resin sheet is cured at a temperature of 5°C to 70°C.

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