WO2021182365A1 - Resin composition and resin sheet - Google Patents

Abstract

This resin composition comprises a thermosetting component (A), a binder component (B), and a filler (C). The thermosetting component (A) comprises a maleimide resin (A1), and the filler (C) comprises a surface-modified polytetrafluoroethylene filler (C1).

Description

Resin composition and resin sheet

The present invention relates to a resin composition and a resin sheet.

As a sealing material for electronic components, a resin composition having high heat resistance and dielectric properties (low dielectric constant, low dielectric loss tangent, etc.) is used.
For example, Patent Document 1 discloses an epoxy resin composition containing a phenol resin composition having a triazine ring, a monomaleimide-modified phenol resin composition obtained from a monomaleimide compound, and an epoxy resin. ..

Japanese Unexamined Patent Publication No. 2006-056921

However, the cured product of the resin composition described in Patent Document 1 has a dielectric constant of 3.9 at 1 GHz and a dielectric loss tangent of 0.004 at 1 GHz, which is not always sufficient in terms of dielectric properties. There wasn't.

An object of the present invention is to provide a resin composition and a resin sheet capable of sufficiently lowering the dielectric constant and the dielectric loss tangent.

The resin composition according to one aspect of the present invention is a resin composition containing (A) a thermosetting component, (B) a binder component, and (C) a filler, and is the above-mentioned (A) thermosetting component. The component contains (A1) maleimide resin and (A2) allyl resin, and the (C) filler contains (C1) surface-modified polytetrafluoroethylene filler.

In the resin composition according to one aspect of the present invention, it is preferable that the (A2) allyl resin has an aromatic ring.

In the resin composition according to one aspect of the present invention, it is preferable that the allyl group in the (A2) allyl resin is directly bonded to the aromatic ring.

In the resin composition according to one aspect of the present invention, it is preferable that the (A2) allyl resin has a hydroxy group and the hydroxy group is directly bonded to the aromatic ring.

In the resin composition according to one aspect of the present invention, the content of the (C1) surface-modified polytetrafluoroethylene filler in the (C) filler is 20 based on the total solid content of the (C) filler. It is preferably mass% or more.

In the resin composition according to one aspect of the present invention, the content of the (C1) surface-modified polytetrafluoroethylene filler is preferably 15% by mass or more based on the total solid content of the resin composition. ..

In the resin composition according to one aspect of the present invention, it is preferable that the surface-modified polytetrafluoroethylene filler (C1) is surface-modified with silica.

The resin composition according to one aspect of the present invention preferably further contains (E) an adhesion-imparting agent.

In the resin composition according to one aspect of the present invention, it is preferable that the (E) adhesion-imparting agent is a compound having a basic group and a triazine skeleton in one molecule.

In the resin composition according to one aspect of the present invention, it is preferable that the (E) adhesion-imparting agent is a compound having a triazine skeleton and an imidazole structure in one molecule.

The resin sheet according to one aspect of the present invention is characterized by being formed from the resin composition according to one aspect of the present invention.

In the resin sheet according to one aspect of the present invention, the dielectric constant at 1 GHz after curing of the resin sheet is preferably 3 or less.

In the resin sheet according to one aspect of the present invention, the dielectric loss tangent at 1 GHz after curing of the resin sheet is preferably 0.005 or less.

In the resin sheet according to one aspect of the present invention, it is preferable that it is used for sealing a power semiconductor element or for interposing it between the power semiconductor element and another electronic component.

In the resin sheet according to one aspect of the present invention, a semiconductor element using any one or more of silicon carbide and gallium nitride is sealed, or any one or more of the silicon carbide and gallium nitride is used. It is preferably used for interposing between a semiconductor element and another electronic component.

According to one aspect of the present invention, it is possible to provide a resin composition and a resin sheet capable of sufficiently lowering the dielectric constant and the dielectric loss tangent.

It is sectional drawing of the laminated body which concerns on one Embodiment.

[Resin composition]
First, the resin composition according to this embodiment will be described.
The resin composition according to the present embodiment contains (A) a thermosetting component, (B) a binder component, and (C) a filler. The (A) thermosetting component according to the present embodiment contains (A1) maleimide resin. Further, the (C) filler according to the present embodiment contains (C1) a surface-modified polytetrafluoroethylene filler.

((A) Thermosetting component)
The thermosetting component (A) (hereinafter, may be simply referred to as “component (A)”) has a property of forming a three-dimensional network when heated and firmly adhering an adherend. As described above, the (A) thermosetting component in the present embodiment includes (A1) maleimide resin (hereinafter, may be simply referred to as “(A1) component”) and (A2) allyl resin (hereinafter, simply “A1) component”. It may be referred to as "(A2) component").

(A1) Maleimide Resin The (A1) maleimide resin in the present embodiment is not particularly limited as long as it is a maleimide resin containing two or more maleimide groups in one molecule.

From the viewpoint of heat resistance, the maleimide resin (A1) in the present embodiment preferably contains, for example, a benzene ring, and more preferably contains a structure in which a maleimide group is linked to the benzene ring. Further, the maleimide compound preferably includes two or more structures in which a maleimide group is linked to a benzene ring.

The (A1) maleimide resin in the present embodiment is a maleimide resin containing two or more maleimide groups and one or more biphenyl skeletons in one molecule (hereinafter, may be simply referred to as "biphenyl maleimide resin"). Is preferable.

The maleimide resin (A1) in the present embodiment is preferably represented by the following general formula (1) from the viewpoint of heat resistance and adhesiveness.

In the general formula (1), k is an integer of 1 or more, and the average value of k is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and 1 or more and 3 or less. It is more preferable to have. m1 and m2 are independently integers of 1 or more and 6 or less, preferably 1 or more and 3 or less, and more preferably 1. n1 and n2 are independently integers of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0. R ¹ and R ² are independently alkyl groups having 1 to 6 carbon atoms, preferably alkyl groups having 1 to 3 carbon atoms, and more preferably methyl groups. A plurality of R ¹ may or different are identical to one another. A plurality of R ² is, or different are identical to one another.

Specific examples of the maleimide resin represented by the general formula (1) in the present embodiment include compounds represented by the following general formula (2) or the following general formula (3).

In the general formulas (2) and (3), k is the same as k in the general formula (1). In the general formula (2), n1, n2, ^{R 1} and ^{R 2} are the same as n1, n2, ^{R 1} and ^{R 2} in the general formula (1).
Examples of the maleimide resin product represented by the general formula (3) include "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

Further, the maleimide resin (A1) in the present embodiment is preferably a maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule. It is preferable to have a substituent on the phenylene group from the viewpoint of increasing the solubility in a solvent and improving the sheet formability. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group, an alkylene group and the like.
Further, the maleimide resin (A1) in the present embodiment is preferably a maleimide resin having an ether bond between the maleimide group and the phenylene group from the viewpoint of sheet formability.

The maleimide resin containing two or more maleimide groups and two or more phenylene groups in the one molecule is represented by, for example, the following general formula (4).

In the general formula (4), R ³ to R ⁶ are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and L ¹ is an alkylene group having 1 to 3 carbon atoms. L ² and L ³ are independently alkylene groups having 1 or more and 2 or less carbon atoms or arylene groups having 6 or more and 10 or less carbon atoms, and p and q are independently 0 or 1, respectively. However, the total number of carbon atoms ^{in L 1} , L ² and L ^{3 is 3 or less.}

The maleimide resin represented by the general formula (4) in the present embodiment is specifically represented by, for example, the following general formula (5) or the following general formula (6).

In the general formulas (5) and (6), L ¹ is an alkylene group having 1 or more carbon atoms and 3 or less carbon atoms.
In the general formula (5), R ³ to R ⁶ are independently hydrogen atoms or alkyl groups having 1 or more and 6 or less carbon atoms.

Further, the maleimide resin (A1) in the present embodiment has two or more maleimide groups in one molecule from the viewpoint of flexibility and heat resistance, and has at least one pair of binding groups linking the maleimide groups. , A maleimide resin having four or more methylene groups in the main chain is preferable.
Here, the bonding group linking the two maleimide groups preferably has 6 or more methylene groups in the main chain, and more preferably 8 or more methylene groups in the main chain, from the viewpoint of flexibility. , It is particularly preferable to have 10 or more methylene groups in the main chain. Further, it is more preferable that these methylene groups are linked to form an alkylene group having 4 or more carbon atoms. In this alkylene group, at least one -CH _2- may be replaced with -CH _2- O- or -O-CH _2-.
Further, the bonding group connecting the two maleimide groups preferably has one or more side chains from the viewpoint of flexibility. Examples of this side chain include an alkyl group and an alkoxy group. Further, when there are two or more side chains, the side chains may be bonded to each other to form an alicyclic structure.

Further, such (A1) maleimide resin is preferably a liquid maleimide resin at a temperature of 25 ° C. Further, a liquid maleimide resin at a temperature of 25 ° C. and a solid maleimide resin at a temperature of 25 ° C. may be used in combination.

From the viewpoint of flexibility and heat resistance, such (A1) maleimide resin is preferably represented by the following general formula (7).

In the general formula (7), n is an integer of 0 or more, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less. The average value of n is preferably 0.5 or more and 5 or less, and more preferably 1 or more and 2 or less.
L ⁴ and L ⁵ are independently substituted or unsubstituted alkylene groups having 4 or more carbon atoms, and in this alkylene group, at least one -CH ₂ -is -CH _2- O- or -O-. It may be replaced by _{CH 2-.} From the viewpoint of flexibility, the alkylene group preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, and particularly preferably 10 or more and 30 or less carbon atoms. When the hydrogen of the alkylene group is substituted, the substituent is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Further, these substituents may be bonded to each other to form an alicyclic structure.
X is independently, having 4 or more substituted or unsubstituted alkylene group having a carbon (at least one -CH ₂ - including those replaced by - is _-CH 2 -O- or -O-CH _2. ), And further preferably a divalent group having a phthalimide group. The phthalimide group also includes a group derived from phthalimide. Specific examples of X include a group represented by the following structural formula (7-1), the following general formula (7-2), or the following general formula (7-3).

In the general formula (7-2), Y ¹ and Y ² are each independently a hydrogen, a methyl group or an ethyl group, and are preferably a methyl group.
Specific examples of the maleimide resin represented by the general formula (7) in the present embodiment include the following general formula (7-1-1), the following general formula (7-2-1), and the following general. Examples thereof include a compound represented by the formula (7-3-1).

In the general formulas (7-1-1) and (7-2-1), n is an integer of 1 or more and 5 or less. The average value of n is 1 or more and 2 or less.
In the general formula (7-3-1), n ₁₁ is an integer of 1 or more and 5 or less.
Examples of the maleimide resin product represented by the general formula (7-1-1) include Designer Moleculars Inc. Examples thereof include "BMI-1500" manufactured by Shin-Etsu Chemical Co., Ltd. and "SLK-1500" manufactured by Shin-Etsu Chemical Co., Ltd.
Examples of the maleimide resin product represented by the general formula (7-2-1) include Designer Molecules Inc. Examples thereof include "BMI-1700" manufactured by the company.
Examples of the maleimide resin product represented by the general formula (7-3-1) include "SLK-3000" manufactured by Shin-Etsu Chemical Co., Ltd.

Specific examples of the (A1) maleimide resin in the present embodiment include the maleimide resin and the screw (3) represented by the general formula (3) from the viewpoint of obtaining a cured product having high sheet formability and heat resistance. -Ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, 4-methyl-1,3-phenylenebismaleimide, polyphenylmethanemaleimide, or 2,2-bis [4- (4-Maleimidephenoxy) phenyl] propane is preferable, and from the viewpoint of sheet formability, the maleimide resin represented by the general formula (3) or bis (3-ethyl-5-methyl-4-maleimide) is preferable. Phenyl) methane is more preferable, and the maleimide resin represented by the general formula (3) is further preferable from the viewpoint of lowering the complex viscosity at a high temperature before curing of the resin sheet according to the present embodiment.
Further, as the (A1) maleimide resin in the present embodiment, specifically, for example, from the viewpoint of flexibility and heat resistance, the maleimide resin represented by the general formula (7) is more preferable. In addition, these maleimide resins can be used individually by 1 type or in combination of 2 or more type. Then, the maleimide resin represented by the general formula (3) and the maleimide resin represented by the general formula (7) may be used in combination.

In the present embodiment, the content of the component (A1) in the component (A) is based on the total amount of the solid content of the component (A) (that is, the amount of the non-volatile content of the component (A) excluding the solvent is 100% by mass. When), it is preferably 60% by mass or more, more preferably 65% by mass or more, and particularly preferably 70% by mass or more. When the content of the component (A1) in the component (A) is in such a range, the heat resistance of the resin composition according to the present embodiment after curing can be improved.

(A2) Allyl Resin The (A) thermosetting component contained in the resin composition in the present embodiment needs to further contain (A2) an allyl resin. The (A2) allyl resin is preferably liquid at room temperature. Since the thermosetting component (A) contains an allyl resin, it is possible to improve the peel strength of the resin sheet after curing while lowering the reaction temperature of the resin sheet according to the present embodiment.

In the present embodiment, the mass ratio (A1 / A2) of the maleimide resin as the component (A1) to the (A2) allyl resin is preferably 1.5 or more, and more preferably 3 or more.
When the mass ratio (A1 / A2) is in the above range, the storage elastic modulus E'at 250 ° C. of the cured product of the resin sheet tends to increase.
Further, when the mass ratio (A1 / A2) is in the above range, the heat resistance of the resin sheet can be improved.
When the mass ratio (A1 / A2) is within the above range, the complex viscosity η of the resin sheet is appropriately adjusted to ensure the fluidity of the resin sheet when applied to an adherend, and the resin sheet is cured. Later, further improvement in heat resistance is realized. Further, when the mass ratio (A1 / A2) is in the above range, bleeding out of the allyl resin from the resin sheet is also suppressed. The upper limit of the mass ratio (A1 / A2) is not particularly limited. For example, the mass ratio (A1 / A2) may be 50 or less, and preferably 10 or less.

The (A2) allyl resin in the present embodiment is not particularly limited as long as it is a resin having an allyl group. The (A2) allyl resin in the present embodiment is preferably, for example, an allyl resin containing two or more allyl groups in one molecule. Further, this (A2) allyl resin preferably has an aromatic ring. Further, it is preferable that the allyl group in the (A2) allyl resin is directly bonded to the aromatic ring. Further, it is preferable that the (A2) allyl resin has a hydroxy group, and the hydroxy group is directly bonded to the aromatic ring.
The allyl resin in the present embodiment is more preferably represented by the following general formula (8), the following general formula (9), or the following general formula (10).

In the general formula (8), R ⁷ and R ⁸ are independently alkyl groups, preferably alkyl groups having 1 to 10 carbon atoms, and preferably alkyl groups having 1 to 4 carbon atoms. More preferably, it is an alkyl group selected from the group consisting of a methyl group and an ethyl group.
In the general formula (9), n3 is 1 or more and 4 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less. Further, in the allyl resin represented by the general formula (9), the ratio of the component having n3 of 1 is preferably 90 mol% or more.

The (A2) allyl resin in the present embodiment is specifically represented by, for example, diallyl bisphenol A (2,2-bis (3-allyl-4-hydroxyphenyl) propane), which is represented by the general formula (9). Examples thereof include an allylphenol resin and an allylphenol resin represented by the general formula (10). These allyl resins can be used alone or in combination of two or more.

(A3) Curing Catalyst In the resin sheet according to the present embodiment, when the resin composition contains a thermosetting resin, it is preferable that the resin sheet further contains a curing catalyst. As a result, the curing reaction of the thermosetting resin can be effectively advanced, and the resin sheet can be cured satisfactorily. Examples of the curing catalyst include an imidazole-based curing catalyst, an amine-based curing catalyst, a phosphorus-based curing catalyst, and the like.

Specific examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-Phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl Examples thereof include -2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-di (hydroxymethyl) imidazole. From the viewpoint of reactivity, it is preferable to use 2-ethyl-4-methylimidazole. When a compound having a triazine skeleton and an imidazole structure is used as the (E) adhesion-imparting agent described later, it also acts as a curing catalyst.

Specific examples of the amine-based curing catalyst include tertiary amine compounds such as 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine.

Specific examples of the phosphorus-based curing catalyst include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine and the like.

The (A) thermosetting component of the present embodiment is a thermosetting resin other than the (A1) component, a cured resin other than the (A2) component, and a non-(A3) component as long as the object of the present invention is not impaired. It may contain a curing catalyst.
The thermosetting resin other than the component (A1) may be a thermosetting resin having high heat resistance, and examples thereof include an epoxy resin, a benzoxazine resin, a cyanate resin, and a melamine resin. These thermosetting resins can be used alone or in combination of two or more. However, from the viewpoint of high heat resistance, it is preferable that the (A) thermosetting component does not substantially contain an epoxy resin.
Examples of the cured resin other than the component (A2) include phenol resins, resins such as resins having a C = C double bond other than the component (A2), acid anhydrides, and resins containing formaldehyde. Be done. These cured resins can be used alone or in combination of two or more.
Examples of the curing catalyst other than the component (A3) include triazole-based compounds and thiazole-based compounds. These curing catalysts can be used alone or in combination of two or more.
When a thermosetting resin other than the component (A1), a curing resin other than the component (A2), and a curing catalyst other than the component (A3) are used, these contents are based on the total amount of the solid content of the component (A). (That is, when the amount of the non-volatile content of the component (A) excluding the solvent is 100% by mass), it is preferably 10% by mass or less, and more preferably 5% by mass or less.

In the present embodiment, the content of the (A) thermosetting component in the resin composition is based on the total amount of the solid content of the resin composition (that is, the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). When), it is preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit of the content of the thermosetting component (A) is preferably 75% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less.
When the content of the thermosetting component (A) is within the above range, the handleability of the resin sheet, the sheet shape retention property, and the heat resistance of the resin composition are improved.

((B) Binder component)
The (B) binder component (hereinafter, may be simply referred to as “(B) component”) in the present embodiment is a resin component other than the (A) component, and has a function of joining the (A) component or other components. Has. By including the binder component (B), film-forming property can be imparted and the resin composition can be easily formed into a sheet. The binder component (B) is preferably a thermoplastic resin. The component (B) may have a functional group as long as it has a function of joining the component (A) or other components. When the (B) binder component has a functional group as described above, even if the (B) binder component can be involved in the curing of the resin sheet by heat, in the present invention, the (B) binder component is (A) thermosetting. Distinguished from sex components.
(B) The binder component can be widely selected regardless of whether it is an aliphatic compound or an aromatic compound. The binder component (B) is preferably at least one resin selected from the group consisting of, for example, phenoxy resin, acrylic resin, methacrylic resin, polyester resin, urethane resin, and polyamideimide resin, and is preferably from the viewpoint of heat resistance. It is more preferable that at least one of the resins selected from the group consisting of phenoxy resin and polyamideimide resin is used. The polyester resin is preferably a total aromatic polyester resin. Further, as the polyamide-imide resin, a rubber-modified polyamide-imide resin is preferable from the viewpoint of improving the flexibility of the resin sheet. (B) The binder component may be used alone or in combination of two or more.

The phenoxy resin includes a bisphenol A skeleton (hereinafter, bisphenol A may be referred to as "BisA"), a bisphenol F skeleton (hereinafter, bisphenol F may be referred to as "BisF"), a biphenyl skeleton, and a naphthalene skeleton. A phenoxy resin having one or more skeletons selected from the above group is preferable, and a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton is more preferable.

(B) The weight average molecular weight (Mw) of the binder component is preferably 10,000 or more and 1 million or less, preferably 30,000 or more and 800,000 or less, from the viewpoint of facilitating the adjustment of the complex viscosity of the resin sheet to a desired range. It is more preferable that it is 50,000 or more and 100,000 or less. The weight average molecular weight in the present specification is a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.

In the present embodiment, the content of the binder component (B) in the resin composition is based on the total amount of the solid content of the resin composition (that is, when the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). ), It is preferably 1.5% by mass or more, more preferably 2% by mass or more, and particularly preferably 2% by mass or more. The upper limit of the content of the binder component (B) is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 15% by mass or less.
By setting the content of the binder component (B) in the resin composition to the above range, it becomes easy to adjust the complex viscosity of the resin sheet before curing to a desired range, and the handleability and sheet formability of the resin sheet are improved. improves.

((C) Filler)
The (C) filler in the present embodiment (hereinafter, may be simply referred to as “(C) component”) is at least (C1) surface-modified polytetrafluoroethylene filler (hereinafter, simply referred to as “(C1) component”). May contain). With this component (C), at least one of the thermal properties and the mechanical properties of the resin composition can be improved. Further, the component (C1) can reduce the dielectric constant and the dielectric loss tangent of the cured product of the resin composition.
(C1) The surface-modified polytetrafluoroethylene filler is obtained by modifying the surface of the polytetrafluoroethylene filler (PTFE filler) to improve the dispersibility in the resin composition. Further, the (C1) surface-modified polytetrafluoroethylene filler is preferably surface-modified with silica. Examples of the product of the component (C1) include a surface-modified PTFE filler manufactured by Admatex Co., Ltd.

The average particle size of the component (C1) is not particularly limited. The average particle size of the component (C1) is preferably 0.1 nm or more, more preferably 10 nm or more, and particularly preferably 1 μm or more. The upper limit of the average particle size of the component (C1) is preferably 100 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The average particle size of the component (C1) in the present specification is a value measured by a laser diffraction type particle size distribution meter.
The specific surface area of the component (C1) is not particularly limited. The specific surface area of the component (C1) ^{is preferably 0.1 m 2} / g or more, more preferably 0.5 m ² / g or more, and ^{particularly preferably 1 m 2} / g or more. The upper limit of the specific surface area of the component (C1) ^{is preferably 10 m 2} / g or less, ^{more preferably 8 m 2} / g or less, and ^{particularly preferably 5 m 2} / g or less.

In the present embodiment, the content of the component (C1) in the component (C) is based on the total amount of the solid content of the component (C) (that is, the amount of the non-volatile content of the component (C) excluding the solvent is 100% by mass. It is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more. The upper limit of the content of the component (C1) is preferably 100% by mass or less.
When the content of the component (C1) in the component (C) is in such a range, the dispersibility of the component (C1) in the resin composition can be improved, and the resin composition or the cured product of the resin sheet can be improved. Dielectric properties can be improved.

The content of the component (C1) in the resin composition is 15% by mass based on the total solid content of the resin composition (that is, when the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). The above is preferable, 20% by mass or more is more preferable, 30% by mass or more is further preferable, and 40% by mass or more is particularly preferable. The upper limit of the content of the component (C1) is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and 50% by mass or less. Is particularly preferred.
By setting the content of the component (C1) in the resin composition within the above range, the dispersibility of the component (C1) in the resin composition can be improved, and the dielectric properties of the resin composition or the cured product of the resin sheet can be improved. Can be improved.

(C1) Surface modification The surface modification material of the polytetrafluoroethylene filler is not particularly limited as long as it can modify the surface of polytetrafluoroethylene. Examples of the surface modification material include oxides (silica (crystalline silica and amorphous silica), alumina, titanium oxide, calcium oxide, magnesium oxide, aluminum oxide, etc.), hydroxides (aluminum hydroxide, and aluminum oxide, etc.). Magnesium hydroxide, etc.), carbonates (calcium carbonate, magnesium carbonate, etc.), silicates (calcium silicate, magnesium silicate, etc.), borates (aluminum borate whiskers, etc.), nitrides (aluminum nitride, etc.) And boron nitride, etc.), glass, composite oxides (mulite, cordierite, etc.), minerals (montmorillonite, smectite, etc.) and the like. These can be used alone or in combination of two or more. Among these, it is preferable to use silica.

The (C) filler in the present embodiment preferably further contains a (C2) inorganic filler (hereinafter, may be simply referred to as “(C2) component”).
Examples of the (C2) inorganic filler include silica filler, alumina filler, and boron nitride filler. Among these, silica filler is preferable.
Examples of the silica filler include molten silica and spherical silica.
(C2) The inorganic filler may be used alone or in combination of two or more. Further, the (C2) inorganic filler may be surface-treated.

(C2) The average particle size of the inorganic filler is not particularly limited. The average particle size of the (C2) inorganic filler is preferably 0.1 nm or more, more preferably 10 nm or more, as a value obtained from a general particle size distribution meter. The upper limit of the average particle size of the (C2) inorganic filler is preferably 100 μm or less, and more preferably 10 μm or less. The average particle size of the (C2) inorganic filler in the present specification is a value measured by a dynamic light scattering method using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., product name "Nanotrack Wave-UT151"). And.

The content of the filler (C) in the resin composition is 10% by mass based on the total solid content of the resin composition (that is, when the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). The above is preferable, 20% by mass or more is more preferable, 40% by mass or more is further preferable, and 60% by mass or more is particularly preferable. The upper limit of the content of the filler (C) is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less.
By setting the content of the filler (C) in the resin composition within the above range, the coefficient of linear expansion of the resin composition can be lowered, and for example, an object to be sealed such as silicon carbide and the resin composition or the resin sheet can be used. The difference in the coefficient of linear expansion can be reduced.

((D) Coupling agent)
In the present embodiment, the resin composition preferably further contains (D) a coupling agent in addition to the components (A) to (C).
The coupling agent preferably has a functional group of the compound contained in the above-mentioned (A) thermosetting component or a group that reacts with the functional group of the binder component, and (A) the thermosetting component. It is more preferable to have a group that reacts with the functional group of the compound contained in.

(D) By using the coupling agent, the peel strength between the cured product of the resin sheet and the adherend is improved.

As the (D) coupling agent, a silane-based (silane coupling agent) is preferable because of its versatility and cost merit. (D) The coupling agent may be used alone or in combination of two or more. The content of the coupling agent as described above is 0.05 based on the total solid content of the resin composition (that is, when the total non-volatile content of the resin composition excluding the solvent is 100% by mass). It is preferably 0% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. The upper limit of the content of the coupling agent is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

((E) Adhesion imparting agent)
In the present embodiment, the resin composition preferably further contains (E) an adhesion-imparting agent in addition to the components (A) to (D). The adhesiveness-imparting agent (E) can further improve the peel strength of the resin composition after curing.
Examples of the adhesion-imparting agent include compounds having a triazine skeleton. As the compound having a triazine skeleton, the following compounds are preferable. That is, the component (E) is preferably a compound having a basic group and a triazine skeleton in one molecule, and has a nitrogen-containing heterocycle and a triazine skeleton in one molecule. It is more preferably a compound, and a compound having a triazine skeleton and an imidazole structure in one molecule is preferable.
Examples of the compound having a triazine skeleton and an imidazole structure include a compound represented by the following general formula (11).

In the general formula (11), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, a hydroxymethyl group, or a phenyl group, and have a hydrogen atom or 1 or more carbon atoms. It is preferably an alkyl group of 10 or less, and more preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms. R ¹³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an allyl group, preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. Is more preferable. L ⁶ is an alkylene group having 1 or more and 5 or less carbon atoms, preferably an alkylene group having 2 or more and 4 or less carbon atoms, and more preferably an ethylene group.

Specific examples of the imidazole compound having a triazine skeleton in the present embodiment include 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, 2 , 4-Diamino-6- [2- (2-ethyl-4-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, and 2,4-diamino-6- [2- (2-undecyl) -1-Imidazolyl) ethyl] -1,3,5-triazine and the like can be mentioned. Among these compounds, 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5 from the viewpoint of peeling strength and reaction temperature of the resin composition and the resin sheet. -Triazine or 2,4-diamino-6- [2- (2-ethyl-4-methyl-1-imidazolyl) ethyl] -1,3,5-triazine is preferred.

In the present embodiment, the content of the (E) adhesion-imparting agent in the resin composition is based on the total amount of the solid content of the resin composition (that is, the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). When), it is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more. The upper limit of the content of the (E) adhesion-imparting agent is preferably 5% by mass or less, and more preferably 3% by mass or less.
When the content of the adhesion-imparting agent is within the above range, the peel strength of the resin composition after curing can be further improved.

As an example of the resin composition according to the present embodiment, a resin composition containing only the component (A), the component (B) and the component (C), the component (A), the component (B), the component (C) and Examples thereof include a resin composition containing only the component (D), and a resin composition containing only the component (A), the component (B), the component (C), the component (D) and the component (E).
Further, as another example of the resin composition according to the present embodiment, as described below, the component (A), the component (B), the component (C), the component (D) and the component (E), and (A). ) To a resin composition containing a component other than the component (E).

(Other ingredients)
In the present embodiment, the resin composition may further contain other components. Other components are selected from the group consisting of, for example, cross-linking agents, pigments, dyes, defoamers, leveling agents, UV absorbers, foaming agents, antioxidants, flame retardants, ion trapping agents, and ion scavengers. At least one of the components can be mentioned.
For example, the resin composition may further contain a cross-linking agent in order to adjust the initial adhesiveness and cohesiveness of the resin sheet before curing.
Examples of the cross-linking agent include organic polyvalent isocyanate compounds and amino resins. The cross-linking agent may be used alone or in combination of two or more.

Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimerics of these polyvalent isocyanate compounds, and Examples thereof include a terminal isocyanate urethane prepolymer obtained by reacting these polyvalent isocyanate compounds with a polyol compound.
More specific examples of the organic polyvalent isocyanate compound include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene. Isocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4 '-Diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysocyanate and the like can be mentioned. The organic multivalent isocyanate compound may be used alone or in combination of two or more.

As the amino resin, urea resin, melamine resin, guanamine resin, cocondensation resin thereof and the like can be used.

When the above-mentioned cross-linking agent is used, the content of the cross-linking agent is preferably 0.01 part by mass or more, and 0.1 part by mass or more with respect to 100 parts by mass of the binder component (B) described above. More preferably. The upper limit of the content of the cross-linking agent is preferably 12 parts by mass or less, and more preferably 10 parts by mass or less.

In the present embodiment, when the resin sheet is formed by coating, the resin composition preferably contains a solvent. As the solvent, in addition to general solvents such as toluene, ethyl acetate and methyl ethyl ketone, cyclohexanone (boiling point: 155.6 ° C.), dimethylformamide (boiling point: 153.6 ° C.), dimethyl sulfoxide (boiling point: 189.0 ° C.), ethylene Examples thereof include high boiling point solvents such as glycol ethers (cellosolve) (boiling point: about 120 to 310 ° C.) and ortho-xylene (boiling point: 144.4 ° C.).

[Resin sheet]
The resin sheet according to the present embodiment is formed from the above-mentioned resin composition according to the present embodiment. In the resin sheet according to the present embodiment, the dielectric constant and the dielectric loss tangent can be further lowered while maintaining heat resistance.
The present embodiment of the present embodiment, from the viewpoint of sealing the semiconductor element and the ability to follow the unevenness of the adherend to be attached when the resin sheet is used for interposing between the semiconductor element and other electronic components. It is preferable that it comprises only the resin composition according to the above. That is, it is preferable that the resin sheet is not a composite material such as a combination of a resin composition and a fiber sheet, such as a prepreg.

The dielectric constant of the resin sheet according to the present embodiment at 1 GHz after heat curing is preferably 3 or less, more preferably 2.9 or less, still more preferably 2.8 or less. It is particularly preferable that it is 7 or less. The lower limit of the dielectric constant at 1 GHz is particularly preferably 1 or more.
When the dielectric constant of the resin sheet according to the present embodiment at 1 GHz after heat curing is not more than the upper limit, the dielectric constant can be sufficiently lowered when the resin sheet is used as a sealing material.

The dielectric loss tangent at 1 GHz after heat curing of the resin sheet according to the present embodiment is preferably 0.005 or less, more preferably 0.004 or less, still more preferably 0.0035 or less. It is particularly preferably 0.003 or less. The lower limit of the dielectric loss tangent at 1 GHz is preferably 0.001 or more.
When the dielectric loss tangent at 1 GHz after heat curing of the resin sheet according to the present embodiment is equal to or less than the upper limit, the dielectric loss tangent can be sufficiently lowered when the resin sheet is used as a sealing material.

The dielectric constant and dielectric loss tangent at 1 GHz after thermosetting of the resin sheet according to the present embodiment can be measured by the following method. That is, a resin sheet was laminated to 200 μm and cured at 200 ° C. for 4 hours to obtain a sample. The relative permittivity and dielectric loss tangent at 1 GHz of the obtained sample were measured by an automatic equilibrium bridge method using an RF impedance / material analyzer E4991A (manufactured by Agilent Technologies, Inc.).

The peel strength of the resin sheet according to the present embodiment after thermosetting is preferably 2.0 N / 10 mm or more, more preferably 3.0 N / 10 mm or more, and 4.0 N / 10 mm or more. Is more preferable, and 6.0 N / 10 mm or more is particularly preferable. The upper limit of the peel strength after thermosetting is preferably 50 N / 10 mm or less, and particularly preferably 40 N / 10 mm or less.
When the peel strength of the resin sheet according to the present embodiment after thermosetting is 2.0 N / 10 mm or more, high adhesiveness to the adherend is maintained when the resin sheet is used as a sealing material. It is possible.
For the peel strength of the resin sheet according to the present embodiment after thermosetting, for example, a component used in the resin composition is selected, and at least one selected from an allyl resin and an adhesion imparting agent is preferably blended in the resin composition. However, it can be adjusted within the above range by adjusting the type and blending amount.
The peel strength of the resin sheet according to the present embodiment after thermosetting is subjected to a peeling test at a peeling angle of 90 degrees between the thermosetting resin sheet and the adherend by using the measurement method described later. Asked by doing. Specifically, as described in the examples, a test piece was prepared and a peeling test was performed.
In the resin sheet according to the present embodiment, since the resin composition is made into a sheet, it becomes easy to apply it to an adherend, and especially when the adherend has a large area, it becomes easy to attach it.
If the resin composition is in the form of a sheet, it is formed in advance in a shape suitable for the shape after the sealing step, so that it can be supplied as a sealing material having a certain degree of uniformity just by applying it. Further, if the resin composition is in the form of a sheet, it has no fluidity and is excellent in handleability.

The method for forming the resin composition into a sheet can be a conventionally known method for forming a sheet, and is not particularly limited. When a resin sheet is formed from the resin composition by applying the resin composition containing a solvent, the solvent may be completely volatilized in the drying step after the application, or a part of the solvent may remain in the resin sheet. You may let me. The resin sheet according to the present embodiment may be a strip-shaped sheet or may be provided in a rolled state. The resin sheet according to the present embodiment wound in a roll shape can be used by being unwound from the roll and cut into a desired size.

The thickness of the resin sheet according to the present embodiment is, for example, preferably 10 μm or more, and more preferably 20 μm or more. The thickness is preferably 500 μm or less, more preferably 400 μm or less, and further preferably 300 μm or less.

The resin sheet according to this embodiment is preferably used for a semiconductor element. Specifically, the resin sheet according to this embodiment is preferably used for sealing a semiconductor element. Further, the resin sheet according to the present embodiment is preferably used for interposing between the semiconductor element and other electronic components.
The semiconductor element is preferably a power semiconductor element.
Since the resin sheet according to this embodiment has excellent heat resistance, it is intended to enclose a power semiconductor element that is expected to operate at a high temperature of 200 ° C. or higher, or to interpose it between the power semiconductor element and other electronic components. Can be used for.

Further, it is preferable that the resin sheet according to the present embodiment is collectively applied to a plurality of semiconductor elements. For example, if the resin composition is in the form of a sheet, a resin sheet is applied to a structure in which semiconductor elements are arranged in each gap of a frame provided with a plurality of gaps, and the frame and the semiconductor element are collectively combined. It can be used for sealing, so-called panel level packages.

Further, the resin sheet according to the present embodiment is preferably used for sealing a semiconductor element using any one or more of silicon carbide and gallium nitride. Alternatively, the resin sheet according to the present embodiment is preferably used for interposing between a semiconductor element using any one or more of silicon carbide and gallium nitride and other electronic components. Examples of other electronic components include a printed wiring board, a lead frame, and the like.
Since the upper limit of the operating temperature of the silicon semiconductor element is about 175 ° C., it is preferable to use a semiconductor element using any one or more of silicon carbide and gallium nitride capable of high temperature operation for the power semiconductor element.
Since the resin sheet according to the present embodiment has excellent heat resistance, a semiconductor element using any one or more of silicon carbide and gallium nitride, which is expected to operate at a high temperature of 200 ° C. or higher, is sealed or silicon carbide is used. It can be used for interposing between a semiconductor device using any one or more of gallium nitride and gallium nitride and another electronic component.

(Thermosetting conditions)
Under the thermosetting conditions of the resin sheet according to the present embodiment, the heating temperature is preferably 50 ° C. or higher and 300 ° C. or lower, and preferably 100 ° C. or higher and 250 ° C. or lower.
Under the thermosetting conditions of the resin sheet according to the present embodiment, the heating time is preferably 10 minutes or more and 10 hours or less, and more preferably 20 minutes or more and 7 hours or less.
When the thermosetting condition of the resin sheet is within the above range, the thermosetting of the resin sheet can be realized.

[Laminate]
FIG. 1 shows a schematic cross-sectional view of the laminated body 1 according to the present embodiment.
The laminate 1 according to the present embodiment has a first release material 2, a second release material 4, and a resin sheet 3 provided between the first release material 2 and the second release material 4. The resin sheet 3 is a resin sheet according to the present embodiment.

The first release material 2 and the second release material 4 have a release property, and there is a difference between the release force of the first release material 2 against the resin sheet 3 and the release force of the second release material 4 against the resin sheet 3. Is preferable. The materials of the first release material 2 and the second release material 4 are not particularly limited. The ratio (P2 / P1) of the peeling force P2 of the second peeling material 4 to the peeling force P1 of the first peeling material 2 is preferably 0.02 ≦ P2 / P1 <1 or 1 <P2 / P1 ≦ 50. ..

The first release material 2 and the second release material 4 may be, for example, a member having a release property in the release material itself, a member having been subjected to a release treatment, a member having a release agent layer laminated, or the like. good. When the first release material 2 and the second release material 4 have not been subjected to the release treatment, examples of the material of the first release material 2 and the second release material 4 include an olefin resin and a fluororesin. Be done.
The first release material 2 and the second release material 4 can be a release material including a release base material and a release agent layer formed on the release base material. By using a release material having a release base material and a release agent layer, handling becomes easy. Further, the first release material 2 and the second release material 4 may have a release agent layer on only one side of the release base material, or may have a release agent layer on both sides of the release base material. The release agent can be formed, for example, by applying a release agent.

Examples of the peeling base material include a paper base material, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper base material, and a plastic film. Examples of the paper base material include glassine paper, coated paper, cast coated paper and the like. Examples of the plastic film include a polyester film (for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), a polyolefin film (for example, polypropylene, polyethylene, etc.) and the like. Of these, polyester film is preferable.

Examples of the release agent include a silicone-based release agent composed of a silicone resin; a long-chain alkyl group-containing compound-based release agent composed of a compound containing a long-chain alkyl group such as polyvinyl carbide and an alkylurea derivative; An alkyd resin-based release agent composed of a resin (for example, a non-convertible alkyd resin, a convertible alkyd resin, etc.); an olefin resin (for example, polyethylene (for example, high-density polyethylene, low-density polyethylene, and linear low-density)). Olefin resin-based release agent composed of polyethylene, etc.), a propylene homopolymer having an isotactic structure or a syndiotactic structure, and a crystalline polypropylene resin such as a propylene-α-olefin copolymer; , And rubber-based release agents composed of rubbers such as synthetic rubbers (eg, butadiene rubbers, isoprene rubbers, styrene-butadiene rubbers, methyl methacrylate-butadiene rubbers, and acrylonitrile-butadiene rubbers); and (meth) acrylic acid esters. Examples thereof include various release agents such as an acrylic resin type release agent composed of an acrylic resin such as a system copolymer, and these can be used alone or in combination of two or more types. Of these, alkyd resin-based release agents are preferable. In particular, when a phenoxy resin or a polyamide-imide resin is used as the binder component (B) of the resin composition contained in the resin sheet 3, if a general silicone-based release agent is used, the release material is unintentionally used as the resin sheet. Since there is a concern that the material 3 may be peeled off before use, it is preferable to use an alkyd resin-based release agent.

The thickness of the first release material 2 and the second release material 4 is not particularly limited. Usually, it is 1 μm or more and 500 μm or less, and preferably 3 μm or more and 100 μm or less.
The thickness of the release agent layer is not particularly limited. When a solution containing a release agent is applied to form a release agent layer, the thickness of the release agent layer is preferably 0.01 μm or more and 3 μm or less, and more preferably 0.03 μm or more and 1 μm or less.

The manufacturing method of the laminated body 1 is not particularly limited. For example, the laminated body 1 is manufactured through the following steps. First, a resin composition containing a solvent is applied onto the first release material 2 to form a coating film. Next, this coating film is dried to form the resin sheet 3. Next, the laminate 1 is obtained by laminating the resin sheet 3 and the second release material 4 at room temperature. In this case, when the types of the release materials of the first release material 2 and the second release material 4 are the same, the ratio of the release force P2 of the second release material 4 to the release force P1 of the first release material 2 (P2). / P1) is likely to be P2 / P1 <1, and even if the release materials of the first release material 2 and the second release material 4 are different, it is first to apply the resin composition. Due to the release material 2, the value of P2 / P1 tends to be small.

[Effect of Embodiment]
According to the resin composition and the resin sheet according to the present embodiment, a resin composition and a resin sheet capable of sufficiently lowering the dielectric constant and the dielectric loss tangent can be obtained.

As described above, the resin sheet according to this embodiment can be suitably used for a power semiconductor element. In other words, in the semiconductor device according to the present embodiment, the semiconductor element is preferably a power semiconductor element. Power semiconductor devices are also expected to operate at high temperatures of 200 ° C. or higher. Therefore, the material used for the semiconductor device having the power semiconductor element is required to have heat resistance. Since the resin sheet according to the present embodiment has excellent heat resistance, it is suitably used for covering a power semiconductor element in a semiconductor device or for interposing it between a power semiconductor element and another component.

As described above, the resin sheet according to this embodiment can be suitably used for a semiconductor device using any one or more of silicon carbide and gallium nitride. In other words, in the semiconductor device according to the present embodiment, the semiconductor element is preferably a semiconductor element using any one or more of silicon carbide and gallium nitride. Semiconductor devices using any one or more of silicon carbide and gallium nitride have characteristics different from those of silicon semiconductor devices. Therefore, power semiconductor devices, high-power devices for base stations, sensors, detectors, Schottky barrier diodes, etc. It is preferably used in the above applications. In these applications, attention is also paid to the heat resistance of semiconductor devices using any one or more of silicon carbide and gallium nitride. Since the resin sheet of the present embodiment has excellent heat resistance, silicon carbide and gallium nitride are used. It is preferably used in combination with a semiconductor device using any one or more of the above.

[Modification of Embodiment]
The present invention is not limited to the above-described embodiment, and modifications and improvements within the range in which the object of the present invention can be achieved are included in the present invention.

In the above embodiment, the laminate having the first release material, the second release material, and the resin sheet provided between the first release material and the second release material has been described, but in addition, the resin sheet has been described. It may be a laminate having a release material on only one surface.

Further, although the semiconductor encapsulation application has been described in the embodiment of the semiconductor device, the resin sheet of the present invention also has other insulating materials for circuit boards (for example, hard printed wiring board materials, flexible wiring board materials, and materials. It can be used as an interlayer insulating material for a build-up substrate, etc.), an adhesive film for build-up, an adhesive, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

[Preparation of resin composition]
The resin compositions according to Examples 1 to 4 and Comparative Example 1 were prepared by dissolving or dispersing each component in a solvent at the blending ratio (mass% (ratio in terms of solid content)) shown in Table 1.
Further, the resin compositions according to Examples 5 to 9 and Comparative Example 2 were prepared by dissolving or dispersing each component in a solvent at the blending ratio (mass% (ratio in terms of solid content)) shown in Table 2. bottom.
The materials used to prepare the resin composition are as follows.

(Thermosetting component)
-Maleimide resin-1: Maleimide resin having a biphenyl group (maleimide resin represented by the general formula (3), "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.)
-Maleimide resin-2: Long-chain alkyl type maleimide resin (maleimide resin represented by the general formula (7-2-1), "BMI-1700" manufactured by Designer Molecules Inc., liquid at a temperature of 25 ° C.)
-Maleimide resin-3: Long-chain alkyl type maleimide resin (maleimide resin represented by the general formula (7-3-1), "SLK-3000" manufactured by Shin-Etsu Chemical Co., Ltd., solid at a temperature of 25 ° C.)
-Maleimide resin-4: Long-chain alkyl type maleimide resin (maleimide resin represented by the general formula (7-1-1), "SLK-1500" manufactured by Shin-Etsu Chemical Co., Ltd., liquid at a temperature of 25 ° C.)
-Allyl resin: Diallyl bisphenol A ("DABPA" manufactured by Daiwa Kasei Kogyo Co., Ltd.)
-Curing catalyst (adhesion-imparting agent): 2,4-diamino-6- [2- (2-ethyl-4-methyl-1-imidazolyl) ethyl] -1,3,5-triazine (Shikoku Kasei Kogyo Co., Ltd.) Made by "2E4MZ-A")
-Epoxy resin: Biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.)
-Phenol resin: Biphenyl-type phenol novolac resin ("MEH-7851-H" manufactured by Meiwa Kasei Co., Ltd.)

(Binder component)
-Binder resin: BisA type phenoxy resin ("YX7200B35" manufactured by Mitsubishi Chemical Corporation)

(Filler)
-Surface-modified PTFE filler: Surface-modified PTFE filler (average particle size 3.0 μm, specific surface area 3.6 m ² / g, manufactured by Admatex Co., Ltd., surface-modified material: silica)
-Silica filler: Fused silica (epoxysilane modification, average particle size 0.5 μm, maximum particle size 2.0 μm)

(Coupling agent)
-Silane coupling agent: 3-glycidoxypropyltriethoxysilane

<Evaluation of resin composition and resin sheet>
[Preparation of laminate including resin sheet]
Resin varnish (cyclohexanone and methyl ethyl ketone) on the first release material (polyethylene terephthalate film provided with a release layer formed from an alkyd resin-based release agent, PET38AL-5 manufactured by Lintec Co., Ltd., thickness 38 μm) with a knife coater. A coating solution in which each component of the resin composition was dissolved or dispersed, and a solid content concentration of 60% by mass) was applied to the mixed solvent, dried at 90 ° C. for 1 minute, and then dried at 115 ° C. for 1 minute. The thickness of the resin composition after drying was 25 μm. Immediately after taking out from the drying furnace, the resin composition after drying and the second release material (polyethylene terephthalate film provided with a release layer formed from a silicone-based release agent, manufactured by Lintec Corporation, SP-PET382150, thickness 38 μm) ) At room temperature to prepare a laminate in which the first release material, the resin sheet made of the resin composition, and the second release material are laminated in this order.

[Measurement of peel strength]
One surface of the resin sheet in the obtained laminate is bonded (laminated) to a wafer piece (thickness 800 μm) obtained by cutting a 6-inch Si wafer into four equal parts in advance by pressure-bonding under reduced pressure at a lamination temperature of 130 ° C. Equipment: "V-130" manufactured by Nikko Materials Co., Ltd .; Conditions: Ultimate pressure 100 Pa, time 60 seconds) Then, on the other surface of the resin sheet, copper foil (size 50 mm x 10 mm, thickness 350 μm, JIS) The H 3100 specification) was bonded by pressure-pressing under the same conditions as above. The second release material and the first release material of the resin sheet in the laminated body were peeled before being attached to the Si wafer and the copper plate, respectively. Then, the resin composition was cured under the thermosetting conditions of 4 hours at a temperature of 200 ° C. to prepare a sample. However, the sample of Comparative Example 1 was cured at a temperature of 100 ° C. for 30 minutes and then at a temperature of 190 ° C. for 2 hours under thermosetting conditions. For this sample, the copper foil was peeled off from the cured resin sheet under the conditions of a peeling speed of 50 mm / min and a peeling angle of 90 degrees using a tensile tester (“Autograph AG-IS” manufactured by Shimadzu Corporation). The peel strength (unit: N / 10 mm) between the copper foil and the cured resin sheet was measured. The measurement was performed in an environment of 23 ° C. and a relative humidity of 50%. The results obtained are shown in Tables 1 and 2.

[Measurement of permittivity and dielectric loss tangent]
Eight of the obtained resin sheets were laminated to obtain a thickness of 200 μm, then peeled from the release material and then cured at a temperature of 200 ° C. under thermosetting conditions for 4 hours to prepare a sample. However, the sample of Comparative Example 1 was cured at a temperature of 100 ° C. for 30 minutes and then at a temperature of 190 ° C. for 2 hours under thermosetting conditions. The relative permittivity and dielectric loss tangent at 1 GHz of the obtained sample were measured by an automatic equilibrium bridge method using an RF impedance / material analyzer E4991A (manufactured by Agilent Technologies, Inc.). The results obtained are shown in Tables 1 and 2.

It was found that the resin compositions and resin sheets according to Examples 1 to 4 had good evaluations of peel strength, dielectric constant, and dielectric loss tangent. Further, Comparative Example 1 was a conventional epoxy-based pressure-sensitive adhesive sheet, but it was found that the results of dielectric constant and dielectric loss tangent were inferior to those of Example 1 and the like. Therefore, it was confirmed that the resin compositions and resin sheets according to Examples 1 to 4 can have a sufficiently low dielectric constant and dielectric loss tangent.

It was found that the resin compositions and resin sheets according to Examples 5 to 9 had good evaluations of peel strength, dielectric constant, and dielectric loss tangent. Further, Comparative Example 2 was a pressure-sensitive adhesive sheet containing no surface-modified PTFE filler, but it was found that the result of the dielectric constant was inferior to that of Example 5 and the like. Therefore, it was confirmed that the resin compositions and resin sheets according to Examples 5 to 9 can have a sufficiently low dielectric constant and dielectric loss tangent.

1 ... Laminated body, 2 ... First release material, 3 ... Resin sheet, 4 ... Second release material.

Claims (15)

1. A resin composition containing (A) a thermosetting component, (B) a binder component, and (C) a filler.
   The (A) thermosetting component contains (A1) maleimide resin and (A2) allyl resin.
   The (C) filler contains (C1) surface-modified polytetrafluoroethylene filler.
   Resin composition.
2. In the resin composition according to claim 1,
   The (A2) allyl resin has an aromatic ring.
   Resin composition.
3. In the resin composition according to claim 2,
   The allyl group in the (A2) allyl resin is directly bonded to the aromatic ring.
   Resin composition.
4. In the resin composition according to any one of claims 1 to 3.
   The (A2) allyl resin has a hydroxy group, and the hydroxy group is directly bonded to an aromatic ring.
   Resin composition.
5. In the resin composition according to any one of claims 1 to 4.
   The content of the (C1) surface-modified polytetrafluoroethylene filler in the (C) filler is 20% by mass or more based on the total solid content of the (C) filler.
   Resin composition.
6. In the resin composition according to any one of claims 1 to 5.
   The content of the (C1) surface-modified polytetrafluoroethylene filler is 15% by mass or more based on the total solid content of the resin composition.
   Resin composition.
7. In the resin composition according to any one of claims 1 to 6.
   The (C1) surface-modified polytetrafluoroethylene filler is surface-modified with silica.
   Resin composition.
8. In the resin composition according to any one of claims 1 to 7.
   Further, (E) containing an adhesion imparting agent,
   Resin composition.
9. In the resin composition according to claim 8,
   The (E) adhesion-imparting agent is a compound having a basic group and a triazine skeleton in one molecule.
   Resin composition.
10. In the resin composition according to claim 9,
    The (E) adhesion-imparting agent is a compound having a triazine skeleton and an imidazole structure in one molecule.
    Resin composition.
11. It is formed from the resin composition according to any one of claims 1 to 10.
    Resin sheet.
12. In the resin sheet according to claim 11,
    The dielectric constant of the resin sheet at 1 GHz after curing is 3 or less.
    Resin sheet.
13. In the resin sheet according to claim 11 or 12.
    The dielectric loss tangent at 1 GHz after curing of the resin sheet is 0.005 or less.
    Resin sheet.
14. In the resin sheet according to any one of claims 11 to 13.
    It is used to seal a power semiconductor element or to intervene between the power semiconductor element and another electronic component.
    Resin sheet.
15. In the resin sheet according to any one of claims 11 to 13.
    Encapsulating a semiconductor device using at least one of silicon carbide and gallium nitride, or between a semiconductor device using at least one of silicon carbide and gallium nitride and another electronic component. Used for intervening,
    Resin sheet.

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