JPWO2018168715A1 - Resin composition and resin sheet - Google Patents

Abstract

(A) A resin composition containing a thermosetting component, wherein the (A) thermosetting component contains (A1) a maleimide resin, and the (A1) maleimide resin contains two components in one molecule. A resin composition containing the above maleimide group and having a complex viscosity η at 90 ° C. before curing of the resin composition of 1.0 × 102 Pa · s or more and 1.0 × 104 Pa · s or less.

Description

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

As a sealing material for a power semiconductor or the like, a resin composition having high heat resistance is used.
For example, Patent Document 1 discloses a maleimide compound, a compound having at least one of an allyl group and an epoxy group, an amine compound, and a radical generator containing at least one of an acetophenone derivative and a tetraphenylethane derivative. A resin composition containing the same is disclosed.

JP-A-2015-147849

  However, the resin composition described in Patent Document 1 has a problem that it does not have both fluidity before curing and heat resistance after curing.

  An object of the present invention is to provide a resin composition and a resin sheet that have both fluidity before curing and heat resistance after curing.

The resin composition according to one embodiment of the present invention is a resin composition containing (A) a thermosetting component, wherein the (A) thermosetting component contains (A1) a maleimide resin, A1) The maleimide resin contains two or more maleimide groups in one molecule, and the complex viscosity η at 90 ° C. of the resin composition before curing is 1.0 × 10 ² Pa · s or more and 1.0 × 10 ² or more. ⁴ Pa · s or less.

  In the resin composition according to one embodiment of the present invention, the thermosetting component (A) preferably further contains (A2) an allyl resin.

  In the resin composition according to one embodiment of the present invention, the mass ratio (A1 / A2) of the (A1) maleimide resin to the (A2) allyl resin is preferably 1.5 or more.

  In the resin composition according to one embodiment of the present invention, the (A1) maleimide resin preferably has a biphenyl skeleton.

  The resin composition according to one embodiment of the present invention preferably further contains (B) a binder component.

  In the resin composition according to one embodiment of the present invention, the content of the (A1) maleimide resin is 20% by mass based on the total amount of the solid content of the (A) thermosetting component and the (B) binder component. It is preferably at least 80% by mass.

  The resin composition according to one embodiment of the present invention preferably further contains (C) an inorganic filler.

  The resin composition according to one embodiment of the present invention preferably further contains (D) a coupling agent.

  The resin composition according to one embodiment of the present invention is preferably used for sealing a power semiconductor element or for interposing the power semiconductor element between the power semiconductor element and another electronic component.

  The resin composition according to one embodiment of the present invention seals a semiconductor element using any one or more of silicon carbide and gallium nitride, or uses any one or more of the silicon carbide and gallium nitride. It is preferably used to intervene between the semiconductor element and another electronic component.

  A resin sheet according to one embodiment of the present invention includes the above-described resin composition according to one embodiment of the present invention.

  According to one embodiment of the present invention, it is possible to provide a resin composition and a resin sheet having both fluidity before curing and heat resistance after curing.

It is a section schematic diagram of a layered product concerning one embodiment.

[Resin composition]
The resin composition according to the present embodiment contains (A) a thermosetting component. This (A) thermosetting component contains (A1) a maleimide resin. The complex viscosity η at 90 ° C. before curing of the resin composition according to this embodiment is from 1.0 × 10 ² Pa · s to 1.0 × 10 ⁴ Pa · s. From the viewpoint of fluidity during heating of the resin composition according to the present embodiment before curing, the complex viscosity η is not less than 5.0 × 10 ² Pa · s and not more than 1.0 × 10 ⁴ Pa · s. Is preferably 5.0 × 10 ² Pa · s or more and 8.0 × 10 ³ Pa · s or less. By maintaining the fluidity at the time of heating before the resin composition is cured, when the resin composition is applied to the object, the ability to follow the surface shape of the object increases. In particular, in the case where the resin composition is in the form of a resin sheet, when the resin composition is heated and applied to the object, the ability to follow the surface shape of the object increases.
The complex viscosity η of the resin composition according to the present embodiment can be adjusted to the above range, for example, by adjusting the components or the amount of the resin composition used.
The complex viscosity η in the present specification is measured by measuring the complex viscosity at 90 ° C. (unit: Pa · s) of this resin sheet using a viscoelasticity measuring device by preparing a resin sheet by applying and drying a resin composition. It was done.

((A) thermosetting component)
The (A) thermosetting component (hereinafter, may be simply referred to as the “(A) component”) has a property of forming a three-dimensional network when heated, and firmly bonding the adherend. The (A) thermosetting component in this embodiment contains (A1) a maleimide resin as described above.

(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 (A1) maleimide resin in the present embodiment preferably contains, for example, a benzene ring, and more preferably contains a benzene ring to which a maleimide group is connected. Further, the maleimide compound preferably has two or more structures in which a maleimide group is connected 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 sometimes simply referred to as “biphenylmaleimide resin”). Is preferred.
(A) When the thermosetting component contains a biphenylmaleimide resin, the adhesiveness of the resin composition to an adherend is improved, and the complex viscosity of the resin composition is easily reduced. In particular, even when the mass ratio (A1 / A2) of the (A1) maleimide resin having a biphenyl skeleton to the (A2) allyl resin in the thermosetting component (A) described later is high, the complex viscosity of the resin composition is high. Easy to fall.

  The (A1) maleimide resin 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. Is more preferable. m1 and m2 are each independently an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1. n1 and n2 are each independently an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0. R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. A plurality of R ¹ are the same or different from each other. A plurality of R ² are the same or different from each other.

  Specific examples of the maleimide resin represented by the general formula (1) in the present embodiment include a compound 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).
As a commercial product of the maleimide resin represented by the general formula (3), “MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd. and the like can be mentioned.

In addition, the maleimide resin (A1) in the present embodiment is also 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, and an alkylene group.
Further, the maleimide resin (A1) in the present embodiment is preferably a maleimide resin having an ether bond between a maleimide group and a phenylene group from the viewpoint of sheet formability.

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

In the general formula (4), R ^{3 to} R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L ¹ is an alkylene group having 1 to 6 carbon atoms, and L ² and ^{L 3} are each independently an alkylene group or an arylene group having 6 to 10 carbon atoms having 1 to 6 carbon atoms, p and q are each independently 0 or 1.

  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 to 6 carbon atoms.
In the general formula (5), R ^{3 to} R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the general formulas (4) and (5), R ³ and R ⁴ are preferably different from each other, and it is more preferable that one of R ³ and R ⁴ is a methyl group and the other is an ethyl group.
In the general formulas (4) and (5), R ⁵ and R ⁶ are preferably different from each other, and more preferably, one of R ⁵ and R ⁶ is a methyl group, and the other is an ethyl group.
In the general formulas (4), (5), and (6), L ¹ is preferably an alkylene group having 1 to 3 carbon atoms.

  As the maleimide resin (A1) in the present embodiment, specifically, for example, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is used from the viewpoint of obtaining a cured product having high heat resistance as well as sheet formability. , N, N'-1,3-phenylenedimaleimide, 4-methyl-1,3-phenylenebismaleimide, polyphenylmethanemaleimide, or 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane From the viewpoint of sheet formability, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is more preferred.

(A2) Allyl resin The (A) thermosetting component in the present embodiment preferably contains (A1) a maleimide resin and (A2) an allyl resin. (A2) The allyl resin is preferably liquid at normal temperature (23 ° C.). (A) When the thermosetting component contains (A2) an allyl resin, an effect of improving the wettability of the resin composition to an adherend before curing of the resin composition is obtained, and After curing, an effect that a denser network can be constructed can be obtained.

In this embodiment, the mass ratio (A1 / A2) of the (A1) maleimide resin to the (A2) allyl resin is preferably 1.5 or more, more preferably 4.5 or more.
When the mass ratio (A1 / A2) is in the above range, the storage modulus E ′ of the cured product of the resin composition at 250 ° C. tends to increase.
When the mass ratio (A1 / A2) is within the above range, the heat resistance of the resin composition can be improved.
When the mass ratio (A1 / A2) is within the above range, in this embodiment, the complex viscosity η of the resin composition satisfies the above range, so that the fluidity of the resin composition when applied to an adherend is reduced. While ensuring, further improvement of the heat resistance of the resin composition after curing is realized. Furthermore, when the mass ratio (A1 / A2) is in the above range, bleed out of the (A2) allyl resin from the resin composition 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.

The (A2) allyl resin in the present embodiment is not particularly limited as long as it has 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.
The (A2) allyl resin in the present embodiment is more preferably represented by the following general formula (7).

In the general formula (7), R ⁷ and R ⁸ are each independently an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group 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.

  Specific examples of (A2) allyl resin in this embodiment include diallyl bisphenol A (2,2-bis (3-allyl-4-hydroxyphenyl) propane).

The (A) thermosetting component in the present embodiment includes the compound represented by the general formula (2) or (3) as the (A1) maleimide resin, and the (A2) allyl resin includes the compound represented by the general formula (7) ) Is also preferable.
The (A) thermosetting component in the present embodiment contains the compound represented by the general formula (5) or (6) as the (A1) maleimide resin, and (A2) the allyl resin as the above-mentioned general formula. It is also preferable to include the compound represented by (7).

The (A) thermosetting component of the present embodiment may contain a thermosetting resin other than the (A1) component and a curing agent other than the (A2) component as long as the object of the present invention is not impaired. .
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.
Examples of the curing agent other than the component (A2) include phenol resins, resins such as a resin having a C ＝ C double bond other than the component (A2), amines, acid anhydrides, and formaldehyde. . These curing agents can be used alone or in combination of two or more.
When a thermosetting resin other than the component (A1) or a curing agent other than the component (A2) is used, the content thereof is based on the total solid content of the component (A) (that is, the total solid content excluding the solvent). 100% by mass), preferably 10% by mass or less, more preferably 5% by mass or less.

  In the present embodiment, the content of the thermosetting component (A) in the resin composition is based on the total solid content of the resin composition (that is, when the total solid content excluding the solvent is 100% by mass), The content is preferably from 2% by mass to 75% by mass, more preferably from 5% by mass to 70% by mass. (A) When the content of the thermosetting component is within the above range, the handleability of the resin sheet, the sheet formability, and the heat resistance of the resin sheet are improved.

In this embodiment, the (A) thermosetting component may contain a curing accelerator.
Examples of the curing accelerator include an imidazole compound (for example, 2-ethyl-4-methylimidazole and the like).
The content of the curing accelerator in the resin composition is 0.005% by mass or more and 12% by mass on the basis of the total solid content of the resin composition (that is, when the total solid content excluding the solvent is 100% by mass). Or less, more preferably 0.01% by mass or more and 10% by mass or less.

((B) binder component)
In the exemplary embodiment, the resin composition preferably contains (B) a binder component (hereinafter, sometimes simply referred to as “(B) component”) in addition to the (A) component. When the resin composition of the present embodiment further contains (B) a binder component, a film-forming property is imparted, and the resin composition can be easily formed into a sheet.
The (B) binder component of the present embodiment is a resin component other than the (A) component, and has a function of bonding the (A) component or other components. (B) The binder component is preferably a thermoplastic resin or the like. The component (B) may have a functional group as long as it has a function of bonding the component (A) or other components. In the case where the binder component (B) has a functional group as described above, even if the binder component (B) can participate in the curing of the resin composition by heat, the binder component (B) is (A) A distinction is made from curable components.
(B) The binder component can be selected widely regardless of whether it is an aliphatic compound or an aromatic compound. (B) The binder component is preferably, for example, at least one resin selected from the group consisting of a phenoxy resin, an acrylic resin, a methacrylic resin, a polyester resin, a urethane resin, and a polyamideimide resin. And more preferably at least one resin selected from the group consisting of a phenoxy resin, a polyamideimide resin, and a polyester resin, and further preferably a phenoxy resin. Note that the polyester resin is preferably a wholly aromatic polyester resin. As the binder component (B), one type can be used alone, or two or more types can be used in combination.

  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 at least one skeleton selected from the following 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 from 100 to 1,000,000, and more preferably from 1,000 to 800,000, from the viewpoint that the complex viscosity of the resin composition is easily adjusted to a desired range. More preferably, it is more preferably 10,000 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 0.1% based on the total solid content of the resin composition (that is, when the total solid content excluding the solvent is 100% by mass). It is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 40% by mass. By setting the content of the binder component (B) in the resin composition in the above range, the complex viscosity of the resin composition before curing of the resin sheet can be easily adjusted to a desired range, and the handling property of the resin sheet, and Sheet formability is improved.

  In the present embodiment, the content of the component (A1) is 20% based on the total amount of the solid contents of the components (A) and (B) (that is, when the total solid content excluding the solvent is 100% by mass). It is preferable that the content is not less than 80% by mass and not more than 80% by mass. When the content of the component (A1) is 20% by mass or more, the heat resistance of the resin composition can be further improved. On the other hand, when the content of the component (A1) is 80% by mass or less, the resin composition can be easily formed into a sheet.

((C) inorganic filler)
In the present embodiment, the resin composition preferably contains (C) an inorganic filler (hereinafter sometimes simply referred to as “(C) component”) in addition to the (A) component and the (B) component. By the component (C), the coefficient of linear expansion of the resin composition can be reduced, and the storage modulus of the resin composition can be increased.
(C) Examples of the inorganic filler include a silica filler, an alumina filler, and a boron nitride filler. Among these, a silica filler is preferable.
Examples of the silica filler include fused silica and spherical silica.
As the inorganic filler (C), one type can be used alone, or two or more types can be used in combination. Further, (C) the inorganic filler may be surface-treated.

  (C) The average particle size of the inorganic filler is not particularly limited. (C) The average particle diameter of the inorganic filler is preferably 0.1 nm or more and 100 μm or less, more preferably 10 nm or more and 10 μm or less, as determined by a general particle size distribution analyzer. In the present specification, the average particle size of the inorganic filler (C) is a value measured by a dynamic light scattering method using a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., product name “Nanotrack Wave-UT151”). I do.

  The content of the inorganic filler (C) in the resin composition is 10% by mass to 90% by mass based on the total solid content of the resin composition (that is, when the total solid content excluding the solvent is 100% by mass). It is preferably at most 20% by mass and at most 80% by mass, more preferably at least 20% by mass and at most 60% by mass.

((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 (D) coupling agent preferably has a functional group of the (A) thermosetting component or a group that reacts with the (B) functional group of the binder component. It is more preferable to have a group that reacts with the functional group.

  (D) By using the coupling agent, the adhesiveness and the adhesiveness can be improved without impairing the heat resistance of the cured resin, and the water resistance (moisture and heat resistance) is also improved.

  As the coupling agent (D), a silane (silane coupling agent) is preferable from the viewpoint of its versatility and cost merit. (D) The coupling agent can be used alone or in combination of two or more. Further, the coupling agent as described above is usually blended in a ratio of 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the thermosetting component (A), and preferably 0.3 part by mass. It is blended at a ratio of at least 15 parts by mass and more preferably at a ratio of 0.5 parts by mass to 10 parts by mass.

Examples of the resin composition according to the present embodiment include a resin composition containing only (A) a thermosetting component, (B) a binder component, (C) an inorganic filler, and (D) a coupling agent. .
Further, as another example of the resin composition according to the present embodiment, (A) a thermosetting component, (B) a binder component, (C) an inorganic filler, (D) a coupling agent, and Resin compositions containing components other than the components (A) to (D) are exemplified.

(Other components)
In this embodiment, the resin composition may further include other components. As the other component, for example, at least one selected from the group consisting of a crosslinking agent, a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, and an ion scavenger. The component of is mentioned.
For example, the resin composition may further contain a crosslinking agent in order to adjust the initial adhesiveness before curing and the cohesiveness.
Examples of the crosslinking agent include an organic polyvalent isocyanate compound and an organic polyvalent imine compound. The crosslinking agents can be used alone or in combination of two or more.

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

  Specific examples of the organic polyvalent imine compound include, for example, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetra Methylolmethane-tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like. The organic polyvalent imine compound can be used alone or in combination of two or more.

  The crosslinking agent as described above is blended in an amount of usually 0.01 to 12 parts by mass, preferably 0.1 to 10 parts by mass based on 100 parts by mass of the binder component (B). You.

More specific examples of the resin composition according to the present embodiment include, for example, the following resin compositions, but the present invention is not limited to such examples.
As an example of the resin composition according to the present embodiment, a resin composition containing (A) a thermosetting component, (B) a binder component, (C) an inorganic filler, and (D) a coupling agent, (A) a thermosetting component containing (A1) a maleimide resin represented by the general formula (3) and (A2) an allyl resin represented by the general formula (7); A resin composition in which the binder component is a phenoxy resin and the inorganic filler (C) is a silica filler is exemplified.

The resin composition according to the present embodiment is preferably used for a semiconductor device. Specifically, the resin composition according to the present embodiment is preferably used for sealing a semiconductor element. Further, the resin composition according to the present embodiment is preferably used for being interposed between a semiconductor element and another electronic component.
The semiconductor element is preferably a power semiconductor.

  Further, the resin composition according to the present embodiment is preferably used for sealing a semiconductor element using at least one of silicon carbide and gallium nitride. Alternatively, the resin composition according to the present embodiment is preferably used to be interposed between a semiconductor element using at least one of silicon carbide and gallium nitride and another electronic component. Other electronic components include, for example, a printed wiring board, a lead frame, and the like.

[Resin sheet]
The resin sheet according to the present embodiment contains the resin composition according to the present embodiment.
By forming the resin composition according to the present embodiment into a sheet, the resin sheet according to the present embodiment can be obtained. When the resin composition is in the form of a sheet, application to an adherend is simplified, and particularly when the adherend has a large area.
If the resin composition is in the form of a sheet, it is preformed in a shape suitable to the shape after the sealing step to a certain extent, so it is supplied as a sealing material that maintains a certain degree of uniformity only by applying it. it can. Further, if the resin composition is in a sheet form, there is no fluidity, so that the handleability is excellent.

  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. The resin sheet according to the present embodiment may be a belt-shaped sheet, or may be provided in a state wound in a roll shape. The resin sheet according to the present embodiment wound in a roll shape can be used after being unwound from a roll and cut into a desired size.

The thickness of the resin sheet according to the present embodiment is preferably, for example, 10 μm or more,
More preferably, it is 20 μm or more. Further, 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 the present embodiment is preferably applied to a plurality of semiconductor elements at once. For example, if the resin composition is in the form of a sheet, a resin sheet is applied to the structure in which the semiconductor elements are arranged in each of the gaps of the frame provided with a plurality of gaps, and the frame and the semiconductor elements are collectively formed. It can be used for sealing, a so-called panel level package.

The storage elastic modulus E ′ of the resin sheet according to the present embodiment after curing is preferably 1.0 × 10 ² MPa or more at a temperature of 250 ° C., more preferably 2.0 × 10 ² MPa or more. preferable. The upper limit of the storage modulus E ′ at a temperature of 250 ° C. after curing is not particularly limited, but is preferably 2.0 × 10 ³ MPa or less, more preferably 1.0 × 10 ³ MPa or less, More preferably, it is 0.8 × 10 ³ MPa or less.
The storage elastic modulus E ′ of the resin sheet after curing can be measured by the method described in Examples.
The storage elastic modulus E ′ after curing can achieve the above-mentioned range by adjusting the components and the amounts used in the resin composition, for example.

[Laminate]
FIG. 1 shows a schematic cross-sectional view of a laminate 1 according to the present embodiment.
The laminate 1 of the present embodiment includes 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 contains the resin composition according to the present embodiment.

  The first release material 2 and the second release material 4 have releasability, and there is a difference between the release force of the first release material 2 on the resin sheet 3 and the release force of the second release material 4 on the resin sheet 3. Is preferred. 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 that has been subjected to a release treatment, a member in which a release agent layer is laminated, or the like, in addition to a member having a release property on the release material itself. Good. When the first release material 2 and the second release material 4 are not subjected to the release treatment, examples of the material of the first release material 2 and the second release material 4 include olefin-based resins and fluororesins. Can be
The first release material 2 and the second release material 4 can be release materials including a release substrate and a release agent layer formed by applying a release agent on the release substrate. The use of a release material including a release substrate and a release agent layer facilitates handling. In addition, the first release material 2 and the second release material 4 may have a release agent layer on only one surface of the release substrate, or may have release agent layers on both surfaces of the release substrate.

  Examples of the release substrate include a paper substrate, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film. Examples of the paper base include glassine paper, coated paper, and cast-coated paper. Examples of the plastic film include a polyester film (for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), and a polyolefin film (for example, polypropylene, polyethylene, and the like). Among these, a polyester film is preferred.

  As the release agent, for example, a silicone release agent composed of a silicone resin; a long-chain alkyl group-containing compound release agent composed of a compound containing a long-chain alkyl group such as polyvinyl carbamate and an alkyl urea derivative; alkyd Alkyd resin-based release agents composed of a resin (for example, an invertible alkyd resin and a convertible alkyd resin); Olefin resin-based release agent composed of propylene homopolymer having isotactic structure or syndiotactic structure, and crystalline polypropylene resin such as propylene-α-olefin copolymer); natural rubber; , And synthetic rubber (for example, butadiene rubber, isoprenego) Styrene-butadiene rubber, methyl methacrylate-butadiene rubber, and acrylonitrile-butadiene rubber), and a rubber-based release agent; and an acrylic resin such as a (meth) acrylate copolymer. Various release agents such as an acrylic resin-based release agent may be mentioned, and these may be used alone or in combination of two or more. Among these, silicone-based release agents are preferred.

The thickness of the first release material 2 and the second release material 4 is not particularly limited. The thickness of the first release material 2 and the second release material 4 is usually 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, more preferably 0.03 μm or more and 1 μm or less.

  The method for manufacturing the laminate 1 is not particularly limited. For example, the laminate 1 is manufactured through the following steps. First, a resin composition is applied on the first release material 2 to form a coating film. Next, the coating film is dried to form the resin sheet 3. Next, the laminate 1 is obtained by bonding the resin sheet 3 and the second release material 4 at room temperature.

[Semiconductor device]
The semiconductor device according to the present embodiment has the semiconductor element sealed with the resin composition or the resin sheet according to the present embodiment.
The sealing of the semiconductor element using the resin sheet of the present embodiment can be performed, for example, as follows. A resin sheet is placed so as to cover the semiconductor element, and the semiconductor element is sealed by pressure bonding by a vacuum lamination method.
When the laminate 1 of the present embodiment is used, a resin sheet is placed so as to cover the semiconductor element after one release material of the laminate 1 is peeled off. Thereafter, the other release material is peeled off. Thereafter, the semiconductor element is sealed by pressure bonding by a vacuum lamination method.
The joining of the semiconductor element and other electronic components using the resin sheet of the present embodiment can be performed, for example, as follows. A resin sheet is placed on other electronic components, and a semiconductor element is further placed on the resin sheet. Thereafter, the resin sheet and the semiconductor element are temporarily press-bonded, and the resin sheet is heated and cured. In this way, the semiconductor element and other electronic components are joined by interposing the resin composition between the semiconductor device and other electronic components.

[Effects of Embodiment]
According to the resin composition and the resin sheet according to the present embodiment, fluidity before curing and heat resistance after curing can be compatible.

  As described above, the resin composition according to the present embodiment can be suitably used for a power semiconductor device. In other words, in the semiconductor device according to the present embodiment, the semiconductor element is preferably a power semiconductor element. The power semiconductor element is also expected to operate at a high temperature of 200 ° C. or higher. Materials used for semiconductor devices having power semiconductor elements are required to have heat resistance. Since the resin composition and the resin sheet according to the present embodiment have excellent heat resistance, they are suitably used for covering a power semiconductor element in a semiconductor device. Alternatively, the resin composition and the resin sheet according to the present embodiment are suitably used for being interposed between a power semiconductor element and another component.

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

[Modification of Embodiment]
The present invention is not limited to the above-described embodiment, and includes modifications and improvements as long as the object of the present invention can be achieved.

  In the embodiment, the first release material, the second release material, and a laminate having a resin sheet provided between the first release material and the second release material, the other, a resin sheet May be a laminate having a release material on only one surface of the laminate.

  In the embodiments of the semiconductor device described above, semiconductor sealing applications are described. However, the resin composition and the resin sheet of the present invention may also be used as other insulating materials for circuit boards (for example, hard printed wiring board materials, flexible wirings, etc.). Substrate materials, interlayer insulating materials for build-up substrates, etc.), adhesive films for build-up, adhesives 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]
Resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 were prepared at the compounding ratio (mass% (ratio in terms of solid content)) shown in Table 1.
The materials used for preparing the resin composition are as follows.

(Thermosetting component)
BMI resin-1: maleimide resin having a biphenyl group (maleimide resin represented by the above general formula (3), "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.)
-BMI resin-2: bis (3-ethyl-5-methyl-4-maleimidophenyl) methane-Allyl resin: diallyl bisphenol A

(Binder component)
Binder resin: BisA / BisF mixed phenoxy resin (“ZX-1356-2” manufactured by Nippon Steel & Sumikin Chemical, weight average molecular weight 65,000)

(Inorganic filler)
・ Silica filler: fused silica (epoxysilane modification, average particle size 0.5 μm, maximum particle size 2.0 μm)

(Other additives)
・ Coupling agent: 3-glycidoxypropyltriethoxysilane

[Preparation of resin sheet]
On a first release material (polyethylene terephthalate provided with a release layer formed of an alkyd resin-based release agent, having a thickness of 38 μm), the resin is dried with a die coater so that the thickness of the resin composition after drying becomes 20 μm. A varnish (application solution prepared by dissolving the resin composition in methyl ethyl ketone at a solid concentration of 40% by mass) was applied, and dried at 100 ° C. for 2 minutes. Immediately after being taken out of the drying oven, the dried resin composition (thickness: 20 μm) and the second release material (polyethylene terephthalate provided with a release layer formed of a silicone-based release agent, thickness: 38 μm) were brought to room temperature ( (23 ° C.) to produce a laminate in which the first release material, the resin sheet made of the resin composition, and the second release material were laminated in this order.

<Evaluation of resin composition before curing>
[Complex viscosity]
The obtained resin composition was applied on a release material and dried at 100 ° C. for 2 minutes to produce a resin sheet having a thickness of 20 μm. Two resin sheets were laminated to produce a resin sheet laminate having a thickness of 40 μm. Further, two resin sheet laminates were laminated to produce a resin sheet laminate having a thickness of 80 μm, and this procedure was repeated to produce a measurement sample having a thickness of 1280 μm. With respect to this measurement sample, the complex viscosity (unit: Pa · s) at 90 ° C. was measured with the following measurement equipment and measurement conditions. Table 1 shows the obtained results.
-Measuring equipment: Viscoelasticity measuring device, "MCR301" manufactured by Anton Paar
-Measurement conditions: frequency 1 Hz, temperature range 30 to 150 ° C, heating rate 5 ° C / min

[Evaluation of stickability to metal]
The obtained resin sheet and the following adherend were bonded under reduced pressure under the following bonding conditions. For the bonding, a vacuum laminator PVL0505S manufactured by Nisshinbo was used.
・ Adherend (1) Si wafer Size: 6 inches, thickness: 800 μm
The resin composition was bonded to the mirror surface of the Si wafer.
(2) Cu plate Size: 30 mm x 30 mm, thickness: 0.3 mm
Specification: JIS H3100 C1100P
・ Lamination conditions Laminating temperature: 90 ° C
Ultimate pressure: 100Pa
Time: 60 sec
After laminating, the case where there was no air bubble and the film was uniformly bonded was evaluated as A, and the case where there was air bubble which could be visually confirmed was evaluated as B. Table 1 shows the evaluation results in the case where the Si wafer was used as the adherend, as the sticking property (vs. Si), and the evaluation results in the case where the Cu plate was used as the adherend, as the sticking property (vs. Cu).

<Evaluation of the cured resin composition>
[Storage modulus E ']
The obtained resin composition was applied on a release material and dried at 100 ° C. for 2 minutes to produce a resin sheet having a thickness of 20 μm. Ten resin sheets were laminated to a thickness of 200 μm, and then peeled from the release material to obtain a sample. This sample was cured under the above-mentioned thermosetting conditions (temperature: 200 ° C., time: 4 hours) to obtain a measurement sample. Using a “DMA Q800” manufactured by TA Instruments, the value of the storage modulus E ′ of the measurement sample at 250 ° C. at a temperature rising rate of 3 ° C./min, a temperature range of 30 to 300 ° C., and a frequency of 11 Hz ( Unit: MPa) was measured. Table 1 shows the obtained results. The brittleness of the resin composition of Comparative Example 3 was too high to measure.

  It was confirmed that the resin compositions according to Examples 1 to 5 had both fluidity before curing and heat resistance after curing as compared with the resin compositions according to Comparative Examples 1 to 3. Since the resin compositions according to Examples 1 to 5 have appropriate fluidity before curing, they are considered to have good sticking properties and good adhesion to adherends. Furthermore, since the resin compositions according to Examples 1 to 5 have a good storage elastic modulus after thermosetting, it is considered that they can be suitably used for producing power modules and the like.

  DESCRIPTION OF SYMBOLS 1 ... Laminate, 2 ... First release material, 3 ... Resin sheet, 4 ... Second release material.

Claims (11)

(A) a resin composition containing a thermosetting component,
The (A) thermosetting component contains (A1) a maleimide resin,
The (A1) maleimide resin contains two or more maleimide groups in one molecule,
The resin composition, wherein the resin composition has a complex viscosity η at 90 ° C before curing of not less than 1.0 × 10 ² Pa · s and not more than 1.0 × 10 ⁴ Pa · s. The resin composition according to claim 1,
The resin composition, wherein the (A) thermosetting component further contains (A2) an allyl resin. The resin composition according to claim 2,
A resin composition, wherein the mass ratio (A1 / A2) of the (A1) maleimide resin to the (A2) allyl resin is 1.5 or more. The resin composition according to any one of claims 1 to 3,
The resin composition, wherein the (A1) maleimide resin has a biphenyl skeleton. In the resin composition according to any one of claims 1 to 4,
A resin composition further comprising (B) a binder component. The resin composition according to claim 5,
The content of the (A1) maleimide resin is 20% by mass or more and 80% by mass or less based on the total amount of the solid content of the (A) thermosetting component and the (B) binder component. Resin composition. In the resin composition according to any one of claims 1 to 6,
The resin composition further comprising (C) an inorganic filler. The resin composition according to any one of claims 1 to 7,
The resin composition further comprising (D) a coupling agent. In the resin composition according to any one of claims 1 to 8,
A resin composition used for sealing a power semiconductor element or for being interposed between the power semiconductor element and another electronic component. In the resin composition according to any one of claims 1 to 8,
Encapsulating a semiconductor element using at least one of silicon carbide and gallium nitride, or between a semiconductor element using at least one of silicon carbide and gallium nitride and another electronic component A resin composition characterized by being used for interposition.   A resin sheet comprising the resin composition according to claim 1.