CN112789323B

CN112789323B - Resin composition, cured product, and semiconductor device

Info

Publication number: CN112789323B
Application number: CN201880098336.2A
Authority: CN
Inventors: 小林庆子; 藤田贤; 石井学
Original assignee: Lishennoco Co ltd
Current assignee: Lishennoco Co ltd
Priority date: 2018-10-02
Filing date: 2018-10-02
Publication date: 2024-02-02
Anticipated expiration: 2038-10-02
Also published as: WO2020070806A1; JP7318657B2; JPWO2020070806A1; CN112789323A

Abstract

The resin composition comprises (A) metal particles, (B) alkoxysilane, and (C) a thermosetting component, wherein the (A) component contains aluminum-containing particles, and the (B) component contains alkylalkoxysilane. Another embodiment of the resin composition contains (a) metal particles, (B) alkoxysilane, and (C) a thermosetting component, wherein the (a) component contains aluminum-containing particles, and the (B) component contains alkoxysilane having 2 or more silicon atoms.

Description

Resin composition, cured product, and semiconductor device

Technical Field

The present invention relates to a resin composition, a cured product, and a semiconductor device.

Background

In general, a semiconductor device for a semiconductor apparatus is manufactured by bonding a semiconductor element such as a semiconductor chip to a supporting member such as a lead frame by an adhesive (die bonding material). Conventionally, as an adhesive for a semiconductor, a gold-silicon eutectic, a solder, a paste-like resin composition, or the like is known, but in recent years, a paste-like resin composition has been widely used from the viewpoints of operability and cost.

With the high integration and miniaturization of semiconductor elements, conductive fillers are sometimes used as constituent materials of resin compositions used as die bonding materials from the viewpoint of improving the characteristics of the semiconductor device such as electrical conductivity and thermal conductivity. As the conductive filler, silver particles may be used from the viewpoint of high oxidation resistance or the like (for example, refer to patent document 1 below).

Technical literature of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 2002-179769

Disclosure of Invention

Technical problem to be solved by the invention

When the semiconductor element is disposed on the adhesive layer after the adhesive layer containing the resin composition is formed on the support member, a rounded portion (fillets) which is warped in the stacking direction of the semiconductor element and the support member tends to be formed on the outer peripheral portion of the adhesive layer. When the rounded portion is formed on the outer peripheral portion of the adhesive layer, the stress relaxation effect is excellent, and peeling between the semiconductor element and the support member is easily suppressed.

Here, since silver is an expensive material, it is desirable to use other inexpensive metals as the conductive filler, and it is considered to use aluminum particles which are inexpensive and excellent in electrical conductivity, thermal conductivity, and the like. According to the findings of the present inventors, in the case of using silver particles alone as the conductive filler, the rounded portions were formed appropriately on the outer peripheral portion of the adhesive layer, whereas in the case of using aluminum particles as the conductive filler, a phenomenon (rounded portion defect) was confirmed in which the rounded portions were broken on the outer peripheral portion of the adhesive layer. Therefore, in the case of using aluminum particles as the conductive filler, it is required to suppress the chipping of the rounded portion.

The purpose of the present invention is to provide a resin composition capable of suppressing the defects of a fillet while using aluminum particles, and a cured product thereof. The present invention aims to provide a semiconductor device using the resin composition or a cured product thereof.

Means for solving the technical problems

The resin composition according to embodiment 1 of the present invention contains (a) metal particles, (B) alkoxysilane, and (C) a thermosetting component, wherein the (a) component contains aluminum-containing particles, and the (B) component contains alkylalkoxysilane. The resin composition according to embodiment 2 of the present invention contains (a) metal particles, (B) alkoxysilane, and (C) a thermosetting component, wherein the (a) component contains aluminum-containing particles, and the (B) component contains alkoxysilane having 2 or more silicon atoms. A cured product according to another embodiment of the present invention is a cured product of the above resin composition.

According to the resin composition and the cured product thereof, the defects of the rounded portions can be suppressed while using aluminum particles. This makes it possible to suppress peeling between the semiconductor element and the support member, while exhibiting a good stress relaxation effect.

A semiconductor device according to another embodiment of the present invention includes a support member, a semiconductor element, and an adhesive layer disposed between the support member and the semiconductor element, wherein the adhesive layer contains the resin composition or a cured product thereof.

Effects of the invention

According to the present invention, it is possible to provide a resin composition capable of suppressing chipping of a fillet portion while using aluminum particles, and a cured product thereof. According to the present invention, a semiconductor device using the resin composition or a cured product thereof can be provided.

According to the present invention, it is possible to provide an application of the resin composition or a cured product thereof in the manufacture of a semiconductor device or a semiconductor device. According to the present invention, it is possible to provide an application of the resin composition or the cured product thereof to adhesion of a semiconductor element to a support member. According to the present invention, it is possible to provide the use of the resin composition in a die bonding material.

Drawings

Fig. 1 is a drawing for explaining the climbing phenomenon.

Fig. 2 is a schematic cross-sectional view showing an example of a semiconductor device.

Fig. 3 is a schematic cross-sectional view showing another example of the semiconductor device.

Fig. 4 is a drawing showing the observation result of the rounded corner defect.

Detailed Description

In the present specification, the numerical range indicated by "to" is a range in which numerical values described before and after "to" are included as a minimum value and a maximum value, respectively. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range at one stage may be arbitrarily combined with the upper limit value or the lower limit value of the numerical range at another stage. In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "A or B" means that either one of A and B may be contained, or both may be contained. The materials exemplified in the present specification can be used singly or in combination of two or more, unless otherwise specified. In the present specification, when a plurality of substances corresponding to the respective components are present in the composition, the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified. In the present specification, the term "layer" means a structure including a shape formed on a part in addition to a structure of a shape formed on the entire surface when seen as a top view. In the present specification, the term "process" means not only an independent process but also a process which cannot be clearly distinguished from other processes, and is included in the term as long as the desired function of the process is achieved. "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid corresponding thereto. The same applies to "(meth) acryl", and the like.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented by various modifications within the scope of the gist thereof.

< resin composition and cured product >

The resin composition according to the present embodiment (embodiment 1 and embodiment 2, hereinafter the same) contains (a) metal particles (hereinafter referred to as "(a) component" as the case may be ". Metal-containing particles, for example, metal powder), (B) alkoxysilane (hereinafter referred to as" (B) component "as the case may be") and (C) a thermosetting component (hereinafter referred to as "(C) component"), (a) contains (a) 1 st particles containing aluminum (aluminum particles. Hereinafter referred to as "(A1) component" as the case may be ". For example, aluminum powder). In embodiment 1, the component (B) contains (B1) alkylalkoxysilane (hereinafter, referred to as "(B1) component", as the case may be). In embodiment 2, the component (B) contains (B2) an alkoxysilane having 2 or more silicon atoms (hereinafter, referred to as "(B2 component", as the case may be ").

The resin composition according to the present embodiment is a conductive composition, and can be used as a resin composition for bonding a semiconductor element to a support member. The resin composition according to the present embodiment is a curable (e.g., thermosetting) composition. The resin composition according to the present embodiment can be used as a paste-like resin composition. The cured product according to the present embodiment is a cured product of the resin composition according to the present embodiment.

According to the resin composition and the cured product thereof according to the present embodiment, the defects of the rounded portions can be suppressed while using aluminum particles. This makes it possible to suppress peeling between the semiconductor element and the support member, while exhibiting a good stress relaxation effect. The reason why the defect of the rounded portion can be suppressed by using the resin composition and the cured product thereof according to the present embodiment is not clear, but the present inventors speculate as follows. However, the reason is not limited to the following. That is, when the dispersibility of the metal particles in the resin component or the affinity of the resin composition with respect to the support member is low, chipping of the rounded portions occurs. On the other hand, in the present embodiment, the (B1) component or the (B2) component is bonded to the (a) component or the support member via the silicon atom of the alkoxysilane, whereby the dispersibility of the (a) component in the (C) component and the affinity of the resin composition with respect to the support member are improved (it is presumed that the alkyl group of the (B1) component and the 2 or more silicon atoms of the (B2) component contribute to the bonding of the (B1) component and the (B2) component to the (a) component or the support member). Therefore, the component (a) is inhibited from separating from other components during the flow of the resin composition, and hence the defect of the rounded portion is inhibited.

Component (A) metal particles

(A) The component (A1) contains aluminum particles. Aluminum particles are inexpensive and excellent in electrical conductivity, thermal conductivity, and the like. By using aluminum particles, the electrical conductivity and thermal conductivity of the resin composition can be improved while the amount of silver particles used is reduced or eliminated. Examples of the shape of the component (A1) include a scale shape, a sphere shape, a block shape, a tree shape, a plate shape, and the like.

(A1) The content of aluminum in at least one particle of the component is preferably 80 mass% or more, more preferably 90 mass% or more, further preferably 95 mass% or more, particularly preferably 98 mass% or more, and most preferably 99 mass% or more. The component (A1) may be at least one particle substantially composed of aluminum (substantially 100 mass% of the particles is aluminum).

(A) The component (c) may contain the 2 nd particles containing a metal other than aluminum (hereinafter, referred to as "(A2) component", if necessary). The shape of the component (A2) may be a scale-like shape, a sphere shape, a block shape, a tree shape, a plate shape, or the like, but the scale-like shape is preferable from the viewpoint that the component (A2) is easily contacted with each other and thus excellent electric conductivity and heat conductivity are easily obtained.

Examples of the metal other than aluminum in the 2 nd particle include silver, gold, copper, nickel, iron, stainless steel, and the like. From the viewpoint of easy availability of excellent electrical conductivity, thermal conductivity, oxidation resistance and dispersibility, the 2 nd particles preferably contain silver-containing particles (hereinafter, referred to as "(a 21) component". For example, silver powder ", as the case may be).

(A21) The content of silver in at least one particle of the component is preferably 80 mass% or more, more preferably 90 mass% or more, further preferably 95 mass% or more, particularly preferably 98 mass% or more, and most preferably 99 mass% or more. The component (a 21) may be at least one particle substantially composed of silver (substantially 100 mass% of the particles is silver).

The average particle diameter of the component (A1) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more, from the viewpoint of easy obtaining of excellent electrical conductivity and thermal conductivity. The average particle diameter of the component (A1) is preferably 6 μm or less, more preferably 5 μm or less, and even more preferably 4 μm or less, from the viewpoint of obtaining excellent wet-spreading properties of the resin composition and from the viewpoint of easily suppressing tilting of the semiconductor element when the semiconductor element is mounted on the support member using the resin composition. From these viewpoints, the average particle diameter of the component (A1) is preferably 1 to 6. Mu.m.

The average particle diameter of the component (A2) in the resin composition is preferably in the following range from the viewpoint that the component (A2) is not likely to settle. (A2) The average particle diameter of the component (A) is preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2 μm or more. (A2) The average particle diameter of the component (A) is preferably 15 μm or less, more preferably 10 μm or less, further preferably 6 μm or less, particularly preferably 5 μm or less, most preferably 4 μm or less, and most preferably 3 μm or less. From these viewpoints, the average particle diameter of the component (A2) is preferably 1 to 15. Mu.m.

(A) The average particle diameter of the component (a) can be obtained using a particle size distribution measuring apparatus (for example, manufactured by MicrotracBEL Corp, microtracX 100) using a laser diffraction method as the median particle diameter. The "median particle diameter" represents a value of the particle diameter (D50) at which the cumulative rate in the number-based particle size distribution is 50%.

The content of the component (A1) is preferably within the following range based on the total amount of the component (A). The content of the component (A1) is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, particularly preferably 30 mass% or more, most preferably 35 mass% or more, and very preferably 40 mass% or more, from the viewpoint of easy obtaining of excellent electrical conductivity and thermal conductivity. The content of the component (A1) is 100 mass% or less, preferably less than 100 mass%, more preferably 90 mass% or less, further preferably 80 mass% or less, particularly preferably 70 mass% or less, most preferably 60 mass% or less, and very preferably 50 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength. From these viewpoints, the content of the component (A1) is preferably 10 to 100% by mass.

The content of the component (A2) is preferably within the following range based on the total amount of the component (a). The content of the component (A2) is preferably more than 0 mass%, more preferably 10 mass% or more, further preferably 20 mass% or more, particularly preferably 30 mass% or more, most preferably 40 mass% or more, and very preferably 50 mass% or more, from the viewpoint of easy obtaining of excellent conductivity. The content of the component (A2) is preferably 90 mass% or less, more preferably 80 mass% or less, further preferably 75 mass% or less, particularly preferably 70 mass% or less, most preferably 65 mass% or less, and very preferably 60 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength and easy reduction of viscosity. From these viewpoints, the content of the component (A2) is preferably more than 0% by mass and 90% by mass or less.

The content of the component (a 21) is preferably within the following range based on the total amount of the component (a). The content of the component (a 21) is preferably more than 0 mass%, more preferably 10 mass% or more, further preferably 20 mass% or more, particularly preferably 30 mass% or more, most preferably 40 mass% or more, and very preferably 50 mass% or more, from the viewpoint of easy obtaining of excellent conductivity. The content of the component (a 21) is preferably 90 mass% or less, more preferably 80 mass% or less, further preferably 75 mass% or less, particularly preferably 70 mass% or less, most preferably 65 mass% or less, and very preferably 60 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength and easy reduction of viscosity. From these viewpoints, the content of the component (a 21) is preferably more than 0% by mass and 90% by mass or less.

The content of the component (A1) is preferably within the following range based on the total amount of the resin composition (total amount of solid components. The same applies hereinafter). The content of the component (A1) is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 15% by mass or more, most preferably 20% by mass or more, and very preferably 25% by mass or more, from the viewpoint of easy obtaining of excellent electrical conductivity and thermal conductivity. The content of the component (A1) is preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 50 mass% or less, particularly preferably 42 mass% or less, most preferably 40 mass% or less, very preferably 35 mass% or less, further preferably 30 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength. From these viewpoints, the content of the component (A1) is preferably 1 to 70 mass%.

The content of the component (A2) is preferably within the following range based on the total amount of the resin composition. The content of the component (A2) is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 20% by mass or more, most preferably 30% by mass or more, and very preferably 35% by mass or more, from the viewpoint of easy obtaining of excellent electrical conductivity and thermal conductivity. The content of the component (A2) is preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 55 mass% or less, particularly preferably 50 mass% or less, most preferably 45 mass% or less, and very preferably 40 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength and easy reduction of viscosity. From these viewpoints, the content of the component (A2) is preferably 1 to 70 mass%.

The content of the component (a 21) is preferably within the following range based on the total amount of the resin composition. The content of the component (a 21) is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 20% by mass or more, most preferably 30% by mass or more, and very preferably 35% by mass or more, from the viewpoint of easy obtaining of excellent electrical conductivity and thermal conductivity. The content of the component (a 21) is preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 55 mass% or less, particularly preferably 50 mass% or less, most preferably 45 mass% or less, and very preferably 40 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength and easy reduction of viscosity. From these viewpoints, the content of the component (a 21) is preferably 1 to 70 mass%.

(A1) The mass ratio of the content of the component to the content of the component (A2) ((content of the component (A1))/(content of the component (A2)) is preferably within the following range. From the viewpoint of easy availability of excellent handleability, the mass ratio is preferably 0.3 or more, more preferably 0.5 or more, still more preferably more than 0.5, particularly preferably 0.6 or more, most preferably 0.7 or more, and very preferably 0.75 or more. From the viewpoint of easy availability of excellent handleability, the mass ratio is preferably 2.5 or less, more preferably 2.3 or less, further preferably 2 or less, particularly preferably 1.5 or less, most preferably 1 or less, very preferably less than 1, further preferably 0.95 or less, further preferably 0.9 or less, particularly preferably 0.85 or less, most preferably 0.8 or less. From these viewpoints, the mass ratio is preferably 0.3 to 2.5, more preferably 0.3 to 2.3.

(A1) The mass ratio of the content of the component to the content of the component (a 21) ((content of the component (A1))/(content of the component (a 21)) is preferably within the following range. From the viewpoint of easy availability of excellent handleability, the mass ratio is preferably 0.3 or more, more preferably 0.5 or more, still more preferably more than 0.5, particularly preferably 0.6 or more, most preferably 0.7 or more, and very preferably 0.75 or more. From the viewpoint of easy availability of excellent handleability, the mass ratio is preferably 2.5 or less, more preferably 2.3 or less, further preferably 2 or less, particularly preferably 1.5 or less, most preferably 1 or less, very preferably less than 1, further preferably 0.95 or less, further preferably 0.9 or less, particularly preferably 0.85 or less, most preferably 0.8 or less. From these viewpoints, the mass ratio is preferably 0.3 to 2.5, more preferably 0.3 to 2.3.

The content of the component (A) (total amount of the component (A1) and the component (A2)) is preferably within the following range based on the total amount of the resin composition. The content of the component (a) is preferably 2% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 40% by mass or more, most preferably 50% by mass or more, very preferably 60% by mass or more, further preferably 65% by mass or more, from the viewpoint of easy obtaining of excellent electrical conductivity and thermal conductivity. The content of the component (a) is preferably less than 100% by mass, more preferably not more than 90% by mass, still more preferably not more than 85% by mass, particularly preferably not more than 80% by mass, most preferably not more than 75% by mass, and very preferably not more than 70% by mass, from the viewpoint of easy obtaining of excellent adhesive strength and easy reduction of viscosity. From these viewpoints, the content of the component (a) is preferably 2% by mass or more and less than 100% by mass.

((B) component: alkoxysilane)

The alkoxysilane is a silane compound having at least one alkoxy group bonded to a silicon atom. The alkoxy group is preferably at least one selected from the group consisting of methoxy and ethoxy, from the viewpoint of easily suppressing defects in the rounded portion.

The alkoxysilane may have one silicon atom or may have 2 or more silicon atoms (may be the (B2) component). When the number of silicon atoms of the alkoxysilane is large, the alkoxysilane is easily bonded to the component (a) or the support member via the silicon atoms. Silicon atoms may also be bonded to each other via an alkylene group. The number of carbon atoms of the alkylene group is preferably in the following range from the viewpoint of easily suppressing defects of the rounded portion. The number of carbon atoms of the alkylene group is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, particularly preferably 4 or more, most preferably 5 or more, and very particularly preferably 6 or more. The number of carbon atoms of the alkylene group is preferably 8 or less, more preferably 7 or less, and further preferably 6 or less.

The number of alkoxy groups in the alkoxysilane is preferably within the following range from the viewpoint of easily suppressing defects in the rounded portions. The number of alkoxy groups is preferably 1 or more, more preferably 2 or more, and still more preferably 3. The number of alkoxy groups is preferably 6 or less, more preferably 5 or less, further preferably 4 or less, and particularly preferably 3 or less.

The alkoxysilane may be an alkylalkoxysilane having at least one alkoxy group bonded to a silicon atom and at least one alkyl group bonded to a silicon atom (may be the (B1) component). In the case where the alkoxysilane has 2 or more silicon atoms, the alkoxysilane may not have an alkyl group bonded to the silicon atom. The alkylalkoxysilane may have 2 or more silicon atoms.

From the viewpoint of easily suppressing defects in the rounded portions, the alkylalkoxysilane preferably has an alkyl group having the following number of carbon atoms (an alkyl group bonded to a silicon atom). The number of carbon atoms of the alkyl group is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The number of carbon atoms of the alkyl group is preferably 12 or less, more preferably 10 or less, further preferably 8 or less, particularly preferably 6 or less, most preferably 4 or less, and very preferably 3 or less. From these viewpoints, the carbon number of the alkyl group is preferably 1 to 12, more preferably 2 to 10, and still more preferably 3 to 10.

The alkoxysilane may contain at least one selected from the group consisting of monoalkoxysilane, monoalkylmonoalkoxysilane, dialkylmonoalkoxysilane, trialkylmonoalkoxysilane, dialkoxysilane, monoalkyldialkoxysilane, dialkyldialkoxysilane, trialkoxysilane, monoalkyltrialkoxysilane, and tetraalkoxysilane. From the viewpoint of easily suppressing defects in the rounded portions, the alkoxysilane preferably contains at least one selected from the group consisting of trialkoxysilane and monoalkyltrialkoxysilane, and more preferably contains monoalkyltrialkoxysilane.

Examples of the monoalkyl trialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, and decyltriethoxysilane.

The alkoxysilane is preferably a bis (alkoxysilyl) alkane, more preferably a bis (trialkoxysilyl) alkane, from the viewpoint of easily suppressing defects in the rounded portions, as an alkoxysilane having 2 or more silicon atoms. Examples of the bis (alkoxysilyl) alkane include 1, 2-bis (triethoxysilyl) ethane, 1, 4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilyl butane, 1, 4-bis (methyldimethoxysilyl) butane, 1, 5-bis (trimethoxysilyl) pentane, 1, 4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilyl pentane, 1, 5-bis (methyldimethoxysilyl) pentane, 1, 6-bis (trimethoxysilyl) hexane, 1, 4-bis (trimethoxysilyl) hexane, 1, 5-bis (trimethoxysilyl) hexane, 2, 5-bis (trimethoxysilyl) hexane and 1, 6-bis (methyldimethoxysilyl) hexane.

The alkoxysilane preferably contains at least one member selected from the group consisting of propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane and 1, 6-bis (trimethoxysilyl) hexane, from the viewpoint of easily suppressing defects in the rounded portions.

(B) The component (B3) may contain an alkoxysilane (hereinafter, referred to as "(B3) component", as the case may be) other than the component (B1) and the component (B2). As the component (B3), phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, vinyl-tris (2-methoxyethoxy) silane, gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl methyldimethoxy silane, methyl tris (methacryloxyethoxy) silane, gamma- (meth) acryloxypropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxy silane, N-beta- (N-vinylbenzyl aminoethyl) -gamma-aminopropyl trimethoxysilane, gamma-anilinopropyl trimethoxysilane, gamma-ureidopropyl triethoxysilane, 3- (4, 5-dihydro imidazolyl) propyl triethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-epoxypropyl trimethoxysilane, gamma-epoxypropyl triethoxysilane, gamma-methylpropyloxy-diethoxy-propyl-triethoxysilane, gamma-glycidoxypropyl silane, gamma-methylpropyloxy-triethoxysilane, gamma-methylpropyloxy silane Gamma-mercaptopropyl methyl dimethoxy silane, trimethylsilyl isocyanate, dimethyl silyl isocyanate, phenylsilyl triisocyanate, tetraisocyanatosilane, methylsilyl triisocyanate, vinylsilyl triisocyanate, and ethoxysilyl triisocyanate. From the viewpoint of easy availability of excellent adhesive strength, the (B3) component preferably contains at least one selected from the group consisting of γ -glycidoxypropyl trimethoxysilane and γ -methacryloxypropyl trimethoxysilane.

The content of the component (B1) or the component (B2) is preferably within the following range based on the total amount of the component (B). The content is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, particularly preferably 20 mass% or more, most preferably 25 mass% or more, and very preferably 30 mass% or more, from the viewpoint of easily suppressing defects in the rounded portions. The content is preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 50 mass% or less, particularly preferably 45 mass% or less, most preferably 40 mass% or less, and very preferably 35 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength. From these viewpoints, the content is preferably 5 to 70 mass%.

The content of the component (B1) or the component (B2) is preferably within the following range based on the total amount of the resin composition. The content is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, further preferably 0.5 mass% or more, particularly preferably 0.7 mass% or more, and most preferably 0.9 mass% or more, from the viewpoint of easily suppressing defects in the rounded portions. The content is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less, particularly preferably 1.5 mass% or less, and most preferably 1 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength. From these viewpoints, the content is preferably 0.1 to 5% by mass.

(B1) The mass ratio of the content of the component to the content of the component (B3) ((content of the component (B1)/(content of the component (B3)) and/or the mass ratio of the content of the component (B2) to the content of the component (B3) ((content of the component (B2))/(content of the component (B3)) is preferably within the following range. The mass ratio is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, particularly preferably 0.4 or more, and most preferably 0.5 or more, from the viewpoint of easily suppressing defects in the rounded portions. The mass ratio is preferably 2 or less, more preferably 1.5 or less, further preferably 1 or less, particularly preferably 0.8 or less, and most preferably 0.6 or less, from the viewpoint of easy obtaining of excellent adhesive strength. From these viewpoints, the mass ratio is preferably 0.1 to 2.

The content of the component (B3) is preferably within the following range based on the total amount of the component (B). The content of the component (B3) is preferably 30 mass% or more, more preferably 40 mass% or more, further preferably 50 mass% or more, particularly preferably 55 mass% or more, most preferably 60 mass% or more, and very preferably 65 mass% or more, from the viewpoint of easy obtaining of excellent adhesive strength. The content of the component (B3) is preferably 95 mass% or less, more preferably 90 mass% or less, further preferably 85 mass% or less, particularly preferably 80 mass% or less, most preferably 75 mass% or less, and very preferably 70 mass% or less, from the viewpoint of easily suppressing defects in the rounded portions. From these viewpoints, the content of the component (B3) is preferably 30 to 95 mass%.

The content of the component (B3) is preferably within the following range based on the total amount of the resin composition. The content of the component (B3) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1 mass% or more, particularly preferably 1.5 mass% or more, and most preferably 1.75 mass% or more, from the viewpoint of easy obtaining of excellent adhesive strength. The content of the component (B3) is preferably 10 mass% or less, more preferably 5 mass% or less, further preferably 3 mass% or less, particularly preferably 2.5 mass% or less, and most preferably 2 mass% or less, from the viewpoint of easily securing the curability of the resin composition sufficiently. From these viewpoints, the content of the component (B3) is preferably 0.1 to 5 mass%.

The content of the component (B) ((total amount of the component (B1), the component (B2) and the component (B3)) is preferably within the following range based on the total amount of the resin composition. The content of the component (B) is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, further preferably 0.8 mass% or more, particularly preferably 1 mass% or more, most preferably 1.5 mass% or more, very preferably 2 mass% or more, further preferably 2.5 mass% or more, from the viewpoint of easy obtaining of excellent adhesive strength. The content of the component (B) is preferably 10 mass% or less, more preferably 8 mass% or less, further preferably 5 mass% or less, particularly preferably 4 mass% or less, most preferably 3.5 mass% or less, and very particularly preferably 3 mass% or less, from the viewpoint of ensuring the curability of the resin composition easily and sufficiently. From these viewpoints, the content of the component (B) is preferably 0.2 to 10 mass%.

((C) component: thermosetting component)

Examples of the component (C) include a compound having a (meth) acryloyl group (hereinafter, referred to as a "(meth) acrylic compound" as the case may be), a thermosetting resin (excluding a compound corresponding to the (meth) acrylic compound), a polymerization initiator, a curing accelerator, and the like.

[ (meth) acrylic acid Compound ]

The component (C) preferably contains a (meth) acrylic compound from the viewpoint of easily suppressing separation of the component (a) from other components (resin component and the like) at the time of flowing of the resin composition. From the viewpoint of further easily suppressing separation of the component (a) from other components (resin component, etc.), the (meth) acrylic compound preferably contains a (meth) acrylate having one or more (meth) acryloyloxy groups. From the viewpoint of further easily suppressing separation of the component (a) from other components (resin component or the like), the (meth) acrylate preferably contains at least one selected from the group consisting of a compound represented by the following general formula (C1), a compound represented by the following general formula (C2), a compound represented by the following general formula (C3), a compound represented by the following general formula (C4), a compound represented by the following general formula (C5), a compound represented by the following general formula (C6), a compound represented by the following general formula (C7), a compound represented by the following general formula (C8), a compound represented by the following general formula (C9), and a compound represented by the following general formula (C10).

[ formula, R ^1a Represents a hydrogen atom or a methyl group, R ^1b Represents a C1-100 aliphatic group having a C1-36 valence, or a hydrocarbon group having a cyclic structure.]

[ formula, R ^2a Represents a hydrogen atom or a methyl group, R ^2b Represents a C1-100 aliphatic group having a C1-36 valence, or a hydrocarbon group having a cyclic structure.]

[ formula, R ^3a Represents a hydrogen atom or a methyl group, R ^3b Represents a hydrogen atom, a methyl group or a phenoxymethyl group, R ^3c Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzoyl group, and n3 represents an integer of 1 to 50.]

[ formula, R ^4a Represents a hydrogen atom or a methyl group, R ^4b Represents phenyl, cyano, -Si (OR) ^4c ) ₃ (R ^4c Alkyl groups having 1 to 6 carbon atoms), or 1-valent groups represented by the following formula, n4 represents an integer of 0 to 3.]

[ formula, R ^4d 、R ^4e R is R ^4f R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms ⁴ g represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group。]

[ formula, R ^5a R is R ^5b Each independently represents a hydrogen atom or a methyl group, R ^5c Represents a C1-100 aliphatic group having a C1-36 valence, or a hydrocarbon group having a cyclic structure.]

[ formula, R ^6a R is R ^6b Each independently represents a hydrogen atom or a methyl group, R ^6c Represents a hydrogen atom, a methyl group or a phenoxymethyl group, and n6 represents an integer of 1 to 50. However, at R ^6c When the hydrogen atom or methyl group is used, n6 is not 1.]

[ formula, R ^7a 、R ^7b 、R ^7c R is R ^7d Each independently represents a hydrogen atom or a methyl group.]

[ formula, R ^8a 、R ^8b 、R ^8c 、R ^8d 、R ^8e R is R ^8f Each independently represents a hydrogen atom or a methyl group, and n81 and n82 each independently represent an integer of 1 to 20.]

[ formula, R ^9a 、R ^9b 、R ^9c 、R ^9d 、R ^9e R is R ^9f Each independently represents a hydrogen atom or a methyl groupN9 represents an integer of 1 to 20.]

[ formula, R ^10a R is R ^10b Each independently represents a hydrogen atom or a methyl group, r, s, t and u are each independently a number of 0 or more, r+t is 0.1 or more (preferably 0.3 to 5), and s+u is 1 or more (preferably 1 to 100), which represents an average of the number of repetitions.]

Examples of the compound represented by the formula (C1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ] ^2，6 ]Decyl (meth) acrylate, 2- (tricyclic) [5.2.1.0 ^2，6 ]Dec-3-en-8 or 9-yloxyethyl (meth) acrylate, and the like. As the compound represented by the formula (C1), ethyl (meth) acrylate is preferable.

Examples of the compound represented by the formula (C2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dimer diol mono (meth) acrylate, and the like.

Examples of the compound represented by the formula (C3) include diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxydiglycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiglycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-benzoyloxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. As the compound represented by the formula (C3), 2-phenoxyethyl (meth) acrylate is preferable.

Examples of the compound represented by the formula (C4) include benzyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrahydropyranyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 1,2, 6-pentamethylpiperidinyl (meth) acrylate, 2, 6-tetramethylpiperidinyl (meth) acrylate, (meth) acryloyloxyethyl phosphate, (meth) acryloyloxyethyl phenyl phosphate, β - (meth) acryloyloxyethyl hydrogen phthalate, β - (meth) acryloyloxyethyl hydrogen succinate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. The compound represented by the formula (C4) is preferably dicyclopentenyloxyethyl (meth) acrylate, from the viewpoint of further easily suppressing separation of the component (a) from other components (resin component or the like).

Examples of the compound represented by the formula (C5) include ethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimer diol di (meth) acrylate, and dimethyloltricyclodecyl (meth) acrylate. As the compound represented by the formula (C5), neopentyl glycol di (meth) acrylate is preferable.

Examples of the compound represented by the formula (C6) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. As the compound represented by the formula (C6), polyethylene glycol di (meth) acrylate is preferable.

Examples of the compound represented by the formula (C7) include a di (meth) acrylate compound obtained by reacting bisphenol a, bisphenol F or bisphenol AD1 mol with glycidyl (meth) acrylate 2 mol.

Examples of the compound represented by the formula (C8) include a di (meth) acrylate compound of a polyethylene oxide adduct of bisphenol a, bisphenol F or bisphenol AD. Examples of bisphenol A include ethoxylated bisphenol A (e.g., EO-modified bisphenol A diacrylate), hydrogenated bisphenol A, and halogenated bisphenol A.

Examples of the compound represented by the formula (C9) include bis ((meth) acryloxypropyl) polydimethylsiloxane and bis ((meth) acryloxypropyl) methylsiloxane-dimethylsiloxane copolymer.

Examples of the compound represented by the formula (C10) include a reactant obtained by reacting polybutadiene to which maleic anhydride is added with 2-hydroxyethyl (meth) acrylate, and a hydride thereof. As the compound represented by the formula (C10), MM-1000-80, MAC-1000-80 (both are JX Nippon Oil & Energy Corporation, trade name) and the like can be given.

The content of the (meth) acrylic compound is preferably within the following range based on the total amount of the resin composition. The content of the (meth) acrylic compound is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, particularly preferably 10% by mass or more, most preferably 15% by mass or more, and very preferably 20% by mass or more, from the viewpoint of easy obtaining of excellent adhesive strength. The content of the (meth) acrylic compound is preferably 50 mass% or less, more preferably 45 mass% or less, further preferably 40 mass% or less, particularly preferably 35 mass% or less, most preferably 30 mass% or less, and very preferably 25 mass% or less, from the viewpoint of easy obtaining of excellent electrical conductivity and thermal conductivity. From these viewpoints, the content of the (meth) acrylic compound is preferably 1 to 50 mass%.

[ thermosetting resin ]

Thermosetting resins can be used as binder resins. Examples of the thermosetting resin include epoxy resin, silicone resin, and urethane resin. The component (C) preferably contains an epoxy resin from the viewpoints of easy obtaining of excellent adhesive strength and easy suppression of separation of the component (a) from other components (resin component and the like).

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Examples of such epoxy resins include bisphenol a type epoxy resins (e.g., AER-X8501 (Asahi Kasei Corporation, trade name), R-301 (Mitsubishi Chemical Corporation, trade name), YL-980 (Mitsubishi Chemical Corporation, trade name)), bisphenol F type epoxy resins (e.g., YDF-170 (Tohto Kasei co., ltd., trade name)), bisphenol AD type epoxy resins (e.g., R-1710 (Mitsui Chemicals, inc., trade name)), phenol novolac type epoxy resins (e.g., N-730S (DIC Corporation, trade name), quatrex-2010 (Dow Chemical Company, trade name)), cresol novolac type epoxy resins (e.g., N-665-EXP (DIC Corporation), trade name), YDCN-702S (Tohto Kasei co., ltd., trade name), EOCN-100 (Nippon Kayaku co., ltd., trade name)), multifunctional epoxy resins (e.g., EPPN-501 (Nippon Kayaku co., ltd., trade name), TACT IX-742 (Dow Chemical Company, trade name), VG-3010 (Mitsui Chemicals, inc., trade name), 1032S (Mitsubishi Chemical Corporation, trade name)), epoxy resins having a naphthalene skeleton (e.g., HP-4032 (DIC Corporation, trade name)), alicyclic epoxy resins (e.g., CEL-3000 (Daicel Corporation, trade name)), epoxidized polybutadiene (e.g., PB-3600 (Daicel Corporation, trade name), E-1000-6.5 (J X Nippon Oil & Energy Corporation, trade name)), amine-type epoxy resins (e.g., ELM-100 (Sumitomo Chemical Co., ltd., trade name), YH-434L (Tohto Kas ei Co., ltd., trade name)), resorcinol-type epoxy resins (e.g., denacol EX-201 (Nagase ChemteX Corporation, trade name)), neopentyl glycol-type epoxy resins (e.g., denacol EX-211 (Nagase ChemteX Corporation, trade name)), 1, 6-hexanediol diglycidyl ether-type epoxy resins (e.g., denacol EX-212 (Nagase ChemteX Corporatio n, trade name)), ethylene-propylene glycol-type epoxy resins (e.g., denacol EX-810, 811, 850, 851, 821, 830, 832, 841, 861 (Nagase ChemteX Corporation, trade name)), epoxy resins represented by the following general formula (C11) (e.g., E-XL-24, E-XL-3L (Mitsui, trade name)), and the like.

[ wherein n11 represents an integer of 0 to 5. ]

The epoxy resin preferably contains at least one selected from the group consisting of bisphenol F type epoxy resin, epoxidized polybutadiene, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. In this case, excellent electrical conductivity, adhesive strength, thermal conductivity, coating workability, and mechanical characteristics are easily obtained.

The epoxy resin may also contain a monofunctional epoxy compound (reactive diluent) which is a compound having one epoxy group in one molecule. Examples of such monofunctional epoxy compounds include phenyl glycidyl ethers (for example, PGE (Nippon Kayaku Co., ltd., trade name)), alkylphenol monoglycidyl ethers (for example, PP-101 (Tohto Kasei Co., ltd., trade name)), aliphatic monoglycidyl ethers (for example, ED-502 (ADEKA CORPORATION, trade name)), alkylphenol monoglycidyl ethers (for example, ED-509 (ADEKA CORPORATION, trade name)), alkylphenol monoglycidyl ethers (for example, YED-122 (Mitsubishi Chemical Corporation, trade name)), and the like.

The thermosetting resin preferably has a number average molecular weight of 160 to 3000. When the number average molecular weight of the thermosetting resin is 160 or more, excellent adhesive strength is easily obtained. When the number average molecular weight of the thermosetting resin is 3000 or less, the viscosity of the resin composition does not excessively increase, and good handleability is easily obtained. The number average molecular weight can be measured by Gel Permeation Chromatography (GPC) under the following conditions, and can be obtained by conversion from a calibration curve using standard polystyrene.

GPC conditions ]

And (3) a pump: hitachi L-6000 type (manufactured by Hitachi, ltd.)

A detector: hitachi L-3300 RI (Hitachi, manufactured by Ltd.)

Column: gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R430 (3 total) (Showa Denko Materials Co., ltd., trade name)

Eluent: THF (tetrahydrofuran)

Sample concentration: 250mg/5mL

Injection amount: 50 mu L

Pressure: 441Pa (45 kgf/cm) ² )

Flow rate: 1.75 mL/min

The epoxy equivalent of the epoxy resin is preferably 80 to 1000, more preferably 100 to 500. When the epoxy equivalent of the epoxy resin is 80 or more, excellent adhesive strength is easily obtained. When the epoxy equivalent of the epoxy resin is 1000 or less, the occurrence of outgas of the cured product of the resin composition, which occurs in the thermal history after curing, is easily suppressed from the viewpoint of easily suppressing the remaining unreacted cured product at the time of curing the resin composition.

The content of the thermosetting resin is preferably within the following range based on the total amount of the resin composition. The content of the thermosetting resin is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 0.8 mass% or more, and particularly preferably 1 mass% or more, from the viewpoint of easy obtaining of excellent adhesive strength. The content of the thermosetting resin is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less, and particularly preferably 1.5 mass% or less, from the viewpoint of suppressing excessive increase in viscosity of the resin composition and facilitating obtaining of good handleability. From these viewpoints, the content of the thermosetting resin is preferably 0.1 to 5 mass%.

[ polymerization initiator ]

The polymerization initiator can be used to promote curing of the resin composition. The polymerization initiator preferably contains a radical polymerization initiator.

The radical polymerization initiator preferably contains a peroxide-based radical polymerization initiator from the viewpoint of easily suppressing the formation of voids during curing of the resin composition. Examples of the peroxide-based radical polymerization initiator include 1, 3-tetramethylperoxy-2-ethylhexanoate, 1-bis (t-butylperoxy) cyclohexane, 1-bis (t-butylperoxy) cyclododecane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne, cumene hydroperoxide, and the like.

The content of the polymerization initiator is preferably within the following range based on the total amount of the resin composition. The content of the polymerization initiator is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, further preferably 0.5 mass% or more, particularly preferably 0.7 mass% or more, and most preferably 0.9 mass% or more, from the viewpoint of easily securing sufficient curability of the resin composition. The content of the polymerization initiator is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less, particularly preferably 1.5 mass% or less, and most preferably 1 mass% or less, from the viewpoint of easy obtaining of excellent adhesive strength. From these viewpoints, the content of the polymerization initiator is preferably 0.1 to 5 mass%.

[ curing accelerator ]

Examples of the curing accelerator include amine compounds (excluding a polymer compound having a polyoxyalkylene group, which will be described later). From the viewpoint of ensuring sufficient curability of the resin composition, the component (C) preferably contains an amine compound. Examples of the amine compound include dicyandiamide, dibasic acid dihydrazide represented by the following general formula (C12) (for example, ADH, PDH, and SDH (all of which are commercially available from Japan Finechem inc)), polyamine, imidazole compound, microcapsule-type curing agent formed from a reactant of epoxy resin and amine compound (for example, novacure (Asahi Kasei Corporation, commercially available from name)), diaminodiphenylmethane, metaphenylene diamine, metaxylene diamine, diaminodiphenyl sulfone, urea derivative, melamine, and the like. Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

[ formula, R ^12a Represents a 2-valent aromatic group such as m-phenylene or p-phenylene, a linear or branched alkylene group having 2 to 12 carbon atoms.]

The content of the curing accelerator is preferably within the following range based on the total amount of the resin composition. The content of the curing accelerator is preferably 0.1 mass% or more, more preferably 0.15 mass% or more, still more preferably 0.2 mass% or more, and particularly preferably 0.25 mass% or more, from the viewpoint of ensuring the curability of the resin composition easily and sufficiently. The content of the curing accelerator is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less, from the viewpoint of easily and sufficiently securing the stability of the resin composition. From these viewpoints, the content of the curing accelerator is preferably 0.1 to 1 mass%.

(Flexible agent)

The resin composition according to the present embodiment may contain a flexibilizer (excluding a compound corresponding to the component (B) or the component (C)). In this case, flexibility can be imparted to the cured product of the resin composition. Examples of the flexible agent include rubber-based compounds and thermoplastic resins (excluding rubber-based compounds).

The rubber compound preferably contains a butadiene rubber having a butadiene skeleton. Examples of the butadiene rubber include liquid rubbers such as epoxidized polybutadiene rubber, maleated polybutadiene, acrylonitrile butadiene rubber, carboxyl terminal acrylonitrile butadiene rubber, amino terminal acrylonitrile butadiene rubber, vinyl terminal acrylonitrile butadiene rubber, and styrene butadiene rubber.

The number average molecular weight of the rubber compound is preferably 500 to 10000, more preferably 1000 to 5000. When the number average molecular weight of the rubber compound is 500 or more, good flexibility is easily imparted to the cured product of the resin composition. When the number average molecular weight of the rubber compound is 10000 or less, the viscosity of the resin composition is less likely to increase, and good handleability of the resin composition is easily obtained. The number average molecular weight of the rubber compound can be measured by the same method as that of the thermosetting resin.

The content of the flexibilizing agent is preferably in the following range based on the total amount of the resin composition. The content of the flexibilizer is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 2.5% by mass or more, and particularly preferably 3% by mass or more, from the viewpoint of easily reducing warpage of the cured product. The content of the flexible agent is preferably 10 mass% or less, more preferably 9 mass% or less, further preferably 6 mass% or less, and particularly preferably 4 mass% or less, from the viewpoint of suppressing excessive increase in viscosity of the resin composition and facilitating obtaining of good handleability. From these viewpoints, the content of the flexibilizer is preferably 1 to 10% by mass.

(Polymer compound having polyoxyalkylene group)

The resin composition according to the present embodiment may contain a polymer compound having a polyoxyalkylene group (hereinafter referred to as "polyoxyalkylene compound" as the case may be). The polyoxyalkylene compound can be used as a dispersant. The polyoxyalkylene compound may be a polymeric amine compound. As the polyoxyalkylene compound, the trade name "ESLEAM AD-374M" manufactured by NOFCORPORATION can be used.

With the progress of higher functionality, miniaturization, weight saving, and thinning of semiconductor devices, there are cases where defects occur when an adhesive layer is formed between a support member and a semiconductor element (for example, a semiconductor element having a thickness of 400 μm or less) using a resin composition, and then a pad portion of the semiconductor element is electrically connected to the outside by wire bonding. For this reason, according to the findings of the present inventors, it is presumed that the above-described problem occurs due to a "rising phenomenon" (phenomenon in which the resin composition reaches the upper surface of the semiconductor element) in which the resin composition extends to the upper surface side of the semiconductor element due to a capillary phenomenon or the like on the side surface of the semiconductor element. In contrast, in the present embodiment, when the resin composition contains a polyoxyalkylene compound, the rising phenomenon can be suppressed. The following can be presumed: since the polyoxyalkylene compound has high affinity for the component (a) and the component (C), the use of the polyoxyalkylene compound improves the dispersibility of the component (a) in the component (C) and the like, and thus the ascending phenomenon can be suppressed. Fig. 1 (a) is a diagram showing an example of the climbing phenomenon. By using a polyoxyalkylene compound, as shown in FIG. 1 (b), the climbing phenomenon can be suppressed.

The content of the polyoxyalkylene compound is preferably in the following range based on the total amount of the resin composition. The content of the polyoxyalkylene compound is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, further preferably 0.5 mass% or more, particularly preferably 0.7 mass% or more, and most preferably 0.9 mass% or more, from the viewpoint of easily suppressing the climbing phenomenon. The content of the polyoxyalkylene compound is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less, particularly preferably 1.5 mass% or less, and most preferably 1 mass% or less, from the viewpoint of easily securing the curability of the resin composition sufficiently. From these viewpoints, the content of the polyoxyalkylene compound is preferably 0.1 to 5 mass%.

(other Components)

The resin composition according to the present embodiment may contain other additives different from the above components. Examples of the additives include fatty acids (oleic acid, stearic acid, lauric acid, etc.), coupling agents (titanate-based coupling agents, aluminum-based coupling agents, zirconate-based coupling agents, zircoaluminate-based coupling agents, etc.), moisture absorbing agents (calcium oxide, magnesium oxide, etc.), wettability improvers (fluorine-based surfactants, nonionic surfactants, higher fatty acids, etc.), antifoaming agents (silicone oils, etc.), ion capturing agents (inorganic ion exchangers, etc.), and the like.

The use of fatty acids can suppress the above-mentioned climbing phenomenon similarly to the polyoxyalkylene compound. As the fatty acid, at least one of a saturated fatty acid and an unsaturated fatty acid can be used. The number of carbon atoms of the fatty acid is preferably 6 or more, more preferably 9 or more, and still more preferably 12 or more, from the viewpoint of easily suppressing the climbing phenomenon. The number of carbon atoms of the fatty acid may be 15 or more, or 18 or more. The number of carbon atoms of the fatty acid is preferably 24 or less, more preferably 21 or less, and even more preferably 18 or less, from the viewpoint of easily suppressing the climbing phenomenon. The number of carbon atoms of the fatty acid may be 15 or less, or may be 12 or less. From the viewpoint of easily suppressing the climbing phenomenon, the fatty acid preferably contains at least one selected from the group consisting of oleic acid, stearic acid, and lauric acid.

< semiconductor device >

The semiconductor device according to the present embodiment includes a support member, a semiconductor element, and an adhesive layer disposed between the support member and the semiconductor element, and the adhesive layer contains the resin composition according to the present embodiment or a cured product thereof. The semiconductor element is mounted on the support member via the adhesive layer. The adhesive layer is in contact with the support member and the semiconductor element. The semiconductor device according to the present embodiment includes the semiconductor device according to the present embodiment.

Examples of the supporting member (supporting member for mounting a semiconductor element) include a 42 alloy lead frame, a copper lead frame, a palladium PPF lead frame, and other lead frames; glass epoxy substrates (substrates made of glass fiber reinforced epoxy resins), BT substrates (substrates using BT resins made of cyanate monomers and oligomers thereof, and bismaleimides), and the like. As the semiconductor element, a IC, LSI, LED chip or the like can be given. The thickness of the semiconductor element may be 600 μm or less, 500 μm or less, or 400 μm or less.

The semiconductor device according to the present embodiment may include a sealing portion for sealing a part or all of the semiconductor element. As a constituent material of the sealing portion, a light-transmitting resin can be used. The sealing portion may seal part or all of the support member.

The method for manufacturing a semiconductor device according to the present embodiment includes an adhesive layer forming step of forming an adhesive layer by disposing the resin composition according to the present embodiment between a support member and a semiconductor element. The resin composition according to the present embodiment can be obtained by mixing the constituent components together or separately using a stirrer, a mixer, a kneader, a 3-roll stirrer, a planetary stirrer, or the like.

The method for manufacturing a semiconductor device according to the present embodiment may include a step of curing (e.g., thermally curing) the adhesive layer after the adhesive layer forming step to obtain a cured product. The method for manufacturing a semiconductor device according to the present embodiment may include a wire bonding step of wire bonding the semiconductor element after the adhesive layer forming step. The method for manufacturing a semiconductor device according to the present embodiment may include a step of sealing the semiconductor element after the adhesive layer forming step.

In order to adhere the semiconductor element to the support member using the resin composition, for example, the semiconductor element is first pressure-bonded after the resin composition is applied to the support member by a dispensing method, a screen printing method, an imprint method, or the like, and then the resin composition is heat-cured using a heating device (oven, heating block, or the like). After the wire bonding process, the semiconductor element can be sealed by a usual method.

The heat curing conditions of the resin composition are different in the case of rapid curing at high temperature and in the case of long-time curing at low temperature. For example, in the case of rapid curing at high temperature, the heat curing of the resin composition can be carried out at 150 to 220 ℃ (preferably 180 to 200 ℃) for 30 seconds to 2 hours (preferably 1 hour to 1 hour 30 minutes).

Fig. 2 is a schematic cross-sectional view showing an example of the semiconductor device according to the present embodiment. As shown in fig. 2, the semiconductor device 10 includes a support member 11, a semiconductor element 13, an adhesive layer 15, and a sealing portion 17. The adhesive layer 15 is disposed between the support member 11 and the semiconductor element 13, and contains the resin composition or the cured product thereof according to the present embodiment. The sealing portion 17 seals the supporting member 11, the semiconductor element 13, and the adhesive layer 15. The semiconductor element 13 is connected to a lead frame 19b via a wire 19 a.

Fig. 3 is a schematic cross-sectional view showing another example of the semiconductor device according to the present embodiment. As shown in fig. 3, the semiconductor device 20 includes a support member 21, a semiconductor element (LED chip) 23, an adhesive layer 25, and a sealing portion 27. The support member 21 includes a substrate 21a and a lead frame 21b formed so as to surround the substrate 21 a. The adhesive layer 25 is disposed between the support member 21 and the semiconductor element 23, and contains the resin composition or the cured product thereof according to the present embodiment. The sealing portion 27 seals the semiconductor element 23 and the adhesive layer 25. The semiconductor element 23 is connected to the lead frame 21b via a wire 29.

Examples

Hereinafter, the present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

< constituent Components of resin composition >

(aluminum particles)

12-0086 (manufactured by TOYO ALUMINIUM K.K., trade name, average particle diameter: 3.5-4.2 μm)

(silver particles)

TC-204B (manufactured by Tokuriki Honten Co.Ltd., trade name, average particle size: 2.0 to 4.0 μm)

(alkoxysilane)

KBM-3033 (n-propyltrimethoxysilane, shin-Etsu Chemical Co., ltd., trade name)

KBE-3033 (n-propyltriethoxysilane, shin-Etsu Chemical Co., ltd., trade name)

KBM-3063 (hexyltrimethoxysilane, shin-Etsu Chemical Co., ltd., trade name)

KBM-3103 (decyl trimethoxysilane, shin-Etsu Chemical Co., ltd., trade name)

KBM-3066 (1, 6-bis (trimethoxysilyl) hexane, shin-Etsu Chemical Co., ltd., trade name)

(coupling agent)

KBM-403 (gamma-glycidoxypropyl trimethoxysilane, shin-Etsu Chemical Co., ltd., trade name)

((meth) acrylic acid compound)

FA-512AS (dicyclopentenyloxyethyl acrylate, showa Denko Materials Co., ltd., trade name, a compound represented by the following formula (C4-1))

SR-349 (EO-modified bisphenol A diacrylate, manufactured by Sartomer Company, trade name, compound represented by the following formula (C8-1))

(thermosetting resin)

N-665-EXP (cresol novolak type epoxy resin, trade name, manufactured by DIC Corporation, epoxy equivalent: 198 to 208)

(polymerization initiator)

Trigonox 22-70E (1, 1-bis (t-butylperoxy) cyclohexane, KAYAKU AKZO CO., LTD. Manufactured by LTD., trade name)

(curing accelerator)

Dicy (dicyandiamide, manufactured by Mitsubishi Chemical Corporation, trade name)

(Flexible agent)

Epoiead PB-4700 (epoxidized polybutadiene manufactured by Daicel Corporation, trade name, epoxy equivalent: 152.4-177.8, number average molecular weight: 3500)

(polyoxyalkylene compound)

ESLEAM AD-374M (polyalkylene glycol derivative, dispersant, manufactured by NOF CORPORATI ON, trade name)

< preparation of resin composition >

After mixing the components (unit of blending amount: parts by mass) in Table 1, the mixture was kneaded using a planetary mixer (manufactured by PRIMIX Corporation, model: T.K.HIVIS MIX 2P-06). Then, a defoaming treatment was performed at 666.61Pa (5 Torr) or less for 10 minutes to obtain a resin composition.

< evaluation >

The fillet defect and the rise were evaluated by the methods shown below. The results are shown in Table 1.

(corner rounding defect)

About 70. Mu.g/mm of a silver spot plated copper lead frame coated with a resin composition ² After the adhesive layer was formed, a 4mm×4mm silicon chip (thickness: 400 μm) was pressure-bonded (die-bonded) to the adhesive layer. Then, the temperature was raised to 180℃in an oven for 30 minutes, and then the resin composition was cured by heating at 180℃for 1 hour, whereby a cured product was obtained. Then, the outer peripheral portion of the cured product was observed with a digital microscope, and the presence or absence of defects in the rounded portions was confirmed. Fig. 4 is a photograph showing a part of the outer periphery of the cured product (fig. 4 (a): example 1, fig. 4 (b): comparative example 1).

(climbing phenomenon)

About 70. Mu.g/mm of a silver spot plated copper lead frame coated with a resin composition ² After the adhesive layer was formed, a silicon chip (thickness: 400 μm) of 7mm×7mm was pressure-bonded (die-bonded) to the adhesive layer. Then, the temperature was raised to 180℃in an oven for 30 minutes, and then the resin composition was cured by heating at 180℃for 1 hour, whereby a cured product was obtained. Further, the presence or absence of the phenomenon (the lifting phenomenon) that the resin composition extended to the upper surface side of the silicon chip was visually confirmed on the side surface of the silicon chip.

As shown in table 1, in the examples, it was confirmed that defects of the rounded portions were suppressed while using aluminum particles. In examples 1 to 6, it was confirmed that the climbing phenomenon was suppressed.

Symbol description

10. 20-semiconductor device, 11, 21-support member, 13, 23-semiconductor element, 15, 25-adhesive layer, 17, 27-sealing part, 19a, 29-wire, 19b, 21 b-lead frame, 21 a-substrate.

Claims

1. A resin composition comprising (A) metal particles, (B) alkoxysilane and (C) a thermosetting component,

the component (A) contains aluminum-containing 1 st particles,

the component (B) comprises: (B1) An alkylalkoxysilane or (B2) an alkoxysilane having 2 or more silicon atoms; and (B3) an alkoxysilane other than the component (B1) and the component (B2),

the (B1) alkylalkoxysilane has an alkyl group having 3 to 10 carbon atoms,

when the component (B) contains the (B1) alkylalkoxysilane, the mass ratio of the content of the component (B1) to the content of the component (B3) is 0.1 to 2,

when the component (B) contains an alkoxysilane having 2 or more silicon atoms in the component (B2), the mass ratio of the content of the component (B2) to the content of the component (B3) is 0.1 to 2.

2. The resin composition according to claim 1, wherein,

the component (B) contains a monoalkyltrialkoxysilane.

3. The resin composition according to claim 1, wherein,

The component (B) contains a bis (trialkoxysilyl) alkane.

4. The resin composition according to any one of claim 1 to 3, wherein,

the average particle diameter of the 1 st particle is 1 to 6 μm.

5. The resin composition according to any one of claim 1 to 3, wherein,

the component (A) further contains a 2 nd particle containing a metal other than aluminum.

6. The resin composition according to claim 5, wherein,

the 2 nd particles contain silver-containing particles.

7. The resin composition according to claim 5, wherein,

the average particle diameter of the 2 nd particles is 1-15 μm.

8. The resin composition according to claim 5, wherein,

the mass ratio of the content of the 1 st particles to the content of the 2 nd particles is 0.3 to 2.3.

9. The resin composition according to any one of claim 1 to 3, wherein,

the component (C) contains a compound having a (meth) acryloyl group.

10. The resin composition according to any one of claim 1 to 3, wherein,

the component (C) contains an epoxy resin.

11. The resin composition according to any one of claim 1 to 3, wherein,

the component (C) contains an amine compound.

12. A cured product of the resin composition according to any one of claims 1 to 11.

13. A semiconductor device includes a support member, a semiconductor element, and an adhesive layer disposed between the support member and the semiconductor element,

the adhesive layer contains the resin composition according to any one of claims 1 to 11 or a cured product thereof.