JP5014774B2 - Addition reaction curable silicone composition and semiconductor device - Google Patents

Description

  The present invention relates to an addition reaction curable silicone composition and a semiconductor device, and in particular, a one-component addition reaction curable silicone composition having self-adhesiveness to various substrates such as plastic, metal, and glass, and The present invention relates to a semiconductor device to which a lid (a lid or a cap) is bonded with this composition.

  Conventionally, in an electronic device such as a semiconductor device, various types of adhesives such as an epoxy resin are used to bond a substrate mainly made of an epoxy resin and a metal base material such as Ni or Cu.

  In recent years, in the field of electrical / electronic parts, the progress of downsizing has been remarkable, and the bonding area of members has been steadily decreasing. Therefore, it is desired to increase the bonding strength per unit area. In particular, in semiconductor devices, as an adhesive for bonding a metal lid that covers a semiconductor element to a substrate, both adhesive strength (shear bond strength) and improved fracture mode and lower viscosity are compatible. However, it has been difficult to satisfy both of them with the conventional adhesive composition.

  That is, an addition reaction curable silicone composition containing a silicone oil having a high degree of polymerization has been proposed in order to improve the shear bond strength and improve the adhesive failure mode.

  However, this composition has a disadvantage that the viscosity becomes too high, and in fact, a reinforcing filler is blended, so that the viscosity becomes even higher and it is difficult to discharge from a small-bore syringe or the like. There was a problem.

  Calcium carbonate and pulverized silica are generally known as fillers that do not easily increase the viscosity, but when these fillers are added, shear bond strength, tensile bond strength, and cohesive failure rate in bond failure mode ( There was a problem that CF) would decrease.

  In addition, various adhesion promoters can be used to improve adhesion, and compositions containing adhesion promoters have also been proposed (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Patents). Reference 5 and Patent Document 6).

  However, in such a composition, the effect of the adhesion promoter as an internal additive is not sufficient, which is economically undesirable. In addition, since the highly active group contained in the adhesion promoter gradually has an adverse effect on storage stability and cross-linking properties, the adhesion promoter can only be improved in a limited manner, but rather the adhesion promoter. It is considered that the content of is kept as low as possible.

  In addition, in a composition containing such an adhesion promoter, it is common to add a reaction retarding agent in order to improve storage stability, but when a reaction retarding agent is added, curing is delayed. There was a problem.

More recently, an adhesive for bonding the lid of the semiconductor element and the substrate is required to be cured at a lower temperature. This requirement is for minimizing the damage of parts due to heating by keeping the temperature of the curing reaction low. Considering continuous production, it is required to lower the curing temperature even if the curing time is extended. It has been.
JP-A-54-80358 Japanese Patent Publication No.53-21026 JP 54-48853 A Japanese Patent Publication No.51-33540 Japanese Examined Patent Publication No. 45-23354 JP 54-37157 A

  The present invention has been made in view of these points, and has an appropriate viscosity (dischargeability) and good thixotropy (non-fluidity), and does not require a primer and has excellent self-adhesiveness. An object is to provide a reaction-curable silicone composition.

Addition reaction-curable silicone composition of the present invention, the diorganopolysiloxane is (A) an alkenyl group bonded to a silicon atom and at least two chromatic per molecule, a viscosity at 23 ° C. is 10~20Pa · s , (B) SiO _4/2 unit (Q unit), ViR ¹ SiO _2/2 unit (D ^Vi unit) and R ¹ ₃ SiO _1/2 unit (M unit) (wherein Vi represents a vinyl group, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond.) A polyorganosiloxane having a resin structure is added to the sum of the components (A) and (B). at least two possess a 30 to 40 wt%, the hydrogen atoms bonded to silicon atoms in a molecule (C) with respect to, organo Hyde kinematic viscosity at 23 ° C. is 10～25CSt (centistokes) The hydrogen atom bonded to the silicon atom of Genpolysiloxane is 1 per mole in total of the alkenyl group bonded to the silicon atom in the component (A) and the vinyl group bonded to the silicon atom in the component (B). An amount of 0.0 to 1.4 mol, an amount of (D) a platinum-based catalyst in an amount of 0.01 to 100 ppm of the total weight of the composition in terms of platinum, and (E) fumed silica, It contains 2 to 20% by weight with respect to the total of the component (A) and the component (B).

  The semiconductor device of the present invention has a substrate, a semiconductor element mounted on the substrate, and a lid that covers the semiconductor element, and the lid is formed on the substrate by the addition reaction curable silicone composition of the present invention. It is characterized by being bonded.

In the addition reaction curable silicone composition of the present invention, (B) SiO _4/2 unit (Q unit), ViR ¹ SiO _2/2 unit (D ^Vi unit) together with (A) alkenyl group-containing diorganopolysiloxane. ) And R ¹ ₃ SiO _1/2 units (M units) and a polyorganosiloxane having a resin structure, and (E) fumed silica as a reinforcing filler. In addition to having a low viscosity that can be discharged from (for example, φ2 mm), it has good thixotropy, and the discharged bead can sufficiently retain its shape. In addition, it has good adhesion to various metal substrates (shear bond strength and tensile bond strength) without the need for a primer, and does not include thin layer fracture (TCF) in the fracture mode. (CF) It has a good adhesiveness of 100%. Furthermore, since it is excellent in storage stability and is quickly cured by heating, it is possible to reliably perform bonding and fixing of the lid in the semiconductor device in a short time.

  Hereinafter, embodiments of the present invention will be described.

The addition reaction curable silicone composition of the embodiment of the present invention comprises (A) an alkenyl group-containing diorganopolysiloxane, (B) SiO _4/2 units (Q units), ViR ¹ SiO _2/2 units (D ^Vi Unit ) and R ¹ ₃ SiO _1/2 unit (M unit), polyorganosiloxane having a resin structure, (C) organohydrogenpolysiloxane, (D) platinum-based catalyst, and (E) fumed silica Each containing.

  The alkenyl group-containing diorganopolysiloxane as component (A) has at least two alkenyl groups bonded to silicon atoms in one molecule, and is used as the base polymer of the silicone composition of the embodiment. This alkenyl group-containing diorganopolysiloxane is basically a straight chain in which the main chain portion is composed of repeating diorganosiloxane units and both ends of the molecular chain are blocked with triorganosiloxy groups. May include a branched structure, or the whole may be annular. From the viewpoint of the mechanical strength of the cured product, linear diorganopolysiloxane is preferred. Further, it is preferable that low molecular weight components having a boiling point of less than 250 ° C. usually present in a small amount in the polyorganosiloxane are removed.

（式中、Ｒ^２は脂肪族不飽和結合を含まない置換または非置換の１価の炭化水素基であり、Ｘはアルケニル基である。Ｙは、アルケニル基またはＲ^２であり、ｎは０または１以上の整数、ｍは０または１以上の整数であり、かつ１分子中にケイ素原子に結合するアルケニル基を少なくとも２個含有する。）で表されるジオルガノポリシロキサンが挙げられる。 The alkenyl group may be present only at both ends of the molecular chain, may be present only in the middle of the molecular chain, or may be present at both ends and in the middle of the molecular chain. Examples of such alkenyl group-containing diorganopolysiloxane include, for example, a general formula:

(In the formula, R ² is a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, X is an alkenyl group, Y is an alkenyl group or R ² , and n is 0. Or an integer of 1 or more, m is 0 or an integer of 1 or more, and at least two alkenyl groups bonded to a silicon atom are contained in one molecule.

In the general formula (1), R ² is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group or a hexyl group; a cyclopentyl group or a cyclohexyl group. An aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a phenylethyl group; and a halogen atom such as fluorine, chlorine or bromine in which at least some of the hydrogen atoms of these groups are And a group substituted with cyano group, for example, a halogen-substituted alkyl group such as chloromethyl group, bromomethyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, cyano-substituted alkyl group, and the like. In particular, a methyl group and a phenyl group are preferable.

  Examples of the alkenyl group for X include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, and an isobutenyl group. In particular, a lower alkenyl group having 2 to 4 carbon atoms such as vinyl group and allyl group is preferable.

Y is an alkenyl group or R ² described above. Specific examples of the alkenyl group include the same ones as exemplified for X above. Two Ys as substituents bonded to silicon atoms at both ends of the molecular chain may be the same or different, but both are preferably alkenyl groups.

  n is preferably an integer of 10 to 10,000, more preferably 50 to 2,000, and m is preferably an integer of 0 to 100.

  In the embodiment of the present invention, as the alkenyl group-containing diorganopolysiloxane as component (A), a long-chain both-end vinyl having a viscosity (23 ° C.) of 60 to 100 Pa · s (more preferably 70 to 90 Pa · s). Group-containing diorganopolysiloxane and short-chain both-end vinyl group-containing diorganopolysiloxane having a viscosity (23 ° C.) of 1.0 to 5.0 Pa · s (more preferably 2.5 to 3.5 Pa · s) Are preferably used in combination. And it is preferable that the viscosity (23 degreeC) of (A) component which is these mixtures shall be 10-20 Pa.s.

The polyorganosiloxane having a resin structure as component (B) is composed of SiO _4/2 units (Q units), ViR ¹ SiO _2/2 units (D ^Vi units ), and R ¹ ₃ SiO _1/2 units (M units). (Wherein Vi represents a vinyl group, and R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond), and has a three-dimensional network structure.

The R ^1, Formula in (1) can be exemplified the same as those exemplified as R ^2, preferably a methyl group.

(B) The polyorganosiloxane which has the resin structure of a component can be used individually by 1 type or in combination of 2 or more types. Such a polyorganosiloxane having a resin structure can be easily synthesized by, for example, cohydrolyzing, in the presence of an acid, a combination of compounds serving as unit sources in the above molar ratio. it can.

  The blending ratio of the component (B) is 30 to 40% by weight, more preferably 32 to 38% by weight, particularly 34 to 36% by weight, based on the total amount of the component (A) and the component (B). It is preferable that By blending the component (B) at such a ratio, it is possible to improve the bond strength, particularly the breakage mode of the bond, and to realize a low viscosity.

  The organohydrogenpolysiloxane as component (C) contains at least 2, preferably 3 or more hydrogen atoms (ie, SiH groups) bonded to silicon atoms in one molecule. It acts as a crosslinking component of the component and the component (B). The organohydrogenpolysiloxane may be linear, branched, cyclic, or three-dimensional network structure.

As a typical example of such an organohydrogenpolysiloxane, the following average composition formula: H _a R ³ _b SiO _{(4-ab) / 2} (2)
The organohydrogen polysiloxane represented by these is mentioned. Here, R ³ is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and examples thereof are the same as those exemplified as R ² in the general formula (1). . Preferably, it is a lower alkyl group having 1 to 3 carbon atoms such as a methyl group, or a phenyl group. a and b are 0 ≦ a <2, 0.7 ≦ b ≦ 2, and 0.8 ≦ a + b ≦ 3, preferably 0.001 ≦ a ≦ 1.2 and 0.8 ≦ b ≦ 2. And 1 ≦ a + b ≦ 2.7. )

  The organohydrogenpolysiloxane of component (C) can be used alone or in combination of two or more. The viscosity at 23 ° C. (kinematic viscosity) is 10 to 25 cSt (centistokes), particularly preferably in the range of 15 to 20 cSt.

  Component (C) is blended in such a way that a hydrogen atom (SiH group) bonded to a silicon atom is bonded to an alkenyl group bonded to a silicon atom in component (A) and a silicon atom bonded to a silicon atom in component (B). The amount is 1.0 to 1.4 mol, more preferably 1.15 to 1.25 mol per mol of the total with the group. If this ratio is less than 1.0 mol, the crosslinking reaction may be insufficient, and there is a concern about a decrease in rubber strength. On the other hand, if it exceeds 1.4 mol, TCF is generated in the adhesive fracture mode, which is not preferable.

  The platinum catalyst as component (D) is a catalyst for promoting the addition reaction (hydrosilylation reaction) of the alkenyl group of component (A) and the vinyl group of component (B) with the SiH group of component (C). It is. As such a platinum-based catalyst, conventionally known catalysts can be used. Specifically, platinum (including platinum black), platinous chloride, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde Alternatively, platinum compounds such as complexes with ketones, platinum / olefin complexes, platinum / diketone complexes, platinum / acetyl acetate complexes, platinum / vinylsiloxane complexes, and the like can be given. In addition to platinum compounds, rhodium compounds such as rhodium triphenylphosphine complex, palladium compounds such as tetrakis (triphenylphosphine) palladium, ruthenium, iridium, iron, cobalt, manganese, zinc, lead, aluminum, Examples thereof include compounds such as nickel and radical initiators such as azo compounds. Among these, platinum compounds are particularly preferably used because of their excellent reaction activity. Moreover, these catalysts may be used alone or in combination of two or more as required.

  The blending amount of the component (D) is not particularly limited as long as it is an amount necessary for curing, and is appropriately determined depending on the types of the component (A), the component (B) and the component (C), the desired curing rate, and the like. It can be increased or decreased. Usually, it may be 0.01 to 100 ppm of the whole composition (total weight) in terms of platinum content, and a range of 1 to 50 ppm is particularly preferable from the viewpoint of curability and cost.

The (E) component fumed silica is a reinforcing filler. In embodiments of the present invention, only fumed silica can be used as the reinforcing filler, and the use of other reinforcing fillers such as ground silica results in TCF in adhesive failure mode. It is not preferable. In embodiments of the present invention, it is preferred to use fumed silica with a surface area of at least 200 m ² / g.

  (E) The amount of the fumed silica that is the component is 2 to 20% by weight, more preferably 5 to 17% by weight, particularly 10 to 12% by weight based on the total of the component (A) and the component (B). % Is preferable. By blending the fumed silica in such a content ratio, the thixotropy of the composition can be improved and CF can be maintained in the fracture mode.

  In addition to the components (A) to (E), (F) an adhesion-imparting agent can be blended in the composition of the embodiment of the present invention. (F) Adhesion imparting agents include alkoxy groups and / or alkenyloxy groups bonded to silicon atoms in the molecule, Si-H groups, alkenyl groups, acrylic groups, methacrylic groups, epoxy groups, mercapto groups, ester groups. An organosilane or an organosiloxane oligomer having 2 to 50 silicon atoms, preferably 4 to 20 silicon atoms, each containing at least one reactive functional group selected from an anhydrous carboxyl group, amino group and amide group. A silicon compound is preferably used. This organosilicon compound is intended to give the silicone composition adhesiveness to semiconductor elements, mounting parts, lead frames, etc., and can be used as a known one, inhibiting the addition reaction of the silicone composition. Anything that does not.

  Examples of such organosilicon compounds include γ-glycidoxypropyltrimethoxysilane, epoxy-functional group-containing alkoxysilanes such as β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, Amino group-containing alkoxysilane such as vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane Alkoxysilanes such as mercapto group-containing alkoxysilanes such as N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-acryloxypropyltrimethoxysilane. All Is addition, the following compounds as the organosiloxane oligomer can be exemplified.

  (F) The compounding amount of the adhesion improver is preferably 5.0 parts by weight or less, and preferably 3.5 parts by weight or less per 100 parts by weight of the total amount of the components (A) to (E). Is more preferable.

  Various additives can be further added to the composition of the embodiment as necessary. In particular, when the composition is used in a one-pack type, a hydrosilylation reaction inhibitor can be blended to improve storage stability. As the reaction inhibitor, conventionally known ones can be used, and examples thereof include acetylene compounds, compounds containing two or more alkenyl groups, compounds containing alkynyl groups, and maleic acid derivatives. Among these, it is desirable to use a compound having an alkenyl group or an alkynyl group. In particular, a compound having two or more alkynyl groups in one molecule, a disiloxane or a maleic acid diester represented by a compound having an alkynyl group and an alcoholic hydroxyl group in one molecule is preferably used. If the addition amount of these reaction inhibitors is too small, the effect of retarding the hydrosilylation reaction cannot be obtained. Conversely, if too large, the curing itself is inhibited, so the total amount of components (A) to (E) is 100. The range of 0.00001 to 10 parts by weight is desirable with respect to parts by weight.

  The addition reaction curable silicone composition of the embodiment of the present invention comprises (A) to (E) components, and (F) other optional components such as adhesion improvers and reaction inhibitors as required. Prepared by mixing. The composition thus obtained has an excellent viscosity with an appropriate viscosity and a thixotropy (1 rpm / 4 rpm viscosity ratio) of 2.5 or more, and is excellent in thixotropy. The cured product obtained by curing the composition at room temperature or by heating is a shear bond strength of 5.0 MPa or more and 100% CF in the fracture mode and does not contain TCF. Good adhesion to Ni alloy adherends.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to a following example. In the examples and comparative examples, the viscosity is a value measured at 23 ° C.

EXAMPLE Dimethylpolysiloxane (M ^Vi D ₉₃₃ M ^Vi ) having a viscosity of 100 Pa · s blocked at both ends of the molecular chain with vinyldimethylsiloxy groups (hereinafter referred to as component A-1) 18 parts by weight (vinyl group-containing siloxane 24.3% by weight based on the whole component) and dimethylpolysiloxane (M ^Vi D ₃₃₉ M ^Vi ) having a viscosity of 3 Pa · s blocked at both ends of the molecular chain with vinyldimethylsiloxy groups (hereinafter referred to as A-2 component) 30 parts by weight (40.6% by weight with respect to the entire vinyl group-containing siloxane component) and (B) a resin-structured polysiloxane containing vinyl groups (the ratio of Q units is 27.4 mol%, D percentage of ^Vi units 39.3 mol%, the proportion of M units 33.3 mol%) vinyl consisting 26 parts by weight (35.1 wt% based on the total vinyl-containing siloxane component) group-containing The siloxane component, (C) organohydrogenpolysiloxane _{^{(MD H 23 D 16 M)}} , 1.25 times by mole the amount of SiH groups relative to the total amount of vinyl groups of the vinyl group-containing siloxane component, i.e. H / Vi An amount that gives a ratio of 1.25, (E) 9.8 parts by weight of fumed silica, and (F) an adhesion improver represented by [Chemical Formula 3] (shown as Adhesion improver-1) is 2.5. 0.4 parts by weight and 0.4 parts by weight of γ-glycidoxypropyltrimethoxysilane (adhesion improver-2), and triallyl isocyanate (represented as reaction inhibitor-1) as a reaction inhibitor are 0. 8 parts by weight and 0.12-parts by weight of 3,5-dimethyl-1-hexyn-3-ol (represented as reaction inhibitor-2), platinum-based catalyst (complex compound having a platinum content of 3.4% by weight) 0.07 parts by weight, and color master (carbon black and 0.5 parts by weight of a mixture with a nyl group-containing silicone oil) were uniformly stirred and mixed to prepare an addition reaction curable silicone composition.

In the composition formula representing siloxane,
M is a monofunctional siloxy unit represented by the formula: Me ₃ SiO _1/2
M ^Vi is a monofunctional siloxy unit represented by the formula: Me ₂ ViSiO _1/2
D is a bifunctional siloxy unit represented by the formula: Me ₂ SiO _2/2 ,
^DH is a bifunctional siloxy unit represented by the formula: HMeSiO _2/2 ,
Q represents a tetrafunctional siloxy unit represented by the formula: SiO _4/2 . Me is a methyl group and Vi is a vinyl group. Table 1 shows the composition (% by weight relative to the whole) of each component in the examples.

  Moreover, as Comparative Examples 1-3, each component shown in Table 1 was mix | blended with the composition (weight% with respect to the whole) shown in the same table, and it stirred and mixed, and prepared the addition reaction hardening type silicone composition, respectively. In Table 1, component A-3 indicates dimethylpolysiloxane having a viscosity of 10 Pa · s in which both ends of the molecular chain are blocked with vinyldimethylsiloxy groups.

  Next, with respect to the compositions obtained in Examples and Comparative Examples 1 to 3, according to the measurement methods shown below, shear adhesive strength, fracture mode adhesiveness (cohesive failure rate), dischargeability (viscosity), and thixotropy Was measured respectively. These results are shown in Table 2.

<Shear bond strength>
In accordance with a method defined in JIS K 6850, which is a citation standard of JIS K 6249, a shear bond strength test was performed as follows. That is, two nickel-plated plates of 80 × 25 × 2 mm are placed in parallel with the long sides overlapped by 10 mm, and the silicone composition has a thickness of 0.2 mm so as to contact two opposing surfaces of the overlapped portions. The layer was formed, heated at 125 ° C. for 90 minutes, and then allowed to cool to prepare a test specimen. Moreover, the test body was produced similarly about the aluminum plate. The test specimen thus obtained was mounted on a tensile tester and 10 mm / min. An adhesion test was conducted at a tensile speed of 5 to confirm whether the fracture surface was cohesive failure (CF) or adhesive failure (AF).

<Destruction mode adhesiveness (cohesive failure rate)>
In the tensile shear adhesion test, the cohesive failure rate was measured when breakage occurred at the joint between the silicone composition layer and the substrate. In addition, when the adhesive strength between the silicone composition layer and the base material is greater than the strength of the silicone composition, cohesive failure occurs in which the silicone composition layer or the base material is destroyed before the joint is destroyed. It can be said that the adhesiveness is good when the tensile shear bond strength is large and the fracture state is cohesive failure.

<Dischargeability (viscosity)>
According to the method defined in JIS K 6249, the viscosity of the composition before curing was measured as shown below. That is, the viscosity was measured under the conditions of 20 rpm (1 minute) and 4 rpm (2 minutes) with a No. 7 rotor of a rotational viscometer (manufactured by Shibaura System Co., Ltd.). When the viscosity measured at 20 rpm (1 minute) is in the range of 80 to 180 Pa · s and the viscosity measured at 4 rpm (2 minutes) is 250 to 550 Pa · s, it can be said that the discharge property is good. It was examined whether the viscosity was within this range. In Comparative Example 2, the viscosity at 20 rpm (1 minute) was overranged, and measurement was impossible.

<Thixotropic properties (thixotropic ratio)>
Viscosity was measured under conditions of 1 rpm, 4 rpm, and 20 rpm with a No. 7 rotor of a rotational viscometer (manufactured by Shibaura System). Then, a sample having a 1 rpm / 4 rpm viscosity ratio of 2.5 or more and a 1 rpm / 20 rpm viscosity ratio of 7 or more was defined as having good thixotropy (◯). In addition, a sample having a 1 rpm / 20 rpm viscosity ratio of 6.0 to 7.0 was evaluated as Δ, and a sample having a viscosity ratio of 6.0 or less as ×.

<Bead shape retention>
The silicone compositions of Examples and Comparative Examples 1 to 3 were discharged in a bead shape, and the shape retention after 5 hours was examined. A case in which the bead shape in the discharged state was substantially maintained was evaluated as ◯, a case in which the mold was broken but the bead shape was maintained in Δ, and a case in which the shape was not maintained by flowing was determined as ×.

  Table 2 shows the following. That is, the silicone compositions obtained in the examples have an extremely high shear bond strength of 5 MPa or more, a good fracture mode adhesion of 100% CF, an excellent ejection property, and a good thixotropy. .

  In contrast, the silicone composition obtained in Comparative Example 1 had not only low shear bond strength but also poor thixotropy. Moreover, although the silicone composition obtained in Comparative Example 2 had a high shear bond strength, the viscosity was too high and the dischargeability was poor. Furthermore, although the silicone composition obtained in Comparative Example 3 had a high shear bond strength and good dischargeability, the failure mode of the shear bond test was not 100% CF and AF occurred. Further, the thixo ratio was low and the thixotropy was not sufficiently good.

  The addition reaction curable silicone composition of the present invention has a low viscosity that can be discharged from a small-diameter nozzle and also has good thixotropy. Moreover, it is excellent in storage stability and hardens rapidly by heating, for example. Furthermore, the cured product has good adhesion to various metal adherends and has a good fracture mode of 100% CF without TCF. Therefore, the addition reaction curable silicone composition of the present invention is useful as a material for bonding a semiconductor device, and particularly suitable as a material for bonding a metal lid such as Ni or Ni alloy covering a semiconductor element to a substrate. Yes.

Claims (6)

(A) an alkenyl group bonded to a silicon atom and at least two chromatic per molecule, and the diorganopolysiloxane a viscosity at 23 ° C. is 10~20Pa · s,
(B) SiO _4/2 units (Q units), ViR ¹ SiO _2/2 units (D ^Vi units) and R ¹ ₃ SiO _1/2 units (M units) (wherein Vi represents a vinyl group, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond.) A polyorganosiloxane having a resin structure is added to the sum of the component (A) and the component (B). 30-40% by weight,
(C) 1 a hydrogen atom bonded to a silicon atom and at least two chromatic in the molecule, a hydrogen atom kinematic viscosity at 23 ° C. is the organohydrogenpolysiloxane is 10～25CSt (centistokes), bonded to the silicon atom Is an amount of 1.0 to 1.4 mol per mol of the total of the alkenyl group bonded to the silicon atom in the component (A) and the vinyl group bonded to the silicon atom in the component (B),
(D) a platinum-based catalyst in an amount of 0.01 to 100 ppm of the weight of the whole composition in terms of platinum content;
(E) a fumed silica, wherein the component (A) and (B) the addition reaction curing silicone composition characterized in that it contains 2 to 20% by weight relative to the total of the components, respectively. The alkenyl group-containing diorganopolysiloxane which is the component (A) has a viscosity at 23 ° C. (hereinafter referred to as viscosity (23 ° C.)) of 60 to 100 Pa · s. The addition reaction curable silicone composition according to claim 1 or 2 , which is a mixture with a vinylorganosiloxane containing both ends vinyl groups having a viscosity (23 ° C) of 1.0 to 5.0 Pa · s. object. The thixo ratio represented by the ratio of the viscosity at 1 rpm to the viscosity at 4 rpm (hereinafter referred to as 1 rpm / 4 rpm viscosity ratio) is 2.5 or more. An addition reaction curable silicone composition. The (F) adhesion promoting agent, wherein (A) ~ (E) component The total amount of 100 parts by weight per 5.0 claims 1 to 3, characterized in that it contains the following parts by weight of any one of Addition reaction curable silicone composition. The (F) adhesion improver comprises an alkoxy group and / or an alkenyloxy group bonded to a silicon atom in the molecule, an Si-H group, an alkenyl group, an acrylic group, a methacryl group, an epoxy group, a mercapto group, and an ester group. 5. An addition reaction curable silicone composition according to claim 4, wherein the composition is an organosilicon compound containing at least one reactive functional group selected from an anhydrous carboxy group, an amino group, and an amide group. . Comprising: a substrate, a semiconductor element mounted on the substrate, the lid covering the semiconductor element, the lid, on the substrate by an addition reaction-curable silicone composition of any one of claims 1 to 5 A semiconductor device which is bonded to a semiconductor device.