JP2009270101A - Curable silicone composition for semiconductor and semiconductor device therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone composition for a semiconductor having excellent adhesiveness for a metallic electrode containing gold or silver, and a highly reliable semiconductor device therewith. <P>SOLUTION: This composition contains (A) a polyorganosiloxane having 2 or more alkenyl groups in a molecule, (B) a polyorganohydrogensiloxane containing a reaction product of an organosiloxane oligomer having 2 or more hydrogen atoms bonded to a silicon atom in a molecule and an isocyanurate compound having at least an alkenyl group, and (C) a hydrosilylation catalyst and/or a radical initiator, and the blending quantity of the component (B) is equivalent to 0.01-3.0 mole hydrogen atom bonded to the silicon atom to a mole of the alkenyl group of the component (A) (This quantity is equivalent to the blending quantity of the reaction product of the organosiloxane oligomer and the isocyanurate to be 0.01-1.5 mole). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable silicone composition for semiconductor and a semiconductor device using the same, in which adhesion to the metal electrode is remarkably improved when the metal electrode disposed on the substrate on which the semiconductor element is mounted contains silver or gold. About.

  Conventionally, a silicone composition is excellent in heat resistance and mechanical properties (for example, hardness and elongation) after curing. For example, in a semiconductor device, a sealing agent for sealing a semiconductor element or a semiconductor element is fixed. Used in die bond materials. In particular, the addition reaction curable silicone composition has good productivity because curing by addition reaction (hydrosilylation) proceeds rapidly by heating in the presence of a platinum-based catalyst.

  When such a silicone composition is used, for example, as a sealant for a semiconductor element, in order to increase the adhesion to a substrate (support base material) on which the semiconductor element is mounted or a metal electrode disposed on the substrate, an adhesive property is used. A silicone composition containing an imparting component has been proposed. For example, Patent Document 1 proposes an addition reaction curable silicone composition containing an isocyanuric acid ester having an epoxy group as an adhesion imparting component.

  However, various metal materials are used as the metal electrode. Particularly, metal electrodes containing Ag and Au (for example, Ag-plated or Au-plated lead frames) are difficult to bond with conventional silicone compositions. There was a case where peeling occurred.

JP 2006-137797 A

  An object of the present invention is to provide a curable silicone composition for a semiconductor having excellent adhesion to a metal electrode containing gold or silver, and a highly reliable semiconductor device using the same.

  As a result of intensive studies to achieve the above object, the present inventors have determined a predetermined amount of the reaction product of the isocyanurate compound and the SiH group-containing siloxane oligomer so as to influence the crosslinking with the alkenyl group-containing polyorganosiloxane. By blending, it was found that the adhesion to a metal electrode containing gold or silver, which was difficult to adhere with a conventional curable silicone composition, was remarkably improved, and the present invention was made.

That is, the curable silicone composition for semiconductor of the present invention is
(A) A polyorganosiloxane having two or more alkenyl groups in one molecule (B) An organosiloxane oligomer having two or more hydrogen atoms bonded to silicon atoms in one molecule and an isocyana having at least one alkenyl group A polyorganohydrogensiloxane containing a reaction product with a nurate compound, and (C) a hydrosilylation reaction catalyst and / or a radical initiator,
The blending amount of the component (B) is such that the hydrogen atom bonded to the silicon atom is 0.01 to 3.0 moles per mole of the alkenyl group of the component (A) (however, the organosiloxane oligomer) And the amount of the reaction product of isocyanurate is 0.01 to 1.5 mol).

  The semiconductor device of the present invention is characterized in that a semiconductor element is bonded and / or sealed with a cured product of a semiconductor curable silicone composition.

  With the above configuration, adhesion to a metal electrode containing gold or silver can be remarkably improved.

FIG. 6 is a cross-sectional view schematically illustrating an example of a configuration of a semiconductor device of the invention. The schematic diagram which shows the test piece and test condition which were used for the measurement of the cohesive failure rate.

  Hereinafter, the curable silicone composition for semiconductors of the present invention will be described in detail.

[(A) component]
Component (A) is a base polymer, and a polyorganosiloxane having two or more alkenyl groups in one molecule is used.

The molecular structure of the component (A) may be any of linear, cyclic, branched, and three-dimensional network, and may be used alone or in combination of two or more. For example, when a reinforcing filler such as silica is not blended in the present composition, a three-dimensional network-like alkenyl group-containing polyorganosiloxane containing SiO _4/2 units (that is, in order to impart mechanical strength to the cured product (ie, , Silicone resin) is preferably used. In this case, it is preferable to use a three-dimensional network-like alkenyl group-containing polyorganosiloxane diluted with a linear alkenyl group-containing polyorganosiloxane.

The three-dimensional network-like alkenyl group-containing polyorganosiloxane has, for example, an average unit formula:
(R ⁴ ₃ SiO _1/2 ) _a (R ⁵ ₂ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d
It is represented by In the formula, R ⁴ , R ⁵ and R ⁶ are each independently a substituted or unsubstituted monovalent hydrocarbon group, and at least one of R ⁴ , R ⁵ and R ⁶ is an alkenyl group.

Examples of R ⁴ include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, cyclohexyl and octyl; vinyl, allyl and butenyl. An alkenyl group such as a group, a petenyl group or a hexenyl 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 at least a part of the hydrogen atoms of these groups are fluorine, Groups substituted with halogen atoms such as chlorine and bromine and cyano groups, such as halogen-substituted alkyl groups such as chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, cyano substitution Examples include an alkyl group and a halogen-substituted aryl group, preferably an alkyl group Alkenyl group, an aryl group, more preferably a methyl group, a vinyl group, a phenyl group.

R ⁵ and R ⁶ are the same as R ⁴ .

  A is a positive number, b is 0 or a positive number, c is 0 or a positive number, d is a positive number, 0 <a / (c + d) <3, and 0 ≦ b / The number is such that (c + d) <2.

  As a method for producing a three-dimensional network-like alkenyl group-containing polyorganosiloxane, a well-known method may be used. For example, after combining the compounds serving as the unit sources at the ratios described above, the compounds are combined in the presence of an acid and an alkali. The method of hydrolyzing is mentioned.

  The alkenyl group of the linear alkenyl group-containing polyorganosiloxane may be bonded to the silicon atom at the end of the molecular chain, may be bonded to the silicon atom in the middle of the molecular chain, or may be bonded to both. From the viewpoint of the curing speed of the composition and the physical properties of the cured product, it is preferably bonded to at least the silicon atoms at the molecular chain terminals, particularly the silicon atoms at both molecular chain terminals.

  Examples of the monovalent hydrocarbon group bonded to the silicon atom other than the alkenyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, and octyl group. Alkyl groups such as: aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl and phenylethyl groups; and at least some of the hydrogen atoms of these groups are halogen atoms such as fluorine, chlorine and bromine Or a group substituted with a cyano group, for example, a halogen-substituted alkyl group such as chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, cyano-substituted alkyl group, halogen-substituted aryl group Preferably, an alkyl group or an aryl group is preferable. Or a methyl group or a phenyl group.

  The viscosity of the component (A) at 25 ° C. is 0.1 to 10.0 Pa · s, preferably 1.0 to 8.0 Pa · s as the whole component (A). When the viscosity is less than 0.1 Pa · s, physical properties after curing (for example, hardness, elongation, strength, etc.) tend to decrease. On the other hand, when it exceeds 10.0 Pa · s, the fluidity of the composition is lowered and the workability is deteriorated.

When the component (A) contains a three-dimensional network-like alkenyl group-containing polyorganosiloxane containing SiO _4/2 units, it is diluted with a linear alkenyl group-containing polyorganosiloxane, and (A) It is preferable to make it the said viscosity (0.1-10.0 Pa.s in 25 degreeC) as the whole component. In this case, the viscosity at 25 ° C. of the linear alkenyl group-containing polyorganosiloxane is preferably 1 to 100,000 mPa · s.

  When the three-dimensional network-like alkenyl group-containing polyorganosiloxane is used as the component (A), the blending amount thereof is 10% by weight or more, preferably 20 to 70% by weight in the component (A). is there. When the blending amount is less than 10% by weight, the mechanical strength after curing becomes insufficient, and a reinforcing filler needs to be blended.

[Component (B)]
The component (B) is a crosslinking agent and an adhesion imparting agent, and is a component that imparts the characteristics of the present invention. That is, in the semiconductor device, it is a component that contributes to improving the adhesion to the metal electrode containing Ag or Au on the substrate.

  The component (B) is a reaction product of an organosiloxane oligomer (preferably 2 to 10 silicon atoms) having two or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule and an isocyanurate compound ( (Hereinafter referred to as (B1)).

  Hereinafter, (B1) will be described in detail. First, the isocyanurate compound will be described.

(Isocyanurate compound)
The isocyanurate compound is represented by the following general formula.

In the formula, R ¹ , R ² and R ³ are independently represented by the formula:
- _{(CH 2)} m -X or wherein:
_{- (CH 2) p -O- (} CH 2) q -Y
It is group represented by these.

Here, m is an integer of 0 to 3, p is an integer of 0 to 3, q is an integer of 0 to 3, and X and Y are groups selected from an alkenyl group, an epoxy group, and an alkoxysilyl group. X and Y include, for example, alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; epoxy groups such as glycidoxyethyl group and glycidoxypropyl group; trimethoxysilyl group and triethoxysilyl group An alkoxysilyl group; and the like. However, at least one of R ¹ , R ² , and R ³ has an alkenyl group as X or Y.

Specific examples of such isocyanurate compounds include the following compounds.

  From the viewpoint of the transparency of the composition, the use of an isocyanurate compound containing no epoxy group is preferred, and TAIC (triallyl isocyanurate) represented by the above [Chemical Formula 4] is particularly preferred. When an isocyanurate compound containing an epoxy group is used, the transparency is lowered, but there is an effect that the adhesion to a hardly adhesive plastic such as PPA (polyphthalamide resin) is improved. Moreover, the isocyanurate compound containing both an epoxy group and an allyl group represented by the above [Chemical Formula 2] and [Chemical Formula 3] was used in combination with the (C1) hydrosilylation reaction catalyst (platinum catalyst) described later. In some cases, particularly excellent adhesion to a metal containing Au and Ag can be obtained. Furthermore, when an isocyanurate compound containing an alkoxysilyl group represented by the above [Chemical Formula 5] and [Chemical Formula 6] (not containing an epoxy group) is used, transparency is improved and Good adhesion is obtained by the interaction between the existing hydroxyl groups and alkoxy groups.

(SiH group-containing siloxane oligomer)
Next, the SiH group-containing siloxane oligomer to be reacted with the isocyanurate compound will be described.

  The SiH group-containing siloxane oligomer has two or more hydrogen atoms bonded to silicon atoms in one molecule. This siloxane oligomer preferably has 2 to 10 silicon atoms, more preferably 2 to 6 silicon atoms. Since the SiH group-containing siloxane oligomer having 2 to 10 silicon atoms has a low molecular weight as compared with a normal polyorganosiloxane, it has good compatibility with the isocyanurate compound and also has excellent reactivity with SiH groups. .

  The molecular structure may be linear, branched or cyclic. The hydrogen atom may be bonded to the silicon atom at the molecular chain end, may be bonded to the silicon atom in the middle of the molecular chain, or may be bonded to both, but from the point of reactivity, at least the molecular chain terminal It is preferable that it is bonded to the silicon atom of the molecular chain, particularly to silicon atoms at both ends of the molecular chain.

  The monovalent hydrocarbon group bonded to the silicon atom is a group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, excluding an aliphatic unsaturated bond, such as a methyl group or an ethyl group. Alkyl groups such as propyl group and isopropyl group; aryl groups such as phenyl group; halogenated alkyl groups such as 3-chloropropyl group, and the like. Among them, methyl group is preferable.

（式中、ｙは０〜２０の整数である。） Examples of the SiH group-containing siloxane oligomer include the following.

(In the formula, y is an integer of 0 to 20.)

  (B1) can be obtained by heating and mixing the above-mentioned isocyanurate compound and SiH group-containing siloxane oligomer together with a hydrosilylation reaction catalyst at a temperature of about 100 ° C. from room temperature. The blending ratio of the isocyanurate compound and the SiH group-containing siloxane oligomer is such that at least more SiH groups than the alkenyl groups in the isocyanurate compound are required, and the resulting (B1) SiH groups are present in the molecule. . By setting it as such a mixture ratio, high adhesiveness can be provided with respect to the metal electrode containing Ag or Au.

  In addition to the above (B1), the component (B) contains polyorganohydrogensiloxane (hereinafter referred to as (B2)) having two or more hydrogen atoms bonded to silicon atoms in one molecule. Yes. By blending this (B2), sufficient hardness can be expressed in the composition.

(B2) is, for example, an average composition formula:
R ⁷ _s H _t SiO _{[4- (s + t)] / 2}
What is shown by is used.

In the formula, R ⁷ is the same or different substituted or unsubstituted monovalent hydrocarbon group excluding an aliphatic unsaturated bond. R ⁷ includes, for example, 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, a hexyl group, a cyclohexyl group, and an octyl group; Aryl groups such as; aralkyl groups such as benzyl and phenylethyl groups; and those in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as fluorine, chlorine, bromine or cyano groups, Examples thereof include monovalent hydrocarbon groups having 1 to 12 carbon atoms such as chloromethyl group, bromoethyl group, trifluoropropyl group, and cyanoethyl group. Among them, from the viewpoint of ease of synthesis and cost, methyl group, ethyl group C1-C4 alkyl groups such as propyl group, isopropyl group, butyl group and isobutyl group are preferred, and methyl group is more preferred. .

  Each of s and t is a positive number, and is a positive number satisfying 0.8 ≦ s ≦ 2.2, 0.002 ≦ t ≦ 1, 0.8 <s + t <3, and preferably 1 ≦ s. It is a positive number that satisfies ≦ 2.2, 0.01 ≦ t ≦ 1, and 1.8 ≦ s + t ≦ 2.5.

  The molecular structure of (B2) may be any of linear, branched, cyclic or three-dimensional network.

  The hydrogen atom of (B2) may be bonded to the silicon atom at the end of the molecular chain, may be bonded to the silicon atom in the middle of the molecular chain, or may be bonded to both.

  The viscosity of (B2) at 25 ° C. is 1000 mPa · s or less, preferably 1 to 500 mPa · s.

  The blending amount of the component (B) is such that the hydrogen atom bonded to the silicon atom of the entire component (B) is 0.01 to 3.0 mol, preferably 1 mol of the alkenyl group of the component (A), The amount is 0.1 to 2.0 mol. If the blending amount is less than 0.01 mol, sufficient crosslinking cannot be obtained. On the other hand, when the amount exceeds 3.0 mol, unreacted SiH groups remain, and the physical properties after curing tend to change with time.

  However, the blending amount of (B1) is 0.01 to 1.5 mol, preferably 0.1 to 1, of hydrogen atoms bonded to the silicon atom of (B1) with respect to 1 mol of the alkenyl group of component (A). It is an amount to be 0.0 mol. When the blending amount of (B1) is less than 0.01 mol, the adhesion to a metal electrode containing Ag or Au becomes insufficient. On the other hand, when the amount exceeds 1.5 mol, the mechanical properties after curing are adversely affected, and furthermore, sufficient hardness cannot be obtained, and unreacted Si—H groups tend to remain.

[Component (C)]
In this composition, two curing mechanisms, a curing mechanism based on a hydrosilylation reaction and a curing mechanism based on a radical reaction, can be used. Both a curing mechanism based on a hydrosilylation reaction and a curing mechanism based on a radical reaction can be used in combination. Also good. When two curing mechanisms are used in combination, first, the curing reaction by the hydrosilylation reaction proceeds at a predetermined temperature, and then the curing reaction by the radical reaction proceeds at a temperature higher than the above temperature.

  When using this composition as a sealing agent for semiconductor elements, it is preferable to use a curing mechanism based on a hydrosilylation reaction alone from the viewpoint of good productivity.

  In the case of a curing mechanism based on a hydrosilylation reaction, (C1) a hydrosilylation reaction catalyst is used, and in the case of a curing mechanism based on a radical reaction, (C2) a radical initiator is used.

  Examples of (C1) hydrosilylation reaction catalysts include platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin or vinyl siloxane, platinum Examples thereof include platinum-based catalysts such as bisacetoacetate.

  (C1) The compounding quantity of a hydrosilylation reaction catalyst should just be a quantity required for hardening of a composition, and can be suitably adjusted according to a desired hardening rate. Usually, the total amount of the component (A) and the component (B) is preferably in the range of 1 to 500 ppm in terms of platinum element. When the blending amount is less than 1 ppm, the composition is not easily cured. On the other hand, if it exceeds 500 ppm, the heat resistance after curing tends to decrease.

  Examples of the (C2) radical initiator include benzoyl peroxide, dicumyl peroxide, t-butyl benzoate, t-butyl peroxybenzoate, di-t-butyl peroxide, di-t-hexyl peroxide, t- Butylcumyl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 1,6- Bis (t-butylperoxycarboxy) hexane, di- (4-methylbenzoyl) peroxide, di- (2-methylbenzoyl) peroxide, t-butylperoxyisopropyl monocarbonate, di- (2-t-butylperoxy) And organic peroxides such as isopropyl) benzene.

  The amount of the (C2) radical initiator is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, based on 100 parts by weight of the component (A). If the blending amount is less than 0.1 parts by weight, sufficient crosslinking cannot be obtained. On the other hand, if it exceeds 20 parts by weight, the cost increases, and the performance improvement corresponding to the cost cannot be obtained.

  In addition, even if it is a case where (C1) and (C2) are used together using two hardening mechanisms, the compounding quantity is the range mentioned above.

[Other optional ingredients]
The curable silicone composition for semiconductors of the present invention comprises the above components (A) to (C) as basic components, and if necessary, when using a curing mechanism by hydrosilylation reaction, hydrosilylation You may add the reaction inhibitor which suppresses reaction.

  Examples of the reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds, acetylenic compounds, compounds containing two or more alkenyl groups, hydro A peroxy compound, a maleic acid derivative, etc. are mentioned, Preferably, it is an acetylene type compound which has hydroxyl groups, such as 3-methyl-1-butyn-3-ol and 1-ethynyl-1-cyclohexanol.

  Furthermore, the curable silicone composition for semiconductors of the present invention is composed of fumed silica, calcined silica, silica aerogel, precipitated silica, fumed titanium oxide, and their surfaces hydrophobized with polyorganosiloxanes, hexamethyldisilazane, etc. Reinforcing filler, diatomaceous earth, ground silica (quartz fine powder), aluminum oxide, zinc oxide, aluminosilicate, calcium carbonate, organic acid surface treatment calcium carbonate, magnesium carbonate, zinc carbonate, calcium silicate, talc, oxidation Non-reinforcing fillers such as ferric iron, conductive fillers such as carbon black, organic solvents such as toluene, xylene, hexane, heptane, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, thixotropic agents, dyes, pigments, Flame retardancy imparting agent, heat resistance improver, oxidation degradation agent, wavelength The Seizai like may be added within a range not to impair the purpose of the present invention. When using this composition for semiconductor elements, such as LED which requires high transparency, it uses in the range which does not affect the transparency after hardening.

  In the method for producing the curable silicone composition for semiconductors of the present invention, the order of addition of the respective components is not particularly limited, and the basic components (A) to (C) and the optional components described above are well-known kneaders. And the like. Examples of the kneader include a planetary mixer, a three-roller, a kneader, and a Shinagawa mixer, which are provided with a heating unit and a cooling unit, if necessary, and these can be used alone or in combination.

  The curable silicone composition for semiconductor is in a liquid state, and the viscosity at 25 ° C. is preferably 0.5 to 100 Pa · s. When the viscosity exceeds 100 Pa · s, for example, when potting an LED, the dispenser is likely to be clogged. On the other hand, if it is less than 0.5 Pa · s, dripping tends to occur when potting.

  The curing method of the curable silicone composition for semiconductor is appropriately adjusted according to the curing mechanism by hydrosilylation reaction and the curing mechanism by radical reaction. In the case of a curing mechanism based on a hydrosilylation reaction, it can be appropriately adjusted according to the type of reaction inhibitor and the amount added, but it is cured by heating at 50 to 200 ° C. for 60 to 120 minutes. Moreover, in the case of the hardening mechanism by radical reaction, it can adjust suitably according to the kind of radical initiator, However, Preferably it is 100 to 250 degreeC for 15 to 60 minutes. The cured product is preferably a hard rubber or flexible resin and has good transparency.

  Next, an example of a semiconductor device to which the curable silicone composition for semiconductors of the present invention is applied as a sealing material will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing a configuration of a semiconductor device, and shows an LED lamp.

  The semiconductor device 1 includes a semiconductor element (LED) 2, a support base 3 made of polyphthalamide resin, an Ag-plated lead electrode 5, and a cured product 4 of a semiconductor curable silicone composition. ing. The semiconductor element 2 is sealed with a cured product 4 of a curable silicone composition for semiconductors.

  For example, the semiconductor device 1 is manufactured as follows.

  First, a semiconductor element (LED) 2 is die-bonded to a support base 3 such as a polyphthalamide resin having an Ag-plated lead electrode 5, and the semiconductor element 2 and the lead electrode 5 are connected by a bonding wire 6.

  Next, after potting the above-mentioned silicone composition for semiconductor encapsulation onto the semiconductor element 2, the cured product 4 is formed by heating and curing at 150 ° C. for 1 hour, for example.

  The semiconductor device 1 obtained in this manner was Ag-plated because the semiconductor element 2 was sealed with the cured product 4 of the curable silicone composition for semiconductors, which was difficult to bond with the conventional silicone composition. It has sufficient adhesion to the lead electrode 5 and is excellent in reliability.

  Further, even if the primer composition is not previously applied to the Ag-plated lead electrode 5 or the like, the curable silicone composition of the present invention alone has excellent adhesion to the Ag-plated lead electrode 5. Thus, the highly reliable semiconductor device 1 can be obtained with high yield.

  In addition, although demonstrated using LED as an example of the semiconductor element 2, the semiconductor element which requires high transparency, such as a phototransistor, a photodiode, CCD, a solar cell module, EPROM, a photocoupler, etc., transparent The present invention can be applied to any semiconductor element that does not require the property.

  Further, here, the description is made using the Ag-plated lead electrode 5, but the same effect can be obtained with the Au-plated lead electrode.

  Moreover, although the curable silicone composition for semiconductors of the present invention was used as a sealing agent for semiconductor devices, in addition to this, adhesion to metal electrodes (particularly Au electrodes and Ag electrodes) such as die bonding materials for bonding and fixing semiconductor elements. It is suitable for applications that require high performance.

  The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In the examples and comparative examples, the viscosity is a value measured at 25 ° C. Moreover, the curable silicone compositions for semiconductors obtained in Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 1. The characteristics shown in Table 1 are values measured at 25 ° C.

[Shear adhesive strength]
As shown in FIG. 2, one of each of the rectangular Ag plating plates 11 and 12 having a width of 25 mm is bonded to each other with a curable silicone composition 13 having a thickness of 1 mm sandwiched therebetween (adhesion area: 25 mm × 10 mm = 250 mm ² ). The test piece was prepared by heating and curing at 150 ° C. for 2 hours. Each end of the test piece was pulled in the direction of the arrow in the drawing with a tensile tester (manufactured by Shimadzu Corporation, Autograph) at a pulling speed of 10 mm / min, and the shear adhesive force on the surfaces of the Ag plated plates 11 and 12 was measured. . It measured similarly about Au plating board.

[Cohesive failure rate]
The surface of the Ag plating plates 11 and 12 when the shear adhesive force was measured was observed, and the ratio of the portion subjected to cohesive failure (breaking at the silicone portion) was measured as the cohesive failure rate. It measured similarly about Au plating board.

で表されるＴＡＩＣ（トリアリルイソシアヌレート）と、式：
Ｈ（ＣＨ_３）_２ＳｉＯＳｉ（ＣＨ_３）_２Ｈ
で表されるＳｉＨ基含有シロキサンオリゴマーとの反応生成物（ＳｉＨ基量４．６ｍｍｏｌ／ｇ）４．２重量部、（Ｂ２）式：
［（ＣＨ_３）_３ＳｉＯ_１／２］［Ｈ（ＣＨ_３）ＳｉＯ］_２３［（ＣＨ_３）_２ＳｉＯ］_１５［（ＣＨ_３）_３ＳｉＯ_１／２］
で表されるポリオルガノハイドロジェンシロキサン（ＳｉＨ基量８．７ｍｍｏｌ／ｇ）２．２重量部、（Ｃ−１）ビニルダイマー白金錯体（Ｐｔ含有量１．８％）０．０３重量部（白金量として５ｐｐｍ）を添加、混練して、硬化性シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。なお、この組成物を硬化させて成る硬化物はは、透明性の高いものであった。 [Example 1]
(A-1) Formula:
[(CH ₃ ) ₃ SiO _1/2 ] ₃₇ [(CH ₂ ═CH) (CH ₃ ) SiO] ₇ (SiO ₂ ) ₅₆
68 parts by weight (34 parts by weight of resin) of a 50 wt% xylene solution of a vinyl group-containing silicone resin represented by the formula (Vi group content 1.0 mmol / g) and (A-2) the viscosity at 25 ° C. is 3000 mPa · s. ,formula:
[(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ] [(CH ₃ ) ₂ SiO] ₃₆₀ [(CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ]
Xylene was removed by heating and kneading 66 parts by weight of polyorganosiloxane containing a vinyl group at both ends represented by the formula (Vi group amount 0.075 mmol / g) at 150 ° C. under reduced pressure. After cooling, the formula (B1-1):
(B1-1) Formula:

TAIC (triallyl isocyanurate) represented by the formula:
H (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ H
A reaction product with a SiH group-containing siloxane oligomer represented by formula (SiH group amount 4.6 mmol / g) 4.2 parts by weight, formula (B2):
[(CH ₃ ) ₃ SiO _1/2 ] [H (CH ₃ ) SiO] ₂₃ [(CH ₃ ) ₂ SiO] ₁₅ [(CH ₃ ) ₃ SiO _1/2 ]
2.2 parts by weight of a polyorganohydrogensiloxane (SiH group content: 8.7 mmol / g), 0.03 parts by weight of (C-1) vinyl dimer platinum complex (Pt content: 1.8%) 5 ppm) was added and kneaded to obtain a curable silicone composition. The properties of this composition were measured and the results are shown in Table 1. A cured product obtained by curing this composition was highly transparent.

[Example 2]
A curable silicone composition was obtained in the same manner as in Example 1 except that (B1-1) of Example 1 was changed to 2.5 parts by weight and (B2) was changed to 3.1 parts by weight. The properties of this composition were measured and the results are shown in Table 1. In addition, the hardened | cured material formed by hardening | curing this composition was a highly transparent thing.

で表される１−アリル−３，５−ジグリルシジルイソシアヌル酸と、式：

で表されるＳｉＨ基含有シロキサンオリゴマーとの反応生成物（ＳｉＨ基量５．８ｍｍｏｌ／ｇ）を３．４重量部、（Ｂ２）を４．４重量部とした以外は、実施例１と同様にして、硬化性シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。 [Example 3]
Formula (B1-2) without blending (B1-1) of Example 1:

1-allyl-3,5-digrilcidyl isocyanuric acid represented by the formula:

The reaction product with the SiH group-containing siloxane oligomer represented by the formula (SiH group amount 5.8 mmol / g) is 3.4 parts by weight and (B2) is 4.4 parts by weight. Thus, a curable silicone composition was obtained. The properties of this composition were measured and the results are shown in Table 1.

[Example 4]
The curability was the same as in Example 1 except that (B1-2) was 2.0 parts by weight and (B2) was 3.1 parts by weight without blending (B1-1) of Example 1. A silicone composition was obtained. The properties of this composition were measured and the results are shown in Table 1.

[Example 5]
Without blending (B1-1) of Example 1, (B1-2) is 2.0 parts by weight, (B2) is 3.1 parts by weight, and (C-1) vinyl dimer platinum complex is not blended. (C-2) A curable silicone composition was obtained in the same manner as in Example 1 except that 0.5 part by weight of p-methylbenzoyl peroxide (organic peroxide) was used. The properties of this composition were measured and the results are shown in Table 1.

[Example 6]
Without blending (B1-1) of Example 1, 2.0 parts by weight of (B1-2), 3.1 parts by weight of (B2), 0.03 parts by weight of (C-1) vinyl dimer platinum complex And (C-2) A curable silicone composition was obtained in the same manner as in Example 1 except that 0.5 part by weight of the organic peroxide was used in combination. The properties of this composition were measured and the results are shown in Table 1.

で表されるＳｉＨ基含有シロキサンオリゴマーと、式：
ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯ（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３
で表されるγ−メタクリロキシプロピルトリメトキシシランとの反応生成物（ＳｉＨ基量４．０ｍｍｏｌ／ｇ）を３．０重量部、（Ｂ２）を６．５重量部とした以外は、実施例１と同様にして、硬化性シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。 [Comparative Example 1]
Formula (B1-3) without blending (B1-1) of Example 1:

A SiH group-containing siloxane oligomer represented by the formula:
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3
The reaction product with γ-methacryloxypropyltrimethoxysilane represented by formula (SiH group amount 4.0 mmol / g) was 3.0 parts by weight, and (B2) was 6.5 parts by weight. In the same manner as in Example 1, a curable silicone composition was obtained. The properties of this composition were measured and the results are shown in Table 1.

で表されるγ−グリシドキシプロピルトリメトキシシラン（ＳｉＨ基量０ｍｍｏｌ／ｇ）を２．０重量部、（Ｂ２）を６．５重量部とした以外は、実施例１と同様にして、硬化性シリコーン組成物を得た。この組成物の特性を測定し、結果を表１に示した。 [Comparative Example 2]
Formula (B1-4) without blending (B1-1) of Example 1:

In the same manner as in Example 1 except that 2.0 parts by weight of γ-glycidoxypropyltrimethoxysilane (SiH group amount 0 mmol / g) represented by the formula (B2) was 6.5 parts by weight, A curable silicone composition was obtained. The properties of this composition were measured and the results are shown in Table 1.

  As can be seen from Table 1, the example in which the reaction product with an isocyanurate compound such as (B1-1) or (B1-2) was blended as the component (B) was compared with the comparative example. The adhesion to the Au plated plate is remarkably improved.

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor device, 2 ... Semiconductor element (LED), 3 ... Support base material, 4 ... Hardened | cured material of the curable silicone composition for semiconductors, 5 ... Lead electrode (Ag plating), 6 ... Bonding wire.

Claims (6)

(A) A polyorganosiloxane having two or more alkenyl groups in one molecule (B) An organosiloxane oligomer having two or more hydrogen atoms bonded to silicon atoms in one molecule and an isocyana having at least one alkenyl group A polyorganohydrogensiloxane containing a reaction product with a nurate compound, and (C) a hydrosilylation reaction catalyst and / or a radical initiator,
The blending amount of the component (B) is such that the hydrogen atom bonded to the silicon atom is 0.01 to 3.0 moles per mole of the alkenyl group of the component (A) (however, the organosiloxane oligomer) The amount of the reaction product of isocyanurate and the amount of isocyanurate is 0.01 to 1.5 mol). A curable silicone composition for semiconductors. The isocyanurate compound has the general formula:

Wherein R ¹ , R ² and R ³ are independently
- _{(CH 2)} m -X or wherein:
_{- (CH 2) p -O- (} CH 2) q -Y
It is group represented by these. Here, m is an integer of 0 to 3, p is an integer of 0 to 3, q is an integer of 0 to 3, and X and Y are groups selected from an alkenyl group, an epoxy group, and an alkoxysilyl group. However, at least one of R ¹ , R ² and R ³ has an alkenyl group as X or Y. The curable silicone composition for semiconductors according to claim 1, wherein   The curable silicone composition for semiconductor according to claim 1 or 2, wherein the organosiloxane oligomer has 2 to 10 silicon atoms.   The said (C) component is a hydrosilylation reaction catalyst, The curable silicone composition for semiconductors of any one of the Claims 1 thru | or 3 characterized by the above-mentioned.   A semiconductor device, wherein a semiconductor element is bonded and / or sealed with a cured product of the curable silicone composition for semiconductor according to any one of claims 1 to 4.   The semiconductor device according to claim 5, wherein the metal electrode disposed on the substrate on which the semiconductor element is mounted contains gold or silver.

Images