Organo-modified silicone resin composition for die bonding, cured product thereof, and optical semiconductor element

Abstract

This organo-modified silicone resin composition for die bonding contains (A) an addition reaction product of (a) a compound represented by general formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, the addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule, (B) an organosilicon compound represented by general formula (2), (C) a platinum group metal catalyst, (D) a compound having two or more glycidyloxy groups in one molecule and being free of addition-reactive carbon-carbon double bonds and silicon atoms, and (E) specific fumed silica, wherein the number of hydrogen atoms bonded to a silicon atom is 1.1-3.0 times the total number of addition-reactive carbon-carbon double bonds in the composition. Accordingly, provided are: a cured product having excellent adhesion between an LED element and a substrate at high temperatures; an organo-modified silicone resin composition for die bonding, which is capable of providing the cured product; and an optical semiconductor element.

Description

Organic modified silicone resin composition for die bonding, cured product thereof, and optoelectronic semiconductor device

[0001] The present invention relates to an organically modified silicone resin composition for die bonding, a cured product thereof, and an optoelectronic semiconductor device.

[0002] Silicone resins and organically modified silicone resins are mainly used as die bonding materials for light-emitting diode (LED) elements (Patent Documents 1-2). However, in recent years, with the advent of blue LED elements and the miniaturization of LED elements, conventional silicone-based die bonding materials have been found to have insufficient adhesive strength between the LED element and the substrate at high temperatures during wire bonding, resulting in bonding failures.

[0003] In addition, since the LED wire bonding process is carried out at high temperatures, there is a need for a die bond material that has high thermal strength, especially around 150°C. However, the organic hybrid silicone die bond material already proposed (Patent Document 3) has a glass transition temperature of less than 150°C, so although its adhesive strength at room temperature is excellent, its adhesive strength at high temperatures is insufficient.

[0004] Japanese Patent Publication No. 2006-342200, Japanese Patent Publication No. 2011-086844, Japanese Patent Publication No. 2015-140372

[0005] Conventional technology has a problem in that the adhesive strength of die bond materials at high temperatures is insufficient.

[0006] The present invention has been made to solve the above problems, and aims to provide a cured product with excellent adhesion between an LED element and a substrate at high temperatures, an organically modified silicone resin composition for die bonding that can provide such a cured product, and an optoelectronic semiconductor element.

[0007] To solve the above problems, the present invention provides an organic modified silicone resin composition for die bonding, wherein (A) an addition reaction product of (a) a compound represented by the following general formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule (In the formula, R１ Each of these is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an addition-reactive carbon-carbon double bond, and R ２ (B) Organosilicon compounds represented by the following general formula (2) (In the formula, R ３ (C) Platinum group metal catalyst (D) Compounds having a glycidyloxy group and lacking addition-reactive carbon-carbon double bonds and silicon atoms, and (E) BET specific surface area of ​​100 m ２ The present invention provides an organically modified silicone resin composition for die bonding, which contains fumed silica of 1 / g or more, and in which the number of hydrogen atoms bonded to silicon atoms is 1.1 to 3.0 times the total number of addition-reactive carbon-carbon double bonds in the composition.

[0008] The organically modified silicone resin composition for die bonding of the present invention can provide a cured product and an optoelectronic semiconductor device that exhibit high strength at high temperatures and have excellent adhesion between the LED element and the substrate.

[0009] Furthermore, it is preferable that component (A) is a compound represented by the following general formula (3). (In the formula, k represents an integer from 0 to 50, R ４ R is a divalent group represented by the following formula (4), ５ This is a base represented by the following formula (5) or formula (6). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

[0010] If component (A) is the specific compound described above, it is preferable because it can yield a cured product with particularly excellent hardness and strength.

[0011] Furthermore, the R of component (B) ３It is preferably a divalent group represented by the following formula (4). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

[0012] When the component (B) is the above specific compound, the compatibility with the component (A) is enhanced, the transparency is improved, and separation of each component can be suppressed when the die bond material is applied to the LED substrate by a die bonder, which is preferable.

[0013] Further, it is preferable that the component (D) is a compound represented by the following structural formula (7), a compound represented by the following structural formula (8), or both.

[0014] When the component (D) is the above specific compound, it is preferable because a cured product having particularly excellent adhesive strength can be provided.

[0015] Further, the present invention provides a cured product obtained by curing the above-described organic-modified silicone resin composition for die bonding.

[0016] The cured product of the present invention has high strength and excellent adhesive strength between the LED element and the substrate at high temperature.

[0017] Further, the present invention provides an optical semiconductor device die-bonded with the above-described cured product.

[0018] The optical semiconductor device of the present invention has high reliability because the LED element and the substrate are bonded with a cured product having high resin strength and excellent adhesive strength at high temperature.

[0019] As described above, the organic-modified silicone resin composition for die bonding of the present invention can provide a cured product having high hardness and excellent adhesive strength between the LED element and the substrate at high temperature. Therefore, the cured product obtained from such an organic-modified silicone resin composition is particularly useful as a die bond material used for die bonding of small LED elements and the like.

[0020] As described above, there has been a demand for a cured product having excellent adhesion between an LED element and a substrate at high temperatures, an organically modified silicone resin composition for die bonding that can provide such a cured product, and a development of an optical semiconductor element.

[0021] As a result of intensive studies on the above problems, the present inventors have found that an organically modified silicone resin composition for die bonding containing the components (A) to (E) described below can solve the above problems, and have completed the present invention.

[0022] That is, the present invention is an organically modified silicone resin composition for die bonding, which is (A) an addition reaction product of (a) a compound represented by the following general formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and having two addition-reactive carbon-carbon double bonds in one molecule (In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an addition-reactive carbon-carbon double bond, and R ２ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.) (B) an organosilicon compound represented by the following general formula (2) (In the formula, R ３ is independently a divalent hydrocarbon group that may contain a silicon atom, m is 0 or 1, and n is a number satisfying 0 to 5.) (C) a platinum group metal-based catalyst (D) a compound having two or more glycidyloxy groups in one molecule and not having an addition-reactive carbon-carbon double bond and a silicon atom, and (E) fumed silica having a BET specific surface area of 100 m ２ / g or more, and the number of hydrogen atoms bonded to silicon atoms with respect to the total number of addition-reactive carbon-carbon double bonds in the composition is 1.1 to 3.0 times, which is an organically modified silicone resin composition for die bonding.

[0023] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0024] [Organic Modified Silicone Resin Composition for Die Bonding] The organic modified silicone resin composition for die bonding of the present invention contains the following components (A) to (E). Each component will be described in detail below.

[0025] <Component (A)> Component (A) in the organic modified silicone resin composition for die bonding of the present invention is an addition reaction product of (a) a compound represented by the following general formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and is an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule. (In the formula, R １ Each of these is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an addition-reactive carbon-carbon double bond, and R ２ (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.)

[0026] In general formula (1), R １ Specific examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, cyclopentyl group, and cyclohexyl group; aryl groups having 6 to 12 carbon atoms such as phenyl group and naphthyl group; alkylaryl groups having 7 to 12 carbon atoms such as tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, and hexylphenyl group; and aralkyl groups having 7 to 12 carbon atoms such as benzyl group and phenethyl group.

[0027] Among these, R １ Preferably, the alkyl group has 1 to 8 carbon atoms, and a methyl group is more preferred.

[0028] Meanwhile, R ２Specific examples of divalent hydrocarbon groups having 1 to 12 carbon atoms include linear, branched, or cyclic alkylene groups having 1 to 12 carbon atoms, such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; arylene groups having 6 to 12 carbon atoms, such as phenylene, biphenylene, and naphthylene; and aralkylene groups having 7 to 12 carbon atoms, such as phenylenemethylene and methylenephenylenemethylene.

[0029] Among these, arylene groups with 6 to 12 carbon atoms are preferred, and phenylene groups are more preferred.

[0030] (a) The components are all R in general formula (1) １ is a methyl group, R ２ It is particularly preferable that the (a) group is a phenylene group. Specific examples of such component (a) include, for example, 1,4-bis(dimethylsilyl)benzene and 1,3-bis(dimethylsilyl)benzene.

[0031] Furthermore, component (a) may be used alone or in combination of two or more types.

[0032] Furthermore, as polycyclic hydrocarbons having two addition-reactive carbon-carbon double bonds in one molecule of component (b), the following can be used: (i) those in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the skeleton of the polycyclic hydrocarbon; (ii) those in which a hydrogen atom bonded to a carbon atom forming the skeleton of the polycyclic hydrocarbon is substituted by an addition-reactive carbon-carbon double bond-containing group; (iii) those in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the skeleton of the polycyclic hydrocarbon, and a hydrogen atom bonded to a carbon atom forming the skeleton of the polycyclic hydrocarbon is substituted by an addition-reactive carbon-carbon double bond-containing group.

[0033] Specific examples of component (b) above include 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene, which are represented by the following structural formulas, and these can also be used as a mixture (hereinafter, when it is not necessary to distinguish between these three, they may be collectively referred to as "vinylnorbornene").

[0034] Furthermore, the substitution position of the vinyl group in vinylnorbornene may be either cis (exo) or trans (endo) configuration, and since there is no particular difference in the reactivity of the compound due to the difference in these configurations, a combination of isomers of both configurations may also be used.

[0035] The addition reaction product of component (A) can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2005-133073.

[0036] For example, it can be prepared by adding component (b) in an amount of more than 1 mole but less than 10 moles, preferably more than 1 mole but less than 5 moles, to 1 mole of component (a) in the presence of a hydrosilylation catalyst.

[0037] In this case, known catalysts can be used for the hydrosilylation reaction. Specific examples include platinum-based catalysts such as platinum-supported carbon powder, platinum black, platinum-dic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetate; as well as platinum group metal catalysts such as palladium-based and rhodium-based catalysts. Furthermore, the addition reaction conditions and the use of solvents are not particularly limited and can be as known.

[0038] In the above reaction, when synthesizing the addition product of component (A), an excess molar amount of polycyclic hydrocarbon (b) is reacted with compound (a) represented by the above general formula (1). Therefore, the addition product of component (A) has two addition-reactive carbon-carbon double bonds derived from polycyclic hydrocarbon (b) in one molecule.

[0039] In the present invention, component (A) is preferably represented by the following general formula (3). Addition reaction products containing such polycyclic hydrocarbons and phenylene groups are particularly suitable for use because they yield cured products with excellent hardness and strength. (In the formula, k represents an integer from 0 to 50, preferably an integer from 0 to 30, and more preferably an integer from 0 to 20. ４ R is a divalent group represented by the following formula (4), ５ This is a base represented by the following formula (5) or formula (6). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

[0040] (A) Component (A) may be used alone or in combination of two or more components.

[0041] <Component (B)> Component (B) is an organosilicon compound represented by the following general formula (2), and has a hydrogen atom bonded to a silicon atom (i.e., a Si-H group), and acts as a crosslinking agent that crosslinks with the addition-reactive carbon-carbon double bond in component (A) through a hydrosilylation reaction. (In the formula, R ３ (where m is a divalent hydrocarbon group that may independently contain a silicon atom, m is 0 or 1, and n is a number satisfying 0 to 5.)

[0042] In the above general formula (2), R ３ Specific examples of divalent hydrocarbon groups that may contain silicon atoms include linear, branched, or cyclic alkylene groups having 1 to 12 carbon atoms, such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups; arylene groups having 6 to 12 carbon atoms, such as phenylene, biphenylene, and naphthylene groups; aralkylene groups having 7 to 12 carbon atoms, such as phenylenemethylene and methylenephenylenemethylene groups; divalent hydrocarbon groups represented by the following formula (4); and divalent groups represented by the following formula (9). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, R ６ Each of these is independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a methyl group or a phenyl group. (An asterisk (*) indicates a bond with an adjacent silicon atom.)

[0043] The R of component (B) ３ However, the divalent group represented by formula (4) above is particularly preferred. In this case, compatibility with component (A) is increased, transparency is improved, and separation of each component can be suppressed when the die bond material is applied to the LED substrate by a die bonder. Furthermore, the resin strength is increased, and the die shear strength can be improved.

[0044] (B) Specific examples of component (B) include organosilicon compounds represented by the following structural formula.

[0045] Such organosilicon compounds can be obtained, for example, by a hydrosilylation reaction of 2,4,6,8-tetramethyltetracyclosiloxane with vinylnorbornene or diphenyldivinylsilane.

[0046] (B) Component may be used alone or in combination of two or more types.

[0047] The amount of component (B) is such that the number of hydrogen atoms bonded to silicon atoms is 1.1 to 3.0 times the total number of addition-reactive carbon-carbon double bonds in the composition, preferably 1.5 to 2.0 times. If it is less than 1.1 times, the reactivity between the glycidyl group in component (C), described later, and the hydrogen atoms bonded to silicon atoms in component (B) decreases, and sufficient adhesive strength is not achieved. If it exceeds 3.0 times, the resulting cured product may become brittle.

[0048] <Component (C)> The platinum group metal catalyst of component (C) is not particularly limited as long as it is a component that promotes the addition reaction between the addition-reactive carbon-carbon double bond in component (A) and the hydrogen atom bonded to the silicon atom in component (B). Specific examples include platinum group metals such as platinum, palladium, and rhodium; platinum-based compounds such as chloroplatinic acid, alcohol-modified chloroplatinic acid, and coordination compounds of chloroplatinic acid with olefins, vinylsiloxanes, or acetylene compounds; and platinum group metal compounds such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. However, platinum-based compounds are preferred, and coordination compounds of chloroplatinic acid and vinylsiloxanes are particularly preferred.

[0049] (C) Component may be used alone or in combination of two or more types.

[0050] The amount of component (C) can be an effective amount as a catalyst, but it is preferably in the range of 1 to 500 ppm, and more preferably in the range of 1 to 100 ppm, in terms of the mass of platinum group metal elements relative to the total amount of components (A) and (B). When this range is satisfied, the reaction rate of the addition reaction becomes appropriate, and a cured product with high strength can be obtained.

[0051] <Component (D)> Component (D) is a compound having two or more, preferably two to six, more preferably two to four glycidyloxy groups in one molecule, and lacking addition-reactive carbon-carbon double bonds and silicon atoms.

[0052] Component (D), having multiple glycidyloxy groups, readily adheres firmly to the substrate. Furthermore, the epoxy groups oriented towards the resin side react with the Si-H groups contained in component (B), enabling the cured products of components (A) and (B) to be connected to the substrate via component (D), resulting in stronger adhesive strength (die shear strength).

[0053] Furthermore, since component (D) does not contain silicon atoms, its compatibility with the siloxane components of components (A) and (B) does not become excessively high, making it easier for it to migrate from the inside of the resin to the resin surface (substrate side). As a result, the presence of a large amount of component (D) on the resin surface makes it possible to achieve higher adhesive strength than epoxy group-containing adhesive aids that are compatible with ordinary silicone resins. Consequently, a cohesive failure mode occurs in which resin remains on the substrate side, especially after die shear tests under heat, making it an even more reliable die bond material for LEDs.

[0054] Component (D) is preferably liquid at room temperature, from the viewpoint of ease of mixing with components (A) and (B) above.

[0055] Component (D) is particularly preferably a compound having a pentaerythritol skeleton or a bisphenol A skeleton. Such a compound exhibits excellent compatibility with components (A) and (B) and enables the development of high adhesive strength.

[0056] Examples of such (D) components include the compound represented by the following structural formula (7) and the compound represented by the following structural formula (8).

[0057] These compounds can be commercially available, such as Showfree PETG and Showfree BATG manufactured by Resonaq Co., Ltd.

[0058] Component (D) may be used alone or in combination of two or more.

[0059] The amount of component (D) added is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). Within this range, excellent compatibility and excellent adhesive strength of the cured product are obtained.

[0060] <Component (E)> Component (E) has a BET specific surface area of ​​100 m². ２ It is fumed silica of a concentration of 1 / g or more, and is a component that imparts thixotropy to the composition of the present invention. The BET specific surface area of ​​component (E) is preferably 100 to 300 m². ２The range is / g, and the BET specific surface area is 100m². ２ If the amount is less than / g, the thixotropy of the composition is poor, and when used as a die bond material, the composition spreads during transfer, resulting in reduced adhesive strength. The BET specific surface area is measured in accordance with JIS Z8830:2013 using a Macsorb® HM Model-1201 manufactured by Mountec Co., Ltd.

[0061] Humed silica is H ２ and O ２ A mixture of gases is burned in a flame at 1,100 to 1,400°C to extract SiCl ４ It is produced by oxidizing and hydrolyzing gases. The primary particles of fumed silica are amorphous silicon dioxide (SiO₂) with an average particle size of about 5 to 50 nm. ２ It is a spherical ultrafine particle mainly composed of ), and these primary particles aggregate to form secondary particles with a particle size of several hundred nm. Fumed silica is an ultrafine particle and is produced by rapid cooling, so the surface structure is in a chemically active state. The average particle size is the median diameter (D) in the volume-based particle size distribution measured by a dynamic light scattering / laser Doppler particle size distribution analyzer (NanoTrack UPA-EX150 manufactured by Nikkiso Co., Ltd.). ５０ )

[0062] Alternatively, silica whose surface has been hydrophobized by reacting the silanol groups present on the surface with a surface modifier may be used. Examples of surface modifiers include alkylsilane compounds, with specific examples including dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

[0063] Specific examples of fumed silica include, for instance, "Aerosil" (registered trademark) manufactured by Nippon Aerosil Co., Ltd. Examples of hydrophilic Aerosil (registered trademark) include "90", "130", "150", "200", and "300", while examples of hydrophobic Aerosil (registered trademark) include "R8200", "R972", "R972V", "R972CF", "R974", "R202", "R805", "R812", "R812S", "RY200", "RY200S", and "RX200". In addition, examples of "Rheoroseal" manufactured by Tokuyama Corporation include "DM-10", "DM-20", and "DM-30S".

[0064] (E) Component may be used alone or in combination of two or more.

[0065] The amount of component (E) is preferably 1 to 50 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). Within this range, it is possible to prevent transfer failure due to insufficient thixotropy and deterioration of workability due to increased viscosity when the composition of the present invention is used as a die bond material.

[0066] <Component (F)> The organic modified silicone resin composition for die bonding of the present invention may contain a reaction control agent as component (F) to adjust the curability. Examples of reaction inhibitors include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene compounds; hydroperoxy compounds; maleic acid derivatives; and known compounds that have a curing inhibitory effect on the platinum group metal catalyst of component (E) above, such as 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyne-3-ol, ethinylmethyldecylcarbinol, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

[0067] The degree of curing inhibition by reaction inhibitors varies depending on the chemical structure of the reaction inhibitor; therefore, when using reaction inhibitors, it is desirable to adjust the amount to the optimal level for each reaction inhibitor. Preferably, the amount is 0.001 to 10 parts by mass per 100 parts by mass of component (A). If the amount is 0.001 parts by mass or more, sufficient long-term storage stability of the composition at room temperature can be obtained. If the amount is 10 parts by mass or less, the curing of the composition will not be inhibited.

[0068] <Component (G)> In order to improve the adhesive strength, an adhesion improver other than component (D) may be added as component (G) to the organic modified silicone resin composition for die bonding of the present invention. As the adhesion improver, organosilicon compounds such as silanes and siloxanes containing functional groups that impart adhesion, non-silicone organic compounds, etc., can be used from the viewpoint of imparting self-adhesion to the organic modified silicone resin composition for die bonding of the present invention, which is of the addition reaction curing type.

[0069] Specific examples of functional groups that impart adhesion include polymerizable groups having carbon-carbon unsaturated bonds bonded to silicon atoms (e.g., vinyl group, allyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group, etc.), epoxy groups bonded to silicon atoms via carbon atoms (e.g., γ-glycidoxypropyl group, β-(3,4-epoxycyclohexyl)ethyl group, etc.), and alkoxysilyl groups (e.g., trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc.).

[0070] Examples of organosilicon compounds containing functional groups that impart adhesive properties include silane coupling agents, siloxanes having alkoxysilyl groups and organic functional groups, and compounds in which alkoxysilyl groups are introduced into organic compounds having reactive organic groups.

[0071] Examples of non-silicone organic compounds include allyl organic acid esters, organotitanium compounds, organozirconium compounds, and organoaluminum compounds.

[0072] When using an adhesion improver, the amount added is preferably 1 to 20 parts by mass, particularly 3 to 10 parts by mass, per 100 parts by mass of component (A). These can be used individually or in combination of two or more.

[0073] <Other Components> Depending on the purpose, the organic modified silicone resin composition for die bonding of the present invention may contain components such as antioxidants and acid / base generators.

[0074] Examples of antioxidants include hindered amines and hindered phenol compounds, and there are no restrictions on their structure. The amount of antioxidant added is preferably in the range of 100 to 10,000 ppm relative to the mass of component (A).

[0075] The organically modified silicone resin composition for die bonding of the present invention may contain an acid or base generating agent to promote the reaction of epoxy groups. The acid or base generating agent is an additive that is activated by heat or light and can be added in any amount.

[0076] Examples of acid and base generating agents include the K-PURE CXC series (onium salt type thermal acid generating agent) manufactured by Kusumoto Kasei Co., Ltd., and U-CAT5002 (thermal base generating agent) and CPI-200K (photoacid generating agent) manufactured by Sunapro Co., Ltd.

[0077] [Cured product] Furthermore, the present invention provides a cured product which is obtained by curing the organic modified silicone resin composition for die bonding described above.

[0078] The organic modified silicone resin composition for die bonding of the present invention can be cured under known conditions, for example, at 100 to 200°C for 10 minutes to 5 hours. In particular, the Shore D hardness of the cured product obtained by curing the composition is preferably 60 or higher, and especially preferably 70 or higher. The curing conditions for achieving a Shore D hardness of 60 or higher can usually be obtained by heating and curing the composition of the present invention at 150 to 200°C for 30 minutes to 5 hours. The Shore D hardness of the cured product can be measured by a method in accordance with JIS K6253-3:2023.

[0079] The cured product of the above-described organic modified silicone resin composition for die bonding of the present invention exhibits excellent adhesion at high temperatures, and is therefore particularly useful as a die bonding material used for die bonding of LED elements and the like.

[0080] [Optical Semiconductor Device] Furthermore, the present invention provides an optical semiconductor device which is die-bonded with the cured product described above.

[0081] One example of a method for die-bonding an optical semiconductor element using the cured product of the present invention is to fill a syringe with the composition of the present invention, apply it to a substrate such as a package to a thickness of 5 to 100 μm in a dry state using a dispenser, place an optical semiconductor element (e.g., a light-emitting diode) on the applied composition, and then cure the composition to die-bond the optical semiconductor element to the substrate. Alternatively, the composition may be placed on a squeegee dish, applied to a substrate to a thickness of 5 to 100 μm in a dry state by stamping while squeezing, place an optical semiconductor element on the applied composition, and then cure the composition to die-bond the optical semiconductor element to the substrate. The curing conditions for the composition may be as described above. In this way, an optical semiconductor element die-bonded with a highly reliable cured product of the organic modified silicone resin composition for die bonding of the present invention can be obtained.

[0082] The present invention will be specifically described below using examples, comparative examples, synthesis examples, and comparative synthesis examples, but the present invention is not limited to these.

[0083] [Comparative Synthesis Example 1] In a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, 48.0 g (0.1 mol) of an organosilicon compound represented by the following structural formula (10) and 240 g of toluene were placed and heated to 80°C. Then, 0.07 g of a toluene solution (platinum concentration 0.5% by mass) of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane was added. Subsequently, 71.8 g (0.63 mol) of allyl glycidyl ether was added dropwise, and the mixture was reacted at 80°C for 5 hours. After cooling to 25°C, 0.5 g of activated carbon was added and stirred for 2 hours to remove the platinum, and then the activated carbon was removed by filtration. The resulting reaction product had a hydrogen generation rate of 0 ml / g, and NMR and GPC (gel column chromatography) results indicated that it was the compound represented by the following structural formula (11).

[0084] [Examples 1-6, Comparative Examples 1-4] Organic modified silicone resin compositions for die bonding were prepared by mixing the following components in the amounts shown in Table 1. The values ​​for each component in Table 1 represent parts by mass. The value of [Si-H] / [addition-reactive carbon-carbon double bond] represents the ratio of the number of hydrogen atoms bonded to silicon atoms to one addition-reactive carbon-carbon double bond in the composition.

[0085] (A) Component: Compound represented by the following structural formula (12)

[0086] (B) Component: Organosilicon compound represented by the following structural formula (10)

[0087] (C) Component: Toluene solution of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane (platinum concentration 0.5% by mass)

[0088] (D) Component (D-1): Compound represented by the following structural formula (7) (manufactured by Resonaq Corporation, Showfree PETG) (D-2): Compound represented by the following structural formula (8) (manufactured by Resonaq Corporation, Showfree BATG) (D-3): Compound represented by the following structural formula (13) (manufactured by Shin-Etsu Chemical Co., Ltd., X-40-2670) (D-4): Organosilicon compound of structural formula (11) obtained in comparative synthesis example 1

[0089] (E) Component (E-1): BET specific surface area 230m ２ / g, fumed silica surface-treated with dichlorodimethylsilane (manufactured by Tokuyama Corporation, Rheoroseal DM30S) (E-2): BET specific surface area 300 m² ２ / g, fumed silica surface-treated with hexamethyldisilazane (manufactured by Shin-Etsu Chemical Co., Ltd., MU-SIL130A)

[0090] (F) Ingredient: Ethinylmethyldecylcarbinol

[0091] (G) Component: Compound represented by the following structural formula (14)

[0092]

[0093] <Measurement Method> The physical properties of cured products made from the organically modified silicone resin compositions for die bonding obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were measured according to the following measurement method. The results are shown in Table 2.

[0094] [Hardness] The composition was poured into a mold to a thickness of 2 mm, and the Type D hardness of the cured product, which was cured at 150°C for 4 hours, was measured in accordance with JIS K6253-3:2023.

[0095] [Die Shear Strength] Using a die bonder (ASM, AD-830), each composition was stamped onto the silver-plated electrode portion of an SMD3020 package (I-CHIUN PRECISION INDUSTRY Co., polyphthalamide resin). A photoelectronic element (SemiLED, element size 10 × 10 ml) was then mounted on top and heated at 200°C for 1 hour. After curing, the die shear strength was measured at 25°C and 150°C using a bond tester (Dage, Series 4000).

[0096] [Delamination State] After measuring the die shear strength at 150°C, the presence or absence of hardened material remaining on the silver-plated electrodes of the package was observed under a microscope. If hardened material remains on the silver plating, it is considered cohesive failure (CF), indicating high adhesion to the substrate as a die bond material. If no hardened material remains on the plating and delamination occurs, it is considered interfacial delamination (AF), indicating insufficient adhesion as a die bond material.

[0097] As shown in Table 2, all of Examples 1 to 6 exhibited excellent die shear strength at 25°C and 150°C, and furthermore, the delamination state in all cases was cohesive failure, indicating high adhesion to the substrate.

[0098] On the other hand, in Comparative Example 1, where the [Si-H] / [addition-reactive carbon-carbon double bond] ratio was 1.0, the die shear strength at 150°C was inferior, and the delamination state was interfacial delamination. It is thought that most of the Si-H groups of component (B) were consumed by hydrosilylation with component (A) and did not react sufficiently with the epoxy groups of component (D), resulting in insufficient adhesive strength.

[0099] Furthermore, in Comparative Examples 2 to 4, which did not contain component (D) of the present invention, the die shear strength at 150°C was insufficient, and interfacial delamination occurred. In Comparative Examples 3 and 4, in which component (D) was replaced with an epoxy group-containing siloxane derivative, the compatibility and dispersibility with components (A) and (B) increased, and it is thought that the adhesive strength was not sufficiently developed because the adhesion-improving component did not orient to the interface with the adherend.

[0100] This specification includes the following embodiments: [1] An organically modified silicone resin composition for die bonding, comprising: (A) an addition reaction product of (a) a compound represented by the following general formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule (In the formula, R １ Each of these is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an addition-reactive carbon-carbon double bond, and R ２(B) Organosilicon compounds represented by the following general formula (2) (In the formula, R ３ (C) Platinum group metal catalyst (D) Compounds having two or more glycidyloxy groups in one molecule and lacking addition-reactive carbon-carbon double bonds and silicon atoms, and (E) BET specific surface area of ​​100 m ２ [1] An organic modified silicone resin composition for die bonding, characterized in that it contains fumed silica of 1 / g or more, and the number of hydrogen atoms bonded to silicon atoms is 1.1 to 3.0 times the total number of addition-reactive carbon-carbon double bonds in the composition. [2] The organic modified silicone resin composition for die bonding according to [1], characterized in that the component (A) is a compound represented by the following general formula (3). (In the formula, k represents an integer from 0 to 50, R ４ R is a divalent group represented by the following formula (4), ５ This is a base represented by the following formula (5) or formula (6). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) [3] The R of component (B) ３ The organic modified silicone resin composition for die bonding according to [1] or [2], characterized in that the group is a divalent group represented by the following formula (4). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) [4] The organic modified silicone resin composition for die bonding according to any one of [1] to [3], characterized in that the (D) component is a compound represented by the following structural formula (7), a compound represented by the following structural formula (8), or both. [5] A cured product characterized by being cured from an organically modified silicone resin composition for die bonding described in any one of [1] to [4]. [6] An optoelectronic semiconductor device characterized by being die-bonded with the cured product described in [5].

[0101] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. An organically modified silicone resin composition for die bonding, comprising: (A) an addition reaction product of (a) a compound represented by the following general formula (1) and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and having two addition-reactive carbon-carbon double bonds in one molecule. (In the formula, R １ is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an addition-reactive carbon-carbon double bond, and R ２ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.) (B) an organosilicon compound represented by the following general formula (2) (In the formula, R ３ is independently a divalent hydrocarbon group which may contain a silicon atom, m is 0 or 1, and n is a number satisfying 0 to 5.) (C) a platinum group metal-based catalyst (D) a compound having two or more glycidyloxy groups in one molecule and not having an addition-reactive carbon-carbon double bond and a silicon atom, and (E) containing fumed silica having a BET specific surface area of 100 m ２ / g or more, wherein the number of hydrogen atoms bonded to silicon atoms relative to the total number of addition-reactive carbon-carbon double bonds in the composition is 1.1 to 3.0 times. An organically modified silicone resin composition for die bonding, characterized by this.

2. The organic modified silicone resin composition for die bonding according to claim 1, characterized in that the component (A) is a compound represented by the following general formula (3). (In the formula, k represents an integer from 0 to 50, R ４ R is a divalent group represented by the following formula (4), ５ This is a base represented by the following formula (5) or formula (6). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) 3. The R of component (B) ３ The organic modified silicone resin composition for die bonding according to claim 1, characterized in that the group is a divalent group represented by the following formula (4). (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) 4. The organic modified silicone resin composition for die bonding according to claim 1, characterized in that the component (D) is a compound represented by the following structural formula (7), a compound represented by the following structural formula (8), or both.

5. A cured product characterized by being obtained by curing an organically modified silicone resin composition for die bonding according to any one of claims 1 to 4.

6. An optoelectronic semiconductor element characterized by being die-bonded with the cured product described in claim 5.

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