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

Abstract

The present invention relates to an organically modified silicone resin composition for die bonding, the organically modified silicone resin composition containing: (A) a compound which is 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, and has two addition-reactive carbon-carbon double bonds in one molecule; (B) an organosilicon compound which has two or more hydrogen atoms bonded to silicon atoms in one molecule and does not have an epoxy-containing group bonded to a silicon atom; (C) an organosilicon compound having, in one molecule, a hydrogen atom bonded to a silicon atom and an epoxy-containing group bonded to a silicon atom; (D) an epoxy compound represented by general formula (2); and (E) a platinum group metal-based catalyst. Accordingly, provided are: 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, which is capable of providing the cured product; and an optical semiconductor element.　

Description

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

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

[0002] Silicone resins and organically modified silicone resins are primarily used as die-bonding materials for light-emitting diode (LED) elements (Patent Documents 1 to 3). However, with the recent emergence of blue LED elements and the miniaturization of LED elements, conventional silicone die-bonding materials have become unable to adhere to the substrate at high temperatures during wire bonding, resulting in bonding defects.

[0003] In addition, because the LED wire bonding process is carried out at high temperatures, die bond materials with high glass transition points (Tg) and high strength at high temperatures are required, but conventional organically modified silicone die bond materials are not sufficient because their Tg exists in the range of room temperature to 50° C. Therefore, there has been a demand for die bond materials with higher glass transition points and excellent adhesion between LED elements and substrates, even at high temperatures.

[0004] Patent Document 4 proposes an organically modified silicone resin composition for die bonding in which the Tg of the cured product is increased by blending a polyfunctional alkenyl group-containing polysiloxane. However, with the miniaturization of LED elements, further improvements in adhesive strength and hot die shear strength are required.

[0005] JP 2006-342200 A JP 2011-086844 A JP 2015-140372 A JP 2020-136281 A

[0006] The present invention has been made in view of the above circumstances, and has as its object to provide a cured product that exhibits excellent adhesive strength between an LED element and a substrate at high temperatures, an organic-modified silicone resin composition for die bonding that can provide such a cured product, and an optical semiconductor element.

[0007] In order to solve the above problems, the present invention provides an organically modified silicone resin composition for die bonding, comprising: (A) (a) a compound represented by the following general formula (1) having two hydrogen atoms bonded to silicon atoms per molecule, and (b) a compound which is an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds per molecule, and which has two addition-reactive carbon-carbon double bonds per molecule: (In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, excluding alkenyl groups, or an alkoxy group having 1 to 6 carbon atoms; R ２ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.) (B) an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule and having no epoxy-containing group bonded to the silicon atom; (C) an organosilicon compound having a hydrogen atom bonded to a silicon atom and an epoxy-containing group bonded to a silicon atom in one molecule; (D) an epoxy compound represented by the following general formula (2), and (In the formula, R ３ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ and R ５ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ One of the R ５ One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ６ and R ７ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ６ One of the R ７ One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ８ and R ９ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ８ One of the R ９ One of them is bonded to -(CH ２ ) ｐ-, where i, j, and k are 0 or 1, m is an integer of 0 to 5, and p is an integer of 1 to 5.) (E) A platinum group metal catalyst.

[0008] The organically modified silicone resin composition for die bonding of the present invention is capable of providing a cured product that has high strength at high temperatures and excellent adhesive strength between an LED element and a substrate.

[0009] The component (A) is preferably a compound represented by the following general formula (3). (In the formula, s represents an integer of 0 to 50.)

[0010] When the component (A) is the above-mentioned specific compound, a cured product having particularly excellent hardness and strength can be obtained.

[0011] The component (B) is preferably an organosilicon compound represented by the following general formula (4). (In the formula, R １０ is a divalent group represented by the following formula (5), and t is a number satisfying 0≦t≦10. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.)

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

[0013] The component (C) is preferably an organosilicon compound represented by the following general formula (6). (In the formula, R １０ is a divalent group represented by the following formula (5), and R １１ are each independently a hydrogen atom or an epoxy-containing group, and R １１ At least one of R is a hydrogen atom, and １１ At least one of the groups is an epoxy-containing group, and u is a number satisfying the relationship 0≦u≦10. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.)

[0014] When the component (C) is the above-mentioned specific compound, the compatibility with the component (A) is increased, the transparency is improved, and separation of the components can be suppressed when the die bond material is applied to the LED substrate by a die bonder.

[0015] Furthermore, the component (D) is preferably at least one selected from the group consisting of an epoxy compound represented by the following structural formula (7), an epoxy compound represented by the following structural formula (8), and an epoxy compound represented by the following structural formula (9).

[0016] When the component (D) is the above-mentioned specific compound, the effects of the present invention are more easily achieved.

[0017] The present invention also provides a cured product obtained by curing the above-described organic-modified silicone resin composition for die bonding.

[0018] The cured product of the present invention has high strength and excellent adhesive strength between the LED element and the substrate even at high temperatures.

[0019] Furthermore, the present invention provides an optical semiconductor element that is die-bonded with the above-described cured product.

[0020] The optical semiconductor element of the present invention is highly reliable because the LED element and the substrate are bonded together by a cured product that has high resin strength and excellent adhesive strength even at high temperatures.

[0021] The organic-modified silicone resin composition for die bonding of the present invention can provide a cured product that has high hardness and excellent adhesive strength between an LED element and a substrate even at high temperatures. Therefore, the cured product obtained from such an organic-modified silicone resin composition is particularly useful as a die bond material used in die bonding of small LED elements, etc.

[0022] FIG. 1 is a diagram of test pieces for adhesion tests prepared using the compositions obtained in the examples and comparative examples.

[0023] As described above, there has been a need for the development of a cured product that exhibits excellent adhesive strength between an LED element and a substrate at high temperatures, an organic-modified silicone resin composition for die bonding that can provide such a cured product, and an optical semiconductor element.

[0024] As a result of extensive research into the above-mentioned problems, the present inventors discovered that an organically modified silicone resin composition containing components (A) to (E) described below can solve the above-mentioned problems, and thus completed the present invention.

[0025] That is, the present invention provides an organically modified silicone resin composition for die bonding, comprising: (A) (a) a compound represented by the following general formula (1) having two hydrogen atoms bonded to silicon atoms per molecule, and (b) a compound which is an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds per molecule, and which has two addition-reactive carbon-carbon double bonds per molecule: (In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, excluding alkenyl groups, or an alkoxy group having 1 to 6 carbon atoms; R ２ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.) (B) an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule and having no epoxy-containing group bonded to the silicon atom; (C) an organosilicon compound having a hydrogen atom bonded to a silicon atom and an epoxy-containing group bonded to a silicon atom in one molecule; (D) an epoxy compound represented by the following general formula (2), and (In the formula, R ３ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ and R ５ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ One of the R ５ One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ６ and R ７ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ６ One of the R ７One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ８ and R ９ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ８ One of the R ９ One of them is bonded to -(CH ２ ) ｐ -, where i, j, and k are 0 or 1, m is an integer of 0 to 5, and p is an integer of 1 to 5.) (E) A platinum group metal catalyst.

[0026] The present invention will be described in detail below, but the present invention is not limited thereto.

[0027] [Organo-modified silicone resin composition for die bonding] The organo-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.

[0028] <Component (A)> Component (A) in the organo-modified silicone resin composition of the present invention is an addition reaction product of (a) a compound represented by the following general formula (1) having two silicon-bonded hydrogen atoms per molecule, and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds per molecule, and is an addition reaction product having two addition-reactive carbon-carbon double bonds per molecule. (In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, excluding alkenyl groups, or an alkoxy group having 1 to 6 carbon atoms; R ２ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.

[0029] R １Specific examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, and cyclohexyl; aryl groups having 6 to 12 carbon atoms, such as phenyl and naphthyl; alkylaryl groups having 7 to 12 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, and hexylphenyl; and aralkyl groups having 7 to 12 carbon atoms, such as benzyl and phenethyl.

[0030] Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0031] Among these, R １ As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group is more preferred.

[0032] On the other hand, R ２ Specific examples of the divalent hydrocarbon group 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.

[0033] Among these, an arylene group having 6 to 12 carbon atoms is preferred, and a phenylene group is more preferred.

[0034] The component (a) is a compound represented by the general formula (1) １ is a methyl group, and R ２is a phenylene group. Specific examples of component (a) include 1,4-bis(dimethylsilyl)benzene and 1,3-bis(dimethylsilyl)benzene.

[0035] The component (a) may be used alone or in combination of two or more.

[0036] Furthermore, examples of the polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds per molecule of component (b) that can be used include: (i) a polycyclic hydrocarbon in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic hydrocarbon skeleton; (ii) a polycyclic hydrocarbon in which a hydrogen atom bonded to a carbon atom forming the polycyclic hydrocarbon skeleton is substituted with an addition-reactive carbon-carbon double bond-containing group; and (iii) a polycyclic hydrocarbon in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic hydrocarbon skeleton, and a hydrogen atom bonded to a carbon atom forming the polycyclic hydrocarbon skeleton is substituted with an addition-reactive carbon-carbon double bond-containing group.

[0037] Specific examples of the component (b) include 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene, which are represented by the following formulas, and these can also be used as a mixture (hereinafter, when there is no need to distinguish between these, they may be collectively referred to as "vinylnorbornene").

[0038] The substitution position of the vinyl group in the vinylnorbornene may be either a cis configuration (exo type) or a trans configuration (endo type). Furthermore, since there is no particular difference in the reactivity of the compound depending on the configuration, a combination of isomers of both configurations may also be used.

[0039] The addition reaction product of component (A) can be synthesized, for example, by the method described in JP-A-2005-133073.

[0040] For example, it can be prepared by adding more than 1 mole and not more than 10 moles, preferably more than 1 mole and not more than 5 moles, of component (b) to 1 mole of component (a) in the presence of a hydrosilylation reaction catalyst.

[0041] In this case, known hydrosilylation reaction catalysts can be used, and specific examples thereof include platinum-based catalysts such as platinum metal-supported carbon powder, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum group metal-based catalysts such as palladium-based catalysts and rhodium-based catalysts. Furthermore, the addition reaction conditions, the use of solvents, and the like are not particularly limited, and known catalysts may be used.

[0042] In the above reaction, when synthesizing the addition reaction product of component (A), an excess molar amount of (b) polycyclic hydrocarbon is reacted with (a) the compound represented by general formula (1) above. Therefore, the addition reaction product of component (A) has two addition-reactive carbon-carbon double bonds derived from (b) polycyclic hydrocarbon per molecule.

[0043] In the present invention, the component (A) is preferably represented by the following general formula (3): Such addition reaction products containing a polycyclic hydrocarbon and a phenylene group are particularly suitable for use because they give cured products with excellent hardness and strength.

[0044] (In the formula, s represents an integer of 0 to 50, preferably an integer of 0 to 30, and more preferably an integer of 0 to 20.)

[0045] The component (A) may be used alone or in combination of two or more types.

[0046] <Component (B)> Component (B) is an organosilicon compound that has two or more silicon-bonded hydrogen atoms (i.e., SiH groups) per molecule and does not have any silicon-bonded epoxy-containing groups. Component (B) acts as a crosslinking agent that crosslinks with the alkenyl groups in component (A) via a hydrosilylation reaction.

[0047] The component (B) is not particularly limited as long as it is an organosilicon compound that has two or more hydrogen atoms bonded to silicon atoms in one molecule and does not have an epoxy-containing group bonded to a silicon atom, and examples thereof include organohydrogensilanes and organohydrogenpolysiloxanes, with organohydrogenpolysiloxanes being preferred. There are no particular limitations on the molecular structure of the organohydrogenpolysiloxane, and for example, linear, cyclic, or branched ones can be used.

[0048] The silicon-bonded organic group in component (B) is preferably a substituted or unsubstituted monovalent hydrocarbon group that does not contain an addition-reactive carbon-carbon double bond. Examples of such substituted or unsubstituted monovalent hydrocarbon groups include alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and groups in which the hydrogen atoms of these groups have been substituted with halogen atoms, with methyl, ethyl, and phenyl groups being particularly preferred.

[0049] Component (B) has at least two silicon-bonded hydrogen atoms (SiH groups) per molecule, preferably 2 to 200, and more preferably 3 to 100. When the organosilicon compound of component (B) has a linear or branched chain structure, these SiH groups may be located either at the molecular chain terminals or non-terminal portions, or may be located at both molecular chain terminals.

[0050] The number of silicon atoms per molecule of the organosilicon compound of component (B) (degree of polymerization) is preferably 2 to 1,000, more preferably 3 to 200, and even more preferably 4 to 100. Furthermore, the organosilicon compound of component (B) is preferably liquid at 25°C, and its viscosity at 25°C measured with a rotational viscometer is preferably 100 to 10,000 mPa·s, more preferably 100 to 3,000 mPa·s.

[0051] Component (B) is a SiO 2 containing no SiH groups. １／２ Units (M units), SiO ２／２ Units (D units), SiO ３／２ units (T units) and / or SiO ４／２ It may contain units (Q units).

[0052] The organosilicon compound of component (B) can be, for example, an organohydrogenpolysiloxane represented by the following average composition formula (10): １２ ｃ H ｄ SiO （４－ｃ－ｄ）／２ (10) (wherein, R １２ is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, and c and d are numbers that satisfy 0.7≦c≦2.1, 0.001≦d≦1.0, and 0.8≦c+d≦3.0, preferably 1.0≦c≦2.0, 0.01≦d≦1.0, and 1.5≦c+d≦2.5.

[0053] In the above formula (10), R １２ Examples of the monovalent hydrocarbon groups include the same monovalent hydrocarbon groups as those listed above for component (A).

[0054] In the present invention, the component (B) is preferably an organosilicon compound represented by the following general formula (4), which has silicon-bonded hydrogen atoms in a cyclic form and is joined by a divalent organic group. The compound represented by the following general formula (4) can be obtained, for example, by the hydrosilylation reaction of 2,4,6,8-tetramethyltetracyclosiloxane with vinylnorbornene. (In the formula, R １０ is a divalent group represented by the following formula (5), and t is a number satisfying 0≦t≦10. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.)

[0055] Such a compound not only increases compatibility with component (A) and improves transparency, but also prevents separation of the components when the die bond material is applied to an LED substrate using a die bonder.

[0056] The component (B) may be used alone or in combination of two or more types.

[0057] The amount of component (B) blended is such that the number of hydrogen atoms bonded to silicon atoms in component (B) per addition-reactive carbon-carbon double bond in component (A) is preferably within a range of 0.4 to 4.0, and more preferably 0.5 to 2.5. Within this range, high strength can be imparted to the resulting cured product.

[0058] <Component (C)> Component (C) is an organosilicon compound containing, per molecule, a silicon-bonded hydrogen atom and a silicon-bonded epoxy-containing group. Examples of the epoxy-containing group include an epoxy group, a glycidyl group, a glycidyloxy group, a 3-glycidyloxypropyl group, a 3,4-epoxycyclohexyl group, a 3,4-epoxycyclohexylmethyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3,4-epoxycyclohexylmethyloxy group, and an oxetanyl group.

[0059] Because component (C) has a hydrogen atom bonded to a silicon atom, it is capable of hydrosilylation reaction with the addition-reactive carbon-carbon double bond of component (A), and because it has an epoxy-containing group bonded to a silicon atom, it also reacts with the epoxy compound of component (D), described below, thereby immobilizing component (D) in the resin, thereby obtaining a cured product with high adhesive strength and die shear strength. On the other hand, if it does not have a hydrogen atom bonded to a silicon atom, a crosslinking reaction with component (A) does not occur, and component (C) is not incorporated into the resin, resulting in insufficient adhesive strength and die shear strength of the cured product. Furthermore, if it does not have an epoxy-containing group bonded to a silicon atom, it does not react with component (D), resulting in insufficient adhesive strength and die shear strength of the cured product.

[0060] Component (C) preferably has one or more silicon-bonded hydrogen atoms per molecule, and preferably has one or more silicon-bonded epoxy-containing groups per molecule.

[0061] In the present invention, the component (C) is preferably an organosilicon compound represented by the following general formula (6): The organosilicon compound represented by the following general formula (6) can be obtained, for example, by subjecting some of the hydrogen atoms bonded to silicon atoms of the organosilicon compound represented by the above general formula (4), which is exemplified as the component (B), to a hydrosilylation reaction with a compound having an epoxy-containing group and an alkenyl group, such as allyl glycidyl ether or 1,2-epoxy-4-vinylcyclohexane. (In the formula, R １０ is a divalent group represented by the above formula (5), and R １１ are each independently a hydrogen atom or an epoxy-containing group, and R １１ At least one of R is a hydrogen atom, and １１ At least one of the groups is an epoxy-containing group, and u is a number satisfying the relationship 0≦u≦10.

[0062] Such a compound not only increases compatibility with component (A) and improves transparency, but also prevents separation of the components when the die bond material is applied to an LED substrate using a die bonder.

[0063] The component (C) may be used alone or in combination of two or more types.

[0064] The amount of component (C) blended is preferably an amount such that the total number of silicon-bonded hydrogen atoms in components (B) and (C) per addition-reactive carbon-carbon double bond in the composition is 0.5 to 5.0, and more preferably 0.7 to 3.0. Satisfying this range allows for the cured product to have high strength.

[0065] <Component (D)> Component (D) is an epoxy compound represented by the following general formula (2), and is a component that improves adhesion to a substrate. Component (D) reacts with the epoxy-containing group in component (C) to be fixed to the resin via component (C), thereby producing a cured product with high adhesive strength and die shear strength. (In the formula, R ３ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ and R ５are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ One of the R ５ One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ６ and R ７ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ６ One of the R ７ One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ８ and R ９ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ８ One of the R ９ One of them is bonded to -(CH ２ ) ｐ -, where i, j, and k are 0 or 1, m is an integer of 0 to 5, and p is an integer of 1 to 5.

[0066] In the present invention, the component (D) is preferably at least one selected from the group consisting of an epoxy compound represented by the following structural formula (7), an epoxy compound represented by the following structural formula (8), and an epoxy compound represented by the following structural formula (9):

[0067] The component (D) may use either a single compound or a combination of two or more compounds.

[0068] From the viewpoints of adhesive strength and compatibility, the blend amount of component (D) is preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of the total of components (A) to (C).

[0069] <Component (E)> The platinum group metal catalyst for component (E) is not particularly limited, so 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 atoms bonded to silicon atoms in components (B) and (C). Specific examples include platinum group metals such as platinum, palladium, and rhodium; platinum 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. Of these, platinum compounds are preferred, and coordination compounds of chloroplatinic acid with vinylsiloxane are particularly preferred.

[0070] The component (E) may use either a single compound or a combination of two or more compounds.

[0071] The amount of component (E) to be blended may be an effective amount as a catalyst, but is preferably in the range of 1 to 500 ppm, and more preferably 1 to 100 ppm, calculated as the mass of platinum group metal element relative to the total amount of components (A), (B), and (C). When this range is satisfied, the reaction rate of the addition reaction becomes appropriate, and a cured product with high strength can be obtained.

[0072] The organo-modified silicone resin composition for die bonding of the present invention can be prepared by mixing components (A) to (E), and, if necessary, components (F), (G), and other components.

[0073] <Component (F)> A reaction inhibitor may be added as component (F) to the organo-modified silicone resin composition for die bonding of the present invention in order to adjust the curing properties. Examples of reaction inhibitors include known compounds that have a curing inhibitory effect against the platinum group metal catalyst of component (E), such as 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; 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, ethynylmethyldecylcarbinol, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

[0074] Since the degree of curing inhibition effect of the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor, it is desirable to adjust the amount of the reaction inhibitor to an optimal amount for each reaction inhibitor used. Preferably, the amount is 0.001 to 5 parts by mass per 100 parts by mass of the total of components (A), (B), and (C). If the amount is 0.001 part by mass or more, the long-term storage stability of the composition at room temperature can be sufficiently obtained. If the amount is 5 parts by mass or less, the curing of the composition is not inhibited.

[0075] <Component (G)> In order to improve reinforcement, the organo-modified silicone resin composition for die bonding of the present invention may contain, as component (G), inorganic fillers such as finely powdered silica, crystalline silica, hollow fillers, and silsesquioxanes; fillers obtained by subjecting these fillers to a surface hydrophobic treatment with an organosilicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organosilazane compound, or a low-molecular-weight siloxane compound; silicone rubber powder; and silicone resin powder.

[0076] As component (G), silica fine particles are particularly preferred, and the silica fine particles may be those whose surfaces are made hydrophobic by reacting silanol groups present on the surface of hydrophilic silica fine particles with a surface modifier. Examples of the surface modifier include alkylsilane compounds, and specific examples include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

[0077] A suitable example of silica fine particles is fumed silica, which is readily available. ２ and O ２ The flame of 1,100 to 1,400°C was generated by burning a mixed gas of SiCl ４ It is produced by oxidizing and hydrolyzing gas. The primary particles of fumed silica are amorphous silicon dioxide (SiO ２ These primary particles aggregate to form secondary particles with diameters of several hundred nanometers. Fumed silica is an ultrafine particle, and because it is produced by rapid cooling, its surface structure is chemically active.

[0078] Specific examples include "Aerosil" (registered trademark) manufactured by Nippon Aerosil Co., Ltd. Examples of hydrophilic Aerosil (registered trademark) include "90", "130", "150", "200", and "300", and examples of hydrophobic Aerosil (registered trademark) include "R8200", "R972", "R972V", "R972CF", "R974", "R202", "R805", "R812", "R812S", "RY200", "RY200S", and "RX200". Furthermore, examples of "Reolosil" (registered trademark) manufactured by Tokuyama Corporation include "DM-10", "DM-20", and "DM-30S".

[0079] The blending amount of component (G) is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass, per 100 parts by mass of the total of components (A), (B), (C), and (D). Within this range, a composition having an appropriate viscosity and thixotropy is obtained, and therefore, when used as a die-bonding material, good transferability is achieved.

[0080] <Other Components> Depending on the purpose, components such as antioxidants, adhesion improvers, acid / base generators, etc. may be added to the organo-modified silicone resin composition for die bonding of the present invention.

[0081] Examples of antioxidants include hindered amines and hindered phenol compounds, and there are no limitations on their structure. The amount of antioxidant added is preferably in the range of 100 to 10,000 ppm based on the total amount of components (A), (B), (C), and (D).

[0082] As the adhesion improver, from the viewpoint of imparting self-adhesiveness to the addition reaction curing type organic-modified silicone resin composition for die bonding of the present invention, an organic silicon compound such as silane or siloxane containing a functional group that imparts adhesiveness, or a non-silicone organic compound, etc., is used.

[0083] Specific examples of functional groups that impart adhesiveness include alkenyl groups such as vinyl groups and allyl groups, or hydrogen atoms bonded to silicon atoms; acryloxy groups (e.g., γ-acryloxypropyl groups, etc.) or methacryloxy groups (e.g., γ-methacryloxypropyl groups, etc.); and alkoxysilyl groups (e.g., trimethoxysilyl groups, triethoxysilyl groups, methyldimethoxysilyl groups, etc., bonded to silicon atoms via alkylene groups which may contain 1 to 2 ester structures, urethane structures, or ether structures).

[0084] Examples of organosilicon compounds containing functional groups that impart adhesiveness include silane coupling agents, siloxanes having an alkoxysilyl group and an organic functional group, and compounds in which an alkoxysilyl group has been introduced into an organic compound having a reactive organic group.

[0085] Examples of non-silicone organic compounds include organic acid allyl esters, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds.

[0086] The organically modified silicone resin composition for die bonding of the present invention may contain an acid or base generator to promote the reaction of the epoxy group. The acid or base generator is an additive that is activated by heat or light, and can be added in any amount.

[0087] Examples of the acid / base generator include K-PURE CXC series (onium salt type thermal acid generators) manufactured by Kusumoto Chemicals Co., Ltd., and U-CAT5002 (thermal base generator) and CPI-200K (photoacid generator) manufactured by San-Apro Co., Ltd.

[0088] [Cured Product] Furthermore, the present invention provides a cured product obtained by curing the above-described organic-modified silicone resin composition for die bonding.

[0089] The organically modified silicone resin composition for die bonding of the present invention may 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 more, and more preferably 70 or more. The curing conditions for achieving a Shore D hardness of 60 or more can usually be achieved by heating and curing the composition of the present invention at 150 to 200° C. for 30 minutes to 5 hours.

[0090] The cured product of the organically modified silicone resin composition for die bonding of the present invention has excellent adhesive properties at high temperatures, and is therefore particularly useful as a die bonding material for use in die bonding of LED elements and the like.

[0091] [Optical Semiconductor Element] Furthermore, the present invention provides an optical semiconductor element that is die-bonded with the cured product described above.

[0092] 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 using a dispenser to a thickness of 5 to 100 μm in a dry state, then place an optical semiconductor element (e.g., a light-emitting diode) on the applied composition, and cure the composition to die-bond the optical semiconductor element to the substrate. Alternatively, the composition may be placed on a squeegee plate, and applied to the substrate by stamping while squeezing to a thickness of 5 to 100 μm in a dry state, then place the optical semiconductor element on the applied composition, and 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, a highly reliable optical semiconductor element can be die-bonded using a cured product of the organo-modified silicone resin composition for die-bonding of the present invention.

[0093] EXAMPLES The present invention will be specifically explained below using Examples, Comparative Examples, Synthesis Examples, and Comparative Synthesis Examples, but the present invention is not limited to these.

[0094] Synthesis Example 1 Into a 500 mL four-neck flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer, 70.7 g of an organosilicon compound represented by the following general formula (4) where t = 2, 75.6 g of toluene, 24.3 g of isopropanol, and 0.05 g of acetonitrile were added and stirred, and 0.037 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added. After heating to 70°C, 40.5 g of allyl glycidyl ether was added dropwise, and the mixture was allowed to react at 70°C for 5 hours. After cooling to 25°C, 0.15 g of activated carbon was added, and the mixture was stirred for 1 hour and filtered to obtain an organosilicon compound (C-1) having a hydrogen atom bonded to a silicon atom and an epoxy-containing group bonded to a silicon atom in one molecule. The obtained target product was a colorless, transparent liquid with a viscosity of 5.1 Pa s, and was represented by the following general formula (6), where u = 2, R １１ Of the total number of silicon compounds, 75% were 3-glycidyloxypropyl groups and 25% were organosilicon compounds represented by hydrogen atoms (SiH content: 0.00115 mol / g). (In the formula, R １０is a divalent group represented by the following formula (5), and t is 2. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.) (In the formula, R １０ is a divalent group represented by the above formula (5), and R １１ is as above. u is 2.)

[0095] Synthesis Example 2 An organosilicon compound (C-2) was synthesized in the same manner as in Synthesis Example 1, except that 40.5 g of allyl glycidyl ether was replaced with 37.2 g of 1,2-epoxy-4-vinylcyclohexane (Celloxide 2000, manufactured by Daicel Corporation). The obtained target product was a colorless, transparent liquid with a viscosity of 29 Pa s, and was represented by the general formula (6) above, where u = 2 and R １１ Of the total number of silicon compounds, 81% were 2-(3,4-epoxycyclohexyl)ethyl groups and 19% were organosilicon compounds represented by hydrogen atoms (SiH content 0.00082 mol / g).

[0096] Comparative Synthesis Example 1 Organosilicon compound (C-3) was synthesized in the same manner as in Synthesis Example 1, except that 40.5 g of allyl glycidyl ether was replaced with a mixture of 20.2 g of allyl glycidyl ether and 18.6 g of 1,2-epoxy-4-vinylcyclohexane (Celloxide 2000, manufactured by Daicel Corporation). The target product obtained was a colorless, transparent liquid with a viscosity of 13.4 Pa s, and was a compound represented by the general formula (6) above, where u=2 and R １１ Of the total number of compounds, 50% were organosilicon compounds represented by 3-glycidyloxypropyl groups and 50% were organosilicon compounds represented by 2-(3,4-epoxycyclohexyl)ethyl groups (SiH content: 0 mol / g).

[0097] Examples 1 to 4, Comparative Examples 1 to 3 The following components were mixed in the amounts shown in Table 1 to prepare organo-modified silicone resin compositions for die bonding. Note that, because components (D-2) and (D-3) are solids, they were mixed with component (D-1) and dissolved before use. The numerical 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 in components (B) and (C) per one addition-reactive carbon-carbon double bond in component (A).

[0098] Component (A): A compound represented by the following general formula (3) where s=1 (addition reactive carbon-carbon double bond: 0.267 mol / 100 g) (Wherein, s is 1.)

[0099] Component (B): an organosilicon compound represented by the following general formula (4) where t=2 (SiH content: 0.00756 mol / g) (In the formula, R １０ is a divalent group represented by the following formula (5), and t is 2. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.)

[0100] Component (C) (C-1): Organosilicon compound obtained in Synthesis Example 1 (C-2): Organosilicon compound obtained in Synthesis Example 2 (C-3): Organosilicon compound obtained in Comparative Synthesis Example 1

[0101] Component (D) (D-1): Epoxy compound represented by the following structural formula (7) (THI-DE, manufactured by ENEOS Corporation) (D-2): Epoxy compound represented by the following structural formula (8) (DE-102, manufactured by ENEOS Corporation) (D-3): Epoxy compound represented by the following structural formula (9) (DE-103, manufactured by ENEOS Corporation)

[0102] Component (E): A toluene solution of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane (platinum concentration: 0.5% by mass)

[0103] Component (F): 1,6-bis(t-butylperoxycarbonyloxy)hexane Component (G): fumed silica (Reolosil DM-30S, manufactured by Tokuyama Corporation)

[0104]

[0105] <Measurement Methods> The physical properties of the cured products made of the organically modified silicone resin compositions for die bonding obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were measured according to the following measurement methods. The results are shown in Table 2.

[0106] [Hardness of Cured Product] The composition was poured into a mold and heated at 150°C for 4 hours to cure, and the hardness of the molded plate having a thickness of 2 mm was measured in accordance with JIS K 6253 using a Shore D hardness tester.

[0107] [Adhesion Strength] A test piece for an adhesion test was prepared as shown in Figure 1. That is, two aluminum substrates 11 and 12 (manufactured by KDS Corporation, width 25 mm x depth 50 mm x thickness 1 mm) were sandwiched between 80 µm thick Teflon (registered trademark) spacers so that the ends of the substrates overlapped by 10 mm, and the obtained organically modified silicone resin composition for die bonding was cured by heating at 150°C for 4 hours, and the substrates were bonded together by the cured product 13 of the organically modified silicone resin composition for die bonding (adhesion area 25 mm x 5 mm = 125 mm ２ A test piece was prepared consisting of two aluminum substrates.

[0108] The ends of the aluminum substrates 11 and 12 of this test piece were pulled in opposite directions (directions of the arrows in Figure 1) at a pulling rate of 50 mm / min using a tensile tester (Shimadzu Corporation, Autograph) to determine the adhesive strength (MPa) per unit area.

[0109] [Die Shear Strength] Using a die bonder (AD-830 manufactured by ASM Corporation), each composition was transferred by stamping onto the silver-plated electrode portion of an SMD3020 package (polyphthalamide resin manufactured by I-CHIUN PRECISION INDUSTRY Co.), and an optical semiconductor element (manufactured by SemiLED Inc., element size 10 × 10 mil) was mounted thereon, followed by heating for 1 hour at 200°C. After curing, the die shear strength was measured at 25°C and 150°C using a bond tester (Series 4000 manufactured by Dage Corporation).

[0110]

[0111] As shown in Table 2 above, it was confirmed that in Examples 1 to 4, which used the organically modified silicone resin composition for die bonding of the present invention, cured products were all excellent in hardness and die shear strength between the LED element and the substrate at 25°C and 150°C.

[0112] On the other hand, Comparative Example 1, which did not contain the component (D) of the present invention, was inferior in adhesive strength and die shear strength. Furthermore, in Comparative Example 2, which did not contain the component (C) of the present invention, and Comparative Example 3, in which the component (C) of the present invention was changed to one having no Si—H groups in the molecule, the component (D) was not fixed in the resin, and the adhesive strength and die shear strength were significantly inferior.

[0113] This specification encompasses the following aspects: [1]: An organically modified silicone resin composition for die bonding, comprising: (A) (a) a compound having two silicon-bonded hydrogen atoms per molecule, represented by the following general formula (1), and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds per molecule, the compound having two addition-reactive carbon-carbon double bonds per molecule: (In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, excluding alkenyl groups, or an alkoxy group having 1 to 6 carbon atoms; R ２represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.) (B) an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule and having no epoxy-containing group bonded to the silicon atom; (C) an organosilicon compound having a hydrogen atom bonded to a silicon atom and an epoxy-containing group bonded to a silicon atom in one molecule; (D) an epoxy compound represented by the following general formula (2), and (In the formula, R ３ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ and R ５ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ４ One of the R ５ One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ６ and R ７ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ６ One of the R ７ One of them is bonded to -(CH ２ ) ｐ - may form a group represented by R ８ and R ９ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ８ One of the R ９ One of them is bonded to -(CH ２ ) ｐ -, wherein i, j, and k are 0 or 1, m is an integer of 0 to 5, and p is an integer of 1 to 5.) (E) A platinum group metal catalyst. [2]: The organo-modified silicone resin composition for die bonding according to [1] above, wherein component (A) is a compound represented by the following general formula (3): (wherein s represents an integer of 0 to 50) [3]: The organo-modified silicone resin composition for die bonding according to [1] or [2] above, characterized in that the component (B) is an organosilicon compound represented by the following general formula (4): (In the formula, R １０ is a divalent group represented by the following formula (5), and t is a number satisfying 0≦t≦10. (In the formula, an asterisk (*) represents a bond to adjacent silicon atoms.) [4]: ​​The organic-modified silicone resin composition for die bonding according to any one of [1] to [3] above, characterized in that the component (C) is an organic silicon compound represented by the following general formula (6): (In the formula, R １０ is a divalent group represented by the following formula (5), and R １１ are each independently a hydrogen atom or an epoxy-containing group, and R １１ At least one of R is a hydrogen atom, and １１ At least one of the groups is an epoxy-containing group, and u is a number satisfying the relationship 0≦u≦10. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.) [5]: The organic-modified silicone resin composition for die bonding according to any one of [1] to [4] above, characterized in that the component (D) is at least one selected from the group consisting of an epoxy compound represented by the following structural formula (7), an epoxy compound represented by the following structural formula (8), and an epoxy compound represented by the following structural formula (9): [6]: A cured product, characterized by being obtained by curing the organic-modified silicone resin composition for die bonding according to any one of [1] to [5] above. [7]: An optical semiconductor element, characterized by being die-bonded with the cured product according to [6] above.

[0114] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits 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) (a) a compound having two hydrogen atoms bonded to silicon atoms in one molecule, represented by the following general formula (1), and (b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, the compound 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 not containing an alkenyl group, or an alkoxy group having 1 to 6 carbon atoms; R ２ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms; (B) an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule and no epoxy-containing group bonded to the silicon atom; (C) an organosilicon compound having a hydrogen atom bonded to a silicon atom and an epoxy-containing group bonded to a silicon atom in one molecule; (D) an epoxy compound represented by the following general formula (2), and (In the formula, R ３ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ４ and R ５ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ４ One of the two and R ５ One of the bonds forms -(CH ２ ) ｐ - may form a group represented by R ６ and R ７ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ６ One of the two and R ７ One of the bonds forms -(CH ２ ) ｐ - may form a group represented by R ８ and R ９ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ８ One of the two and R ９ One of the bonds forms -(CH ２ ) ｐ -, i, j and k are 0 or 1, m is an integer of 0 to 5, and p is an integer of 1 to 5. (E) An organo-modified silicone resin composition for die bonding, comprising:

2. The organomodified silicone resin composition for die bonding according to claim 1, wherein the component (A) is a compound represented by the following general formula (3): (In the formula, s represents an integer of 0 to 50.) 3. The organo-modified silicone resin composition for die bonding according to claim 1, characterized in that the component (B) is an organosilicon compound represented by the following general formula (4): (In the formula, R １０ is a divalent group represented by the following formula (5), and t is a number satisfying 0≦t≦10. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.) 4. The organo-modified silicone resin composition for die bonding according to claim 1, characterized in that the component (C) is an organosilicon compound represented by the following general formula (6): (In the formula, R １０ is a divalent group represented by the following formula (5), R １１ are each independently a hydrogen atom or an epoxy-containing group, R １１ At least one of R １１ At least one of the groups is an epoxy-containing group. u is a number satisfying 0≦u≦10. (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.) 5. The organic-modified silicone resin composition for die bonding according to claim 1, characterized in that the component (D) is at least one selected from the group consisting of an epoxy compound represented by the following structural formula (7), an epoxy compound represented by the following structural formula (8), and an epoxy compound represented by the following structural formula (9).

6. A cured product, characterized in that it is obtained by curing an organic modified silicone resin composition for die bonding according to any one of claims 1 to 5.

7. An optical semiconductor element, which is die-bonded with the cured product according to claim 6.

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