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

Abstract

To provide a hardening material having an excellent adhesive force of an LED element and a substrate at a high temperature, a die bonding organic modified silicone resin composition applying the hardening material, and an optical semiconductor element.SOLUTION: A composition contains: a predetermined chemical compound that contains a monovalent hydrocarbon group of the number of substituted or unsubstituted carbon atoms of 1 to 12 excluding an alkenyl group, or an alkoxy group of the number of carbon atoms of 1 to 6 and a divalent hydrocarbon group of the number of substituted or unsubstituted carbon atoms of 1 to 12; a chemical compound that is an additional reaction product of a polycyclic hydrocarbon containing two additional reaction carbon-carbon double couplings in a molecule, and contains two of additional reaction carbon-carbon double couplings in a molecule; an organic silicon chemical compound that contains two or more hydrogen atoms coupled to a silicon atom in a molecule and does not contain an epoxy containing group coupled to the silicon atom; and an organic silicon chemical compound and an epoxy chemical compound, having the hydrogen atom coupled to the silicon atom in a molecule and an epoxy containing group coupled to the silicon atom, and a platinum group metal system catalyst.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Silicone resins and organically modified silicone resins are mainly used as die bonding materials for light-emitting diode (LED) elements (Patent Documents 1-3). However, in recent years, with the advent of blue LED elements and the miniaturization of LED elements, conventional silicone-based die bonding materials have a problem in that the adhesive strength between the LED element and the substrate is insufficient 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, a die bond material with a high glass transition temperature (Tg) and high thermal strength is required. However, conventional organic modified silicone die bond materials have a Tg in the range of room temperature to 50°C, which is insufficient. Therefore, there was a need for a die bond material with a higher glass transition temperature and excellent adhesion between LED elements and substrates, including 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 incorporating a polyfunctional alkenyl group-containing polysiloxane. However, with the miniaturization of LED elements, further improvements in adhesive strength and thermal die shear strength are required. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2006-342200 [Patent Document 2] Japanese Patent Publication No. 2011-086844 [Patent Document 3] Japanese Patent Publication No. 2015-140372 [Patent Document 4] Japanese Patent Publication No. 2020-136281 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention has been made in view of the above circumstances, and aims to provide a cured product that exhibits 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. [Means for solving the problem]

[0007] To solve the above problems, the present invention provides an organically modified silicone resin composition for die bonding, (A)(a) A compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule, and (b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the compound having two addition-reactive carbon-carbon double bonds in one molecule, [ka] (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 alkenyl group, or an alkoxy group having 1 to 6 carbon atoms, and R 2 (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.) (B) An organosilicon compound having two or more hydrogen atoms bonded to a silicon atom in one molecule, and not having an epoxy-containing group bonded to a 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) Epoxy compounds represented by the following general formula (2), and [ka] (In the formula, R 3is 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, and one of R 4 and one of R 5 may combine to form a group represented by -(CH2) p -, R 6 and R 7 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and one of R 6 and one of R 7 may combine to form a group represented by -(CH2) p -, R 8 and R 9 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and one of R 8 and one of R 9 may combine to form a group represented by -(CH2) p (where i, j, 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-based catalyst To provide an organically modified silicone resin composition for die bonding containing the same.

[0008] The organically modified silicone resin composition for die bonding of the present invention is high-strength at high temperatures and can provide a cured product having excellent adhesion between an LED element and a substrate.

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

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

[0011] Furthermore, it is preferable that component (B) is an organosilicon compound represented by the following general formula (4). [ka] (In the formula, R 10 (5) is a divalent base represented by the following equation, where t is a number satisfying 0 ≤ t ≤ 10. [ka] (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

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

[0013] Furthermore, it is preferable that the (C) component is an organosilicon compound represented by the following general formula (6). [ka] (In the formula, R 10 R is a divalent group represented by the following formula (5), 11 Each is independently a hydrogen atom or an epoxy-containing group, and R 11 One or more of them are hydrogen atoms, and R 11 One or more of these are epoxy-containing groups. (u is a number satisfying 0 ≤ u ≤ 10.) [ka] (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

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

[0015] Furthermore, it is preferable that component (D) is one or more selected from the epoxy compound represented by the following structural formula (7), the epoxy compound represented by the following structural formula (8), and the epoxy compound represented by the following structural formula (9). [ka] [ka] [ka]

[0016] If component (D) is the specific compound described above, the effects of the present invention are more likely to be achieved.

[0017] Furthermore, the present invention provides a cured product which is obtained by curing the organically modified silicone resin composition for die bonding described above.

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

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

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

[0021] The organically modified silicone resin composition for die bonding of the present invention can provide a cured product with high hardness and excellent adhesion between the LED element and the substrate at high temperatures. Therefore, the cured product obtained from such an organically modified silicone resin composition is particularly useful as a die bonding material used for die bonding of small LED elements and the like. [Brief explanation of the drawing]

[0022] [Figure 1] This figure shows test pieces for adhesion testing prepared using the compositions obtained in the examples and comparative examples. [Modes for carrying out the invention]

[0023] As described above, there was a need for the development of a cured product with excellent adhesion between LED elements and substrates at high temperatures, an organically modified silicone resin composition for die bonding that can produce such a cured product, and an optoelectronic semiconductor device.

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

[0025] In other words, the present invention is an organically modified silicone resin composition for die bonding, (A)(a) A compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule, and (b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the compound having two addition-reactive carbon-carbon double bonds in one molecule, [ka] (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 alkenyl group, or an alkoxy group having 1 to 6 carbon atoms, and R 2 (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.) (B) An organosilicon compound having two or more hydrogen atoms bonded to a silicon atom in one molecule, and not having an epoxy-containing group bonded to a 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) Epoxy compounds represented by the following general formula (2), and [ka] (In the formula, R 3 R is independently a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. 4 and R 5 R is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 4 One of them and R 5 It combines with one of them to form -(CH2) p - may form a group represented by R 6 and R 7 R is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 6 One of them and R 7 It combines with one of them to form -(CH2) p - may form a group represented by R 8 and R 9 R is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 8 One of them and R 9 It combines with one of them to form -(CH2) p The base may be represented by -, where i, j, and k are 0 or 1, m is an integer from 0 to 5, and p is an integer from 1 to 5. (E) Platinum group metal catalyst This is an organically modified silicone resin composition for die bonding that contains [the specified ingredient].

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

[0027] [Organic modified silicone resin composition for die bonding] The organically 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] <(A) component> Component (A) in the organically modified silicone resin composition of the present invention is an addition reaction product of (a) a compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule, 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. [ka] (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 alkenyl group, or an alkoxy group having 1 to 6 carbon atoms, and R 2 (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.)

[0029] 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.

[0030] Furthermore, specific examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, and cyclohexyloxy groups.

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

[0032] On the other hand, R 2 Specific 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 methylenephenylmethylene.

[0033] Among these, arylene groups with 6 to 12 carbon atoms are preferred, and phenylene groups are more preferred.

[0034] (a) The components include all R in general formula (1) 1 is a methyl group, R 2 A phenylene group is particularly preferred. Specific examples of such component (a) include, for example, 1,4-bis(dimethylsilyl)benzene and 1,3-bis(dimethylsilyl)benzene.

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

[0036] 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 backbone of the polycyclic hydrocarbon; (ii) those in which a hydrogen atom bonded to a carbon atom forming the backbone of the polycyclic hydrocarbon is substituted by an addition-reactive carbon-carbon double bond-containing group; and (iii) those in which an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the backbone of the polycyclic hydrocarbon, and a hydrogen atom bonded to a carbon atom forming the backbone of the polycyclic hydrocarbon is substituted by an addition-reactive carbon-carbon double bond-containing group.

[0037] Specific examples of component (b) above include 5-vinylbicyclo[2.2.1]hepto-2-ene and 6-vinylbicyclo[2.2.1]hepto-2-ene, which are represented by the following formulas and can also be used as a mixture (hereinafter, when it is not necessary to distinguish between them, they may be collectively referred to as "vinylnorbornene"). [ka]

[0038] 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.

[0039] The addition reaction product of component (A) can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2005-133073.

[0040] 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.

[0041] 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 catalysts and rhodium-based catalysts. Furthermore, the addition reaction conditions and the use of solvents are not particularly limited and should be as known.

[0042] 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.

[0043] 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.

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

[0045] (A) Component may be used alone or in combination of two or more components.

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

[0047] Component (B) is not particularly limited as long as it is an organosilicon compound having two or more hydrogen atoms bonded to a silicon atom in one molecule and not having an epoxy-containing group bonded to a silicon atom, and examples include organohydrogensilanes and organohydrogenpolysiloxanes, but organohydrogenpolysiloxanes are preferred. There are no particular restrictions on the molecular structure of the organohydrogenpolysiloxane, and for example, linear, cyclic, and branched structures can be used.

[0048] (B) The organic group bonded to silicon 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, or groups in which the hydrogen atoms of these groups are substituted with halogen atoms. Particularly preferred are methyl groups, ethyl groups, or phenyl groups.

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

[0050] The number of silicon atoms in one 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 the viscosity at 25°C measured by a rotational viscometer is preferably 100 to 10,000 mPa·s, more preferably 100 to 3,000 mPa·s.

[0051] (B) Component is SiO that does not contain SiH groups. 1 / 2 Unit (in M units), SiO 2 / 2 Unit (D units), SiO 3 / 2 Unit (T units) and / or SiO 4 / 2 It may include units (Q units).

[0052] As the organosilicon compound of component (B), for example, an organohydrogenpolysiloxane represented by the following average composition formula (10) can be used. R 12 c H d SiO (4-c-d) / 2 (10) (In the formula, R 12(where c is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, and c and d are numbers satisfying 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 equation (10), R 12 Examples include monovalent hydrocarbon groups similar to those listed in component (A) above.

[0054] Furthermore, in the present invention, it is preferable that component (B) is an organosilicon compound represented by the following general formula (4), having a hydrogen atom bonded to a silicon atom as a cyclic structure and joined by a divalent organic group. The compound represented by the following general formula (4) can be obtained, for example, by a hydrosilylation reaction between 2,4,6,8-tetramethyltetracyclosiloxane and vinylnorbornene. [ka] (In the formula, R 10 (5) is a divalent base represented by the following equation, where t is a number satisfying 0 ≤ t ≤ 10. [ka] (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

[0055] Such compounds have high compatibility with component (A), improving transparency, and also suppress the separation of each component when the die bond material is applied to the LED substrate by a die bonder.

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

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

[0058] <(C) component> Component (C) is 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. Examples of epoxy-containing groups include epoxy groups, glycidyl groups, glycidyloxy groups, 3-glycidyloxypropyl groups, 3,4-epoxycyclohexyl groups, 3,4-epoxycyclohexylmethyl groups, 2-(3,4-epoxycyclohexyl)ethyl groups, 3,4-epoxycyclohexylmethyloxy groups, and oxetanyl groups.

[0059] Component (C) has hydrogen atoms bonded to silicon atoms, enabling hydrosilylation with the addition-reactive carbon-carbon double bond of component (A). Furthermore, because it has epoxy-containing groups bonded to silicon atoms, it reacts with the epoxy compound of component (D), described later. This immobilizes component (D) in the resin, resulting in a cured product with high adhesive strength and die-shear strength. On the other hand, if it does not have hydrogen atoms bonded to silicon atoms, crosslinking with component (A) does not occur, so component (C) is not incorporated into the resin, resulting in insufficient adhesive strength and die-shear strength of the cured product. Also, if it does not have epoxy-containing groups bonded to silicon atoms, 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 hydrogen atoms bonded to a silicon atom in one molecule, and preferably has one or more epoxy-containing groups bonded to a silicon atom in one molecule.

[0061] Furthermore, in the present invention, it is preferable that component (C) is 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 hydrosilylation reaction of a portion of the hydrogen atoms bonded to the silicon atoms of the organosilicon compound represented by the general formula (4) exemplified in component (B) above with a compound having an epoxy-containing group and an alkenyl group, such as allyl glycidyl ether or 1,2-epoxy-4-vinylcyclohexane. [ka] (In the formula, R 10 R is a divalent group represented by the above formula (5), 11 Each is independently a hydrogen atom or an epoxy-containing group, and R 11 One or more of them are hydrogen atoms, and R 11 One or more of these are epoxy-containing groups. (u is a number satisfying 0 ≤ u ≤ 10.)

[0062] Such compounds have high compatibility with component (A), improving transparency, and also suppress the separation of each component when the die bond material is applied to the LED substrate by a die bonder.

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

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

[0065] <(D) component> Component (D) is an epoxy compound represented by the following general formula (2), and is a component that improves adhesion to the substrate. Component (D) reacts with the epoxy-containing group in component (C) and is immobilized on the resin via component (C), thereby obtaining a cured product with high adhesive strength and die shear strength. [ka] (In the formula, R 3 R is independently a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. 4 and R 5 R is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 4 One of them and R 5 It combines with one of them to form -(CH2) p - may form a group represented by R 6 and R 7 R is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 6 One of them and R 7 It combines with one of them to form -(CH2) p - may form a group represented by R 8 and R 9 R is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 8 One of them and R 9 It combines with one of them to form -(CH2) p The base may be represented by -, where i, j, and k are 0 or 1, m is an integer from 0 to 5, and p is an integer from 1 to 5.

[0066] Furthermore, in the present invention, it is preferable that component (D) is one or more selected from the epoxy compound represented by the following structural formula (7), the epoxy compound represented by the following structural formula (8), and the epoxy compound represented by the following structural formula (9). [ka] [ka] [ka]

[0067] (D) Component may be used alone or in combination of two or more.

[0068] The amount of component (D) is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, relative to 100 parts by mass of the total of components (A) to (C), from the viewpoint of adhesive strength and compatibility.

[0069] <(E) component> The platinum group metal catalyst of component (E) 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 atoms bonded to the silicon atoms of components (B) and (C). 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.

[0070] (E) Component may be used alone or in combination of two or more.

[0071] The amount of component (E) 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, when calculated by mass of platinum group metal elements 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 organically 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] <(F) component> 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.

[0074] The degree of curing inhibition by the reaction inhibitor varies depending on the chemical structure of the reaction inhibitor; therefore, it is desirable to adjust the amount of reaction inhibitor used to the optimal amount for each reaction inhibitor. 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 parts by mass or more, sufficient long-term storage stability of the composition at room temperature can be obtained. If the amount is 5 parts by mass or less, the curing of the composition will not be inhibited.

[0075] <(G) component> The organic modified silicone resin composition for die bonding of the present invention may contain, in order to improve reinforcing properties, inorganic fillers such as fine silica powder, crystalline silica, hollow fillers, and silsesquioxane as component (G), and fillers obtained by surface hydrophobizing these fillers with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds; silicone rubber powder, silicone resin powder, etc.

[0076] (G) Component is preferably silica nanoparticles, and as silica nanoparticles, for example, those obtained by reacting hydrophobic silica nanoparticles with silanol groups present on the surface with a surface modifier may be used. Examples of surface modifiers include alkylsilane compounds, and specific examples include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

[0077] A suitable example of silica nanoparticles, due to its availability, is fumed silica. Fumed silica is produced by oxidizing and hydrolyzing SiCl4 gas with a flame at 1,100-1,400°C, which is produced by burning a mixture of H2 and O2 gases. The primary particles of fumed silica are spherical ultrafine particles mainly composed of amorphous silicon dioxide (SiO2) with an average particle size of about 5-50 nm. These primary particles aggregate to form secondary particles with a particle size of several hundred nm. Because fumed silica is made of ultrafine particles and is produced by rapid cooling, its surface structure is in a chemically active state.

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

[0079] The 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 with appropriate viscosity and thixotropy is obtained, resulting in good transferability when used as a die bond material.

[0080] <Other ingredients> Depending on the purpose, the organically modified silicone resin composition for die bonding of the present invention may contain components such as antioxidants, adhesion improvers, and acid / base generators.

[0081] 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 total amount of components (A), (B), (C), and (D).

[0082] As an adhesion enhancer, from the viewpoint of imparting self-adhesion to the organic modified silicone resin composition for die bonding of the present invention, which is an addition reaction curing type, organosilicon compounds such as silanes and siloxanes, non-silicone organic compounds, etc., containing functional groups that impart adhesion are used.

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

[0084] 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.

[0085] Examples of non-silicone organic compounds include allyl organic acid esters, organotitanium compounds, organozirconium compounds, and organoaluminum compounds.

[0086] 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 / base generating agent is an additive that is activated by heat or light and can be added in any amount.

[0087] Examples of acid-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.

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

[0089] The organic modified silicone resin composition for die bonding of the present invention can be cured under known conditions, for example, by heating at 100-200°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 150-200°C for 30 minutes to 5 hours.

[0090] 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.

[0091] [Optical semiconductor device] Furthermore, the present invention provides an optical semiconductor element which 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 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 can be die-bonded with a highly reliable cured product of the organic modified silicone resin composition for die bonding of the present invention. [Examples]

[0093] 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.

[0094] [Synthesis Example 1] In a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, 70.7 g of an organosilicon compound represented by t=2 in the following general formula (4), 75.6 g of toluene, 24.3 g of isopropanol, and 0.05 g of acetonitrile were added and stirred. Then, 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 reacted 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. The mixture was then 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 product was a colorless, transparent liquid with a pressure of 5.1 Pa·s, and in the following general formula (6), u=2, R 11Of the total number, 75% were organosilicon compounds represented by a 3-glycidyloxypropyl group and 25% by hydrogen atoms (SiH content 0.00115 mol / g). [ka] (In the formula, R 10 (This is a divalent group represented by the following formula (5), where t is 2.) [ka] (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) [ka] (In the formula, R 10 R is a divalent group represented by the above formula (5), 11 As stated above, u is 2.

[0095] [Synthesis Example 2] In Synthesis Example 1, organosilicon compound (C-2) was synthesized using the same method 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 (Celoxide 2000, manufactured by Daicel Corporation). The resulting product was a colorless, transparent liquid with a pH of 29 Pa·s, and in the above general formula (6), u=2, R 11 Of the total number, 81% were organosilicon compounds represented by 2-(3,4-epoxycyclohexyl)ethyl groups and 19% by hydrogen atoms (SiH content 0.00082 mol / g).

[0096] [Comparative Synthesis Example 1] In 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 (Celoxide 2000, manufactured by Daicel Corporation). The resulting product was a colorless, transparent liquid with a viscosity of 13.4 Pa·s, and in the above general formula (6), u=2, R 11Of the total number, 50% were organosilicon compounds represented by a 3-glycidyloxypropyl group and 50% by a 2-(3,4-epoxycyclohexyl)ethyl group (SiH content 0 mol / g).

[0097] [Examples 1-4, Comparative Examples 1-3] An organic modified silicone resin composition for die bonding was prepared by mixing the following components in the proportions shown in Table 1. Since components (D-2) and (D-3) are solids, they were mixed and dissolved with component (D-1) before use. 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 in component (B) and component (C) to one addition-reactive carbon-carbon double bond in component (A).

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

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

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

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

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

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

[0104] [Table 1]

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

[0106] [Hardness of hardened material] The composition was poured into a mold and heated at 150°C for 4 hours to cure. The hardness of the 2 mm thick plate-shaped molded product was measured using a Shore D hardness tester in accordance with JIS K 6253.

[0107] [Adhesive strength] A test piece for adhesion testing was prepared as shown in Figure 1. Specifically, the obtained organic modified silicone resin composition for die bonding was sandwiched between two aluminum substrates 11 and 12 (manufactured by KDS Co., Ltd., 25 mm wide x 50 mm deep x 1 mm thick) with their edges overlapping by 10 mm, using a Teflon® spacer to create an 80 μm thickness. The organic modified silicone resin composition for die bonding was cured by heating at 150°C for 4 hours, and the cured organic modified silicone resin composition 13 bonded together (bonding area 25 mm x 5 mm = 125 mm). 2 A test piece was fabricated consisting of two aluminum substrates.

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

[0109] [Die share 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 mil) was then mounted on top and heated at 200°C for 1 hour. After curing, die shear strength was measured at 25°C and 150°C using a bond tester (Dage, Series 4000).

[0110] [Table 2]

[0111] As shown in Table 2 above, in Examples 1 to 4 using the organically modified silicone resin composition for die bonding of the present invention, it was confirmed that the cured products all exhibited excellent 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 component (D) of the present invention, showed inferior adhesive strength and die shear strength. Furthermore, in Comparative Example 2, which did not contain component (C) of the present invention, and in Comparative Example 3, in which component (C) of the present invention was changed to one that does not have a Si-H group in its molecule, component (D) was not immobilized in the resin, resulting in significantly inferior adhesive strength and die shear strength.

[0113] This specification includes the following embodiments: [1]: Organic modified silicone resin composition for die bonding, (A)(a) A compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule, and (b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the compound having two addition-reactive carbon-carbon double bonds in one molecule, [ka] (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 alkenyl group, or an alkoxy group having 1 to 6 carbon atoms, and R 2 (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.) (B) An organosilicon compound having two or more hydrogen atoms bonded to a silicon atom in one molecule, and not having an epoxy-containing group bonded to a 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) Epoxy compounds represented by the following general formula (2), and [ka] (In the formula, R 3 is 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, one of R 4 and one of R 5 may be bonded to form a group represented by -(CH2) p (CH2) 6 and R 7 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, one of R 6 and one of R 7 may be bonded to form a group represented by -(CH2) p (CH2) 8 and R 9 are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, one of R 8 and one of R 9 may be bonded to form a group represented by -(CH2) p (CH2) (E) A platinum group metal-based catalyst is contained, and the organic modified silicone resin composition for die bonding is characterized in that it contains a platinum group metal-based catalyst. [2]: The organic modified silicone resin composition for die bonding according to [1] above, wherein the component (A) is a compound represented by the following general formula (3). [Chemical formula] (In the formula, s represents an integer of 0 to 50.) [3]: The organic modified silicone resin composition for die bonding according to [1] or [2] above, wherein the component (B) is an organosilicon compound represented by the following general formula (4). [Chemical formula] (In the formula, R 10 is a divalent group represented by the following formula (5), and t is a number satisfying 0 ≤ t ≤ 10.) [ka] (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 the above [1] to [3], characterized in that the (C) component is an organosilicon compound represented by the following general formula (6). [ka] (In the formula, R 10 R is a divalent group represented by the following formula (5), 11 Each is independently a hydrogen atom or an epoxy-containing group, and R 11 One or more of them are hydrogen atoms, and R 11 One or more of these are epoxy-containing groups. (u is a number satisfying 0 ≤ u ≤ 10.) [ka] (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.) [5]: An organic modified silicone resin composition for die bonding according to any one of the above [1] to [4], characterized in that the (D) component is one or more selected from the epoxy compound represented by the following structural formula (7), the epoxy compound represented by the following structural formula (8), and the epoxy compound represented by the following structural formula (9). [ka] [ka] [ka] [6]: A cured product characterized by being obtained by curing any one of the organic modified silicone resin compositions for die bonding described in [1] to [5] above. [7]: An optoelectronic semiconductor device characterized in that it is die-bonded with the cured product of [6] above.

[0114] 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. [Explanation of Symbols]

[0115] 11…Aluminum substrate, 12…Aluminum substrate, 13…Cured product.

Claims

1. A composition of organically modified silicone resin for die bonding, (A) (a) A compound having two hydrogen atoms bonded to a silicon atom represented by the following general formula (1) in one molecule, and (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, wherein the compound has two addition-reactive carbon-carbon double bonds in one molecule. 【Chemistry 1】 (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 alkenyl group, or an alkoxy group having 1 to 6 carbon atoms, R ２ (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.) (B) Organosilicon compounds having two or more hydrogen atoms bonded to a silicon atom in one molecule, and not having epoxy-containing groups bonded to a 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) Epoxy compounds represented by the following general formula (2), and 【Chemistry 2】 (wherein, R ３ is 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, and one of R ４ and one of R ５ may combine to form a group represented by -(CH ２ ) ｐ -, R ６ and R ７ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and one of R ６ and one of R ７ may combine to form a group represented by -(CH ２ ) ｐ -, R ８ and R ９ are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and one of R ８ and one of R ９ may combine to form a group represented by -(CH ２ ) ｐ -, i, j, k are 0 or 1, m is an integer of 0 to 5, and p is an integer of 1 to 5.) (E) Platinum group metal catalyst An organically modified silicone resin composition for die bonding, characterized by containing [a specific compound / substance].

2. The organic modified silicone resin composition for die bonding according to claim 1, characterized in that the aforementioned component (A) is a compound represented by the following general formula (3). 【Transformation 3】 (In the formula, s represents an integer between 0 and 50.)

3. The organic modified silicone resin composition for die bonding according to claim 1, characterized in that the (B) component is an organosilicon compound represented by the following general formula (4). 【Chemistry 4】 (In the formula, R １０ (This is a divalent base represented by the following formula (5), where t is a number satisfying 0 ≤ t ≤ 10.) 【Transformation 5】 (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 (C) component is an organosilicon compound represented by the following general formula (6). 【Transformation 6】 (In the formula, R １０ R is a divalent group represented by the following formula (5), １１ Each is independently a hydrogen atom or an epoxy-containing group, R １１ One or more of them are hydrogen atoms, and R １１ One or more of these are epoxy-containing groups. (u is a number satisfying 0 ≤ u ≤ 10.) 【Transformation 7】 (In the formula, an asterisk (*) represents a bond with an adjacent silicon atom.)

5. The organic modified silicone resin composition for die bonding according to claim 1, characterized in that the (D) component is one or more selected from the epoxy compound represented by the following structural formula (7), the epoxy compound represented by the following structural formula (8), and the epoxy compound represented by the following structural formula (9). 【Transformation 8】 【Chemistry 9】 【Chemistry 10】

6. 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 5.

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

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