Die bonding organic modified silicone resin composition, hardening material of them, and optical semiconductor element

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 optical 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 to 3). However, in recent years, with the emergence of blue LED elements and the miniaturization of LED elements, there is a problem that the adhesive strength between the LED element and the substrate at high temperatures during wire bonding with conventional silicone-based die-bonding materials is insufficient, 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 heat are required, but conventional organic modified silicone die bond materials are not sufficient because their Tg exists in the range from room temperature to 50°C. Therefore, there was a need 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, as LED elements become smaller, there is a need for further improvements in adhesive strength and hot die shear strength. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2006-342200 A [Patent Document 2] JP 2011-086844 A [Patent Document 3] JP 2015-140372 A [Patent Document 4] JP 2020-136281 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in consideration of the above circumstances, and has an 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. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention provides an organic 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, and the compound having two addition reactive carbon-carbon double bonds in one molecule: [ka] (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 having no 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 the following general formula (2), and [ka] (In the formula, R 3are 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 R 4 One of the two and R 5 One of the bonds forms -(CH2) p -, and 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 two and R 7 One of the bonds forms -(CH2) p -, and 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 two and R 9 One of the bonds forms -(CH2) 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) Platinum group metal catalyst The present invention provides an organic modified silicone resin composition for die bonding, which comprises:

[0008] The organic modified silicone resin composition for die bonding of the present invention has high strength at high temperatures and can give a cured product that has 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). [ka] (In the formula, s represents an integer of 0 to 50.)

[0010] When the component (A) is the above 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). [ka] (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 to an adjacent silicon atom.)

[0012] When component (B) is the above-mentioned specific compound, the compatibility with component (A) is enhanced, 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). [ka] (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, 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. [ka] (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.)

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

[0015] 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). [ka] [ka] [ka]

[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] The present invention further provides an optical semiconductor element which 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. Effect of the Invention

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

[0022] [Figure 1] FIG. 2 is a diagram of test pieces for adhesion tests prepared using the compositions obtained in the Examples and Comparative Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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 organic 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, and the compound having two addition reactive carbon-carbon double bonds in one molecule: [ka] (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 having no 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 the following general formula (2), and [ka] (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, and R 4 One of the two and R 5 One of the bonds forms -(CH2) p -, and 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 two and R 7 One of the bonds forms -(CH2) p -, and 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 two and R 9 One of the bonds forms -(CH2) 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) Platinum group metal catalyst The present invention relates to an organic modified silicone resin composition for die bonding, which comprises

[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 organic modified silicone resin composition for die bonding of the present invention comprises the following components (A) to (E), each of which will be described in detail below.

[0028] <Component (A)> The 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 silicon 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, and is also an addition reaction product having two addition-reactive carbon-carbon double bonds per molecule. [ka] (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.

[0029] R 1 Specific 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 alkoxy groups 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 preferable, and a methyl group is more preferable.

[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 preferable, and a phenylene group is more preferable.

[0034] As the component (a), all of R in the general formula (1) 1 is a methyl group, and R 2 It is particularly preferable that the (a) component is a phenylene group. Specific examples of the (a) component include 1,4-bis(dimethylsilyl)benzene, 1,3-bis(dimethylsilyl)benzene, and the like.

[0035] The component (a) may use either a single type alone or a combination of two or more types.

[0036] In addition, 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 above 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"). [ka]

[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). In addition, since there is no particular difference in the reactivity of the compound depending on the difference in these configurations, a combination of isomers of both configurations may be used.

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

[0040] As an example, it can be prepared by adding more than 1 mole and not more than 10 moles, and 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 catalysts can be used, and specific examples thereof include platinum-based catalysts such as carbon powder carrying platinum metal, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, and other platinum group metal 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 may be as known in the art.

[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, and 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 an addition reaction product containing a polycyclic hydrocarbon and a phenylene group is particularly suitable for use because it gives a cured product with excellent hardness and strength.

[0044] [ka] (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 use either a single type alone, or two or more types in combination.

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

[0047] The (B) component is not particularly limited as long as it is an organosilicon compound having two or more hydrogen atoms bonded to silicon atoms in one molecule and not having an epoxy-containing group bonded to a silicon atom, and includes organohydrogensilanes, organohydrogenpolysiloxanes, etc., and is preferably organohydrogenpolysiloxane. There is no particular limit to the molecular structure of the organohydrogenpolysiloxane, and for example, linear, cyclic, and branched ones can be used.

[0048] 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 a substituted or unsubstituted monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or groups in which the hydrogen atoms of these groups are substituted with halogen atoms, and particularly preferred are a methyl group, an ethyl group, or a phenyl group.

[0049] Component (B) has at least 2 hydrogen atoms bonded to silicon 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.

[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 its viscosity at 25°C measured with a rotational viscometer is preferably 100 to 10,000 mPa s, and more preferably 100 to 3,000 mPa s.

[0051] Component (B) is SiO that does not contain a SiH group. 1 / 2 Unit (M unit), SiO 2 / 2 Unit (D unit), 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). R 12 c H d SiO (4-c-d) / 2 (10) (In the formula, R 12is a substituted or unsubstituted monovalent hydrocarbon group not containing 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 formula (10), R 12 Examples of the monovalent hydrocarbon groups include the same monovalent hydrocarbon groups as those exemplified for component (A) above.

[0054] In the present invention, the component (B) is preferably an organosilicon compound represented by the following general formula (4), which has hydrogen atoms bonded to silicon atoms as rings and is joined by divalent organic groups. The compound represented by the following general formula (4) can be obtained, for example, by the hydrosilylation reaction of 2,4,6,8-tetramethyltetracyclosiloxane and vinylnorbornene. [ka] (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 to an adjacent silicon atom.)

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

[0056] The component (B) may use either a single compound, or a combination of two or more different compounds.

[0057] The amount of component (B) 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 the 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] <(C) component> Component (C) is 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. 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] Since component (C) has a hydrogen atom bonded to a silicon atom, it can undergo a hydrosilylation reaction with the addition reactive carbon-carbon double bond of component (A), and since it has an epoxy-containing group bonded to a silicon atom, it also reacts with the epoxy compound of component (D) described below, so that component (D) is fixed in the resin, and a cured product having high adhesive strength and die shear strength is obtained. On the other hand, if component (C) does not have a hydrogen atom bonded to a silicon atom, a crosslinking reaction with component (A) does not occur, so component (C) is not incorporated into the resin, and the adhesive strength and die shear strength of the cured product are insufficient. Also, if component (C) does not have an epoxy-containing group bonded to a silicon atom, it does not react with component (D), so the adhesive strength and die shear strength of the cured product are insufficient.

[0060] Component (C) preferably has one or more hydrogen atoms bonded to silicon atoms per molecule, and preferably has one or more epoxy-containing groups bonded to silicon atoms 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 the silicon atoms of the organosilicon compound represented by the above general formula (4) 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. [ka] (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, 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.

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

[0063] The component (C) may use either a single compound, or a combination of two or more different compounds.

[0064] The amount of component (C) 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, more preferably 0.7 to 3.0. If this range is satisfied, high strength can be imparted to the resulting cured product.

[0065] <(D) component> Component (D) is an epoxy compound represented by the following general formula (2), which 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. [ka] (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, and R 4 One of the two and R 5 One of the bonds forms -(CH2) p -, and 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 two and R 7 One of the bonds forms -(CH2) p -, and 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 two and R 9 One of the bonds forms -(CH2) 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). [ka] [ka] [ka]

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

[0068] From the standpoint 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 components (A) to (C) combined.

[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 bonds 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, rhodium, etc.; 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, with platinum compounds being preferred, and coordination compounds of chloroplatinic acid with vinylsiloxane being particularly preferred.

[0070] The component (E) may use either a single compound, or a combination of two or more different 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, 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). If the amount is in this range, the reaction rate of the addition reaction becomes appropriate, and a cured product having high strength can be obtained.

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

[0073] <(F) Component> In order to adjust the curing property, a reaction inhibitor may be added as component (F) to the organic modified silicone resin composition for die bonding of the present invention. Examples of reaction inhibitors include phosphorus-containing compounds such as triphenylphosphine, nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, sulfur-containing compounds, acetylene-based compounds, hydroperoxy compounds, maleic acid derivatives, and known compounds that have a curing inhibitory effect against the platinum group metal catalyst of component (E) such as 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyne-3-ol, ethynylmethyldecylcarbinol, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

[0074] Since the degree of the 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. The amount is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of the (A), (B), and (C) components. 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] <(G) component> In order to improve the reinforcing properties, the organic 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, as well as fillers obtained by subjecting the surfaces of these fillers to hydrophobic treatment with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds; silicone rubber powder, silicone resin powder, and the like.

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

[0077] A suitable example of silica fine particles is fumed silica, which is easily available. Fumed silica is produced by oxidizing and hydrolyzing SiCl4 gas in a flame of 1,100 to 1,400°C obtained by burning a mixed gas of H2 and O2. 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 to 50 nm, and these primary particles aggregate to form secondary particles with a particle size of several hundred nm. Fumed silica is an ultrafine particle and is produced by rapid cooling, so that the surface structure is chemically active.

[0078] Specifically, for example, "Aerosil" (registered trademark) manufactured by Nippon Aerosil Co., Ltd. can be mentioned, and 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". In addition, examples of "Reolosil" (registered trademark) manufactured by Tokuyama Corporation include "DM-10", "DM-20", and "DM-30S".

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

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

[0081] The antioxidant may be, for example, a hindered amine or a hindered phenol compound, and there is no restriction on its structure. The amount of the 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, a non-silicone organic compound, or the like 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, and other alkoxysilyl groups 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 a functional group that imparts 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] An acid or base generator may be added to the organic modified silicone resin composition for die bonding of the present invention in order 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 generator) manufactured by Kusumoto Chemicals Co., Ltd., 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 organic 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 Shore D hardness of the cured product may be 60 or more, and the composition of the present invention may be usually cured by heating the composition at 150 to 200° C. for 30 minutes to 5 hours.

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

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

[0092] An example of a method for die-bonding an optical semiconductor element using the cured product of the present invention is a method in which the composition of the present invention is filled into a syringe, and applied to a substrate such as a package using a dispenser to a thickness of 5 to 100 μm in a dry state, and then an optical semiconductor element (e.g., a light-emitting diode) is placed on the applied composition, and the composition is cured to die-bond the optical semiconductor element to the substrate. Alternatively, the composition may be placed on a squeegee plate, and applied to a substrate by stamping while squeezing to a thickness of 5 to 100 μm in a dry state, and then an optical semiconductor element is placed on the applied composition, and the composition is cured 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 with the cured product of the organic modified silicone resin composition for die bonding of the present invention. EXAMPLES

[0093] EXAMPLES 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-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, while 0.037 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5 mass%) was added. After heating to 70°C, 40.5 g of allyl glycidyl ether was added dropwise and reacted at 70°C for 5 hours. After cooling to 25°C, 0.15 g of activated carbon was added, 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 11Of the total, 75% were organosilicon compounds represented by 3-glycidyloxypropyl groups and 25% were organosilicon compounds represented by hydrogen atoms (SiH content 0.00115 mol / g). [ka] (In the formula, R 10 is a divalent group represented by the following formula (5), and t is 2. [ka] (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.) [ka] (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, Daicel Corporation). The target product obtained was a colorless, transparent liquid with a viscosity of 29 Pa s, and was represented by the general formula (6) above, where u = 2, R 11 Of the total, 81% were organosilicon compounds represented by 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] An 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 obtained target product was a colorless, transparent liquid with a viscosity of 13.4 Pa s, and was represented by the above general formula (6), where u = 2, R 11Of the total number, 50% were organosilicon compounds represented by the 3-glycidyloxypropyl group and 50% were organosilicon compounds represented by the 2-(3,4-epoxycyclohexyl)ethyl group (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 an organically modified silicone resin composition for die bonding. Note that components (D-2) and (D-3) are solids, and therefore 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) in which s=1 (addition reactive carbon-carbon double bond: 0.267 mol / 100 g) [ka] (In the formula, 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) [ka] (In the formula, R 10 is a divalent group represented by the following formula (5), and t is 2. [ka] (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.)

[0100] (C) Component (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] (D) Component (D-1): An 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] Component (E): A 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) Component: Fumed silica (Reolosil DM-30S, manufactured by Tokuyama Corporation)

[0104] [Table 1]

[0105] <Measurement method> The physical properties of the cured products made of the organic 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 cured by heating at 150° C. for 4 hours. 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] [Adhesive strength] A test piece for an adhesion test was prepared as shown in Fig. 1. That is, the obtained organically modified silicone resin composition for die bonding was sandwiched between a spacer made of Teflon (registered trademark) with a thickness of 80 µm so that the ends of two aluminum substrates 11 and 12 (manufactured by KDS Corporation, width 25 mm × depth 50 mm × thickness 1 mm) 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 test piece was bonded (adhesion area 25 mm × 5 mm = 125 mm) by the cured product 13 of the organically modified silicone resin composition for die bonding. 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 (arrow directions in Figure 1) at a tensile speed 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), each composition was transferred by stamping to the silver-plated electrode part of an SMD3020 package (polyphthalamide resin, manufactured by I-CHIUN PRECISION INDUSTRY Co.), and an optical semiconductor element (10×10 mil, manufactured by SemiLED Inc.) was mounted thereon and heated 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 Inc.).

[0110] [Table 2]

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

[0112] On the other hand, in Comparative Example 1, which does not contain the component (D) of the present invention, the adhesive strength and die shear strength were inferior. Furthermore, in Comparative Example 2, which does 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] The present specification includes the following aspects. [1]: An organic 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, and the compound having two addition reactive carbon-carbon double bonds in one molecule: [ka] (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 having no 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 the following general formula (2), and [ka] (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, and R 4 One of the two and R 5 One of the bonds forms -(CH2) p -, and 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 two and R 7 One of the bonds forms -(CH2) p -, and 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 two and R 9 One of the bonds forms -(CH2) 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) Platinum group metal catalyst 1. An organic modified silicone resin composition for die bonding, comprising: [2]: The organic modified silicone resin composition for die bonding according to the above [1], wherein the component (A) is a compound represented by the following general formula (3): [ka] (In the formula, s represents an integer of 0 to 50.) [3]: The organo-modified silicone resin composition for die bonding according to the above [1] or [2], characterized in that the component (B) is an organosilicon compound represented by the following general formula (4): [ka] (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 to an adjacent silicon atom.) [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): [ka] (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, 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. [ka] (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): [ka] [ka] [ka] [6]: A cured product, characterized in that it is obtained by curing any one of the organic-modified silicone resin compositions for die bonding according to [1] to [5] above. [7]: An optical semiconductor element, characterized in that it is die-bonded with the cured product of [6] above.

[0114] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0115] 11...aluminum substrate, 12...aluminum substrate, 13...cured product.

Claims

1. An organic 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, and the compound having two addition reactive carbon-carbon double bonds in one molecule: 【Chemistry 1】 (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 having no 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 the following general formula (2), and 【Chemistry 2】 (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 -, 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) Platinum group metal catalyst 1. An organic modified silicone resin composition for die bonding, comprising:

2. 2. The organic modified silicone resin composition for die bonding according to claim 1, wherein the component (A) is a compound represented by the following general formula (3): 【Chemistry 3】 (In the formula, s represents an integer of 0 to 50.)

3. 2. The organo-modified silicone resin composition for die bonding according to claim 1, wherein the component (B) is an organosilicon compound represented by the following general formula (4): 【Chemistry 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. 【Chemistry 5】 (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.)

4. 2. The organo-modified silicone resin composition for die bonding according to claim 1, wherein the component (C) is an organosilicon compound represented by the following general formula (6): 【Chemistry 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. 【Chemistry 7】 (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): 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】

6. A cured product, which is obtained by curing the 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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