Organic modified silicone composition, cured product thereof, die bond material, and optoelectronic device.

Abstract

The present invention provides a cured product that exhibits excellent adhesion between LED elements and substrates at high temperatures, and an organically modified silicone composition capable of producing such a cured product. [Solution] An organically modified silicone composition comprising (A) an addition reaction product of (i) a specific Si-H group-containing compound and (ii) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and having two or more alkenyl groups bonded to silicon atoms in one molecule, (B) a cyclic methylhydrogensiloxane derivative represented by general formula (2), and (C) a platinum group metal catalyst. TIFF2026131308000040.tif54145

Description

Technical Field

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

Background Art

[0002] Silicone resins and organically modified silicone resins are mainly used as die bonding materials for light-emitting diode (LED) elements (Patent Document 1). However, in recent years, due to the emergence of blue LED elements and the miniaturization and reduction in area of LED elements, when wire bonding is performed using conventional silicone-based die bonding materials, there has been a problem that the adhesive force between the LED element and the substrate at high temperatures is insufficient, resulting in bonding defects.

[0003] In addition, since the wire bonding process of LEDs is performed at high temperatures, there is a particular need for a die bonding material with high heat strength even around 150°C. However, in the organohybrid silicone die bonding material that has already been proposed (Patent Document 2), the glass transition temperature is less than 150°C, so although the adhesive strength at room temperature is excellent, the adhesive strength at high temperatures is not sufficient.

[0004] On the other hand, in Patent Document 3, an organically modified silicone resin composition containing a crosslinkable organopolysiloxane resin has been proposed in order to increase the crosslink density of the resulting cured product and impart high Tg and high strength.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, due to the further miniaturization of LED elements, further improvement in the resin strength and die shear strength at high temperatures has been required.

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a cured product having excellent adhesion between an LED element and a substrate at high temperatures, and an organically modified silicone composition capable of providing the cured product. Another object is to provide a die bonding material comprising the above organically modified silicone composition, and further, an optical semiconductor device provided with the above cured product.

Means for Solving the Problems

[0008] In order to solve the above problems, in the present invention, there is provided an organically modified silicone composition comprising: (A) (i) A compound represented by the following general formula (1), and (ii) an addition reaction product of an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and an addition reaction product having two or more alkenyl groups bonded to silicon atoms in one molecule,

Chemical Formula

Chemical Formula

[0009] The organically modified silicone composition of the present invention can provide a cured product, a die bonding material, and an optoelectronic device element that have high strength at high temperatures and excellent adhesion between the LED element and the substrate.

[0010] The R in the general formula (1) 1 is a methyl group, and it is preferable that the R 2 is a compound that is a phenylene group.

[0011] If the component (i) is the above specific compound, a cured product having particularly excellent hardness and strength can be provided.

[0012] It is preferable that the component (ii) contains one or more compounds selected from the compounds represented by the following general formula (3), the compounds represented by the following general formula (4), and the compounds represented by the following general formula (5).

Chemical formula

Chemical formula

Chemical formula

[0013] The component (ii) preferably contains one or more of the above compounds.

[0014] Furthermore, the R of the compound represented by the general formula (3) 4 However, it is a vinyl group, and the R 5 The R of the compound represented by the general formula (4) or (5) is a methyl group, where a is 3 or 4, and b is 0. 4 However, it is a vinyl group, and the R 5 However, a methyl group is preferred.

[0015] If component (ii) is the specific compound described above, a cured product with particularly excellent hardness and strength can be obtained.

[0016] The R in the general formula (2) 3 However, it is preferable that it be a divalent hydrocarbon group represented by the following formula (6). [ka] (In the equation, lines with a wavy line represent connections.)

[0017] If component (B) is the specific compound described 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.

[0018] Furthermore, the present invention provides a die bond material comprising the organically modified silicone composition described above.

[0019] The die bond material of the present invention can provide a cured product and an optoelectronic device that exhibit high die shear strength at high temperatures and excellent adhesion between optical semiconductor elements such as LED elements and substrates.

[0020] Furthermore, the present invention provides a cured product obtained by curing the organically modified silicone composition described above.

[0021] The cured product of the present invention has high strength and excellent adhesion between the LED element and the substrate at high temperatures.

[0022] Furthermore, the present invention provides an optical semiconductor device comprising the cured material.

[0023] The optical semiconductor device of the present invention is highly reliable because it is equipped with a cured material that has high strength and excellent adhesive strength at high temperatures. [Effects of the Invention]

[0024] As described above, the organic modified silicone composition 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 the organic modified silicone resin composition of the present invention is particularly useful as a die bonding material used for die bonding of small LED elements and the like, and an optoelectronic device can be provided in which an optoelectronic semiconductor element is die-bonded with the above cured product. [Modes for carrying out the invention]

[0025] 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 composition capable of producing such a cured product, a die bond material, and an optoelectronic device.

[0026] As a result of diligent research into the above problems, the inventors of the present invention have found that an organically modified silicone composition containing components (A) to (C) described later can solve the above problems, and have completed the present invention.

[0027] In other words, the present invention is Organically modified silicone composition, (A)(i) an addition reaction product of a compound represented by the following general formula (1) and (ii) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and an addition reaction product having two or more alkenyl groups bonded to silicon atoms in one molecule, [ka] (In the formula, R 1Each of these is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an addition-reactive carbon-carbon double bond, and R 2 (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.) (B) A cyclic methylhydrogensiloxane derivative represented by the following general formula (2), [ka] (In the formula, R 3 (where m is a divalent hydrocarbon group which may independently contain a silicon atom, m is independently 0 or 1, and n is a number satisfying 0 to 5.) (C) An organically modified silicone composition characterized by containing a platinum group metal catalyst.

[0028] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0029] [Organically modified silicone composition] The organically modified silicone composition of the present invention contains the following components (A) to (C). Each component will be described in detail below.

[0030] <(A) component> Component (A) in the organically modified silicone composition of the present invention is an addition reaction product of (i) a compound represented by the following general formula (1) and (ii) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and is an addition reaction product having two or more alkenyl groups bonded to silicon atoms 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 addition-reactive carbon-carbon double bond, and R 2 (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.)

[0031] In the above general formula (1), R 1 Specific examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, cyclopentyl group, and cyclohexyl group; aryl groups having 6 to 12 carbon atoms such as phenyl group and naphthyl group; alkylaryl groups having 7 to 12 carbon atoms such as tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, and hexylphenyl group; and aralkyl groups having 7 to 12 carbon atoms such as benzyl group and phenethyl group.

[0032] Among these, the above R 1 Preferably, the alkyl group has 1 to 8 carbon atoms, and a methyl group is more preferred.

[0033] On the other hand, the above 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 methylenephenylenemethylene.

[0034] Among these, arylene groups with 6 to 12 carbon atoms are preferred, and phenylene groups are more preferred.

[0035] The (i) component of the above general formula (1) is all of the R in general formula (1). 1 is a methyl group, R 2 It is particularly preferable that the (i) group is a phenylene group. Specific examples of such component (i) include, for example, 1,4-bis(dimethylsilyl)benzene and 1,3-bis(dimethylsilyl)benzene.

[0036] Furthermore, component (i) may be used alone or in combination of two or more types.

[0037] The above component (ii) is an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, preferably 2 to 5, more preferably 3 or 4, and may have any of the following structures: linear, branched, cyclic, or three-dimensional network. The above component (ii) preferably contains one or more compounds selected from the compounds represented by the following general formula (3), the compounds represented by the following general formula (4), and the compounds represented by the following general formula (5). [ka] (In the formula, R 4 These are independently alkenyl groups with 2 to 12 carbon atoms, and R 5 (where a is independently a methyl group or a phenyl group, a is an integer between 2 and 5, b is an integer between 0 and 5, a+b is an integer between 2 and 5, and the sequence of siloxane units may be arbitrary.) [ka] (In the formula, R 4 and R 5 This is synonymous with the above. [ka] (In the formula, R 4 and R 5 This is synonymous with the above.

[0038] In the above general formulas (3) to (5), R 4 Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl groups, allyl groups, butenyl groups, hexenyl groups, and octenyl groups, with alkenyl groups having 2 to 6 carbon atoms being preferred, and vinyl groups being more preferred.

[0039] In the above general formula (3), a is an integer between 2 and 5, preferably 3 or 4. b is an integer between 0 and 5, preferably 0. a+b is an integer between 2 and 5, preferably 3 or 4.

[0040] The R of the compound represented by the general formula (3) 4 However, it is a vinyl group, and the R 5 The R of the compound represented by the general formula (4) or (5) is a methyl group, where a is 3 or 4, and b is 0. 4 However, it is a vinyl group, and the R 5 However, a methyl group is preferred.

[0041] Of the above component (ii), organopolysiloxanes represented by the following structural formula are particularly preferred. [ka]

[0042] Furthermore, component (ii) may be used alone or in combination of two or more.

[0043] Component (A) above may contain hydrogen atoms (Si-H groups) bonded to unreacted silicon atoms derived from component (i) above, but it is preferable that all Si-H groups undergo hydrosilylation. That is, an addition reaction product of a k molecule of the organosilicon compound of component (i) above and a k+1 molecule of the organopolysiloxane of component (ii) above is preferred, for example, one represented by the following formula. [ka] [In the equation, k is an integer between 1 and 10, p and q are integers satisfying p+q+(p+2)=k+1, and r, s, and t are integers satisfying r+s+t+(2r+s+2)=k+1. Dashed lines represent connections.]

[0044] The above component (A) can be obtained by mixing component (ii) in excess, preferably more than 1.0 mole and up to 6.0 moles, and more preferably in the range of 1.2 to 4.0 moles, with 1 mole of component (i), and carrying out a hydrosilylation reaction in the presence of both. By using such a range, it is possible to prevent the residue of unreacted component (i), thus eliminating the need for a step to remove component (i), and enabling safer and simpler production.

[0045] As catalysts used in the hydrosilylation reaction, known catalysts can be used. 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; and platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. Furthermore, there are no particular limitations on the addition reaction conditions, purification conditions, and solvent use, and known methods may be used.

[0046] The alkenyl group content of component (A) is preferably 0.1 to 0.7 moles per 100g, and more preferably 0.2 to 0.6 moles.

[0047] The weight-average molecular weight (Mw) of component (A) above, measured by gel permeation chromatography on a standard polystyrene basis, is preferably 500 to 20,000, and more preferably 1,000 to 10,000.

[0048] The viscosity of component (A) at 25°C, as measured by a rotational viscometer, is preferably 10 to 10,000 mPa·s, and more preferably 50 to 5,000 mPa·s. Within this range, the resulting composition tends to have good workability and handling properties, and is less prone to the entrapment of bubbles and air during molding and curing.

[0049] The above component (A) may be used alone or in combination of two or more types.

[0050] <(B) component> In the organically modified silicone composition of the present invention, component (B) is a cyclic methylhydrogensiloxane derivative represented by the following general formula (2), and functions as a crosslinking agent that crosslinks with alkenyl groups bonded to silicon atoms contained in component (A) through a hydrosilylation reaction. [ka] (In the formula, R 3 (where m is a divalent hydrocarbon group which may independently contain a silicon atom, m is independently 0 or 1, and n is a number satisfying 0 to 5.)

[0051] The above R 3 Examples of divalent hydrocarbon groups that may contain silicon atoms include linear, branched, or cyclic alkylene groups such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups; arylene groups such as phenylene groups; aralkylene groups such as phenylenemethylene and methylenephenylenemethylene groups; divalent hydrocarbon groups represented by the following formula (6); and divalent groups represented by the following formula (7). [ka] (In the equation, lines with a wavy line represent connections.) [ka] (In the formula, R 6 Each of these is independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a methyl group or a phenyl group. (The wavy lines indicate bonding.)

[0052] In the above general formula (2), the above R 3 Preferably, this is a divalent hydrocarbon group represented by formula (6) above. In this case, compatibility with component (A) is increased, transparency is improved, and separation of each component can be suppressed when the die bond material is applied to the LED substrate by a die bonder.

[0053] The above value n is a number between 0 and 5, preferably 0 or 1, and more preferably 0.

[0054] Specific examples of component (B) above include, for example, organohydrogenpolysiloxane derivatives represented by the following structural formula. [ka]

[0055] Such organosilicon compounds can be obtained, for example, by a hydrosilylation reaction of 2,4,6,8-tetramethyltetracyclosiloxane with vinylnorbornene or diphenyldivinylsilane.

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

[0057] The amount of component (B) blended is preferably such that the number of hydrogen atoms bonded to silicon atoms in component (B) is 0.5 to 5.0 times the number of alkenyl groups bonded to silicon atoms in component (A), and more preferably 0.7 to 3.0 times the number of moles. Within this range, crosslinking proceeds sufficiently, and a cured product with excellent hardness and strength can be obtained.

[0058] <(C) component> The platinum group metal catalyst of component (C) in the organic modified silicone composition of the present invention is not particularly limited as long as it is a component that promotes the addition reaction between the alkenyl group in component (A) and the hydrogen atom bonded to the silicon atom in component (B). Specific examples include platinum group metals such as platinum, palladium, and rhodium; platinum-based compounds such as chloroplatinic acid, alcohol-modified chloroplatinic acid, and coordination compounds of chloroplatinic acid with olefins, vinylsiloxanes, or acetylene compounds; and platinum group metal compounds such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. However, platinum-based compounds are preferred, and coordination compounds of chloroplatinic acid and vinylsiloxanes are particularly preferred.

[0059] The above component (C) may be used alone or in combination of two or more types.

[0060] The amount of component (C) described above should be an effective amount as a catalyst, but it is preferably in the range of 0.01 to 500 ppm, and more preferably in the range of 0.1 to 50 ppm, when calculated by mass of platinum group metal elements relative to the total amount of components (A) and (B). Within this range, the reaction rate of the addition reaction will be appropriate, and a cured product with high strength can be obtained.

[0061] <(D) component> The organically modified silicone composition of the present invention may include a filler as component (D). Specifically, inorganic fillers such as fumed silica, crystalline silica, hollow fillers, silsesquioxane, and nanoalumina, 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. can be used.

[0062] It is preferable to use a filler that can impart thixotropy to the above-mentioned filler, as imparting thixotropy allows for the production of a cured product with excellent workability and die shear strength. Particularly preferable is a filler with a BET specific surface area of ​​100 to 300 m². 2 This is fumed silica in units of / g. The BET specific surface area is measured using Macsorb® HM Model-1201, manufactured by Mountec Co., Ltd., in accordance with JIS Z 8830:2013.

[0063] Alternatively, silica whose surface has been hydrophobized by reacting the silanol groups present on the surface with a surface modifier may be used. Examples of surface modifiers include alkylsilane compounds, with specific examples including dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

[0064] Specific examples of the above-mentioned fumed silica include, for example, "Aerosil" (registered trademark) manufactured by Nippon Aerosil Co., Ltd. Examples of hydrophilic Aerosil (registered trademark) include "90", "130", "150", "200", and "300", while examples of hydrophobic Aerosil (registered trademark) include "R8200", "R972", "R972V", "R972CF", "R974", "R202", "R805", "R812", "R812S", "RY200", "RY200S", and "RX200". In addition, examples of "Rheoroseal" manufactured by Tokuyama Corporation include "DM-10", "DM-20", and "DM-30S".

[0065] The above component (D) may be used alone or in combination of two or more types.

[0066] The amount of component (D) is preferably 1 to 50 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). Within this range, it is possible to prevent transfer failure due to insufficient thixotropy and deterioration of workability due to increased viscosity when using the organically modified silicone composition of the present invention as a die bond material.

[0067] <(E) component> The organically modified silicone composition of the present invention may contain a reaction control agent as component (E) to adjust the curability. Examples of reaction control agents 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 (C) above, such as 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-dodecine-3-ol, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

[0068] The degree of curing inhibition by the above-mentioned reaction control agent varies depending on the chemical structure of the reaction control agent; therefore, when using a reaction control agent, it is desirable to adjust the amount to the optimal level for each reaction control agent. Preferably, the amount is 0.001 to 10 parts by mass per 100 parts by mass of component (A). If the amount is 0.001 parts by mass or more, sufficient long-term storage stability of the composition at room temperature can be obtained. If the amount is 10 parts by mass or less, the curing of the composition will not be inhibited.

[0069] <(F) component> The organic modified silicone resin composition of the present invention may contain an adhesion improver as component (F) to improve adhesive strength. As the adhesion improver for component (F), organosilicon compounds such as silanes and siloxanes containing functional groups that impart adhesion, non-silicone organic compounds, etc., can be used.

[0070] Specific examples of functional groups that impart adhesiveness include polymerizable groups having carbon-carbon unsaturated bonds bonded to silicon atoms (e.g., vinyl group, allyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group, etc.), epoxy groups bonded to silicon atoms via carbon atoms (e.g., γ-glycidoxypropyl group, β-(3,4-epoxycyclohexyl)ethyl group, etc.), and alkoxysilyl groups (e.g., trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc.).

[0071] 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 obtained by introducing alkoxysilyl groups into organic compounds having reactive organic groups.

[0072] Examples of the non-silicone organic compounds mentioned above include allyl organic acid esters, organotitanium compounds, organozirconium compounds, and organoaluminum compounds.

[0073] The amount of the above-mentioned adhesion improver added is preferably 1 to 20 parts by mass per 100 parts by mass of component (A), and more preferably 3 to 10 parts by mass. These can be used individually or in combination of two or more.

[0074] Furthermore, to improve workability in die bonding (transfer method), the viscosity of the organically modified silicone composition of the present invention is preferably 5 to 100 Pa·s, and more preferably 20 to 50 Pa·s, at 25°C. The viscosity was measured using a B-type rotational viscometer at 25°C.

[0075] [Diebond material] Furthermore, the present invention provides a die bond material comprising the organically modified silicone composition of the present invention. Examples of the die bond material include a die bond material used to connect semiconductor elements to a wiring board.

[0076] The organically modified silicone composition of the present invention can be suitably used to fix LED chips to a package. It can also be suitably used for other optoelectronic semiconductor devices such as organic electroluminescent devices (organic EL), laser diodes, and LED arrays.

[0077] [Cured product] Furthermore, the present invention provides a cured product obtained by curing the organically modified silicone composition of the present invention.

[0078] The organically modified silicone composition of the present invention can be cured under known conditions, for example, at 100 to 160°C for 10 minutes to 5 hours.

[0079] The Shore D hardness of the cured product obtained by curing the organically modified silicone composition of the present invention is preferably 60 or higher, and more preferably 70 or higher. Furthermore, the die shear strength of the above cured product is preferably 30 MPa or higher at 150°C, and the modulus of elasticity is 8.0 × 10 at 150°C. 7 It is preferable that the Pa level is above a certain level.

[0080] [Optical Semiconductor Equipment] Furthermore, the present invention provides an optoelectronic device comprising a cured product of the organically modified silicone composition of the present invention. An example of such an optoelectronic device is one in which an optoelectronic semiconductor element is die-bonded with the cured product.

[0081] The method for die bonding an optoelectronic semiconductor device using a cured product of the organically modified silicone composition of the present invention is not particularly limited and includes, for example, spin coating, printing, and compression molding. The thickness of the die bonding material can be appropriately selected, and is usually preferably 5 to 50 μm, and more preferably 10 to 30 μm. For example, using a dispensing device at a temperature of 23°C and a load of 0.5 to 5 kgf / cm². 2 The material can be easily applied by dispensing it under pressure. Alternatively, it can be easily applied by using a stamping device to transfer a predetermined amount of die bond material onto the substrate.

[0082] The mounting method for the optical semiconductor device is not particularly limited; for example, a die bonder can be used. Factors determining the thickness of the die bond material include the viscosity of the die bond material mentioned above, as well as the bonding load of the optical semiconductor device, bonding time, and bonding temperature. These conditions can be appropriately selected according to the external shape of the optical semiconductor device and the desired die bond material thickness. The bonding load is generally preferably 1 gf or more and 1 kgf or less, and more preferably 10 gf or more and 100 gf or less. A bonding load of 1 gf or more allows for sufficient bonding of the die bond material. Using a bonding load of 1 kgf or less prevents damage to the light-emitting layer on the surface of the optical semiconductor device. The bonding time can be appropriately selected in consideration of process productivity, preferably exceeding 0 seconds and 1 second or less, and more preferably 1 millisecond or more and 30 milliseconds. 1 second or less is preferable in terms of productivity. There are no particular restrictions on the bonding temperature, but 15°C or more and 80°C or less is preferred. At 15°C or higher, the viscosity of the die bond material does not become too high, allowing for sufficient bonding. If the temperature is below 80°C, it is below the curing temperature of the die bond material, so it can be bonded to the desired thickness. [Examples]

[0083] The present invention will be specifically described below using synthesis examples, examples, and comparative examples, but the present invention is not limited to these. The weight-average molecular weight is the standard polystyrene equivalent value obtained by gel permeation chromatography (GPC). The viscosity at 25°C is measured using a B-type rotational viscometer.

[0084] [Synthesis Example 1] 189.56 g (0.55 mol) of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane was placed in a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, and the temperature was raised to 100°C while stirring. 0.05 g of acetic acid and 0.2 g of a toluene solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 0.5% by mass) were added and the mixture was stirred. 48.61 g (0.25 mol) of 1,4-bis(dimethylsilyl)benzene was added dropwise using a dropping funnel, and the mixture was stirred at 100°C for 10 hours. After cooling to 25°C, activated carbon was added and the mixture was stirred for 1 hour. The mixture was then filtered, and concentrated under reduced pressure at 150°C and below 2000 Pa for 2 hours to obtain 480 g of the addition reaction product (A-1).

[0085] The obtained addition reaction product (A-1) is presumed to be a mixture of addition reaction products resulting from the reaction of k+1 molecules of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane with k molecules of 1,4-bis(dimethylsilyl)benzene, represented by the following formula. Its viscosity at 25°C was 2530 mPa·s, its weight-average molecular weight was 4900, and its vinyl group content was 0.54 mol / 100g. [ka] [In the equation, k is an integer between 1 and 10, and r, s, and t are integers satisfying r+s+t+(2r+s+2)=k+1. Dashed lines represent connections.]

[0086] [Synthesis Example 2] 303.16 g (1.3 mol) of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane was placed in a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, and the temperature was raised to 100°C while stirring. 0.2 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 0.5% by mass) was added and the mixture was stirred. 97.21 g (0.5 mol) of 1,4-bis(dimethylsilyl)benzene was added dropwise using a dropping funnel. After stirring at 100°C for 5 hours, the mixture was cooled to 25°C, activated carbon was added, and the mixture was stirred for 1 hour. The mixture was then filtered, and concentrated under reduced pressure at 150°C and below 2000 Pa for 2 hours to obtain 281 g of the addition reaction product (A-2).

[0087] The obtained addition reaction product (A-2) is presumed to be a mixture of addition reaction products resulting from the reaction of k+1 molecules of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane with k molecules of 1,4-bis(dimethylsilyl)benzene, represented by the following formula. At 25°C, the viscosity was 4000 mPa·s, the weight-average molecular weight was 2900, and the vinyl group content was 0.43 mol / 100g. [ka] [In the equation, k is an integer between 1 and 10, and p and q are integers satisfying p + q + (p + 2) = k + 1. Dashed lines represent connections.]

[0088] [Synthesis Example 3] 184.98 g (0.5 mol) of branched organopolysiloxane represented by the following formula was placed in a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, and the temperature was raised to 80°C while stirring. 0.1 g of a toluene solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 0.5% by mass) was added and stirred. 48.16 g of 1,4-bis(dimethylsilyl)benzene was added dropwise using a dropping funnel. After stirring at 90°C for 3 hours, the mixture was cooled to 25°C, activated carbon was added, and the mixture was stirred for 1 hour. After filtration, the mixture was concentrated under reduced pressure at 150°C and below 2000 Pa for 2 hours to obtain 158 g of the addition reaction product (A-3). [ka]

[0089] The obtained addition reaction product (A-3) is presumed to be a mixture of addition reaction products resulting from the reaction of k+1 molecules of branched organopolysiloxane represented by the above formula with k molecules of 1,4-bis(dimethylsilyl)benzene represented by the following formula. At 25°C, the viscosity was 95 mPa·s, the weight-average molecular weight was 3300, and the vinyl group content was 0.32 mol / 100g. [ka] [In the equation, k is an integer between 1 and 10, and p and q are integers satisfying p + q + (p + 2) = k + 1. Dashed lines represent connections.]

[0090] [Examples 1-5, and Comparative Examples 1 and 2] A silicone composition was prepared by mixing the following components in the composition ratios shown in Table 1 below (the values ​​represent parts by mass).

[0091] The [Si-H] / [Vi] value represents the molar ratio of the number of hydrogen atoms (Si-H groups) bonded to silicon atoms in component (B) to the total number of alkenyl groups in component (A).

[0092] (A) Ingredients: (A-1) Addition reaction product obtained in Synthesis Example 1 (A-2) Addition reaction product obtained in synthesis example 2 (A-3) Addition reaction product obtained in synthesis example 3 (A-4) Organosilicon compounds represented by the following formula (comparative component) [ka] (A-5) 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (comparative component)

[0093] (B) Component: A cyclic methylhydrogensiloxane derivative represented by the following formula. [ka]

[0094] (C) Components: Toluene solution of the reaction product of hexachloroplatinic acid and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum concentration 0.5% by mass)

[0095] (D) Ingredients: Fumed silica (manufactured by Shin-Etsu Chemical Co., Ltd., Musil120A)

[0096] (E) Ingredient: 3-methyl-1-dodecine-3-ol

[0097] (F) Component: Compound represented by the following formula [ka]

[0098] [Table 1]

[0099] The physical properties of cured products made from the organically modified silicone compositions obtained in Examples 1-5 and Comparative Examples 1 and 2 were measured according to the following measurement method. The results are shown in Table 2.

[0100] [Shore D hardness] The composition was poured into a mold to a thickness of 2 mm, and the Type D hardness of the cured product, which was cured at 150°C for 4 hours, was measured in accordance with JIS K 6253-3:2023.

[0101] [Die share strength] Using a die bonder (ASM, AD-830), each composition was stamped onto the silver-plated electrode portion of an SMD5050 package (I-CHIUN PRECISION INDUSTRY Co., polyphthalamide resin). A photoelectronic element (0.23 × 0.18 mm) was then mounted on top and heated at 150°C for 4 hours. After curing, die shear strength was measured at 23°C and 150°C using a bond tester (Dage, Series 4000).

[0102] [modulus of elasticity] The storage modulus (Pa) of a 2 mm thick cured product, prepared by curing the composition at 150°C for 4 hours, was measured using a DMS7100 manufactured by Hitachi High-Tech Science Co., Ltd.

[0103] [Table 2]

[0104] As shown in Table 2 above, the cured products obtained from the organically modified silicone compositions of Examples 1 to 5, which include the addition reaction products (A-1) to (A-3) having the polyfunctional alkenylsiloxane structure of the present invention, exhibited excellent hardness and die shear strength at 23°C and 150°C, and also showed a small difference in elastic modulus at 23°C and 150°C.

[0105] On the other hand, the cured product obtained from the organically modified silicone composition of Comparative Example 1, in which component (A) was changed to component (A-4) which does not have a polyfunctional alkenylsiloxane structure, showed inferior die shear strength at 150°C and a larger difference in elastic modulus between 23°C and 150°C.

[0106] Furthermore, in Comparative Example 2, in which component (A-5), a cyclic organopolysiloxane having multiple alkenyl groups, was added to component (A) of the composition of Comparative Example 1, it was not possible to improve the die shear strength or elastic modulus at 150°C.

[0107] As described above, the organically modified silicone composition of the present invention provides a silicone cured product with excellent hardness and die shear strength, and the cured product is particularly useful as a die bonding material used for die bonding of optical semiconductor devices and the like. In particular, because defects such as chip delamination at high temperatures are less likely to occur, optical semiconductor devices in which optical semiconductor devices are die-bonded with a cured product of the organically modified silicone composition of the present invention are highly reliable. For this reason, the organically modified silicone composition of the present invention and its cured product have high utility value in the field of optical semiconductor devices.

[0108] This specification includes the following embodiments. [1]: Organic modified silicone composition, (A)(i) an addition reaction product of a compound represented by the following general formula (1) and (ii) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and an addition reaction product having two or more alkenyl groups bonded to silicon atoms 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 addition-reactive carbon-carbon double bond, and R 2 (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.) (B) A cyclic methylhydrogensiloxane derivative represented by the following general formula (2), [ka] (In the formula, R 3 (where m is a divalent hydrocarbon group which may independently contain a silicon atom, m is independently 0 or 1, and n is a number satisfying 0 to 5.) (C) An organically modified silicone composition characterized by containing a platinum group metal catalyst. [2]: The R in the general formula (1) 1 However, it is a methyl group, and the R 2The organically modified silicone composition according to [1], characterized in that it is a phenylene group. [3]: The organic modified silicone composition according to [1] or [2], characterized in that the component (ii) contains one or more compounds selected from the compounds represented by the following general formula (3), the compounds represented by the following general formula (4), and the compounds represented by the following general formula (5). [ka] (In the formula, R 4 These are independently alkenyl groups with 2 to 12 carbon atoms, and R 5 (where a is independently a methyl group or a phenyl group, a is an integer between 2 and 5, b is an integer between 0 and 5, a+b is an integer between 2 and 5, and the sequence of siloxane units may be arbitrary.) [ka] (In the formula, R 4 and R 5 This is synonymous with the above. [ka] (In the formula, R 4 and R 5 This is synonymous with the above. [4]: The R of the compound represented by the general formula (3) 4 However, it is a vinyl group, and the R 5 The R of the compound represented by the general formula (4) or (5) is a methyl group, where a is 3 or 4, and b is 0. 4 However, it is a vinyl group, and the R 5 The organically modified silicone composition according to any one of [1] to [3], characterized in that the group is a methyl group. [5]: The R in the general formula (2) 3 The organically modified silicone composition according to any one of [1] to [4], characterized in that it is a divalent hydrocarbon group represented by the following formula (6). [ka] (In the equation, lines with a wavy line represent connections.) [6]: A die bond material characterized by comprising an organically modified silicone composition as described in any one of items [1] to [5]. [7]: A cured product characterized by being obtained by curing an organically modified silicone composition described in any one of items [1] to [5]. [8]:[7] A photoelectronic device characterized by comprising the cured material described above.

[0109] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. Organically modified silicone composition, (A) (i) an addition reaction product of a compound represented by the following general formula (1) and (ii) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and an addition reaction product having two or more alkenyl groups bonded to silicon atoms 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 addition-reactive carbon-carbon double bond, and R ２ (This represents a substituted or unsubstituted divalent hydrocarbon group with 1 to 12 carbon atoms.) (B) A cyclic methylhydrogensiloxane derivative represented by the following general formula (2), 【Chemistry 2】 (In the formula, R ３ (where m is a divalent hydrocarbon group which may independently contain a silicon atom, m is independently 0 or 1, and n is a number satisfying 0 to 5.) (C) An organically modified silicone composition characterized by containing a platinum group metal catalyst.

2. The R in the general formula (1) １ However, it is a methyl group, and the R ２ The organically modified silicone composition according to claim 1, characterized in that it is a phenylene group.

3. The organically modified silicone composition according to claim 1, characterized in that the (ii) component contains one or more compounds selected from the compounds represented by the following general formula (3), the compounds represented by the following general formula (4), and the compounds represented by the following general formula (5). 【Transformation 3】 (In the formula, R ４ These are independently alkenyl groups having 2 to 12 carbon atoms, and R ５ (where a is independently a methyl group or a phenyl group, a is an integer from 2 to 5, b is an integer from 0 to 5, a+b is an integer from 2 to 5, and the arrangement of siloxane units may be arbitrary.) 【Chemistry 4】 (wherein, R ４ and R ５ are as defined above.) 【Transformation 5】 (In the formula, R ４ and R ５ (This is synonymous with the above.)

4. The R of the compound represented by the general formula (3) ４ However, it is a vinyl group, and the R ５ The R of the compound represented by the general formula (4) or (5) is a methyl group, a is 3 or 4, b is 0, or ４ However, it is a vinyl group, and the R ５ The organically modified silicone composition according to claim 3, characterized in that the group is a methyl group.

5. The R in the general formula (2) ３ The organically modified silicone composition according to claim 1, characterized in that it is a divalent hydrocarbon group represented by the following formula (6). 【Transformation 6】 (In the equation, lines with a wavy line represent connections.)

6. A die bond material characterized by comprising an organically modified silicone composition according to any one of claims 1 to 5.

7. A cured product characterized by being obtained by curing an organically modified silicone composition according to any one of claims 1 to 5.

8. An optoelectronic device characterized by comprising the cured product described in claim 7.

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