Addition curing type silicone composition, cured product of the same and optical semiconductor device

Abstract

To provide an addition curing type silicone composition which gives a cured product having high adhesion to a resin and a metal substrate and a highly reliable optical semiconductor device encapsulated by the cured product.SOLUTION: There is provided an addition curing type silicone composition comprising the components (A) to (F). (A) A linear organosilicon compound containing at least two addition-reactive carbon-carbon double bonds and one or more aryl groups having 6 to 12 carbon atoms in one molecule. (B) An organopolysiloxane resin having an alkenyl group having 2 to 12 carbon atoms represented by a specific formula. (C) An organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule and having neither an addition-reactive carbon-carbon double bond and nor an epoxy group. (D) An organosilicon compound having an addition-reactive carbon-carbon double bond represented by a specific formula. (E) An organosilicon compound having one or more epoxy groups in one molecule and having no addition-reactive carbon-carbon double bond. (F) A hydrosilylation reaction catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an addition-curable silicone composition, a cured product thereof, and an optical semiconductor device. [Background technology]

[0002] Devices that have light-emitting diodes (LEDs) as optical semiconductor elements are generally constructed by encapsulating the LEDs mounted on a substrate with a transparent resin encapsulant. Silicone resin compositions have attracted attention as encapsulating materials due to their heat resistance and resistance to thermal discoloration. Addition-reaction curing silicone resin compositions can be cured in a short time by heating, which allows for high productivity, and they are therefore used as encapsulating materials for LEDs (Patent Documents 1 to 4). However, with the recent trend toward higher output LEDs, conventional technology has been plagued by the problem of peeling from the metal and resin parts of the package due to thermal shock, which has led to a demand for the development of an encapsulating material with better adhesion to the substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-292714 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-105217 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-132795 [Patent Document 4] Japanese Patent Application Laid-Open No. 2004-186168 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made in view of the above problems, and has as its object to provide an addition-curable silicone composition that provides a cured product that exhibits high adhesion to resins and metal substrates, and a highly reliable optical semiconductor device that is encapsulated with the cured product. [Means for solving the problem]

[0005] In order to solve the above problems, the present invention provides an addition-curable silicone composition characterized by containing the following components (A) to (F): (A) a linear organosilicon compound containing at least two addition-reactive carbon-carbon double bonds and one or more aryl groups having 6 to 12 carbon atoms per molecule; (B) an organopolysiloxane resin represented by the following formula (3): (R 4 3SiO 1 / 2 ) c (R 5 R 4 2SiO 1 / 2 ) d (R 4 2SiO 2 / 2 ) e (R 5 R 4 SiO 2 / 2 ) f (R 4 SiO 3 / 2 ) g (R 5 SiO 3 / 2 ) h (SiO 4 / 2 ) i (3) (In the formula, R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, provided that R 4 10 mol % or more of R are aryl groups having 6 to 12 carbon atoms, 5 represents an alkenyl group having 2 to 12 carbon atoms, and c, d, e, f, g, h, and i are numbers that satisfy c≧0, d≧0, e≧0, f≧0, g≧0, h≧0, and i≧0, with the proviso that d+f+h>0, g+h+i>0, and c+d+e+f+g+h+i=1; (C) an organosilicon compound having at least two silicon-bonded hydrogen atoms in one molecule and having no addition-reactive carbon-carbon double bonds or epoxy groups; (D) A compound represented by the following formula (9): [ka] (wherein X is —Si(OR 6 ) represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a group represented by 3), and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A wavy line represents a cis-isomer, a trans-isomer, or both. (E) an organosilicon compound having one or more epoxy groups in one molecule and no addition-reactive carbon-carbon double bond; (F) Hydrosilylation reaction catalyst.

[0006] The addition-curable silicone composition of the present invention can provide a cured product that has high adhesion to resins and metal substrates.

[0007] In the present invention, the component (A) preferably contains an organopolysiloxane represented by the following formula (1). [ka] (In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, and R 2 is a methyl group or a phenyl group, a is an integer of 0 to 50, and b is an integer of 0 to 300. However, when a is 0, R 2 is a phenyl group, and b is an integer of 1 to 300. The siloxane units in the parentheses followed by a and the siloxane units in the parentheses followed by b may be arranged randomly, in blocks, or alternately.

[0008] Such a composition can provide an addition-curable silicone composition that more effectively exhibits the effects of the present invention.

[0009] In the present invention, the component (A) is R 1 is preferably a methyl group or a phenyl group.

[0010] Such a compound can be suitably used as component (A) in the addition-curable silicone composition of the present invention.

[0011] In the present invention, it is also preferable that the component (A) contains an addition reaction product of an organopolysiloxane represented by the following formula (1) and a compound represented by the following formula (2), the addition reaction product having two addition-reactive carbon-carbon double bonds in each molecule. [ka] (In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, and R 2 is a methyl group or a phenyl group, a is an integer of 0 to 50, and b is an integer of 0 to 300. However, when a is 0, R 2 is a phenyl group, and b is an integer of 1 to 300. The siloxane units in the parentheses followed by a and the siloxane units in the parentheses followed by b may be arranged randomly, in blocks, or alternately. [ka] (In the formula, R 3 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms and not having an addition-reactive carbon-carbon double bond).

[0012] Such a compound can be suitably used as component (A) in the addition-curable silicone composition of the present invention.

[0013] In the present invention, in the formula (1), R 1 is a methyl group or a phenyl group, and R 2 is a methyl group or a phenyl group, and in the formula (2), R 3 is preferably a phenylene group.

[0014] Such a compound can be more suitably used as component (A) in the addition-curable silicone composition of the present invention.

[0015] The present invention also provides a cured product obtained by curing the addition-curable silicone composition described above.

[0016] Such a cured product will have high adhesiveness to resins and metal substrates.

[0017] Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is encapsulated with the above-mentioned cured product.

[0018] The cured product of the present invention has high adhesion to resins and metal substrates. Therefore, an optical semiconductor device in which an optical semiconductor element is encapsulated with such a cured product is highly reliable and is less susceptible to problems such as peeling from the metal or resin parts of the package. [Effects of the Invention]

[0019] As described above, the addition-curable silicone composition of the present invention can provide a cured product that exhibits high adhesion to resins and metal substrates. Therefore, such cured products of the present invention are suitable for use as encapsulation materials for optical semiconductor elements such as LEDs, semiconductor lasers, photodiodes, phototransistors, solar cells, and CCDs. DETAILED DESCRIPTION OF THE INVENTION

[0020] As described above, there has been a need for the development of an addition-curable silicone composition that provides a cured product that exhibits high adhesion to resin and metal substrates, and for the development of a highly reliable optical semiconductor device in which an optical semiconductor element is encapsulated with the cured product.

[0021] As a result of extensive research into the above-mentioned problems, the present inventors discovered that an addition-curable silicone composition containing the following components (A), (B), (C), (D), and (F) could solve the above-mentioned problems, and thus completed the present invention.

[0022] That is, the present invention provides: The addition-curable silicone composition comprises the following components (A) to (F): (A) a linear organosilicon compound containing at least two addition-reactive carbon-carbon double bonds and one or more aryl groups having 6 to 12 carbon atoms per molecule; (B) an organopolysiloxane resin represented by the following formula (3): (R 4 3SiO 1 / 2 ) c (R 5 R 4 2SiO 1 / 2 ) d (R 4 2SiO 2 / 2 ) e (R 5 R 4 SiO 2 / 2 ) f (R 4 SiO 3 / 2 ) g (R 5 SiO 3 / 2 ) h (SiO 4 / 2 ) i (3) (In the formula, R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, provided that R 4 10 mol % or more of R are aryl groups having 6 to 12 carbon atoms, 5 represents an alkenyl group having 2 to 12 carbon atoms, and c, d, e, f, g, h, and i are numbers that satisfy c≧0, d≧0, e≧0, f≧0, g≧0, h≧0, and i≧0, with the proviso that d+f+h>0, g+h+i>0, and c+d+e+f+g+h+i=1; (C) an organosilicon compound having at least two silicon-bonded hydrogen atoms in one molecule and having no addition-reactive carbon-carbon double bonds or epoxy groups; (D) A compound represented by the following formula (9): [ka] (wherein X is —Si(OR 6 ) represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a group represented by 3), and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A wavy line represents a cis-isomer, a trans-isomer, or both. (E) an organosilicon compound having one or more epoxy groups in one molecule and no addition-reactive carbon-carbon double bond; (F) Hydrosilylation reaction catalyst.

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

[0024] [Addition-curable silicone composition] The addition-curable silicone composition of the present invention contains the following components (A), (B), (C), (D), and (F). Each component will be described in detail below. <Component (A)> (A) Component (A) is a linear organosilicon compound containing at least two addition-reactive carbon-carbon double bonds and one or more aryl groups having 6 to 12 carbon atoms in each molecule. The component (A) preferably contains an organopolysiloxane represented by the following formula (1). [ka] (In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, and R 2 is a methyl group or a phenyl group, a is an integer of 0 to 50, and b is an integer of 0 to 300. However, when a is 0, R 2 is a phenyl group, and b is an integer of 1 to 300. The siloxane units in the parentheses followed by a and the siloxane units in the parentheses followed by b may be arranged randomly, in blocks, or alternately.

[0025] In formula (1), R 1Examples of the substituted or unsubstituted 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 groups; aryl groups having 6 to 12 carbon atoms, such as phenyl and naphthyl groups; alkylaryl groups having 7 to 12 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, and hexylphenyl groups; and aralkyl groups having 7 to 12 carbon atoms, such as benzyl and phenethyl groups. Among these, alkyl groups having 1 to 6 carbon atoms and phenyl groups are preferred. 1 is particularly preferably a methyl group or a phenyl group.

[0026] a is an integer of 0 to 50, preferably an integer of 1 to 30, more preferably an integer of 1 to 20, and even more preferably an integer of 2 to 10. If a is within this range, it is preferable in terms of the heat discoloration resistance of the resulting cured product. b is an integer of 0 to 300, preferably an integer of 0 to 100, more preferably an integer of 1 to 50, and even more preferably an integer of 2 to 30. If b is within this range, it is preferable from the viewpoint of workability.

[0027] Furthermore, it is preferable that the component (A) contains an addition reaction product between an organopolysiloxane represented by the following formula (1) and a compound represented by the following formula (2), and that the addition reaction product has two addition-reactive carbon-carbon double bonds in each molecule. [ka] (In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, and R 2 is a methyl group or a phenyl group, a is an integer of 0 to 50, and b is an integer of 0 to 300. However, when a is 0, R 2is a phenyl group, and b is an integer of 1 to 300. The siloxane units in the parentheses followed by a and the siloxane units in the parentheses followed by b may be arranged randomly, in blocks, or alternately. [ka] (In the formula, R 3 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms and not having an addition-reactive carbon-carbon double bond.

[0028] R 3 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 groups; arylene groups having 6 to 12 carbon atoms, such as phenylene, biphenylene, and naphthylene groups; and aralkylene groups having 7 to 12 carbon atoms, such as phenylenemethylene and methylenephenylenemethylene groups. Among these, R 3 is preferably an arylene group having 6 to 12 carbon atoms, more preferably a phenylene group.

[0029] In the formula (1), R 1 is a methyl group or a phenyl group, and R 2 is a methyl group or a phenyl group, and in the formula (2), R 3 is particularly preferably a phenylene group.

[0030] Specific examples of component (A) include, but are not limited to, those represented by the following formula: In addition, Me represents a methyl group, and Ph represents a phenyl group (the same applies hereinafter). [ka] (In the formula, the siloxane units in parentheses may be arranged in any order.)

[0031] The component (A) may be used alone or in combination of two or more.

[0032] <(B) component> Component (B) is an organopolysiloxane resin represented by the following formula (3): Component (B) is a component that improves the mechanical strength of the cured product. (R 4 3SiO 1 / 2 ) c (R 5 R 4 2SiO 1 / 2 ) d (R 4 2SiO 2 / 2 ) e (R 5 R 4 SiO 2 / 2 ) f (R 4 SiO 3 / 2 ) g (R 5 SiO 3 / 2 ) h (SiO 4 / 2 ) i (3) (In the formula, R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, provided that R 4 10 mol % or more of R are aryl groups having 6 to 12 carbon atoms, 5 is an alkenyl group having 2 to 12 carbon atoms, and c, d, e, f, g, h, and i are numbers that satisfy c≧0, d≧0, e≧0, f≧0, g≧0, h≧0, and i≧0, provided that d+f+h>0, g+h+i>0, and c+d+e+f+g+h+i=1.

[0033] In the above formula (3), the total R 4 Of these, 10 mol % or more, and preferably 20 mol % or more, are aryl groups having 6 to 12 carbon atoms. The presence of aryl groups can improve the refractive index, improve the light extraction efficiency in optical semiconductor devices, and impart gas barrier properties, etc. Examples of aryl groups having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, and naphthyl groups, with phenyl being particularly preferred.

[0034] Above R 4 In R, the group other than the aryl group is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an alkenyl group, and examples thereof include unsubstituted or halogen-substituted monovalent hydrocarbon groups typically having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms, such as alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl groups. 4 is particularly preferably a methyl group.

[0035] Above R 5 Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, such as vinyl, allyl, and ethynyl groups, with vinyl groups being particularly preferred.

[0036] The content of silicon-bonded alkenyl groups in component (B) is preferably in the range of 0.01 to 1 mol, and more preferably 0.1 to 0.6 mol, per 100 g of component (D). When this content is in the range of 0.01 to 1 mol, the crosslinking reaction proceeds sufficiently, resulting in a cured product with higher hardness.

[0037] In the above formula (3), g, h, and i are numbers that satisfy g+h+i>0 (i.e., a branched structure is essential), but are preferably numbers that satisfy 0.05≦g+h+i≦0.9, and more preferably numbers that satisfy 0.1≦g+h+i≦0.7.

[0038] Specific examples of the organopolysiloxane resin of component (B) include the following: [(CH3)3SiO 1 / 2 ] 0.3 [(CH2=CH)(CH3)2SiO 1 / 2 ] 0.1 [(C6H5)2SiO 2 / 2 ] 0.45 [SiO 4 / 2 ]0.15 ,

[0039] [(CH2=CH)(CH3)(C6H5)SiO 1 / 2 ] 0.2 [(C6H5)2SiO 2 / 2 ] 0.4 [SiO 4 / 2 ] 0.4

[0040] [(CH2=CH)(CH3)(C6H5)SiO 1 / 2 ] 0.13 [(CH2=CH)(CH3)2SiO 1 / 2 ] 0.29 [(C6H5)2SiO 2 / 2 ] 0.05 [SiO 4 / 2 ] 0.53

[0041] The component (B) may be used alone or in combination of two or more types.

[0042] The organopolysiloxane resin of component (B) is preferably a wax or solid at 25°C for ease of isolation.

[0043] The blending amount of component (B) is preferably in the range of 1 to 70 mass % and more preferably in the range of 20 to 60 mass % based on the total mass of components (A) and (B). A blending amount of component (B) within this range is preferable in terms of the hardness and adhesiveness of the resulting cured product.

[0044] <(C) component> Component (C) is an organosilicon compound that has at least two silicon-bonded hydrogen atoms in each molecule and that does not have any addition-reactive carbon-carbon double bonds or epoxy groups. Component (C) is an organosilicon compound that has at least two, and preferably 2 to 100, silicon-bonded hydrogen atoms (SiH groups) per molecule, and that does not contain any addition-reactive carbon-carbon double bond-containing groups or epoxy groups. It acts as a crosslinking agent that crosslinks via a hydrosilylation reaction with the addition-reactive carbon-carbon double bonds contained in components (A) and (B).

[0045] Substituents other than hydrogen atoms bonded to silicon atoms in component (C) include substituted or unsubstituted monovalent hydrocarbon groups that do not contain aliphatic unsaturated bonds, with substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms being preferred. Specific examples include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenylethyl; and halogenated hydrocarbon groups such as chloromethyl, chloropropyl, and chlorocyclohexyl, with methyl and phenyl being particularly preferred.

[0046] Examples of the organosilicon compound of component (C) that can be used include a cyclic organohydrogensiloxane derivative represented by the following formula (4), an organohydrogenpolysiloxane represented by the following formula (6), an organohydrogenpolysiloxane represented by the following formula (7), and an organosilicon compound represented by the following formula (8). [ka] (In the formula, R 6 is a divalent group represented by the following formula (5), where p is independently 0 or 1, and q is an integer of 1 to 5. [ka] (In the formula, an asterisk (*) represents a bond to an adjacent silicon atom.) [ka] (wherein r is 2 or 3). [ka] (In the formula, R 1 and R 2 is R in the formula (1). 1 and R 2 where j is an integer of 0 to 50 and k is an integer of 0 to 100. The siloxane units in the parentheses to which j and k are attached may be arranged randomly, in blocks, or alternately. [ka] (In the formula, m is an integer of 1 to 10.)

[0047] The viscosity of component (C) at 25°C measured with a rotational viscometer is preferably in the range of 1 to 100,000 mPa s, and more preferably 5 to 60,000 mPa s. If the viscosity of component (C) measured with a rotational viscometer is within this range, it is preferable from the standpoint of workability.

[0048] Specific examples of component (C) are shown below, but are not limited to these. [ka]

[0049] The component (C) may use either a single compound or a combination of two or more compounds.

[0050] The amount of component (C) blended is preferably 1 to 50 parts by mass per 100 parts by mass of the total of components (A) and (B). Furthermore, the total number of hydrogen atoms bonded to silicon atoms (SiH groups) per addition-reactive carbon-carbon double bond contained in the composition is preferably in the range of 0.5 to 5.0, more preferably 0.7 to 3.0. When this range is satisfied, the resulting cured product can be endowed with high mechanical strength.

[0051] <(D) component> The component (D) is a compound represented by the following formula (9): The component (D) is a component that imparts adhesiveness. [ka] (wherein X is —Si(OR 6 ) represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a group represented by 3), and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The wavy line represents a cis-isomer, a trans-isomer, or both.

[0052] R 6 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups, with methyl and ethyl groups being preferred.

[0053] Specific examples of X include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl; and trialkoxysilyl-substituted alkyl groups such as trimethoxysilylmethyl, triethoxysilylmethyl, 2-trimethoxysilylethyl, 2-triethoxysilylethyl, 3-trimethoxysilylpropyl, 3-triethoxysilylpropyl, 8-trimethoxysilyloctyl, and 8-triethoxysilyloctyl.

[0054] In the above formula (9), the wavy line represents a cis-isomer, a trans-isomer, or both.

[0055] As represented by the following formula (10), component (D) can be produced by a 1,4-addition reaction of a trialkoxyhydrosilane to an acrylic ester. [ka] (Wherein, X and R 6 is the same as above.)

[0056] Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, and 3-acryloxypropyltrimethoxysilane (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), and preferred are ethyl acrylate and 3-acryloxypropyltrimethoxysilane.

[0057] Examples of trialkoxyhydrosilanes include triethoxysilane and trimethoxysilane.

[0058] The amounts of acrylic acid ester and trialkoxyhydrosilane used in the above reaction are preferably 0.8 to 1.2 moles of trialkoxyhydrosilane per mole of acrylic acid ester.

[0059] The reaction is typically carried out in the presence of an addition reaction catalyst. Examples of such catalysts include platinum group metal catalysts, such as platinum, palladium, and rhodium catalysts, with platinum catalysts being particularly preferred. Examples of platinum catalysts include solid platinum supported on a carrier such as platinum black, alumina, or silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid with an olefin, or a complex of platinum with a vinylsiloxane. The amount of these catalysts used may be a catalytic amount, and is typically 0.1 to 1,000 ppm, particularly 0.5 to 100 ppm, calculated as platinum group metal, relative to the total amount of the acrylic ester and trialkoxyhydrosilane.

[0060] The reaction is generally carried out at a temperature of 50 to 120°C, particularly 60 to 100°C, for 0.5 to 12 hours, particularly 1 to 6 hours. The reaction can be carried out without using a solvent. If necessary, a suitable solvent such as toluene or xylene can be used.

[0061] In the above reaction, in addition to component (D), isomers such as α-adducts and β-adducts to the acrylic group may be produced, but these by-products can be used without separation.

[0062] Specific examples of component (D) are shown below, but the present invention is not limited to these specific examples. [ka] The component (D) may be used alone or in combination of two or more types.

[0063] The blend amount of component (D) is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the combined total of components (A) and (B). When the blend amount of component (D) satisfies this range, it is preferable in terms of the hardness and adhesiveness of the resulting cured product.

[0064] The component (D) may be used alone or in combination of two or more types.

[0065] <(E) component> Component (E) is an organosilicon compound that has one or more epoxy groups per molecule and no addition-reactive carbon-carbon double bonds. Component (E) is a component that improves adhesion when used in combination with component (D). Component (E) is distinguished from component (C) above in that it contains an epoxy group, and from component (A) above in that it does not contain an addition-reactive carbon-carbon double bond. Specific examples of the component (E) include 3-glycidyloxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and 8-glycidyloxyoctyltrimethoxysilane (trade name: KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, cyclic siloxane compounds represented by the following structural formula can also be suitably used. [ka]

[0066] The component (E) may be used alone or in combination of two or more.

[0067] The blend amount of component (E) is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the combined total of components (A) and (B).

[0068] <(F) Component> Component (F) is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst for component (F) is not particularly limited, so long as it is a component that promotes the addition reaction between an addition-reactive carbon-carbon double bond contained in the composition and a hydrogen atom bonded to a silicon atom. 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, with platinum-based compounds being preferred, and coordination compounds of chloroplatinic acid with vinylsiloxane being particularly preferred.

[0069] The component (F) may be used alone or in combination of two or more types.

[0070] The amount of component (F) to be blended may be an effective amount as a catalyst, but is preferably in the range of 0.1 to 1000 ppm, more preferably 1 to 500 ppm, calculated as the mass of platinum group metal relative to the total amount of components (A) and (B). When this range is satisfied, the reaction rate of the addition reaction becomes appropriate, and a cured product with high strength can be obtained.

[0071] <Other ingredients> In addition to the above components (A) to (F), the addition-curable silicone composition of the present invention may also contain other components, such as those exemplified below.

[0072] (adhesion aid) The composition of the present invention may contain an adhesion aid other than components (D) and (E) in order to improve adhesion to substrates. The adhesion promoter may be a compound containing one or more of the functional groups consisting of an addition-reactive carbon-carbon double bond-containing group, an alkoxysilyl group, and a carboxylic acid anhydride group.

[0073] Specific examples of the adhesion aid include vinyltrimethoxysilane (trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), and 3-trimethoxysilylpropylsuccinic anhydride (trade name: X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, organosilicon compounds represented by the following structural formulas can also be suitably used as adhesion promoters. [ka]

[0074] Furthermore, silicon-free adhesion promoters can also be used, and specific examples thereof include allyl glycidyl ether, vinylcyclohexene monoxide, diethyl 2-allylmalonate, allyl benzoate, diallyl phthalate, pyromellitic acid tetraallyl ester (trade name: TRIAM805, Wako Pure Chemical Industries, Ltd.), triallyl isocyanurate, and the like.

[0075] When an adhesive aid other than the components (D) and (E) is used, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the components (A) and (B).

[0076] (Reaction inhibitor) A reaction inhibitor may be added to the composition of the present invention to adjust the curing rate.

[0077] Examples of reaction inhibitors include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene compounds; hydroperoxy compounds; maleic acid derivatives; 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, and ethynylmethyldecylcarbinol.

[0078] Since the degree of curing inhibition effect of a reaction inhibitor varies depending on the chemical structure of the reaction inhibitor, it is desirable to adjust the amount of reaction inhibitor to an optimal amount for each reaction inhibitor used. Preferably, the amount is 0.001 to 5 parts by mass per 100 parts by mass of the total of the above components (A) and (B). 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, there is no risk of inhibiting curing of the composition.

[0079] (antioxidant) An antioxidant may be added to the composition of the present invention in order to prevent discoloration over time. Examples of antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), sebacate bis(1,2,2,6,6-pentamethyl-4-piperidine), etc. These may be used alone or in combination of two or more.

[0080] When an antioxidant is used, its amount is not particularly limited as long as it is an effective amount as an antioxidant, but it is usually preferably about 1 to 10,000 ppm, and particularly about 10 to 1,000 ppm, based on the total mass of components (A) and (B). By using an amount within this range, the antioxidant ability is fully exerted, and a cured product with excellent optical properties can be obtained without the occurrence of coloration, cloudiness, oxidative degradation, etc.

[0081] (light stabilizer) A light stabilizer may be added to the composition of the present invention in order to impart resistance to deterioration caused by light energy from sunlight, fluorescent lamps, and the like. As a light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidative degradation is suitable, and by using it in combination with an antioxidant, the antioxidant effect is further improved.Specific examples of light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, and 4-benzoyl-2,2,6,6-tetramethylpiperidine.

[0082] When a light stabilizer is used, its amount is not particularly limited as long as it is an effective amount as a light stabilizer, but it is usually preferably about 1 to 10,000 ppm, and particularly about 10 to 1,000 ppm, based on the total mass of components (A), (D), and (E). By using an amount within this range, the antioxidant ability is fully exerted, and a cured product with excellent optical properties is obtained without the occurrence of coloration, cloudiness, oxidative degradation, etc.

[0083] (filler) Furthermore, in addition to fumed silica, the composition of the present invention may also contain inorganic fillers such as crystalline silica, hollow silica, titanium oxide, and alumina, as well as fillers obtained by subjecting the surface of these fillers to hydrophobic treatment with an organosilicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organosilazane compound, or a low-molecular-weight siloxane compound; silicone rubber powder, silicone resin powder, and the like.

[0084] The filler should have a specific surface area (BET method) of 50 m from the viewpoint of imparting thixotropy to the composition of the present invention and reinforcing properties to the cured product. 2 / g or more, and more preferably 50 to 400m 2 / g, particularly preferably 100 to 300m 2 / g.

[0085] It is also preferable to use fillers that have been treated with organosilicon compounds such as methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane, dimethylpolysiloxane, and hexaorganodisilazanes such as hexamethyldisilazane, divinyltetramethyldisilazane, and dimethyltetravinyldisilazane.

[0086] Examples of such fillers include Reolosil DM30 (manufactured by Tokuyama Corporation), Aerosil NSX-200 (manufactured by Nippon Aerosil Co., Ltd.), and Musil 120A (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0087] When a filler is used, the blending amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the (A) and (B) components. This range can prevent precipitation of the fumed silica in the composition, ensuring sufficient reinforcing properties. Furthermore, there is no risk of imparting excessive thixotropy, which could result in a decrease in workability.

[0088] The viscosity of the addition-curable silicone composition of the present invention is preferably 0.1 to 50 Pa·s, and more preferably 1 to 10 Pa·s, at 25° C. If the viscosity of the addition-curable silicone composition of the present invention is within this range, this is preferable in terms of workability when sealing semiconductor devices.

[0089] [Cured product] Furthermore, the present invention provides a cured product (cured silicone product) of the addition-curable silicone composition.

[0090] The addition-curable silicone composition of the present invention can be cured under known conditions, for example, at 60 to 180° C. for 10 minutes to 5 hours.

[0091] The cured product of the addition-curable silicone composition of the present invention has high adhesive properties to resins and metal substrates, making it useful as an encapsulant for optical semiconductor devices and the like.

[0092] [Optical semiconductor device] Furthermore, the present invention provides an optical semiconductor device in which an optical semiconductor element is encapsulated with the above-mentioned cured product. Optical semiconductor elements (optical elements) that can be encapsulated with an encapsulant made from the composition of the present invention include, for example, LEDs, semiconductor lasers, photodiodes, phototransistors, solar cells, and CCDs. Such optical elements can be encapsulated by applying an encapsulating material made from the composition of the present invention to the optical element and curing the applied encapsulating material by a known curing method under known curing conditions, specifically as described above. [Example]

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

[0094] [Synthesis Example 1] Synthesis of component (A-2) A 5-L four-neck flask equipped with a stirrer, condenser, dropping funnel, and thermometer was charged with 2100 g of the compound represented by formula (11) below (vinyl group content: 0.103 mol / 100 g) and 2100 g of toluene, and the mixture was heated to 85°C using an oil bath. 0.7 g of a toluene solution (platinum concentration: 0.5% by mass) of the reaction product of platinum hexachloride and 1,3-divinyltetramethyldisiloxane was added, and 181 g of 1,4-bis(dimethylsilyl)benzene, a compound represented by formula (2), was added dropwise over 30 minutes while stirring. After the addition was complete, the mixture was stirred at 95°C for 3 hours and then cooled to 25°C. 23 g of activated carbon was then added, and the mixture was stirred for 1 hour. It was then filtered and concentrated under reduced pressure, yielding 2200 g of a colorless, transparent reaction product represented by formula (12) below (A-2, viscosity at 25°C: 90,000 mPa·s). [ka] (In the formula, the order of the siloxane units in parentheses is not specified.) [ka] (In the formula, n is a number that results in the above viscosity, and the arrangement order of the siloxane units in the parentheses is not specified.)

[0095] [Synthesis Example 2] Synthesis of component (C-2) A 1 L four-neck flask equipped with a stirrer, condenser, dropping funnel, and thermometer was charged with 262.8 g (1.35 mol) of p-dimethylsilylbenzene (Shin-Etsu Chemical Co., Ltd.) and 0.12 g of 5% Pt carbon powder (N.E. Chemcat Corporation), and heated to 85°C using an oil bath. 28.0 g (0.15 mol) of phenyltrivinylsilane (Shin-Etsu Chemical Co., Ltd.) was added dropwise. After the dropwise addition was complete, the mixture was stirred at a temperature between 90 and 100°C for 5 hours. After stirring, the mixture was returned to room temperature, 2.9 g of activated carbon was added, and the mixture was stirred for 1 hour. After filtration and vacuum concentration, 99.7 g of a colorless, transparent reaction product (C-2, viscosity at 25°C: 30 Pa·s) was obtained. The reaction product was 1Analysis by H-NMR and GPC revealed that this was a mixture of the following structural formulas (13):(14):(15):(16) = 55:25:10:15 (mol %) (SiH group content 0.0035 mol / g). [ka]

[0096] [Examples 1 to 5 and Comparative Examples 1 to 2] Addition-curable silicone compositions were prepared by mixing the following components in the amounts shown in Tables 1 and 2. The numerical values ​​for each component in Tables 1 and 2 represent parts by mass.

[0097] (A) component; (A-1) Organopolysiloxane represented by the following formula (17): [ka] (A-2) Reaction product obtained in Synthesis Example 1

[0098] (B) Ingredients; (B-1) A silicone resin represented by the following formula (18): [ka] (B-2) A silicone resin represented by the following formula (19): [ka]

[0099] (C) Component; (C-1) A compound represented by the following formula (20): [ka] (C-2) Reaction product obtained in Synthesis Example 2 (C-3) A cyclic organohydrogensiloxane derivative represented by the following structural formula (21): [ka]

[0100] (D) Component; (D-1) A mixture of a compound represented by the following formula (22a) and a compound represented by the following formula (22b): [ka] (D-2) A mixture of a compound represented by the following formula (23a) and a compound represented by the following formula (23b): [ka] (E) Ingredients; (E-1) A compound represented by the following formula (24): [ka] (E-2) A compound represented by the following formula (25): [ka] (E-3) A compound represented by the following formula (26): [ka] (E-4) 3-Glycidyloxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0101] (F) component; (F-1) A catalyst (platinum concentration 1% by mass) prepared by diluting the reaction product of platinum hexachloride and 1,3-divinyltetramethyldisiloxane with an organopolysiloxane represented by the following formula (27): [ka]

[0102] Other ingredients: (G-1) Reaction inhibitor: ethynylmethyldecylcarbinol (H-1) Adhesion aid: a compound represented by the following formula (28): [ka]

[0103] [Table 1] [Table 2]

[0104] [Hardness] The addition-curable silicone compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were poured onto a substrate to a thickness of 2 mm, and then heated at 150°C for 4 hours. Three 2 mm-thick cured compositions were stacked (6 mm thick), and the hardness was measured using a Shore D hardness tester (Examples 1 and 2, Comparative Example 1) or a Type A hardness tester (Examples 3 to 5, Comparative Example 2).

[0105] [Light transmittance] The addition-curable silicone compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were poured onto a substrate to a thickness of 2 mm, and then heated at 150°C for 4 hours. The light transmittance of the resulting 2 mm-thick cured product at 400 nm (optical path length 2 mm) was measured at 25°C using a spectrophotometer.

[0106] [Adhesion strength evaluation] Two aluminum substrates or PA9T (Genestar) substrates (25 mm wide x 50 mm deep x 2 mm thick) were sandwiched between two substrates, with the addition-curable silicone compositions of Examples 1 to 5 and Comparative Examples 1 and 2 sandwiched between them to a thickness of 2 mm, and heated at 150°C for 4 hours to cure the addition-curable silicone compositions, resulting in adhesion (adhesion area 25 mm x 10 mm = 250 mm). 2 A test piece was prepared consisting of two substrates bonded together. The test piece was subjected to a tensile shear adhesive strength test in accordance with JIS-K6850:1999, and the adhesive strength of the cured product of the addition-curable silicone composition was evaluated.

[0107] [Table 3] [Table 4]

[0108] The results are summarized in Table 3. Comparing the cases where the compositions of Examples 1 and 2 were used with the case where the composition of Comparative Example 1, which does not contain component (D), the cured products derived from the compositions of both Examples and Comparative Example had excellent adhesion when evaluated on an aluminum substrate. On the other hand, in the evaluation carried out on a PA9T substrate, the compositions of Examples 1 and 2 showed excellent adhesiveness, but the cured product of the Comparative Example showed significantly inferior results. Furthermore, as shown in Table 4, in both the evaluation using a PA9T substrate and the evaluation using an aluminum substrate, the results using the compositions of Examples 3 to 5 showed superior adhesion compared to the results using the composition of Comparative Example 2 which did not contain component (D). Table 3 shows the results of shear adhesive strength evaluation achieved by compositions that give cured products with high hardness as shown in Table 1, while Table 4 shows the results of shear adhesive strength evaluation achieved by compositions that give cured products with low hardness as shown in Table 2. For each system, the difference in shear adhesive strength between the presence and absence of component (D) is shown.

[0109] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. An addition-curable silicone composition comprising the following components (A) to (F): (A) a linear organosilicon compound containing at least two addition-reactive carbon-carbon double bonds and one or more aryl groups having 6 to 12 carbon atoms per molecule; (B) An organopolysiloxane resin represented by the following formula (3): (R ４ ３ SiO １ / ２ ) ｃ (R ５ R ４ ２ SiO １ / ２ ) ｄ (R ４ ２ SiO ２ / ２ ) ｅ (R ５ R ４ SiO ２ / ２ ) ｆ (R ４ SiO ３ / ２ ) ｇ (R ５ SiO ３ / ２ ) ｈ (SiO ４ / ２ ) ｉ (3) (In the formula, R ４ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, provided that R ４ 10 mol % or more of R are aryl groups having 6 to 12 carbon atoms, ５ represents an alkenyl group having 2 to 12 carbon atoms, and c, d, e, f, g, h, and i are numbers that satisfy c≧0, d≧0, e≧0, f≧0, g≧0, h≧0, and i≧0, with the proviso that d+f+h>0, g+h+i>0, and c+d+e+f+g+h+i=1. (C) an organosilicon compound having at least two silicon-bonded hydrogen atoms in one molecule and having no addition-reactive carbon-carbon double bonds or epoxy groups; (D) A compound represented by the following formula (9): 【Chemistry 1】 (Wherein, X is —Si(OR ６ ) ３ R represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a group represented by ６ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; a wavy line represents a cis-isomer, a trans-isomer, or both. (E) an organosilicon compound having one or more epoxy groups in one molecule and no addition-reactive carbon-carbon double bond; (F) A hydrosilylation reaction catalyst.

2. 2. The addition-curable silicone composition according to claim 1, wherein component (A) comprises an organopolysiloxane represented by the following formula (1): 【Chemistry 2】 (In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, R ２ is a methyl group or a phenyl group, a is an integer of 0 to 50, and b is an integer of 0 to 300. However, when a is 0, R ２ is a phenyl group, and b is an integer of 1 to 300. The siloxane units in the parentheses followed by a and the siloxane units in the parentheses followed by b may be arranged randomly, in blocks, or alternately.

3. In the formula (1), R １ 3. The addition-curable silicone composition according to claim 2, wherein is a methyl group or a phenyl group.

4. The addition-curable silicone composition according to claim 1, wherein component (A) is an addition reaction product of an organopolysiloxane represented by the following formula (1) and a compound represented by the following formula (2), and the addition reaction product contains two addition-reactive carbon-carbon double bonds per molecule: 【Transformation 3】 (In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond, R ２ is a methyl group or a phenyl group, a is an integer of 0 to 50, and b is an integer of 0 to 300. However, when a is 0, R ２ is a phenyl group, and b is an integer of 1 to 300. The siloxane units in the parentheses followed by a and the siloxane units in the parentheses followed by b may be arranged randomly, in blocks, or alternately. 【Chemistry 4】 (In the formula, R ３ represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms and no addition-reactive carbon-carbon double bond.

5. In the formula (1), R １ is a methyl group or a phenyl group, and R ２ is a methyl group or a phenyl group, and in the formula (2), R ３ The addition-curable silicone composition according to claim 4, wherein is a phenylene group.

6. A cured product, characterized in that the cured product is obtained by curing the addition-curable silicone composition according to any one of claims 1 to 5.

7. An optical semiconductor device, comprising an optical semiconductor element encapsulated with the cured product according to claim 6.

Images