Curable silicone composition, optoelectronic device, and method for manufacturing an optoelectronic device

Abstract

To provide a curable silicone composition to be used for encapsulating, coating or bonding an optical semiconductor element, where the curable silicone composition can form a cured product with sufficiently low gas-permeability, and with little weight decrease and little change in hardness even on long-term exposure to high temperatures.SOLUTION: The above-mentioned problem can be solved by a curable silicone composition comprising resinous organopolysiloxane that contains at least one (Ar2SiO2 / 2) unit (Ar denotes an aryl group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable silicone composition, and more specifically, to a curable silicone composition used for encapsulating, coating, or bonding optical semiconductor elements. The present invention also relates to an optical semiconductor device comprising a cured product of such a curable silicone composition and a method for manufacturing the same. [Background technology]

[0002] Curable silicone compositions are widely used in various industrial fields because they harden to form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water-resistant properties, and transparency. In particular, their cured products are less prone to discoloration and exhibit less deterioration in physical properties compared to other organic materials, making them suitable for optical materials.

[0003] For example, Patent Documents 1 to 3 describe resin compositions for encapsulating optical semiconductor devices or optical lenses, which use a curable silicone resin composition comprising an organopolysiloxane having two or more non-covalent double bond groups in one molecule, an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule, and a catalytic amount of a platinum-based catalyst. Furthermore, Patent Documents 4 and 5 describe hot-melt silicone resin compositions that are non-flowing at 25°C, have low surface tackiness, and melt easily upon heating. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2006-299099 [Patent Document 2] Japanese Patent Publication No. 2007-246894 [Patent Document 3] Japanese Patent Publication No. 2006-324596 [Patent Document 4] Japanese Patent Publication No. 2013-001794 [Patent Document 5] International Publication No. 2015 / 194158 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, conventional silicone resin compositions typically have high air permeability, which poses a problem when used for encapsulating optical semiconductor devices such as LED chips. This is because they easily allow corrosive gases such as sulfur compounds (e.g., hydrogen sulfide, sulfuric acid) from the atmosphere to permeate, causing yellowing of the silicone encapsulant or corrosion of metal electrodes on the substrate, particularly silver (Ag) electrodes. Furthermore, when conventional silicone resin compositions are used in power LED devices such as CSPs, high-temperature conditions can lead to weight loss and reduced flexibility of the cured resin, resulting in discoloration and cracking of the cured resin.

[0006] The object of the present invention is to provide a curable silicone composition for sealing, coating, or bonding optical semiconductor devices that achieves sufficiently low gas permeability and can form a cured product with minimal weight loss and hardness change even when exposed to high-temperature conditions for a long period of time.

[0007] Another object of the present invention is to provide an optical semiconductor device and a method for manufacturing the same that are highly reliable and have excellent high-temperature durability. [Means for solving the problem]

[0008] In order to solve the above problem, the inventors of this invention have conducted diligent studies and found that at least one (Ar2SiO 2 / 2 We discovered that the above problems can be solved by a curable silicone composition containing a resinous organopolysiloxane containing units (Ar represents an aryl group), and thus arrived at the present invention.

[0009] The resinous organopolysiloxane of the present invention is preferably a hydrosilylation reaction curing type resinous organopolysiloxane.

[0010] The resinous organopolysiloxane of the present invention is preferably an alkenyl group-containing organopolysiloxane having at least two silicon atom-bonded alkenyl groups in one molecule.

[0011] The resinous organopolysiloxane of the present invention preferably has an average unit formula (A-3): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (Ar2SiO 2 / 2 ) b‘ (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e (In the formula, R 1 is the same or different halogen-substituted or unsubstituted monovalent hydrocarbon group, Ar is an aryl group, provided that 0.01 to 50 mol% of the total of R 1 is an alkenyl group, X is a hydrogen atom or an alkyl group, the R 1 2SiO 2 / 2 unit represents a unit other than Ar2SiO 2 / 2 , and a, b, b', c, d, and e are numbers such that 0≦a≦1.0, 0≦b≦1.0, 0<b'≦1.0, 0≦c<0.9, 0≦d<0.5, 0≦e<0.4, a + b + b' + c + d = 1.0, and c + d>0.) It is represented by

[0012] The curable silicone composition according to the present invention may further contain a linear alkenyl group-containing organopolysiloxane having at least two silicon atom-bonded alkenyl groups in one molecule.

[0013] In the curable silicone composition according to the present invention, the ratio of linear alkenyl group-containing organopolysiloxane to resinous alkenyl group-containing organopolysiloxane: linear alkenyl group-containing organopolysiloxane / resinous alkenyl group-containing organopolysiloxane is preferably greater than 0.2.

[0014] The curable silicone composition according to the present invention may contain the resin-like organopolysiloxane in an amount of 10% by mass or more and 90% by mass or less, based on the total mass of the composition.

[0015] The curable silicone composition according to the present invention may further comprise (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and (C) a catalyst for the hydrosilylation reaction.

[0016] The present invention also relates to an optoelectronic device comprising a cured product of the curable silicone composition according to the present invention.

[0017] The present invention also relates to a method for manufacturing an optoelectronic device, comprising the step of encapsulating, coating, or bonding an optoelectronic semiconductor element using a curable silicone composition according to the present invention. [Effects of the Invention]

[0018] The curable silicone composition according to the present invention achieves sufficiently low gas permeability and can form a cured product with minimal weight loss and hardness change even when exposed to high-temperature conditions for a long period of time. Therefore, by using the curable silicone composition of the present invention to encapsulate, coat, or bond optical semiconductor elements, it is possible to form optical semiconductor devices with excellent reliability and high-temperature durability. [Modes for carrying out the invention]

[0019] The invention will be described in detail below.

[0020] [Curing silicone composition] The curable silicone composition according to the present invention comprises at least one (Ar2SiO 2 / 2 The present invention is characterized by comprising a curable silicone composition comprising a resinous organopolysiloxane containing a unit (Ar2SiO2) (Ar represents an aryl group). 2 / 2 It may contain a resinous organopolysiloxane containing units (Ar represents an aryl group), or at least one of two or more (Ar2SiO 2 / 2 It may also contain a resinous organopolysiloxane containing units (Ar represents an aryl group).

[0021] In this specification, a resinous organopolysiloxane means an organopolysiloxane having a branched or network structure in its molecular structure. In one embodiment, the resinous organopolysiloxane has at least one RSiO in its molecular structure 3 / 2 It contains siloxane units (T units) represented by .

[0022] The present invention provides at least one (Ar2SiO 2 / 2 The resinous organopolysiloxane containing the ) units preferably has a proportion of T units in its molecular structure of 0.1 or more, more preferably 0.2 or more, even more preferably 0.25 or more, and particularly 0.3 or more. In a preferred embodiment, the resinous organopolysiloxane of the present invention has a proportion of T units in its molecular structure of 0.9 or less, preferably 0.85 or less, and more preferably 0.8 or less.

[0023] In another preferred embodiment, the resinous organopolysiloxane of the present invention has SiO in its molecular structure. 4 / 2 The proportion of siloxane units (Q units) represented by R3SiO is 0.2 or less, preferably 0.1 or less, and more preferably does not contain any Q units. The proportions of T units and Q units are as follows: 1 / 2 Siloxane units (M units) represented by the general formula: R2SiO 2 / 2 Siloxane units (D units) represented by the general formula: RSiO3 / 2 Siloxane units (T units) represented by the formula: SiO 4 / 2 It can be calculated based on the amount of siloxane units (Q units) represented by .

[0024] (Ar2SiO 2 / 2 In the unit, Ar means an aryl group. The aryl group may be unsubstituted or substituted, and is preferably an aryl group having 6 to 20 carbon atoms. Examples include phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, and groups in which the hydrogen atoms of these aryl groups are substituted with alkyl groups such as methyl and ethyl groups; alkoxy groups such as methoxy and ethoxy groups; and halogen atoms such as chlorine and bromine atoms. Particularly preferred is a substituted or unsubstituted phenyl group, and more preferably an unsubstituted phenyl group.

[0025] The resinous organopolysiloxane of the present invention preferably has (Ar2SiO) in its molecular structure. 2 / 2 The proportion of units is 0.05 or more, more preferably 0.1 or more, even more preferably 0.15 or more, and preferentially 0.2 or more. In a preferred embodiment, the resinous organopolysiloxane of the present invention has (Ar2SiO in its molecular structure. 2 / 2 The proportion of the units is 0.5 or less, preferably 0.45 or less, and more preferably 0.4 or less.

[0026] At least one (Ar2SiO 2 / 2 In a resinous organopolysiloxane containing units, preferably, 40 mol% or more of the monovalent hydrocarbon groups bonded to the silicon atom are aryl groups, more preferably 50 mol% or more, and particularly 60 mol% or more are aryl groups.

[0027] The curable silicone composition of the present invention preferably comprises at least one (Ar2SiO 2 / 2The composition contains a resinous organopolysiloxane containing units of ) at an amount of 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on the total mass of the composition. In a preferred embodiment, the curable silicone composition of the present invention contains at least one (Ar2SiO 2 / 2 The composition contains a resinous organopolysiloxane containing units in an amount of 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total mass of the composition.

[0028] The curing mechanism of the curable silicone composition of the present invention is not particularly limited, and examples include a hydrosilylation reaction curing type involving an alkenyl group and a silicon atom-bonded hydrogen atom, a de-alcoholization condensation reaction curing type involving a silanol group and a silicon atom-bonded alkoxy group, and a radical reaction curing type induced by ultraviolet irradiation. Among these, the hydrosilylation reaction curing type is preferred because the entire composition hardens relatively quickly.

[0029] When the curing mechanism of the curable silicone composition of the present invention is of the hydrosilylation reaction curing type, the curable silicone composition may include (A) an alkenyl group-containing organopolysiloxane having at least two silicon atom-bonded alkenyl groups in one molecule, (B) an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, and (C) a catalyst for the hydrosilylation reaction. Herein, at least one (Ar2SiO 2 / 2 A resinous organopolysiloxane containing the ) unit may correspond to component (A), or to component (B), or to both component (A) and component (B). That is, at least one of the present invention (Ar2SiO 2 / 2 A resinous organopolysiloxane containing units may be an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule, or an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, or both.

[0030] The following describes in more detail the case where the curing mechanism of the curable silicone composition of the present invention is of the hydrosilylation reaction curing type.

[0031] (A) Alkenyl group-containing organopolysiloxane Component (A) is an alkenyl group-containing organopolysiloxane, which is the main component of a hydrosilylation reaction-curable silicone composition and has at least two silicon atom-bonded alkenyl groups in one molecule.

[0032] Examples of alkenyl groups included in component (A) are alkenyl groups having 2 to 12 carbon atoms, such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, and dodecenyl group, with vinyl group being preferred.

[0033] Examples of molecular structures of component (A) include linear, partially branched linear, branched, cyclic, and three-dimensional network structures. Component (A) may be a single organopolysiloxane having one of these molecular structures, or a mixture of two or more organopolysiloxanes having one of these molecular structures.

[0034] In one embodiment of the present invention, component (A) is (A-1) General formula: R 1 3SiO(R 1 2SiO) m SiR 1 3 (In the formula, R 1 R is the same or different halogen-substituted or unsubstituted monovalent hydrocarbon group, provided that there are at least two R groups in one molecule. 1 is an alkenyl group, and m is an integer from 5 to 1,000. ) A linear organopolysiloxane represented by , and / or (A-2) Equivalent unit formula: (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b(R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e (In the formula, R 1 The same applies as described above, except that at least two R molecules are present in one molecule. 1 X is an alkenyl group, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e are numbers satisfying 0 ≤ a ≤ 1.0, 0 ≤ b ≤ 1.0, 0 ≤ c < 0.9, 0 ≤ d < 0.5, 0 ≤ e < 0.4, a + b + c + d = 1.0, and c + d > 0. This can be a branched organopolysiloxane (i.e., a resinous organopolysiloxane) represented by ).

[0035] The curable silicone composition of the present invention preferably contains both linear organopolysiloxane and resinous organopolysiloxane as component (A). The ratio of resinous organopolysiloxane and linear organopolysiloxane content as component (A) is not particularly limited, but preferably the ratio of linear organopolysiloxane to resinous organopolysiloxane content is greater than 0.1, and more preferably greater than 0.2. Furthermore, the ratio of linear organopolysiloxane to resinous organopolysiloxane content as component (A) is preferably 1 or less, more preferably 0.9 or less, even more preferably 0.8 or less, and particularly 0.7 or less. By including linear organopolysiloxane in addition to resinous organopolysiloxane as component (A) in such ratios, it is possible to form a cured product with little change in hardness even when exposed to high temperature conditions for a long period of time.

[0036] R in the above formula 1Examples of halogen-substituted or unsubstituted monovalent hydrocarbon groups include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups; aryl groups with 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, and naphthyl groups; aralkyl groups with 7 to 20 carbon atoms such as benzyl, phenethyl, and phenylpropyl groups; alkenyl groups with 2 to 12 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, or bromine. R 1 This may be a small amount of hydroxyl group, methoxy group, ethoxy group, or other alkoxy group, as long as it does not impair the objective of the present invention.

[0037] R 1 Preferably, the group is selected from a phenyl group, an alkyl group or cycloalkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.

[0038] (A) The amount of alkenyl groups contained in the molecule of component is not particularly limited, however, R 1 Preferably, 0.01 to 50 mol%, 0.05 to 40 mol%, or 0.09 to 32 mol% of the total are alkenyl groups. The alkenyl group content can be determined, for example, by analysis such as Fourier transform infrared spectrophotometer (FT-IR) or nuclear magnetic resonance (NMR).

[0039] In a preferred embodiment, at least one (Ar2SiO 2 / 2 A resinous organopolysiloxane containing the ) unit corresponds to component (A) above. In this case, the resinous organopolysiloxane can be represented by the following average unit formula (A-3): (A-3)(R 1 3SiO 1 / 2 )a (R 1 2SiO 2 / 2 ) b (Ar2SiO 2 / 2 ) b‘ (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e (In the formula, R 1 And Ar is the same as above, except that there are at least two R in one molecule 1 is an alkenyl group, X is a hydrogen atom or an alkyl group, and R 1 2SiO 2 / 2 Ar2SiO 2 / 2 The units other than are shown, and a, b, b', c, d, and e are 0≦a≦1.0, 0≦b≦1.0, 0 <b’≦1.0、0≦c<0.9、0≦d<0.5、0≦e<0.4であり、a+b+b’+c+d=1.0であり、かつc+d> It is a number that satisfies the condition 0.

[0040] In the average unit formula (A-3), a is preferably in the range of 0 ≤ a ≤ 0.5, more preferably in the range of 0 ≤ a ≤ 0.3, preferentially in the range of 0 ≤ a ≤ 0.2, and particularly in the range of 0 ≤ a ≤ 0.1. In the average unit formula (A-3), b is preferably in the range of 0 ≤ b ≤ 0.8, more preferably in the range of 0.1 ≤ b ≤ 0.7, and particularly in the range of 0.15 ≤ b ≤ 0.6. In the average unit formula (A-3), b' is preferably in the range of 0.1 ≤ b' ≤ 0.7, more preferably in the range of 0.2 ≤ b' ≤ 0.6, and particularly in the range of 0.25 ≤ b' ≤ 0.5. In the average unit formula (A-3), c is preferably in the range of 0.1 ≤ c ≤ 0.95, more preferably in the range of 0.2 ≤ c ≤ 0.85, and particularly in the range of 0.3 ≤ c ≤ 0.8. In the average unit formula (A-3), d is preferably in the range of 0 ≤ d ≤ 0.4, more preferably in the range of 0 ≤ d ≤ 0.3, and particularly in the range of 0 ≤ d ≤ 0.2. In the average unit formula (A-3), e is preferably in the range of 0 ≤ e ≤ 0.3, more preferably in the range of 0 ≤ e ≤ 0.2, and particularly in the range of 0 ≤ e ≤ 0.1.

[0041] When the curable silicone composition of the present invention is a hydrosilylation reaction curable type and the resinous organopolysiloxane containing at least one (Ar2SiO 2 / 2 ) unit corresponds to the component (A), preferably, at least one (Ar2SiO 2 / 2 ) unit-containing resinous organopolysiloxane as this component (A) is contained at 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more based on the total mass of the composition. In a preferred embodiment, at least one (Ar2SiO 2 / 2 ) unit-containing resinous organopolysiloxane as the component (A) is contained at 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less based on the total mass of the composition.

[0042] Further, the curable silicone composition of the present invention preferably contains both a linear organopolysiloxane and a resinous organopolysiloxane containing at least one (Ar2SiO 2 / 2 ) unit as the component (A). The ratio of the content of the resinous organopolysiloxane containing at least one (Ar2SiO 2 / 2 ) unit and the linear organopolysiloxane as the component (A) is not particularly limited, but preferably, the ratio of the content of the linear organopolysiloxane / the resinous organopolysiloxane containing at least one (Ar2SiO 2 / 2 ) unit is greater than 0.1, more preferably greater than 0.2. Also, the ratio of the content of the linear organopolysiloxane / the resinous organopolysiloxane containing at least one (Ar2SiO 2 / 2 ) unit as the component (A) is preferably 1 or less, more preferably 0.9 or less, still more preferably 0.8 or less, particularly 0.7 or less. With such a ratio, at least one (Ar2SiO 2 / 2By including linear organopolysiloxanes in addition to resin-like organopolysiloxanes containing ) units, it is possible to form a cured product with minimal change in hardness even when exposed to high-temperature conditions for a long period of time.

[0043] (B) Organohydrogenpolysiloxane The organohydrogenpolysiloxane of component (B), having at least two silicon-bonded hydrogen atoms in one molecule, acts as a crosslinking agent for a curable silicone composition that is hydrosilylated reaction curing type. Preferably, component (B) is a linear organohydrogenpolysiloxane containing silicon-bonded hydrogen atoms at least at both ends of the molecular chain. Component (B) may be a single organopolysiloxane or a combination of two or more organopolysiloxanes.

[0044] The silicon-bonded hydrogen atoms of component (B) are preferably contained at least at both ends of the molecular chain, and may also be contained in the side chains of the molecular chain, or may be contained only at both ends of the molecular chain. Examples of groups that bond to silicon atoms other than hydrogen atoms in component (B) include alkyl groups with 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group; aryl groups with 6 to 20 carbon atoms such as phenyl group, tolyl group, xylyl group, and naphthyl group; aralkyl groups with 7 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, and bromine. Furthermore, the silicon atoms in component (B) may have small amounts of hydroxyl groups, methoxy groups, ethoxy groups, or other alkoxy groups, as long as this does not impair the objectives of the present invention. Examples of such component (B) include dimethylpolysiloxane with dimethylhydrogensiloxy groups sealed at both ends of the molecular chain.

[0045] (B) component's molecular structure includes linear, linear with a partial branch, branched chain, cyclic, and three-dimensional network structures. Preferably, it is a linear with a partial branch, branched chain, or three-dimensional network structure.

[0046] In one embodiment of the present invention, the (B) component is a (B-1) average compositional formula: (R 2 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R 2 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e (wherein, R 2 is a hydrogen atom or the same or different halogen-substituted or unsubstituted monovalent hydrocarbon group, provided that at least two R 2 are hydrogen atoms, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e are numbers satisfying 0≦a≦1. (), 0≦b≦1.0, 0≦c<0.9, 0≦d<0.5, 0≦e<0.4, and a + b + c + d = 1.0). It can be an organohydrogenpolysiloxane represented by this average compositional formula. In this average compositional formula, examples of the halogen-substituted or unsubstituted monovalent hydrocarbon group of R 2 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, and decyl group; aryl groups such as phenyl group, tolyl group, xylyl group, and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group; and halogen-substituted alkyl groups such as 3-chloropropyl group, 2-bromoethyl group, and 3,3,3-trifluoropropyl group.

[0047] In a preferred embodiment of the present invention, the (B) component can be represented by the following structural formula: [HR 4 2SiO 1 / 2]2[R 4 2SiO 2 / 2 ] y In the formula, R 4 R is the same or different halogen-substituted or unsubstituted monovalent hydrocarbon group, and y is a number in the range of 1 to 100, preferably 1 to 10. 4 As for halogen-substituted or unsubstituted monovalent hydrocarbon groups, R 2 The same example shown can be applied.

[0048] In one embodiment of the present invention, at least one (Ar2SiO 2 / 2 The above component (B) may be a resinous organopolysiloxane containing the ) unit. That is, in one embodiment of the present invention, component (B) is at least one (Ar2SiO 2 / 2 It contains a resinous organopolysiloxane containing units. In this case, this (B) component is (B-2) average unit formula: (R 3 3SiO 1 / 2 ) a (R 3 2SiO 2 / 2 ) b (Ar2SiO 2 / 2 ) b‘ (R 3 SiO 3 / 2 ) c (SiO 4 / 2 ) d (XO 1 / 2 ) e (In the formula, R 3 R 2 It is the same as, and Ar indicates an aryl group, however, at least two R 3 is a hydrogen atom, X is a hydrogen atom or an alkyl group, and a, b, b', c, d, and e are such that 0 ≤ a ≤ 1.0, 0 ≤ b ≤ 1.0, 0 <b’≦1.0、0≦c<0.9、0≦d<0.5、0≦e<0.4であり、a+b+b’+c+d=1.0であり、かつc+d> It is a number that satisfies 0.) It may be a resinous organohydrogenpolysiloxane represented by ).

[0049] (B) Component is at least one (Ar2SiO2 / 2 If the resin-like organopolysiloxane contains units of (A), then the (Ar2SiO) contained in component (A) 2 / 2 A resinous organopolysiloxane containing units of (B), and at least one (Ar2SiO) contained in component (B). 2 / 2 The total amount of resinous organopolysiloxane containing the ) unit is at least one of the (Ar2SiO) units of the present invention. 2 / 2 The amount of resinous organopolysiloxane containing units of (Ar2SiO) is such that the curable silicone composition of the present invention contains at least one (Ar2SiO) contained in component (A) and component (B). 2 / 2 The total amount of resinous organopolysiloxane containing the ) units is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferentially 40% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and particularly 70% by mass or less, based on the total mass of the composition.

[0050] The content of component (B) is such that, for every mole of silicon-bonded alkenyl groups in component (A), there are 0.1 to 10 moles of silicon-bonded hydrogen atoms in this component, preferably 0.5 to 5 moles, and particularly 0.8 to 1.2 moles. The content of silicon-bonded hydrogen atoms in component (B) can be determined, for example, by analysis such as Fourier transform infrared spectrophotometer (FT-IR) or nuclear magnetic resonance (NMR).

[0051] (C) Catalyst for hydrosilylation reaction The catalyst for the hydrosilylation reaction of component (C) is a catalyst for accelerating the curing of a hydrosilylation reaction-curing type silicone composition. Examples of such component (C) include platinum-based catalysts such as chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a complex of platinum and an olefin, a complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and platinum-supported powder; palladium-based catalysts such as tetrakis(triphenylphosphine)palladium, palladium black, and a mixture with triphenylphosphine; and rhodium-based catalysts, with platinum-based catalysts being particularly preferred.

[0052] The amount of component (C) is the amount of catalyst, and when a platinum-based catalyst is used as component (C), the amount of platinum metal contained in this platinum-based catalyst is practically preferable to be in the range of 0.01 to 1000 ppm by weight in the silicone composition, and in particular, it is preferable to be in the range of 0.1 to 500 ppm.

[0053] The curable silicone composition of the present invention may contain optional components as long as they do not impair the objectives of the present invention. Examples of these optional components include acetylene compounds, organophosphorus compounds, vinyl group-containing siloxane compounds, hydrosilylation reaction inhibitors; inorganic fillers (also called "inorganic fillers") such as fumed silica, wet silica, pulverized quartz, titanium dioxide, magnesium carbonate, zinc oxide, iron oxide, and diatomaceous earth; inorganic fillers obtained by hydrophobic treatment of the surface of an inorganic filler with an organosilicon compound; organopolysiloxanes that do not contain silicon atom-bonded hydrogen atoms or silicon atom-bonded alkenyl groups; tackifiers; heat resistance imparters; cold resistance imparters; thermal conductivity fillers; flame retardants; thixotropic agents; phosphors; coloring components such as pigments and dyes such as carbon black; and solvents.

[0054] Hydrosilylation reaction inhibitors are components for suppressing the hydrosilylation reaction of silicone compositions. Specifically, examples include acetylene-based, amine-based, carboxylic acid ester-based, and phosphite-based reaction inhibitors such as ethinylcyclohexanol. The amount of reaction inhibitor added is usually 0.001 to 5% by mass of the total silicone composition.

[0055] Examples of inorganic fillers include fumed silica, crystalline silica, precipitated silica, hollow fillers, silsesquioxane, fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, zinc carbonate, layered mica, diatomaceous earth, and glass fibers; 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 and silicone resin powder may also be incorporated. However, the amount of inorganic filler is preferably 20% by mass or less, and particularly preferably 10% by mass or less, of the silicone composition.

[0056] Examples of phosphors include yellow, red, green, and blue phosphors, and mixtures of at least two of these, which are widely used in light-emitting diodes (LEDs), consisting of oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, oxysulfide-based phosphors, fluoride-based phosphors, etc. Examples of oxide-based phosphors include YAG-type green to yellow phosphors containing cerium ions (yttrium, aluminum, garnet), TAG-type yellow phosphors containing cerium ions (terbium, aluminum, garnet), and silicate-type green to yellow phosphors containing cerium or europium ions. Examples of oxynitride-based phosphors include sialon-type red to green phosphors containing europium ions (silicon, aluminum, oxygen, nitrogen). Examples of nitride-based phosphors include cousin-type red phosphors containing europium ions (calcium, strontium, aluminum, silicon, nitrogen). Examples of sulfide-based phosphors include ZnS-based green phosphors containing copper and aluminum ions. Examples of oxysulfide-based phosphors include Y2O2S-based red phosphors containing europium ions. Examples of fluoride-based phosphors include KSF phosphors (K2SiF6:Mn 4+ ) are some examples.

[0057] As coloring components, one type of organic or inorganic pigment and dye, or a combination of two or more types, can be used. When using phosphors, the amount blended is 90% by mass or less, preferably 80% by mass or less, and particularly preferably 70% by mass or less of the silicone composition. In addition, black pigments can be used from the viewpoint of preventing light interference and improving color contrast in displays. Examples of black pigments include iron oxide, aniline black, activated carbon, graphite, carbon nanotubes, and carbon black. Specifically, the amount of coloring components blended is 30% by mass or less, preferably 15% by mass or less, and particularly preferably 5% by mass or less of the silicone composition.

[0058] Examples of adhesion promoters include epoxy group-containing alkoxysilanes, acrylic group-containing alkoxysilanes, amino group-containing alkoxysilanes, reaction condensates of silane coupling agents, organotitanium compounds, organoaluminum compounds, organozirconium compounds, and ethyl polysilicate [average molecular formula Si m O (m-1) (OC2H5) 2(m+1) Examples include (where m in the formula is 5 on average). Among these, the aforementioned organotitanium compounds, reaction condensates of silane coupling agents, and ethyl polysilicate [average molecular formula Si m O (m-1) (OC2H5) 2(m+1) (where m in the formula is 5 on average), it is preferable to use a SiO2 content of 40% by weight, viscosity of 5 mPa·s, or a combination thereof.

[0059] The curable silicone composition of the present invention can be prepared by mixing its components. The method of mixing the components is not particularly limited and can be any conventionally known method, but usually a homogeneous mixture is obtained by simple stirring. Furthermore, if the composition includes solid components such as inorganic fillers as optional components, mixing using a mixing device is more preferable. Such mixing devices are not particularly limited, and examples include single-screw or twin-screw continuous mixers, double-roll mixers, Ross mixers, Hobart mixers, Dental mixers, Planetary mixers, Kneader mixers, Henschel mixers, and the like.

[0060] The curable silicone composition of the present invention is used for encapsulating, coating, or bonding optoelectronic semiconductor devices. The cured product obtained using the curable silicone composition of the present invention has sufficiently low gas permeability (water vapor permeability and / or oxygen permeability), and exhibits little weight loss and hardness change even when exposed to high-temperature conditions for extended periods. Therefore, discoloration of the cured product is less likely to occur even when exposed to corrosive gases, and corrosion of electrodes encapsulated, coated, or bonded by the cured product can be suppressed. Furthermore, even when the curable silicone composition of the present invention is used in power LED devices such as CSPs that are used for extended periods under high-temperature conditions, discoloration and cracking of the cured product can be suppressed. As a result, the curable silicone composition of the present invention can be used to manufacture optoelectronic devices with excellent reliability and high-temperature durability.

[0061] [Optical Semiconductor Equipment] The optical semiconductor device of the present invention comprises an optical semiconductor element that is a cured product of the curable silicone composition of the present invention. Specifically, the optical semiconductor element is sealed, coated, or bonded with the cured product of the curable silicone composition of the present invention. Examples of this optical semiconductor element include light-emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state imaging devices, and light-emitting and light-receiving elements for photocouplers, with light-emitting diodes (LEDs) being particularly preferred.

[0062] Since light-emitting diodes (LEDs) emit light from all sides (top, bottom, left, and right) of the optical semiconductor element, materials that absorb light are undesirable for the components of an LED, and materials with high light transmittance or high reflectance are preferred. For this reason, the substrate on which the optical semiconductor element is mounted is also preferably made of a material with high light transmittance or high reflectance. Examples of substrates on which such optical semiconductor elements are mounted include conductive metals such as silver, gold, and copper; non-conductive metals such as aluminum and nickel; thermoplastic resins mixed with white pigments such as PPA and LCP; thermosetting resins containing white pigments such as epoxy resin, BT resin, polyimide resin, and silicone resin; and ceramics such as alumina and alumina nitride.

[0063] The optical semiconductor device of the present invention is sealed, coated, or bonded with a cured product of the curable silicone composition of the present invention, and therefore exhibits excellent reliability and high-temperature durability.

[0064] [Manufacturing method for optoelectronic devices] The semiconductor device manufacturing method according to the present invention is a method for manufacturing an optoelectronic semiconductor device using the curable silicone composition of the present invention. Therefore, the semiconductor device manufacturing method according to the present invention includes a step of sealing, coating, or bonding an optoelectronic semiconductor element using the curable silicone composition, and includes, for example, a step of using the curable silicone composition of the present invention as a encapsulant, coating agent, and / or adhesive for the optoelectronic semiconductor element. By using such a semiconductor device manufacturing method, since the curable silicone composition of the present invention is used, it is possible to provide a semiconductor device with high reliability and high temperature durability. [Examples]

[0065] The curable silicone composition of the present invention will be described in detail by the following examples and comparative examples.

[0066] [Examples 1-6 and Comparative Examples 1-5] A curable silicone composition was prepared by mixing each component in the composition (parts by weight) shown in Table 1. In Table 1, H / Vi represents the molar ratio of silicon-bonded hydrogen atoms in the silicon-bonded hydrogen atom-containing organopolysiloxane to 1 mole of alkenyl groups in the alkenyl group-containing organopolysiloxane in this composition. Furthermore, below, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

[0067] Component a-1: Average structural formula (ViMeSiO 2 / 2 ) 25 (Ph2SiO 2 / 2 ) 30 (PhSiO 3 / 2 ) 45 Alkenyl group-containing organopolysiloxane resin represented by Component a-2: Average structural formula (ViPhMeSiO 1 / 2 ) 23 (PhSiO 3 / 2 ) 77 Alkenyl group-containing organopolysiloxane represented by Component a-3: Average structural formula (ViMe2SiO 1 / 2 ) 25 (PhSiO 3 / 2 ) 75 Alkenyl group-containing organopolysiloxane represented by Component a-4: General formula (ViMe2SiO 1 / 2 )(PhMeSiO 2 / 2 ) 20 (ViMe2SiO 1 / 2 Alkenyl group-containing organopolysiloxanes represented by ) Component a-5: Average structural formula (ViMeSiO 2 / 2 ) 25 (Ph2SiO 2 / 2 ) 24 (PhSiO 3 / 2 ) 51 Alkenyl group-containing organopolysiloxane resin represented by Component a-6: Average structural formula (ViMeSiO 2 / 2 ) 25 (Ph2SiO 2 / 2 ) 38 (PhSiO 3 / 2 ) 37 Alkenyl group-containing organopolysiloxane resin represented by Component a-7: Average structural formula (ViMeSiO 2 / 2 ) 25 (Ph2SiO 2 / 2 ) 35 (PhSiO 3 / 2 ) 40 Alkenyl group-containing organopolysiloxane resin represented by Component a-8: Average structural formula (ViMeSiO 2 / 2 ) 30 (Ph2SiO 2 / 2 ) 30 (PhSiO 3 / 2 ) 40 Alkenyl group-containing organopolysiloxane resin represented by Component a-9: Average structural formula (ViMeSiO2 / 2 ) 27 (Ph2SiO 2 / 2 ) 27 (PhSiO 3 / 2 ) 46 Alkenyl group-containing organopolysiloxane resin represented by Component a-10: Average structural formula (ViMe2SiO 1 / 2 ) 25 (Ph2SiO 2 / 2 ) 25 (PhSiO 3 / 2 ) 50 Alkenyl group-containing organopolysiloxane resin represented by Component a-11: Average structural formula (ViPhMeSiO 1 / 2 ) 25 (Ph2SiO 2 / 2 ) 30 (PhSiO 3 / 2 ) 45 Alkenyl group-containing organopolysiloxane resin represented by Component a-12: Average structural formula (ViMe2SiO 1 / 2 ) 25 (Ph2SiO 2 / 2 ) 30 (PhSiO 3 / 2 ) 45 Alkenyl group-containing organopolysiloxane resin represented by Component b: General formula (HMe2SiO 1 / 2 )(Ph2SiO 2 / 2 )(HMe2SiO 1 / 2 Diphenylsiloxane with dimethylhydrogensiloxy groups sealed at both ends of the molecular chain, represented as ) Component c: A complex of platinum with a platinum concentration of 4.0% by mass and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. Component d: 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane

[0068] The curable silicone compositions obtained from Examples 1-6 and Comparative Examples 1 and 2 were evaluated as follows. The results are shown in the table below. Note that the silicone compositions from Comparative Examples 3-5 did not cure, so they were not evaluated below.

[0069] [Heating loss] A curable silicone composition was heated at 150°C for 2 hours to produce a cured product. The weight loss of 20g of this cured product was measured after holding it at 200°C for 1000 hours. A weight loss of less than 6% was classified as "good," while a weight loss of 6% or more was classified as "poor."

[0070] [Changes in storage modulus at high temperatures (200°C)] A curable silicone composition was heated at 150°C for 2 hours to produce a cured product. The storage modulus of this cured product at high temperatures was measured before and after heat treatment (200°C, 1000 hours), and the ratio of change in storage modulus due to high temperature holding was calculated. Products with a change in storage modulus of less than 10 times before and after heat treatment were classified as "good," and products with a change in storage modulus of 10 times or more before and after heat treatment were classified as "poor." Anton Paar's MCR302 was used to measure the storage modulus under a heating rate of 3°C / min.

[0071] A cured material that shows little change in storage modulus even after being held at high temperatures for a long time indicates that its hardness does not change and its flexibility does not decrease even after being held at high temperatures for a long time. A cured material that shows little weight loss and little change in storage modulus even after being held at high temperatures for a long time is less likely to discolor or crack when used as an LED encapsulant, for example, and can prevent cracks and misbonding when used for bonding chip bonding pads, etc.

[0072] [Water vapor transmission rate] A curable silicone composition was cured using a press at 150°C for 2 hours to produce a 1 mm thick sheet-like cured material. The water vapor transmission rate of this film-like cured material was measured using a Systech illinois water vapor transmission rate meter (Model 7002) under conditions of 40°C and 90% relative humidity. The water vapor transmission rate was 13 g / m². 2 A result of less than 24 hours is considered "good," and the value is 13 g / m². 2 If the time was 24 hours or more, it was indicated as "defective".

[0073] [Oxygen permeability] A curable silicone composition was cured using a press at 150°C for 2 hours to produce a 1 mm thick sheet of cured material. The oxygen permeability of this cured material was measured at 23°C using an oxygen permeability meter (Model 8001) manufactured by Systech illinois. The oxygen permeability was 600 cc / m³. 2 A result of less than 24 hours is considered "good," and an oxygen permeability of 600 cc / m³ is considered "good." 2 If the time was 24 hours or longer, it was indicated as "defective".

[0074] [Table 1] [Table 2] [Table 3] [Industrial applicability]

[0075] The curable silicone composition of the present invention is useful as a encapsulant, coating agent, or adhesive for optical semiconductor elements such as light-emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state imaging devices, and light-emitting and light-receiving elements for photocouplers. Furthermore, the optical semiconductor device of the present invention is useful as an optical semiconductor device such as an optical device, optical instrument, lighting equipment, or lighting device.

Claims

1. A curable silicone composition for encapsulating, coating, or bonding optical semiconductor devices, wherein the cured product is light-transmitting, The curable silicone composition, (A) A linear alkenyl group-containing organopolysiloxane having at least two silicon atom-bonded alkenyl groups in one molecule, and The following average unit formula (R 1 2 SiO 2 / 2 ) b (Ar 2 SiO 2 / 2 ) b' (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (In the formula, R1 is the same or different halogen-substituted or unsubstituted monovalent hydrocarbon group, Ar is an aryl group, provided that 0.01 to 50 mol% of the total R1 is an alkenyl group, the unit (R1 2 SiO 2 / 2) represents a unit other than Ar 2 SiO 2 / 2, and b, b', c, and d are numbers satisfying 0 ≤ b < 1.0, 0 < b' < 1.0, 0 < c < 0.9, 0 ≤ d < 0.5, b + b' + c + d = 1.0, and c + d > 0) Resinous organopolysiloxanes represented by: (B) An organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, wherein the following average unit formula (HR 4 2 SiO 1 / 2 ) 2 (R 4 2 SiO 2 / 2 ) y (In the formula, R 4 is a hydrogen atom or the same or different halogen-substituted or unsubstituted monovalent hydrocarbon group, y is 1 to 100, and at least one (R 4 2 SiO 2 / 2) is (Ar 2 SiO 2 / 2), where Ar is an aryl group.) Organohydrogenpolysiloxanes represented by, and (C) Catalyst for hydrosilylation reaction Includes, The ratio of the content of the linear alkenyl group-containing organopolysiloxane to the resinous alkenyl group-containing organopolysiloxane is greater than 0.

2. A curable silicone composition in which the amount of silicon-bonded hydrogen atoms in component (B) is 0.8 to 1.2 moles relative to 1 mole of silicon-bonded alkenyl groups in component (A).

2. The resin-like organopolysiloxane (R １ ２ SiO ２／２ ) Both R in the unit １ The curable silicone composition according to claim 1, wherein the alkyl group is not also an alkyl group.

3. The curable silicone composition according to claim 1 or 2, wherein d in the resinous organopolysiloxane is 0.

4. The curable silicone composition according to any one of claims 1 to 3, comprising the resin-like organopolysiloxane in an amount of 10% by mass or more and 90% by mass or less based on the total mass of the composition.

5. An optoelectronic device comprising a cured product of a curable silicone composition according to any one of claims 1 to 4.

6. A method for manufacturing an optoelectronic device, comprising the step of encapsulating, coating, or bonding an optoelectronic semiconductor element using a curable silicone composition according to any one of claims 1 to 4.

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