JP6302816B2 - Silicone resin composition and optical semiconductor device - Google Patents

Description

  A composition containing an epoxy resin having no UV absorption, such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin or an alicyclic epoxy resin having excellent adhesion and mechanical strength, a curing agent, and a curing catalyst is an optical semiconductor. It is frequently used as a sealing resin composition for elements. However, as the luminance and output of the LED element increase, the cured product obtained from these resin compositions is subject to discoloration and cracking due to light and heat from the LED element.

  As a resin that does not absorb UV and gives a flexible cured product, a resin in which an epoxy group is introduced into a silicone resin is known. For example, Patent Document 1 discloses a reaction product of an alkoxysilane having one or more cyclic ether-containing groups such as a glycidyl group and an alicyclic epoxy group, and a polyorganosiloxane having both terminal silanol groups and / or alkoxy groups. Is described. However, the silicone resin has a very high gas permeability compared to the epoxy resin. Therefore, as the silicone content increases, it becomes difficult to use in applications that require low gas permeability. Patent Document 2 describes that a phenyl group is introduced into polyorganosiloxane in order to improve low gas permeability. Specifically, it describes that a composition containing an organopolysiloxane having an epoxy group and a predetermined amount of diphenylsiloxane units is a sealing material excellent in heat resistance and moisture permeability resistance.

JP 2014-31522 A JP 2012-92172 A

  The organopolysiloxane described in Patent Document 2 includes an organosilicon compound such as diphenyldimethoxysilane, diphenylsilanediol, dimethyldimethoxysilane, cyclohexylmethyldimethoxysilane, and 2- (3′4′-epoxycyclohexyl) ethyltrimethoxysilane. It is manufactured by reacting with The organopolysiloxane has an alicyclic epoxy group on the T unit siloxane structure. When the amount of diphenylsiloxane units is increased in order to obtain low gas permeability in such an organopolysiloxane, the viscosity of the organopolysiloxane becomes very high and the workability of the resin composition is inferior. Therefore, development of a sealing resin material that is excellent in workability, in particular, has a low viscosity and is excellent in low gas permeability is desired.

  An object of this invention is to provide the silicone resin composition which has many diphenylsiloxane units and has low viscosity in view of the said situation.

The present inventors have intensively studied to solve the above problems, and organopolysiloxane having a D unit siloxane structure having an alicyclic epoxy group has a low viscosity even if the amount of diphenylsiloxane units is large, and the resulting composition Has been found to be excellent in workability, and has led to the present invention.

（式（１）中、Ｒ^１は炭素数６〜１２の一価芳香族炭化水素基であり、Ｒ^２は炭素数１〜１２の、不飽和結合を有してもよい一価脂肪族炭化水素基であり、Ｒ^３は下記のいずれかの構造で表される基であり、

、

（上記構造中、Ｒ’は水素原子または炭素数１〜６のアルキル基であり、Ｒ ^４ は炭素数１〜２０の２価の炭化水素基である）
ＲはＲ^１、Ｒ^２、及びＲ^３のための選択肢から選ばれる基であり、０≦ｋ＜０．５、０．１≦ｍ≦０．５、０≦ｎ＜０．８、０．０１≦ｐ≦０．５、０≦ｑ＜０．６であり、ｋ＋ｍ＋ｎ＋ｐ＋ｑ＝１であり、但し、ｋ及びｎは同時に０でない。上記括弧内にある各シロキサン単位の結合順序は制限されないが、−Ｏ_１／２Ｘの少なくとも２つは末端に結合されており、Ｘは水素原子または炭素数１〜１０のアルキル基であり、ｒは−Ｏ_１／２Ｘの個数であり、ｑ＝０のときｒは２であり、ｑ≠０のときｒは（ＲＳｉＯ_３／２）単位の個数＋２である）
（Ｂ）エポキシ基と反応する官能基を有する硬化剤 （Ａ）成分中のエポキシ基１個に対する（Ｂ）成分中のエポキシ基と反応する官能基の個数が０．３〜１個となる量、及び
（Ｃ）硬化触媒 触媒量
を含有するシリコーン樹脂組成物を提供する。
That is, the present invention
(A) Organopolysiloxane represented by the following formula (1)

(In formula (1), R ¹ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ² is a monovalent aliphatic carbonized carbon atom having 1 to 12 carbon atoms and may have an unsaturated bond. A hydrogen group, and R ³ is a group represented by any of the following structures:

,

(In the above structure, R ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms)
R is a group selected from the options for R ¹ , R ² , and R ³ , 0 ≦ k <0.5, 0.1 ≦ m ≦ 0.5, 0 ≦ n <0.8, 0. 01 ≦ p ≦ 0.5, 0 ≦ q <0.6, and k + m + n + p + q = 1, provided that k and n are not 0 at the same time. The bonding order of each siloxane unit in the parenthesis is not limited, but at least two of -O1 _/ 2X are bonded to the terminal, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, r is the number of -O _1/2 X, r is 2 when q = 0, and r is the number of (RSiO _3/2 ) units + 2 when q ≠ 0)
(B) Curing agent having a functional group that reacts with an epoxy group (A) Amount that the number of functional groups that react with an epoxy group in component (B) is 0.3 to 1 with respect to one epoxy group in component (A) And (C) a curing catalyst. A silicone resin composition containing a catalytic amount is provided.

  The present invention also provides an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the silicone resin composition.

  The silicone resin composition of the present invention can give a cured product having excellent low gas permeability, and has a low viscosity and excellent workability. Moreover, it is excellent also in heat resistance and UV resistance. Therefore, it can be suitably used as a resin composition for sealing an optical semiconductor element.

（１）
（式（１）中、Ｒ^１は炭素数６〜１２の一価芳香族炭化水素基であり、Ｒ^２は炭素数１〜１２の、不飽和結合を有してもよい一価脂肪族炭化水素基であり、Ｒ^３は炭素数７〜５０の一価脂環式エポキシ基であり、ＲはＲ^１、Ｒ^２、及びＲ^３のための選択肢から選ばれる基であり、０≦ｋ＜０．５、０．１≦ｍ≦０．５、０≦ｎ＜０．８、０．０１≦ｐ≦０．５、０≦ｑ＜０．６であり、ｋ＋ｍ＋ｎ＋ｐ＋ｑ＝１であり、但し、ｋ及びｎは同時に０でない。上記括弧内にある各シロキサン単位の結合順序は制限されないが、−Ｏ_１／２Ｘの少なくとも２つは末端に結合されており、Ｘは水素原子または炭素数１〜１０のアルキル基であり、ｒは−Ｏ_１／２Ｘの個数であり、ｑ＝０のときｒは２であり、ｑ≠０のときｒは（ＲＳｉＯ_３／２）単位の個数＋２である） Hereinafter, the present invention will be described in detail.
(A) The organopolysiloxane (A) component is an organopolysiloxane represented by the following formula (1).

(1)
(In formula (1), R ¹ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ² is a monovalent aliphatic carbonized carbon atom having 1 to 12 carbon atoms and may have an unsaturated bond. A hydrogen group, R ³ is a monovalent alicyclic epoxy group having 7 to 50 carbon atoms, R is a group selected from the options for R ¹ , R ² , and R ³ , and 0 ≦ k < 0.5, 0.1 ≦ m ≦ 0.5, 0 ≦ n <0.8, 0.01 ≦ p ≦ 0.5, 0 ≦ q <0.6, k + m + n + p + q = 1, provided that k and n are not simultaneously 0. Although the bonding order of each siloxane unit in the parentheses is not limited, at least two of —O _1/2 X are bonded to the terminal, and X is a hydrogen atom or a carbon number of 1 -10, r is the number of —O _1/2 X, r is 2 when q = 0, and r is (RSiO _{3 / 2} ) Number of units + 2)

In the above formula (1), R ¹ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms. Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group, and aralkyl groups such as benzyl group, 2-phenylethyl group and 2-phenylpropyl group. Among these, a phenyl group, a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group are preferable, and a phenyl group is more preferable.

In the above formula (1), R ² is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, which may have an unsaturated bond. Examples of the monovalent aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, heptyl group, 2-ethylhexyl group, heptyl group, octyl group and the like. Examples thereof include saturated monovalent aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups such as vinyl groups, allyl groups, isopropenyl groups, and butenyl groups. Among them, a saturated monovalent aliphatic hydrocarbon group is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a heptyl group are particularly preferable, and a methyl group is more preferable. It is a group.

上記構造中、Ｒ’は水素原子または炭素数１〜６のアルキル基であり、特に好ましくは水素原子である。上記において、Ｒ^４は炭素数１〜２０の２価の炭化水素基である。例えば、メチレン基、エチレン基、プロピレン基等のアルキレン基、オキシメチレン基、オキシエチレン基、オキシプロピレン基等のオキシアルキレン基（即ち−ＯＲ^５−、ここでＲ^５はアルキレン基でありシクロヘキサン環に結合する）、カルボニル基、及びオキシカルボニル基（即ち−ＯＣ（＝Ｏ）−であり、カルボニル基側がシクロヘキサン環に結合する）が挙げられる。 In the above formula (1), R ³ is a monovalent alicyclic epoxy group having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, and more preferably 7 to 30 carbon atoms. The alicyclic epoxy group is represented by the following structure, for example.

In the above structure, R ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. In the above, R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms. For example, an alkylene group such as a methylene group, an ethylene group, or a propylene group, an oxyalkylene group such as an oxymethylene group, an oxyethylene group, or an oxypropylene group (that is, —OR ⁵ —, where R ⁵ is an alkylene group, Carbonyl group, and oxycarbonyl group (that is, —OC (═O) —, and the carbonyl group side is bonded to the cyclohexane ring).

（２）
（Ｒ^４は好ましくは炭素数１〜２０のアルキレン基であり、より好ましくはエチレン基である。）
特に好ましくは下記構造の脂環式エポキシ基（β−（３，４−エポキシシクロへキシル）エチル基）である。

Especially, the alicyclic epoxy group represented by following formula (2) is preferable.

(2)
(R ⁴ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an ethylene group.)
Particularly preferred is an alicyclic epoxy group (β- (3,4-epoxycyclohexyl) ethyl group) having the following structure.

In the above formula (1), R is a group selected from the options described for R ¹ , R ² , and R ³ above.

  The above formula (1) is a composition formula, and k, m, n, p, and q represent the number ratio (molar ratio) of each siloxane unit. 0 ≦ k <0.5, 0.1 ≦ m ≦ 0.5, 0 ≦ n <0.8, 0.01 ≦ p ≦ 0.5, and 0 ≦ q <0.6, k + m + n + p + q = 1 It is. However, k and n are not 0 at the same time. The bonding order of the siloxane units in the parentheses is not limited.

p represents the content (molar ratio) of the alicyclic epoxy group-containing D units (that is, (R ³ R ² SiO _2/2 ) units). Preferably 0.03 ≦ p ≦ 0.5, more preferably 0.05 ≦ p ≦ 0.5, and particularly preferably 0.05 ≦ p ≦ 0.4. When the value of p is in the above range, an organopolysiloxane having a low viscosity can be provided.

m represents the content (molar ratio) of siloxane units having two monovalent aromatic hydrocarbon groups (that is, (R ¹ ₂ SiO _2/2 ) units). m is preferably 0.12 ≦ m ≦ 0.5, more preferably 0.14 ≦ m ≦ 0.48, and particularly 0.15 ≦ m ≦ 0.45. When the value of m is in the above range, a cured product having excellent low gas permeability can be provided.

In order to achieve both low gas permeability and low viscosity in the present invention, the (R ² ₂ SiO _2/2 ) unit and the (R ¹ R ² SiO ₂ ) unit are combined with the above (R ¹ ₂ SiO _2/2 ) unit. _{/ 2} ) It is necessary to include at least one of the units. If the unit is not included, the low gas permeability and low viscosity of the organopolysiloxane cannot be achieved. Therefore, n and k must not be 0. A preferable range of n is 0 <n ≦ 0.7, more preferably 0.5 ≦ n ≦ 0.78, and particularly 0.6 ≦ n ≦ 0.7. A preferable range of k is 0 <k ≦ 0.45, more preferably 0.1 ≦ k ≦ 0.38, and particularly 0.2 ≦ k ≦ 0.35.

When the (R ¹ ₂ SiO _2/2 ) unit is included in combination with the (R ¹ R ² SiO _2/2 ) unit, m is preferably 0.12 ≦ m ≦ 0.2, more preferably 0.14 ≦ m ≦ 0.19, in particular 0.15 ≦ m ≦ 0.18, and n is preferably 0.5 ≦ n ≦ 0.78, more preferably 0.6 ≦ n ≦ 0.7. Good. By including the combination, low gas permeability and low viscosity can be achieved satisfactorily.

When including (R ¹ ₂ SiO _2/2 ) units in combination with (R ² ₂ SiO _2/2 ) units, m is preferably 0.3 ≦ m ≦ 0.5, more preferably 0.35 ≦ m. ≦ 0.48, especially 0.38 ≦ m ≦ 0.45, k is preferably 0.1 ≦ k ≦ 0.45, more preferably 0.2 ≦ k ≦ 0.38. . By including the combination, low gas permeability and low viscosity can be achieved satisfactorily.

The organopolysiloxane of the present invention may have T units (branched). In the above, the unit represented by q represents the content (molar ratio) of T unit (that is, (RSiO _3/2 ) unit). The value of q is preferably 0 ≦ q ≦ 0.5, more preferably 0 ≦ q ≦ 0.3, and particularly preferably 0 ≦ q ≦ 0.1.

The organopolysiloxane is blocked with —O _1/2 X at the ends. X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. r means the number of —O _1/2 X contained in one molecule. When q = 0, r is 2. When q ≠ 0, r is the number of (RSiO _3/2 ) units + 2. X is preferably a hydrogen atom or a methyl group, particularly a methyl group.

In the organopolysiloxane, the number of monovalent aromatic hydrocarbon groups (R ¹ ) is preferably 40% or more and 95% or less of the total number of R, R ¹ , R ² , and R ³ , and more preferably Is 45% or more and 75% or less, and particularly preferably 50% or more and 65% or less. By being in the said range, heat resistance, UV resistance, and low gas permeability can be improved more. When the content of the monovalent aromatic hydrocarbon group is larger than the above upper limit, the viscosity of the composition is very high and workability is deteriorated. When the content of the monovalent aromatic hydrocarbon group is smaller than the lower limit, a cured product having sufficient low gas permeability cannot be formed. The monovalent aromatic hydrocarbon group (R ¹ ) is preferably a phenyl group.

  The organopolysiloxane preferably has a weight average molecular weight (Mw) of 2,000 to 10,000 in terms of polystyrene as measured by gel permeation chromatography (GPC), more preferably 2,500 to 6,000. . When the weight average molecular weight (Mw) is within the above range, the composition has good workability and is easy to handle when sealing the optical semiconductor element. Moreover, the hardened | cured material obtained from the said composition has sufficient mechanical characteristics as an optical semiconductor sealing material.

上記各式において、ｋ、ｍ、ｎ、ｐ、ｑ、及びｒは上記の通りである。上記括弧内にある各シロキサン単位の結合順序は制限されない。Ｍｅはメチル基を示す。Ｘは水素原子またはメチル基である。 Examples of the organopolysiloxane represented by the above formula (1) include a structure represented by the following formula.

In the above formulas, k, m, n, p, q, and r are as described above. The bonding order of the siloxane units in the parentheses is not limited. Me represents a methyl group. X is a hydrogen atom or a methyl group.

The method for producing the organopolysiloxane represented by the above formula (1) is not particularly limited. (R ² ₂ SiO _2/2 ) unit, (R ¹ ₂ SiO _2/2 ) unit, (R ¹ R ² SiO _2/2 ) unit, (R ³ R ² SiO _2/2 ) unit, and (RSiO _{3 / 2} ) It can be obtained by subjecting one or more organosilicon compounds having at least two silanol groups or alkoxysilyl groups per molecule to a condensation reaction in the presence of a catalyst. R ¹ , R ² , R ³ , and R are as described above. The reaction ratio of the raw material compounds may be appropriately adjusted so that the molar ratio of each siloxane unit falls within the above-described range.

Examples of the organosilicon compound used as a raw material for the (R ¹ ₂ SiO _2/2 ) unit include diphenylsilanediol represented by the following formula.

（式中、Ｒ^２は上記の通りであり、好ましくはメチル基である）
The ^(R 3 R 2 ^SiO _2/2) organosilicon compounds comprising units of the raw material, for example, alicyclic epoxy group-containing silane compound represented by the following formula.

(Wherein R ² is as described above, preferably a methyl group)

Examples of the organosilicon compound that is a raw material for the (R ³ SiO _3/2 ) unit include an alicyclic epoxy group-containing silane compound represented by the following formula.

（７）
（式（７）中、Ｒ^６はＲ^１またはＲ^２であり、Ｒ^１及びＲ^２は上記の通りであり、Ｘは水素原子または炭素数１〜１０のアルキル基であり、好ましくはメチル基である。ｅは１〜２０の整数である） Examples of the organosilicon compound that is a raw material for the (R ² ₂ SiO _2/2 ) unit and the (R ¹ R ² SiO _2/2 ) unit include organo (poly) siloxanes represented by the following formula (7).

(7)
(In Formula (7), R ⁶ is R ¹ or R ² , R ¹ and R ² are as described above, and X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a methyl group. E is an integer from 1 to 20)

（上記式においてＸ及びＲ^６は上述の通りであり、好ましくは、Ｘは水素原子またはメチル基であり、Ｒ^６はメチル基またはフェニル基である。） Examples of the silane compound represented by the above formula (7) include methyl dialkoxysilane represented by the following formula. Dimethoxysilane is preferred.

(In the above formula, X and R ⁶ are as described above, preferably X is a hydrogen atom or a methyl group, and R ⁶ is a methyl group or a phenyl group.)

（上記式においてＸ及びＲ^６は上述の通りであり、好ましくは、Ｘは水素原子またはメチル基であり、Ｒ^６はメチル基またはフェニル基である。ｅ''は２〜１０の整数である。） Examples of the organopolysiloxane represented by the above formula (7) include dialkoxysilane oligomers represented by the following formula having 2 to 10 repeating units.

(In the above formula, X and R ⁶ are as described above. Preferably, X is a hydrogen atom or a methyl group, R ⁶ is a methyl group or a phenyl group. E ″ is an integer of 2 to 10. .)

（８）
（式（８）中、Ｒは上記の通りであり、Ｒ^７は炭素数１〜１２の一価脂肪族炭化水素基あるいは炭素数１〜１０のアルコキシ基であり、少なくとも１のＲ^７は炭素数１〜１０のアルコキシ基であり、Ｘは水素原子または炭素数１〜１０のアルキル基であり、好ましくはメチル基である。ｅは１〜２０の整数である） Examples of the organosilicon compound that is a raw material for the (RSiO _3/2 ) unit include organo (poly) siloxanes represented by the following formula (8).

(8)
(In Formula (8), R is as described above, R ⁷ is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one R ⁷ is carbon. An alkoxy group having 1 to 10 carbon atoms, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, and e is an integer of 1 to 20)

（上記式においてＸ及びＲは上述の通りであり、好ましくは、Ｘは水素原子またはメチル基であり、Ｒはメチル基またはフェニル基である。） Examples of the silane compound represented by the above formula (8) include trialkoxysilane represented by the following formula. Trimethoxysilane is preferred.

(In the above formula, X and R are as described above, preferably X is a hydrogen atom or a methyl group, and R is a methyl group or a phenyl group.)

（上記式においてＸ及びＲは上述の通りであり、好ましくは、Ｘは水素原子またはメチル基であり、Ｒはメチル基またはフェニル基である。ｅ''は２〜５の整数である。） Examples of the organopolysiloxane represented by the above formula (8) include the following trialkoxysilane oligomers having 3 or more hydrolyzable groups in one molecule and 2 to 5 repeating units. .

(In the above formula, X and R are as described above. Preferably, X is a hydrogen atom or a methyl group, R is a methyl group or a phenyl group, and e ″ is an integer of 2 to 5.)

  Among the above oligomers, dimethoxysilane oligomers are particularly preferred from the viewpoints of reactivity, workability, and low gas permeability.

  The condensation reaction may be performed using a conventionally known catalyst. For example, as a condensation reaction between an organo (poly) siloxane having a phenyl group-containing silanol group and / or an alkoxy group and an alkoxysilane compound having a substituent such as an alicyclic epoxy group, sodium hydroxide, water There are methods using strong bases such as potassium oxide, tetramethylammonium hydroxide, diazabicycloundecene, 1,4-diazabicyclo [2,2,2] octane. However, this method can cause siloxane bond (Si—O—Si) cleavage and rearrangement during the condensation reaction. In addition, the production method has a problem that a large amount of cyclic siloxane having a phenyl group is generated.

As a method for producing the organopolysiloxane of the present invention, a method capable of controlling the structure while minimizing the rearrangement of the organopolysiloxane chain is desirable. Therefore, for example, it is preferable to use a specific catalyst as described in Patent Documents 3 to 6 below.
JP-A-2-235933 Japanese Patent Laid-Open No. 3-197486 Special table 2006-508216 gazette JP 2014-55234 A

  Patent Document 3 describes a method for producing an organosilicone condensation product using sodium or potassium borate or phosphate as a catalyst. Patent Document 4 describes a method for producing a polyorganosiloxane using at least one catalyst selected from alkali metal or alkaline earth metal hydroxides, chlorides, oxides or basic metal salts. . Patent Document 5 describes that a condensation reaction of a silanol group-containing siloxane and an alkoxysilane is carried out using magnesium and calcium hydroxide as a catalyst in the presence of a protic solvent. In Patent Document 6, a silane coupling agent includes at least one selected from the group consisting of a hydroxide of Group 2 element of the periodic table, a hydrate of the hydroxide, and an oxide of Group 2 element of the periodic table. Describes a method for producing an organosilicone condensate using as a catalyst the product obtained by surface treatment in (1). By using these production methods, the structure of the organopolysiloxane chain can be suitably controlled.

  Since the catalysts described in Patent Documents 3 to 6 are solid, the catalyst can be easily removed from the obtained organopolysiloxane by filtration. This advantage is advantageous in fields that require precise control of materials used, such as optical materials and electronic materials, and fields in which residual impurities are not allowed. Therefore, the organopolysiloxane produced by the method can be suitably used for a resin composition for sealing an optical semiconductor element.

  As a particularly preferred catalyst for producing the organopolysiloxane of the present invention, a hydroxide of a Group 2 element of the periodic table, a hydroxide hydrate of a Group 2 element of the periodic table, and a Group 2 element of the periodic table And at least one selected from the group consisting of these oxides (hereinafter referred to as Group 2 element compounds). The group 2 element compound may be a compound having a catalytic function capable of proceeding a condensation reaction of an organosilicon compound having a silanol group (—SiOH) and / or an alkoxysilyl group (—SiOR). For example, radium hydroxide, barium hydroxide, strontium hydroxide, calcium hydroxide, magnesium hydroxide, beryllium hydroxide, barium hydroxide octahydrate, barium hydroxide monohydrate, strontium hydroxide octahydrate, Examples thereof include barium oxide, strontium oxide, calcium oxide, magnesium oxide, and beryllium oxide. Among these, barium hydroxide octahydrate, barium hydroxide monohydrate, barium hydroxide, barium oxide, calcium hydroxide, strontium hydroxide, and strontium hydroxide octahydrate are preferable, and in particular, barium hydroxide And strontium hydroxide are preferred.

  The amount of the catalyst is such that the molar amount of the catalyst is 0.0001 to 20 mol%, preferably 0.01 to 10 mol%, more preferably 0, relative to the total molar amount of the starting organosilicon compound to be subjected to the condensation reaction. The quantity which becomes 1-1 mol% is good. If the amount of the catalyst is within the above range, a sufficient catalytic effect can be obtained in the condensation reaction, and the target compound can be efficiently obtained without clogging the filter paper in the step of removing the catalyst by filtration after the reaction. It is preferable because it can be obtained.

(B) The hardening agent hardening | curing agent should just use the conventionally well-known hardening | curing agent which has a functional group reactive with an epoxy group. For example, an amine type hardening | curing agent, a phenol type hardening | curing agent, and an acid anhydride type hardening | curing agent are mentioned. In the present invention, “functional group having reactivity with an epoxy group” means an amino group possessed by an amine curing agent, a phenolic hydroxyl group possessed by a phenol curing agent, and an acid anhydride group possessed by an acid anhydride curing agent. To do. The acid anhydride group in the acid anhydride curing agent is represented by -CO-O-CO-. Of these, acid anhydride curing agents are preferred.

  Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, A mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2 , 3-dicarboxylic acid anhydride, 2,4-diethylglutaric acid anhydride, etc., among which hexahydrophthalic anhydride and its derivatives are preferred.

  (B) The compounding quantity of a hardening | curing agent is the quantity from which the ratio of the number of the functional group which has the reactivity with the epoxy group in (B) component with respect to the total number of the epoxy group in (A) component will be 0.3-1. The amount is preferably 0.4 to 0.8. If it is more than the said lower limit, the heat resistance of a hardened | cured material and transparency will improve. Moreover, if it is below the said upper limit, since the mechanical characteristic of hardened | cured material improves, it is preferable.

(C) Curing catalyst The curing catalyst is not particularly limited, and may be selected from curing catalysts conventionally used for silicone resin compositions. For example, quaternary phosphonium salts such as tetrabutylphosphonium-o, o-diethyl phosphorodithioate, tetraphenylphosphonium tetraphenylborate, organic phosphine-based curing catalysts such as triphenylphosphine, diphenylphosphine, 1,8- Tertiary amine-based curing catalyst such as diazabicyclo (5,4,0) undecene-7, triethanolamine, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, 1,8- Diazabicyclo (5,4,0) undecene-7 octylate, 1,8-diazabicyclo (5,4,0) undecene-7p-toluenesulfonate, 1,8-diazabicyclo (5,4,0) undecene 7 Quaternary ammonium salts such as formate, zinc octylate, naphthylic acid Organic carboxylates such as aluminum bisethylacetoacetate / monoacetylacetonate, aluminum chelate compounds such as aluminum ethylacetoacetate / diisopropylate, imidazoles such as 2-methylimidazole and 2-phenyl-4-methylimidazole, etc. Is mentioned. Of these, quaternary phosphonium salts and quaternary ammonium salts are preferred.

  The blending amount of the curing catalyst is not particularly limited as long as it is an effective amount (catalyst amount) that promotes the reaction between the component (A) and the component (B). Preferably it is 0.01-3 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, More preferably, it is 0.05-1.5 mass parts. If the amount of the curing catalyst is less than the lower limit, the effect of promoting the reaction between the epoxy resin and the curing agent may not be sufficiently obtained. Moreover, when there are more compounding quantities of a curing catalyst than the said upper limit, there exists a possibility of causing the discoloration at the time of hardening or a reflow test.

(D) Antioxidant The silicone resin composition of the present invention preferably further contains an antioxidant. Examples of the antioxidant include phosphorous acid compounds and hindered phenol antioxidants. In particular, hindered phenol antioxidants are preferred. Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, N, N′-propane-1,3- Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 6,6′-di-tert-butyl-2,2′-thiodi-p-cresol, N, N′-hexane-1 , 6-Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 2,2 '-Ethylidenebis [4,6-di-tert-butylphenol], 3,3', 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(mesitylene-2 , 4,6-triyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octyl) Thiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy) Cy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) -1,3,5-triazine-2,4,6-trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 6,6'-di-tert-butyl-4,4'-thiodi-m-cresol, diphenylamine, N- Reaction product of phenylbenzeneamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino ) Phenol, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-1-benzopyran-6-ol, 2 ', 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, didodecyl 3,3′-thiodipropionate, dioctadecyl 3,3′-thiodipropionate Illustrated.

  (D) As for the compounding quantity of component, 0.1-0.5 mass part is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.1-0.3 mass part. When the compounding quantity of antioxidant exceeds the said upper limit, there exists a possibility that the remaining antioxidant may precipitate on the surface of resin after hardening. Moreover, if it is less than the said lower limit, there exists a possibility that the heat resistance and transparency of the hardened | cured material obtained may fall.

In addition to the above components (A) to (D), the silicone resin composition of the present invention includes conventionally known additives such as ultraviolet absorbers, light or thermal deterioration inhibitors, phosphors, thermoplastics, and diluents. Etc. may be contained. As the ultraviolet absorber, for example, a hindered amine ultraviolet absorber can be preferably used. The phosphor is added to change the wavelength of light emitted from the optical semiconductor element sealed with the cured product of the silicone resin composition. Examples of the phosphor include YAG (yttrium, aluminum, garnet) phosphor, ZnS phosphor, Y ₂ O ₂ S phosphor, red light emitting phosphor, and blue light emitting phosphor widely used in LEDs. And green light emitting phosphors. The blending amount of these additives can be appropriately selected according to a conventionally known technique as long as the effects of the present invention are not impaired.

  The silicone resin composition of this invention can be manufactured by melt | dissolving or melt-mixing each said component and various additives as needed. The melt mixing may be performed by a known method. For example, the above components may be charged into a reactor and melt mixed in a batch system. Moreover, each said component can also be thrown into kneading machines, such as a kneader and a heat | fever three roll, and can also be continuously melt-mixed. In particular, the (C) curing catalyst is preferably preliminarily heated and dissolved and mixed in the (B) curing agent, and dispersed and mixed with the components (A) and (D) at the final stage of mixing.

  The silicone resin composition of the present invention has a viscosity at 23 ° C. of 0.5 Pa · s or more and 30 Pa · s or less, more preferably 2 Pa · s or more, as measured by a B-type viscometer according to JIS K 7117-1: 1999. 20 Pa · s or less. When the viscosity is larger than the above upper limit, the workability of the composition is deteriorated. If the viscosity is smaller than the lower limit, bleeding or the like may occur when sealing with the composition.

  The curing of the silicone resin composition may be appropriately set according to the target device. For example, when sealing an optical semiconductor element using a silicone resin composition, it is usually heated (precured) at 100 ° C. for about 1 to 2 hours, and further heated at 150 to 200 ° C. for 0.1 to 2 hours (aftercuring). )

  The silicone resin composition of the present invention has a low viscosity, excellent handleability, and gives a cured product excellent in low gas permeability. Therefore, the silicone resin composition of the present invention can be suitably used as a resin composition for sealing an optical semiconductor element, and provides an optical semiconductor device having excellent reliability. As a method for manufacturing the optical semiconductor device, a known method may be adopted depending on the type of the optical semiconductor element.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. "Part" in the following means a part by mass, Me represents a methyl group, and Ph represents a phenyl group.

The weight average molecular weight (Mw) shown in the following Examples and Comparative Examples is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are shown below.
[GPC measurement conditions]
Developing solvent: Tetrahydrofuran Flow rate: 0.6 mL / min
Column: TSK Guardcolumn SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection amount: 20 μl (sample concentration: 0.5 wt% -tetrahydrofuran solution)
Detector: Differential refractometer (RI)

（１４） [Synthesis Example 1]
[Synthesis of β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane]
In a 2 L separable flask, 0.39 g of 0.5 mass% chloroplatinic acid toluene solution, 10 g of methanol, and 546 g of Celoxide 2000 (1,2-epoxy-4-vinylcyclohexane, manufactured by Daicel Chemical Industries, Ltd.) were added and stirred. Thereafter, the internal temperature was raised to 50 ° C. Thereafter, 425 g of dimethoxymethylsilane was added dropwise over 3 hours and reacted at 70 ° C. for 3 hours. After toluene was distilled under reduced pressure, Antage W-500 (2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), manufactured by Kawaguchi Chemical Co., Ltd.) 0.9 g and Accel DM (2-benzo 0.9 g of thiazoyl-disulfide (manufactured by Kawaguchi Chemical Co., Ltd.) was added and stirred. After confirming that it was dissolved, vacuum distillation (110 ° C., 5 mmHg) was performed to obtain 568 g (yield 63%) of a compound represented by the following formula (14).

(14)

（１５）
上記式（１５）において、ｍ、ｎ、及びｐは、各シロキサン単位のモル比として、ｍ＝０．１８、ｎ＝０．６４、ｐ＝０．１８であった。−Ｏ_１／２Ｘの数（ｒ）は２個であり、両末端に存在する。Ｘは水素原子またはメチル基である。
上記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は５０％であった。
得られたオルガノポリシロキサン１の、ＧＰＣ測定によるポリスチレン換算の重量平均分子量は２５００であり、エポキシ当量は８８５ｇ／ｅｑであった。 Synthesis of organopolysiloxanes 1 to 4 for Examples [Synthesis Example 2]
[Synthesis of Organopolysiloxane 1]
In a 2 L separable flask, 216 g of diphenylsilane diol, 486 g of XO— (MePhSiO) _a —X (where X is a hydrogen atom or a methyl group, a is an integer of 3 to 10 and an average of 7), and in Synthesis Example 1 230 g of the obtained β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane was added and stirred, and then the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain linear organopolysiloxane 1 represented by the following formula (15).

(15)
In the above formula (15), m, n, and p were m = 0.18, n = 0.64, and p = 0.18 as the molar ratio of each siloxane unit. The number (r) of —O _1/2 X is 2 and exists at both ends. X is a hydrogen atom or a methyl group.
There is no particular limitation on the order of bonding of the units shown in the parentheses.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 50%.
The obtained organopolysiloxane 1 had a polystyrene-equivalent weight average molecular weight of 2500 by GPC measurement, and an epoxy equivalent of 885 g / eq.

（１６）
上記式（１６）において、ｍ、ｎ、及びｐは、各シロキサン単位のモル比として、ｍ＝０．１５、ｎ＝０．６９、ｐ＝０．１６であった。−Ｏ_１／２Ｘの数（ｒ）は２個であり、両末端に存在する。Ｘは水素原子またはメチル基である。
上記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は５０％であった。
得られたオルガノポリシロキサン２の、ＧＰＣ測定によるポリスチレン換算の重量平均分子量は２６００であり、エポキシ当量は９５９ｇ／ｅｑであった。 [Synthesis Example 3]
[Synthesis of Organopolysiloxane 2]
In a 2 L separable flask, 195 g of diphenylsilanediol, 583 g of XO— (MePhSiO) _a —X (where X is a hydrogen atom or a methyl group, a is an integer of 3 to 10 and an average of 7), After stirring 115 g of the obtained β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain linear organopolysiloxane 2 represented by the following formula (16).

(16)
In the above formula (16), m, n, and p were m = 0.15, n = 0.69, and p = 0.16 as the molar ratio of each siloxane unit. The number (r) of —O _1/2 X is 2 and exists at both ends. X is a hydrogen atom or a methyl group.
There is no particular limitation on the order of bonding of the units shown in the parentheses.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 50%.
The obtained organopolysiloxane 2 had a polystyrene-reduced weight average molecular weight of 2600 as measured by GPC, and an epoxy equivalent of 959 g / eq.

（１７）

上記式（１７）において、ｍ、ｎ、ｐ、及びｑは、各シロキサン単位のモル比として、ｍ＝０．１８、ｎ＝０．６４、ｐ＝０．０９、ｑ＝０．０９であった。−Ｏ_１／２Ｘの数（ｒ）はＴ単位の数＋２個である。Ｘは水素原子またはメチル基である。
上記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は５２％であった。
得られたオルガノポリシロキサン３の、ＧＰＣ測定によるポリスチレン換算の重量平均分子量は２８００であり、エポキシ当量は８７８ｇ／ｅｑであった。 [Synthesis Example 4]
[Synthesis of Organopolysiloxane 3]
In a 2 L separable flask, 216 g of diphenylsilane diol, 486 g of XO— (MePhSiO) _a —X (where X is a hydrogen atom or a methyl group, a is an integer of 3 to 10 and an average of 7), and in Synthesis Example 1 After stirring 115 g of the obtained β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane and 123 g of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) The internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain organopolysiloxane 3 having a branched structure represented by the following formula (17).

(17)

In the above formula (17), m, n, p, and q are m = 0.18, n = 0.64, p = 0.09, q = 0.09 as the molar ratio of each siloxane unit. It was. The number (r) of −O _1/2 X is the number of T units + 2. X is a hydrogen atom or a methyl group.
There is no particular limitation on the order of bonding of the units shown in the parentheses.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 52%.
The obtained organopolysiloxane 3 had a polystyrene-equivalent weight average molecular weight of 2800 as measured by GPC, and an epoxy equivalent of 878 g / eq.

（１８）
上記式（１８）において、ｋ、ｍ、及びｐは、各シロキサン単位のモル比として、ｋ＝０．２３、ｍ＝０．４４、ｐ＝０．３３であった。−Ｏ_１／２Ｘの数（ｒ）は２個であり、両末端に存在する。Ｘは水素原子またはメチル基である。
上記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は５３％であった。
得られたオルガノポリシロキサン４の、ＧＰＣ測定によるポリスチレン換算の重量平均分子量は３１００であり、エポキシ当量は５１３ｇ／ｅｑであった。 [Synthesis Example 5]
[Synthesis of Organopolysiloxane 4]
In a 2 L separable flask, 281 g of diphenylsilanediol, XO— (Me ₂ SiO) _a —X (X is a hydrogen atom or a methyl group, a is an integer of 2 to 5, and the average is 3.5) 55 g After stirring 230 g of β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane obtained in Synthesis Example 1, the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain linear organopolysiloxane 4 represented by the following formula (18).

(18)
In the above formula (18), k, m, and p were k = 0.23, m = 0.44, and p = 0.33 as the molar ratio of each siloxane unit. The number (r) of —O _1/2 X is 2 and exists at both ends. X is a hydrogen atom or a methyl group.
There is no particular limitation on the order of bonding of the units shown in the parentheses.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 53%.
The obtained organopolysiloxane 4 had a polystyrene-equivalent weight average molecular weight of 3100 as measured by GPC, and an epoxy equivalent of 513 g / eq.

（１９）
上記式（１８）において、ｍ、ｎ、及びｑは、各シロキサン単位のモル比として、ｍ＝０．１８、ｎ＝０．６４、ｑ＝０．１８であった。−Ｏ_１／２Ｘの数（ｒ）はＴ単位の個数＋２個である。Ｘは水素原子またはメチル基である。
上記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は５０％であった。
得られたオルガノポリシロキサン５の、ＧＰＣ測定によるポリスチレン換算の重量平均分子量は３２００であり、エポキシ当量は８７１ｇ／ｅｑであった。 Synthesis of Comparative Examples Organopolysiloxanes 5 to 8 [Synthesis Example 6]
[Synthesis of Organopolysiloxane 5]
In a 2 L separable flask, 216 g of diphenylsilanediol, XO— (MePhSiO) _a —X (where X is a hydrogen atom or a methyl group, a is an integer of 3 to 10 and the average is 7), 486 g, β- ( After stirring 246 g of 3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.), the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain a branched organopolysiloxane 5 represented by the following formula (19).

(19)
In the above formula (18), m, n, and q were m = 0.18, n = 0.64, and q = 0.18 as the molar ratio of each siloxane unit. The number (r) of −O _1/2 X is the number of T units + 2. X is a hydrogen atom or a methyl group.
There is no particular limitation on the order of bonding of the units shown in the parentheses.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 50%.
The resulting organopolysiloxane 5 had a polystyrene-equivalent weight average molecular weight of 3200 as measured by GPC, and an epoxy equivalent of 871 g / eq.

（２０）
上記式（２０）において、ｎ及びｑは、各シロキサン単位のモル比として、ｎ＝０．８８、ｑ＝０．１２であった。−Ｏ_１／２Ｘの数（ｒ）はＴ単位の個数＋２個である。Ｘは水素原子またはメチル基である。
上記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は４７％であった。
得られたオルガノポリシロキサン６のＧＰＣ測定によるポリスチレン換算の重量平均分子量は５４００であり、エポキシ当量は１１７１ｇ／ｅｑであった。 [Synthesis Example 7]
[Synthesis of Organopolysiloxane 6]
In a 2 L separable flask, 486 g of XO- (MePhSiO) _a -X (X is a hydrogen atom or a methyl group, a is an integer of 3 to 10 and the average is 7), β- (3,4-epoxy After stirring 123 g of (cyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.), the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 600 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain a branched organopolysiloxane 6 represented by the following formula (20).

(20)
In the above formula (20), n and q were n = 0.88 and q = 0.12 as the molar ratio of each siloxane unit. The number (r) of −O _1/2 X is the number of T units + 2. X is a hydrogen atom or a methyl group.
There is no particular limitation on the order of bonding of the units shown in the parentheses.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 47%.
The obtained polypolysiloxane 6 had a polystyrene-reduced weight average molecular weight of 5400 as measured by GPC and an epoxy equivalent of 1171 g / eq.

（２１）
上記式（２１）において、ｍ及びｑは、各シロキサン単位のモル比として、ｍ＝０．４、ｐ＝０．６であった。−Ｏ_１／２Ｘの数（ｒ）は２個であり、両末端に存在する。Ｘは水素原子またはメチル基である。
上記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は４０％であった。
得られたオルガノポリシロキサン７のＧＰＣで測定されたポリスチレン換算の重量平均分子量は２３００であり、エポキシ当量は４２６ｇ／ｅｑであった。 [Synthesis Example 8]
[Synthesis of Organopolysiloxane 7]
After stirring 216 g of diphenylsilanediol and 345 g of β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane obtained in Synthesis Example 1 in a 2 L separable flask, the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain linear organopolysiloxane 7 represented by the following formula (21).

(21)
In the said Formula (21), m and q were m = 0.4 and p = 0.6 as molar ratio of each siloxane unit. The number (r) of —O _1/2 X is 2 and exists at both ends. X is a hydrogen atom or a methyl group.
There is no particular limitation on the order of bonding of the units shown in the parentheses.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 40%.
The weight average molecular weight of polystyrene conversion measured by GPC of the obtained organopolysiloxane 7 was 2300, and the epoxy equivalent was 426 g / eq.

（２２）
上記式（２２）において、ｍ、ｎ、及びｐは、各シロキサン単位のモル比として、ｍ＝０．０６、ｎ＝０．８２、ｐ＝０．１２であった。−Ｏ_１／２Ｘの数（ｒ）は２個であり、両末端に存在する。Ｘは水素原子またはメチル基である。
記括弧内に示す各単位の結合順序は特に制限されない。
フェニル基、メチル基、及び脂環式エポキシ基の合計個数に対するフェニル基の含有量は４７％であった。
得られたオルガノポリシロキサン８の、ＧＰＣ測定によるポリスチレン換算の重量平均分子量は３０００であり、エポキシ当量は１１４０ｇ／ｅｑであった。 [Synthesis Example 9]
[Synthesis of Organopolysiloxane 8]
In a 2 L separable flask, 108 g of diphenylsilanediol, XO— (MePhSiO) _a —X (where X is a hydrogen atom or a methyl group, a is an integer of 3 to 10 and the average is 7), 971 g, Synthesis Example 1 After stirring 230 g of β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane obtained in (1), the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled under reduced pressure to obtain linear organopolysiloxane 8 represented by the following formula (22).

(22)
In the above formula (22), m, n, and p were m = 0.06, n = 0.82, and p = 0.12 as the molar ratio of each siloxane unit. The number (r) of —O _1/2 X is 2 and exists at both ends. X is a hydrogen atom or a methyl group.
There are no particular restrictions on the order in which the units shown in brackets are combined.
The phenyl group content relative to the total number of phenyl groups, methyl groups, and alicyclic epoxy groups was 47%.
The resulting organopolysiloxane 8 had a polystyrene-equivalent weight average molecular weight of 3,000 by GPC measurement and an epoxy equivalent of 1140 g / eq.

[Examples 1-4, Comparative Examples 1-4]
A silicone resin composition was prepared with the composition and formulation (parts by mass) shown in Table 1 below. Each component described in Table 1 is as follows. In the table, a blank column means “0”.
(B) Curing agent: 4-methylhexahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd., Ricacid MH)
(C) Curing catalyst: quaternary phosphonium salt (manufactured by Sun Apro, U-CAT5003)
(D) Antioxidant: Pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation, ADK STAB AO-60)

[Evaluation test]
In the following, the composition was cured by heating at 100 ° C. for 1 hour and then at 150 ° C. for 4 hours. Each composition and each cured product were evaluated by the following methods.
(1) Viscosity The viscosity of each composition was measured at 23 ° C. using a Toki Sangyo B-type rotational viscometer (product name: TVB-15M). The results are shown in Table 1.
(2) Hardness Each composition was cured by the above method to prepare a rod-shaped cured product. The hardness (type D) of each cured product was measured according to JIS K6301. The results are shown in Table 1.
(3) UV resistance Each composition was cured by the above method to prepare a 1 mm thick sheet-like cured product. The light transmittance (T ₀ ) at a wavelength of 450 nm of the cured product was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech). Subsequently, the cured product was irradiated with UV for 24 hours using a UV irradiation device (illuminance: 100 mW / cm ² ) equipped with a 365 nm band pass filter. The light transmittance (T ₁ ) of each cured product after UV irradiation was measured by the same method as described above. Table 1 shows the value of T ₁ / T ₀ (%).
(4) Heat resistance Each composition was cured by the above method to prepare a 1 mm thick sheet-like cured product. The light transmittance (T ₀ ) at a wavelength of 450 nm of the cured product was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech). The cured product was then heated at 150 ° C. for 400 hours. The light transmittance (T ₁ ) of each cured product after heating was measured by the same method as described above. Table 1 shows the value of T ₁ / T ₀ (%).
(5) Water vapor transmission rate Each composition was cured by the above method to prepare a sheet-like cured product having a thickness of 1 mm. The water vapor transmission rate of each cured product was measured based on JIS K 7129. The results are shown in Table 1.

In the silicone resin composition of Comparative Example 1, the organopolysiloxane has a diphenylsiloxane unit, a methylphenylsiloxane unit, and a T unit having an alicyclic epoxy group, but does not have a D unit having an alicyclic epoxy group. . The composition containing the organopolysiloxane is too viscous.
The silicone resin composition of Comparative Example 2 does not have diphenylsiloxane units. The composition containing the organopolysiloxane is inferior in low gas permeability.
In the silicone resin composition of Comparative Example 3, the organopolysiloxane has a diphenylsiloxane unit and an alicyclic epoxy group-containing D unit, but does not have a dimethylsiloxane unit and a methylphenylsiloxane unit. The composition containing the organopolysiloxane is too viscous.
In the silicone resin composition of Comparative Example 4, the organopolysiloxane has diphenylsiloxane units, phenylmethylsiloxane units, and alicyclic epoxy group-containing D units, but the content ratio of the diphenylsiloxane units is too small. The composition containing the organopolysiloxane is inferior in low gas permeability.
On the other hand, the silicone resin composition of the present invention has a low viscosity and excellent workability, gives a cured product excellent in low gas permeability, and is excellent in heat resistance and UV resistance.

The silicone resin composition of the present invention gives a cured product excellent in low gas permeability, has low viscosity, excellent workability, and excellent heat resistance and UV resistance. The silicone resin composition of the present invention can be suitably used as a resin composition for sealing an optical semiconductor element.

Claims (8)

(A) Organopolysiloxane represented by the following formula (1)

(In formula (1), R ¹ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ² is a monovalent aliphatic carbonized carbon atom having 1 to 12 carbon atoms and may have an unsaturated bond. A hydrogen group, and R ³ is a group represented by any of the following structures:

,

(In the above structure, R ′ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms)
R is a group selected from the options for R ¹ , R ² , and R ³ , 0 ≦ k <0.5, 0.1 ≦ m ≦ 0.5, 0 ≦ n <0.8, 0. 01 ≦ p ≦ 0.5, 0 ≦ q <0.6, and k + m + n + p + q = 1, provided that k and n are not 0 at the same time. The bonding order of each siloxane unit in the parenthesis is not limited, but at least two of -O1 _/ 2X are bonded to the terminal, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, r is the number of -O _1/2 X, r is 2 when q = 0, and r is the number of (RSiO _3/2 ) units + 2 when q ≠ 0)
(B) Curing agent having a functional group that reacts with an epoxy group (A) Amount that the number of functional groups that react with an epoxy group in component (B) is 0.3 to 1 with respect to one epoxy group in component (A) (C) Curing catalyst A silicone resin composition containing a catalytic amount. Monovalent aromatic hydrocarbon group (R ¹⁾ is a phenyl group, claim 1 silicone resin composition. The silicone resin composition according to claim 1 or 2 , wherein R ³ in the formula (1) is represented by the following formula (2).

(In the formula, R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms) The silicone resin composition according to any one of claims 1 to 3 , further comprising (D) an antioxidant. The said (A) organopolysiloxane has the weight average molecular weight (Mw) 2,000 or more and 10,000 or less in polystyrene conversion measured by a gel permeation chromatography (GPC), Any one of Claims 1-4 . 2. The silicone resin composition according to 1. JIS K 7117-1: 1999 with the following viscosity 0.5 Pa · s or higher 30 Pa · s at 23 ° C. as measured by compliant B-type viscometer, the silicone resin of any one of claims 1 to 5 Composition. It is for an optical semiconductor element encapsulation, silicone resin composition of any one of claims 1-6. An optical semiconductor device provided with the hardened | cured material obtained by hardening | curing the silicone resin composition of any one of Claims 1-6 .