JP2020143206A - Curable organosilicon resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable organosilicon resin composition excellent in mechanical properties, crack resistance and workability, and an optical semiconductor device sealed with the composition. SOLUTION: (A) An organopolysiloxane having at least two silicon atom-bonded alkenyl groups in one molecule, having SiO4 / 2 units and R1SiO3 / 2 units, SiO4 with respect to the number of moles of the total siloxane units. Organopolysiloxane, the ratio of 2 units is 0.1 mol% or more and 10 mol% or less, and the content of hydroxyl group bonded to silicon atom is 0.001 mol / 100 g or more, (B) hydrogen atom bonded to silicon atom. Organohydrogenpolysiloxane having two or more in one molecule and one or more silicon atom-bonded aromatic hydrocarbon groups in one molecule: Hydrosilyl of the component (B) with respect to the number of alkenyl groups in the component (A). A curable organic silicon resin composition comprising an amount of 0.1 to 4.0 groups and (C) a platinum group metal-based catalyst: a catalytic amount. [Selection diagram] None

Description

The present invention relates to curable organic silicon resin compositions and semiconductor devices.

Materials with excellent heat resistance, light resistance, workability, adhesiveness, gas barrier properties, and curing properties are required for LED encapsulants, and conventionally, epoxy resins, poly (meth) acrylates, polycarbonates, and the like are required. Thermoplastic resins have been widely used. However, with the recent increase in output of LED light emitting devices, it has been found that problems of heat resistance and discoloration resistance occur when these thermoplastic resins are used in a high temperature environment for a long period of time.

Recently, lead-free solder is often used when soldering an optical element to a substrate. This lead-free solder has a higher melting temperature than conventional solder, and usually needs to be soldered at a temperature of 260 ° C. or higher. However, when soldering is performed at such a temperature, the above-mentioned It has also been found that the conventional thermoplastic resin encapsulant has problems such as deformation or yellowing of the encapsulant due to high temperature.

As described above, with the increase in output of the LED light emitting device and the use of lead-free solder, the sealing material is required to have higher heat resistance than ever before. So far, optical resin compositions in which a thermoplastic resin is filled with nanosilica have been proposed for the purpose of improving heat resistance (Patent Documents 1 and 2), but the heat resistance of the thermoplastic resin is limited and sufficient. No heat resistance was obtained.

Silicone resins, which are thermosetting resins, have been studied as sealing materials for LEDs because they are excellent in heat resistance, light resistance, and light transmission (Patent Documents 3 to 5). However, this silicone resin has a drawback that the resin strength is weaker than that of an epoxy resin or the like.

As a countermeasure for this, it has been studied to increase the refractive index by introducing an aromatic substituent such as a phenyl group (Patent Document 6), but when an aromatic substituent is introduced, the change in viscoelasticity during heating is large. Therefore, there are problems that the crack resistance is lowered as compared with the methyl silicone resin and the adhesion to the LED package is deteriorated (Patent Document 7).

Japanese Unexamined Patent Publication No. 2012-214554 Japanese Unexamined Patent Publication No. 2013-204029 Japanese Unexamined Patent Publication No. 2006-213789 Japanese Unexamined Patent Publication No. 2007-131694 Japanese Unexamined Patent Publication No. 2011-252175 Japanese Unexamined Patent Publication No. 2014-88513 WO2013 / 005859

The present invention has been made in view of the above problems, and is a curable organic silicon resin composition having excellent mechanical properties, crack resistance, and workability, and an optical semiconductor device sealed with the composition. The purpose is to provide.

As a result of diligent studies, the present inventors have determined that the resin-structured organopolysiloxane having RSiO _3/2 units (T units) as an essential constituent unit has a predetermined amount of SiO _4/2 units (Q units). We have found that the problem can be solved, and have come to the present invention.

That is, the present invention
(A) An organopolysiloxane having at least two silicon atom-bonded alkenyl groups in one molecule.
It has _4/2 units of SiO and _3/2 units of R ¹ SiO, and the ratio of _4/2 units of SiO to the number of moles of all siloxane units is 0.1 mol% or more and 10 mol% or less, and at least two in one molecule. The organopolysiloxane having a silicon atom-bonded alkenyl group and having a hydroxyl group bonded to a silicon atom having a content of 0.001 mol / 100 g or more (in the above, R ¹ has 2 to 2 carbon atoms independently of each other). (10 alkenyl groups, substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms, or aromatic hydrocarbon groups with 6 to 10 carbon atoms)
(B) Organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule and one or more silicon atom-bonded aromatic hydrocarbon groups in one molecule: component (A) The amount at which the ratio of the number of hydrosilyl groups of the component (B) to the number of alkenyl groups is 0.1 to 4.0, and (C) platinum group metal-based catalyst: catalytic amount,
Provided is a curable organic silicon resin composition comprising.

With such a curable organic silicon resin composition, excellent mechanical properties, crack resistance, and workability can be obtained.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[(A) Organopolysiloxane]
The component (A) is an organopolysiloxane having a resin structure, which is a main component of the curable organic silicon resin composition of the present invention. The component (A) contains both SiO _4/2 units (Q units) and R ¹ SiO _3/2 units (T units), and the ratio of the number of Q units to the total number of siloxane units is 0.1 mol. It is characterized in that it is% or more and 10 mol% or less, preferably 0.2 mol% or more and 8 mol% or less, more preferably 0.3 mol% or more and 6 mol% or less, and further preferably 0.4 mol% or more and 5 mol% or less. If the amount of the Q unit is less than the above lower limit value, the crack resistance is inferior. Further, if the above upper limit value is exceeded, the viscosity becomes high and the workability may be deteriorated.

The amount of R ¹ SiO _3/2 unit (T unit) in the component (A) is preferably 50 mol% or more, more preferably 50 to 90 mol%, and further preferably 60 to 80 mol%. The R ¹ has 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, 1 to 10 carbon atoms, preferably 1 to 5 substituted or unsubstituted alkyl groups, or 6 to 6 carbon atoms independently of each other. It is 10, preferably 6-8 aromatic hydrocarbon groups. For example, lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group; cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group, trill group and xsilyl group; benzyl group, phenylethyl group and Aralkyl groups such as phenylpropyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, and octenyl group; and hydrogen bonded to the carbon atom of the alkyl group. Examples thereof include a group in which a part or all of the atoms are substituted with a halogen atom such as fluorine, bromine or chlorine or a cyano group, for example, a chloromethyl group, a cyanoethyl group, a 3,3,3-trifluoropropyl group and the like. Of these, a methyl group, a phenyl group, and a vinyl group are preferable.

The component (A) has at least two silicon atom-bonded alkenyl groups in one molecule. More preferably, the amount of the silicon atom-bonded alkenyl group is preferably 0.01 to 0.5 mol / 100 g, more preferably 0.05 to 0.3 mol / 100 g, still more preferably 0.1 to 0.25 mol. / 100g. When the amount of the alkenyl group is equal to or higher than the lower limit, sufficient cross-linking points can be formed for the composition to solidify. Further, if it is not more than the upper limit value, it is possible to prevent a decrease in toughness due to an excessive increase in the crosslink density. In addition to the Q unit and the T unit, the component (A) may contain (R ⁴ ) ₂ SiO _2/2 unit (D unit) in an amount of 0 to 30 mol%, preferably 0 to 20 mol%. , And (R ¹ ) ₃ SiO _1/2 unit (M unit) may be contained in an amount of 10 to 30 mol%, preferably 20 to 28 mol%. R ¹ is as described above. In R ¹ in the component (A), at least two, preferably 2 to 6 silicon atom-bonded alkenyl groups are contained in one molecule. R ^4, independently of one another, 1 to 10 carbon atoms, preferably 1 to 5, a substituted or unsubstituted alkyl group carbon atoms or 6 to 10, preferably an aromatic hydrocarbon group of 6 to 8. Further, the D unit having an alkenyl group may be contained in a small amount as long as the effect of the present invention is not impaired. The small amount preferably means that the number of moles of D units having an alkenyl group is less than 0.1 mol% with respect to the number of moles of all siloxane units.

In R ¹ and R ⁴ in the component (A), at least one in one molecule is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a total substituent (which is bonded to a silicon atom). That is, the number of aromatic hydrocarbon groups is 18 to 90 mol%, preferably 20 to 88 mol%, more preferably more than 30 mol% to 85 mol%, still more preferably 40 mol to 83 mol%, based on the total number of R ¹ and R ⁴ ). Most preferably, it is 50 mol% to 82 mol%. It is preferable that the component (A) has an aromatic hydrocarbon group in an amount in the above range because the mechanical properties are improved. If the amount of aromatic hydrocarbon groups is too small, the resin strength may decrease. The molar ratio of Q units / T units is preferably 0.001 to 0.2, more preferably 0.001 to 0.15, still more preferably 0.003 to 0.13, and most preferably 0.005 to 0. It should be .08. It is preferable that the molar ratio of Q unit / T unit is in the above range because crack resistance is improved. If the molar ratio of Q unit / T unit is too small, the crack resistance is lowered, and if it is too large, the resin may become brittle.

The component (A) is characterized by having a hydroxyl group bonded to a silicon atom in an amount of 0.001 mol / 100 g or more. If the amount of hydroxyl groups bonded to the silicon atom is less than the above lower limit, the curable organic silicon resin composition may not adhere to the substrate. It is preferably 0.005 mol / 100 g or more, more preferably 0.008 mol / 100 g or more, and further preferably 0.001 mol / 100 g or more. However, if the amount of hydroxyl groups bonded to the silicon atom is too large, the cured product has poor surface tackiness and may cause stickiness. Therefore, the upper limit is preferably 1.0 mol / 100 g or less, and more preferably 0.8 mol / 100 g or less. As a result, it is possible to provide a cured product that satisfies the mechanical properties, crack resistance, and workability, which are the problems of the present invention, and has excellent surface tackiness.

Further, in the component (A), the amount of the alkoxy group bonded to the silicon atom having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms is preferably 1.0 mol / 100 g or less, more preferably 0.8 mol. It is preferably / 100 g or less, more preferably 0.5 mol / 100 g or less. If the amount of alkoxy groups exceeds the above upper limit, alcohol gas as a by-product is generated during curing, and voids may remain in the cured product. The lower limit is not particularly limited, and the smaller the value, the better. The amount of hydroxyl groups and alkoxy groups bonded to the silicon atom in the present invention are values measured by ¹ H-NMR and ²⁹ Si-NMR.

The component (A) preferably has a weight average molecular weight (Mw) of 1,000 to 5,000, and more preferably 1,100 to 3,000. When the weight average molecular weight is not more than the above lower limit value, there is no possibility that the composition becomes brittle. Further, if the weight average molecular weight is not more than the above upper limit value, the viscosity of the composition becomes high and there is no possibility that the composition will not flow. Preferably, the component having a molecular weight of 5,000 or more is 0.5% by weight or more of the whole, and more preferably 1.0% by weight or more. By containing the polysiloxane having a molecular weight of 5,000 or more in the above amount, good cracking property can be imparted to the resin. In the present invention, the weight average molecular weight (Mw) is a weight average molecular weight using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions. The amount of polysiloxane having a molecular weight of 5,000 or more is determined by obtaining a differential molecular weight distribution curve from a gel permeation chromatography chromatogram obtained under the following conditions and using the curve.
[Measurement condition]
Developing solvent: tetrahydrofuran (THF)
Flow rate: 0.6 mL / min
Detector: Differential Refractometer (RI)
Column: TSK Guardcolomn SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both made by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5% by mass)

The method for producing the component (A) is not particularly limited, and it can be obtained by, for example, hydrolyzing and condensing a silane compound as a raw material for each structural unit. For example, examples of the raw material compound that gives _4/2 units of SiO (Q units) include, but are not limited to, sodium silicate, tetraalkoxysilane, or a condensation reaction product thereof.

（上記式中、Ｍｅはメチル基を示す） Examples of the raw material compound that gives R ¹ SiO _3/4 unit (T unit) include organosilicon compounds such as organotrichlorosilane and organotrialkoxysilane represented by the following structural formulas, and condensed reactants thereof. However, it is not limited to these.

(In the above formula, Me represents a methyl group)

（上記式中、Ｍｅはメチル基を示す。ｎは５〜８０の整数、ｍは５〜８０の整数であり、ただしｎ＋ｍ≦７８である）

（上記式中、Ｍｅはメチル基を示す） The (R ⁴⁾ starting compound to give ₂ SiO _2/2 units (D units), e.g., diorganodichlorosilane represented by the following structural formula, and organic silicon compounds such as diorganodialkoxysilanes, and the like , Not limited to these.

(In the above formula, Me represents a methyl group. N is an integer of 5 to 80, m is an integer of 5 to 80, where n + m ≦ 78).

(In the above formula, Me represents a methyl group)

（上記式中、Ｍｅはメチル基を示す） Examples of the raw material for giving R ¹ ₃ SiO _1/2 unit (M unit) include organosilicon compounds such as triorganochlorosilane, triorganoalkoxysilane, and hexaorganodisiloxane represented by the following structural formulas. , Not limited to these.

(In the above formula, Me represents a methyl group)

[(B) Organohydrogenpolysiloxane]
The component (B) is an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule and one or more silicon atom-bonded aromatic hydrocarbon groups in one molecule. The component (B) is preferably represented by the following average composition formula (2).
R ³ _{h Hi} SiO _{(4-h-i) / 2} ... (2)
In the above formula, R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and h and i are preferably 0.7 ≦ h ≦ 2.1, 0. .001 ≦ i ≦ 1.0 and 0.8 ≦ h + i ≦ 3.0, more preferably 1.0 ≦ h ≦ 2.0, 0.01 ≦ i ≦ 1.0, and 1 It is a number that satisfies .5 ≦ h + i ≦ 2.5.

Examples of R ³ include saturated aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, saturated alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group, phenyl group and trill. Aromatic hydrocarbon groups such as aryl groups such as groups and xsilyl groups, benzyl groups, phenylethyl groups and aralkyl groups such as phenylpropyl groups, and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine. Examples thereof include those substituted with a halogen atom such as bromine and chlorine, for example, a halogenated hydrocarbon group such as a trifluoropropyl group and a chloropropyl group. Among these, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group, and a phenyl group are preferable.

The component (B) of the present invention has one or more silicon atom-bonded aromatic hydrocarbons in one molecule. Therefore, at least one R ³ is preferably an aromatic hydrocarbon group, more preferably having 1 to 100 aryl groups. The organohydrogenpolysiloxane of the component (B) has at least two hydrogen atoms (hydrosilyl groups) bonded to silicon atoms (usually 2 to 200), preferably 3 or more (usually 3 to 100). Is good. The component (B) reacts with the component (A) and acts as a cross-linking agent.

The molecular structure of the component (B) is not particularly limited, and may have any molecular structure such as linear, cyclic, branched, and three-dimensional network (resin). Further, the bonding site of the hydrosilyl group is not limited. For example, when the component (B) has a linear structure, it is bonded to the silicon atom at either the end of the molecular chain, the side chain of the molecular chain, or both. You may. The number of silicon atoms (or degree of polymerization) in one molecule is usually 2 to 200, preferably 3 to 100, and is an organohydro that is liquid or solid at room temperature (25 ° C.). Genpolysiloxane is preferred.

Examples of the organohydrogenpolysiloxane represented by the above average composition formula (2) include tris (hydrogendimethylsiloxy) phenylsilane, both-terminal trimethylsiloxy group-blocking methylhydrogensiloxane / diphenylsiloxane copolymer, and both-terminal trimethylsiloxy. Group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-terminal trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both-terminal dimethylhydrogensiloxy group-blocked methylhydrogensiloxane Didimethylsiloxane / diphenylsiloxane copolymer, both-terminal dimethylhydrogensiloxy group-blocking methylhydrogensiloxane / dimethylsiloxane / methylphenylsiloxane copolymer, and (CH ₃ ) ₂ HSiO _1/2 unit and SiO _4/2 unit And (C ₆ H ₅ ) ₃ SiO _1/2 unit of copolymer and the like.

（ｐ、ｑ、ｒは正の整数である） Further, an organohydrogenpolysiloxane shown by the following structure can also be used, but the present invention is not limited to these.

(P, q, r are positive integers)

The amount of the component (B) is such that the ratio of the number of hydrosilyl groups in the component (B) to the number of alkenyl groups bonded to the silicon atom in the component (A) is 0.1 to 4.0, preferably 0. The amount is preferably 5 to 3.0, more preferably 0.8 to 2.0. If the amount of the component (B) is less than the above lower limit, the curing reaction of the composition of the present invention does not proceed, and it is difficult to obtain a cured silicone product. Further, the obtained cured product also has an excessively low crosslink density, insufficient mechanical strength, and adversely affects heat resistance. On the other hand, if it is more than the above upper limit value, a large number of unreacted hydrosilyl groups remain in the cured product, so that the physical properties may change with time or the heat resistance of the cured product may decrease. Further, it causes foaming due to dehydrogenation reaction in the cured product.

When the curable organic silicon resin composition of the present invention contains the component (D) and / or the component (E) described later, the composition is based on the total number of silicon atom-bonded alkenyl groups of the components contained in the composition. The number ratio of the hydrosilyl groups contained in the product may be 0.1 to 4.0, preferably 0.5 to 3.0, and more preferably 0.8 to 2.0.

[(C) Platinum group metal catalyst]
The platinum group metal-based catalyst of the component (C) promotes the addition reaction of the components (A) and (B). Any known catalyst for addition reaction curing may be used. For example, there are platinum-based, palladium-based, and rhodium-based catalysts. Considering cost, platinum-based materials such as platinum, platinum black, and chloroplatinic acid, for example, H ₂ PtCl ₆・ pH ₂ O, K ₂ PtCl ₆ , KH PtCl ₆・ pH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · pH ₂ O, PtO ₂ · pH ₂ O, PtCl ₄ · pH ₂ O, PtCl ₂ , H ₂ PtCl ₄ · pH ₂ O (where p is a positive integer), etc. , A complex with a hydrocarbon such as olefin, an alcohol or a vinyl group-containing organopolysiloxane, and the like. The catalyst may be one type alone or a combination of two or more types.

The blending amount of the component (C) may be an effective amount (so-called catalyst amount) for advancing the addition reaction. Usually, it is in the range of 0.1 to 500 ppm, particularly preferably 0.5 to 100 ppm, in terms of mass as a platinum group metal with respect to the total amount of the components (A) and (B).

The curable organic silicon resin composition of the present invention can further contain at least one selected from the following components (D) to (F) in addition to the above components (A) to (C).

上記式中、Ｒ^２は互いに独立に、水素原子、炭素数２〜１０のアルケニル基、炭素数１〜１０の置換または非置換のアルキル基、または炭素数６〜１０の芳香族炭化水素基であり、ｎは１もしくは２の整数である。アルケニル基、アルキル基、及び芳香族炭化水素基は上記Ｒ^１の為に例示したものが挙げられる。 [(D) Cyclic polysiloxane]
The component (D) is a cyclic polysiloxane represented by the following formula (1). By including the cyclic polysiloxane, the viscosity, curability and curability of the composition can be adjusted.

In the above formula, R ² is a hydrogen atom, an alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms independently of each other. Yes, n is an integer of 1 or 2. Alkenyl group, an alkyl group, and aromatic hydrocarbon groups include those exemplified for the above R ^1.

As the cyclic organopolysiloxane represented by the above formula (1), a cyclic polysiloxane represented by the following structure can be used, but the cyclic polysiloxane is not limited thereto.

The amount of the cyclic polysiloxane is preferably 0.1 to 30 parts by mass, preferably 0.2 to 20 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). More preferred. However, in the composition containing the component (D) and / or the component (E) described later, the hydrosilyl group contained in the composition relative to the total number of silicon atom-bonded alkenyl groups of the component contained in the composition. The ratio of the total number is preferably 0.1 to 4.0, preferably 0.5 to 3.0, and more preferably 0.8 to 2.0.

[(E) Organopolysiloxane]
The component (E) has one or more silicon atom-bonded aromatic hydrocarbon groups having 6 to 10 carbon atoms in one molecule, and two silicon atom-bonded alkenyl groups having 2 to 10 carbon atoms in one molecule. It is a linear or branched organopolysiloxane having the above and having a viscosity of 10 to 100,000 mPa · s at 25 ° C. measured by the method described in JIS K 7117-1: 1999. When the curable organic silicon resin composition contains the component (E), the viscosity of the composition and the hardness of the cured product can be optimally adjusted according to the intended use.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms include an aryl group such as a phenyl group, a tolyl group and a xsilyl group, and an aralkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group. Be done. Of these, a phenyl group is preferable. The component (E) preferably has one or more aromatic hydrocarbon groups in one molecule, and more preferably 2 to 100 aromatic hydrocarbon groups. Examples of the alkenyl group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, an octenyl group and the like. Is preferable. The component (E) preferably has two or more alkenyl groups in one molecule, more preferably 2 to 5 alkenyl groups.

The organopolysiloxane preferably has a viscosity of 10 to 100,000 mPa · s at 25 ° C. measured by a method according to JIS K 7117-1: 1999, more preferably 100 to 50,000 mPa · s, still more preferably. Has 1,000 to 30,000 mPa · s. If the viscosity is 10 mPa · s or more, the composition is not likely to become brittle, and if it is 100,000 mPa · s or less, good workability can be obtained.

（式中、ｘ、ｙ、ｚはそれぞれ０以上の整数であり、かつｘ＋ｙ≧１を満たす数である）

（式中、ｘ、ｙ、ｚはそれぞれ０以上の整数であり、かつｘ＋ｙ≧１を満たす数である）

（式中、ｘ、ｙ、ｚはそれぞれ０以上の整数であり、かつｘ＋ｙ≧１を満たす数である）

（上記式において、ｓ、ｔ、ｕ、ｐはそれぞれ０以上の整数であり、かつｓ＋ｔ＋ｕ＋ｐ≧１を満たす数である）
前記（Ｅ）オルガノポリシロキサンの量は、（Ａ）成分及び（Ｂ）成分の合計１００質量部に対して０．１〜１００質量部が好ましく、０．５〜８０質量部がより好ましい。但し、組成物中に含まれるケイ素原子結合アルキル基の合計個数に対して、組成物中に含まれるヒドロシリル基の個数比が０．１〜４．０となる量である。 Examples of the (E) organopolysiloxane include, but are not limited to, compounds having the following structures.

(In the formula, x, y, and z are integers of 0 or more, respectively, and are numbers satisfying x + y ≧ 1.)

(In the formula, x, y, and z are integers of 0 or more, respectively, and are numbers satisfying x + y ≧ 1.)

(In the formula, x, y, and z are integers of 0 or more, respectively, and are numbers satisfying x + y ≧ 1.)

(In the above equation, s, t, u, and p are integers of 0 or more, respectively, and are numbers satisfying s + t + u + p ≧ 1.)
The amount of the (E) organopolysiloxane is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 80 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). However, the ratio of the number of hydrosilyl groups contained in the composition to the total number of silicon atom-bonded alkyl groups contained in the composition is 0.1 to 4.0.

[(F) Fluorescent material]
Further, the curable organic silicon resin composition of the present invention may further contain the (F) phosphor. Since the curable organic silicon resin composition of the present invention is excellent in heat resistance and light resistance, there is no possibility that the fluorescent characteristics will be significantly deteriorated as in the past even when a phosphor is contained. The amount of the phosphor is preferably 0 to 500 parts by mass, more preferably 0 to 300 parts by mass, based on 100 parts by mass of the total of the components (A) to (E).

In addition to the above-mentioned components (A) to (F), the curable organic silicon resin composition of the present invention contains, if necessary, additives such as known adhesion-imparting agents, curing inhibitors, and white pigments. be able to.
Examples of the adhesion-imparting agent include phenyltrimethoxysilane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4). -Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-Methylmethacryloxypropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyl Alkoxysilanes such as triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-cyanopropyltriethoxysilane, and oligomers thereof. Can be mentioned. These adhesives can be blended alone or in combination of two or more.
The amount of the adhesive-imparting agent is preferably 0 to 10 parts by mass, particularly preferably 0 to 5 parts by mass, based on 100 parts by mass of the total of the components (A) and (B).

The curing inhibitor is selected from the group consisting of, for example, triallyl isocyanurate, alkylmaleate, acetylene alcohols and their silane modified products and siloxane modified products, hydroperoxide, tetramethylethylenediamine, benzotriazole and mixtures thereof. Examples include compounds. The curing inhibitor may be used alone or in combination of two or more. The amount of the curing inhibitor is usually 0.001 to 1.0 parts by mass, preferably 0.005 to 0.5 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). ..

Examples of the white pigment include inorganic white pigments such as titanium oxide, zinc oxide, zirconium oxide, calcium carbonate, magnesium oxide, aluminum hydroxide, barium carbonate, magnesium silicate, zinc sulfate and barium sulfate. The amount of the white pigment is 600 parts by mass or less (for example, 0 to 600 parts by mass, usually 1 to 600 parts by mass, preferably 10 to 400 parts by mass) per 100 parts by mass of the total components (A) to (E). Can be appropriately blended with.

Other additives include, for example, reinforcing inorganic fillers such as silica, glass fiber, and fumed silica, calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, cerium fatty acid salt, and barium fatty acid salt. , Cerium alkoxide, non-reinforcing inorganic filler such as barium alkoxide, silicon dioxide (silica: SiO ₂ ), aluminum oxide (alumina: Al ₂ O ₃ ), iron oxide (FeO ₂ ), triiron tetroxide (Fe ₃ O) ₄ ), lead oxide (PbO ₂ ), tin oxide (SnO ₂ ), cerium oxide (Ce ₂ O _3, CeO ₂ ), calcium oxide (CaO), trimanganese tetroxide (Mn ₃ O ₄ ), barium oxide (BaO) ) And the like, and these are 600 parts by mass or less (for example, 0 to 600 parts by mass, usually 1 to 600 parts by mass, preferably 1 to 600 parts by mass) per 100 parts by mass of the above components (A) to (E). It can be appropriately blended in an amount of 10 to 400 parts by mass).

The curable organic silicon resin composition of the present invention can be applied to a predetermined substrate and then cured depending on the intended use. As for the curing conditions, it is sufficiently cured even at room temperature (25 ° C.), but it may be cured by heating if necessary. The temperature for heating can be, for example, 60 to 200 ° C.

Further, the curable organic silicon resin composition of the present invention is a cured product which is heat-cured to a thickness of 1 mm and has a direct light transmittance of 70% or more, preferably 80% or more at a wavelength of 400 to 800 nm, particularly at a wavelength of 450 nm. It is preferable to give. For the measurement of the direct light transmittance, for example, a spectrophotometer U-4100 manufactured by Hitachi can be used.

Further, the curable organic silicon resin composition of the present invention is heat-cured so that the refractive index at 23 ° C. at 589 nm measured by the JIS K 7142: 2014 A method is in the range of 1.47 to 1.57. It is preferable to give a cured product.

Any material that provides a cured product having such direct light transmittance and refractive index can be particularly preferably used for optical applications such as LED encapsulants because of its excellent transparency.

Such a curable organic silicon resin composition of the present invention provides a cured product having excellent mechanical properties, transparency, crack resistance, and heat resistance.

<Semiconductor device>
Further, the present invention provides a semiconductor device in which a semiconductor element is sealed with a cured product of the above-mentioned curable organic silicon resin composition of the present invention.

As described above, the curable organic silicon resin composition of the present invention provides a cured product having excellent transparency and heat resistance, and is therefore suitable as a material for a lens of a light emitting semiconductor device, a protective coating agent, a molding agent, and the like. In particular, it is useful for encapsulating LED elements such as blue LEDs, white LEDs, and ultraviolet LEDs. Further, since the curable organic silicon resin composition of the present invention has excellent heat resistance, it can be used as a material for a wavelength conversion film by adding a silicate-based phosphor or a quantum dot phosphor for a long period of time under high humidity. It is possible to provide a light emitting semiconductor device which can secure reliability and has good moisture resistance and long-term color playability.

When sealing a light emitting semiconductor element such as an LED with the curable organic silicon resin composition of the present invention, for example, the curable organic silicon resin composition of the present invention is placed on an LED element mounted in a premold package made of a thermoplastic resin. By applying an object and curing the composition on the LED element, the LED element can be sealed with the cured product of the curable organic silicon resin composition. Further, the composition can be applied onto the LED element in the state of a varnish prepared by dissolving the composition in an organic solvent such as toluene, xylene or PGMEA (propylene glycol monomethyl ether acetate).

The curable organic silicon resin composition of the present invention has properties such as excellent heat resistance, ultraviolet resistance, transparency, crack resistance, and long-term reliability, so that it is a display material, an optical recording medium material, an optical equipment material, and light. It is the most suitable material for optical applications such as component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials.

で示されるオルガノハイドロジェンポリシロキサン、
（Ｃ）成分として塩化白金酸のオクチルアルコール変性溶液（白金元素含有率：１質量％）０．０１部を加え、よく撹拌して、硬化性有機ケイ素樹脂組成物を調製した。該組成物を１５０℃にて４時間加熱成形して硬化物（１２０ｍｍ×１１０ｍｍ×１ｍｍ）を形成し、下記物性の測定を行った。結果を表１に示す。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, part shows a mass part, Me shows a methyl group, Vi shows a vinyl group, Ph shows a phenyl group. In the following, the method and conditions for measuring the weight average molecular weight are as described above. The amount of hydroxyl groups and the amount of alkoxy groups bonded to the silicon atom are values measured by ¹ H-NMR and ²⁹ Si-NMR.
[Example 1]
As the component (A), a branched phenylmethylpolysiloxane (Mw = 2,500) consisting of _4/2 units of SiO (0.5 mol%), _3/2 units of PhSiO (75 mol%), and _1/2 unit of ViPhMeSiO (24.9 mol%). , 1.0% of the total molecular weight of 5,000 or more components, 0.01 mol / 100 g of hydroxyl groups bonded to silicon atoms, 0.05 mol / 100 g of alkoxy groups bonded to silicon atoms), 30 parts.
As the component (B), the ratio of the total number of silicon atom-bonded hydrogen atoms in the component (B) to the total number of silicon atom-bonded vinyl groups in the component (A) (hereinafter referred to as SiH / SiVi ratio) is 1. The following formula (3) for the amount to be 0

Organohydrogenpolysiloxane, indicated by
0.01 part of an octyl alcohol-modified solution of platinum chloride acid (platinum element content: 1% by mass) was added as a component (C) and stirred well to prepare a curable organic silicon resin composition. The composition was heat-molded at 150 ° C. for 4 hours to form a cured product (120 mm × 110 mm × 1 mm), and the following physical properties were measured. The results are shown in Table 1.

で示される環状ポリシロキサン２部を加え、よく撹拌して、硬化性有機ケイ素樹脂組成物を調製した。該組成物を１５０℃にて４時間加熱成形して硬化物（１２０ｍｍ×１１０ｍｍ×１ｍｍ）を得た。 [Example 2]
As a component (A), a branched phenylmethylpolysiloxane (Mw = 4,900, molecular weight) composed of SiO _4/2 unit 10 mol%, PhSiO _3/2 unit 65 mol%, and ViMe ₂ SiO _1/2 unit 25 mol%. 30 parts of 10.7% of the total of 5,000 or more components, 0.02 mol / 100 g of hydroxyl groups bonded to silicon atoms, 0.03 mol / 100 g of alkoxy groups bonded to silicon atoms).
As the component (B), the ratio of the total number of silicon atom-bonded hydrogen atoms in the component (B) to the total number of silicon atom-bonded vinyl groups in the components (A) and (D) below (hereinafter, SiH / SiVi ratio). Organohydrogenpolysiloxane represented by the above formula (3) in an amount of 1.0.
As a component (C), 0.01 part of an octyl alcohol-modified solution of platinum chloride acid (platinum element content: 1% by mass),
And as the component (D), the following formula (4)

Two parts of the cyclic polysiloxane shown in (1) were added and stirred well to prepare a curable organic silicon resin composition. The composition was heat-molded at 150 ° C. for 4 hours to obtain a cured product (120 mm × 110 mm × 1 mm).

[Example 3]
Instead of component (A) used in Example _{2, SiO 4/2} units 0.1 mol%, _{PhSi [theta] 3/2} units 75 mol%, and ViPhMeSiO consisting _1/2 units 24.9Mol% branched phenylmethyl Polysiloxane (Mw = 1,900, 0.5% of the components having a molecular weight of 5,000 or more, the amount of hydroxyl groups bonded to silicon atoms, 0.2 mol / 100 g, the amount of alkoxy groups bonded to silicon atoms 0.4 mol / Example 2 was repeated except that 30 parts of 100 g) was used to prepare a curable organic silicon resin composition to obtain a cured product.

[Example 4]
Instead of the component (A) used in Example 1, it consists of 5 mol% of SiO _4/2 unit, 50 mol% of PhSiO _3/2 unit, 20 mol% of PhMeSiO _2/2 unit, and 25 mol% of ViMe ₂ SiO _1/2 unit. Branched chain phenylmethylpolysiloxane (Mw = 3,000, 5.6% of the total molecular weight of 5,000 or more components, 0.1 mol / 100 g of hydroxyl group bonded to silicon atom, alkoxy group bonded to silicon atom Example 1 was repeated except that 30 parts (molecular weight: 1.0 mol / 100 g) was used to prepare a curable organic silicon resin composition to obtain a cured product.

で示される環状ポリシロキサン５部を用いたこと以外は、実施例２を繰り返して、硬化性有機ケイ素樹脂組成物を調製し、硬化物を得た。 [Example 5]
Instead of the component (D) used in Example 2, the following formula (5)

Example 2 was repeated except that 5 parts of the cyclic polysiloxane shown in (1) was used to prepare a curable organic silicon resin composition to obtain a cured product.

（式中、ｐ＝３０（平均値）である）
で示されるオルガノポリシロキサンを１０部加え、よく撹拌して、硬化性有機ケイ素樹脂組成物を調製した。この組成物を１５０℃にて４時間加熱成形して硬化物（１２０ｍｍ×１１０ｍｍ×１ｍｍ）を得た。 [Example 6]
As the component _{(A), SiO 4/2} units 0.6 mol%, _{PhSi [theta] 3/2} units 55 mol%, _{MeSiO 3/2} units 25 mol%, and ViMe ₂ made of SiO _1/2 units 19.4Mol% branched Phenylmethylpolysiloxane (Mw = 5,000, 30% of the total molecular weight of 5,000 or more components, 1.0 mol / 100 g of hydroxyl groups bonded to silicon atoms, 0.5 mol / 100 g of alkoxy groups bonded to silicon atoms ) 30 copies,
As the component (B), the ratio of the total number of silicon atom-bonded hydrogen atoms in the component (B) to the total number of silicon atom-bonded vinyl groups in the components (A), (D) and (E) (hereinafter, SiH / Organohydrogenpolysiloxane represented by the above formula (3) in an amount such that (expressed as SiVi ratio) is 1.0.
0.01 parts of an octyl alcohol-modified solution of platinum chloride acid (platinum element content: 1% by mass) as a component (C), and the following formula (6) as a component (E).

(In the formula, p = 30 (average value))
10 parts of the organopolysiloxane shown in (1) was added and stirred well to prepare a curable organic silicon resin composition. This composition was heat-molded at 150 ° C. for 4 hours to obtain a cured product (120 mm × 110 mm × 1 mm).

[Example 7]
Instead of component (A) used in Example _{1, SiO 4/2} units 5 mol%, _{PhSi [theta] 3/2} units 70 mol%, and ViMe ₂ made of SiO _1/2 units 25 mol% branched phenylmethyl polysiloxane (Mw = 3,000, the amount of hydroxyl groups in which components having a molecular weight of 5,000 or more are bonded to 4.7% silicon atoms of the whole is 0.7 mol / 100 g, and the amount of alkoxy groups bonded to silicon atoms is 1.3 mol / 100 g). Except for the above, Example 1 was repeated to prepare a curable organic silicon resin composition to obtain a cured product.

[Example 8]
Instead of component (A) used in Example _{1, SiO 4/2} units 5 mol%, _{PhSi [theta] 3/2} units 70 mol%, and ViMe ₂ made of SiO _1/2 units 25 mol% branched phenylmethyl polysiloxane (Mw = 3,000, 3.9% of the components having a molecular weight of 5,000 or more, 1.2 mol / 100 g of hydroxyl groups bonded to silicon atoms, 0 mol / 100 g of alkoxy groups bonded to silicon atoms) were used. Except for this, Example 1 was repeated to prepare a curable organic silicon resin composition to obtain a cured product.

[Comparative Example 1]
Instead of component (A) used in Example 1, _{PhSi [theta] 3/2} units 80 mol%, and ViPhMeSiO _1/2 composed of units 20 mol% branched phenylmethyl polysiloxane (Mw = 2,000, molecular weight 5, Example 1 was used except that 0.05% of the total components were 000 or more, the amount of hydroxyl groups bonded to the silicon atom was 0.5 mol / 100 g, and the amount of alkoxy groups bonded to the silicon atom was 0.05 mol / 100 g). A curable organic silicon resin composition was repeatedly prepared to obtain a cured product.

[Comparative Example 2]
Instead of component (A) used in Example _{1, SiO 4/2} units 0.05mol%, _{PhSiO 3/2} units 80 mol%, and consists of ViMe ₂ SiO _1/2 units 19.95Mol% branched Phenylmethylpolysiloxane (Mw = 2,100, 0.2% of the total molecular weight of 5,000 or more components, 0.2 mol / 100 g of hydroxyl groups bonded to silicon atoms, 0.04 mol of alkoxy groups bonded to silicon atoms A curable organic silicon resin composition was prepared by repeating Example 1 except that / 100 g) was used to obtain a cured product.

[Comparative Example 3]
Instead of component (A) used in Example _{1, SiO 4/2} units 15 mol%, _{PhSi [theta] 3/2} units 70 mol%, and ViMe ₂ made of SiO _1/2 units 15 mol% branched phenylmethyl polysiloxane (Mw = 6,100, 56% of the components having a molecular weight of 5,000 or more, 0.3 mol / 100 g of hydroxyl groups bonded to silicon atoms, 0.1 mol / 100 g of alkoxy groups bonded to silicon atoms) were used. Except for this, Example 1 was repeated to prepare a curable organic silicon resin composition to obtain a cured product.

[Comparative Example 4]
Instead of the component (A) used in Example 1, SiO _4/2 unit 0.5 mol%, PhSiO _3/2 unit 70 mol%, Me ₂ SiO _2/2 unit 9.5 mol%, and ViMe ₂ SiO _{1 /.} Branched chain phenylmethylpolysiloxane consisting of ₂ units of 20 mol% (Mw = 3,000, 2.4% of the total components having a molecular weight of 5,000 or more, 0.0005 mol / 100 g of hydroxyl groups bonded to silicon atoms, silicon Example 1 was repeated to prepare a curable organic silicon resin composition, except that the amount of alkoxy groups bonded to the atom was 0.05 mol / 100 g), and a cured product was obtained.

[Comparative Example 5]
Instead of the component (A) used in Example 1, a branched phenylmethylpolysiloxane (Mw = 3,100, silicon atom) composed of PhSiO _3/2 unit 65 mol% and ViPhSiO _2/2 unit 35 mol%. Example 1 was repeated to prepare a curable organic silicon resin composition, except that the amount of bonded hydroxyl groups was 0.02 mol / 100 g and the amount of alkoxy groups bonded to silicon atoms was 0.2 mol / 100 g). Got

The physical properties of the curable organic silicon resin composition and the cured product obtained in the above Examples and Comparative Examples were measured by the following methods. The results are shown in Tables 1 and 2.
(1) Appearance The color and transparency of the cured product (thickness 1 mm) obtained by curing each composition at 150 ° C. for 4 hours were visually confirmed.
(2) Properties The fluidity of each composition before curing was confirmed. 50 g of the composition was added to a 100 ml glass bottle, and the glass bottle was laid on its side and allowed to stand at 25 ° C. for 10 minutes. If the resin flows out during that time, it is judged to be liquid.
(3) Viscosity The viscosity of each composition before curing at 25 ° C. was measured by the method described in JIS K 7117-1: 1999.
(4) Refractive index The refractive index of each composition before curing was measured at 25 ° C. using a digital refractometer RX-9000α manufactured by ATAGO to measure the refractive index of light having a wavelength of 589 nm.
(5) Transmittance The light transmittance of the cured product (thickness 1 mm) obtained by curing each composition at 150 ° C. for 4 hours at a wavelength of 450 nm was measured at 23 ° C. using a spectrophotometer U-4100 manufactured by Hitachi. It was measured. The results are shown in Tables 1 and 2.
(6) Hardness (Type A)
The hardness of the cured product obtained by curing each composition at 150 ° C. for 4 hours was measured using a durometer D hardness tester in accordance with JIS K 6249: 2003.
(7) Elongation and tensile strength during cutting The elongation and tensile strength during cutting of the cured product obtained by curing each composition at 150 ° C. for 4 hours was measured in accordance with JIS K 6249: 2003.
(8) Surface tackiness Each composition was cured at 150 ° C. for 4 hours, the state of the surface of the cured product (thickness 1 mm) was examined by touch, and the tackiness was evaluated according to the following criteria.
(Criteria)
◯: No stickiness Δ: Slightly sticky ×: With stickiness (9) Workability Each composition was filled in a syringe (Nordson, Optimum syringe, 5cc), and a needle nozzle (Saneitech, SH23-0. After mounting 25-B), each composition was dispensed into a Tiger3528 package (manufactured by Shin-Etsu Chemical Co., Ltd.) using a dispenser (manufactured by Musashi Engineering Co., Ltd., ML-606GX) to determine workability.
(Criteria)
◯: The resin was wet and spread easily and could be sealed ×: The resin was not easily wet and spread and it took time to seal (10) Adhesiveness 0.25 g of each composition was placed on a silver plate having an area of 180 mm ² and had a bottom area. After molding to a size of 45 mm ² and curing at 150 ° C. for 4 hours, the cured product was broken using a microspatula, and when peeled from the silver plate, the ratio of the cohesive broken part to the peeled part was determined. The adhesiveness was determined.
(Criteria)
◯: Good adhesiveness (60% or more of cohesive failure)
X: Adhesiveness is poor (less than 60% of the cohesive failure part)
The presence or absence of dust adhesion on the surface of the cured product obtained by curing each composition at 150 ° C. for 4 hours was visually confirmed.
(11) Crack resistance Each composition was sealed in SMD type LED3528PPA 10 times each, cured at 150 ° C. for 4 hours, and then subjected to a thermal shock test at −40 ° C. to 120 ° C. for 1,000 cycles. After the test, the cured product was checked under a microscope for cracks and peeling.
(Criteria)
◯: No cracks △: Less than 5 cracks ×: 5 or more cracks

As shown in Table 2, cracks were generated in the cured product obtained from the compositions of Comparative Examples 1 and 5 containing the organopolysiloxane resin containing _4/2 units of SiO in the thermal shock test. Further, even in the cured product obtained from the composition of Comparative Example 2 containing an organopolysiloxane resin having a low content of SiO _4/2 units, cracks were generated in the thermal shock test. Further, in the cured product obtained from the composition of Comparative Example 4 in which the amount of silicon atom-bonded hydroxyl groups contained in the organopolysiloxane resin was less than 0.001 mol / 100 g, the adhesiveness was lowered. The composition of Comparative Example 3 containing an organopolysiloxane resin having a high content of _4/2 units of SiO had a high viscosity and was inferior in workability.
On the other hand, as shown in Table 1, the curable organic silicon resin composition of the present invention is colorless and transparent, has sufficient hardness, elongation at cutting, and tensile strength, and has a good refractive index. It had heat resistance, crack resistance, and adhesiveness. Among them, the curable organic silicon resin compositions of Examples 1 to 6 have the above-mentioned characteristics and have surface tackiness by further specifying the amount of hydroxyl groups bonded to silicon atoms and the amount of alkoxy groups. A cured product without dust adhesion was obtained.

The curable organic silicon resin composition of the present invention has fluidity, a cured product can be obtained quickly, and a cured product having excellent mechanical properties, crack resistance, and workability can be provided. The composition is suitable as a sealing material for a semiconductor device including a semiconductor element such as a light emitting element.

Claims (10)

(A) An organopolysiloxane having at least two silicon atom-bonded alkenyl groups in one molecule.
It has _4/2 units of SiO and _3/2 units of R ¹ SiO, and the ratio of _4/2 units of SiO to the number of moles of all siloxane units is 0.1 mol% or more and 10 mol% or less, and at least two in one molecule. The organopolysiloxane having a silicon atom-bonded alkenyl group and having a hydroxyl group bonded to a silicon atom having a content of 0.001 mol / 100 g or more (in the above, R ¹ has 2 to 2 carbon atoms independently of each other). (10 alkenyl groups, substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms, or aromatic hydrocarbon groups with 6 to 10 carbon atoms)
(B) Organohydrogenpolysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule and one or more silicon atom-bonded aromatic hydrocarbon groups in one molecule: component (A) The amount at which the ratio of the number of hydrosilyl groups of the component (B) to the number of alkenyl groups is 0.1 to 4.0, and (C) platinum group metal-based catalyst: catalytic amount,
A curable organic silicon resin composition comprising. The component (A) contains 0.1 to 10 mol% of SiO _4/2 units, 50 to 90 mol% of R ¹ SiO _3/2 units, and (R ⁴ ) ₂ SiO _{2 with} respect to the number of moles of all siloxane units. _It has 0 to 30 mol% of _{/ 2} units and 10 to 30 mol% of (R ¹ ) ₃ SiO _1/2 units (in the above formula, R ¹ is the same as above, and R ⁴ is substituted or substituted independently of each other. An unsubstituted alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms), the amount of hydroxyl groups bonded to a silicon atom is 0.001 to 1.0 mol / 100 g, and silicon. The curable organic silicon resin composition according to claim 1, which has 1.0 mol / 100 g or less of an alkoxy group having 1 to 10 carbon atoms bonded to an atom. The first or second claim, wherein the component (A) has an aromatic hydrocarbon group bonded to a silicon atom in an amount of 18 mol% or more and 90 mol% or less based on the total number of moles of all substituents bonded to the silicon atom. Curable organic silicon resin composition. The amount of organopolysiloxane in which the component (A) has a polystyrene-equivalent weight average molecular weight of 1,000 to 5,000 as measured by gel permeation chromatography and has a molecular weight of 5,000 or more in the component (A). The curable organic silicon resin composition according to any one of claims 1 to 3, wherein the content is 0.5% by weight or more. Further, as the component (D), the following formula (1)

(In the above formula, R ² is a hydrogen atom, an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted, or an aromatic hydrocarbon group having 6 to 10 carbon atoms independently of each other. And n is 1 or 2)
The cyclic siloxane represented by (1) is contained in an amount of 0.1 to 30 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B).
When the component (D) has an alkenyl group and / or a hydrosilyl group, the ratio of the number of SiH groups in the components (B) and (D) to the total number of alkenyl groups in the components (A) and (D). Is an amount of 0.1 to 4.0.
The curable organic silicon resin composition according to any one of claims 1 to 4. Further, as the component (E), one or more silicon atom-bonded aromatic hydrocarbon groups having 6 to 10 carbon atoms are contained in one molecule, and two silicon atom-bonded alkenyl groups having 2 to 10 carbon atoms are contained in one molecule. The component (A) is a linear or branched organopolysiloxane having one or more and having a viscosity of 10 to 100,000 mPa · s at 25 ° C. measured by the method described in JIS K 7117-1: 1999. And (B) is contained in 0.1 to 100 parts by mass with respect to 100 parts by mass in total.
Any one of claims 1 to 5, wherein the ratio of the number of hydrosilyl groups contained in the composition to the total number of silicon atom-bonded alkyl groups contained in the composition is 0.1 to 4.0. The curable organic silicon resin composition according to. The curable organic silicon resin composition according to any one of claims 1 to 6, further comprising at least one inorganic white pigment. A semiconductor device comprising a cured product obtained by curing the curable organic silicon resin composition according to any one of claims 1 to 7 and a semiconductor element. A semiconductor device including a cured product obtained by curing the curable organic silicon resin composition according to any one of claims 1 to 6 and a semiconductor element, wherein the cured product has a thickness of 1 mm at a wavelength of 450 nm. The semiconductor device having a direct light transmittance of 70% or more. The semiconductor device according to claim 8 or 9, wherein the semiconductor element is a light emitting element.