JP2022146347A - Organosilicon compound, thermosetting resin composition, molded body, and optical semiconductor device - Google Patents

Abstract

To provide an organosilicon compound and a thermosetting resin composition from which a molded body having high light transmittance and gas barrier property can be obtained, and a molded body and an optical semiconductor device obtained using the thermosetting resin composition.SOLUTION: An organosilicon compound (A1) is represented by formula (1-1). In the formula (1-1), R0 is independently phenyl or a six-membered ring group obtained by subjecting phenyl to nucleus hydrogenation; R1 is independently H or OH; and n is a number satisfying 0≤n≤10 as an average value of the compound.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an organosilicon compound, a thermosetting resin composition, a molded article, and an optical semiconductor device produced using the composition.

2. Description of the Related Art Optical semiconductor devices including optical semiconductor elements such as light emitting diodes (LEDs) have been put to practical use in various lighting devices, electronic bulletin boards, traffic lights, backlights of liquid crystal display devices, LED displays, and the like. In these optical semiconductor devices, the optical semiconductor element is generally sealed with a transparent sealing material. Silicone resins are widely used as one of sealing materials for optical semiconductor elements. Although silicone resins are excellent in heat resistance and light transmittance, they have the problem of low barrier properties against corrosive gases and water vapor. In addition, thermal shock resistance and low dielectric properties are also required as devices become higher in output and frequency.

Patent Document 1 describes that a crosslinkable silicon compound having a double-decker silsesquioxane structure and a crosslinkable functional group is excellent in optical transparency, optical refractive index, and thermal shock. However, the crosslinkable silicon compound has no description of gas barrier properties and low dielectric properties.

Patent Document 2 describes that a thermosetting resin composition obtained by using the above-mentioned crosslinkable silicon compound and a siloxane polymer containing a silsesquioxane structure is excellent in molded articles that are less prone to cracking in a high-temperature environment. ing. However, since the siloxane polymer is a cloudy viscous liquid, it is inferior in light transmittance.

JP 2010-280766 A JP 2020-090593 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting resin composition which has good light transmittance and excellent gas barrier properties. Another object of the present invention is to provide a siloxane polymer excellent in light transmittance and a cured product excellent in thermal shock resistance and low dielectric properties.

The present invention has been made under the circumstances as described above, and an object of the present invention is to provide an organosilicon compound and a thermosetting resin composition capable of obtaining a molded article having high light transmittance and gas barrier properties, and An object of the present invention is to provide a molded article and an optical semiconductor device obtained using such a thermosetting resin composition.

The invention made to solve the above-mentioned problems is an organosilicon compound obtained by hydrogenating 30% or more of phenyl in an organosilicon compound containing a double-decker silsesquioxane structure having phenyl.

Examples of the organosilicon compound include an organosilicon compound (A1) represented by formula (1-1), an organosilicon compound (A2) represented by formula (1-2), or formula (1-3). Organosilicon compounds (A3) represented by Here, n is 0 or more and 10 or less as an average value of the compound, R ⁰ is independently a six-membered ring group obtained by hydrogenating phenyl typified by cyclohexyl or cyclohexenyl, or phenyl, and R ¹ , R ² , and R ³ are independently hydrogen or hydroxy.

As R ⁰ of the organosilicon compound, it is preferable to select a combination of groups such that the compound has a hydrogenation rate of 30% or more, more preferably 60% or more, and more preferably 90%. The above combination is more preferable.

In the organosilicon compound (A1), the organosilicon compound (A2), and the organosilicon compound (A3), n is preferably 0 or more and 6 or less as the average value of the compounds.

式（２－１）中のｎは３≦ｎ≦８を満たす整数である。
式（２－２）中のｍは０≦ｍ≦５０を満たす平均値であり、Ｖｉはビニルを表す。 Another invention, which has been made to solve the above problems, is to combine an organosilicon compound (A1) and a compound selected from compounds represented by formulas (2-1) and (2-2) with an acid catalyst. It is an organosilicon compound (A4) obtained by equilibration polymerization under the following conditions.

n in formula (2-1) is an integer satisfying 3≦n≦8.
m in formula (2-2) is an average value satisfying 0≦m≦50, and Vi represents vinyl.

Organosilicon compound (A4) is represented by formula (2-3). Here, m is an average value satisfying 1 to 5, n is an average value satisfying 2 to 50, and R ⁰ is independently a 6-membered phenyl represented by cyclohexyl or cyclohexenyl. It is a cyclic group or phenyl, and Vi represents vinyl.

Yet another invention made to solve the above problems is
Organosilicon compound (A): an organosilicon compound or an organosilicon compound in which R ¹ , R ² , and R ³ are hydrogen among the organosilicon compound (A1), the organosilicon compound (A2), or the organosilicon compound (A3) (A4),
Organosilicon compound (B): an organosilicon compound having a plurality of crosslinkable groups in the molecule other than the organosilicon compound (A);
and a hydrosilylation catalyst (C),
The organosilicon compound (B) is a thermosetting resin composition containing at least an organosilicon compound (A) and a crosslinkable compound.

式（３）中、Ｒ^３は独立して、炭素数１～４のアルキル、シクロペンチル、またはシクロヘキシルである。Ｘは独立して、式（Ｘ１）、式（Ｘ２）、または式（Ｘ３）で表される基である。
式（３）で表される化合物１分子あたりの式（Ｘ１）で表される基の平均数をｘ_１、式（Ｘ２）で表される基の平均数をｘ_２、式（Ｘ３）で表される基の平均数をｘ_３としたとき、ｘ_１＋２ｘ_２＋ｘ_３＝４ｒ、０＜ｘ_１＜４ｒ、０≦ｘ_２＜２ｒ、かつ０＜ｘ_３＜４ｒを満たす。ｒは、１～１００を満たす平均値である。 The organosilicon compound (B) preferably contains a compound represented by formula (3).

In formula (3), R ³ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, or cyclohexyl. X is independently a group represented by formula (X1), formula (X2), or formula (X3).
x ₁ is the average number of groups represented by formula (X1) per molecule represented by formula (3), x ₂ is the average number of groups represented by formula (X2), and formula (X3) When the average number of represented groups is x ₃ , x ₁ +2x ₂ +x ₃ =4r, 0<x ₁ <4r, 0≦x ₂ <2r, and 0<x ₃ <4r are satisfied. r is an average value satisfying 1-100.

式（Ｘ１）、式（Ｘ２）、および式（Ｘ３）中、＊は、結合部位を示す。
式（Ｘ２）中、Ｒ^４は独立して、炭素数１～４のアルキル、シクロペンチル、シクロヘキシル、またはフェニルである。ｓは、２～２０を満たす平均値である。
式（Ｘ３）中、Ｒ^５は独立して、炭素数１～４のアルキル、シクロペンチル、シクロヘキシル、またはフェニルである。Ｒ^６は、炭素数２～５のアルケニルである。Ｒ^７は、Ｒ^６と同じ炭素数のアルカンジイルである。ｔは、２～２０を満たす平均値である。）

In Formula (X1), Formula (X2), and Formula (X3), * indicates a binding site.
In formula (X2), R ⁴ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. s is an average value that satisfies 2-20.
In formula (X3), R ⁵ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. R ⁶ is alkenyl having 2 to 5 carbon atoms. ^R7 is an alkanediyl with the ^same number of carbons as R6. t is an average value that satisfies 2-20. )

式（４）中のｙは０≦ｙ≦５０を満たす平均値であり、Ｒ^３はビニルまたは水素である。 The organosilicon compound (B) preferably contains a compound represented by formula (4).

y in formula (4) is an average value that satisfies ^0≤y≤50 , and R3 is vinyl or hydrogen.

It is preferred that the organosilicon compound (B) contains a compound having three or more SiH groups.
Examples of compounds having three or more SiH groups include compounds represented by formulas (5-1) to (5-4).

式（６－１）、式（６－２）、および式（６－３）中、ｎは化合物の平均値として１≦ｎ≦１０を満たす The organosilicon compound (B) preferably contains a compound represented by formula (6-1), formula (6-2), or formula (6-3).

In formula (6-1), formula (6-2), and formula (6-3), n satisfies 1 ≤ n ≤ 10 as the average value of the compound

In the thermosetting resin composition, the content of the organosilicon compound (A) is preferably 30% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more. .

In the thermosetting resin composition, the organosilicon compound (A) is preferably at least 30% by mass with respect to the total 100% by mass of the organosilicon compound (A) and the organosilicon compound (B).

Preferably, the thermosetting resin composition further contains an adhesion imparting agent (D), and the adhesion imparting agent (D) contains a compound represented by formula (7).

In formula (7), R ¹⁸ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, or cyclohexyl. Z is independently a group represented by formula (Z1), formula (Z2), formula (Z31), formula (Z32), formula (Z33), or formula (Z41). The average number of groups represented by formula (Z1) per molecule represented by formula (7) is z ₁ , the average number of groups represented by formula (Z2) is z ₂ , formula (Z31), When the average number of groups represented by formula (Z32) or (Z33) is z ₃ and the average number of groups represented by formula (Z41) is z ₄ , z ₁ +2z ₂ +z ₃ +z ₄ = 4w, 0.5w≦z ₁ ≦3w, 0.5w≦2z ₂ ≦2w, 0.1w≦z ₃ ≦2w, and 0≦z ₄ ≦w. w is an average value satisfying 1-100.

式（Ｚ１）、式（Ｚ２）、式（Ｚ３１）、式（Ｚ３２）、式（Ｚ３３）、および式（Ｚ４１）中、＊は、結合部位を示す。
式（Ｚ２）中、Ｒ^１９は独立して、炭素数１～４のアルキル、シクロペンチル、シクロヘキシル、またはフェニルである。ｉは、１～２０を満たす平均値である。
式（Ｚ４１）中、Ｒ^２０は独立して、メチル、エチル、ブチル、またはイソプロピルである。

In Formula (Z1), Formula (Z2), Formula (Z31), Formula (Z32), Formula (Z33), and Formula (Z41), * indicates a binding site.
In formula (Z2), R ¹⁹ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. i is an average value satisfying 1-20.
In formula (Z41), R ²⁰ is independently methyl, ethyl, butyl, or isopropyl.

In the thermosetting resin composition, the content of the adhesion imparting agent (D) is preferably 0.1% by mass or more and 5% by mass or less, and is preferably 0.5% by mass or more and 2% by mass or less. More preferred.

The thermosetting resin composition preferably further contains a phosphor (E) or a white pigment (F).

Yet another invention made to solve the above problems is a molded article obtained by curing the thermosetting resin composition.

Yet another invention made to solve the above problems is an optical semiconductor device comprising an optical semiconductor element and a molded body for encapsulating the optical semiconductor element.

INDUSTRIAL APPLICABILITY According to the present invention, an organosilicon compound and a thermosetting resin composition capable of obtaining a molded article having high light transmittance and gas barrier properties, and a molded article obtained using such a thermosetting resin composition. and an optical semiconductor device.

Hereinafter, an organosilicon compound, a thermosetting resin composition, a molded article, and a semiconductor device according to one embodiment of the present invention will be described in detail.

<Organosilicon compound of the present invention>
The organosilicon compound according to one embodiment of the present invention, which includes the organosilicon compound (A1), the organosilicon compound (A2), or the organosilicon compound (A3), has a double-decker silsesquioxane structural unit as a nucleus. , has a hydrocarbon group obtained by nuclear hydrogenation of the phenyl directly bonded to the silicon atom of the double-decker silsesquioxane structural unit, and has hydrosilyl or hydroxy as a terminal group. It may also have a dimethylsiloxane unit linked between the double-decker silsesquioxane structural unit and the terminal group.

The hydrogenation rate of the phenyl group of the organosilicon compound is (average number of hydrogen molecules per molecule added to the organosilicon compound) / (double-decker silsesquioxylate having a phenyl group, which is the raw material of the organosilicon compound). The number of phenyl groups contained in the organosilicon compound containing a san structure is multiplied by 3). For example, when 2.5 phenyls on average in the organosilicon compound (A1) are nuclear hydrogenated to cyclohexyl, the hydrogenation rate is 31%, and for example, 4 phenyls on average in the organosilicon compound (A2) If the nucleus is hydrogenated to cyclohexenyl and an average of 4 phenyls are nucleus-hydrogenated to cyclohexanediyl, the hydrogenation rate is 50%.

By setting the phenyl hydrogenation rate of the organosilicon compound to 30% or more, the compatibility between the dimethylsiloxane structure and the double-decker silsesquioxane structure is improved, and phase separation is less likely to occur, thereby The light transmittance of the molded article obtained using the thermosetting resin composition containing the organosilicon compound is improved. This effect becomes more remarkable as the hydrogenation rate is increased, and the hydrogenation rate is preferably 60% or more, more preferably 90% or more.

By setting the hydrogenation rate in the nuclear hydrogenation of the phenyl group of the organosilicon compound to 30% or more, the packing between the double-decker silsesquioxane structures becomes dense, and the thermosetting composition containing the organosilicon compound The gas barrier property of the molded article obtained using the resin composition is improved. This effect becomes more remarkable as the hydrogenation rate is increased, and the hydrogenation rate is preferably 60% or more, more preferably 90% or more.

Hydrogenation of the phenyl group of the organosilicon compound can be carried out by a method generally known as a hydrogenation method for aromatic compounds.

<Organosilicon compound (A1)>
The organosilicon compound (A1) according to one embodiment of the present invention is represented by the formula (1-1), has a double-decker silsesquioxane structural unit as a nucleus, and has a double-decker silsesquioxane structural unit It has a hydrocarbon group obtained by nuclear hydrogenation of a phenyl directly bonded to silicon, and has a hydrosilyl group or hydroxy as a terminal group. It may also have a dimethylsiloxane unit linked between the double-decker silsesquioxane structural unit and the terminal group.

In formula (1-1), R ⁰ is independently a hydrocarbon group obtained by nuclear hydrogenation of phenyl typified by cyclohexyl or cyclohexenyl, or phenyl, and R ¹ is independently hydrogen or hydroxy.

n in the formula (1-1) is the average length of two dimethylsiloxane units in the organosilicon compound (A1), preferably 0 to 10, more preferably 0 to 6.

<Organosilicon compound (A2)>
The organosilicon compound (A2) according to one embodiment of the present invention is represented by the formula (1-2), has a double-decker silsesquioxane structural unit as a nucleus, and has a double-decker silsesquioxane structural unit It has a hydrocarbon group obtained by nuclear hydrogenation of a phenyl directly bonded to silicon, and has a hydrosilyl group or hydroxy as a terminal group. It may also have a dimethylsiloxane unit linked between the double-decker silsesquioxane structural unit and the terminal group.

In formula (1-2), R ⁰ is independently a hydrocarbon group obtained by nucleating phenyl typified by cyclohexyl or cyclohexenyl, or phenyl, and R ² is independently hydrogen or hydroxy.

n in the formula (1-2) is the average length of the four dimethylsiloxane units in the organosilicon compound (A2), preferably 0 or more and 10 or less, more preferably 0 or more and 6 or less.

<Organosilicon compound (A3)>
The organosilicon compound (A3) according to one embodiment of the present invention is represented by the formula (1-3), has a double-decker silsesquioxane structural unit as a nucleus, and has a double-decker silsesquioxane structural unit It has a hydrocarbon group obtained by hydrogenating a phenyl directly bonded to silicon, and has hydrosilyl or hydroxy as a terminal group. It may also have a dimethylsiloxane unit linked between the double-decker silsesquioxane structural unit and the terminal group.

In formula (1-3), R ⁰ is independently a hydrocarbon group obtained by nuclear hydrogenation of phenyl represented by cyclohexyl or cyclohexenyl, or phenyl, and R ³ is independently hydrogen or a hydroxy group.

n in formula (1-3) is the average length of the four dimethylsiloxane units in the organosilicon compound (A2), preferably 0 to 10, more preferably 0 to 6.

<Organosilicon compound derivative (A4)>
The organosilicon compound (A4) according to one embodiment of the present invention is represented by the formula (2-3) and is obtained by nuclear hydrogenation of the phenyl directly bonded to the silicon of the double-decker silsesquioxane structural unit. Having a double-decker type silsesquioxane structural unit having a hydrocarbon group, a dimethylsiloxane unit, and vinyl as a terminal group, an organosilicon compound (A1) and formula (2-1) or formula (2-2 ) can be obtained by equilibration polymerization of a compound represented by ) in the presence of an acid catalyst.

n in formula (2-1) is an integer satisfying 3≦n≦8.
m in formula (2-2) is an average value satisfying 0≦m≦50, and Vi represents vinyl.
In formula (2-3), m is an average value satisfying 1 to 5, n is an average value satisfying 2 to 50, R ⁰ is independently a phenyl nucleus represented by cyclohexyl or cyclohexenyl It is a hydrocarbon group obtained by hydrogenation, or phenyl, and Vi represents vinyl.

<Thermosetting resin composition>
The thermosetting resin composition according to one embodiment of the present invention includes an organosilicon compound (A1) or an organosilicon compound (A2), an organosilicon compound (A3), or an organosilicon compound derivative (A4) (hereinafter referred to as "( A) organosilicon compound” or “(A) component”), an organosilicon compound having a plurality of crosslinkable groups other than the organosilicon compound (A) (hereinafter referred to as “(B) organosilicon compound” or “( (also referred to as "component B)"), and a hydrosilylation catalyst (C). The organosilicon compound (B) contains at least a compound that can be crosslinked with the organosilicon compound (A). Since the thermosetting resin composition contains the organosilicon compound (A), the compatibility between the dimethylsiloxane structure and the double-decker silsesquioxane structure is high, and phase separation is unlikely to occur. Packing between silsesquioxane structures becomes dense, and the molded article obtained by curing is excellent in light transmittance and gas barrier properties. The thermosetting resin composition may further contain other components. Each component constituting the thermosetting resin composition will be described in detail below.

<(A) component: organosilicon compound (A)>
The organosilicon compound (A) is the organosilicon compound (A1), the organosilicon compound (A2), or the organosilicon compound (A3) in which R ¹ , R ² , and R ³ are hydrogen, or It is an organosilicon compound derivative (A4). The organosilicon compound (A) may be one or a mixture of two or more.

The lower limit of the content of the organosilicon compound (A) in the total organosilicon compounds in the thermosetting resin composition is preferably 1% by mass, more preferably 5% by mass, and even more preferably 10% by mass. . On the other hand, the upper limit of this content is preferably 90% by mass, more preferably 70% by mass, and even more preferably 50% by mass and 30% by mass in some cases. For example, when the organosilicon compound (A) has hydrosilyl groups at both ends, the content of the organosilicon compound (A) is relatively small and the content of the organosilicon compound (B) is large. , the resulting molded article tends to have improved light transmittance, gas barrier properties, thermal shock resistance and dielectric properties.

By setting the content of the organosilicon compound (A) to 1% by mass or more and 90% by mass or less, the thermosetting resin composition can be cured by optimizing the mixing ratio with other components. The light transmittance and gas barrier properties of the molded article to be obtained are further improved.

<(B) Component: Organosilicon Compound (B)>
The organosilicon compound (B) is an organosilicon compound (excluding the organosilicon compound (A)) having a plurality of crosslinkable groups in its molecule. Examples of crosslinkable groups include alkenyl such as vinyl, alkynyl such as ethynyl, and hydrosilyl, with vinyl and hydrosilyl being preferred. The organosilicon compound (B) may be one or a mixture of two or more. The organosilicon compound (B) contains at least one crosslinkable with the organosilicon compound (A). In the case where the organosilicon compound (A) has a terminal vinyl, a compound containing a hydrosilyl group as a crosslinkable group can be crosslinked with the organosilicon compound (A) by a hydrosilylation reaction. In the case of a form in which a hydrosilyl is present at the end of the organosilicon compound (A), a compound containing vinyl as a crosslinkable group can be crosslinked with the organosilicon compound (A) by a hydrosilylation reaction. Among the organosilicon compounds (B), compounds having a hydrosilyl group include organosilicon compounds (B1), (B2), (B3), and (B4) described later. Of the organosilicon compounds (B), examples of organosilicon compounds having vinyl include organosilicon compounds (B1) and (B2) described later.

In the thermosetting resin composition, the organosilicon compound (A) and at least one of the organosilicon compounds (B) undergo a cross-linking reaction in the presence of the hydrosilylation catalyst (C) to obtain a cured product. A cross-linking reaction may occur between the organosilicon compounds (B). The organosilicon compounds (B1) to (B4) suitable as the organosilicon compound (A) are described below. That is, the organosilicon compound (B) preferably contains one or more of the organosilicon compounds (B1) to (B4).

<Organosilicon compound (B1)>
The organosilicon compound (B1) is an organosilicon compound having hydrosilyl, vinyl and silsesquioxane structures. Since the organosilicon compound (B1) has a silsesquioxane structure, it is possible to further improve the heat resistance of the resulting molded article. Examples of the organosilicon compound (B1) include compounds represented by formula (3).

In formula (3), R ³ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, or cyclohexyl. X is independently a group represented by formula (X1), formula (X2), or formula (X3). x ₁ is the average number of groups represented by formula (X1) per molecule represented by formula (3), x ₂ is the average number of groups represented by formula (X2), and formula (X3) When the average number of represented groups is x ₃ , x ₁ +2x ₂ +x ₃ =4r, 0<x ₁ <4r, 0≦x ₂ <2r, and 0<x ₃ <4r are satisfied. r is an average value satisfying 1-100.

R ³ is preferably alkyl, more preferably methyl.

x ₁ preferably exceeds r, more preferably exceeds 2r. Also, x ₁ is preferably less than 3r. The above x2 is preferably less _than or equal to r. Preferably, _x3 above exceeds r. In addition, _x3 is preferably less than 3r, more preferably less than 2r. It is also preferable to satisfy x ₁ >x ₃ . _In one form, x2 may be zero. At this time, r becomes 1.

In Formula (X1), Formula (X2), and Formula (X3), * indicates a binding site.

式（Ｘ２）中、Ｒ^４は独立して、炭素数１～４のアルキル、シクロペンチル、シクロヘキシル、またはフェニルである。ｓは、２～２０を満たす平均値である。

In formula (X2), R ⁴ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. s is an average value that satisfies 2-20.

In formula (X3), R ⁵ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. R ⁶ is alkenyl having 2 to 5 carbon atoms. ^R7 is an alkanediyl with the ^same number of carbons as R6. t is an average value that satisfies 2-20.

^R5 is preferably alkyl, more preferably methyl. The number of carbon atoms in R ⁶ and R ⁷ is preferably 2. The upper limit of t is preferably 10, more preferably 5, and even more preferably 3.

The compound represented by Formula (3) can be synthesized, for example, by the method described in International Publication No. 2011/145638.

The lower limit of the content of the organosilicon compound (B1) in the total organosilicon compounds in the thermosetting resin composition is preferably 0.01% by mass, more preferably 30% by mass, and still more preferably 50% by mass. There is also On the other hand, the upper limit of this content is preferably 90% by mass, more preferably 70% by mass, and even more preferably 50% by mass. By setting the content of the organosilicon compound (B1) to 0.01% by mass or more and 90% by mass or less, the thermosetting resin composition can be cured by optimizing the mixing ratio with other components. The light transmittance and gas barrier properties of the resulting molded article are further improved.

<Organosilicon compound (B2)>
The organosilicon compound (B2) is a compound represented by formula (4).

式（４）中のｙは０≦ｙ≦５０を満たす平均値であり、Ｒ^３はビニルまたは水素である。

y in formula (4) is an average value that satisfies ^0≤y≤50 , and R3 is vinyl or hydrogen.

The lower limit of the content of the organosilicon compound (B2) in the total organosilicon compounds in the thermosetting resin composition is preferably 0.5% by mass, more preferably 1% by mass. On the other hand, the upper limit of this content is preferably 20% by mass, more preferably 10% by mass, and even more preferably 5% by mass. By setting the content of the organosilicon compound (B2) to 0.5% by mass or more and 20% by mass or less, the thermosetting resin composition can be cured by optimizing the mixing ratio with other components. The light transmittance and gas barrier properties of the resulting molded article are further improved.

<Organosilicon compound (B3)>
Organosilicon compound (B3) is a compound having three or more SiH groups.

Examples of compounds having three or more SiH groups include compounds represented by formulas (5-1) to (5-4).

The lower limit of the content (B3) of the organosilicon compound in all the organosilicon compounds in the thermosetting resin composition is preferably 0.5% by mass, more preferably 1% by mass, and 3% by mass or 5% by mass. is more preferred in some cases. On the other hand, the upper limit of this content is preferably 40% by mass, more preferably 30% by mass, and even more preferably 25% by mass or 20% by mass. By setting the content of the organosilicon compound (B3) to 0.5% by mass or more and 40% by mass or less, the thermosetting resin composition can be cured by optimizing the mixing ratio with other components. The light transmittance and gas barrier properties of the resulting molded article are further improved.

<Organosilicon compound (B4)>
The organosilicon compound (B4) is a compound represented by formula (6-1), formula (6-2), or formula (6-3).

式（６－１）、式（６－２）、および式（６－３）中、ｎは化合物の平均値として１≦ｎ≦１０を満たす

In formula (6-1), formula (6-2), and formula (6-3), n satisfies 1 ≤ n ≤ 10 as the average value of the compound

n in formulas (6-1), (6-2), and (6-3) is the average length of the dimethylsiloxane units in the organosilicon compound (B4), and is preferably 1 or more and 10 or less. , more preferably 2 or more and 6 or less.

The lower limit of the content of the organosilicon compound (B4) in the total organosilicon compounds in the thermosetting resin composition is preferably 0.5% by mass, more preferably 1% by mass, and 3% by mass or 5% by mass. is more preferred in some cases. On the other hand, the upper limit of this content is preferably 40% by mass, more preferably 30% by mass, and even more preferably 25% by mass or 20% by mass. By setting the content of the organosilicon compound (B4) to 0.5% by mass or more and 40% by mass or less, the thermosetting resin composition can be cured by optimizing the mixing ratio with other components. The light transmittance and gas barrier properties of the resulting molded article are further improved.

The lower limit of the content of the organosilicon compound (B) in the total organosilicon compounds in the thermosetting resin composition is preferably 10% by mass, more preferably 30% by mass, still more preferably 40% by mass, and 60% by mass. % or 75% by weight are even more preferred in some cases. On the other hand, the upper limit of this content is preferably 90% by mass, and may be more preferably 70% by mass or 65% by mass. By setting the content of the organosilicon compound (B) to 10% by mass or more and 90% by mass or less, the thermosetting resin composition can be cured by optimizing the mixing ratio with other components. The light transmittance and gas barrier properties of the molded article to be obtained are further improved.

Further, regarding the content of each component in the thermosetting resin composition, the lower limit of the ratio of the number of moles of all vinyl in all components to the number of moles of all hydrosilyl in all components (vinyl/hydrosilyl) is as follows: 0.6 is preferred, 0.7 is more preferred, 0.8 is even more preferred, and 0.9 is even more preferred. Moreover, in some cases, this ratio is more preferably greater than one. On the other hand, the upper limit of this ratio is preferably 1.6, more preferably 1.4. When the molar ratio between the hydrosilyl group and the vinyl group is within the above range, the cross-linking reaction proceeds more effectively, and heat resistance and the like can be further enhanced.

<Component (C): Hydrosilylation catalyst (C)>
The hydrosilylation catalyst (C) is not particularly limited as long as it is a catalyst that causes a hydrosilylation reaction between the organosilicon compound (A) and the organosilicon compound (B). Examples of such catalysts include platinum catalysts such as chloroplatinic acid and Karstedt catalysts.

The lower limit of the content of the hydrosilylation catalyst (C) in the thermosetting resin composition is, for example, 0.1 ppm, preferably 0.5 ppm. Sufficient reaction can be caused by setting the content of the hydrosilylation catalyst (C) to 0.1 ppm or more. On the other hand, the upper limit of this content is, for example, 1,000 ppm, preferably 100 ppm, more preferably 10 ppm or 3 ppm. By setting the content of the catalyst (C) to 1,000 ppm or less, it is possible to improve the crack resistance, light transmittance, etc. of the resulting molded article.

<(D) Component: Adhesion Imparting Agent (D)>
The thermosetting resin composition preferably further contains an adhesion imparting agent (D). The adhesion-imparting agent (D) is preferably an organosilicon compound containing hydrosilyl and epoxy, more preferably containing alkoxysilyl. Such a compound can undergo a binding reaction with components such as a base material on which the thermosetting resin composition is laminated, while cross-linking with other components in the thermosetting resin composition. Adhesion of the molded article can be enhanced. Further, the adhesion-imparting agent (D) more preferably has a silsesquioxane structure from the viewpoint of heat resistance. As such a suitable adhesion-imparting agent (D), a compound represented by the formula (7) can be mentioned.

In formula (7), R ¹⁸ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, or cyclohexyl. Z is independently a group represented by formula (Z1), formula (Z2), formula (Z31), formula (Z32), formula (Z33), or formula (Z41). The average number of groups represented by formula (Z1) per molecule represented by formula (7) is z ₁ , the average number of groups represented by formula (Z2) is z ₂ , formula (Z31), When the average number of groups represented by formula (Z32) or (Z33) is z ₃ and the average number of groups represented by formula (Z41) is z ₄ , z ₁ +2z ₂ +z ₃ +z ₄ = 4w, 0.5w≦z ₁ ≦3w, 0.5w≦2z ₂ ≦2w, 0.1w≦z ₃ ≦2w, and 0≦z ₄ ≦w. w is an average value satisfying 1-100.

R ¹⁸ is preferably alkyl, more preferably methyl. z ₁ , z ₂ , z ₃ , and z ₄ are w≦z ₁ ≦2w, 0.3w≦z ₂ ≦w, 0.3w≦z ₃ ≦w, and 0.3w≦z ₄ ≦w, respectively is preferably The lower limit of w may be 3 or 5. Also, the upper limit of w may be 30 or 15.

In Formula (Z1), Formula (Z2), Formula (Z31), Formula (Z32), Formula (Z33), and Formula (Z41), * indicates a binding site.

In formula (Z2), R ¹⁹ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. i is an average value satisfying 1-20. R ¹⁹ is preferably alkyl, more preferably methyl.

In formula (Z41), R ²⁰ is independently methyl, ethyl, butyl, or isopropyl. Methyl is preferred as R ²⁰ .

The lower limit of the content of the adhesion imparting agent (D) in the thermosetting resin composition is preferably 0.1% by mass, more preferably 1% by mass. Sufficient adhesion can be imparted by setting the content of the adhesion imparting agent (D) to 0.1% by mass or more. On the other hand, the upper limit of this content is preferably 10% by mass, more preferably 3% by mass. By setting the content of the adhesion-imparting agent (D) to 10% by mass or less, the mixing ratio with other components and the cross-linking density of the resulting molded product are optimized, resulting in a molding obtained by curing. Crack resistance is further improved in a high temperature environment of the body. Further, the adhesion imparting agent (D) may be an organosilicon compound.

<(E) Component: Phosphor (E)>
<(F) component: white pigment (F)>
The thermosetting resin composition preferably further contains a phosphor (E) or a white pigment (F). The phosphor (E) or white pigment (F) is usually dispersedly contained in the thermosetting resin composition. When the thermosetting resin composition further contains a phosphor (E) or a white pigment (F), the thermosetting resin composition can be used more preferably as a sealing material for optical semiconductor elements.

Examples of the phosphor (E) include inorganic phosphors such as YAG phosphors, TAG phosphors, and silicate phosphors, and organic phosphors such as allylsulfamide/melamine formaldehyde co-condensation dyes and perylene phosphors. can be mentioned.

Examples of the white pigment (F) include titanium oxide, alumina, barium titanate, magnesium oxide, antimony oxide, zirconium oxide, and inorganic hollow particles.

<Other ingredients>
The thermosetting resin composition may contain components other than the components (A) to (E) described above. Other components include fillers, flame retardants, ion adsorbents, antioxidants, curing retarders, curing inhibitors, ultraviolet absorbers, and the like.

The content of components other than components (A) to (F) can be appropriately set according to the application. On the other hand, there are cases where it is preferable that these other components are small. When the upper limit of the content of other components other than components (A) to (F) in the thermosetting resin composition is preferably 10% by mass, 1% by mass, 0.1% by mass or 0.01% by mass There is also On the other hand, the lower limit of the content of components other than components (A) to (F) may be, for example, 0.01% by mass, 0.1% by mass, or 1% by mass.

The thermosetting resin composition may or may not contain a solvent or other volatile components. However, since the organosilicon compound (A) is usually liquid, it can exhibit good fluidity without using a solvent. Moreover, by making the composition substantially free of volatile components such as solvents, it can be used more preferably as a sealing material for optical semiconductor elements. The upper limit of the content of the solvent or volatile component in the thermosetting resin composition is preferably 1% by mass, more preferably 0.1% by mass, and more preferably 0.01% by mass.

<Preparation method>
The method for preparing the thermosetting resin composition is not particularly limited. The method for preparing the thermosetting resin composition is, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll, a bead mill, etc., and heating at room temperature or 40 ° C. to 200 ° C. A method of mixing each component under temperature can be mentioned.

<Application>
The thermosetting resin composition can be suitably used as a sealing material for optical semiconductor elements, a sealing material for other semiconductor elements, an insulating film, a sealing material, a material for forming optical lenses, and other adhesives. . Among them, the molded article obtained by curing is excellent in light transmittance and gas barrier properties, so that it can be particularly suitably used as a sealing material for optical semiconductor elements.

<Molded body>
A molded article according to one embodiment of the present invention is a molded article obtained by curing the thermosetting resin composition. That is, the molded article is a cured product of the thermosetting resin composition. One embodiment of the present invention also includes a cured product of the thermosetting resin composition. Examples of the molded body include a sealing material for semiconductor elements such as optical semiconductor elements, an insulating film, a sealing material, an optical lens, and the like, and among these, the sealing material for optical semiconductor elements is preferable.

The molded article is obtained by curing the thermosetting resin composition described above by heating. The heating temperature at this time is, for example, 60 to 200.degree. C., preferably 80 to 160.degree. Also, the heating time can be, for example, 1 to 24 hours.

<Optical semiconductor device>
An optical semiconductor device according to one embodiment of the present invention includes an optical semiconductor element and a molded body that seals the optical semiconductor element.

The optical semiconductor element is not particularly limited. For example, when the optical semiconductor element is an LED, it may be formed by laminating a semiconductor material on a substrate. In this case, examples of semiconductor materials include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

The optical semiconductor device is obtained by encapsulating an optical semiconductor element with the thermosetting resin composition according to one embodiment of the present invention. This sealing method includes, for example, (1) a method in which the thermosetting resin composition is preliminarily injected into a mold frame, and a lead frame or the like to which an optical semiconductor element is fixed is immersed therein, followed by thermal curing; 2) A method of injecting the thermosetting resin composition into a mold into which the optical semiconductor element is inserted and thermally curing the composition. Examples of methods for injecting the thermosetting resin composition include injection using a dispenser, transfer molding, and injection molding. Furthermore, other sealing methods include, for example, dropping, printing, or applying the thermosetting resin composition onto the optical semiconductor element, followed by thermal curing.

Since the thermosetting resin composition according to one embodiment of the present invention is used as a sealing material in the optical semiconductor device, the sealing material is excellent in transparency and is resistant to exposure to sulfide gas or water vapor gas. It is an optical semiconductor device that does not cause an element failure, and does not cause cracks even in a hot and cold environment, and is excellent in reliability. (It also becomes an optical semiconductor device having an insulating film with excellent dielectric properties.) The optical semiconductor device can be used for various lighting devices, electronic bulletin boards, traffic signals, backlights for liquid crystal display devices, LED displays, and the like.

The present invention will be described in more detail based on examples. In addition, the present invention is not limited to the following examples. In the chemical formula, "Me" represents methyl, "Vi" represents vinyl, and "Ph" represents phenyl. Methods for analyzing the synthesized organosilicon compounds are shown below.

<Number average molecular weight and weight average molecular weight>
A high performance liquid chromatograph system CO-1565plus manufactured by JASCO Corporation was used, and 20 μL of a THF solution having a sample concentration of 1% by mass was used as an analysis sample and measured by the GPC method under the following conditions. The number average molecular weight and weight average molecular weight were obtained by converting to polystyrene.
Column: Shodex KF402HQ, Shodex KF402.5HQ [manufactured by Showa Denko KK]
Column temperature: 40°C
Detector: RI
Eluent: THF
Eluent flow rate: 0.3 mL per minute

<NMR (nuclear magnetic resonance spectrum)>
Using a 400 MHZ NMR spectrometer manufactured by JEOL Ltd., ¹ H-NMR and ¹³ C-NMR were measured by dissolving a measurement sample in heavy chloroform (manufactured by ACROS ORGANICS), and ²⁹ Si-NMR was measured. was measured by dissolving the measurement sample in tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). Further, the nuclear hydrogenation rate of the phenyl group in the synthesized organosilicon compound was calculated from the integral ratio of ¹ H-NMR or ²⁹ Si-NMR. Also, from the integration ratio of ¹ H-NMR or ²⁹ Si-NMR, the average polysiloxane chain length (n in formula (2-3)) introduced in the synthesized organosilicon compound derivative was determined.

<UV-Vis absorption spectrum>
Using a UV-Vis absorption spectrometer V-660 manufactured by JASCO Corporation, a THF solution with a sample concentration of 1 millimole % was prepared and measured by placing it in a quartz cell with an optical path length of 10 mm. The degree of nuclear hydrogenation of the phenyl group in the synthesized organosilicon compound was calculated by comparing the absorbance of the light absorption peak derived from phenyl.

<Viscosity>
Using a TV-22 cone plate type viscometer manufactured by Toki Sangyo Co., Ltd., the viscosity was measured at a constant temperature bath temperature of 25°C.

<MALDI-TOFMS>
Measurement was performed using a MALDI-TOFMS measuring device autoflex III manufactured by Bruker Daltonics in Refractor Positive mode (measurement range: m/z = 400 to 2000). A sample for measurement was prepared using DIT as a matrix and LiTFA as an ionizing agent at a molar ratio of matrix/ionizing agent/target sample=100/10/1.

[Synthesis Example 1]
<Synthesis of organosilicon compound (8-1)>
An organosilicon compound represented by formula (8-1) was synthesized by the method described in Japanese Patent No. 4379120.

[Synthesis Example 2]
<Synthesis of organosilicon compound (B4-1)>
18.0 g of hexamethylcyclotrisiloxane (D3) and 36.1 g of toluene were placed in a reaction vessel equipped with a thermometer and a reflux tube, and cooled to 10° C. or less while stirring. 6.4 g of dimethylchlorosilane (DMCS) and g of N,N-dimethylformamide (DEA) were added thereto and aged for 5 hours. After that, 20.0 g of organosilicon compound (8-1) and 40.0 g of toluene were added, 6.0 g of triethylamine (TEA) was added dropwise, and the mixture was aged overnight. Subsequently, 2.8 g of DMCS was added, and after further aging for 5 hours, the reaction liquid was washed with acetic acid water, sodium bicarbonate water and pure water, and low-boiling components were removed by an evaporator to obtain a white viscous liquid. The obtained liquid is judged to be an organosilicon compound (B4-1) from the analysis results.

(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): 7.66-7.22 (40H), 4.76-4.67 (2H), 0.38-0.34 (6H), 0 .20-0.00 (42H).
²⁹ Si-NMR (solvent: THF): δ (ppm): -3.9 (s, 0.4Si), -6.5 (s, 1.5Si), -19.5 to -20.8 (s , 4.5Si), −62.9 (s, 0.3Si), −64.6 (s, 1.5Si), −78.5 to −79.0 (m, 8.0Si).
Viscosity = 3150 mPa s
Number average molecular weight: Mn = 1435
Weight average molecular weight: Mw = 1525
n=3.5

[Synthesis Example 3]
<Synthesis of organosilicon compound (8-2)>
An organosilicon compound represented by formula (8-2) was synthesized by the method described in Japanese Patent No. 4379120.

[Synthesis Example 4]
<Organosilicon compound (B4-2)>
26.9 g of hexamethylcyclotrisiloxane (D3) and 53.9 g of toluene were placed in a reaction vessel equipped with a thermometer and a reflux tube, and cooled to 10° C. or lower while stirring. 9.5 g of dimethylchlorosilane (DMCS) and 8.1 g of N,N-diethylformamide (DEA) were added thereto and aged for 5 hours. After that, 15.0 g of organosilicon compound (8-2) and 60.0 g of toluene were added, and 10.6 g of triethylamine (TEA) was added dropwise, followed by aging overnight. Subsequently, 2.2 g of DMCS was added and aged for 2 hours, then the reaction liquid was washed with acetic acid water, sodium bicarbonate water and pure water, and low-boiling components were removed by an evaporator to obtain a white viscous liquid. The obtained liquid is determined to be an organosilicon compound (B4-2) from the analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): 7.67-7.05 (40H), 4.88-4.66 (4H), 0.15- -0.01 (74H).
²⁹ Si-NMR (solvent: THF): δ (ppm): -3.0 (s, 1.1Si), -7.0 (s, 1.9), -19.7 to -20.9 (m , 5.6 Si), −78.7 to −79.3 (m, 6.2 Si), −106.2 to −109.5 (m, 1.8 Si).
Viscosity = 663 mPa s
Number average molecular weight: Mn = 1670
Weight average molecular weight: Mw = 1951
n=3.1

[Synthesis Example 5]
<Synthesis of organosilicon compound (8-3)>
An organosilicon compound represented by formula (8-3) was synthesized by the method described in Japanese Patent No. 5704168.

[Synthesis Example 6] <Synthesis of organosilicon compound (B4-3)>
An organosilicon compound represented by formula (B4-3) was synthesized by the method described in JP-A-2012-031354.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): 8.02-7.17 (40H), 4.90-4.65 (4H), 4.6- -0.19 (74H).
²⁹ Si-NMR (solvent: THF): δ (ppm): -3.9 (s, 0.8Si), -7.0 (s, 3.5Si), -19.3 to -21.9 (m , 9.5 Si), −75.3 to −80.0 (m, 8.0 Si).
Viscosity = 1960 mPa s
Number average molecular weight: Mn = 1592
Weight average molecular weight: Mw = 1735
n=3.1

[Comparative Synthesis Example 1]
An attempt was made to synthesize an organosilicon compound represented by formula (9-1) by the method described in Japanese Patent No. 4379120 using cyclohexyltrimethoxysilane, sodium hydroxide and 2-propanol as raw materials. From the analysis results of the obtained compound by NMR, MALDI-TOFMS, etc., it is determined that the main component of the obtained compound is the organosilicon compound represented by formula (9-2).

(result of analysis)
¹ H-NMR (solvent: heavy THF): δ (ppm): 0.49-0.68 (m, 8.0H), 0.97-0.1.24 (m, 40.9H), 1. 45-1.87 (m, 41.4H), 5.55 (s, 1.4H), 5.82 (s, 1.5H), 6.42 (s, 0.7H)
²⁹ Si-NMR (solvent: heavy THF): δ (ppm): -61.9 (s, 2.3Si), -61.8 (s, 2.3Si), -61.6 (s, 2.2Si ), -61.5 (s, 0.3Si), -51.5 (s, 1.0Si)
MALDI-TOFMS: m/z = 997.4 ([(9-2) + Li] ⁺ )

In addition, reagents and the like used in synthesizing the following organosilicon compounds are shown below.

<Nuclear hydrogenation catalyst>
・Ru/C, B type (5% Ru) (containing water) (manufactured by NE Chemcat)

<Compound Represented by Formula (2-1)>
・ Octamethylcyclotetrasiloxane (D4: manufactured by Momentive Performance Materials)
(Compound where n is 4 in formula (2-1))

<Compound Represented by Formula (2-2)>
・ 1,3-divinyltetramethyldisiloxane (DVDS: manufactured by Shin-Etsu Chemical Co., Ltd.)
(Compound where m in formula (2-2) is 0)

<Acid catalyst>
・Trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Example 1]
<Synthesis of organosilicon compound (A1-1)>
A reactor equipped with a thermometer and a pressure gauge was charged with 37.8 g of organosilicon compound (8-1), 143.0 g of diethylene glycol dimethyl ether, and 3.8 g of Ru/C. After the inside of the reaction vessel was replaced with hydrogen, the temperature and pressure were raised to 120° C. and 3.0 MPaG, and aging was performed for 5 hours until hydrogen absorption stopped. Subsequently, after cooling and purging the inside of the reaction vessel with nitrogen, Ru/C was separated by filtration. After that, the solvent was distilled off with an evaporator, and the resulting solid was washed with acetone and dried under reduced pressure to obtain 30.5 g of a white solid. The obtained solid is determined to be the organosilicon compound (A1-1) based on the following analytical results.
(result of analysis)
¹ H-NMR (solvent: heavy chloroform): δ (ppm): 0.16 (s, 6.0H), 0.60-0.79 (m, 7.5H), 1.11-1.38 ( m, 48.8H), 1.61 to 1.89 (m, 38.4H), 2.33 (s, 1.7H)
¹³ C-NMR (solvent: heavy chloroform): δ (ppm): -4.2 (s), 22.5 to 24.5 (m), 26.5 to 28.0 (m)
²⁹ Si-NMR (solvent: THF): δ (ppm): -70.5 to -69.8 (m, 3.3Si), -68.7 to -68.1 (m, 3.5Si), - 56.2 to -55.6 (m, 2.0Si)
Nuclear hydrogenation rate: >99%
Number average molecular weight: Mn = 874
Weight average molecular weight: Mw = 884

[Example 2]
<Synthesis of organosilicon compound (A1-2)>
A reactor equipped with a thermometer and a pressure gauge was charged with 15.3 g of organosilicon compound (8-1), 57.4 g of diethylene glycol dimethyl ether, and 1.5 g of Ru/C. After the inside of the reaction vessel was replaced with hydrogen, the temperature and pressure were raised to 120° C. and 2.0 MPaG, and aging was performed for 4 hours. Subsequently, after cooling and purging the inside of the reaction vessel with nitrogen, Ru/C was separated by filtration. After that, the solvent was distilled off with an evaporator, and the resulting solid was washed with acetone and dried under reduced pressure to obtain 12.3 g of a white solid. The obtained solid is judged to be an organosilicon compound (A1-2) from the analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy chloroform): δ (ppm): 0.14-0.41 (m, 6.0H), 0.48-0.86 (m, 4.6H), 0.86- 1.47 (m, 23.1H), 1.47-1.92 (m, 24.8H), 2.19-2.84 (m, 1.3H), 6.06-6.44 (m , 0.3H), 6.98 to 7.80 (m, 15.5H)
¹³ C-NMR (solvent: heavy chloroform): δ (ppm): -3.89 (s), 23.1-24.5 (m), 25.9-28.0 (m), 127.3- 128.3 (m), 129.8-130.8 (m), 133.7-134.5 (m)
²⁹ Si-NMR (solvent: THF): δ (ppm): -80.8 to -77.0 (m, 3.0Si), -71.3 to -65.8 (m, 4.3Si), - 56.8 to -54.4 (m, 2.0Si)
Nuclear hydrogenation rate: 74%
Number average molecular weight: Mn = 884
Weight average molecular weight: Mw = 896

[Example 3]
<Synthesis of organosilicon compound (A1-3)>
A reactor equipped with a thermometer and a pressure gauge was charged with 37.8 g of organosilicon compound (8-1), 143.1 g of diethylene glycol dimethyl ether, and 3.8 g of Ru/C. After the inside of the reaction vessel was replaced with hydrogen, the temperature and pressure were raised to 120° C. and 2.5 MPaG, and aging was performed for 2 hours. Subsequently, after cooling and purging the inside of the reaction vessel with nitrogen, Ru/C was separated by filtration. After that, the solvent was distilled off with an evaporator, and the resulting solid was washed with acetone and dried under reduced pressure to obtain 24.0 g of a white solid. The obtained solid is determined to be an organosilicon compound (A1-3) from the analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy chloroform): δ (ppm): 0.15-0.39 (m, 6.0H), 0.51-0.87 (m, 2.7H), 0.87- 1.46 (m, 13.6H), 1.46-2.15 (m, 16.9H), 2.32-2.74 (m, 1.7H), 7.00-7.78 (m , 15.5H)
¹³ C-NMR (solvent: heavy chloroform): δ (ppm): -3.79 (s), 23.1-24.5 (m), 25.7-28.0 (m), 127.4- 128.1 (m), 130.0-130.8 (m), 133.7-134.4 (m)
²⁹ Si-NMR (solvent: THF): δ (ppm): -79.3 to -75.1 (m, 4.8Si), -69.5 to -64.9 (m, 3.0Si), - 55.4 to -52.8 (m, 2.0Si)
Nuclear hydrogenation rate: 34%
Number average molecular weight: Mn = 885
Weight average molecular weight: Mw = 899

[Example 4]
<Synthesis of organosilicon compound (A1-4)>
A reactor equipped with a thermometer and a pressure gauge was charged with 9.8 g of organosilicon compound (B4-1), 77.5 g of diethylene glycol dimethyl ether, and 2.0 g of Ru/C. After the inside of the reaction vessel was replaced with hydrogen, the temperature and pressure were raised to 150° C. and 5.0 MPaG, and aging was performed for 7.5 hours until hydrogen absorption stopped. Subsequently, after cooling and purging the inside of the reaction vessel with nitrogen, Ru/C was separated by filtration. After that, the solvent was distilled off with an evaporator, and the resulting solid was washed with heptane and dried under reduced pressure to obtain 8.2 g of a white solid. The obtained solid is determined to be an organosilicon compound (A1-4) from the analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy chloroform): δ (ppm): -0.15 to 0.28 (m, 35.9H), 0.54 to 0.77 (m, 8.0H), 0.98 ~1.37 (m, 47.3H), 1.61 ~ 1.90 (m, 40.0H), 6.92 ~ 7.08 (m, 0.4H), 7.18 ~ 7.31 ( m), 7.32 to 7.49 (m, 0.5H)
²⁹ Si-NMR (solvent: THF): δ (ppm): -78.4 (s, 0.2Si), -70.1 (s, 4.2Si), -68.5 (s, 4.2Si) , −65.0 (s, 2.0Si), −56.1 (s, 0.2Si), −46.8 (s, 0.3Si), −21.3 to −18.9 (m, 5 .6Si), −14.0 to −11.9 (m, 1.7Si)
Nuclear hydrogenation rate: >99%

[Example 5]
<Synthesis of organosilicon compound (A3-1)>
A reactor equipped with a thermometer and a pressure gauge was charged with 20.0 g of organosilicon compound (B4-3), 77.8 g of diethylene glycol dimethyl ether, and 5.6 g of Ru/C. After the inside of the reaction vessel was replaced with hydrogen, the temperature and pressure were raised to 150° C. and 5.0 MPaG, and aging was performed for 10 hours. Subsequently, after cooling and purging the inside of the reaction vessel with nitrogen, Ru/C was separated by filtration. After adding cyclopentyl methyl ether (CPME) to the filtrate and washing with hydrochloric acid and pure water, the solvent was distilled off with an evaporator and dried under reduced pressure to obtain 11.0 g of a brown solid. The obtained solid is determined to be an organosilicon compound (A3-1) from the analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy chloroform): δ (ppm): -0.33 to 0.40 (m, 119H), 0.64 to 0.90 (m, 8.0H), 0.9 to 1 .99 (m), 4.92-5.30 (m, 3.6H), 6.82-7.90 (m, 18.9H)
²⁹ Si-NMR (solvent: THF): δ (ppm): -91 to -88 (m, 1.6Si), -82 to -74 (m, 5.0Si), -73 to -62 (m, 14 .5Si), −46.7 (s, 0.2Si), −25 to −17 (m, 24.2Si), −15 to −12 (m, 4.0Si)
Nuclear hydrogenation rate: 68%

[Example 6]
<Synthesis of organosilicon compound derivative (A4-1)>
Organosilicon compound (A1-1) 25.1 g, octamethylcyclotetrasiloxane (D4) 25.4 g, 1,3-divinyltetramethyldisiloxane (DVDS) 6.4 g were placed in a reaction vessel equipped with a thermometer and a reflux tube. , 57.5 g of toluene and 0.4 g of trifluoromethanesulfonic acid were charged and aged at a set temperature of 120° C. for 5 hours. After cooling, the reaction liquid was washed with aqueous sodium bicarbonate and pure water, and low-boiling components were removed from the organic layer by an evaporator to obtain 29.6 g of a colorless viscous liquid. The obtained liquid is determined to be the organosilicon compound derivative (A4-1) from the analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy chloroform): δ (ppm): -0.16 to 0.30 (m, 165.1H), 0.57 to 0.80 (m, 14.2H), 0.97 ~1.39 (m, 72.3H), 1.62 ~ 1.95 (m, 71.3H), 5.68 ~ 6.19 (m, 6.0H)
¹³ C-NMR (solvent: heavy chloroform): δ (ppm): -2.9 (s), 0.32 (s), 0.7 to 1.6 (m), 24.3 (d), 26 .9(d), 27.7(d), 131.7(s), 139.4(s)
²⁹ Si-NMR (solvent: THF): δ (ppm): -69.3 (s, 4.4Si), -67.8 (s, 4.3Si), -64.3 (s, 2.0Si) , -21.0 to -17.5 (m, 16.7 Si), -1.9 (s, 1.2 Si)
Viscosity = 14.5 Pa s
Number average molecular weight: Mn = 3780
Weight average molecular weight: Mw = 6460
n=12.0
m=2.5

[Comparative Synthesis Example 2]
<Synthesis of organosilicon compound derivative (a-2)>
An organosilicon compound derivative represented by formula (a-2) was synthesized by the method described in JP-A-2020-090593.
(result of analysis)
¹ H-NMR (solvent: heavy chloroform): δ (ppm): -0.15 to 0.42 (m, 187.0H), 5.60 to 6.19 (m, 6.0H), 6.95 ~7.72 (m, 89.9H)
²⁹ Si-NMR (solvent: THF): δ (ppm): -78.1 to -76.9 (m, 9.0Si), -63.4 (s, 2.0Si), -21.3 to - 17.5 (m, 13.2Si), -2.4 (s, 1.3Si)
Viscosity = 11.6 Pa s
Number average molecular weight: Mn = 3960
Weight average molecular weight: Mw = 6760
n=9.5
m=3.2

Components other than the synthesized organosilicon compound ((A) organosilicon compound) used in the preparation of the following thermosetting resin composition are shown below.

<(B) Organosilicon compound>

（式（４）におけるＲ^３が水素、ｙが１０であるジメチルシロキサンポリマー） - B2-1: an organosilicon compound represented by the formula (B2-1) (product name "FM-1111": manufactured by JNC Corporation)

(Dimethylsiloxane polymer in which R ³ in formula (4) is hydrogen and y is 10)

（式（４）におけるＲ^３がビニル、ｙが７であるジメチルシロキサンポリマー） · B2-3: a compound represented by the formula (B2-3) (product name "FM-2205": manufactured by JNC Co., Ltd.)

(Dimethylsiloxane polymer in which R ³ in formula (4) is vinyl and y is 7)

・ B3-1: Tetrakis (dimethylsilyloxy) silane (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Hydroxylation catalyst (C)>
・ C-1: Karstedt catalyst (product name “Pt-VTS-3.0X”: 3 wt% xylene solution, manufactured by Umicore)

<Other ingredients>
- Curing retarder: 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (MVS-H: manufactured by GELEST)
・ Curing inhibitor: 1-ethynylcyclohexanol (ECYH-OH: manufactured by Tokyo Kasei Co., Ltd.)

[Examples 7-8, Comparative Examples 1-2]
<Evaluation of properties of composition and cured product>
A resin composition was prepared according to the formulation shown in the table, and a cured product was obtained by heating the composition at 150° C. for 2 hours by the following method.
4 mm-thick hardened material: Naflon SP packing (manufactured by NICHIAS Corporation) having a diameter of 4 mm was sandwiched between two sheets of glass as a spacer, and the resin composition was poured into this. Then, the cured product was cured by heating, and the glass was peeled off to obtain a cured product with a thickness of 4 mm and a smooth surface.
1 mm thick cured product: A 1 mm thick SUS plate was sandwiched between two glass sheets as a spacer, and the resin composition was poured into this. Then, it was cured by heating, and the glass was peeled off to obtain a cured product with a thickness of 1 mm and a smooth surface.
The properties of the obtained compositions and cured products were evaluated by the following methods.

<Viscosity>
The viscosity (25° C.) of the composition liquid was measured with an E-type rotational viscometer (TV-25: manufactured by Toki Sangyo Co., Ltd.).

<Light transmittance>
A 4 mm thick cured product was measured for light transmittance at a wavelength of 400 nm using a UV-visible spectrophotometer (V-650: manufactured by JASCO Corporation).

<Hardness>
A cured product having a thickness of 4 mm was measured using an automatic hardness tester (GX-610II: manufactured by Teclock Co., Ltd.) according to JIS K6301 (type A).

<Optical refractive index>
A plate-shaped test piece with a thickness of 30 mm × 10 mm × 4 mm is prepared, and an Abbe refractometer (NAR-2T: manufactured by Atago Co., Ltd.) uses the D line of a sodium lamp to measure the optical refractive index at one point of the test piece. was measured. 1-bromonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the intermediate solution.

<DMA>
A plate-shaped test piece with a thickness of 30 mm × 10 mm × 1.0 mm was prepared, and the storage elastic modulus (
E′) and the loss modulus (E″), and the temperature at the maximum point of the loss coefficient (tan δ=E″/E′) was determined.
Measurement temperature: -100°C to 250°C (heating rate: 10°C/min)
Measurement frequency: 10Hz

<Water vapor transmission rate>
A test piece of 70 mmΦ×1 mm thickness was prepared and measured based on the cup method according to JIS Z-0208 (1976) using the following equipment and test conditions.
Apparatus: Small environmental tester (SH-242: manufactured by Espec Co., Ltd.)
Test conditions: 40°C, 90% RH

<Adhesion>
A cured product (about 0.1 mm thick) of methyl silicone (OE-7340: manufactured by Dow Corning) is prepared on a glass plate, and a composition (about 0.1 mm thick) is prepared on this cured product to form a laminate. got This laminate was evaluated for adhesion to the lower layer based on the cross-cut method according to JIS K5600-5-6. Cutting interval: 2mm
Number of cuts: 10 × 10 Judgment: ○: Peeling area ≤ 30%
×: 30% < peeling area

<Dielectric constant>
A cured product having a thickness of about 30 μm was prepared on a chromium substrate cut to 9 cm×7 cm, and aluminum was vapor-deposited on the film using a vacuum vapor deposition apparatus (VE-2030: Vacuum Device Co., Ltd.) to form an electrode. The dielectric constant and dielectric loss tangent were measured using an LCR meter (E4980A Precision: manufactured by Agilent Technologies, Inc.).

<Thermal shock>
A plate-shaped test piece of 20 mm length × 3 mm width × 1.0 mm thickness was prepared, and a thermomechanical analyzer (TMA / SS7100: manufactured by Hitachi High-Tech Science Co., Ltd.) was used in length control mode from 30 ° C. to -80 ° C. C. (cooling rate: 10.degree. C./min) to measure the stress.

Table 1. Composition of resin composition and property evaluation result 1 of cured product

As shown in Table 1, Example b has excellent light transmittance at a wavelength of 400 nm, whereas Comparative Example b, which is a composition that does not contain component (A), has poor light transmittance at a wavelength of 400 nm. rice field.

Table 2. Composition of resin composition and property evaluation result 2 of cured product

As shown in Table 2, Example c has excellent water vapor barrier properties and excellent adhesion to the methyl silicone resin, whereas Comparative Example c, which is a composition that does not contain component (A), has water vapor barrier properties and excellent adhesion to the methyl silicone resin. Adhesion to methyl silicone resin was poor.

Table 3. Composition of resin composition and property evaluation result 3 of cured product

As shown in Table 3, Examples d and e are excellent in low dielectric properties and thermal stress during quenching, while Comparative Examples d and e, which are compositions that do not contain component (A), are low. Poor dielectric properties and thermal stress during quenching.

From the above, it has been clarified that the organosilicon compound of the present invention and the thermosetting resin composition containing the same provide cured products having excellent light transmittance, gas barrier properties, low dielectric properties, and thermal shock resistance. rice field.

The organosilicon compound of the present invention and the thermosetting resin composition containing the same can be used as sealing materials for optical semiconductor elements, sealing materials for other semiconductor elements, insulating films, sealing materials, optical lenses, and the like.

Claims (15)

Organosilicon compound (A1) represented by formula (1-1), organosilicon compound (A2) represented by formula (1-2), and organosilicon compound (A3) represented by formula (1-3) ).

In formula (1-1), formula (1-2), and formula (1-3), R ⁰ is independently phenyl or a six-membered ring group obtained by hydrogenating phenyl, and R ¹ , R ² and R ³ are independently hydrogen or hydroxy, and n satisfies 0≦n≦10 as the average value of the compound. 2. The organosilicon compound according to claim 1, wherein ^R0 is selected from a group such that the compound has a hydrogenation rate of 30% or more by nuclear hydrogenation with respect to phenyl. Equilibrium polymerization of the organosilicon compound (A1) according to claim 1 or 2 and a compound selected from compounds represented by formulas (2-1) and (2-2) in the presence of an acid catalyst Organosilicon compound (A4) obtained by.

In formula (2-1), n is an integer satisfying 3≦n≦8.
In formula (2-2), m is an average value that satisfies 0≦m≦50, and Vi represents vinyl. 3. Among the organosilicon compound (A1), the organosilicon compound (A2), or the organosilicon compound (A3) according to claim 1 or 2, an organosilicon compound in which R ¹ , R ² , and R ³ are hydrogen, or Organosilicon compound (A) consisting of one or a mixture of two or more of the organosilicon compounds (A4) according to claim 3
An organosilicon compound (B) having a plurality of crosslinkable groups in the molecule other than the organosilicon compound (A), and a hydrosilylation catalyst (C)
contains
A thermosetting resin composition in which the organosilicon compound (B) contains a compound that can be crosslinked with the organosilicon compound (A). 5. The thermosetting resin composition according to claim 4, wherein the organosilicon compound (B) contains a compound represented by formula (3).

In formula (3), R ³ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, or cyclohexyl, and X is independently formula (X1), formula (X2), or formula (X3). It is a group represented.
x ₁ is the average number of groups represented by formula (X1) per molecule represented by formula (3), x ₂ is the average number of groups represented by formula (X2), and formula (X3) When the average number of represented groups is x ₃ , x ₁ + 2x ₂ + x ₃ = 4r, 0 < x ₁ < 4r, 0 ≤ x ₂ < 2r, and 0 < x ₃ < 4r, where r is It is an average value that satisfies 1 to 100.

In Formula (X1), Formula (X2), and Formula (X3), * indicates a binding site.
In formula (X2), R ⁴ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. s is an average value that satisfies 2-20.
In formula (X3), R ⁵ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl. R ⁶ is alkenyl having 2 to 5 carbon atoms. R ⁷ is an alkanediyl having the same carbon number as R ⁶ and t is an average value satisfying 2-20. 5. The thermosetting resin composition according to claim 4, wherein the organosilicon compound (B) contains a compound represented by formula (4).

y in formula (4) is an average value that satisfies ^0≤y≤50 , and R3 is vinyl or hydrogen. 5. The thermosetting resin composition according to claim 4, wherein the organosilicon compound (B) contains a compound having 3 or more SiH groups. 5. The thermosetting resin composition according to claim 4, wherein the organosilicon compound (B) contains a compound represented by formula (6-1), formula (6-2), or formula (6-3).

In formulas (6-1), (6-2), and (6-3), n satisfies 1≦n≦10 as the average value of the compounds. The thermosetting resin composition according to any one of claims 4 to 8, wherein the content of the organosilicon compound (B) is 30% by mass or more. 9. The thermosetting according to any one of claims 4 to 8, wherein the organosilicon compound (A) accounts for 30% by mass or more with respect to the total 100% by mass of the organosilicon compound (A) and the organosilicon compound (B). elastic resin composition. Further containing an adhesion imparting agent (D),
The thermosetting resin composition according to any one of claims 4 to 10, wherein the adhesion imparting agent (D) contains a compound represented by formula (7).

In formula (7), R ¹⁸ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, or cyclohexyl, and Z is independently formula (Z1), formula (Z2), formula (Z31), formula (Z32), a group represented by formula (Z33), or formula (Z41).
The average number of groups represented by formula (Z1) per molecule represented by formula (7) is z ₁ , the average number of groups represented by formula (Z2) is z ₂ , formula (Z31), When the average number of groups represented by formula (Z32) or (Z33) is z ₃ and the average number of groups represented by formula (Z41) is z ₄ , z ₁ +2z ₂ +z ₃ +z ₄ = 4w, 0.5w ≤ z ₁ ≤ 3w, 0.5w ≤ 2z ₂ ≤ 2w, 0.1w ≤ z ₃ ≤ 2w, and 0 ≤ z ₄ ≤ w, where w is an average value satisfying 1 to 100 be.

In Formula (Z1), Formula (Z2), Formula (Z31), Formula (Z32), Formula (Z33), and Formula (Z41), * indicates a binding site.
In formula (Z2), R ¹⁹ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl, and i is an average value satisfying 1 to 20.
In formula (Z41), R ²⁰ is independently methyl, ethyl, butyl, or isopropyl. 12. The thermosetting resin composition according to claim 11, wherein the content of the adhesion imparting agent (D) is 0.1% by mass or more and 5% by mass or less. 13. The thermosetting resin composition according to any one of claims 4 to 12, further comprising a phosphor (E) or a white pigment (F). A molded article obtained by curing the thermosetting resin composition according to any one of claims 4 to 13. An optical semiconductor device comprising the molded article according to claim 14 and an optical semiconductor element encapsulated by the molded article.