JP7423892B2 - Organosilicon compound, method for producing organosilicon compound, thermosetting resin composition, molded article, and optical semiconductor device - Google Patents

Description

The present invention relates to an organosilicon compound, a method for producing an organosilicon compound, a thermosetting resin composition, a molded article, and an optical semiconductor device.

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 for 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. In recent years, in the optical semiconductor industry, demands such as higher output and smaller and thinner packages have progressed, and the heat density per unit volume has tended to increase. For this reason, sealing materials for optical semiconductor devices are particularly required to have heat resistance in addition to light transmittance and light refraction properties.

Silicone resin is widely used as one of the sealing materials for optical semiconductor devices. Patent Document 1 proposes a crosslinkable silicon compound having a double-decker silsesquioxane structure and a crosslinkable functional group. Double-decker type silsesquioxane is said to have high heat resistance because it has a controlled structure. Patent Document 1 also describes that the silicone film obtained using the crosslinkable silicon compound has excellent heat resistance. Specifically, in Patent Document 1, it is evaluated in Examples that the obtained silicone film (crosslinked film) does not easily lose mass due to thermal decomposition even under heating and has excellent thermal stability.

Japanese Patent Application Publication No. 2010-116464

Regarding heat resistance, a sealing material for an optical semiconductor element is required to be resistant to cracking even at high temperatures, in addition to being resistant to thermal decomposition. When the crosslinkable compound of Patent Document 1 is used, the crosslinks become too dense, reducing the stress relaxation ability. Cracks are likely to occur in high-temperature environments.

The present invention has been made based on the above-mentioned circumstances, and its purpose is to provide an organosilicon compound and a thermosetting resin composition capable of obtaining a molded article that does not easily crack even in a high-temperature environment, and a thermosetting resin composition thereof. An object of the present invention is to provide a molded article and an optical semiconductor device obtained using such a thermosetting resin composition.

（式（ｉ）中、Ｒ^１は、それぞれ独立して、炭素数１～８の炭化水素基である。
式（ｉｉ）中、Ｒ^２は、それぞれ独立して、炭素数１～８の炭化水素基である。） The invention made to solve the above problem includes a structural unit (i) represented by the following formula (i) and a structural unit (ii) represented by the following formula (ii), and both ends of the molecular chain. is an organosilicon compound in which a vinyl group or a hydrosilyl group is present, respectively, the weight average molecular weight is 1,000 or more and 20,000 or less, the degree of polymerization of the structural unit (i) is 1 or more and 5 or less, and the structural unit (ii) is ) is an organosilicon compound (α) having a degree of polymerization of 4 or more and 200 or less.

(In formula (i), each R ¹ is independently a hydrocarbon group having 1 to 8 carbon atoms.
In formula (ii), R ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. )

（式（１）中、Ｒ^０は、それぞれ独立して、ビニル基又は水素原子である。Ｒ^１は、それぞれ独立して、炭素数１～８の炭化水素基である。Ｒ^２は、それぞれ独立して、炭素数１～８の炭化水素基である。ｍは、１～５を満たす平均値である。ｎは、２～５０を満たす平均値である。） Another invention made to solve the above problem is an organosilicon compound (β) represented by the following formula (1).

(In formula (1), R ⁰ is each independently a vinyl group or a hydrogen atom. R ¹ is each independently a hydrocarbon group having 1 to 8 carbon atoms. R ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. (Independently, they are hydrocarbon groups having 1 to 8 carbon atoms. m is an average value satisfying 1 to 5. n is an average value satisfying 2 to 50.)

In the organosilicon compound (α) and the organosilicon compound (β), R ² is preferably an alkyl group.

（式（２－１）中、Ｒ^１は、それぞれ独立して、炭素数１～８の炭化水素基である。
式（２－２）中、Ｒ_ａ ^２は、それぞれ独立して、炭素数１～８の炭化水素基である。ｐは、３～８の整数である。
式（２－３）中、Ｒ^０は、それぞれ独立して、ビニル基又は水素原子である。Ｒ_ｂ ^２は、それぞれ独立して、炭素数１～８の炭化水素基である。ｑは、０～５０を満たす平均値である。） Yet another invention made to solve the above problems includes a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3). This is a method for producing the organosilicon compound (α) or the organosilicon compound (β), which comprises a step of equilibrium polymerizing the compound represented by the following in the presence of an acid catalyst.

(In formula (2-1), each R ¹ is independently a hydrocarbon group having 1 to 8 carbon atoms.
In formula (2-2), each R _a ² is independently a hydrocarbon group having 1 to 8 carbon atoms. p is an integer from 3 to 8.
In formula (2-3), R ⁰ is each independently a vinyl group or a hydrogen atom. Each R _b ² is independently a hydrocarbon group having 1 to 8 carbon atoms. q is an average value satisfying 0 to 50. )

Yet another invention made to solve the above problem is (A) the organosilicon compound (α) or the organosilicon compound (β), (B) the organosilicon compound (α) and the organosilicon compound (β). A thermosetting resin containing an organosilicon compound having a plurality of crosslinkable groups other than the above, and (C) a catalyst, wherein the organosilicon compound (B) contains at least a compound crosslinkable with the organosilicon compound (A). It is a composition.

In the thermosetting resin composition, the content of the organosilicon compound (A) is preferably 1% by mass or more and 90% by mass or less.

（式（３）中、Ｒ^３は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基又はシクロヘキシル基である。Ｘは、それぞれ独立して、下記式（Ｘ１）、式（Ｘ２）又は式（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。）

（式（Ｘ１）、（Ｘ２）及び（Ｘ３）中、＊は、結合部位を示す。
式（Ｘ２）中、Ｒ^４は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基、シクロヘキシル基又はフェニル基である。ｓは、２～２０を満たす平均値である。
式（Ｘ３）中、Ｒ^５は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基、シクロヘキシル基又はフェニル基である。Ｒ^６は、炭素数２～５のアルケニル基である。Ｒ^７は、Ｒ^６と同じ炭素数のアルカンジイル基である。ｔは、２～２０を満たす平均値である。） It is preferable that the organosilicon compound (B) above includes a compound represented by the following formula (3).

(In formula (3), R ³ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. ) or a group represented by formula (X3).The average number of groups represented by formula (X1) per molecule of the compound represented by formula (3) is x ₁ , and the group represented by formula (X2) is When the average number of groups represented by formula (X3) is x ₂ and the average number of groups represented by formula (X3) is x ₃ , x ₁ +2x ₂ +x ₃ =4r, 0< _x1 <4r, 0≦ _x2 <2r , and 0<x ₃ <4r. r is an average value satisfying 1 to 100.)

(In formulas (X1), (X2) and (X3), * indicates a binding site.
In formula (X2), R ⁴ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group. s is an average value satisfying 2 to 20.
In formula (X3), R ⁵ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group. R ⁶ is an alkenyl group having 2 to 5 carbon atoms. R ⁷ is an alkanediyl group having the same number of carbon atoms as R ⁶ . t is an average value satisfying 2 to 20. )

（式（４）中、Ｒ^８及びＲ^９は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基、シクロヘキシル基又は炭素数６～１２の芳香族炭化水素基である。ｕは、１～５０を満たす平均値である。） It is preferable that the organosilicon compound (B) above includes a compound represented by the following formula (4).

(In formula (4), R ⁸ and R ⁹ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. u is , is an average value that satisfies 1 to 50.)

（式（５）中、Ｒ^１０及びＲ^１１は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基、シクロヘキシル基又は炭素数６～１２の芳香族炭化水素基である。Ｒ^１２は、炭素数２～５のアルケニル基である。Ｒ^１３は、炭素数２～５のアルケニル基又は水素原子である。ｖは、１～５０を満たす平均値である。） It is preferable that the organosilicon compound (B) above includes a compound represented by the following formula (5).

(In formula (5), R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ¹² is an alkenyl group having 2 to 5 carbon atoms. R ¹³ is an alkenyl group having 2 to 5 carbon atoms or a hydrogen atom. v is an average value satisfying 1 to 50.)

（式（６）中、Ｒ^１４及びＲ^１５は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基、シクロヘキシル基又は炭素数６～１２の芳香族炭化水素基である。Ｒ^１６は、それぞれ独立して、炭素数２～５のアルケニル基である。Ｒ^１７は、炭素数２～５のアルカンジイル基である。ｊは、１～５を満たす平均値である。ｋは、１～５０を満たす平均値である。） It is preferable that the organosilicon compound (B) above includes a compound represented by the following formula (6).

(In formula (6), R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ¹⁶ are each independently an alkenyl group having 2 to 5 carbon atoms. R ¹⁷ is an alkanediyl group having 2 to 5 carbon atoms. j is an average value satisfying 1 to 5. k is (This is an average value satisfying 1 to 50.)

（式（７）中、Ｒ^１８は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基又はシクロヘキシル基である。Ｚは、それぞれ独立して、下記式（Ｚ１）、式（Ｚ２）、式（Ｚ３１）、式（Ｚ３２）、式（Ｚ３３）又は式（Ｚ４１）で表される基である。式（６）で表される化合物１分子あたりの式（Ｚ１）で表される基の平均数をｚ_１、式（Ｚ２）で表される基の平均数をｚ_２、式（Ｚ３１）、式（Ｚ３２）又は式（Ｚ３３）で表される基の平均数をｚ_３、式（Ｚ４１）で表される基の平均数をｚ_４としたとき、ｚ_１＋２ｚ_２＋ｚ_３＋ｚ_４＝４ｗ、０．５ｗ≦ｚ_１≦３ｗ、０．５ｗ≦２ｚ_２≦２ｗ、０．１ｗ≦ｚ_３≦２ｗ、かつ０≦ｚ_４≦ｗを満たす。ｗは、１～１００を満たす平均値である。）

（式（Ｚ１）、（Ｚ２）、（Ｚ３１）、（Ｚ３２）、（Ｚ３３）及び（Ｚ４１）中、＊は、結合部位を示す。
式（Ｚ２）中、Ｒ^１９は、それぞれ独立して、炭素数１～４のアルキル基、シクロペンチル基、シクロヘキシル基又はフェニル基である。ｉは、１～２０を満たす平均値である。
式（Ｚ４１）中、Ｒ^２０は、それぞれ独立して、メチル基、エチル基、ブチル基又イソプロピル基である。） The thermosetting resin composition further contains (D) an adhesion-imparting agent, and it is preferable that the adhesion-imparting agent (D) includes a compound represented by the following formula (7).

(In formula (7), R ¹⁸ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. Z is each independently the following formula (Z1), formula (Z2 ), a group represented by formula (Z31), formula (Z32), formula (Z33), or formula (Z41).Represented by formula (Z1) per molecule of the compound represented by formula (6) The average number of groups is z ₁ , the average number of groups represented by formula (Z2) is z ₂ , the average number of groups represented by formula (Z31), formula (Z32) or formula (Z33) is z ₃ , When 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 to 100.)

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

It is preferable that the thermosetting resin composition further contains (E) a phosphor or a white pigment.

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

Yet another invention made to solve the above problem is an optical semiconductor device including an optical semiconductor element and the molded body that seals the optical semiconductor element.

According to the present invention, there is provided an organosilicon compound and a thermosetting resin composition capable of obtaining a molded product that is difficult to crack even in a high-temperature environment, and a molded product obtained using such a thermosetting resin composition. An optical semiconductor device can be provided.

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

<Organosilicon compound (α)>
The organosilicon compound (α) according to one embodiment of the present invention includes a structural unit (i) and a structural unit (ii). Further, a vinyl group or a hydrosilyl group is present at both ends of the molecular chain of the organosilicon compound (α).

(Structural unit (i))
Structural unit (i) is represented by the following formula (i).

In formula (i), each R ¹ independently represents a hydrocarbon group having 1 to 8 carbon atoms.

The hydrocarbon group represented by R ¹ includes an aliphatic chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the aliphatic chain hydrocarbon group include alkyl groups such as methyl, ethyl and propyl groups, alkenyl groups such as vinyl and propenyl groups, and alkynyl groups such as ethynyl and propynyl groups. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and a cyclohexenyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a tolyl group.

R ¹ is preferably an aliphatic chain hydrocarbon group or an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group. Among the aliphatic chain hydrocarbon groups, alkyl groups are more preferred, and methyl groups are even more preferred. Among aromatic hydrocarbon groups, phenyl group is more preferred.

The lower limit of the degree of polymerization of the structural unit (i) in the organosilicon compound (α), that is, the double-decker silsesquioxane structural unit, is 1, preferably 1.4, and sometimes more preferably 2. Moreover, the upper limit of this degree of polymerization is 5, and 4 or 3 is preferable in some cases. Note that the degree of polymerization refers to the average number of structural units contained in one molecule.

(Structural unit (ii))
Structural unit (ii) is represented by the following formula (ii).

In formula (ii), R ² is each independently a hydrocarbon group having 1 to 8 carbon atoms.

The hydrocarbon group represented by R ² is the same as that exemplified as the hydrocarbon group represented by R ¹ . The upper limit of the number of carbon atoms in R ² is preferably 5, more preferably 3. R ² is preferably an aliphatic chain hydrocarbon group, more preferably an alkyl group, and even more preferably a methyl group. When R ² is an alkyl group, the structural unit (ii) does not contain a crosslinkable group, and the crosslink density upon curing becomes appropriate. This increases the stress relaxation ability of the molded product obtained, thereby further increasing its crack resistance in high-temperature environments.

The lower limit of the degree of polymerization of the structural unit (ii) in the organosilicon compound (α), that is, the siloxane structural unit, is 4, preferably 8, more preferably 20, and even more preferably 40. Moreover, the upper limit of this degree of polymerization is 200, preferably 150, and more preferably 100.

In the organosilicon compound (α), it is preferable that a plurality of structural units (ii) form a linked polysiloxane chain. The organosilicon compound may have one or more polysiloxane chains in one molecule. The degree of polymerization of the structural unit (ii) in the polysiloxane chain is, for example, 2 or more and 50 or less. The lower limit of this degree of polymerization is preferably 3, more preferably 5, and even more preferably 9. On the other hand, the upper limit of this degree of polymerization is preferably 40, more preferably 30. That is, the polysiloxane chain is formed by, for example, an average of 2 or more and 50 or less structural units (ii).

The organosilicon compound (α) usually has a linear molecular chain structure. In the organosilicon compound (α), a vinyl group or a hydrosilyl group is present at both ends of the molecular chain. The hydrosilyl group refers to a group formed by bonding a silicon atom to a hydrogen atom (-Si-H). That is, the hydrosilyl group is not limited to a trihydrosilyl group (-SiH ₃ ), and one or two hydrogen atoms of the trihydrosilyl group are substituted with a substituent (for example, a hydrocarbon group such as an alkyl group). It also includes things. Examples of the hydrosilyl group include a group represented by -SiR ² ₂ H. The definition and preferred form of R ² in -SiR ² ₂ H are the same as R ² in formula (ii). Moreover, the hydrosilyl groups at both ends of the molecular chain may overlap with a part of the structural unit (i) and the structural unit (ii).

The arrangement of structural units such as structural unit (i) and structural unit (ii) in the organosilicon compound (α) is not particularly limited. Further, the orientations of the structural unit (i) and the structural unit (ii) are not limited either. The organosilicon compound (α) has hydrogen atoms, vinyl groups, or - at both ends of the polymer chain formed from one or more structural units (i) and one or more structural units (ii). It may be a structure formed by bonding groups represented by SiR ⁰ R ² ₂ . -SiR ⁰ R ⁰ in R ² ₂ is a hydrogen atom or a vinyl group, and the definition and preferred form of R ² are the same as R ² in formula (ii). When the terminal atom of the polymer chain composed of structural unit (i) and structural unit (ii) is a silicon atom, a hydrogen atom or a vinyl group is usually bonded to the terminal silicon atom. When a hydrogen atom is bonded to a silicon atom, a hydrosilyl group is formed. On the other hand, when the most terminal atom of the polymer chain is an oxygen atom, a group represented by -SiR ⁰ R ² ₂ is usually bonded to the most terminal oxygen atom. Furthermore, the structural units located at both ends of the polymer chain are preferably structural units (ii).

A preferred form of the organosilicon compound (α) is a polymer chain consisting of a repeating polysiloxane chain formed by connecting one structural unit (i) and a plurality of structural units (ii), at both ends of the polymer chain, Examples include polymers in which a hydrogen atom, a vinyl group, or a group represented by -SiR ⁰ R ² ₂ is bonded, respectively. More specifically, the organosilicon compound (α) preferably has a repeating structure of each structural unit as shown below as an organosilicon compound (β).

The organosilicon compound (α) may further have a structural unit other than the structural unit (i) and the structural unit (ii). However, the other structural units preferably do not contain vinyl groups or other crosslinkable groups. Note that the crosslinkable group refers to a group capable of crosslinking reaction, and examples thereof include a vinyl group, a hydrosilyl group, and the like. It is more preferable that the organosilicon compound (α) has a structure having crosslinkable groups only at both ends. The number (average number) of crosslinkable groups that the organosilicon compound (α) has is preferably 5 or less, more preferably 3 or less, and particularly preferably 2. Further, the content of the other structural units in the total structural units of the organosilicon compound (α) is preferably 10 mol% or less, more preferably 1 mol% or less.

The lower limit of the weight average molecular weight of the organosilicon compound (α) is 1,000, preferably 2,000, more preferably 5,000, and even more preferably 6,000. Moreover, the upper limit of this weight average molecular weight is 20,000, preferably 15,000, and more preferably 12,000. When the weight average molecular weight of the organosilicon compound (α) is within the above range, the crosslinking density in the resulting molded product becomes appropriate and the stress relaxation ability increases, resulting in improved crack resistance in high temperature environments. It increases. Moreover, since the weight average molecular weight is below the above upper limit, the liquid becomes a liquid with appropriate viscosity, and can be suitably used for sealing material applications.

The lower limit of the viscosity of the organosilicon compound (α) at 25° C. is preferably 0.1 Pa·s, and more preferably 1 Pa·s or 10 Pa·s. On the other hand, the upper limit of this viscosity is preferably 1,000 Pa·s, and may be more preferably 100 Pa·s or 10 Pa·s. When the organosilicon compound (α) has such a viscosity, it has appropriate fluidity and becomes more useful as a sealing material for semiconductors and the like. The viscosity of the organosilicon compound (α) can be adjusted by adjusting the weight average molecular weight, the degree of polymerization of each structural unit, and the like.

The organosilicon compound (α) contains a structural unit (i) and a structural unit (ii) with a predetermined degree of polymerization, has a vinyl group or a hydrosilyl group at both ends, and has a weight average molecular weight within a predetermined range. Accordingly, it is possible to obtain a molded article having excellent crack resistance in a high-temperature environment. Moreover, the obtained molded article also has sufficiently high light transmittance and optical refractive index.

<Organosilicon compound (β)>
The organosilicon compound (β) according to one embodiment of the present invention is represented by the following formula (1).

In formula (1), R ⁰ is each independently a vinyl group or a hydrogen atom. Each R ¹ is independently a hydrocarbon group having 1 to 8 carbon atoms. Each R ² is independently a hydrocarbon group having 1 to 8 carbon atoms. m is an average value satisfying 1 to 5. n is an average value satisfying 2 to 50.

Specific examples and preferred examples of the hydrocarbon groups represented by R ¹ and R ² in formula (1) are R ¹ and R in the structural unit (i) and structural unit (ii) in the organosilicon compound (α). This is the same as the hydrocarbon group represented by ² .

The lower limit of m is 1, preferably 1.4, and more preferably 2. Moreover, the upper limit of this m is 5, and 4 or 3 may be preferable.

The lower limit of n is 2, preferably 3, and sometimes 5 and even more preferably 9. Further, the upper limit of n is 50, preferably 40, and more preferably 30.

It can be said that m represents the degree of polymerization of the structural unit (i) in the organosilicon compound (β). It can be said that n represents the average number of the structural units (ii) in the polysiloxane chain formed by consecutive structural units (ii) (degree of polymerization of the polysiloxane chain). Furthermore, it can be said that mn+n+1 is substantially equal to the degree of polymerization of the structural unit (ii) in the organosilicon compound.

The specific structure of the organosilicon compound (β) represented by the above formula (1) is as follows when the structural unit (i) is X, the structural unit (ii) is Y, and m=2 and n=5. It will be as follows. However, since m and n are each average values, even in one molecule, the number of consecutive Y (structural units (ii)), that is, the average number of structural units (ii) in the polysiloxane chain, differs. You can leave it there.

The weight average molecular weight and viscosity of the organosilicon compound (β) are not particularly limited, but their preferred ranges are the same as the ranges for the organosilicon compound (α) described above.

Since the organosilicon compound (β) has the above structure, it is possible to obtain a molded article having excellent crack resistance in a high-temperature environment. Moreover, the obtained molded article also has sufficiently high light transmittance and optical refractive index.

<Method for producing organosilicon compound>
Although the method for producing the organosilicon compound (α) and the organosilicon compound (β) is not particularly limited, they can be suitably produced, for example, by the following method. That is, the method for producing an organosilicon compound according to an embodiment of the present invention includes a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-2). -3) and a step of equilibrating polymerization in the presence of an acid catalyst.

In formula (2-1), R ¹ is each independently a hydrocarbon group having 1 to 8 carbon atoms.
In formula (2-2), each R _a ² is independently a hydrocarbon group having 1 to 8 carbon atoms. p is an integer from 3 to 8.
In formula (2-3), R ⁰ is each independently a vinyl group or a hydrogen atom. Each R _b ² is independently a hydrocarbon group having 1 to 8 carbon atoms. q is an average value satisfying 0 to 50.

Specific examples and preferred examples of R ¹ in the above formula (2-1) are the same as R ¹ in the above formula (i) and formula (1). Specific examples and preferred examples of R _a ² in the above formula (2-2) and R _b ² in the formula (2-3) are the same as R ² in the above formula (ii) and formula (1). . The above p is preferably an integer of 3 to 6, more preferably 4. The above q is preferably 0 to 10, more preferably 0 to 4, and even more preferably 0. Note that n in the above (1) depends on the values of p and q, that is, the structure of the compound represented by the above formula (2-2) and the above formula (2-3).

One type each of the compound represented by the above formula (2-1), the compound represented by the above formula (2-2), and the compound represented by the above formula (2-3) may be used. , two or more types may be used. The usage ratio of the compound represented by the above formula (2-1), the above formula (2-2), and the above formula (2-3) is determined based on the target organosilicon. It can be appropriately set depending on the degree of polymerization of each structural unit in the compound.

In the above step, polymerization usually occurs through an equilibration reaction between the compound represented by the above formula (2-1) and the compound represented by the above formula (2-2), and the compound represented by the above formula (2-3) is The compounds represented function as so-called terminal capping agents.

Examples of the acid catalyst used in the above step include cation exchange resins as acid catalysts such as hydrochloric acid, sulfuric acid, fluorosulfuric acid, trifluoromethanesulfonic acid, activated clay, and sulfonic acid-based ion exchange resins. Among these, trifluoromethanesulfonic acid, activated clay, and cation exchange resin are preferred.

The above steps are preferably performed using a solvent. As a solvent, a compound represented by the above formula (2-1), a compound represented by the above formula (2-2), and a compound represented by the above formula (2-3) are dissolved, and an acid catalyst is used. The solvent is not particularly limited as long as it does not react with the solvent. Examples of such solvents include aliphatic hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, and cyclopentyl methyl ether. and halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride. The solvent may be a single solvent or a mixed solvent.

The reaction temperature in the above step is not particularly limited, and can be, for example, between 30 and 200°C. Furthermore, the reaction time can also be, for example, between 1 and 72 hours. After the reaction, if necessary, the desired organosilicon compound can be isolated and purified by a conventionally known method.

<Thermosetting resin composition>
The thermosetting resin composition according to one embodiment of the present invention includes (A) an organosilicon compound (α) or an organosilicon compound (β) (hereinafter also referred to as "(A) organosilicon compound"), (B ) Contains (A) an organosilicon compound having a plurality of crosslinkable groups other than the organosilicon compound (hereinafter also referred to as "(B) organosilicon compound"), and (C) a catalyst. The organosilicon compound (B) includes at least a compound crosslinkable with the organosilicon compound (A). Since the thermosetting resin composition contains the organosilicon compound (A), the molded article obtained by curing the composition has excellent crack resistance in a high-temperature environment. Moreover, the obtained molded article also has sufficiently high light transmittance and optical refractive index. The thermosetting resin composition may further contain other components. Each component constituting the thermosetting resin composition will be explained in detail below.

((A) Organosilicon compound)
The organosilicon compound (A) is the organosilicon compound (α) or organosilicon compound (β) described above. (A) The organosilicon compound may be one type or a mixture of two or more types.

The lower limit of the content of the organosilicon compound (A) in the thermosetting resin composition is preferably 1% by mass, more preferably 5% by mass, 10% by mass, 20% by mass, 30% by mass or 40% by mass. may be even more preferable. 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, 30% by mass, or 15% by mass. For example, if (A) the organosilicon compound is in a form in which hydrosilyl groups are present at both ends, by making the content of (A) the organosilicon compound relatively small and (B) increasing the content of the organosilicon compound, There is a tendency for the crack resistance of the resulting molded product to be improved.

Moreover, it is preferable that the upper and lower limits of the content of the organosilicon compound (A) in the total organosilicon compounds in the thermosetting resin composition are also the above values. (A) By setting the content of the organosilicon compound within the above range, the mixing ratio with other components and the crosslinking density of the obtained molded product are optimized, so that the molded product obtained by curing can be produced at a high temperature. Crack resistance under environmental conditions is further improved.

((B) Organosilicon compound)
The organosilicon compound (B) is an organosilicon compound (excluding the organosilicon compound (A)) having a plurality of crosslinkable groups. Examples of the crosslinkable group include alkenyl groups such as vinyl groups, alkynyl groups such as ethynyl groups, and hydrosilyl groups, with vinyl groups and hydrosilyl groups being preferred. (B) The organosilicon compound may be one type or a mixture of two or more types. (B) The organosilicon compound contains at least one species capable of crosslinking with the organosilicon compound (A). In the case of a form in which vinyl groups are present at both ends of the organosilicon compound (A), 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 group is present at both ends of the organosilicon compound (A), a compound containing a vinyl group as a crosslinkable group can be crosslinked with the organosilicon compound (A) by a hydrosilylation reaction. Among the (B) organosilicon compounds, examples of compounds having a hydrosilyl group include (B1) organosilicon compounds and (B2) organosilicon compounds described below. Among the organosilicon compounds (B), examples of the organosilicon compound having a vinyl group include (B1) organosilicon compounds, (B3) organosilicon compounds, and (B4) organosilicon compounds described below.

In the thermosetting resin composition, (A) the organosilicon compound and at least one of the organosilicon compounds (B) undergo a crosslinking reaction under the catalyst (C) to obtain a cured product. Note that a crosslinking reaction may occur between the (B) organosilicon compounds. The organosilicon compounds (B1) to (B4) suitable as the organosilicon compound (B) will be explained below. That is, the organosilicon compound (B) preferably contains one or more of the organosilicon compounds (B1) to (B4).

((B1) Organosilicon compound)
(B1) The organosilicon compound is an organosilicon compound having a hydrosilyl group, a vinyl group, and a silsesquioxane structure. (B1) Since the organosilicon compound has a silsesquioxane structure, it is possible to further improve the heat resistance of the obtained molded article. (B1) As the organosilicon compound, a compound represented by the following formula (3) can be mentioned.

In formula (3), R ³ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. X is each independently a group represented by the following formula (X1), formula (X2) or formula (X3). The average number of groups represented by formula (X1) per molecule of the compound represented by formula (3) is x ₁ , the average number of groups represented by formula (X2) is x ₂ , and formula (X3) is When the average number of groups represented is _x3 , _x1 + _2x2 + _x3 =4r, 0< _x1 <4r, 0≦ _x2 <2r, and 0< _x3 <4r are satisfied. r is an average value satisfying 1 to 100.

The above R ³ is preferably an alkyl group, more preferably a methyl group.

The above x ₁ preferably exceeds r, and more preferably exceeds 2r. Further, the above x ₁ is preferably less than 3r. The above x ₂ is preferably equal to or less than r. It is preferable that the above x ₃ exceeds r. Further, x ₃ 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 formulas (X1), (X2) and (X3), * indicates a binding site.

In formula (X2), R ⁴ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group. s is an average value satisfying 2 to 20.

In formula (X3), R ⁵ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group. R ⁶ is an alkenyl group having 2 to 5 carbon atoms. R ⁷ is an alkanediyl group having the same number of carbon atoms as R ⁶ . t is an average value satisfying 2 to 20.

The above R ⁵ is preferably an alkyl group, more preferably a methyl group. 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 the above 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 thermosetting resin composition is preferably 10% by mass, more preferably 30% by mass, even more preferably 40% by mass, and 50% by mass or 65% by mass. In some cases, it may be even more preferable. On the other hand, the upper limit of this content is preferably 90% by mass, more preferably 80% by mass, and even more preferably 70% by mass or 65% by mass. Moreover, it is preferable that the upper and lower limits of the content of the organosilicon compound (B1) in all the organosilicon compounds in the thermosetting resin composition are also the above values. (B1) By setting the content of the organosilicon compound within the above range, the mixing ratio with other components and the crosslinking density of the obtained molded product are optimized, so that the molded product obtained by curing can be produced at a high temperature. Crack resistance under environmental conditions is further improved.

((B2) Organosilicon compound)
(B2) The organosilicon compound is a compound represented by the following formula (4).

In formula (4), R ⁸ and R ⁹ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. u is an average value satisfying 1 to 50.

The above R ⁸ is preferably an alkyl group, more preferably a methyl group.

The above R ⁹ is preferably an alkyl group or an aromatic hydrocarbon group, and more preferably a methyl group or a phenyl group. The upper limit of u is preferably 30, more preferably 15.

The lower limit of the content of the organosilicon compound (B2) 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. Moreover, it is preferable that the upper and lower limits of the content of the (B2) organosilicon compound in the total organosilicon compounds in the thermosetting resin composition are also the above values. (B2) By setting the content of the organosilicon compound within the above range, the mixing ratio with other components and the crosslinking density of the obtained molded product are optimized, so that the molded product obtained by curing can be produced at a high temperature. Crack resistance under environmental conditions is further improved.

((B3) Organosilicon compound)
(B3) The organosilicon compound is a compound represented by the following formula (5).

In formula (5), R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ¹² is an alkenyl group having 2 to 5 carbon atoms. R ¹³ is an alkenyl group having 2 to 5 carbon atoms or a hydrogen atom. v is an average value satisfying 1 to 50.

The above R ¹⁰ is preferably an alkyl group, more preferably a methyl group. The above R ¹¹ is preferably an alkyl group or an aromatic hydrocarbon group, and more preferably a methyl group or a phenyl group. The above R ¹² is preferably a vinyl group. The above R ¹³ is preferably an alkenyl group, more preferably a vinyl group. The upper limit of v is preferably 10, more preferably 5, even more preferably 3, and even more preferably 1.

The lower limit of the content of the organosilicon compound (B3) in the thermosetting resin composition is preferably 0.5% by mass, more preferably 1% by mass, and even more preferably 3% by mass or 5% by mass. . On the other hand, the upper limit of this content is preferably 20% by mass, more preferably 15% by mass, and even more preferably 10% by mass or 7% by mass. Moreover, it is preferable that the upper and lower limits of the content of the organosilicon compound (B3) in all the organosilicon compounds in the thermosetting resin composition are also the above values. (B3) By setting the content of the organosilicon compound within the above range, the mixing ratio with other components and the crosslinking density of the obtained molded product are optimized, so that the molded product obtained by curing can be produced at a high temperature. Crack resistance under environmental conditions is further improved.

((B4) Organosilicon compound)
(B4) The organosilicon compound is a compound represented by the following formula (6).

In formula (6), R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Each R ¹⁶ is independently an alkenyl group having 2 to 5 carbon atoms. R ¹⁷ is an alkanediyl group having 2 to 5 carbon atoms. j is an average value satisfying 1 to 5. k is an average value satisfying 1 to 50.

The above R ¹⁴ is preferably an alkyl group, more preferably a methyl group. The above R ¹⁵ is preferably an aromatic hydrocarbon group, and more preferably a phenyl group. The above R ¹⁶ is preferably a vinyl group. R ¹⁷ is preferably an ethane-1,2-diyl group. The upper limit of j is preferably 3, and more preferably 1. The upper limit of k is preferably 10, more preferably 5, and even more preferably 3.

The lower limit of the content of the organosilicon compound (B4) 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 10% by mass, more preferably 5% by mass, and even more preferably 3% by mass. Moreover, it is preferable that the upper and lower limits of the content of the (B4) organosilicon compound in the total organosilicon compounds in the thermosetting resin composition are also the above values. (B4) By setting the content of the organosilicon compound within the above range, the mixing ratio with other components and the crosslinking density of the obtained molded product are optimized, so that the molded product obtained by curing can be produced at a high temperature. Crack resistance under environmental conditions is further improved.

The lower limit of the content of the organosilicon compound (B) in the thermosetting resin composition is preferably 10% by mass, more preferably 30% by mass, even more preferably 40% by mass, and 60% by mass or 75% by mass. In some cases, it may be even more preferable. On the other hand, the upper limit of this content is preferably 90% by mass, and more preferably 70% by mass or 65% by mass. Moreover, it is preferable that the upper and lower limits of the content of the organosilicon compound (B) in all the organosilicon compounds in the thermosetting resin composition are also the above values. (B) By setting the content of the organosilicon compound within the above range, the mixing ratio with other components and the crosslinking density of the obtained molded product are optimized, so that the molded product obtained by curing can be heated to a high temperature. Crack resistance under environmental conditions is further improved.

Regarding the content of each component in the thermosetting resin composition, the ratio of the number of moles of all vinyl groups in all components to the number of moles of all hydrosilyl groups in all components (vinyl group/hydrosilyl group) The lower limit is preferably 0.6, more preferably 0.7, even more preferably 0.8, and even more preferably 0.9. Furthermore, this ratio may be more preferably greater than 1. On the other hand, the upper limit of this ratio is preferably 1.6, more preferably 1.4. When the molar ratio of the hydrosilyl group to the vinyl group is within the above range, the crosslinking reaction proceeds more effectively and heat resistance etc. can be further improved.

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

The lower limit of the content of the (C) catalyst in the thermosetting resin composition is, for example, 0.1 ppm, preferably 0.5 ppm. (C) By setting the content of the catalyst to the above lower limit or more, a sufficient reaction can be caused. On the other hand, the upper limit of this content is, for example, 1,000 ppm, preferably 100 ppm, and more preferably 10 ppm and 3 ppm. (C) By controlling the content of the catalyst to be less than or equal to the above upper limit, the crack resistance, light transmittance, etc. of the obtained molded product can be improved.

((D) Adhesion imparting agent)
It is preferable that the thermosetting resin composition further contains (D) an adhesion imparting agent. (D) As the adhesion imparting agent, an organosilicon compound having a hydrosilyl group and an epoxy group is preferable, and one having an alkoxysilyl group is more preferable. Such a compound can undergo a crosslinking reaction with other components in the thermosetting resin composition, and can also undergo a bonding reaction with components such as the base material on which the thermosetting resin composition is laminated, and the resulting The adhesion of the molded body can be improved. Furthermore, it is more preferable that the adhesion imparting agent (D) has a silsesquioxane structure from the viewpoint of heat resistance and the like. As such a suitable adhesion imparting agent (D), a compound represented by the following formula (7) can be mentioned.

In formula (7), R ¹⁸ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. Z is each independently a group represented by the following formula (Z1), formula (Z2), formula (Z31), formula (Z32), formula (Z33) or formula (Z41). The average number of groups represented by formula (Z1) per molecule of the compound 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 formula (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 to 100.

The above R ¹⁸ is preferably an alkyl group, more preferably a methyl group. z ₁ , z ₂ , z ₃ and z ₄ are respectively w≦z ₁ ≦2w, 0.3w≦z ₂ ≦w, 0.3w≦z ₃ ≦w, and 0.3w≦z ₄ ≦w. It is preferable that there be. The lower limit of w may be 3 or 5. Further, the upper limit of w may be 30 or 15.

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

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

In formula (Z41), R ²⁰ is each independently a methyl group, ethyl group, butyl group or isopropyl group. The above R ²⁰ is preferably a methyl group.

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. (D) Sufficient adhesion can be imparted by setting the content of the adhesion imparting agent to the above lower limit or more. On the other hand, the upper limit of this content is preferably 10% by mass, more preferably 3% by mass. (D) By setting the content of the adhesion imparting agent below the above upper limit, the mixing ratio with other components and the crosslinking density of the resulting molded product are optimized, so the molded product obtained by curing is achieved. Crack resistance in high-temperature environments is further improved. In addition, when the adhesion-imparting agent (D) is an organosilicon compound, the upper and lower limits of the content of the adhesion-imparting agent (D) in the total organosilicon compounds in the thermosetting resin composition are also the above values. It is preferable that there be.

((E) Phosphor or white pigment)
It is preferable that the thermosetting resin composition further contains (E) a phosphor or a white pigment. (E) The phosphor or white pigment is usually dispersed and contained in the thermosetting resin composition. When the thermosetting resin composition further contains (E) a phosphor or a white pigment, the thermosetting resin composition can be more suitably used as a sealing material for an optical semiconductor element.

Examples of the phosphor include inorganic phosphors such as YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors, and organic phosphors such as allylsulfamide/melamine formaldehyde co-condensed dyes and perylene-based phosphors. can.

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

The content of the (E) phosphor or white pigment in the thermosetting resin composition can be, for example, 1 to 50% by mass.

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

The contents of components other than the above-mentioned components (A) to (E) can be appropriately set depending on the use and the like. On the other hand, it may be preferable to have a smaller amount of these other components. The upper limit of the content of components other than the above components (A) to (E) in the thermosetting resin composition is preferably 10% by mass, 1% by mass, 0.1% by mass, or 0.01% by mass. In some cases. On the other hand, the lower limit of the content of components other than the above components (A) to (E) 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 and other volatile components. However, since the organosilicon compound (A) is usually liquid, it can exhibit good fluidity without using a solvent. Furthermore, by making the composition substantially free of volatile components such as solvents, it can be more suitably used as a sealing material for optical semiconductor devices. 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 even more preferably 0.01% by mass.

(Preparation method)
The method for preparing the thermosetting resin composition is not particularly limited. The thermosetting resin composition can be prepared using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three-roll mill, or a bead mill, at room temperature or at a temperature of 40°C to 200°C. An example is a method of mixing each component at room temperature.

(Application)
The thermosetting resin composition can be suitably used as an encapsulant for optical semiconductor elements, an encapsulant for other semiconductor elements, an insulating film, a sealant, a forming material for optical lenses, etc., and other adhesives. . Among these, the molded product obtained by curing has excellent crack resistance in high-temperature environments and can have good light transmittance and light refraction, so it is particularly suitable as a sealing material for optical semiconductor devices. Can be used.

<Molded object>
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 a semiconductor element such as an optical semiconductor element, an insulating film, a sealing material, an optical lens, etc. Among these, a sealing material for an optical semiconductor element is preferable.

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

The optical refractive index of the molded article is preferably 1.4 or more, more preferably 1.48 or more, and even more preferably 1.50 or more. When it has such a high refractive index, it has excellent light extraction efficiency from the optical semiconductor device, and is more useful as a sealing material for the optical semiconductor device. Note that the upper limit of this optical refractive index is, for example, 2, and may be 1.8, 1.7, or 1.6.

The light transmittance of the molded article at a wavelength of 400 nm is preferably 95% or more, more preferably 97% or more. When it has such a high light transmittance, it becomes more useful as a sealing material for optical semiconductor devices. Note that the upper limit of this light transmittance is, for example, 99.9%, and may be 99%.

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

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

The optical semiconductor device is obtained by sealing an optical semiconductor element with a thermosetting resin composition according to an embodiment of the present invention. This sealing method includes, for example, (1) a method in which the thermosetting resin composition is injected into a mold in advance, a lead frame or the like on which an optical semiconductor element is fixed is immersed therein, and then thermally cured; 2) A method may be mentioned in which the thermosetting resin composition is injected into a mold into which the optical semiconductor element is inserted and then thermally cured. 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, a method in which the thermosetting resin composition is dropped, printed, or applied onto the optical semiconductor element, and then thermally cured.

Since the optical semiconductor device uses the thermosetting resin composition according to an embodiment of the present invention as a sealant, the sealant has excellent crack resistance in a high-temperature environment. Therefore, the optical semiconductor device has excellent durability even if it has high output and high power density. The optical semiconductor device can be used for various lighting devices, electronic bulletin boards, traffic lights, backlights for liquid crystal display devices, LED displays, and the like.

The present invention will be explained in more detail based on examples. Note that the present invention is not limited to the following examples. In the chemical formula, "Me" represents a methyl group, "Vi" represents a vinyl group, and "Ph" represents a phenyl group. A method for analyzing the synthesized organosilicon compound will be shown below.

<Number average molecular weight and weight average molecular weight>
Using a high-performance liquid chromatography system CO-2065plus manufactured by JASCO Corporation, 20 μL of a THF solution with a sample concentration of 1% by mass was used as an analysis sample, and measurement was performed by GPC under the following conditions. The number average molecular weight and weight average molecular weight were determined by polystyrene conversion.
Column: Shodex KF804L [manufactured by Showa Denko K.K.] (2 connected in series)
Column temperature: 40℃
Detector: RI
Eluent: THF
Eluent flow rate: 1.0mL/min

<NMR (Nuclear Magnetic Resonance Spectrum)>
A 400 _MHZ NMR measuring device manufactured by JEOL Ltd. was used, and the measurement sample was dissolved in heavy acetone (manufactured by Wako Pure Chemical Industries, Ltd.) for measurement. Furthermore, the average polysiloxane chain length (n in the above formula (1)) etc. introduced in the synthesized organosilicon compound were determined from the integral ratio of ¹ H-NMR or ²⁹ Si-NMR.

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

[Synthesis Example 1] <Synthesis of silsesquioxane derivative (DD-4OH)>
A silsesquioxane derivative (DD-4OH) represented by the following formula was synthesized by the method described in Japanese Patent No. 5704168.

[Synthesis Example 2] <Synthesis of silsesquioxane derivative (DD(Me)-OH)>
A silsesquioxane derivative (DD(Me)-OH) represented by the following formula was synthesized by the method described in Japanese Patent No. 4379120.

[Synthesis Example 3] Synthesis of silsesquioxane derivative (DD(Ph)-OH) In a reaction vessel equipped with a thermometer and a dropping funnel, 100.0 g of silsesquioxane derivative (DD-4OH) and 49 g of phenyltrichlorosilane were added. .4 g and 660 mL of THF were charged. After cooling to 5° C., 42.6 g of triethylamine was added and stirred at room temperature for 4 hours. After cooling to 5° C., 100 mL of pure water was added, and the mixture was stirred at room temperature for 1 hour. After adding 500 mL of cyclopentyl methyl ether, the organic phase was washed with water until it became neutral. The solvent was distilled off under reduced pressure, and the obtained solid was dispersed in 140 mL of methanol, and then filtered under reduced pressure. Drying was performed under reduced pressure at 45° C. to obtain 110.0 g of a white solid represented by the following formula. The obtained white solid is judged to be a silsesquioxane derivative (DD(Ph)-OH) represented by the following formula from the following analysis results.
¹ H-NMR (solvent: heavy acetone): δ (ppm): 6.7-6.8 (m, 1.2H), 7.2-7.8 (m, 50H)

In addition, the reagents used in the synthesis of the following organosilicon compounds are shown below.

<Compound represented by the above formula (2-2)>
・Octamethylcyclotetrasiloxane (D4: manufactured by Momentive Performance Materials)
(Compound in which R _a ² in the above formula (2-2) is a methyl group and p is 4)
・Tetramethyltetravinylcyclotetrasiloxane (MVS-H)
(Compound in which R _a ² in the above formula (2-2) is a methyl group or a vinyl group, and p is 4)

<Compound represented by the above formula (2-3)>
・1,3-divinyltetramethyldisiloxane (DVDS: manufactured by Shin-Etsu Chemical Co., Ltd.)
(A compound in which R ⁰ in the above formula (2-3) is a vinyl group, R _b ² is a methyl group, and q is 0)
・Tetramethyldisiloxane (M'M': manufactured by Shin-Etsu Chemical Co., Ltd.)
(Compound in which R ⁰ in the above formula (2-3) is a hydrogen atom, R _b ² is a methyl group, and q is 0)

<Acid catalyst>
・Cation exchange resin RCP-160M (manufactured by Mitsubishi Chemical Corporation), which is a solid acid catalyst

[Example 1] Synthesis of organosilicon compound (A-1) In a reaction vessel equipped with a thermometer and a reflux tube, 20.0 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane ( D4) 17.2 g, 1,3-divinyltetramethyldisiloxane (DVDS) 5.78 g, cation exchange resin RCP-160M 1.23 g, and toluene 43.0 g were charged. The temperature was raised stepwise from 40°C to 130°C, and the mixture was aged for a total of 26 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 20.6 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-1) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 71.25H), 5.5 to 6.2 (m, 3.96H), 7.1 ~7.9 (m, 50H)
Viscosity=21.2Pa・s
Number average molecular weight: Mn=2381
Weight average molecular weight: Mw=3675
Degree of polymerization of structural unit (i) = 1.69
Degree of polymerization of structural unit (ii) = 19.98

[Example 2] Synthesis of organosilicon compound (A-2) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane ( D4) 48.12 g, 1,3-divinyltetramethyldisiloxane (DVDS) 8.54 g, cation exchange resin RCP-160M 2.50 g, and toluene 86.6 g were charged. The temperature was raised stepwise from 40°C to 130°C, and the mixture was aged for a total of 33 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 50.9 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-2) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 126.82H), 5.5 to 6.2 (m, 3.22H), 7.1 ~7.9 (m, 50H)
Viscosity=6.83Pa・s
Number average molecular weight: Mn=4439
Weight average molecular weight: Mw=7092
Degree of polymerization of structural unit (i) = 2.47
Degree of polymerization of structural unit (ii) = 52.23

[Example 3] Synthesis of organosilicon compound (A-3) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane ( D4) 25.66 g, 1,3-divinyltetramethyldisiloxane (DVDS) 5.11 g, cation exchange resin RCP-160M 1.74 g, and toluene 60.7 g were charged. The temperature was raised stepwise from 40°C to 130°C, and the mixture was aged for a total of 33 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 35.1 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-3) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 66.91H), 5.5 to 6.2 (m, 2.60H), 7.1 ~7.9 (m, 50H)
Viscosity=98.7Pa・s
Number average molecular weight: Mn=3587
Weight average molecular weight: Mw=5738
Degree of polymerization of structural unit (i) = 2.70
Degree of polymerization of structural unit (ii) = 30.13

[Example 4] Synthesis of organosilicon compound (A-4) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane ( D4) 17.69 g, 1,3-divinyltetramethyldisiloxane (DVDS) 5.99 g, cation exchange resin RCP-160M 1.54 g, and toluene 53.6 g were charged. The temperature was raised stepwise from 40° C. to 130° C., and after aging for a total of 29 hours, it was allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 30.4 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-4) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 54.57H), 5.5 to 6.2 (m, 2.49H), 7.1 ~7.9 (m, 50H)
Viscosity=372Pa・s
Number average molecular weight: Mn=3131
Weight average molecular weight: Mw=5275
Degree of polymerization of structural unit (i) = 2.68
Degree of polymerization of structural unit (ii) = 24.35

[Example 5] Synthesis of organosilicon compound (A-5) 30.0 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane ( D4) 13.55 g, 1,3-divinyltetramethyldisiloxane (DVDS) 8.56 g, cation exchange resin RCP-160M 1.50 g, and toluene 52.2 g were charged. The temperature was raised stepwise from 40°C to 130°C, and the mixture was aged for a total of 33 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 27.1 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-5) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 41.51H), 5.5 to 6.2 (m, 3.49H), 7.1 ~7.9 (m, 50H)
Viscosity=384Pa・s
Number average molecular weight: Mn=1868
Weight average molecular weight: Mw=2885
Degree of polymerization of structural unit (i) = 1.59
Degree of polymerization of structural unit (ii) = 10.97

[Example 6] Synthesis of organosilicon compound (A-6) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane ( D4) 28.4 g, 1,3-divinyltetramethyldisiloxane (DVDS) 9.57 g, cation exchange resin RCP-160M 1.95 g, and toluene 68.0 g were charged. The temperature was raised stepwise from 40°C to 110°C, aged for a total of 21 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 38.1 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-6) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 79.74H), 5.5 to 6.2 (m, 3.25H), 7.1 ~7.9 (m, 40H)
Viscosity=7.40Pa・s
Number average molecular weight: Mn=3033
Weight average molecular weight: Mw=4563
Degree of polymerization of structural unit (i) = 2.18
Degree of polymerization of structural unit (ii) = 26.77

[Example 7] Synthesis of organosilicon compound (A-7) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane ( D4) 28.4 g, 1,3-divinyltetramethyldisiloxane (DVDS) 9.56 g, cation exchange resin RCP-160M 1.94 g, and toluene 67.9 g were charged. The temperature was raised stepwise from 40°C to 95°C, aged for a total of 21 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 31.2 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-7) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 70.22H), 5.5 to 6.2 (m, 4.01H), 7.1 ~7.9 (m, 40H)
Viscosity=6.14Pa・s
Number average molecular weight: Mn=2311
Weight average molecular weight: Mw=3408
Degree of polymerization of structural unit (i) = 1.72
Degree of polymerization of structural unit (ii) = 18.43

[Example 8] Synthesis of organosilicon compound (A-8) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane ( D4) 28.4 g, 1,3-divinyltetramethyldisiloxane (DVDS) 9.54 g, cation exchange resin RCP-160M 1.95 g, and toluene 68.0 g were charged. The temperature was raised stepwise from 40°C to 70°C, and the mixture was aged for a total of 13 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 22.9 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-8) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 70.91H), 5.5 to 6.2 (m, 4.64H), 7.1 ~7.9 (m, 40H)
Viscosity=3.55Pa・s
Number average molecular weight: Mn=1677
Weight average molecular weight: Mw=2453
Degree of polymerization of structural unit (i) = 1.48
Degree of polymerization of structural unit (ii) = 15.96

[Example 9] Synthesis of organosilicon compound (A-9) In a reaction vessel equipped with a thermometer and a reflux tube, 30.1 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane ( D4) 15.0 g, 1,3-divinyltetramethyldisiloxane (DVDS) 9.45 g, cation exchange resin RCP-160M 1.56 g, and toluene 54.5 g were charged. The temperature was raised stepwise from 40°C to 85°C, aged for a total of 30 hours, and then allowed to cool to room temperature. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain a cloudy viscous liquid. After adding an equal weight of methanol to this and shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off at 120° C. and 0.3 kPaA to obtain 18.5 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-9) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 39.04H), 5.5 to 6.2 (m, 3.80H), 7.1 ~7.9 (m, 40H)
Viscosity=203Pa・s
Number average molecular weight: Mn=1699
Weight average molecular weight: Mw=2448
Degree of polymerization of structural unit (i) = 1.52
Degree of polymerization of structural unit (ii) = 8.34

[Example 12] Synthesis of organosilicon compound (A-12) 30 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane (D4) were placed in a reaction vessel equipped with a reflux condenser and a thermometer. 25.6 g of tetramethyldisiloxane (M'M'), 1.8 g of ion exchange resin RCP160M, and 63 g of toluene were charged. After reacting at 40°C for 12 hours, it was further reacted at 70°C for 10 hours, and further at 90°C for 3 hours. After returning the temperature to room temperature, the ion exchange resin was filtered off, and a liquid separation operation using water was performed. Thereafter, toluene and unreacted low-boiling components were removed under reduced pressure conditions of 120° C. and 1 mmHg to obtain 43 g of a cloudy white liquid. After washing this cloudy white liquid with 100 g of isopropyl alcohol, the solvent was distilled off under reduced pressure at 60°C to obtain 22 g of a slightly cloudy white liquid.
The obtained slightly cloudy liquid material is judged to be an organosilicon compound (A-12) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 98.44H), 4.5 to 4.9 (m, 1.48H), 7.1 ~7.9 (m, 50H)
Viscosity=474Pa・s
Number average molecular weight: Mn=2500
Weight average molecular weight: Mw=3900
Degree of polymerization of structural unit (i) = 2.22
Degree of polymerization of structural unit (ii) = 16.16

[Example 13] Synthesis of organosilicon compound (A-13) 30 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane (D4) were placed in a reaction vessel equipped with a reflux condenser and a thermometer. 81.3 g of tetramethyldisiloxane (M'M'), 3.4 g of ion exchange resin RCP160M, and 118 g of toluene were charged. After reacting at 40°C for 12 hours, it was further reacted at 70°C for 10 hours, and further at 90°C for 3 hours. After returning the temperature to room temperature, the ion exchange resin was filtered off, and a liquid separation operation using water was performed. Thereafter, toluene and unreacted low-boiling components were removed under reduced pressure conditions of 120° C. and 1 mmHg to obtain 86 g of a cloudy white liquid. After washing this cloudy white liquid with 320 g of methanol, the solvent was distilled off under reduced pressure at 60°C to obtain 62 g of a slightly cloudy white liquid.
The obtained slightly cloudy liquid material is judged to be an organosilicon compound (A-13) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 227.18H), 4.6 to 4.8 (m, 1.44H), 7.1 ~7.9 (m, 50H)
Viscosity=0.6Pa・s
Number average molecular weight: Mn=4700
Weight average molecular weight: Mw=6700
Degree of polymerization of structural unit (i) = 1.39
Degree of polymerization of structural unit (ii) = 52.59

[Example 14] Synthesis of organosilicon compound (A-14) 90 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane (D4) were placed in a reaction vessel equipped with a reflux condenser and a thermometer. 85.1 g, 20.5 g of tetramethyldisiloxane (M'M'), 5.6 g of ion exchange resin RCP160M, and 196 g of toluene were charged. After reacting at 40°C for 12 hours, it was further reacted at 70°C for 10 hours, and further at 90°C for 3 hours. After returning the temperature to room temperature, the ion exchange resin was filtered off, and a liquid separation operation using water was performed. Thereafter, toluene and unreacted low-boiling components were removed under reduced pressure conditions of 120° C. and 1 mmHg to obtain 147 g of a cloudy white liquid. After washing this cloudy white liquid with 270 g of methanol, the solvent was distilled off under reduced pressure at 60°C to obtain 89 g of a slightly cloudy white liquid.
The obtained slightly cloudy liquid material is judged to be an organosilicon compound (A-14) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.3 (m, 72.65H), 4.6 to 4.8 (m, 1.48H), 7.1 ~7.8 (m, 40H)
Viscosity=2.9mPa・s
Number average molecular weight: Mn=2100
Weight average molecular weight: Mw=3100
Degree of polymerization of structural unit (i) = 1.35
Degree of polymerization of structural unit (ii) = 15.01

[Comparative Synthesis Example 1] Synthesis of organosilicon compound (a-1) 30.1 g of silsesquioxane derivative (DD(Me)-OH) and octamethyltetracyclosiloxane were placed in a reaction vessel equipped with a thermometer and a reflux tube. (D4) 22.5g, 1,3-divinyltetramethyldisiloxane (DVDS) 0.94g, tetramethyltetravinylcyclotetrasiloxane (MVS-H) 7.00g, cation exchange resin RCP-160M 2.47g, toluene 60.2 g and 0.3 g of pure water were charged. After raising the temperature to reflux temperature and refluxing for 2 hours, it was aged at 50°C for 51 hours. After the ion exchange resin was filtered off, the filtrate was washed with water and separated, and the organic phase was concentrated under reduced pressure at 120° C. and 0.3 kPaA to obtain 47.1 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (a-1) having the following structure from the following analysis results.
(result of analysis)
²⁹ Si-NMR (solvent: heavy acetone): δ (ppm): -82 to 79 (m, 6.0Si), -67 to -64 (m, 1.8Si), -37 to -34 (m, 1 .4Si), -23 to -18 (m, 6.4Si), -5 to -4 (m, 0.2Si)
Viscosity=250Pa・s
Number average molecular weight: Mn=9236
Weight average molecular weight: Mw=17646
Degree of polymerization of structural unit (i) = 9.89
Degree of polymerization of structural unit (ii) = 76.2

上記構造は、各構造単位の構造及び重合度を示しているのみであり、各構造単位が上記の順に連結したブロック共重合体であることを表すものでは無い。

The above structure only shows the structure and degree of polymerization of each structural unit, and does not represent a block copolymer in which each structural unit is connected in the above order.

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

（上記式（３）におけるＲ^３がメチル基、ｒが１、式（Ｘ３）におけるＲ^５がメチル基、Ｒ^６がビニル基、Ｒ^７がエタン－１，２－ジイル基、ｔが２、ｘ_１［式（Ｘ１）］＝２．３４、ｘ_２［式（Ｘ２）］＝０、ｘ_３［式（Ｘ３）］＝１．６６である化合物）
この有機ケイ素化合物（Ｂ１－１）は国際公開２０１１／１４５６３８号に記載の方法にて合成した。 <(B) Organosilicon compound>
・B1-1: Organosilicon compound represented by the following formula

(R ³ in the above formula (3) is a methyl group, r is 1, R ⁵ in the formula (X3) is a methyl group, R ⁶ is a vinyl group, R ⁷ is an ethane-1,2-diyl group, t is 2, A compound in which x ₁ [formula (X1)] = 2.34, x ₂ [formula (X2)] = 0, x ₃ [formula (X3)] = 1.66)
This organosilicon compound (B1-1) was synthesized by the method described in International Publication No. 2011/145638.

（上記式（４）におけるＲ^８がメチル基、Ｒ^９がフェニル基、ｕが１である化合物） ・B2-1: Organosilicon compound represented by the following formula (product name "2BH": manufactured by Biogen Co., Ltd.)

(Compound in which R ⁸ in the above formula (4) is a methyl group, R ⁹ is a phenyl group, and u is 1)

（上記式（４）におけるＲ^８及びＲ^９がメチル基、ｕが１０であるジメチルシロキサンポリマー） ・B2-2: Organosilicon compound represented by the following formula (product name "FM-1111": manufactured by JNC Corporation)

(Dimethylsiloxane polymer in which R ⁸ and R ⁹ in the above formula (4) are methyl groups and u is 10)

（上記式（５）におけるＲ^１０及びＲ^１１がメチル基、Ｒ^１２及びＲ^１３がビニル基、ｖが１である化合物） ・B3-1: Compound represented by the following formula (DVTS: manufactured by JNC Co., Ltd.)

(A compound in which R ¹⁰ and R ¹¹ in the above formula (5) are methyl groups, R ¹² and R ¹³ are vinyl groups, and v is 1)

（上記式（５）におけるＲ^１０がメチル基、Ｒ^１１がフェニル基、Ｒ^１２及びＲ^１３がビニル基、ｖが１である化合物） ・B3-2: Compound represented by the following formula (product name "2PV": manufactured by Biogen Co., Ltd.)

(A compound in which R ¹⁰ in the above formula (5) is a methyl group, R ¹¹ is a phenyl group, R ¹² and R ¹³ are a vinyl group, and v is 1)

（上記式（５）におけるＲ^１０及びＲ^１１がメチル基、Ｒ^１２及びＲ^１３がビニル基、ｖが７である化合物） ・B3-3: Compound represented by the following formula (product name "FM-2205": manufactured by JNC Co., Ltd.)

(A compound in which R ¹⁰ and R ¹¹ in the above formula (5) are methyl groups, R ¹² and R ¹³ are vinyl groups, and v is 7)

（上記式（６）におけるＲ^１４がメチル基、Ｒ^１５がフェニル基、Ｒ^１６がビニル基、Ｒ^１７がエタン－１，２－ジイル基、ｊが１、ｋが２である化合物） ・B4-1: Compound represented by the following formula

(A compound in which R ¹⁴ in the above formula (6) is a methyl group, R ¹⁵ is a phenyl group, R ¹⁶ is a vinyl group, R ¹⁷ is an ethane-1,2-diyl group, j is 1, and k is 2)

The above organosilicon compound (B4-1) is 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (DVDPTS: manufactured by Bio-Gen, Korea) as shown in the following formula. ) and 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (DHDPTS: manufactured by Bio-Gen, Korea) through a hydrosilylation reaction. Hydrosilylation was carried out by placing DVDPTS and DHDPTS in a flask, adding 2 ppm of Pt catalyst, and heating at 70° C. for 8 hours.

<(C) Catalyst>
・C-1: Karstedt catalyst (product name "Pt-VTS-3.0X": 3wt% xylene solution, manufactured by Umicore)

（上記式（７）におけるＲ^１８がメチル基、ｗが８．８、式（Ｚ２）におけるＲ^１９がメチル基、式（Ｚ４１）におけるＲ^２０がメチル基、ｚ_１［式（Ｚ１）］＝１．３２ｗ、ｚ_２［式（Ｚ２）］＝０．６９ｗ、ｚ_３［式（Ｚ３１）］＝０．６５ｗ、ｚ_４［式（Ｚ４１）］＝０．６５ｗである化合物）
この密着性付与剤（Ｄ－１）は、特許第５８８０５５６号公報に記載の方法にて合成した。 <(D) Adhesion imparting agent>
・D-1: Compound represented by the following formula

(R ¹⁸ in the above formula (7) is a methyl group, w is 8.8, R ¹⁹ in the formula (Z2) is a methyl group, R ²⁰ in the formula (Z41) is a methyl group, z ₁ [formula (Z1)] = 1.32w, z ₂ [formula (Z2)] = 0.69w, z ₃ [formula (Z31)] = 0.65w, z ₄ [formula (Z41)] = 0.65w)
This adhesion imparting agent (D-1) was synthesized by the method described in Japanese Patent No. 5880556.

<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 15 to 26, 29 to 31, Comparative Examples 1 to 2] Preparation of thermosetting resin composition The above components were uniformly mixed in the proportions (mass%) shown in Table 1, and Examples 15 to 26 were prepared. , 29 to 31 and Comparative Examples 1 to 2 were prepared. Table 1 also shows the ratio of the number of moles of vinyl groups to the number of moles of hydrosilyl groups of all components in each thermosetting resin composition (functional group ratio Vi/SiH). The following evaluations were performed using each of the obtained thermosetting compositions. The results are shown in Table 1.

<Light transmittance>
A NAFLON SP packing (4 mm diameter) manufactured by Nichias Co., Ltd. was sandwiched between two pieces of glass as a spacer, and the thermosetting resin composition was poured into the spacer. Next, it was cured by heating at 150° C. for 2 hours, and the glass was peeled off to obtain a cured product measuring 30 mm x 35 mm x 4 mm and having a smooth surface. At one location in the center of the cured product, the transmittance of light at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer "V-650" manufactured by JASCO Corporation.

<Light refractive index>
A NAFLON SP packing (4 mm diameter) manufactured by Nichias Co., Ltd. was sandwiched between two pieces of glass as a spacer, and the thermosetting resin composition was poured into the spacer. Next, it was cured by heating at 150° C. for 2 hours, and the glass was peeled off to obtain a cured product measuring 30 mm x 35 mm x 4 mm and having a smooth surface. A test piece (30 mm x 10 mm x 4 mm) was prepared from this cured product according to JIS K7142 (2014). The optical refractive index at one point on the test piece was measured using an Abbe refractometer ("NAR-2T" manufactured by Atago Co., Ltd.) using the D line of a sodium lamp. 1-bromonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the intermediate solution.

<250℃ heat crack test>
The thermosetting resin composition was applied to a slide glass ("MICRO SLIDE GLASS S9213" manufactured by Matsunami Glass) to a thickness of about 0.1 mm. This was placed in an oven set at 250° C., taken out every 168 hours, returned to room temperature, observed its appearance, and recorded the time at which cracks occurred.

As shown in Table 1, in the case of each of the thermosetting resin compositions of Examples 15 to 26 and 29 to 31, the time required for cracks to occur in the crack resistance test at 250° C. exceeded 500 hours. In addition, the initial performance regarding light transmittance and optical refractive index was also sufficient. On the other hand, in the case of the thermosetting resin compositions of Comparative Examples 1 and 2, the time for cracks to occur was 500 hours or less. From this, it is clear that the organosilicon compounds obtained in Examples 1 to 9 and 12 to 14 are substances that improve the crack resistance of molded articles obtained by thermosetting.

The organosilicon compound of the present invention and the thermosetting resin composition containing the same can be used in encapsulants for optical semiconductor devices, encapsulants for other semiconductor devices, insulating films, sealants, optical lenses, and the like.

Claims (13)

An organosilicon compound represented by the following formula (1).

(In formula (1), R ⁰ is each independently a vinyl group or a hydrogen atom. R ¹ is each independently an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 8 carbon atoms, A hydrocarbon group having the formula hydrocarbon group, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.R ² is each independently an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 8 carbon atoms. , or an aromatic hydrocarbon group having 6 to 8 carbon atoms. m is an average value satisfying 1 to 5. n is an average value satisfying 2 to 50.) The organosilicon compound according to claim 1, wherein ^R2 is an alkyl group. Equilibrium polymerization of a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3) in the presence of an acid catalyst. The method for producing an organosilicon compound according to claim 1 or 2, comprising the step of :

(In formula (2-1), R ¹ is each independently an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms. It is a hydrogen group.
In formula (2-2), R _a ² is each independently an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 8 carbon atoms, or an aromatic carbonization group having 6 to 8 carbon atoms. It is a hydrogen group. p is an integer from 3 to 8.
In formula (2-3), R ⁰ is each independently a vinyl group or a hydrogen atom. R _b ² is each independently an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms. q is an average value satisfying 0 to 50. ) (A) the organosilicon compound according to claim 1 or claim 2 ;
(B) an organosilicon compound having a plurality of crosslinkable groups other than the organosilicon compound (A), and (C) a catalyst;
A thermosetting resin composition in which the organosilicon compound (B) contains at least a compound crosslinkable with the organosilicon compound (A). The thermosetting resin composition according to claim 4 , wherein the content of the organosilicon compound (A) is 1% by mass or more and 90% by mass or less. The thermosetting resin composition according to claim 4 or 5 , wherein the organosilicon compound (B) contains a compound represented by the following formula (3).

(In formula (3), R ³ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. ) or a group represented by formula (X3).The average number of groups represented by formula (X1) per molecule of the compound represented by formula (3) is x ₁ , and the group represented by formula (X2) is When the average number of groups represented by formula (X3) is x ₂ and the average number of groups represented by formula (X3) is x ₃ , x ₁ +2x ₂ +x ₃ =4r, 0< _x1 <4r, 0≦ _x2 <2r , and 0<x ₃ <4r. r is an average value satisfying 1 to 100.)

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

(In formula (4), R ⁸ and R ⁹ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. u is , is an average value that satisfies 1 to 50.) The thermosetting resin composition according to any one of claims 4 to 7 , wherein the organosilicon compound (B) contains a compound represented by the following formula (5).

(In formula (5), R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ¹² is an alkenyl group having 2 to 5 carbon atoms. R ¹³ is an alkenyl group having 2 to 5 carbon atoms or a hydrogen atom. v is an average value satisfying 1 to 50.) The thermosetting resin composition according to any one of claims 4 to 8 , wherein the organosilicon compound (B) contains a compound represented by the following formula (6).

(In formula (6), R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. R ¹⁶ are each independently an alkenyl group having 2 to 5 carbon atoms. R ¹⁷ is an alkanediyl group having 2 to 5 carbon atoms. j is an average value satisfying 1 to 5. k is (This is the average value satisfying 1 to 50.) (D) further contains an adhesion imparting agent,
The thermosetting resin composition according to any one of claims 4 to 9 , wherein the adhesion imparting agent (D) contains a compound represented by the following formula (7).

(In formula (7), R ¹⁸ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. Z is each independently the following formula (Z1), formula (Z2 ), a group represented by formula (Z31), formula (Z32), formula (Z33), or formula (Z41).Represented by formula (Z1) per molecule of the compound represented by formula (7) The average number of groups is z ₁ , the average number of groups represented by formula (Z2) is z ₂ , the average number of groups represented by formula (Z31), formula (Z32) or formula (Z33) is z ₃ , When 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 to 100.)

(In formulas (Z1), (Z2), (Z31), (Z32), (Z33) and (Z41), * indicates a binding site.
In formula (Z2), R ¹⁹ is each independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, a cyclohexyl group, or a phenyl group. i is an average value satisfying 1 to 20.
In formula (Z41), R ²⁰ is each independently a methyl group, ethyl group, butyl group or isopropyl group. ) (E) The thermosetting resin composition according to any one of claims 4 to 10 , further comprising a phosphor or a white pigment. A molded article obtained by curing the thermosetting resin composition according to any one of claims 4 to 11 . An optical semiconductor device comprising an optical semiconductor element and a molded body according to claim 12 , which seals the optical semiconductor element.