JP2020090593A - Organic silicon compound, manufacturing method of organic silicon compound, thermosetting resin composition, molded body and optical semiconductor device - Google Patents

Abstract

To provide an organic silicon compound and a thermosetting resin composition, capable of providing a molded body hardly generating crack even under high temperature environment, and the molded body and an optical semiconductor device obtained by using the thermosetting resin composition.SOLUTION: There is provided an organic silicon compound having a cage-like silsesquioxane structure unit (i) consisting of 10 silicon atoms, 8 phenyl group-containing T unit residues and 2 T unit residues containing Rgroup, and a dialkylsiloxyl structure unit (-OSiR), and having a vinyl group or a hydrosilyl group existing at both terminals of a molecule chain, in which weight average molecular weight of 1,000 to 20,000, polymerization degree of the structural unit (i) of 1 to 5, and polymerization degree of the structural unit (ii) of 4 to 200. In the structural unit (i), Ris each independently a hydrocarbon group having 1 to 8 carbon atoms. In the structural unit (ii), Ris each independently a hydrocarbon group having 1 to 8 carbon atoms.SELECTED DRAWING: None

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 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. In recent years, in the optical semiconductor industry, there has been a demand for higher output and smaller and thinner packages, and the heat density per unit volume tends to increase. For this reason, heat resistance is particularly required for the encapsulant for optical semiconductor elements, in addition to light transmissivity, light refraction, and the like.

Silicone resin is widely used as one of sealing materials for optical semiconductor elements. Patent Document 1 proposes a crosslinkable silicon compound having a double-decker type silsesquioxane structure and a crosslinkable functional group. Double-decker type silsesquioxane is said to have high heat resistance because it has a controlled structure. The above Patent Document 1 also describes that the silicone film obtained by 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) is less likely to undergo mass reduction due to thermal decomposition even under heating and has excellent thermal stability.

JP, 2010-116464, A

In terms of heat resistance, the encapsulant for optical semiconductor elements is required to be resistant to cracking even at high temperatures, in addition to being resistant to thermal decomposition. When the crosslinkable compound of the above-mentioned Patent Document 1 is used, the crosslink becomes too dense, the stress relaxation ability is reduced, and heat deterioration is likely to proceed from the densely formed crosslink site. Cracks are likely to occur in a high temperature environment.

The present invention has been made based on the above circumstances, and an object thereof is to obtain an organosilicon compound and a thermosetting resin composition capable of obtaining a molded body in which cracks are unlikely to occur even in a high temperature environment, and It is intended to provide a molded product and an optical semiconductor device obtained by 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-mentioned problems 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 a molecular chain An organic silicon compound having a vinyl group or a hydrosilyl group respectively, the weight average molecular weight of 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, the structural unit (ii ) Is an organosilicon compound (α) having a degree of polymerization of 4 or more and 200 or less.

(In the formula (i), each R ¹ is independently a hydrocarbon group having 1 to 8 carbon atoms.
In formula (ii), R< ² > is respectively independently a C1-C8 hydrocarbon group. )

（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 problems 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, it is a hydrocarbon group having 1 to 8 carbon atoms, m is an average value satisfying 1 to 5, and 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。） Still another invention made to solve the above-mentioned problems is a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a following formula (2-3). A method for producing the organosilicon compound (α) or the organosilicon compound (β), comprising a step of equilibrium polymerization of the compound represented by the formula (1) in the presence of an acid catalyst.

(In the formula (2-1), ^{R 1} is each independently a hydrocarbon group having 1 to 8 carbon atoms.
In formula (2-2), R _a ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. p is an integer of 3-8.
In formula (2-3), R ⁰ is each independently a vinyl group or a hydrogen atom. R _b ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. q is an average value that satisfies 0 to 50. )

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

In the thermosetting resin composition, the content of the (A) organosilicon compound 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。） The (B) organosilicon compound preferably contains a compound represented by the following formula (3).

(In the formula (3), R ^3's each independently represent an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. X's each independently represent the following formula (X1) or formula (X2 Or the average number of the group represented by the formula (X1) per molecule of the compound represented by the formula (3) is x ₁ , represented by the formula (X2). Where x ₂ is the average number of groups represented by the formula (X3) and x ₃ is the average number of groups represented by the formula (X3), x ₁ +2x ₂ +x ₃ =4r, 0<x ₁ <4r, 0≦x ₂ <2r , And 0<x ₃ <4r, where r is an average value that satisfies 1 to 100.)

(In the formulas (X1), (X2) and (X3), * represents 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 that satisfies 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 carbon number as R ⁶ . t is an average value that satisfies 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。） The above (B) organosilicon compound preferably contains a compound represented by the following formula (4).

(In the 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. , 1 to 50 are average values.)

（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。） The (B) organosilicon compound preferably contains a compound represented by the following formula (5).

(In the formula ^{(5), R 10} and ^{R 11} are each independently, ^{.R 12} is an alkyl group, a cyclopentyl group, a cyclohexyl group or an aromatic hydrocarbon group having 6 to 12 carbon atoms having 1 to 4 carbon atoms 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, and 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。） The (B) organosilicon compound preferably contains a compound represented by the following formula (6).

(In the formula ^{(6), R 14} and ^{R 15} are each independently, ^{.R 16} is an alkyl group, a cyclopentyl group, a cyclohexyl group or an aromatic hydrocarbon group having 6 to 12 carbon atoms having 1 to 4 carbon atoms 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, and k is It is an average value that satisfies 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。） It is preferable that the thermosetting resin composition further contains (D) an adhesion promoter, and the (D) adhesion promoter contains a compound represented by the following formula (7).

(In formula (7), R< ¹⁸ > is respectively independently a C1-C4 alkyl group, a cyclopentyl group, or a cyclohexyl group. Z is each independently the following formula (Z1) and formula (Z2. ), a formula (Z31), a formula (Z32), a formula (Z33) or a formula (Z41), represented by the formula (Z1) per molecule of the compound represented by the 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 the groups represented by the 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 are satisfied, where w is an average value that satisfies 1 to 100.)

(In formulas (Z1), (Z2), (Z31), (Z32), (Z33) and (Z41), * represents a binding site.
In formula (Z2), each R ¹⁹ is 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 that satisfies 1 to 20.
In formula (Z41), R ^20's are each independently a methyl group, an ethyl group, a butyl group or an isopropyl group. )

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

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

Yet another invention made to solve the above problems 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, an organosilicon compound and a thermosetting resin composition capable of obtaining a molded body in which cracks are unlikely to occur even in a high temperature environment, and a molded body 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 described 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, vinyl groups or hydrosilyl groups are present at both ends of the molecular chain of the organosilicon compound (α).

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

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

Examples of the hydrocarbon group represented by R ¹ include an aliphatic chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the aliphatic chain hydrocarbon group include an alkyl group such as a methyl group, an ethyl group and a propyl group, an alkenyl group such as a vinyl group and a propenyl group, an alkynyl group such as an ethynyl group and a propynyl group. 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.

As R ¹ , an aliphatic chain hydrocarbon group and an aromatic hydrocarbon group are preferable, and an aromatic hydrocarbon group is more preferable. Among the aliphatic chain hydrocarbon groups, an alkyl group is more preferable, and a methyl group is still more preferable. Among the aromatic hydrocarbon groups, a phenyl group is more preferable.

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

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

In formula (ii), R< ² > is respectively independently a C1-C8 hydrocarbon group.

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 carbon number of R ² is preferably 5, and more preferably 3. As R ² , an aliphatic chain hydrocarbon group is preferable, an alkyl group is more preferable, and a methyl group is further preferable. When R ² is an alkyl group, the structural unit (ii) does not contain a crosslinkable group, and the crosslink density when cured becomes appropriate. As a result, the stress relaxation capability of the obtained molded body is enhanced, and the crack resistance in a high temperature environment is further enhanced.

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, is preferably 8, more preferably 20, and even more preferably 40. The upper limit of the degree of polymerization is 200, preferably 150, more preferably 100.

In the organosilicon compound (α), it is preferable that a plurality of structural units (ii) are linked to form a polysiloxane chain. The organosilicon compound may have one or more of the above 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 the degree of polymerization is preferably 3, and more preferably 5 and even 9 in some cases. On the other hand, the upper limit of the degree of polymerization is preferably 40, more preferably 30. That is, the polysiloxane chain is formed of, for example, 2 to 50 structural units on average (ii).

The organosilicon compound (α) usually has a linear molecular chain structure. In the organosilicon compound (α), vinyl groups or hydrosilyl groups are present at both ends of this molecular chain. The hydrosilyl group refers to a group (-Si-H) in which a silicon atom is bonded to a hydrogen atom. That is, the hydrosilyl group is not limited to the trihydrosilyl group (—SiH ₃ ), and one or two hydrogen atoms of the trihydrosilyl group may be substituted with a substituent (for example, a hydrocarbon group such as an alkyl group). Also included. Examples of the hydrosilyl group include a group represented by -SiR ² ₂ H. Definitions and preferred forms of ^{R 2} of -SiR ² ₂ in H is the same as ^{R 2} in formula (ii). In addition, the hydrosilyl groups at both ends of the molecular chain may overlap with the structural unit (i) and a part of the structural unit (ii).

The arrangement of structural units such as the structural unit (i) and the 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. The organosilicon compound (α) has a hydrogen atom, a vinyl group, or-at both ends of a polymer chain formed from one or more structural units (i) and one or more structural units (ii). SiR ⁰ R ² ₂ group represented by may be a structure formed by bonding. ^{R 0} of -SiR ⁰ R ² ₂ is a hydrogen atom or a vinyl group, definitions and preferred forms of ^{R 2} is the same as ^{R 2} in formula (ii). When the terminal atom of the polymer chain composed of the structural unit (i) and the 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, if the atom of the top end of the polymer chain is an oxygen atom, typically a group represented by -SiR ⁰ R ² ₂ is bonded to the oxygen atom of the innermost end. The structural units located at both ends of the polymer chain are preferably structural units (ii).

As a preferred form of the organosilicon compound (α), at both ends of a polymer chain composed of a repeating polysiloxane chain formed by connecting one structural unit (i) and a plurality of structural units (ii), each represent a hydrogen atom, a vinyl group, or -SiR ⁰ R ² ₂ is a group represented by may be mentioned polymers obtained by coupling. 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 unit preferably does not contain a vinyl group or other crosslinkable groups. The crosslinkable group means a group capable of undergoing a crosslinking reaction, and examples thereof include a vinyl group and a hydrosilyl group. The organosilicon compound (α) more preferably has a structure having a crosslinkable group only at both ends. The number (average number) of crosslinkable groups contained in the organosilicon compound (α) is preferably 5 or less, more preferably 3 or less, and particularly preferably 2. Further, the content ratio of the above-mentioned other structural units in all the 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. 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 cross-linking density in the obtained molded body becomes appropriate and the stress relaxation ability is enhanced, so that the crack resistance in a high temperature environment is improved. Increase. Further, when the weight average molecular weight is not more than the above upper limit, it becomes a liquid having an appropriate viscosity and can be suitably used for sealing material applications and the like.

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

The organosilicon compound (α) contains a structural unit (i) and a structural unit (ii) having a predetermined degree of polymerization, has vinyl groups or hydrosilyl groups at both ends, and has a weight average molecular weight within a predetermined range. This makes it possible to obtain a molded product having excellent crack resistance in a high temperature environment. Further, the obtained molded product has sufficiently high light transmittance and light 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. R ¹ is each independently a hydrocarbon group having 1 to 8 carbon atoms. R ^{2 s} are each independently a hydrocarbon group having 1 to 8 carbon atoms. m is an average value that satisfies 1 to 5. n is an average value that satisfies 2 to 50.

Specific examples and preferred examples of the hydrocarbon group represented by R ¹ and R ² in the formula (1), R ¹ and R in the structural units in the organosilicon compound (alpha) (i) and the structural unit (ii) It is the same as the hydrocarbon group represented by ² .

The lower limit of m is 1, preferably 1.4, and more preferably 2 in some cases. The upper limit of m is 5, and 4 or 3 may be preferable in some cases.

The lower limit of n is 2, 3 is preferable, 5 is even more preferable, and 9 may be more preferable. 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 in which the structural units (ii) are continuous (the degree of polymerization of the polysiloxane chains). It can also 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 becomes the street. However, since m and n are average values, the number of Ys (structural units (ii)) continuously arranged in one molecule, that is, the average number of structural units (ii) in the polysiloxane chain is different. May be.

The weight average molecular weight and the viscosity of the organosilicon compound (β) are not particularly limited, but their preferable ranges are the same as the above-mentioned range of the organosilicon compound (α).

Since the organosilicon compound (β) has the above structure, a molded product having excellent crack resistance in a high temperature environment can be obtained. Further, the obtained molded product has sufficiently high light transmittance and light refractive index.

<Method for producing organosilicon compound>
The method for producing the organosilicon compound (α) and the organosilicon compound (β) is not particularly limited, but can be suitably produced by, for example, the following method. That is, a method for producing an organosilicon compound according to an embodiment of the present invention is 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) and a compound represented by 3) in equilibrium 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), R _a ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. p is an integer of 3-8.
In formula (2-3), R ⁰ is each independently a vinyl group or a hydrogen atom. R _b ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. q is an average value that satisfies 0 to 50.

Specific examples and preferred examples of ^{R 1} in the formula (2-1) is the same as ^{R 1} in the formula (i) and (1). Specific examples and preferred examples of _R ^{b 2} in the formula (2-2) _R ^{a 2} and in the formula (2-3) in is the same as ^{R 2} in the formula (ii) and (1) .. The above p is preferably an integer of 3 to 6, and more preferably 4. 0-10 are preferable, as for said q, 0-4 are more preferable, and 0 is still more preferable. 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 formula (2-2) and the compound represented by the formula (2-3).

Each of the compound represented by the formula (2-1), the compound represented by the formula (2-2), and the compound represented by the formula (2-3) may be used alone. You may use 2 or more types each. The use ratio of the compound represented by the formula (2-1), the compound represented by the formula (2-2), and the compound represented by the formula (2-3) is an organosilicon which is a target product. It can be appropriately set depending on the degree of polymerization of each structural unit in the compound.

In the above step, usually, polymerization by an equilibrium reaction between the compound represented by the formula (2-1) and the compound represented by the formula (2-2) occurs, and the compound represented by the formula (2-3) The compounds represented function as so-called end terminators.

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 ion exchange resins. Among these, trifluoromethanesulfonic acid, activated clay, and cation exchange resin are preferable.

The above steps are preferably performed using a solvent. As the 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. Examples of such a solvent include aliphatic hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane and cyclopentyl methyl ether. Examples thereof include system solvents, 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 may be, for example, 30 to 200°C. Also, the reaction time can be, for example, 1 to 72 hours. After the reaction, the desired organosilicon compound can be isolated by separation and purification by a conventionally known method, if necessary.

<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). ) An organosilicon compound having a plurality of crosslinkable groups other than the above-mentioned (A) organosilicon compound (hereinafter, also referred to as “(B) organosilicon compound”), and (C) catalyst. The (B) organosilicon compound contains at least a compound capable of crosslinking with the (A) organosilicon compound. Since the thermosetting resin composition contains the (A) organosilicon compound, the molded product obtained by curing is excellent in crack resistance under a high temperature environment. Further, the obtained molded product has sufficiently high light transmittance and light refractive index. The thermosetting resin composition may further contain other components. Hereinafter, each component constituting the thermosetting resin composition will be described in detail.

((A) Organosilicon compound)
The (A) organosilicon compound is the above-mentioned organosilicon compound (α) or organosilicon compound (β). The (A) organosilicon compound may be one kind or a mixture of two or more kinds.

The lower limit of the content of the (A) organosilicon compound 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 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, in the case where the (A) organosilicon compound has a hydrosilyl group at both ends, by making the content of the (A) organosilicon compound relatively small and the (B) content of the organosilicon compound large, The crack resistance of the obtained molded body tends to be improved.

Further, the upper limit and the lower limit of the content of the (A) organosilicon compound in all the organosilicon compounds in the thermosetting resin composition are also preferably the above values. By adjusting the content of the (A) organosilicon compound in the above range, the mixing ratio with other components and the cross-linking density of the obtained molded article are optimized, and the high temperature of the molded article obtained by curing is improved. The crack resistance under the environment is further improved.

((B) Organosilicon compound)
The (B) organosilicon compound is an organosilicon compound having a plurality of crosslinkable groups (excluding the (A) organosilicon compound). Examples of the crosslinkable group include an alkenyl group such as a vinyl group, an alkynyl group such as an ethynyl group, and a hydrosilyl group. A vinyl group and a hydrosilyl group are preferable. The (B) organosilicon compound may be one kind or a mixture of two or more kinds. The (B) organosilicon compound contains at least one crosslinkable with the (A) organosilicon compound. In the case where 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 where 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 organosilicon compounds (B), examples of the compound having a hydrosilyl group include (B1) organosilicon compounds and (B2) organosilicon compounds described later. 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 later.

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

((B1) Organosilicon compound)
The (B1) organosilicon compound is an organosilicon compound having a hydrosilyl group, a vinyl group and a silsesquioxane structure. Since the organosilicon compound (B1) has a silsesquioxane structure, the heat resistance of the obtained molded article can be further enhanced. Examples of the (B1) organosilicon compound include compounds 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. Each X is 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 is represented by formula (X3). When the average number of groups represented 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 that satisfies 1 to 100.

As R ³ , an alkyl group is preferable, and a methyl group is more preferable.

The above x ₁ is preferably more than r, and more preferably more than 2r. Further, x ₁ is preferably less than 3r. The x ₂ is preferably r or less. It is preferable that x ₃ be greater than 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, x ₂ can be zero. At this time, r becomes 1.

In formulas (X1), (X2) and (X3), * represents 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 that satisfies 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 carbon number as R ⁶ . t is an average value that satisfies 2 to 20.

As R ⁵ , an alkyl group is preferable, and a methyl group is more preferable. The carbon number of 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 (B1) organosilicon compound in the thermosetting resin composition is preferably 10% by mass, more preferably 30% by mass, further preferably 40% by mass, 50% by mass or 65% by mass. In some cases, it is 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. Further, the upper limit and the lower limit of the content of the (B1) organosilicon compound in all the organosilicon compounds in the thermosetting resin composition are also preferably the above values. By adjusting the content of the (B1) organosilicon compound in the above range, the mixing ratio with other components and the crosslinking density of the resulting molded article are optimized, and the high temperature of the molded article obtained by curing is improved. The crack resistance under the environment is further improved.

((B2) Organosilicon compound)
The (B2) 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 that satisfies 1 to 50.

As R ⁸ , an alkyl group is preferable, and a methyl group is more preferable.

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

As a minimum of content of the (B2) organosilicon compound in the thermosetting resin constituent, 0.5 mass% is preferred and 1 mass% is more preferred. On the other hand, as the upper limit of this content, 20 mass% is preferable, 10 mass% is more preferable, and 5 mass% is further preferable. Further, the upper limit and the lower limit of the content of the (B2) organosilicon compound in all the organosilicon compounds in the thermosetting resin composition are also preferably the above values. By adjusting the content of the (B2) organosilicon compound in the above range, the mixing ratio with other components and the cross-linking density of the obtained molded body are optimized, and the high temperature of the molded body obtained by curing is improved. The crack resistance under the environment is further improved.

((B3) Organosilicon compound)
The (B3) 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 that satisfies 1 to 50.

As R ¹⁰ , an alkyl group is preferable, and a methyl group is more preferable. As R ¹¹ , an alkyl group and an aromatic hydrocarbon group are preferable, and a methyl group and a phenyl group are more preferable. As R ¹² , the vinyl group is preferable. As R ¹³ , an alkenyl group is preferable, and a vinyl group is more preferable. As the upper limit of v, 10 is preferred, 5 is more preferred, 3 is more preferred, and 1 is even more preferred.

The lower limit of the content of the (B3) organosilicon compound 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. Further, the upper and lower limits of the content of the (B3) organosilicon compound in all the organosilicon compounds in the thermosetting resin composition are also preferably the above values. (B3) When the content of the organosilicon compound is in the above range, the mixing ratio with other components, the cross-linking density of the resulting molded article are optimized, and the high temperature of the molded article obtained by curing is improved. The crack resistance under the environment is further improved.

((B4) Organosilicon compound)
The (B4) 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. R ^16's 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 that satisfies 1 to 5. k is an average value that satisfies 1 to 50.

As R ¹⁴ , an alkyl group is preferable, and a methyl group is more preferable. As R ¹⁵ , an aromatic hydrocarbon group is preferable, and a phenyl group is more preferable. As R ¹⁶ , a vinyl group is preferable. 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.

As a minimum of content of the (B4) organosilicon compound in the thermosetting resin constituent, 0.5 mass% is preferred and 1 mass% is more preferred. On the other hand, as the upper limit of this content, 10 mass% is preferable, 5 mass% is more preferable, and 3 mass% is further preferable. Further, the upper limit and the lower limit of the content of the (B4) organosilicon compound in all the organosilicon compounds in the thermosetting resin composition are also preferably the above values. (B4) When the content of the organosilicon compound is in the above range, the mixing ratio with other components and the cross-linking density of the obtained molded article are optimized, so that the molded article obtained by curing has a high temperature. The crack resistance under the environment is further improved.

The lower limit of the content of the (B) organosilicon compound in the thermosetting resin composition is preferably 10% by mass, more preferably 30% by mass, further preferably 40% by mass, 60% by mass or 75% by mass. In some cases, it is 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. Further, the upper limit and the lower limit of the content of the (B) organosilicon compound in all the organosilicon compounds in the thermosetting resin composition are also preferably the above values. By adjusting the content of the (B) organosilicon compound in the above range, the mixing ratio with other components and the crosslinking density of the obtained molded article are optimized, and the high temperature of the molded article obtained by curing is improved. The crack resistance under the environment is further improved.

Further, 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. Further, in some cases, a ratio of more than 1 is more preferable. 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 and the vinyl group is within the above range, the crosslinking reaction proceeds more effectively and the heat resistance and the like can be further enhanced.

((C) catalyst)
The (C) catalyst is not particularly limited as long as it is a catalyst that causes a hydrosilylation reaction between the (A) organosilicon compound and the (B) 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. When the content of the catalyst (C) is at least the above lower limit, 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, more preferably 10 ppm and 3 ppm. By setting the content of the catalyst (C) to the upper limit or less, it is possible to further improve the crack resistance and the light transmittance of the obtained molded product.

((D) Adhesion imparting agent)
The thermosetting resin composition preferably further contains (D) an adhesion promoter. The (D) adhesion promoter is preferably an organosilicon compound having a hydrosilyl group and an epoxy group, and more preferably an alkoxysilyl group. Such a compound is capable of undergoing a cross-linking reaction with other components in the thermosetting resin composition while being capable of undergoing a binding reaction with components such as a substrate on which the thermosetting resin composition is laminated. It is possible to improve the adhesiveness of the molded body. Further, the adhesiveness imparting agent (D) more preferably has a silsesquioxane structure from the viewpoint of heat resistance and the like. Examples of such a suitable adhesion-imparting agent (D) include compounds 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. Each Z is 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 , then 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 that satisfies 1 to 100.

As R ¹⁸ , the alkyl group is preferable, and the methyl group is more preferable. 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. Preferably. The lower limit of w may be 3, or may be 5. The upper limit of w may be 30 or 15.

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

In formula (Z2), each R ¹⁹ is 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 that satisfies 1 to 20. As R ¹⁹ , the alkyl group is preferable, and the methyl group is more preferable.

In formula (Z41), R ^20's are each independently a methyl group, an ethyl group, a butyl group or an isopropyl group. As R ²⁰ , the methyl group is preferable.

The lower limit of the content of the (D) adhesion-imparting agent in the thermosetting resin composition is preferably 0.1% by mass, more preferably 1% by mass. When the content of the (D) adhesion-imparting agent is at least the above lower limit, sufficient adhesion can be imparted. 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 to the above upper limit or less, the mixing ratio with other components, the cross-linking density of the obtained molded product are optimized, and the like. The crack resistance under high temperature environment is further improved. Moreover, when the (D) adhesion-imparting agent is an organosilicon compound, the upper and lower limits of the content of the (D) adhesion-imparting agent in the total organosilicon compound in the thermosetting resin composition are also the above values. Preferably.

((E) Phosphor or white pigment)
The thermosetting resin composition preferably further contains (E) a phosphor or a white pigment. The (E) phosphor or the white pigment is usually dispersed and contained in the thermosetting resin composition. When the said thermosetting resin composition further contains (E) fluorescent substance or a white pigment, the said thermosetting resin composition can be used more suitably as a sealing material etc. of an optical semiconductor element.

Examples of the phosphors include inorganic phosphors such as YAG phosphors, TAG phosphors, silicate phosphors, and organic phosphors such as allylsulfoamide/melamine formaldehyde co-condensation dyes and perylene phosphors. it can.

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

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

(Other ingredients)
The thermosetting resin composition may contain components other than the components (A) to (E) described above. Examples of other components include a filler, a flame retardant, an ion adsorbent, an antioxidant, a curing retarder, a curing inhibitor, and an ultraviolet absorber.

The contents of the components other than the above components (A) to (E) can be appropriately set depending on the application and the like. On the other hand, it may be preferable that the amounts of these other components are small. The upper limit of the content of components other than the 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 the components other than the 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 (A) organosilicon compound is usually liquid, it can exhibit good fluidity without using a solvent. Further, by having a composition that does not substantially contain a volatile component such as a solvent, it can be more suitably used as a sealing material or the like for an optical semiconductor element. As a maximum of content of a solvent or a volatile ingredient in the thermosetting resin constituent concerned, 1 mass% is preferred, 0.1 mass% is more preferred, and 0.01 mass% is more preferred.

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

(Use)
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 forming material such as an optical lens, and other adhesives. .. Among them, the molded product obtained by curing is excellent in crack resistance under a high temperature environment, and may have good light transmittance and photorefractive property, and thus is particularly suitable as a sealing material for an optical semiconductor element. Can be used.

<Molded body>
The molded body according to one embodiment of the present invention is a molded body obtained by curing the thermosetting resin composition. That is, the molded product 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, and the like, and among these, a sealing material for an optical semiconductor element is preferable.

The molded body 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. The heating time may be, for example, 1 to 24 hours.

The optical refractive index of the molded body is preferably 1.4 or more, more preferably 1.48 or more, and further preferably 1.50 or more. When it has such a high refractive index, it is excellent in the extraction efficiency of the light from an optical-semiconductor element, and becomes more useful as a sealing material of an optical-semiconductor element. 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 elements. 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 when the optical semiconductor element is an LED, for example, an optical semiconductor element formed by laminating a semiconductor material on a substrate can be used. 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 encapsulating an optical semiconductor element with the thermosetting resin composition according to one embodiment of the present invention. This encapsulation method is, for example, (1) a method of injecting the thermosetting resin composition into a mold frame in advance, immersing a lead frame or the like having an optical semiconductor element fixed therein, and then thermosetting the same. 2) A method of injecting the thermosetting resin composition into a mold into which an optical semiconductor element is inserted and thermosetting the same is mentioned. Examples of the method of injecting the thermosetting resin composition include injection with a dispenser, transfer molding, and injection molding. Further, as another sealing method, for example, a method in which the thermosetting resin composition is dropped on the optical semiconductor element, printed or applied, and then heat-cured may be used.

In the optical semiconductor device, the thermosetting resin composition according to the embodiment of the present invention is used as a sealing material, and thus the sealing material has excellent crack resistance in a high temperature environment. Therefore, the optical semiconductor device is excellent in 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 of liquid crystal display devices, LED displays, and the like.

The present invention will be described in more detail based on examples. The present invention is not limited to the examples below. In the chemical formula, “Me” represents a methyl group, “Vi” represents a vinyl group, and “Ph” represents a phenyl group. The analysis method of the synthesized organosilicon compound is shown below.

<Number average molecular weight and weight average molecular weight>
Using a high performance liquid chromatograph system CO-2065plus manufactured by JASCO Corporation, 20 μL of a THF solution having a sample concentration of 1% by mass was used as an analysis sample, and measurement was performed by the GPC method under the following conditions. By converting into polystyrene, the number average molecular weight and the weight average molecular weight were obtained.
Column: Shodex KF804L [Showa Denko KK] (two connected in series)
Column temperature: 40°C
Detector: RI
Eluent: THF
Eluent flow rate: 1.0 mL/min

<NMR (nuclear magnetic resonance spectrum)>
Using the NMR measuring apparatus JEOL Co., Ltd. 400MH _Z, the measurement sample was measured and dissolved in deuterated acetone (manufactured by Wako Pure Chemical Industries, Ltd.). Further, the average polysiloxane chain length (n in the above formula (1)) introduced into the synthesized organosilicon compound was determined from the ¹ H-NMR or ²⁹ Si-NMR integration ratio.

<Viscosity>
The viscosity was measured using a TV-22 type 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) 100.0 g of silsesquioxane derivative (DD-4OH) and phenyltrichlorosilane 49 were placed in a reaction vessel equipped with a thermometer and a dropping funnel. 0.4 g and 660 mL of THF were charged. After cooling to 5° C., 42.6 g of triethylamine was added, and the mixture was 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, it was washed with water until the organic phase became neutral. The solvent was distilled off under reduced pressure, the obtained solid was dispersed in 140 mL of methanol, and then filtered under reduced pressure. It was dried 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 based on 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 and the like used in the synthesis of the following organosilicon compounds are shown below.

<Compound represented by the above formula (2-2)>
Octamethylcyclotetrasiloxane (D4: Momentive Performance Materials, Inc.)
(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.)
(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) 20.0 g of silsesquioxane derivative (DD(Ph)-OH), octamethylcyclotetrasiloxane (in a reaction vessel equipped with a thermometer and a reflux tube) 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., 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=21.2 Pa·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) 30.0 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane (in a reaction vessel equipped with a thermometer and a reflux tube). 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., 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=6.83 Pa·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) 30.0 g of silsesquioxane derivative (DD(Ph)-OH) and octamethylcyclotetrasiloxane (in a reaction vessel equipped with a thermometer and a reflux tube). D4) 25.66 g, 1,3-divinyltetramethyldisiloxane (DVDS) 5.11 g, cation exchange resin RCP-160M1.74 g, and toluene 60.7 g were charged. The temperature was raised stepwise from 40° C. to 130° C., 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=98.7 Pa·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) 30.0 g of silsesquioxane derivative (DD(Ph)-OH), octamethylcyclotetrasiloxane (in a reaction vessel equipped with a thermometer and a reflux tube) 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., the mixture was aged for a total of 29 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=372 Pa·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) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Ph)-OH), 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., 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=384 Pa·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) 30.0 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane (in a reaction vessel equipped with a thermometer and a reflux tube). 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 21 hours in total, 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=7.40 Pa·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), 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=6.14 Pa·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) 30.0 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane (in a reaction vessel equipped with a thermometer and a reflux tube). 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., aged for 13 hours in total, 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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, 70.91 H), 5.5 to 6.2 (m, 4.64 H), 7.1 ~ 7.9 (m, 40H)
Viscosity = 3.55 Pa·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), 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. An equal weight of methanol was added to this, and after shaking, the methanol phase was removed by decantation. The remaining methanol was distilled off under the conditions of 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=203 Pa·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 10 Synthesis of Organosilicon Compound (A-10) 100.6 g of silsesquioxane derivative (DD(Me)-OH) and octamethylcyclotetrasiloxane (in a reaction vessel equipped with a thermometer and a reflux tube). D4) 85.7 g, 1,3-divinyltetramethyldisiloxane (DVDS) 26.8 g, cation exchange resin RCP-160M 9.59 g, toluene 212.7 g, and pure water 2.0 g were charged. The temperature was raised stepwise from 40° C. to 130° C., aged for a total of 17 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 under the conditions of 120° C. and 0.3 kPaA to obtain 150.4 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-10) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.5 (m, 207.54H), 5.6 to 6.2 (m, 6.00H) 7.0. 7.9 (m, 103.77H)
Viscosity=28.4 Pas
Number average molecular weight: Mn=4464
Weight average molecular weight: Mw=8214
Degree of polymerization of structural unit (i)=3.91
Degree of polymerization of structural unit (ii)=48.17

Example 11 Synthesis of Organosilicon Compound (A-11) In a reaction vessel equipped with a thermometer and a reflux tube, 30.0 g of silsesquioxane derivative (DD(Me)-OH), octamethyltetracyclosiloxane ( D4) 25.7 g, 1,3-divinyltetramethyldisiloxane (DVDS) 7.97 g, cation exchange resin RCP-160M 1.96 g, toluene 63.7 g, and pure water 0.4 g were charged. The temperature was raised to the reflux temperature, the mixture was aged for a total of 9 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 under the conditions of 120° C. and 0.3 kPaA to obtain 44.9 g of a cloudy viscous liquid.
The obtained cloudy viscous liquid is judged to be an organosilicon compound (A-11) having the following structure from the following analysis results.
(result of analysis)
¹ H-NMR (solvent: heavy acetone): δ (ppm): -0.2 to 0.2 (m, 321.15H), 5.6 to 6.2 (m, 6.00H) 6.9 to 7.9 (m, 167.58H)
Viscosity=86.7 Pas
Number average molecular weight: Mn=5024
Weight average molecular weight: Mw=10043
Degree of polymerization of structural unit (i)=4.89
Degree of polymerization of structural unit (ii)=57.58

[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, tetramethyldisiloxane (M'M') 6.3 g, ion exchange resin RCP160M 1.8 g, and toluene 63 g 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 to room temperature, the ion exchange resin was filtered off, and a liquid separation operation using water was performed. Then, toluene and unreacted low-boiling components were removed under reduced pressure of 120° C. and 1 mmHg to obtain 43 g of a cloudy liquid. The cloudy liquid was washed with 100 g of isopropyl alcohol and the solvent was distilled off under reduced pressure at 60° C. to obtain 22 g of a slightly cloudy liquid.
The obtained slightly cloudy liquid 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=474 Pa·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, tetramethyldisiloxane (M′M′) 6.1 g, ion exchange resin RCP160M 3.4 g, and toluene 118 g 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 to room temperature, the ion exchange resin was filtered off, and a liquid separation operation using water was performed. Then, toluene and unreacted low-boiling components were removed under a reduced pressure condition of 120° C. and 1 mmHg to obtain 86 g of a cloudy liquid. This cloudy liquid was washed with 320 g of methanol and then the solvent was distilled off under reduced pressure at 60° C. to obtain 62 g of a slightly cloudy liquid.
The obtained slightly cloudy liquid 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, tetramethyldisiloxane (M'M') 20.5 g, ion exchange resin RCP160M 5.6 g, and toluene 196 g 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 to room temperature, the ion exchange resin was filtered off, and a liquid separation operation using water was performed. Then, toluene and unreacted low-boiling components were removed under a reduced pressure condition of 120° C. and 1 mmHg to obtain 147 g of a white turbid liquid. This cloudy liquid was washed with 270 g of methanol and the solvent was distilled off under reduced pressure at 60° C. to obtain 89 g of a slightly cloudy liquid.
The obtained slightly cloudy liquid 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=2.9 mPa·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) 22.5 g, 1,3-divinyltetramethyldisiloxane (DVDS) 0.94 g, tetramethyltetravinylcyclotetrasiloxane (MVS-H) 7.00 g, cation exchange resin RCP-160M2.47 g, toluene 60.2 g and pure water 0.3 g were charged. After heating to the reflux temperature and refluxing for 2 hours, the mixture 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, 6.0 Si), -67 to -64 (m, 1.8 Si), -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 the degree of polymerization of each structural unit, and does not indicate that each structural unit is a block copolymer in which the structural units are linked in the above order.

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, 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 WO 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)

(A 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 Corporation)

(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.)

(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 vinyl groups, 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 Corporation)

(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: a compound represented by the following formula

(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 organosilicon compound (B4-1) is represented by the following formula: 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (DVDPTS: manufactured by Korea Bio-Gen). ) And 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (DHDPTS: manufactured by Bio-Gen, Korea) were hydrosilylated. Hydrosilylation was performed 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": 3 wt% 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) Adhesiveness 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 31, Comparative Examples 1 and 2] Preparation of Thermosetting Resin Compositions The components described above were uniformly mixed at the compounding ratio (mass %) shown in Table 1, and Examples 15 to 31 and Comparative Example 1 were prepared. Each thermosetting resin composition of -2 was prepared. Table 1 also shows the ratio of the number of moles of vinyl groups to the number of moles of hydrosilyl groups (functional group ratio Vi/SiH) of all components in each thermosetting resin composition. The following evaluations were performed using the obtained thermosetting compositions. The results are shown in Table 1.

<Light transmittance>
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 this. Then, it was cured by heating at 150° C. for 2 hours, and the glass was peeled off to obtain a cured product having a smooth surface of 30 mm×35 mm×4 mm. The light transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer "V-650" manufactured by JASCO Corporation at one location in the center of the cured product.

<Optical refractive index>
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 this. Then, it was cured by heating at 150° C. for 2 hours, and the glass was peeled off to obtain a cured product having a smooth surface of 30 mm×35 mm×4 mm. A test piece (30 mm×10 mm×4 mm) was produced from this cured product according to JIS K7142 (2014). The photorefractive index at one location of the test piece was measured using an Abbe refractometer (“NAR-2T” manufactured by Atago Co., Ltd.) using the D line of a sodium lamp. As the intermediate liquid, 1-bromonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

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

As shown in Table 1, in the case of each of the thermosetting resin compositions of Examples 15 to 31, the time in which cracks occurred in the crack resistance test at 250°C exceeded 500 hours. In addition, the initial performance regarding the light transmittance and the light 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 when cracks occurred was 500 hours or less. From this, it is clear that the organosilicon compounds obtained in Examples 1 to 14 are substances that improve the crack resistance of the molded products obtained by thermosetting.

The organosilicon compound and the thermosetting resin composition containing the same of the present invention can be used as a sealing material for optical semiconductor elements, a sealing material for other semiconductor elements, an insulating film, a sealing material, an optical lens and the like.

Claims (14)

Structural unit (i) represented by the following formula (i), and structural unit (ii) represented by the following formula (ii)
Including,
An organosilicon compound having a vinyl group or a hydrosilyl group at both ends of a molecular chain,
Weight average molecular weight of 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,
An organosilicon compound in which the degree of polymerization of the structural unit (ii) is 4 or more and 200 or less.

(In the formula (i), each R ¹ is independently a hydrocarbon group having 1 to 8 carbon atoms.
In formula (ii), R< ² > is respectively independently a C1-C8 hydrocarbon group. ) 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 a hydrocarbon group having 1 to 8 carbon atoms. R ² is each. Independently, it is a hydrocarbon group having 1 to 8 carbon atoms, m is an average value satisfying 1 to 5, and n is an average value satisfying 2 to 50.) The organosilicon compound according to claim 1 or ^{2, wherein} R ² 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, 2 or 3, further comprising:

(In the formula (2-1), ^{R 1} is each independently a hydrocarbon group having 1 to 8 carbon atoms.
In formula (2-2), R _a ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. p is an integer of 3-8.
In formula (2-3), R ⁰ is each independently a vinyl group or a hydrogen atom. R _b ² is each independently a hydrocarbon group having 1 to 8 carbon atoms. q is an average value that satisfies 0 to 50. ) (A) The organosilicon compound according to claim 1, claim 2 or claim 3,
(B) contains an organosilicon compound having a plurality of crosslinkable groups other than (A) the organosilicon compound, and (C) a catalyst,
The thermosetting resin composition in which the organosilicon compound (B) contains at least a compound capable of crosslinking with the organosilicon compound (A). Content of the said (A) organosilicon compound is 1 mass% or more and 90 mass% or less, The thermosetting resin composition of Claim 5. The thermosetting resin composition according to claim 5 or 6, wherein the organosilicon compound (B) contains a compound represented by the following formula (3).

(In the formula (3), R ^3's each independently represent an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. X's each independently represent the following formula (X1) or formula (X2 Or the average number of the group represented by the formula (X1) per molecule of the compound represented by the formula (3) is x ₁ , represented by the formula (X2). Where x ₂ is the average number of groups represented by the formula (X3) and x ₃ is the average number of groups represented by the formula (X3), x ₁ +2x ₂ +x ₃ =4r, 0<x ₁ <4r, 0≦x ₂ <2r , And 0<x ₃ <4r, where r is an average value that satisfies 1 to 100.)

(In the formulas (X1), (X2) and (X3), * represents 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 that satisfies 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 carbon number as R ⁶ . t is an average value that satisfies 2 to 20. ) The thermosetting resin composition according to any one of claims 5 to 7, wherein the (B) organosilicon compound contains a compound represented by the following formula (4).

(In the 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. , 1 to 50 are average values.) The thermosetting resin composition according to any one of claims 5 to 8, wherein the organosilicon compound (B) contains a compound represented by the following formula (5).

(In the formula ^{(5), R 10} and ^{R 11} are each independently, ^{.R 12} is an alkyl group, a cyclopentyl group, a cyclohexyl group or an aromatic hydrocarbon group having 6 to 12 carbon atoms having 1 to 4 carbon atoms 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, and v is an average value satisfying 1 to 50.) The thermosetting resin composition according to any one of claims 5 to 9, wherein the organosilicon compound (B) contains a compound represented by the following formula (6).

(In the formula ^{(6), R 14} and ^{R 15} are each independently, ^{.R 16} is an alkyl group, a cyclopentyl group, a cyclohexyl group or an aromatic hydrocarbon group having 6 to 12 carbon atoms having 1 to 4 carbon atoms 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, and k is It is an average value that satisfies 1 to 50.) (D) further contains an adhesion-imparting agent,
The thermosetting resin composition according to any one of claims 5 to 10, wherein the adhesion-imparting agent (D) contains a compound represented by the following formula (7).

(In the formula (7), R ¹⁸ is independently an alkyl group having 1 to 4 carbon atoms, a cyclopentyl group, or a cyclohexyl group. Z is independently the following formula (Z1) or formula (Z2 ), a formula (Z31), a formula (Z32), a formula (Z33) or a formula (Z41), represented by the formula (Z1) per molecule of the compound represented by the 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 the 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 are satisfied, where w is an average value that satisfies 1 to 100.)

(In formulas (Z1), (Z2), (Z31), (Z32), (Z33) and (Z41), * represents a binding site.
In formula (Z2), each R ¹⁹ is 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 that satisfies 1 to 20.
In formula (Z41), R ^20's are each independently a methyl group, an ethyl group, a butyl group or an isopropyl group. ) The thermosetting resin composition according to claim 5, further comprising (E) a phosphor or a white pigment. A molded body obtained by curing the thermosetting resin composition according to any one of claims 5 to 12. An optical semiconductor device comprising an optical semiconductor element and the molded body according to claim 13 which seals the optical semiconductor element.