JP2020094093A - Transparent thermosetting resin composition, cured product of the same, encapsulating agent for optical element using the same, and optical semiconductor device - Google Patents

Abstract

Kind Code: A1 A transparent thermosetting resin composition that suppresses warpage during curing and suppresses cracks in a thermal shock test while maintaining the transparency of the cured product is provided. A compound (A) containing a cyclic ether group and having an average of two or more hydrosilyl groups per molecule, a compound (B) having an average of two or more alkenyl groups per molecule, and a hydrosilylation catalyst Transparent heat comprising (C) and an inorganic filler (D) having a refractive index difference of 30% or less from the cured product obtained by curing the above compound (A), compound (B), and hydrosilylation catalyst (C). A curable resin composition. [Selection figure] None

Description

By monodispersing the inorganic filler having a small refractive index difference with the resin composition, the effect of lowering the linear expansion coefficient and the effect of improving the resin strength can be obtained while maintaining the transparency of the resin composition.

A light emitting device using a light emitting diode (LED) has features such as long life, low power consumption, impact resistance, high-speed response, lightness, thinness, and miniaturization, and is used in liquid crystal displays, mobile phones, information terminals, etc. Back-lighting, vehicle-mounted lighting, indoor/outdoor advertising, indoor/outdoor lighting, etc. are rapidly expanding in various fields. In addition, diversification of applications is required, and further higher efficiency is required, and in particular, for display applications, research and development for improving color reproducibility and expanding contrast ratio are being actively conducted.

In the backlight of the display, there are a pattern in which LEDs are arranged directly below the display (direct type), and a pattern in which LEDs are arranged at an edge part of the display and combined with a diffusion plate to make the entire display emit light (edge type). The direct contrast type can obtain a wide contrast ratio, but in recent years, in order to further increase the contrast ratio, research and development of a technique called miniLED, in which a small light emitting element is mounted on a substrate and the whole is sealed with resin, has been actively conducted. Is being advanced to. In the miniLED, the area of the display that emits light for each light-emitting element is narrowed, so that the contrast of the image displayed on the display can be set finely, and a bright and dark image can be obtained.

On the other hand, since small light emitting elements are mounted at high density, the distance between the light emitting elements is short, and higher resistance to thermal shock during the reliability evaluation test of the LED is required. Further, when the sealant is applied onto the substrate and cured, the contraction of the sealant during curing may cause the substrate to warp. Therefore, until now, in order to improve the thermal shock resistance and suppress the warp of the substrate, an attempt has been made to solve the problem by adding an inorganic filler. (Patent Documents 1 and 2)

JP, 2008-44067, A Patent No. 5923331

When an inorganic filler is added to suppress the warp of the substrate, the transparency of the resin is impaired due to the difference in refractive index and the dispersibility of the filler, and the light extraction efficiency from the light emitting element of the optical semiconductor device is reduced.

As a result of intensive studies, the present inventors have combined a compound containing a cyclic ether group with an inorganic filler having a refractive index difference of 30% or less, and have a high affinity with the cyclic ether group filler to disperse the inorganic filler. It is possible to obtain the effect of lowering the linear expansion coefficient and the effect of improving the resin strength while suppressing the warp of the substrate and improving the thermal shock resistance while maintaining the transparency of the resin composition. The inventors have found out that, and have reached the present invention.

That is, the present invention includes a compound (A) containing a cyclic ether group and having an average of 2 or more hydrosilyl groups in one molecule, a compound (B) having an average of 2 or more alkenyl groups in a molecule, and a hydrosilyl group. Thermosetting resin composition comprising an inorganic filler (D) having a refractive index difference of 30% or less between the oxidization catalyst (C) and the cured product obtained by curing the above (A), (B) and (C). It is a thing.

The cyclic ether group contained in the compound (A) is at least one selected from the group consisting of an epoxy group, an alicyclic epoxy group, a glycidyl group and an oxetane group.

The compound (A) is a compound obtained by reacting a compound (α1) having an alkenyl group with a compound (α2) having at least two hydrosilyl groups in one molecule in the presence of a hydrosilylation catalyst. The compound (A) is a compound having a structure derived from a cyclic ether compound (α3) having one alkenyl group in one molecule, and at least one of the following two compounds (A1 or A2) Is.

(A1): a compound obtained by reacting the polysiloxane compound (α1-1) having an alkenyl group with the above (α2) in the presence of a hydrosilylation catalyst, wherein the compound (A1) is the above (A1). A compound having a structure derived from α3) is preferable.

(A2): by reacting the above-mentioned (α2) with an organic compound (α1-2) having a heterocyclic skeleton having at least one polar group in the ring skeleton in one molecule in the presence of a hydrosilylation catalyst. A compound obtained, which has a structure derived from the above (α3).

The compound (B) is at least one of the following three components (B1) to (B3). (B1): Polysiloxane having two or more alkenyl groups in one molecule, (B2): Heterocyclic skeleton having two or more alkenyl groups in one molecule and having at least one polar group in the ring skeleton (B3): a compound having two or more alkenyl groups in one molecule obtained by reacting (B3): (B1) and/or (B2) with the component (α2) in the presence of a hydrosilylation catalyst.

At least one of the compound (A) and the compound (B) is preferably a compound containing a structure derived from an organic compound having a heterocyclic skeleton having at least one polar group in the ring skeleton in one molecule. ..

The above-mentioned (α1-1) is preferably an alkenyl group-containing polyhedral polysiloxane compound, and the above-mentioned (α1-2) is preferably a compound having an isocyanuric skeleton or a glycoluril skeleton.

The above (α2) is preferably a cyclic siloxane and/or a linear siloxane and/or a branched siloxane having a hydrosilyl group and/or a silphenylene compound, and the above (α3) has a molecular weight of less than 1,000. preferable.

Another aspect of the present invention is a cured product obtained by using the transparent thermosetting resin composition, a sealant for optical elements, and an optical semiconductor device.

By pre-adding an inorganic filler having a refractive index difference of 30% or less with the sealant after curing to the sealant cured by the hydrosilylation reaction, while maintaining the transparency of the cured product, The effect of suppressing warpage during curing and the effect of suppressing cracks during a thermal shock test can be obtained.

Hereinafter, the present invention will be described in detail.

<Curable resin composition>
The curable resin composition in the present invention comprises the above compound (A), compound (B), hydrosilylation catalyst (C) and inorganic filler (D). From the viewpoint of resin strength, at least one of the compounds (A) and (B) is a compound containing a structure derived from an organic compound having a heterocyclic structure having at least one polar group in the ring skeleton. desirable. Both the compounds (A) and (B) may be compounds containing a structure derived from an organic compound having a heterocyclic structure having one polar group in the ring skeleton, but the compounds having heat resistance and light resistance may be used. From the viewpoint, one of them is preferably a polysiloxane compound.

The hydrosilylation curable resin composition used in the semiconductor light emitting device of the present invention can be obtained by mixing a phosphor, a curing retarder, or the like, if necessary.

<Compound (A) containing a cyclic ether group and having an average of two or more SiH groups in one molecule>
The compound (A) used in the resin composition of the present invention comprises a compound (α1) having an alkenyl group and a polysiloxane compound (α2) having at least two hydrosilyl groups in one molecule in the presence of a hydrosilylation catalyst. The compound (A) is characterized by having a structure derived from a cyclic ether compound (α3) having one alkenyl group in one molecule.

The compound (A) is obtained by reacting a polysiloxane compound (α1-1) having an alkenyl group with a polysiloxane compound (α2) having at least a hydrosilyl group in one molecule in the presence of a hydrosilylation catalyst. The compound (A) obtained is a modified polysiloxane-based compound (A1) having a structure derived from a cyclic ether compound (α3) having one alkenyl group in one molecule, or an alkenyl group. However, an organic compound (α1-2) having a heterocyclic skeleton having at least one polar group in the ring skeleton in one molecule and a polysiloxane compound (α2) having at least two hydrosilyl groups in one molecule (α2) ) In the presence of a hydrosilylation catalyst, wherein the compound (A) is a heterocycle having a structure derived from a cyclic ether compound (α3) having one alkenyl group in one molecule. It is a modified body (A2) having a skeleton, and these may be used alone or in combination.

<Polysiloxane-based modified product (A1), modified product having a heterocyclic skeleton (A2)>
The modified polysiloxane compound (A1) and the modified compound (A2) having a heterocyclic skeleton in the present invention have an alkenyl group-containing polysiloxane compound (α1-1) or an alkenyl group in the presence of a hydrosilylation catalyst described later. Obtained by reacting the organic compounds (α1-1) and (α1-2) with the cyclic ether compound (α3) having one alkenyl group in one molecule with the compound (α2) having a hydrosilyl group. ..

The method for obtaining the polysiloxane-based modified product (A1) of the present invention is not particularly limited and various methods can be set. In advance, the (α1-1) component or the (α1-2) component and the (α2) component are reacted with each other. After that, the component (α3) may be reacted, or the component (α2) and the component (α3) may be reacted, and then the component (α1-1) or the component (α1-2) may be reacted. Alternatively, the (α1-1) component or the (α1-2) component and the (α3) component may be allowed to coexist and the (α2) component may be reacted. After the completion of each reaction, the volatile unreacted components may be removed, for example, under reduced pressure and heating conditions and used as a target product or an intermediate for the next step. In order to suppress the production of a compound that does not contain the (α1-1) component or the (α1-2) component, which is the reaction of only the (α3) component and the (α2) component, the (α1-1) component or the (α1-) A method of reacting the component (2) with the component (α2) is preferable.

In the polysiloxane-based modified product (A1) and the modified product having a heterocyclic skeleton thus obtained, even if a part of the alkenyl group of the component (α1-1) or the component (α1-2) used in the reaction remains. good.

The amount of the hydrosilylation catalyst used during the synthesis of the modified polysiloxane (A1) and the modified product (A2) having a heterocyclic skeleton is not particularly limited, but the component (α1-1) or (α1-) used in the reaction is used. It is preferable to use it in the range of 10 ^-1 to 10 ^-10 mol, and more preferably 10 ^-4 to 10 ^-8 mol, per 1 mol of the alkenyl group of the component 2) and the component (α3). Good. When the addition amount of the hydrosilylation catalyst is large, depending on the type of the hydrosilylation catalyst, it may absorb light having a short wavelength, which may cause coloration or reduce the light resistance of the obtained cured product. The cured product may foam. Further, if the amount of the hydrosilylation catalyst is small, the reaction may not proceed and the desired product may not be obtained.

The reaction temperature of the hydrosilylation reaction is preferably 30 to 400°C, more preferably 40 to 250°C, and further preferably 45 to 140°C. If the temperature is too low, the reaction will not proceed sufficiently, and if the temperature is too high, gelation may occur and the handling property may be deteriorated.

The polysiloxane-based modified product (A1) and the modified product (A2) having a heterocyclic skeleton thus obtained are reacted with compounds having various alkenyl groups because a hydrosilyl group is introduced into the molecule. It becomes possible. Specifically, a cured product can be obtained by reacting with a compound (B) having two or more alkenyl groups in one molecule described later.

Further, the modified polysiloxane (A1) and the modified product (A2) having a heterocyclic skeleton in the present invention can be liquid at a temperature of 20°C. The liquid form is preferable because it is excellent in handleability.

The polysiloxane-based modified product (A1) and the modified product (A2) having a heterocyclic skeleton thus obtained are added with the components (α1-1), (α1-2), (α2) and (α3). The viscosity can be controlled by controlling the amount, the reaction sequence, the reaction time, the reaction temperature and the like. It is also possible to adjust the viscosity of the resin composition in the present invention by controlling the viscosity of the modified polysiloxane (A1) and the modified product (A2) having a heterocyclic skeleton. The viscosity is not particularly limited, but when it is liquid at a temperature of 20° C., the viscosity is preferably 0.01 Pa·s to 500 Pa·s, more preferably 1 Pa·s to 300 Pa·s. If the viscosity is too low, the viscosity of the resin composition of the present invention may be low, and the resin composition may easily flow out from the substrate. If the viscosity is too high, the handling property may be deteriorated.

Further, the modified polysiloxane (A1) and the modified product (A2) having a heterocyclic skeleton have at least 3 in the molecule from the viewpoint of strength and hardness of the obtained cured product, and further heat resistance and light resistance. It is preferable to have 4 hydrosilyl groups.

<Polysiloxane Compound (α1-1) Having Alkenyl Group>
Examples of the alkenyl group-containing polysiloxane compound (α1-1) include linear polysiloxane, cyclic polysiloxane, and polyhedral polysiloxane described below.

Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer with methylphenylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane end-capped with dimethylvinylsilyl group, end-capped with dimethylvinylsilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular end include polysiloxanes whose ends are blocked with a dimethylvinylsilyl group, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxanes having at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-Trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1, 3,5-Trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1 , 3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.

The polyhedral polysiloxane having an alkenyl group in the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. Specifically, for example, the following formula [R ¹ SiO _3/2 ] _x [R ² SiO _3/2 ] _y
(X+y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ¹ is an alkenyl group or a group having an alkenyl group; R ² is any organic group, or other An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by (a group linked to the polyhedral skeleton polysiloxane) can be preferably used, and further, a compound represented by the formula [Z1 R ³ ₂ SiO- SiO _3/2 ] _a1 [R ⁴ ₃ SiO-SiO _3/2 ] _a2
(A1 + a2 is an integer of 6 to 24, a1 is an integer of 1 or more, a2 is 0 or an integer of 1 or more; Z1 is alkenyl group; ^{R 3} is an alkyl group or an aryl group; ^{R 4} is a hydrogen atom, an alkyl group, an aryl group , Or a group linked to another polyhedral skeleton polysiloxane)
An alkenyl group-containing polyhedral polysiloxane compound composed of siloxane units represented by is exemplified as a preferable example.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group and the like, but a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ³ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group, and examples of the aryl group include an aryl group such as a phenyl group and a tolyl group. To be done. As R ³ in the present invention, a methyl group is preferable from the viewpoint of heat resistance and light resistance.

R ⁴ is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group, and examples of the aryl group include an aryl group such as a phenyl group and a tolyl group. To be done. From the viewpoint of heat resistance and light resistance, R ⁴ in the present invention is preferably a methyl group.

a1 is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more in view of handleability of the compound and physical properties of the cured product obtained. Further, a2 is not particularly limited as long as it is an integer of 0 or 1 or more.

The sum of a1 and a2 (=a1+a2) is an integer of 6 to 24, but from the viewpoint of the stability of the compound and the stability of the obtained cured product, it is 6 to 12, and further 6 to 10. preferable.

The synthesis method is not particularly limited, and a known method can be used for synthesis. As a synthesis method, for example, a silane of R ⁵ SiX ^a3 ₃ (wherein R ⁵ represents R ¹ and R ² described above, and X ^a3 represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by a hydrolytic condensation reaction of a compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by a hydrolytic condensation reaction of R ⁵ SiX ^a3 ₃ , the same or different trifunctional silane compound is further reacted to ring-close the polyhedral polyhedron. Methods for synthesizing structural polysiloxanes are also known.

In addition, for example, a method of hydrolyzing and condensing a tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide can be used. In the present synthetic method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is reacted with a silylating agent such as an alkenyl group-containing silyl chloride. Thus, it becomes possible to obtain a polyhedral polysiloxane in which Si atoms forming a polyhedral structure and an alkenyl group are bonded via a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husks instead of tetraalkoxysilane.

<Organic compound having an alkenyl group (α1-2)>
The organic compound (α1-2) having an alkenyl group is not particularly limited as long as it is a compound having two or more alkenyl groups in one molecule, but it is an organic compound represented by the general formula (1) or (2). Examples of the compound include organic compounds having an alkenyl group in one molecule.

(In the formula, R ^{6 to} R ⁸ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ^{6 to} R ⁸ may be different or the same. R ^{6 to} R ⁸ At least two of them are alkenyl groups.)

(In formula, R< ⁹ >-R< ¹² > represents a C1-C50 monovalent organic group or a hydrogen atom, R< ⁹ >-R< ¹² > may be different or may be the same. R< ⁹ >-R< ¹² >. At least two of them are alkenyl groups.)
The component (α1-2) preferably has a number average molecular weight of less than 900 from the viewpoint of compatibility of the resulting curable resin composition. Further, the component (α1-2) may have a functional group other than an alkenyl group in the skeleton, but from the viewpoint of the balance of heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl is used. It is more preferable to use monomethyl isocyanurate, tetraallyl glycoluril, monomethyltriallyl glycoluril, or dimethyldiallyl glycoluril, and diallyl monomethyl isocyanurate and dimethyldiallyl glycoluril are particularly preferred from the viewpoint of thermal shock resistance. These may be used alone or in combination of two or more. Since the component (α1-2) contains an average of two or more alkenyl groups in one molecule, the resulting cured product has excellent strength, gas barrier properties, heat resistance, light resistance, and the like.

<Compound (α2) having a hydrosilyl group>
The compound (α2) having a hydrosilyl group used in the present invention is not particularly limited as long as it has at least one hydrosilyl group in the molecule, but the transparency, heat resistance and light resistance of the resulting polysiloxane modified product are not limited. From the viewpoint of properties, a siloxane compound having a hydrosilyl group is preferable, and a cyclic siloxane having a hydrosilyl group or a linear polysiloxane is more preferable. From the viewpoint of gas barrier properties, cyclic siloxane is preferable.

Examples of the linear polysiloxane having a hydrosilyl group include a copolymer of a dimethylsiloxane unit with a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymerization of a diphenylsiloxane unit with a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxanes end-capped with dimethylhydrogensilyl groups, polyendcapped with dimethylhydrogensilyl groups. Examples thereof include diphenylsiloxane and polymethylphenylsiloxane whose end is blocked with a dimethylhydrogensilyl group.

Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1-propyl-3,5,7-trihydrogen-1. ,3,5,7-Tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen -1,3,5-Trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. The cyclic siloxane in the present invention is specifically, for example, 1,3,5,7-tetrahydro, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, etc. of the obtained cured product. Gen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.

The compound having a hydrosilyl group, which is the component (α2), may be used alone or in combination of two or more kinds.

<Cyclic ether compound (α3) having one alkenyl group in one molecule>
The cyclic ether compound (α3) is not particularly limited as long as it has one alkenyl group and at least one cyclic ether group in one molecule, but from the viewpoint of industrial utilization, the cyclic ether group is an epoxy group. It is preferably any one of an alicyclic epoxy group, a glycidyl group and an oxetane group. Specific examples thereof include vinyl cyclohexene oxide, 2-vinyl oxetane, and allyl glycidyl ether, but the present invention is not limited thereto, but preferably has a high affinity with an inorganic filler and is a three-membered cyclic ether. It is preferable to use a compound from the viewpoint of transparency of the curable resin composition. The above compounds may be used alone or in admixture of two or more.

<Compound (B) having an average of two or more alkenyl groups in one molecule>
The compound (B) having an average of 2 or more alkenyl groups in one molecule used in the present invention is, for example, a polysiloxane (B1) having an average of 2 or more alkenyl groups in one molecule or an alkenyl group in one molecule. An organic compound (B2) having a heterocyclic structure having at least one polar group in the ring skeleton, or a compound (B1) and/or a compound (B2) with a (α2) component and hydrosilylation Examples thereof include a compound (B3) having two or more alkenyl groups in one molecule which is reacted in the presence of a catalyst. The compound (B1), the compound (B2) and the compound (B3) may be used in combination.

The addition amount of the compound (B) can be variously set, but 0.3 to 5, preferably 0.5 to 3, hydrosilyl groups contained in the compound (A) per one alkenyl group of the compound (B). It is desirable to add it in a ratio that If the proportion of alkenyl groups is low, poor appearance tends to occur due to foaming, and if the proportion of alkenyl groups is high, the physical properties after curing may be adversely affected.

<Polysiloxane (B1) having an average of two or more alkenyl groups in one molecule>
The number of siloxane units of the polysiloxane (B1) having two or more alkenyl groups in one molecule that can be contained in the curable resin composition of the present invention is not particularly limited, but is preferably two or more, and more preferably It is 2 to 10. When the number of siloxane units in one molecule is small, the composition is likely to volatilize, and desired physical properties may not be obtained after curing. In addition, when the number of siloxane units is large, the tackiness of the obtained cured product may be deteriorated and handling as an optical semiconductor device may be difficult.

The polysiloxane having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. Further, in the polysiloxane having two or more alkenyl groups in one molecule having an aryl group, it is preferable that the aryl group is directly bonded to the Si atom from the viewpoint of heat resistance and light resistance. The aryl group may be present on either the side chain or the terminal of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited, and may be, for example, a straight chain, a branched chain, or a partially branched chain. It may have a cyclic structure in addition to the chain structure.

Examples of such an aryl group include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group. Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group Group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxy Examples thereof include a phenyl group, a 3-glycidylphenyl group and a 4-glycidylphenyl group. Of these, a phenyl group is a preferred example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

From the viewpoint of heat resistance and light resistance, the polysiloxane having two or more alkenyl groups in one molecule of the present invention is a linear polysiloxane having two or more alkenyl groups, and two or more alkenyl groups at the molecular end. Preferable examples thereof include polysiloxanes and cyclic siloxanes having two or more alkenyl groups.

Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer with methylphenylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane end-capped with dimethylvinylsilyl group, end-capped with dimethylvinylsilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular end include polysiloxanes whose ends are blocked with a dimethylvinylsilyl group, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxanes having at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-Trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1, 3,5-Trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1 , 3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified. These polysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

<Organic compound (B2)>
The organic compound (B2) having an alkenyl group is not particularly limited as long as it is a compound having two or more alkenyl groups in one molecule, and is an organic compound represented by the general formula (3) or (4). There is an organic compound having an alkenyl group in one molecule.

(In formula, R< ¹³ >-R< ¹⁵ > represents a C1-C50 monovalent organic group or a hydrogen atom, R< ¹³ >-R< ¹⁵ > may be different or the same. Moreover, R< ¹³ >-R< ¹⁵ >. At least two of them are alkenyl groups.)

(In the formula, R ^{16 to} R ¹⁹ represent a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and R ^{16 to} R ¹⁹ may be different or the same. R ^{16 to} R ¹⁹ are also the same. At least two of them are alkenyl groups.)
From the viewpoint of compatibility of the resulting curable resin composition, the compound (B2) preferably has a number average molecular weight of less than 900. Further, the skeleton of the compound (B2) may have a functional group other than an alkenyl group, but from the viewpoint of the balance between heat resistance and light resistance, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate. , Tetraallylglycoluril, monomethyltriallylglycoluril, and dimethyldiallylglycoluril are more preferred, and diallylmonomethylisocyanurate and dimethyldiallylglycoluril are particularly preferred from the viewpoint of thermal shock resistance. These may be used alone or in combination of two or more. Since the compound (B2) contains an average of two or more alkenyl groups in one molecule, the resulting cured product has excellent strength, gas barrier properties, heat resistance, light resistance, and the like.

<Compound (B3) obtained by reacting compound (B1) with compound (B2)>
The compound (B3) that can be contained in the resin composition of the present invention is a compound obtained by reacting the alkenyl group of the compound (B1) and/or the compound (B2) with the hydrosilyl group of the component (α2) in the presence of a hydrosilylation catalyst. is there. A part of the hydrosilyl group of the component (α2) used in the reaction may remain in the obtained compound (B3).

The amount of the hydrosilylation catalyst used during the synthesis of the compound (B3) obtained by the reaction is not particularly limited, but it is 10 per 1 mol of the alkenyl group of the compound (B1) and/or the compound (B2) used in the reaction. ^It is preferable to use it in the range of ⁻¹ to 10 ⁻¹⁰ mol, preferably 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light of a short wavelength, which may cause coloration, decrease the light resistance of the obtained cured product, and foam the cured product. There is a fear. Further, if the amount of the hydrosilylation catalyst is small, the reaction may not proceed and the desired product may not be obtained.

The reaction temperature of the hydrosilylation reaction is preferably 30 to 400°C, more preferably 40 to 250°C, and further preferably 45 to 140°C. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and the handling property may be deteriorated.

<Hydrosilylation catalyst (C)>
The hydrosilylation catalyst that can be used in the present invention can be selected from those commonly known as hydrosilylation catalysts and is not particularly limited. Specifically, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) on which solid platinum is supported; a platinum-vinylsiloxane complex, for example, Pt _n ( _{ViMe 2 SiOSiMe 2 Vi) n,} Pt _{[(MeViSiO) 4] m;} platinum - phosphine complex, _{e.g., Pt (PPh 3) 4,} Pt (PBu 3) 4; platinum - phosphite complex, e.g., Pt [P ( OPh) ₃ ] ₄ , Pt[P(OBu) ₃ ] ₄ (in the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers), Pt(acac) ₂ and also the platinum-hydrocarbon composites described in Ashby et al., US Pat. Nos. 3,159,601 and 3,159,662, and the platinum arcora described in Lamoreaux, et al., US Pat. No. 3,220,972. -A catalyst is also included.

Further, examples of catalysts other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, Rh / Αl 2 O 3, RuCl 3, IrCl 3, FeCl 3, ΑlCl 3, PdCl 2 · 2H 2 O, NiCl 2 , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt(acac) _{2 and the} like are preferable.

<Inorganic filler D>
As the inorganic filler that can be used in the present invention, the difference between the refractive index of the curable resin composition and the refractive index of the inorganic filler is 30% or less, more preferably 20% or less, and further preferably 10% or less. Therefore, it is necessary to select an inorganic substance or a compound containing an inorganic substance. The smaller the difference in refractive index, the easier the transparency of the curable resin composition is, which is preferable.

As the material of the inorganic filler, specifically, quartz, fumed silica, silicic acid anhydride, fused silica, deflagration silica, crystalline silica, amorphous silica, filler formed by condensing alkoxysilane, ultrafine powder amorphous silica, etc. Examples thereof include silica-based inorganic filler, silicon nitride, boron nitride, aluminum nitride, glass, silicone rubber, and silicone resin. These may be used alone or in combination of two or more.

The inorganic filler may be appropriately surface-treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, silane coupling agent, mechanical treatment and the like.

Examples of the shape of the inorganic filler include a spherical shape, a spherical shape, a flaky shape, a flat shape, a needle shape, a fibrous shape, an amorphous shape, a hollow shape, and a shape obtained by crushing a filler of these shapes. It is not limited. The particle size of the inorganic filler is 5 μm or less in average primary particle size in order to prevent light scattering. The thickness is more preferably 0.001 to 1 μm, and further preferably 0.005 to 0.5 μm. The smaller the particle size, the less likely it is that light will be scattered, but the handling property tends to deteriorate when highly filled.

The addition amount of the inorganic filler is not particularly limited, but is 0.0001 to 1000 parts by weight, more preferably 0.001 to 500 parts by weight, and further preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the resin composition. Is. If the added amount is large, the fluidity is lowered, and if the added amount is small, the thermal shock resistance may be lowered and the resin may easily flow out from the substrate at a high temperature during curing.

The means for mixing the inorganic filler is not particularly limited, and specifically, for example, a two-roll or a three-roll, a planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer, and other agitators, Examples thereof include melt kneaders such as plastomill. The mixing of the inorganic filler may be performed at room temperature or with heating, or may be performed under normal pressure or under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.

<Additive of curable resin composition>
A curing retarder may be used to improve the storage stability of the curable resin composition used in the present invention or to adjust the hydrosilylation reactivity in the curing process. As the curing retarder, a known one used in an addition type curable resin composition with a hydrosilylation catalyst can be used, and specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound. , Nitrogen-containing compounds, tin compounds, organic peroxides and the like. These may be used alone or in combination of two or more.

Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1-. Examples include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic anhydride, and maleic acid esters such as dimethyl maleate.

Specific examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphons, triorganophosphites and the like.

Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like.

Specific examples of the nitrogen-containing compound include N,N,N',N'-tetramethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, N,N-dibutyl. -1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N,N',N'-tetraethylethylenediamine, N,N-dibutyl-1,4-butanediamine, 2,2 Examples include'-bipyridine and the like.

Specific examples of the tin compound include stannous halide dihydrate and stannous carboxylate.

Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferable curing retarders.

The addition amount of the curing retarder is not particularly limited, but it is preferably used in the range of 10 ⁻¹ to 10 ³ mol, and more preferably 1 to 100 mol, based on 1 mol of the hydrosilylation catalyst. preferable. Further, these curing retardants may be used alone or in combination of two or more kinds.

An adhesiveness imparting agent can be added to the curable resin composition used in the semiconductor light emitting device of the present invention, if necessary.

The adhesiveness-imparting agent is used, for example, for the purpose of improving the adhesiveness between the polysiloxane composition of the present invention and the substrate, and is not particularly limited as long as it has such an effect. A coupling agent can be exemplified as a preferable example.

The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and at least one hydrolyzable silicon group in the molecule. As a group reactive with an organic group, at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group is preferable from the viewpoint of handleability, and curing From the viewpoints of properties and adhesiveness, an epoxy group, a methacrylic group and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl)ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, and other alkoxysilanes having a methacrylic group or an acryl group Can be mentioned. These may be used alone or in combination of two or more.

The amount of the silane coupling agent added is preferably 0.05 to 30 parts by weight, and more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the curable resin composition. If the added amount is small, the effect of improving the adhesiveness will not be exhibited, and if the added amount is large, the physical properties of the cured product may be adversely affected.

Further, in order to enhance the effect of the adhesion-imparting agent, a known adhesion-promoting agent can be used. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronate compounds, organoaluminum compounds, and organotitanium compounds.

An antioxidant may be used in the curable resin composition used in the semiconductor light emitting device of the invention, if necessary. By using the antioxidant, it is possible to improve the reliability of the obtained optical semiconductor device in various reliability tests such as a heat cycle test, a high temperature storage test, and an electric current test. Examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, amine-based antioxidants and the like.

Examples of the hindered phenol compound include 2,6-di-t-butyl-3-methylphenol (BHT) and tetrakis(methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate. ) Methane, n-octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)-propionate, n-octadecyl 3-(3'-methyl-5'-t-butyl-4' -Hydroxyphenyl)-propionate, n-tetradecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)-propionate, 1,6-hexanediolbis[3-(3,5-di -T-Butyl-4-hydroxyphenyl)-propionate], 1,4-butanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate], 2,2'-methylene -Bis(4-methyl-t-butylphenol), triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)-propionate], tetrakis[methylene-3-(3',5) '-Di-t-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1, 1-Dimethylethyl]2,4,8,10-tetraoxaspiro(5,5)undecane, N,N'-bis-3-(3',5'-di-t-butyl-4'-hydroxyphenyl ) Propionylhexamethylenediamine, N,N'-tetramethylene-bis[3-(3'-methyl-5'-t-butyl-4'-hydroxyphenyl)propionyl]diamine, N,N'-bis[3- (3,5-di-t-butyl-4-hydroxyphenyl)-propionyl]hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3-(N-salicyloyl)amino-1,2,4-triazole, Examples thereof include N,N'-bis[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}ethyl]oxyamide.

The phosphor is one that absorbs the light emitted from the light-emitting element and generates light of different wavelengths, and the phosphor used in the optical semiconductor device of the present invention is not particularly limited, and generally known inorganic phosphors. A body or an organic phosphor can be used. Specifically, for example, YAG-based phosphor, TAG-based phosphor, orthosilicate alkaline earth-based phosphor, α-sialon-based phosphor, β-sialon-based phosphor, CASN-based phosphor, S-CASN-based phosphor. , Nitride and oxynitride-based phosphors, KSF-based phosphors, and the like, but are not limited thereto. These phosphors may be used alone or in combination of two or more in any ratio and combination. The amount of the phosphor used is not particularly limited, and any amount can be used to obtain the emission color required for the optical semiconductor device, but if it is intentionally exemplified, it is preferable in the curable resin composition. Is 0.1% by weight or more, more preferably 1% by weight or more, further preferably 2% by weight or more, preferably 150% by weight or less, more preferably 100% by weight or less. When the amount of the phosphor used is small, wavelength conversion by the phosphor may be insufficient, and the desired emission color may not be obtained, and when the amount of the phosphor used is large, the handling property of the composition may be deteriorated. However, there is a possibility that the utilization efficiency of the phosphor may be lowered due to the optical interference effect.

The method for mixing the phosphor with the curable resin composition is not particularly limited as long as it is a method capable of uniformly mixing the phosphor without damaging the crystal structure of the phosphor, and examples thereof include a mixer and a high-speed disperser. , A homogenizer, a three-roll, a two-roll, a kneader, a bead mill, etc. can be used. Among the above, a planetary agitation mixer, three rolls, two rolls, etc. that generate less heat upon mixing and that contain less metal abrasion particles from the mixer are preferred, among which a planetary agitation mixer may damage the phosphor. It is preferable because it can be mixed while defoaming little. These mixing methods may be performed alone or in combination of two or more.

The curable resin composition used in the semiconductor light emitting device of the present invention is a roll, a Banbury mixer, or a kneader such as a kneader, or a planetary stirring defoaming machine to uniformly mix the above components, and the necessary components may be mixed. You may perform heat processing according to it.

<Viscosity range of curable resin composition>
The viscosity of the curable resin composition used in the present invention is not particularly limited, but is preferably 0.1 Pa·s to 500 Pa·s at a temperature of 23° C., more preferably 0.3 Pa·s to 300 Pa·s. s. When the viscosity of the curable resin composition is low, the phosphor may settle and the chromaticity deviation between the individuals may increase or flow out from a flat substrate. If the viscosity is high, the curability of the curable resin composition may be improved. May worsen.

<Curing of curable resin composition>
When the temperature is applied when the curable resin composition is cured, the temperature is preferably 30 to 400°C, more preferably 50 to 250°C. When the curing temperature is high, the resulting cured product tends to have a poor appearance, and when the curing temperature is low, the curing becomes insufficient. Further, curing may be performed by combining temperature conditions of two or more stages. Specifically, for example, by raising the curing temperature stepwise such as 80° C., 120° C., 150° C., 170° C., 220° C., a good cured product can be obtained, which is preferable.

The curing time can be appropriately selected depending on the curing temperature, the amount of the hydrosilylation catalyst to be used and the amount of the reactive group, and other combinations of the curable resin composition formulation. A good cured product can be obtained by performing the treatment for 24 hours, preferably 1 minute to 12 hours.

<Use of the present invention>
The optical semiconductor device of the present invention can be used in various conventionally known applications. Specifically, for example, a backlight such as a light emitting and receiving device liquid crystal display device, lighting, a sensor light source, a vehicle instrument light source, a signal light, an indicator light, a display device, a light source of a planar light emitter, a display, decoration, various lights, etc. Can be mentioned.

INDUSTRIAL APPLICABILITY The transparent curable resin composition of the present invention is suitable as a sealant for a large and thin semiconductor device such as a substrate because of its low linear expansion coefficient and high thermal shock resistance. Specifically, there is a mini LED which has recently been launched.

Hereinafter, the present invention will be further described based on Examples, but the present invention is not limited thereto.

(Synthesis example 1)
1459 g of tetraethoxysilane was added to 1803 g of a 48% choline aqueous solution (trimethyl-2-hydroxyethylammonium hydroxide aqueous solution), and the mixture was vigorously stirred at room temperature for 2 hours. When heat was generated in the reaction system and a uniform solution was formed, the stirring was slowed down and the reaction was continued for 12 hours. Next, 1400 mL of methanol was added to the solid substance generated in the reaction system to form a uniform solution.

While vigorously stirring a solution of 1149 g of dimethylvinylchlorosilane, 830 g of trimethylsilyl chloride and 1400 mL of hexane in a two-necked flask, the above methanol solution was slowly added dropwise from above. After completion of the dropwise addition, the reaction was carried out for 1 hour, and then the organic layer was extracted and concentrated by removing the solvent such as hexane and methanol using a rotary evaporator to obtain a solid. Next, the resulting solid is washed in methanol with vigorous stirring, and is filtered off to obtain tetrakis (a polyhedral polysiloxane containing an alkenyl machine having 16 Si atoms and 4 vinyl groups). 760 g of vinyldimethylsiloxane)tetrakis(trimethylsiloxy)octasilsesquioxane (Fw=1175.8) was obtained as a white solid (reactant I).

(Synthesis example 2)
30.0 g of reaction product I was dissolved in 60.0 g of toluene, and 23.3 g of allyl glycidyl ether, which is a cyclic ether compound, and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious Metals) 1.46 μL of Pt-VTSC-3X manufactured by Japan) was added. The solution thus obtained was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (30.7 g) and toluene (30.7 g). And reacted at 105° C. for 2 hours. After the completion of the reaction, 2.8 μL of ethynylcyclohexanol and 0.65 μL of dimethyl maleate were added to remove toluene and unreacted components, thereby having a liquid polysiloxane modified product having a cyclic ether group and a hydrosilyl group ( 80.8 g of reaction product II) was obtained.

(Synthesis example 3)
23.3 g of toluene, 23.3 g of allyl glycidyl ether which is a cyclic ether compound, and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 1 0.46 μL was added. The solution thus obtained was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (30.7 g) and toluene (30.7 g). And reacted at 105° C. for 2 hours. After completion of the reaction, 30.0 g of the reaction product I was dissolved in 60.0 g of toluene, slowly added dropwise, and reacted at 105° C. for 2 hours. After the completion of the reaction, 2.8 μL of ethynylcyclohexanol and 0.65 μL of dimethyl maleate were added to remove toluene and unreacted components, thereby having a liquid polysiloxane modified product having a cyclic ether group and a hydrosilyl group ( 80.8 g of reactant III) was obtained.

(Synthesis example 4)
Reactant I (30.0 g) was dissolved in toluene (60.0 g), and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% of platinum, Umicore Precious Metals Japan, Pt-VTSC-3X) 1.46 μL Was added. The solution thus obtained was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (30.7 g) and toluene (30.7 g). And reacted at 105° C. for 2 hours. After the reaction was completed, toluene and unreacted components were removed. 50.4 g of the obtained reaction intermediate was dissolved in 50.4 g of toluene, and a mixed solution of 23.3 g of allyl glycidyl ether, which is a cyclic ether compound, and 23.3 g of toluene was slowly added dropwise to this solution, and the mixture was heated at 105° C. for 2 hours. Reacted for hours. After completion of the reaction, 2.8 μL of ethynylcyclohexanol and 0.65 μL of dimethyl maleate were added to remove toluene and unreacted components, thereby having a liquid polysiloxane modified product having a cyclic ether group and a hydrosilyl group ( 72.8 g of reaction product IV) was obtained.

(Synthesis example 5)
30.0 g of the reaction product I was dissolved in 60.0 g of toluene, and 25.4 g of 1,2-epoxy-4-vinylcyclohexane, which is a cyclic ether compound, and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl containing 3 wt% as platinum). 1.46 μL of a siloxane complex, Pt-VTSC-3X, made by Umicore Precious Metals Japan, was added. The solution thus obtained was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (30.7 g) and toluene (30.7 g). And reacted at 105° C. for 2 hours. After the completion of the reaction, 2.8 μL of ethynylcyclohexanol and 0.65 μL of dimethyl maleate were added to remove toluene and unreacted components, thereby having a liquid polysiloxane modified product having a cyclic ether group and a hydrosilyl group ( 81.1 g of reaction product V) was obtained.

(Synthesis example 6)
30.0 g of reaction product I was dissolved in 60.0 g of toluene, and 17.2 g of 2-vinyl oxetane, which is a cyclic ether compound, and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious). Metals Japan make, Pt-VTSC-3X) 1.46 microliters was added. The solution thus obtained was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (30.7 g) and toluene (30.7 g). And reacted at 105° C. for 2 hours. After the completion of the reaction, 2.8 μL of ethynylcyclohexanol and 0.65 μL of dimethyl maleate were added to remove toluene and unreacted components, thereby having a liquid polysiloxane modified product having a cyclic ether group and a hydrosilyl group ( 72.2 g of reaction product VI) was obtained.

(Synthesis example 7)
5.0 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 60.0 g of toluene, and 23.3 g of allyl glycidyl ether, which is a cyclic ether compound, and platinum vinyl. 1.46 μL of a xylene solution of a siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (30.7 g) and toluene (30.7 g). And reacted at 105° C. for 2 hours. After the completion of the reaction, 2.8 μL of ethynylcyclohexanol and 0.65 μL of dimethyl maleate were added to remove toluene and unreacted components, thereby having a liquid polysiloxane modified product having a cyclic ether group and a hydrosilyl group ( 50.2 g of reaction product VII) was obtained.

(Synthesis example 8)
Dissolving 30.0 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane in 60.0 g of toluene, 45.1 g of allyl glycidyl ether which is a cyclic ether compound, platinum vinyl 4.51 μL of a xylene solution of a siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was slowly added dropwise to a solution of 57.0 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 57.0 g of toluene. And reacted at 105° C. for 2 hours. After the completion of the reaction, 8.60 μL of ethynylcyclohexanol and 2.00 μL of dimethyl maleate were added to remove toluene and unreacted components, thereby having a liquid polysiloxane modified product having a cyclic ether group and a hydrosilyl group ( 122.8 g of reaction product VIII) was obtained.

(Synthesis example 9)
A stirring device, a dropping funnel, and a cooling tube were set in a 5 L four-necked flask. 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in this flask, and heated and stirred in an oil bath at 120°C. A mixed solution of 200 g of triallyl isocyanurate, 687.1 g of allyl glycidyl ether which is a cyclic ether compound, 200 g of toluene, and 1.44 mL of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) was added dropwise over 50 minutes. The obtained solution was heated and stirred as it was for 6 hours, and then unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were removed under reduced pressure, and an organic group having a cyclic ether group and a hydrosilyl group was formed. An inorganic modified product (reactant IX) was obtained.

(Synthesis example 10)
A stirring device, a dropping funnel, and a cooling tube were set in a 5 L four-necked flask. 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in this flask, and heated and stirred in an oil bath at 120°C. A mixed solution of 300 g of diallyl monomethyl isocyanurate, 687.1 g of allyl glycidyl ether that is a cyclic ether compound, 200 g of toluene, and 1.44 mL of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% of platinum) was added dropwise over 50 minutes. The obtained solution was heated and stirred as it was for 6 hours, and then unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were removed under reduced pressure, and an organic group having a cyclic ether group and a hydrosilyl group was formed. An inorganic modified product (reaction product X) was obtained.

(Synthesis example 11)
A stirring device, a dropping funnel, and a cooling tube were set in a 5 L four-necked flask. 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in this flask, and heated and stirred in an oil bath at 120°C. A mixed solution of 180 g of tetraallylglycoluril, 687.1 g of allyl glycidyl ether which is a cyclic ether compound, 200 g of toluene, and 1.44 mL of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% as platinum) was added dropwise over 50 minutes. The resulting solution is heated and stirred as it is for 6 hours, and then unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene are removed under reduced pressure to have a heterocyclic ring having a cyclic ether group and a hydrosilyl group. A modified organic-inorganic modified product (reactant XI) having a skeleton was obtained.

(Synthesis example 12)
A stirring device, a dropping funnel, and a cooling tube were set in a 5 L four-necked flask. To this flask, 500 g of triallyl isocyanurate, 500 g of toluene, and 3.12 mL of a xylene solution of a platinum vinyl siloxane complex (containing 3 wt% of platinum) were placed, and heated and stirred in an oil bath at 120°C. A mixed solution of 374 g of 1,5-dihydrogen-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and 374 g of toluene was added dropwise over 50 minutes. The obtained solution was heated and stirred as it was for 6 hours, and then unreacted materials and toluene were removed under reduced pressure to obtain an organic-inorganic modified product having an alkenyl group having no cyclic ether group (reactant XII).

(Synthesis example 13)
30.0 g of the reaction product I was dissolved in 123.0 g of toluene, and 31.5 g of vinyldiphenylmethylsilane and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt) -VTSC-3X) 1.46 μL was added. The solution thus obtained was slowly added dropwise to a solution of 24.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 24.6 g of toluene. And reacted at 105° C. for 2 hours. After completion of the reaction, 2.8 μl of ethynylcyclohexanol and 0.65 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain a liquid polysiloxane-based modification having a hydrosilyl group and having no cyclic ether group. 80.8 g of a body (A2) (referred to as reaction product XIII) was obtained.

(Synthesis Example 14)
A stirrer, a cooling tube, and a dropping funnel were set in a 5 L two-necked flask. 1800 g of toluene and 340 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in this flask, and the mixture was heated with stirring in an oil bath at 120°C. To this solution, a mixed solution of 180 g of triallyl isocyanurate, 200 g of toluene, and 1.44 ml of a xylene solution of a platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 50 minutes. The obtained solution was heated as it was for 6 hours at 120° C. and stirred. After adding 2.95 mg of 1-ethynyl-1-cyclohexanol, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a hydrosilyl group having no cyclic ether group. To obtain a modified polysiloxane (A2) (referred to as reaction product XIV).

(Synthesis example 15)
A stirrer, a cooling tube, and a dropping funnel were set in a 5 L two-necked flask. 1800 g of toluene and 340 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in this flask, and the mixture was heated with stirring in an oil bath at 120°C. To this solution, a mixed solution of 270 g of diallyl monomethyl isocyanurate, 200 g of toluene, and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise over 50 minutes. The obtained solution was heated as it was for 6 hours at 120° C. and stirred for 6 hours. After adding 2.95 mg of 1-ethynyl-1-cyclohexanol, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a hydrosilyl group having no cyclic ether group. To obtain a modified polysiloxane (A2) (referred to as reaction product XV).

(Synthesis example 16)
A stirring device, a dropping funnel, and a cooling tube were set in a 5 L four-necked flask. 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in this flask, and heated and stirred in an oil bath at 120°C. A mixed solution of 180 g of tetraallylglycoluril, 200 g of toluene, and 1.44 mL of a xylene solution (containing 3 wt% as platinum) of a platinum vinyl siloxane complex was added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and then unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were removed under reduced pressure to obtain a polysilyl group having a hydrosilyl group having no cyclic ether group. A siloxane modified product (A2) (reaction product XVI) was obtained.

(Formulation example 1)
76.12 g of the reaction product II having a cyclic ether group obtained in Synthesis Example 2 was added with 23.81 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, umicore precious Metals Japan, Pt-VTSC-3X) 0.029 g, ethynyl cyclohexanol 0.055 g, and dimethyl maleate 0.0032 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did .

(Formulation example 2)
To 76.12 g of the reaction product III having a cyclic ether group obtained in Synthesis Example 3, 23.81 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, umicore precious Metals Japan, Pt-VTSC-3X) 0.029 g, ethynyl cyclohexanol 0.055 g, and dimethyl maleate 0.0032 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 3)
78.12 g of the reaction product IV having a cyclic ether group obtained in Synthesis Example 4 was added with 21.82 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious). Metals Japan, Pt-VTSC-3X) 0.026 g, ethynylcyclohexanol 0.050 g, and dimethyl maleate 0.029 g are added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group is blended. did.

(Formulation Example 4)
75.48 g of the reaction product V having a cyclic ether group obtained in Synthesis Example 5 was added with 24.37 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious). Metals Japan, Pt-VTSC-3X) 0.030 g, ethynylcyclohexanol 0.057 g, and dimethyl maleate 0.0033 g were added and mixed uniformly with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation example 5)
To 74.85 g of the reaction product VI having a cyclic ether group obtained in Synthesis Example 6, diallyl monomethyl isocyanurate 25.07 g, a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, umicore precious) Metals Japan, Pt-VTSC-3X) 0.030 g, ethynylcyclohexanol 0.058 g, and dimethyl maleate 0.0034 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation example 6)
71.84 g of the reaction product VII having a cyclic ether group obtained in Synthesis Example 7 was added with 28.05 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious). Metals Japan, Pt-VTSC-3X) 0.034 g, ethynylcyclohexanol 0.065 g, and dimethyl maleate 0.0038 g were added and uniformly stirred and mixed, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 7)
74.97 g of the reaction product VIII having a cyclic ether group obtained in Synthesis Example 8 was added with 24.93 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious). Metals Japan, Pt-VTSC-3X) 0.030 g, ethynylcyclohexanol 0.058 g, and dimethyl maleate 0.0034 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 8)
70.09 g of the reaction product IX having a cyclic ether group obtained in Synthesis Example 9 was added with 29.81 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious). Metals Japan, Pt-VTSC-3X) 0.036 g, ethynylcyclohexanol 0.069 g, and dimethyl maleate 0.0040 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 9)
73.01 g of the reaction product X having a cyclic ether group obtained in Synthesis Example 10 was added with 26.88 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, Yumicore Precious Metals Japan, Pt-VTSC-3X) 0.033 g, ethynylcyclohexanol 0.062 g, and dimethyl maleate 0.0036 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 10)
To 83.22 g of the reaction product XI having a cyclic ether group obtained in Synthesis Example 11, 16.72 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Umicore precious Metals Japan, Pt-VTSC-3X) 0.020 g, ethynylcyclohexanol 0.039 g, and dimethyl maleate 0.0022 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 11)
42.33 g of the reaction product II having a cyclic ether group obtained in Synthesis Example 2 and 31.11 g of the reaction product IX having a cyclic ether group obtained in Synthesis Example 9 were added with 26.45 g of diallyl monomethyl isocyanurate and a platinum vinylsiloxane complex. Xylene solution (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.032 g, ethynylcyclohexanol 0.061 g, and dimethyl maleate 0.0036 g are added uniformly. After stirring and mixing, a base resin using a reaction product having a cyclic ether group was blended.

(Formulation Example 12)
81.06 g of the reaction product II having a cyclic ether group obtained in Synthesis Example 2 was added with 18.84 g of triallyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% of platinum, Yumicore Precious Metals Japan, Pt-VTSC-3X) 0.031 g, ethynylcyclohexanol 0.059 g, and dimethyl maleate 0.0034 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 13)
75.87 g of the reaction product IX having a cyclic ether group obtained in Synthesis Example 9 was added with 24.01 g of triallyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% of platinum, Yumicore Precious). Metals Japan, Pt-VTSC-3X) 0.039 g, ethynylcyclohexanol 0.075 g, and dimethyl maleate 0.0043 g were added and uniformly mixed with stirring, and a base resin using a reaction product having a cyclic ether group was blended. did.

(Formulation Example 14)
57.76 g of the reaction product IX having a cyclic ether group obtained in Synthesis Example 9 was added to 42.24 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and platinum vinyl. A xylene solution of a siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.036 g, ethynylcyclohexanol 0.069 g, and dimethyl maleate 0.0040 g were added. The mixture was uniformly stirred and mixed, and a base resin using a reaction product having a cyclic ether group was blended.

(Formulation Example 15)
61.22 g of the reaction product X having a cyclic ether group obtained in Synthesis Example 10 was added to 38.78 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and platinum vinyl. 0.033 g of a xylene solution of a siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X), 0.062 g of ethynylcyclohexanol, and 0.0036 g of dimethyl maleate were added. The mixture was uniformly stirred and mixed, and a base resin using a reaction product having a cyclic ether group was blended.

(Formulation Example 16)
25.68 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and platinum vinyl were added to 74.32 g of the reaction product X I having a cyclic ether group obtained in Synthesis Example 11. 0.020 g of a xylene solution of a siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X), 0.039 g of ethynylcyclohexanol, and 0.0022 g of dimethyl maleate were added. The mixture was uniformly stirred and mixed, and a base resin using a reaction product having a cyclic ether group was blended.

(Formulation Example 17)
42.33 g of the reaction product II having a cyclic ether group obtained in Synthesis Example 2 and 31.11 g of the reaction product IX having a cyclic ether group obtained in Synthesis Example 9 were added with 26.45 g of diallyl monomethyl isocyanurate and a platinum vinylsiloxane complex. Xylene solution (platinum vinyl siloxane complex containing 3 wt% as platinum, Pt-VTSC-3X manufactured by Umicore Precious Metals Japan) 0.032 g, ethynylcyclohexanol 0.061 g, and dimethyl maleate 0.0036 g are added uniformly. After stirring and mixing, a base resin using a reaction product having a cyclic ether group was blended.

(Formulation Example 18)
70.18 g of the reaction product II having a cyclic ether group obtained in Synthesis Example 2 was added with 18.86 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and diallylmonomethyl. Isocyanurate 10.97 g, xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, Umicore Precious Metals Japan Pt-VTSC-3X) 0.031 g, ethynyl cyclohexanol 0.059 g, malein 0.0034 g of dimethyl acid was added and uniformly mixed with stirring to blend a base resin using a reaction product having a cyclic ether group.

(Formulation Example 19)
63.36 g of the reaction product IX having a cyclic ether group obtained in Synthesis Example 9 was added to 23.17 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and diallylmonomethyl. 13.47 g of isocyanurate, xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.031 g, ethynyl cyclohexanol 0.059 g, malein 0.0034 g of dimethyl acid was added and uniformly mixed with stirring to blend a base resin using a reaction product having a cyclic ether group.

(Formulation Example 20)
To 66.06 g of the reaction product II having a cyclic ether group obtained in Synthesis Example 2, 33.94 g of a reaction product XII having no cyclic ether group obtained in Synthesis Example 12, a xylene solution of a platinum vinylsiloxane complex (as platinum Platinum vinyl siloxane complex containing 3 wt%, Umicore Precious Metals Japan, Pt-VTSC-3X) 0.031 g, ethynylcyclohexanol 0.059 g, and dimethyl maleate 0.0034 g were added and uniformly stirred and mixed to form a cyclic ether. A base resin using a reactant having a group was blended.

(Formulation example 21)
To 58.86 g of the reaction product IX having a cyclic ether group obtained in Synthesis Example 9, 41.14 g of the reaction product XII obtained in Synthesis Example 12 and a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane containing 3 wt% as platinum) Complex, Umicore Precious Metals Japan, Pt-VTSC-3X) 0.031 g, ethynylcyclohexanol 0.059 g, and dimethyl maleate 0.0034 g are added with uniform stirring and mixing, and a reaction product having a cyclic ether group is used. Was mixed with the base resin.

(Formulation Example 22)
In 83.14 g of the reaction product XIII having no cyclic ether group obtained in Synthesis Example 13, 16.73 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumi Core Precious Metals Japan, Pt-VTSC-3X) 0.020 g, ethynylcyclohexanol 0.039 g, and dimethyl maleate 0.0023 g are added with uniform stirring and mixing, and a base containing no reaction product having a cyclic ether group is used. The resin was compounded.

(Formulation Example 23)
To 50.36 g of the reaction product XIV having no cyclic ether group obtained in Synthesis Example 14, 29.55 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumi Core Precious Metals Japan, Pt-VTSC-3X) 0.060 g, ethynylcyclohexanol 0.114 g, and dimethyl maleate 0.0067 g are added with uniform stirring and mixing, and a base containing no reaction product having a cyclic ether group is used. The resin was compounded.

(Formulation Example 24)
57.87 g of the reaction product XV having no cyclic ether group obtained in Synthesis Example 15 was added with 42.04 g of diallyl monomethyl isocyanurate and a xylene solution of a platinum vinyl siloxane complex (a platinum vinyl siloxane complex containing 3 wt% as platinum, Yumi Core Precious Metals Japan, Pt-VTSC-3X) 0.051 g, ethynylcyclohexanol 0.097 g, and dimethyl maleate 0.0056 g are added and uniformly mixed with stirring, and a base not using a reactant having a cyclic ether group is used. The resin was compounded.

(Formulation Example 25)
74.22 g of the reaction product XIII having no cyclic ether group obtained in Synthesis Example 13 was added to 25.89 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane. 0.020 g of a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X), 0.039 g of ethynylcyclohexanol, and 0.0023 g of dimethyl maleate. In addition, the mixture was stirred and mixed uniformly, and a base resin containing no reaction product having a cyclic ether group was blended.

(Compound example 26)
37.19 g of the reaction product XIV having no cyclic ether group obtained in Synthesis Example 14 was added to 62.81 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane. 0.060 g of a xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X), 0.114 g of ethynylcyclohexanol, and 0.0067 g of dimethyl maleate. In addition, the mixture was stirred and mixed uniformly, and a base resin containing no reaction product having a cyclic ether group was blended.

(Formulation Example 27)
To 44.49 g of the reaction product XV having no cyclic ether group obtained in Synthesis Example 15, 55.51 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, A xylene solution of a platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.051 g, ethynyl cyclohexanol 0.097 g, and dimethyl maleate 0.0056 g. In addition, the mixture was stirred and mixed uniformly to blend the base resin.

(Formulation Example 28)
78.45 g of the reaction product XIII obtained in Synthesis Example 13 was added with 7.92 g of diallyl monomethyl isocyanurate and 13.67 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane. , Xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.051 g, ethynyl cyclohexanol 0.097 g, dimethyl maleate 0.0056 g Was added, and the mixture was stirred and mixed uniformly to blend the base resin.

(Formulation Example 29)
42.82 g of the reaction product XIV obtained in Synthesis Example 14 was added with 21.03 g of diallyl monomethyl isocyanurate and 36.16 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane. , Xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, Umicore Precious Metals Japan Pt-VTSC-3X) 0.020 g, ethynyl cyclohexanol 0.039 g, dimethyl maleate 0.0023 g Was added, and the mixture was stirred and mixed uniformly to blend the base resin.

(Formulation Example 30)
50.34 g of the reaction product XV obtained in Synthesis Example 15 was added with 18.26 g of diallyl monomethyl isocyanurate and 31.40 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane. , Xylene solution of platinum vinyl siloxane complex (platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.051 g, ethynyl cyclohexanol 0.097 g, dimethyl maleate 0.0056 g Was added, and the mixture was stirred and mixed uniformly to blend the base resin.

(Formulation Example 31)
75.07 g of the reaction product XIII obtained in Synthesis Example 13 was mixed with 24.93 g of the reaction product XII having no cyclic ether group obtained in Synthesis Example 12 and a xylene solution of a platinum vinylsiloxane complex (platinum containing 3 wt% of platinum. Vinyl siloxane complex, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.020 g, ethynylcyclohexanol 0.039 g, and dimethyl maleate 0.0023 g are added and uniformly mixed with stirring to form a reaction product having a cyclic ether group. Was blended with a base resin that was not used.

(Formulation Example 32)
To 38.25 g of the reaction product XIV having no cyclic ether group obtained in Synthesis Example 14, 61.75 g of the reaction product XII having no cyclic ether group obtained in Synthesis Example 12, and a xylene solution of a platinum vinylsiloxane complex ( Platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.020 g, ethynylcyclohexanol 0.039 g, and dimethyl maleate 0.0023 g were added and uniformly stirred and mixed, A base resin was compounded without the reactants having cyclic ether groups.

(Formulation Example 33)
To 45.61 g of the reaction product XV having no cyclic ether group obtained in Synthesis Example 15, 54.39 g of the reaction product XII having no cyclic ether group obtained in Synthesis Example 12, a xylene solution of a platinum vinylsiloxane complex ( Platinum vinyl siloxane complex containing 3 wt% as platinum, made by Umicore Precious Metals Japan, Pt-VTSC-3X) 0.020 g, ethynylcyclohexanol 0.039 g, and dimethyl maleate 0.0023 g were added and uniformly stirred and mixed, A base resin was compounded without the reactants having cyclic ether groups.

(Example 1)
1.0 g of fumed silica R974 manufactured by Nippon Aerosil Co., Ltd. was added to 5.0 g of the base resin prepared in Formulation Example 1, and Akitori Kentarou ARV-300 manufactured by Thinky was used under reduced pressure at 1200 rpm for 5 times. Min, 500 rpm for 5 minutes, and 1200 rpm for 5 minutes in this order to produce a curable resin composition containing an inorganic filler. The obtained curable resin composition was poured into a glass cell having a thickness of 2 mm, and heated in a convection oven at 80° C. for 60 minutes, 120° C. for 120 minutes, and 150° C. for 180 minutes in this order to cure. The light transmittance of the obtained cured product at 450 nm was measured using V-770 manufactured by JASCO. When the result of the light transmittance was 85% or more, "⊚" was given.

Separately, the curable resin composition is applied to a glass epoxy substrate having a thickness of 0.6 mm so as to have a thickness of 0.5 mm, and the mixture is heated in a convection oven in the order of 80° C. for 60 minutes, 120° C. for 120 minutes, and 150° C. for 180 minutes. It was heated to cure. The warp of the obtained coated substrate was measured with a gap gauge. When the warp of the substrate was 0.1 mm or less, it was designated as "A", when it was greater than 0.1 mm and less than 0.3 mm, it was designated as "O", and when it was greater than 0.3 mm, it was designated as "X". In addition, by using a thermal shock tester manufactured by Hitachi Appliances Co., Ltd. for the above substrate, a temperature range of -40[deg.] C. on the low temperature side for 30 minutes and 100[deg.] C. on the high temperature side for 30 minutes can be switched every 30 minutes. A thermal shock test was conducted. The number of tests was 1000 cycles. It was observed using an optical microscope to confirm the presence or absence of peeling or cracking. A sample in which at least either peeling or cracking occurred was used as a thermal shock test NG.

(Examples 2 to 25, Comparative Examples 6 to 23)
In the same procedure as in Example 1, the base resin and the inorganic filler R974 (fumed silica) manufactured by Nippon Aerosil Co., Ltd. were blended as shown in Table 1, and the same test was performed.

(Examples 26 to 46, Comparative Examples 24 to 26)
A base resin and an inorganic filler were blended as shown in Table 1 in the same procedure as in Example 1 except that CF0027-03C (glass filler) manufactured by Nippon Frit Co., Ltd. was used as the inorganic filler, and the same test was performed. ..

(Comparative Examples 1-5)
The test was conducted in the same manner as in Example 1 except that the inorganic filler was not used.

Regarding the results, in the example in which the filler was added, the effect of suppressing the warp of the substrate and the improvement of resistance to thermal shock were confirmed.

Generally, the warp occurs because the volume of the resin becomes small and the volume of the substrate does not change when it is cured. When the filler is added here, the volume of the curable resin in the whole is reduced, but since the volume change during curing is small, warpage is suppressed.

With respect to resistance to thermal shock, the addition of filler reduces the proportion of resin in the whole, and the volume change due to temperature change becomes small, so the burden due to volume change becomes small and cracks are less likely to occur. .. Further, since the resin strength is raised by adding the filler, cracks are less likely to occur due to cold thermal shock. On the other hand, in the example using the compound having a cyclic ether group, the light transmittance was high and transparent, but in the comparative example, the cyclic ether did not contain, and the light transmittance was low and the light transmittance was low. It was

From the above results, the cured product of the curable resin composition of the present invention has a good compatibility with the filler due to the presence of the cyclic ether group in the resin composition, the dispersibility of the filler is improved, and the light at 450 nm is increased. The transmittance was excellent, and the effect of suppressing warpage and the effect of improving thermal shock resistance were obtained. This has been confirmed by TEM. On the other hand, in Comparative Examples 1 to 5, since no filler is added, the warp suppressing effect and the thermal shock resistance are low, and Comparative Examples 6 to 25 do not have a cyclic ether group, and therefore the dispersibility of the filler is low. Was low and the light transmittance at 450 nm was low.

Claims (14)

A compound (A) containing a cyclic ether group and having an average of two or more hydrosilyl groups in one molecule;
A compound (B) having an average of two or more alkenyl groups in one molecule,
A hydrosilylation catalyst (C),
An inorganic filler (D) having a refractive index difference of 30% or less with respect to a cured product obtained by curing the compound (A), the compound (B), and the hydrosilylation catalyst (C). A transparent thermosetting resin composition. The transparent thermosetting resin composition according to claim 1, wherein the cyclic ether group contained in the compound (A) is one or more selected from the group consisting of an epoxy group, an alicyclic epoxy group, a glycidyl group and an oxetane group. .. The compound (A) is a compound obtained by reacting a compound (α1) having an alkenyl group with a compound (α2) having at least two hydrosilyl groups in one molecule in the presence of a hydrosilylation catalyst. hand,
The transparent thermosetting resin composition according to claim 1, wherein the compound (A) has a structure derived from a cyclic ether compound (α3) having one alkenyl group in one molecule. The compound (B) is
Polysiloxane (B1) having two or more alkenyl groups in one molecule,
An organic compound (B2) having a heterocyclic skeleton having two or more alkenyl groups in one molecule and having at least one polar group in the ring skeleton, and
A compound (B3) having two or more alkenyl groups in one molecule obtained by reacting the compound (B1) and/or the compound (B2) with the component (α2) in the presence of a hydrosilylation catalyst;
The transparent thermosetting resin composition according to any one of claims 1 to 3, which is at least one selected from the group of. The compound (A) reacts with a polysiloxane compound (α1-1) having an alkenyl group and a polysiloxane compound (α2) having at least two hydrosilyl groups in one molecule in the presence of a hydrosilylation catalyst. A compound obtained by
The transparent thermosetting resin according to any one of claims 1 to 4, wherein the compound (A) is a compound (A1) having a structure derived from a cyclic ether compound (α3) having one alkenyl group in one molecule. Composition. The compound (A) is an organic compound (α1-2) having a heterocyclic skeleton having at least one polar group in the ring skeleton in one molecule, and a polysiloxane having at least two hydrosilyl groups in one molecule. A compound obtained by reacting the system compound (α2) in the presence of a hydrosilylation catalyst,
The transparent thermosetting according to any one of claims 1 to 4, wherein the compound (A) is a compound (A2) having a structure derived from a cyclic ether compound (α3) having one alkenyl group in one molecule. Resin composition. The transparent thermosetting resin composition according to claim 5, wherein the polysiloxane compound (α1-1) having an alkenyl group is an alkenyl group-containing polyhedral polysiloxane compound. The transparent thermosetting resin composition according to claim 6, wherein the organic compound (α1-2) having an alkenyl group has an isocyanuric skeleton or a glycoluril skeleton. The compound (α2) having at least two hydrosilyl groups in one molecule is a cyclic siloxane and/or a linear siloxane and/or a branched siloxane having a hydrosilyl group and/or a silphenylene compound. The transparent thermosetting resin composition according to claim 1. At least one of the compound (A) and the compound (B) is a compound having a skeleton derived from an organic compound having a heterocyclic skeleton having at least one polar group in the ring skeleton. The transparent thermosetting resin composition according to item 1. The transparent thermosetting resin composition according to claim 1, wherein the cyclic ether compound (a′) having one alkenyl group in one molecule has a molecular weight of less than 1,000. A cured product of the transparent thermosetting resin composition according to claim 1. An encapsulant for optical elements, which comprises the transparent thermosetting resin composition according to claim 1. An optical semiconductor device comprising the transparent thermosetting resin composition according to claim 1 as a sealant.