JPWO2010026714A1 - Siloxane compound, curable resin composition, cured product thereof and optical semiconductor element - Google Patents

Abstract

The present invention is a block type having a chain silicone segment and a hydrolytic condensation segment of tri (C1-C10) alkoxysilane having a reactive functional group having an epoxy group, a group selected from the group consisting of a methyl group and an ethyl group Novel reactive functional group-containing siloxane compound (A), which is a siloxane oligomer of the above, and wherein at least one hydrolytic condensation segment is a segment containing a reactive functional group having at least one epoxy group, and a curing agent therefor The present invention relates to a curable resin composition containing (B) and an optical semiconductor element (for example, LED) encapsulated with the cured product, and the encapsulated optical semiconductor element is excellent in light resistance and low elastic modulus at low temperature. . In the first stage reaction, the siloxane compound reacts with 1 equivalent of the silanol group of the silanol-terminated silicone oil (b) by reacting the alkoxy group of the alkoxysilane compound within the range of 1.5 to 200 as an equivalent value. As a two-stage reaction, it can be obtained by performing a hydrolysis-condensation reaction of the alkoxy group in the alkoxysilane and the product of the first-stage reaction in the presence of water.

Description

 The present invention relates to a novel reactive functional group-containing siloxane compound, a production method thereof, and a composition thereof. More specifically, the present invention relates to a curable resin composition for optical semiconductors excellent in transparency, light resistance, and low elastic modulus characteristics at low temperature, and an optical semiconductor element sealed with the cured product.

Conventionally, epoxy resin has been adopted as a sealing material for optical semiconductor elements such as LEDs in terms of a balance between performance and economy. In particular, bisphenol A type epoxy resins, alicyclic epoxy resins, and the like, which are excellent in balance of heat resistance, transparency, and mechanical properties, have been widely used.
In recent years, it has been pointed out that as a result of the shortening of the LED emission wavelength (360 nm to 480 nm) and the improvement of the emission intensity, the sealing material is colored by the influence of light and ultimately the characteristics of the LED are deteriorated. ing.
In view of this, silicone resins have been studied for the purpose of avoiding coloring of the sealing material by light. However, since the silicone resin is inferior to the epoxy resin in mechanical properties and adhesiveness, only a sealing form in a gel state can be selected. Therefore, the problem that surface tack and deformation occur after sealing has been pointed out in the market.
In order to improve the durability of the epoxy resin and the tackiness of the silicone resin, in Patent Document 1, a silane compound having an epoxy group and a silane compound having no epoxy group are combined with an organic solvent, an organic base and water. It is heated in the presence to obtain a polyorganosiloxane having a weight average of 500 to 1,000,000. The polyorganosiloxane is improved from the conventional epoxy resin in terms of light resistance. In addition, tackiness and hardness are improved by increasing the amount of the trifunctional alkoxysilane compound introduced relative to the bifunctional alkoxysilane compound. However, in order to improve surface tackiness and deformation, by hardening the cured product, the elastic modulus is increased particularly in a low temperature region (a level of −30 ° C. or lower). As a result, in the heat cycle test, the low elastic modulus characteristic is lowered at a low temperature (−30 ° C. or lower).
The fact that the cured sealant has a low elastic modulus even at a low temperature is one of important characteristics in an optical semiconductor sealant, and improvement of this point is an important issue.

WO2005 / 100445 publication

  The present invention relates to a siloxane compound having a novel reactive functional group having both light resistance and low elastic modulus at low temperature as an LED sealing material, a curable resin composition using the same, and the curable resin composition. An object is to provide an optical semiconductor element used as a sealing material.

As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have a silanol-terminated silicone oil (silicon compound) represented by the following general formula (2) and a reactive functional group-containing trialkoxysilane containing an epoxy group. It has been found that a reactive functional group-containing siloxane compound having a chain-like silicone segment obtained by reaction with a compound (silicon compound) and a trialkoxysilane hydrolytic condensation segment is useful for solving the above-mentioned problems. That is, it has been found that the curable resin composition containing the siloxane compound satisfies the above-mentioned problems. Furthermore, it has been found that the siloxane compound can be efficiently synthesized by a two-step reaction. As a result, the present invention has been completed.
As can be seen from the above, the siloxane compound of the present invention is an oligomer (polymer) composed of a hydrolytic condensation segment (preferably a silsesquioxane segment) of a linear silicone segment and an alkoxysilane, and at least the hydrolytic condensation segment. A part of contains a reactive functional group with at least one epoxy group.
The present invention is described below.

That is, the present invention
(1) A block type having a chain silicone segment and a hydrolytic condensation segment of tri (C1-C10) alkoxysilane having a group selected from the group consisting of a reactive functional group having an epoxy group, a methyl group and a phenyl group A reactive functional group-containing siloxane compound, wherein the at least one hydrolytic condensation segment is a segment containing a reactive functional group having at least one epoxy group,
(2) The reactive functional group-containing siloxane compound according to (1), wherein the hydrolysis-condensation segment is a silsesquioxane segment,
(3) As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m represents an average value of 2 to 2000, and a general formula (1)
XSi (OR ₂ ) ₃ (1)
(Wherein X represents a reactive functional group having an epoxy group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms)
Is reacted in the range of 1.5 to 200 equivalents of the alkoxy group equivalent of the alkoxysilane compound to 1 equivalent of the silanol group of the silanol-terminated silicone oil (b), Reactive functional group-containing product according to claim 1 or 2 obtained by condensing and then adding water to the resulting reaction solution as a second stage reaction to hydrolyze and condense the remaining alkoxy groups Siloxane compounds,
(4) The reactive functional group-containing siloxane compound according to claim 3, wherein m is 2 to 200.
(5) As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 200), and the general formula (1)
XSi (OR ₂ ) ₃ (1)
(Wherein X represents a reactive functional group having an epoxy group, R ₂ represents an alkyl group having 1 to 10 carbon atoms) and the general formula (3)
R ₄ Si (OR ₂ ) ₃ (3)
(Wherein, R ₄ is a methyl group or a phenyl group, R ₂ is Formula (may be the same or different as R ₂ in 1) each independently represent an alkyl group having 1 to 10 carbon atoms .)
Both of the alkoxysilane compounds (c) represented by formula (1) are the total equivalents of the alkoxy groups of the alkoxysilane compounds (a) and (c) with respect to 1 equivalent of silanol groups of the silanol-terminated silicone oil (b). The above-mentioned (1) obtained by reacting in the range of 5 to 200 equivalents and condensing, and then adding water to the resulting reaction solution to hydrolyze and condense the remaining alkoxy groups as the second stage reaction. ) Reactive functional group-containing siloxane compound according to
(6) R _{3 in the} general formula (2) independently represents a methyl group or a phenyl group, R _{2 in the} general formula (1) independently represents a methyl group or an ethyl group, and R in the general formula (3) ₂ may be the same as or different from R ₂ in the general formula (1), and each independently represents a methyl group or an ethyl group, according to any one of the above (3) to (5). Reactive functional group-containing siloxane compounds,
(7) The reactive functional group-containing siloxane compound according to any one of (3) to (6), wherein X in the general formula (1) is an epoxycyclohexylethyl group,
(8) The reactive functional group according to any one of (3) to (6), wherein the silanol-terminated silicone oil (b) of the general formula (2) has a weight average molecular weight (Mw) of 300 to 18,000. Group-containing siloxane compounds,

(9) The reactive functional group-containing siloxane compound according to any one of (1) to (8), wherein the weight average molecular weight (Mw) is 800 to 20,000,
(10) The reactive functional group-containing siloxane as described in (1) or (2) above, wherein the substituent on the silicone in the chain silicone segment is one or both of a methyl group and a phenyl group Compound,
(11) The reactive functional group-containing siloxane compound according to (1) or (10) above, wherein the reactive functional group having an epoxy group in the silsesquioxane segment contains an epoxycyclohexyl group,
(12) As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, and each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or 6 to 14 carbon atoms. An silanol-terminated silicone oil (b) represented by an aryl group or an alkenyl group having 2 to 10 carbon atoms, and m represents an average value of 2 to 2000, and a general formula (1)
XSi (OR ₂ ) ₃ (1)
(In the formula, X represents a reactive functional group having an epoxy group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms.)
In the range of 1.5 to 200 equivalents, the equivalent of the alkoxy group of the alkoxysilane compound (a) is equivalent to 1 equivalent of the silanol group of the silanol-terminated silicone oil (b). A reactive functional group characterized by reacting in the presence of a catalyst, condensing, and then adding water to the resulting reaction solution to hydrolyze and condense the remaining alkoxy groups as a second step reaction A method for producing a siloxane compound,
(13) The method for producing a reactive functional group-containing siloxane compound according to (12), wherein m is 2 to 200,
(14) As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same or different from each other, and each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or aryl having 6 to 14 carbon atoms. A silanol-terminated silicone oil (b) represented by a group or an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 200.
XSi (OR ₂ ) ₃ (1)
(In the formula, X represents a reactive functional group having an epoxy group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms.)
And an alkoxysilane compound (a) represented by the following general formula (3)
R ₄ Si (OR ₂ ) ₃ (3)
(Wherein, R ₄ is a methyl group, a phenyl group, R ₂ is Formula (may be the same or different as R ₂ in 1), an alkyl group having 1 to 10 carbon atoms independently. )
The alkoxysilane compound (c) represented by the formula (1) is a total equivalent of alkoxy groups of the alkoxysilane compounds (a) and (c) with respect to 1 equivalent of silanol groups of the silanol-terminated silicone oil (b), and 1.5 to A reaction characterized in that a condensation reaction is carried out in the presence of a catalyst in the range of 200 equivalents, and then, as a second stage reaction, water is added to the resulting reaction product to hydrolyze and condense the remaining alkoxy groups. A method for producing a functional functional group-containing siloxane compound,
(15) The method for producing a reactive functional group-containing siloxane compound as described in (12) to (14) above, wherein the first step reaction and the second step reaction are sequentially carried out in one pot as the production step,

(16) The above (wherein the alkoxysilane compound represented by the general formula (1) is β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane or β- (3,4-epoxycyclohexyl) ethyltriethoxysilane ( 11) to a method for producing a reactive functional group-containing siloxane compound according to (15),
(17) In the silanol-terminated silicone oil (b) represented by the general formula (2), R ₃ may be the same as or different from each other, and each is independently a methyl group or a phenyl group (12 ) To (16), a method for producing a reactive functional group-containing siloxane compound,
(18) The alkoxysilane compound represented by the general formula (3) is at least one selected from the group consisting of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. (13) A method for producing a reactive functional group-containing siloxane compound according to (15),
(19) A curable resin composition comprising the reactive functional group-containing siloxane compound (A) according to any one of (1) to (11) above, and a curing agent (B),
(20) The curable resin composition according to (19), further comprising a curing accelerator (C),
(21) A cured product for an optical semiconductor obtained by thermosetting the curable resin composition according to (19) or (20),
(22) An optical semiconductor element sealed with the optical semiconductor cured product according to (20),
It is about.

  The cured product of the curable resin composition containing the siloxane compound of the present invention has no tackiness or deformation, and is excellent in transparency, light resistance, and low elastic modulus characteristics at low temperatures. Therefore, the curable resin composition of the present invention is extremely useful as an optical semiconductor sealing material.

The reactive functional group-containing siloxane compound of the present invention (hereinafter also simply referred to as the siloxane compound of the present invention) comprises a chain-like silicone segment and a hydrolysis-condensation segment of trialkoxysilane, preferably a reactive functional group having an epoxy group. The silsesquioxane segment to be contained, more preferably, the three-dimensional network silsesquioxane segment is contained in one molecule.
The siloxane compound of the present invention is usually a hydrolytic condensation segment of trialkoxysilane, preferably a silsesquioxane segment having a three-dimensional network structure called silsesquioxane, which is a chain-like structure. The structure is such that the silicone segment extends and is linked to the next hydrolysis-condensation segment of trialkoxysilane, preferably the silsesquioxane segment. This structure provides a balance between hardness and flexibility in the cured product of the curable composition of the present invention.
As described above, the siloxane compound of the present invention has a hydrolysis-condensation segment of trialkoxysilane, preferably a silsesquioxane segment and a chain-like silicone segment, and is called a block-type siloxane compound because they are repeated. You can also.

The siloxane compound of the present invention includes, for example, the following general formula (10)
XSi (R ₁ ) n (OR ₂ ) _3-n (10)
Wherein X is a reactive functional group having an epoxy group, R ₁ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, or a substituted or unsubstituted group an alkenyl group having 2 to 10 carbon atoms, _{R 2} is an alkyl group having 1 to 10 carbon atoms, n represents an integer of 0 to 2, _{if R 1} there are a plurality, even several _{R 1} are identical to each other May be different)
An alkoxysilane compound (a-1) (hereinafter also referred to as alkoxysilane (a-1)), preferably represented by the following general formula (1)
XSi (OR ₂ ) ₃ (1)
(Wherein X and R ₂ represent the same meaning as in formula (10)).
And the silicone oil (b) represented by the general formula (2) can be produced as raw materials, and the above-mentioned as necessary. The alkoxysilane (a-1), preferably together with (a), can be used together with the alkoxysilane compound (c) represented by the general formula (3) as a raw material. The chain silicone segment in the siloxane compound of the present invention is formed from silicone oil (b), and is a hydrolysis-condensation segment of trialkoxysilane, preferably a silsesquioxane segment, more preferably a three-dimensional network of silsesquioxane. The sun segment is an alkoxysilane compound (a-1), preferably (a) (when used in combination with an alkoxysilane compound (c) (hereinafter also referred to as alkoxysilane (c)), an alkoxysilane (a-1). ), Preferably (a) and alkoxysilane (c)}.
The hydrolysis-condensation segment is preferably a segment in which the alkoxysilane (a) and optionally (c) are formed by a two-stage reaction of hydrolysis of the alkoxy group and dealcoholization condensation. By this hydrolysis condensation, a structure in which a plurality of structural units of X (and optionally R ₄ ) SiO 3/2 are bonded is obtained. Since the siloxane compound formed from the structural unit is referred to as silsesquioxane, the hydrolytic condensation segment can be referred to as a silsesquioxane segment.

Hereinafter, each raw material will be described in detail.
X in the alkoxysilane compound (a-1) or (a) represented by the general formula (10) or (1) is not particularly limited as long as it is an organic group having an epoxy group. For example, β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl and the like glycidoxy having 1 to 4 carbon atoms; glycidyl group; β- (3,4-epoxycyclohexyl) ethyl group, γ -(3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group And an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy ring (oxirane ring) such as a β- (3,4-epoxycyclohexyl) pentyl group. Among these, an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy ring, such as β- A glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4-epoxycyclohexyl) ethyl group are preferable, and a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.

R ₂ in the general formula (10) or (1) each independently represents an alkyl group having 1 to 10 carbon atoms, and may be linear, branched or cyclic. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R ₂ is preferably a methyl group or an ethyl group, particularly preferably a methyl group, from the viewpoint of reaction conditions such as compatibility and reactivity.
Moreover, as R < ₁ > of General formula (10), description of each group in description of R < ₃ > in postscript General formula (2) can be quoted as it is.

Specific preferred examples of the alkoxysilane (a-1) or (a) represented by the general formula (10) or (1) include β-glycidoxyethyltrimethoxysilane and β-glycidoxyethyltriethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane In particular, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferable. These alkoxysilane compounds (a) may be used independently, may use 2 or more types, and can also be used together with the alkoxysilane (c) represented by General formula (3) mentioned later.
Silicone oil (b) has the following formula (2)

(Wherein R ₃ and m are the same as above)
Is a chain silicone oil having a silanol group at the end having a structure represented by:
In the formula of the general formula (2), a plurality of R ₃ may be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 to 10 carbon atoms. An alkenyl group of
Examples of the alkyl group having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like. Among these, considering light resistance, a methyl group, an ethyl group, or a cyclohexyl group is preferable.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group, and hexenyl group.
From the viewpoints of light resistance and heat resistance, R ₃ is preferably independently a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group, and particularly preferably a methyl group or a phenyl group. Specifically, there may be mentioned a case where two R _{3 in} the general formula (2) are methyl or phenyl, one is methyl and the other is phenyl. In many cases, these combinations are usually the same in all repeating units. However, as long as the effects of the present invention are achieved, different combinations may be included in the repeating units. For example, it may be different for each repeating unit, or different ones may be mixed regularly or randomly.

  M of the compound of the general formula (2) is an average value of 2 to 2000, preferably 2 to 200, more preferably 3 to 100, and particularly preferably 3 to 50. If m is too low, the cured product becomes too hard and the low elastic modulus characteristics are deteriorated. If m is too high, the mechanical properties of the cured product tend to deteriorate.

The weight average molecular weight (Mw) of the silicone oil (b) is usually in the range of 300 to 50,000, preferably in the range of 300 to 30,000, more preferably 300 to 18,000 (GPC measurement). Value). Among these, when considering the elastic modulus at low temperature, those having a molecular weight of 300 to 10,000 are more preferable, and when considering compatibility at the time of composition, those having a molecular weight of 300 to 5,000 are more preferable, and particularly 500 to Those of 3,000 are preferred. When the weight average molecular weight is less than 300, the properties of the chain silicone segment portion may be difficult to be obtained. In the present invention, as the molecular weight of the silicone oil (b), polystyrene conversion and weight average molecular weight (Mw) measured under the following conditions were calculated using GPC (gel permeation chromatography).
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The kinematic viscosity of the silicone oil (b) is preferably in the range of 10 to 200 cSt, more preferably 30 to 90 cSt. If the viscosity is too low, the viscosity of the target siloxane compound of the present invention will be low, which may not be suitable as an optical semiconductor sealing agent, and if it is too high, the viscosity of the block type siloxane compound (A) will increase. There is a tendency for the workability to be adversely affected.

Specific examples of the silicone-terminated dimethyl silicone oil in which R ₃ of the silicone oil (b) is a methyl group include the following product names. For example, as products of Toray Dow Corning Silicone Co., Ltd., PRX413, BY16-873, as products of Shin-Etsu Chemical Co., Ltd., X-21-5841, KF-9701, as products of Momentive Co., Ltd., XC96-723 , TSR160, YR3370, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XF3905, and products of Gelest Co., Ltd. include DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31. , DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, and the like. Preferable specific examples of the silicone-terminated methylphenyl silicone oil in which R ₃ of the silicone oil (b) is a methyl group and a phenyl group include the following product names. For example, as products of Momentive Co., Ltd., YF3804, and as products of Gelest Co., Ltd., PDS-0332, PDS-1615, and the like can be given. As silicone-terminated diphenyl silicone oil in which R ₃ of the silicone oil (b) is a phenyl group, for example, PDS-9931 of Gelest Co., Ltd. can be mentioned as a specific example of a preferable product name. Among the above specific examples, from the viewpoint of molecular weight and kinematic viscosity, PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS -S21 and PDS-1615 are preferred. Among these, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight in order to give the silicone segment flexibility characteristics. These silicone oils (b) may be used alone or in combination of two or more.

Next, the alkoxysilane compound (c) will be described in detail.
The alkoxysilane compound (c) has a structure of the following formula (3).
R ₄ Si (OR ₂ ) ₃ (3)
R ₄ in the general formula (3) represents a methyl group or a phenyl group.

_{R 2} in the general formula (3) has the general formula (10) or may be the same or different as _{R 2} (1), each independently, represent an alkyl group having 1 to 10 carbon atoms, straight It may be any of a chain, a branch, or a ring. Specifically, including a preferable group and a more preferable group, it is the same as illustrated in the description of R ₂ in the general formula (10) or (1).

  Specific examples of preferable alkoxysilane compound (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Among the above, methyltrimethoxysilane or phenyltrimethoxysilane is preferable.

  In the present invention, the alkoxysilane compound (c) adjusts the molecular weight of the block type siloxane compound (A), the compatibility with the composition, the heat resistance of the cured product, the light resistance, the low moisture permeability, the low gas permeability, and the like. Therefore, it can be used in combination with the alkoxysilane compound (a-1), preferably (a).

  The usage-amount of the alkoxysilane compound (c) is 0-70 mol% with respect to the sum total of ((a-1), preferably (a) and (c)) of an alkoxysilane compound, Preferably it is 0-70 mol%. It is 55 mol%, More preferably, it is 0-40 mol%. When the alkoxysilane compound (c) is used in combination with the alkoxysilane compound (a), the alkoxysilane compound (c) is preferably used in a range of 5 to 70 mol% with respect to the total alkoxysilane compound, and 5 to 50 mol. % Is more preferable, and 10 to 40 mol% is particularly preferable.

The method for producing the siloxane compound of the present invention will be described below.
As described above, the siloxane compound of the present invention is an alkoxysilane compound (a-1) (hereinafter also referred to as alkoxysilane (a-1)), preferably an alkoxysilane compound (a) (hereinafter also referred to as alkoxysilane (a)). ) And the silicone oil (b) can be produced as raw materials, and the alkoxysilane compound (c) can be used together as a raw material if necessary.
For the production of the siloxane compound of the present invention, any method can be adopted as long as the siloxane compound of the present invention having the two segments can be produced.
The most suitable method is that the silanol-terminated silicone oil (b), alkoxysilane (a-1), preferably (a), and, if necessary, alkoxysilane (c) are silanol-terminated as the first stage reaction. With respect to 1 equivalent of the silanol group of the silicone oil (b), the reaction is conducted in the range of 1.5 to 200 equivalents with the equivalent of the alkoxy group of the alkoxysilane compound, followed by condensation. In this method, water is added to the resulting reaction solution to hydrolyze and condense the remaining alkoxy groups (one-pot method).

The first stage reaction is preferably carried out in the absence of water in the presence of an acid or base catalyst, preferably a base catalyst.
The alkoxysilane (a-1) in the first stage reaction, preferably (a) (along with alkoxysilane (c) if necessary) and the silicone oil (b) in the reaction of the alkoxysilane compound and the silicone oil ( The proportion of b) is usually within alkoxysilane (a-1), preferably (a) (along with alkoxysilane (c) if necessary) with respect to 1 equivalent of silanol group of silicone oil (b). Equivalent of alkoxy group (when alkoxysilane (c) is used in combination, alkoxysilane (a-1), preferably the total alkoxy equivalent of (a) and alkoxysilane (c)), 1.5 to 200 equivalents, Preferably it is 2-200 equivalent, More preferably, it is 2-150 equivalent, More preferably, it is 2-100 equivalent. Further, the ratio may be 3 to 100 equivalents, preferably 4 to 100 equivalents, with respect to 1 equivalent of the silanol group of the silicone oil (b), the alkoxy equivalent of the alkoxysilane compound. More preferably, it may be 5 to 100 equivalents.
When the amount of the above alkoxysilane compound greatly exceeds the above upper limit range, the preferred physical properties of the obtained siloxane compound of the present invention may be lost.

Patent Document 1 (WO2005 / 100445) does not use a silanol-terminated silicone oil (b), and hydrolyzes a silane compound having an epoxy group and a silane compound having no epoxy group at a time in the presence of water. It is what is condensed. For synthesizing a silsesquioxane having a normal functional group, a method of hydrolytic condensation of an alkoxysilane compound having a functional group and an alkoxysilane compound having no functional group at a time in the presence of water as in Patent Document 1. Is done.
However, when using silicone oil (b) as a raw material in addition to alkoxysilane (a-1), preferably (a) (optionally alkoxysilane (c)) as in the present invention, those When the raw materials are reacted together in the presence of a catalyst and water, hydrolysis / condensation reaction between alkoxy groups of alkoxysilane (a-1), preferably (a) (optionally alkoxysilane (c)) is performed. Since the process proceeds with priority, in some cases, the formed silsesquioxane compound and the unreacted silicone oil (b) remain and are not compatible with each other. Such cloudy polyorganosiloxane is not suitable for optical applications.
In addition, even when the transparency is not affected, the molecular weight of the synthesized compound tends to be low, and there is a possibility that the heat resistance is reduced and “stickiness” may occur. Thus, a preferable siloxane compound of the present invention is obtained. Is difficult.

It is preferable that the manufacturing method of the reactive functional group containing siloxane compound of this invention including said optimal method passes through the manufacturing process shown by the following (i) and (ii).
Production step (i): Step of forming an alkoxysilane-modified product (d) by subjecting the silanol-terminated silicone oil (b) and the alkoxysilane to dealcohol condensation and modifying the silicone oil end with alkoxysilane. Segment formation process),
Production step (ii): Hydroxy-condensation of alkoxysilanes in the alkoxysilane-modified product (d) and the alkoxysilane compound is carried out in the presence of water to produce a hydrolytic condensation segment of alkoxysilane, preferably a silsesquioxane segment Step (Hydrolysis condensation segment formation step of alkoxysilane).
In the production steps (i) and (ii), the reaction may be performed in any order as long as each step is passed.
In some cases, the silanol-terminated silicone oil (b) and the alkoxysilane compound are reacted with each other by a method such as dropwise addition of water, and the reaction in the production steps (i) and (ii) described above is performed. You may carry out in one process.
Furthermore, when using silsesquioxane having two or more alkoxy substitutions synthesized separately instead of the alkoxysilane in (i), the siloxane compound of the present invention can be obtained only in the production step (i). it can.

Specific examples of preferable production methods include the following three types of production methods, including the optimum method described above.
<Manufacturing method (I)>
First, as a production step (i), by a dealcoholization condensation reaction between a silicone oil having a silanol group at the terminal (b) and an alkoxysilane (a) (alkoxysilane (c) may be used in combination as necessary), A step of obtaining a modified alkoxysilane (d) is performed by changing the terminal of the silicone oil to alkoxysilane.
Next, as the production step (ii), preferably, the alkoxysilane-modified product of the silicone oil obtained in the production step (i) (d) in the presence of alkoxysilane (a) (along with alkoxysilane (c) if necessary) (d) In the presence of water between the alkoxy groups of the modified alkoxysilane (d) and the alkoxysilane compound, in the presence of water. By performing a chain-like silicone segment {usually represented by-(OSi (R ₃ ) ₂ ) m- (where R ₃ represents the same meaning as in formula (2))} and an alkoxysilane hydrolytic condensation segment, A method for producing a block-type siloxane compound of the present invention preferably having a silsesquioxane segment.
<Manufacturing method (b)>
First, a hydrolysis condensation reaction between alkoxy groups in the presence of water of alkoxysilane (a) (along with alkoxysilane (c) if necessary) is carried out to hydrolyze alkoxysilane having an alkoxy group in the molecule. A step of obtaining a decomposition condensate, preferably silsesquioxane (e) is performed.
Next, preferably, the hydrolyzed condensate of alkoxysilane synthesized above, preferably silsesquioxane (e), is isolated and preferably in the absence of water, a silicone oil having a silanol group at the terminal A method for producing the siloxane compound of the present invention by subjecting (b) to a hydrolytic condensate of the alkoxysilane obtained above, preferably a silsesquioxane (e), to carry out a dealcohol condensation reaction.
<Manufacturing method (c)>
First, as a production step (i), a dealcoholization condensation reaction between a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) (along with an alkoxysilane (c) if necessary) is preferably water. In the absence, in the presence of excess alkoxysilane, the alkoxysilane-modified product (d) is formed. Then, as a production step (ii), the remaining alkoxysilane ( a) (When alkoxysilane (c) is used in combination as necessary, the remaining alkoxysilanes (a) and (c)) and the hydrolytic condensation reaction between the alkoxy groups of the modified alkoxysilane (d) are performed. A one-pot method for producing the siloxane compound of the present invention.

In the present invention, from the viewpoint of shortening the production process, it is preferable to use the production method (c) described above in which the second-stage reaction is directly performed without isolating the first-stage reactant and the reaction is sequentially performed in one pot. .
Hereinafter, the production method (c) (the aforementioned most preferred production method) will be described more specifically.
Assuming that the production process (i) in the one pot is the first stage reaction and the production process (ii) is the second stage reaction, first, in the first stage reaction (production process (i)), the silicone oil (b) and alkoxy The dealcohol condensation of silane (a) (alkoxysilane (c) if necessary) is performed, and the hydrogen atom of the terminal silanol group of silicone oil (b) is modified to alkoxysilyl to obtain a modified alkoxysilane (d). . In the first stage reaction, since it is preferably carried out without adding water, hydrolysis condensation between alkoxy groups does not occur, and when the reaction is carried out using 3 equivalents or more of alkoxy groups per 1 equivalent of silanol groups, The alkoxysilane-modified product (d) is considered to exist in the structure represented by the following formula (4). After the formation of such a modified product (d), hydrolysis of the next alkoxy groups is performed. It may be preferable to perform the condensation. Therefore, the aspect which makes this reaction react using 3 equivalent-200 equivalent of alkoxy groups with respect to 1 equivalent of silanol groups of silicone oil (b) is one of the preferable aspects.

In formula (4), R ₂ , R ₃ , and m have the same meaning as described above, and R ₆ may be the same or different, and each independently represents X and / or R ₄ .

In the first stage reaction, if the alkoxy group is reacted in an amount less than 1.0 equivalent with respect to 1 equivalent of the silanol group, the alkoxy group does not exist at the end of the first stage reaction. Moreover, when an alkoxy group is made to react between 1.0-1.5 equivalent, two or more alkoxy groups in alkoxysilane (a) (the alkoxysilane (c) as needed) will become silanol of silicone oil (b). It will react with the group, and at the end of the first stage reaction, it becomes a polymer and gelation occurs. For this reason, it is necessary to make an alkoxy group react with 1.5 equivalent or more with respect to 1 equivalent of silanol groups. From the viewpoint of reaction control, 2.0 equivalents or more are preferable.
Further, from the viewpoint of making the hydrolysis-condensation segment of alkoxysilane a preferable silsesquioxane segment, the alkoxy group is 3 equivalents or more, preferably 4 equivalents or more, more preferably 5 equivalents or more, per 1 equivalent of silanol group. It is preferable to use it.
The silsesquioxane segment in the present invention may be a general ladder type, a partially ring-opened type of a saddle type, or a structure called a random type, and usually a mixture thereof. Conceivable.

After the completion of the first stage reaction, the second stage reaction (manufacturing step (ii)) is performed in which water is added to the reaction solution as it is to hydrolyze and condense alkoxy groups.
The amount of water added is about 0.5 to 100 equivalents with respect to 1 equivalent of the alkoxy group of the alkoxysilane compound used as the raw material. Preferably, about 1 to 10 times, preferably 1 to 5 times the amount of water is used relative to the theoretical amount of water required for the hydrolytic condensation of the remaining alkoxy groups after the first stage reaction.
In the second stage reaction, the following reactions (I) to (III) are considered to occur.
(I) Hydrolytic condensation reaction between alkoxy groups of the alkoxysilane (a) remaining in the system (and alkoxysilane (c) when used in combination as necessary).
(II) Hydrolytic condensation between alkoxy groups of the alkoxysilane-modified product (d) and alkoxysilane (a) obtained in the first stage reaction (and alkoxysilane (c) when used in combination as necessary) reaction.
(III) The alkoxysilane modified product (d) obtained in the first stage reaction and the alkoxysilane (a) produced by the reaction of the above (I) (and alkoxysilane (c )) Condensation reaction between alkoxy groups of the hydrolysis condensate.
In the second stage reaction, the above reactions occur in combination, and the formation of the hydrolytic condensation segment, preferably the silsesquioxane segment, and the condensation with the chain silicone segment derived from the silicone oil (b) are performed simultaneously. .

  The block-type siloxane compound of the present invention produced through the above first-stage reaction and second-stage reaction is excellent in transparency, and the cured product obtained from the resin composition using the block-type siloxane compound has transparency and low elastic modulus. Excellent in properties.

The production of the block type siloxane compound having a reactive functional group of the present invention can be carried out without a catalyst. However, when no catalyst is used, the progress of the reaction is slow. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases such as alkali metal carbonates and ammonia, and organic bases such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base is particularly preferable in terms of easy catalyst removal from the product, and sodium hydroxide and potassium hydroxide are particularly preferable. The addition amount of the catalyst is usually 0.001 to 7.5% by weight, preferably based on the total weight of the alkoxysilane (a) in the reaction system (the alkoxysilane (c) may be used in combination as necessary). Is 0.01 to 5% by weight. The amount added may be about 0.01 to 1% by weight.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. At this time, adding as an aqueous solution using water or the like causes the condensation of alkoxysilane (a) (alkoxysilane (c) used in combination as necessary) to proceed unilaterally as described above. There is a possibility that the silsesquioxane oligomer produced by the above and the silicone oil (b) are incompatible and become cloudy.

 The reactive functional group-containing siloxane compound of the present invention can be produced without a solvent or in a solvent. Moreover, a solvent can also be added in the middle of a manufacturing process. As a solvent, the solvent which melt | dissolves alkoxysilane (a), silicone oil (b) (the alkoxysilane (c) may be used together as needed), and the alkoxysilane modified body (d) is preferable. Examples of such solvents include aprotic polar solvents such as dimethylformamide, dimethylacetamide, and tetrahydrofuran, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and butanoic acid. Examples thereof include esters such as isopropyl, alcohols such as methanol, ethanol, propanol and butanol, hydrocarbons such as hexane, cyclohexane, toluene and xylene. In the present invention, the reaction in alcohols is preferable from the viewpoint of reaction control, and methanol or / and ethanol are more preferable. The amount of the solvent used is not particularly limited as long as the reaction proceeds smoothly, and alkoxysilane (a) (alkoxysilane (c) may be used in combination as necessary) and silicone oil (b), Usually, about 0 to 900 parts by weight is used per 100 parts by weight. The reaction temperature is usually 20 to 160 ° C, preferably 40 to 140 ° C, particularly preferably 50 to 150 ° C, although it depends on the amount of catalyst. Moreover, reaction time is 1 to 40 hours normally in each manufacturing process, Preferably it is 5 to 30 hours.

 After completion of the reaction, the catalyst is removed by neutralization and / or washing with water as necessary. When washing with water, depending on the type of solvent used, it is preferable to add a solvent that can be separated from water. Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.

In this reaction, the catalyst may be removed only by washing with water, but since the reaction is carried out under either acidic or basic conditions, the catalyst is washed with water after neutralization or the catalyst is removed using an adsorbent. It is preferable to remove the adsorbent by filtration after adsorption. When using an adsorbent, add the adsorbent to the reaction solution, stir, heat, etc., adsorb the catalyst, filter the adsorbent, and wash the residue to remove the catalyst and adsorbent. be able to.
For neutralization, a compound showing acidity or basicity can be used.
Examples of the compound exhibiting acidity include inorganic acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sodium dihydrogen phosphate, and organic acids such as formic acid, acetic acid, and oxalic acid. Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide; sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Alkali metal carbonates; basic phosphates such as disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid, sodium tripolyphosphate; inorganic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylamino Organic bases such as ethanol, triethanolamine, tetramethylammonium hydroxide can be used. Among these, an inorganic base or an inorganic acid compound is particularly preferable in that it can be easily removed from the target product, and more preferably sodium dihydrogen phosphate or the above base, which is easier to adjust the pH to near neutrality. Phosphates such as soluble phosphates.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
As the activated clay, for example, Toshin Kasei Co., Ltd. products: activated clay (SA35, SA1, T, R-15, or E), or nikkanite (G-36, G-153, or G-168), Products of Mizusawa Chemical Co., Ltd .: Galeon Earth, or Mizuka Ace ^RTM (superscript ^RTM represents a registered trademark; the same applies hereinafter).
Examples of the activated carbon include products of Ajinomoto Fine Techno Co., Ltd .: CL-H, Y-10S or Y-10SF, products of Phutamura Chemical Co., Ltd .: S, Y, FC, DP, SA1000, K, A, KA, M. , CW130BR, CW130AR, or GM130A.
Examples of zeolite include Union Showa Co., Ltd. products: Molecular Sieve 3A, 4A, 5A or 13X.
Synthetic adsorbents include, for example, products of Kyowa Chemical Co., Ltd .: Kyoward ^RTM 100, 200, 300, 400, 500, 600, ^700, 1000, 2000, and products of Rohm and Haas Co., Ltd .: Amberlyst ^RTM 15JWET, 15DRY, 16WET, 31WET, A21, Amberlite ^RTM IRA400JCl, IRA403BLCl, IRA404JCl, and products of Dow Chemical Co., Ltd .: Dowex ^RTM 66, HCR-S, HCR-W2 or MAC-3.

 After completion of the reaction or neutralization, it can be purified by conventional separation and purification means other than washing with water and filtration. Examples of the purification means include column chromatography, vacuum concentration, distillation, extraction and the like. These purification means may be performed singly or in combination.

 When the reaction is carried out using a solvent that is mixed with water as the reaction solvent, after removing the reaction solvent mixed with water by distillation or concentration under reduced pressure after neutralization, a solvent that can be separated from water is added to the reaction system. Thus, it is preferable to perform water washing after dissolving the target reaction product.

 After washing with water, the reactive functional group-containing siloxane compound of the present invention can be obtained by removing the solvent used above by vacuum concentration or the like.

The appearance of the siloxane compound of the present invention is usually colorless and transparent, and is a liquid having fluidity at 25 ° C.
The siloxane compound of the present invention obtained by the above reaction is a chain silicone segment as described above, preferably-(Si (R ₃ ) ₂ O) m- (R ₃ and m have the same meaning as in the above formula (2). (R ₆ SiO3 / 2) nx (R ₆ is the same as the formula (4), and nx represents an average value of 2 to 20). Reactive functional group-containing block type siloxane, characterized in that at least one part of the silsesquioxane segment has a reactive functional group having at least one epoxy group A compound.
In the silsesquioxane segment, the number of reactive functional groups having an epoxy group represented by X derived from the alkoxysilane (a) is, on average, one silicon atom in the silsesquioxane segment. A ratio of 0.3 to 1 is preferable, a ratio of 0.45 to 1 is more preferable, and a ratio of 0.6 to 1 is particularly preferable. In addition, the group represented by R ₄ derived from the alkoxysilane (c) preferably has an average ratio of 0 to 0.7 with respect to one silicon atom in the silsesquioxane segment, A ratio of 0 to 0.55 is more preferable, and a ratio of 0 to 0.4 is particularly preferable.

A preferred molecular weight of the siloxane compound of the present invention is a weight average molecular weight measured by GPC, which is about 500 to 20,000, more preferably about 800 to 20,000, still more preferably about 1,000 to 10,000, in particular. Preferably, it is about 1,500 to 6,000. If the weight average molecular weight is too low, the heat resistance may be reduced. If it is too high, the viscosity will increase and the workability will be adversely affected.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured under the following conditions using GPC (gel permeation chromatography).
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)

  The epoxy equivalent (measured by the method described in JIS K-7236) of the siloxane compound of the present invention is preferably 300 to 1,600 g / eq, more preferably 400 to 1,000 g / eq, particularly 450 to 900 g. / Eq is preferred. If the epoxy equivalent is too small, the cured product will be too hard and the low elastic modulus may be inferior. If it is too large, the mechanical properties of the cured product will deteriorate.

  The viscosity of the siloxane compound of the present invention (E-type viscometer, measured at 25 ° C.) is usually about 50 to 20,000 mPa · s, preferably about 150 to 10,000 mPa · s, preferably 200 to 10,000 mPa · s. More preferable is about s, and most preferable is about 200 to 5000 mPa · s. Moreover, the thing of 500-10,000 mPa * s is more preferable depending on the case, and the thing of 800-5,000 mPa * s is still more preferable especially.

In the siloxane compound of the present invention, the ratio of silicon atoms bonded to three oxygens belonging to the hydrolysis-condensation segment of alkoxysilane, preferably the silsesquioxane segment, to the total silicon atoms is about 5 to 95 mol%. However, 5 to 50 mol% is preferable for sealing an optical semiconductor element, 8 to 30 mol% is more preferable, and 10 to 25 mol% is particularly preferable. The balance is the proportion of silicon atoms belonging to the chain silicone segment. The above-mentioned “total silicon atoms” means all silicon atoms in the siloxane compound of the present invention. When the ratio of silicon atoms belonging to the silsesquioxane segment to three oxygen atoms with respect to all silicon atoms is less than 5 mol%, the characteristics of the chain silicone segment are strongly exhibited, and as a result, the curable resin composition described later When used as a component, the cured product of the resin composition tends to be too soft, and there is a concern of surface tack and scratches. Moreover, when it exceeds 50 mol%, as a result of the strong characteristics of the silsesquioxane segment, when used as a component of a curable resin composition to be described later, the cured product of the resin composition becomes too hard and the low elastic modulus characteristic is lowered. However, the result of the heat cycle test tends to deteriorate.
As described above, the siloxane compound of the present invention has a chain silicone segment and a hydrolysis-condensation segment (preferably a silsesquioxane segment) of the alkoxysilane, and the latter segment has a reactive functional group having an epoxy group. In particular, the siloxane compound of the present invention in which the proportion of the chain silicone segment is increased is also a great feature in that it is suitable for optical semiconductor encapsulation. For example, as described above, when the ratio of the silicon atom belonging to the hydrolysis-condensation segment (preferably silsesquioxane segment) of the alkoxysilane to the total silicon atoms in the siloxane compound of the present invention is 5 to 50 mol% The proportion of silicon atoms belonging to the chain silicone segment is 50 to 95 mol%. Moreover, the preferable ratio of the silicon atom which belongs to a chain silicone segment is 70-92 mol%, More preferably, it is 75-90 mol%.
The ratio of silicon atoms in the two segments in the siloxane compound of the present invention may be calculated from the raw material charge ratio, or determined by ¹ H NMR, ²⁹ Si NMR, elemental analysis, or the like of the obtained siloxane compound of the present invention. You can also.

The siloxane compounds of the present invention are summarized as follows.
(I) a block type having a linear silicone segment and a hydrolytic condensation segment of tri (C1-C10) alkoxysilane having a group selected from the group consisting of a reactive functional group having an epoxy group, a methyl group and a phenyl group A reactive functional group-containing siloxane compound, wherein the at least one hydrolytic condensation segment is a segment containing a reactive functional group having at least one epoxy group.
(Ii) The chain silicone segment is represented by the following formula (2A)
_{- (Si (R 3) 2} O) m- (2A)
(In the formula, R ₃ may be the same or different from each other, and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 carbon atoms. 10 represents an alkenyl group, and m represents an average value of 2 to 2000)
The reactive functional group-containing siloxane compound according to (i), which is a segment represented by
(Iii) The reactive functional group-containing siloxane compound according to (ii), wherein R ₃ is an alkyl group having 1 to 10 carbon atoms, and m is an average of 2 to 200.
(Iv) The reactive functional group-containing siloxane compound according to any one of (i) to (iii), wherein R ₃ is a methyl group.

(V) Any of the above (i) to (iv), wherein the reactive functional group having an epoxy group is an alkyl group having 1 to 3 carbon atoms substituted with an cycloalkyl group having 5 to 8 carbon atoms having an epoxy group The reactive functional group-containing siloxane compound according to one item.
(Vi) A tri (C1-C10) alkoxysilane having a reactive functional group having an epoxy group, a group selected from the group consisting of a methyl group and a phenyl group is substituted with a C5-C8 cycloalkyl group having an epoxy group The reactive functional group-containing siloxane compound according to any one of (i) to (iv), which is a tri (C1-C10) alkoxysilane having an alkyl group having 1 to 3 carbon atoms.
(Vii) Tri (C1-C10) alkoxysilane having an alkyl group having 1 to 3 carbon atoms substituted with an cycloalkyl group having 5 to 8 carbon atoms having an epoxy group is β- (3,4 epoxy cyclohexyl) ethyl. The reactive functional group-containing siloxane compound according to (vi), which is trimethoxysilane.
(Viii) A tri (C1-C10) alkoxysilane having a reactive functional group having an epoxy group, a tri (C1-C10) alkoxysilane having a group selected from the group consisting of a methyl group and a phenyl group (C1- The reactivity according to any one of (i) to (vii) above, which is both C10) alkoxysilane and tri (C1-C10) alkoxysilane having a group selected from the group consisting of a methyl group and a phenyl group. Functional group-containing siloxane compound.
(Ix) Reactive functional group-containing siloxane according to (viii) above, wherein the tri (C1-C10) alkoxysilane having a group selected from the group consisting of a methyl group and a phenyl group is phenyltrimethoxysilane or methyltrimethoxysilane. Compound.
(X) The reactive functional group-containing siloxane compound according to any one of (i) to (ix), wherein the weight average molecular weight measured by GPC is 500 to 20,000.

(Xi) As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or An alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 2000)
A silanol-terminated silicone oil (b) represented by:
General formula (1)
XSi (OR ₂ ) ₃ (1)
(In the formula, X represents a reactive functional group having an epoxy group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms.)
Is reacted in the range of 1.5 to 200 equivalents of the alkoxy group equivalent of the alkoxysilane compound to 1 equivalent of the silanol group of the silanol-terminated silicone oil (b), Any one of the above (i) to (x) obtained by condensing and then adding water to the resulting reaction solution as a second stage reaction to hydrolyze and condense the remaining alkoxy groups The reactive functional group-containing siloxane compound described in 1.

(Xii) The silanol-terminated silicone oil (b) represented by the general formula (2) measured by GPC (gel permeation chromatography) has a weight average molecular weight of 300 to 30,000, as described in (xi) above. Reactive functional group-containing siloxane compound.
(Xiii) The above (xi) or (xi) wherein the equivalent of the alkoxy group of the alkoxysilane compound (a) represented by the general formula (1) is 2 to 100 equivalents relative to 1 equivalent of the silanol group of the silanol-terminated silicone oil (b) A reactive functional group-containing siloxane compound as described in xii).
(Xiv) The silanol-terminated silicone oil (b) represented by the general formula (2) is a silanol-terminated dimethyl silicone oil or a silanol-terminated methylphenyl silicone oil (xi) to (xiii) Reactive functional group-containing siloxane compound.
(Xv) The alkoxysilane compound (a) represented by the general formula (1) is β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ Any one of (xi) to (xiv) which is glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane or β- (3,4-epoxycyclohexyl) ethyltriethoxysilane The reactive functional group-containing siloxane compound according to one item.

(Xvi) As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 200), and the general formula (1)
XSi (OR ₂ ) ₃ (1)
(Wherein X represents a reactive functional group having an epoxy group, R ₂ represents an alkyl group having 1 to 10 carbon atoms) and the general formula (3)
R ₄ Si (OR ₂ ) ₃ (3)
(Wherein, R ₄ is a methyl group or a phenyl group, R ₂ is Formula (may be the same or different as R ₂ in 1) each independently represent an alkyl group having 1 to 10 carbon atoms .)
Both of the alkoxysilane compounds (c) represented by formula (1) are the total equivalents of the alkoxy groups of the alkoxysilane compounds (a) and (c) with respect to 1 equivalent of silanol groups of the silanol-terminated silicone oil (b). The above (i) obtained by reacting in the range of 5 to 200 equivalents and condensing, and then adding water to the resulting reaction solution to hydrolyze and condense the remaining alkoxy groups as the second stage reaction. The reactive functional group-containing siloxane compound according to any one of (1) to (x).
(Xvii) The reactive functional group-containing siloxane compound according to (xvi), wherein the silanol-terminated silicone oil (b) represented by the general formula (2) is the silicone oil according to (xii) or (xiv) .
(Xviii) The reactive functional group-containing siloxane compound according to (xvi) or (xvii), wherein the alkoxysilane compound (a) represented by the general formula (1) is a compound according to (xv) above.
(Xix) The reactive functional group according to any one of (xvi) to (xviii) above, wherein the alkoxysilane compound (c) represented by the general formula (3) is methyltrimethoxysilane or phenyltrimethoxysilane. Containing siloxane compound.

Next, the curable resin composition of the present invention will be described.
The siloxane compound of the present invention can be used as a component of a curable resin composition. Hereinafter, the siloxane compound of the present invention is referred to as “siloxane compound (A) of the present invention” or simply “siloxane compound (A)” in the description of the curable resin composition. In this case, the siloxane compound (A) may be the reactive functional group-containing siloxane compound described in any one of (i) to (xix) above, and includes all combinations with the siloxane compound. .
The curable resin composition of the present invention contains the siloxane compound (A) of the present invention as an epoxy resin component, and further contains a curing agent (B). Furthermore, you may contain other epoxy resins other than a siloxane compound (A), and / or a hardening accelerator (C) as needed. The other epoxy resin is a property of the siloxane compound (A) of the present invention, for example, a property as a cured product when used in a curable resin composition, specifically, transparency, heat resistance / light resistance, low temperature. It can be used in combination as long as the low elastic modulus characteristics, non-tack property, heat cycle resistance, hardness and the like are not lost. In some cases, the other epoxy resin improves the physical properties of the cured product of the curable resin composition. The ratio of the siloxane compound (A) of the present invention to the entire epoxy resin component is 20 to 100% by weight, preferably 30 to 100% by weight, more preferably 50 to 100% by weight. It may be 100% by weight, or 70 to 100% by weight, and further 80 to 100% by weight.
When used in combination, the proportion of the siloxane compound of the present invention in the total epoxy resin including the siloxane compound (A) of the present invention and other epoxy resins is preferably 20 to 90% by weight, particularly 30 to 90% by weight. % Is preferred.
Furthermore, in the curable resin composition of the present invention, the ratio of the total epoxy resin obtained by combining the siloxane compound (A) of the present invention alone or the siloxane compound (A) of the present invention and another epoxy resin is the composition. It is about 30-90 weight% with respect to the whole thing, More preferably, it is 40-90 weight%, Preferably it is about 50-90 weight%. Depending on the embodiment, 40 to 80% by weight, preferably about 50 to 80% by weight is also preferred.
Specific examples of other epoxy resins include polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds, polyfunctional epoxy resins that are glycidyl etherified products of various novolak resins, nuclear hydrides of aromatic epoxy resins, and alicyclic epoxies. Examples thereof include resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, or glycidylated silicone resins.

The polyphenol compounds used in the polyfunctional epoxy resin include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, and tetramethyl. Bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4 -Hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), Trishydroxyphenyl Tan, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having fluorene skeleton such as 1,1-di-4-hydroxyphenyl fluorene, may be mentioned a polyphenol compound of phenolic polybutadiene or the like. Accordingly, specific examples of the polyfunctional epoxy resin that is a glycidyl etherified product of the polyphenol compound include glycidyl etherified products of the above polyphenol compounds.
Examples of the various novolak resins used in the polyfunctional epoxy resin include novolac resins using various phenols as raw materials. Examples of the various phenols used as raw materials include phenol, cresols, ethylphenols, butylphenols, Novolak resin, xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, fluorene skeleton Various novolak resins such as a phenol novolak resin can be given. Accordingly, specific examples of the polyfunctional epoxy resin that is a glycidyl etherified product of various novolak resins include glycidyl etherified products of these novolak resins.

Examples of the nuclear hydride of the aromatic epoxy resin include a nuclear hydride of a glycidyl ether product of a novolak resin using the above-mentioned novolac resin as a raw material, and specifically, various phenols such as bisphenol A and bisphenol. F, bisphenol S, 4,4'-biphenol and other glycidyl etherified products, or phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc. And a nuclear hydride of a glycidyl etherified product of a novolak resin.
Examples of the alicyclic epoxy resins include 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2- (3 , 4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, and the like, an alicyclic ring having an aliphatic skeleton such as cyclohexane An epoxy resin can be mentioned.
Aliphatic epoxy resins include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, xylylene glycol derivatives and the like. Examples thereof include glycidyl ethers.
Examples of the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
Examples of the glycidyl ester epoxy resin include epoxy resins composed of glycidyl esters of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine epoxy resin include epoxy resins obtained by glycidylation of amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative.
Halogenated phenols such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol A are used as epoxy resins obtained by glycidylation of halogenated phenols. Examples thereof include epoxy resins obtained by glycidylation of phenols.

  Although there is no restriction | limiting in particular in the use of these epoxy resins, A thing with little coloring property is more preferable from a viewpoint of transparency. Usually, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- ( 4-hydroxyphenyl) ethyl) phenyl] propane, trishydroxyphenylmethane, resorcinol, 2,6-ditert-butylhydroquinone, phenols having a diisopropylidene skeleton, or 1,1-di-4-hydroxyphenylfluorene Polyfunctional epoxy resins that are glycidylated phenols having a fluorene skeleton such as: Novolak resins made from various phenols such as phenol, cresols, bisphenol A, bisphenol S, naphthols, and phenol novolacs containing dicyclopentadiene skeleton Glycidyl etherified products of various novolak resins such as fat, biphenyl skeleton-containing phenol novolac resin, fluorene skeleton-containing phenol novolak resin; glycidyl etherified products of phenol compounds such as bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, or Nuclear hydrides of glycidyl ethers of novolak resins made from various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols; 3,4-epoxy Cycloaliphatic epoxy resins having a cyclohexane skeleton such as cyclohexylmethyl 3 ′, 4′-cyclohexylcarboxylate; 1,6-hexanediol, polyethylene Glycidyl ethers of polypropylene glycol, polypropylene glycol; or triglycidyl isocyanurate or diglycidyl ester of hexahydrophthalic acid; and the like. From the viewpoint of heat-resistant transparency and light-resistant transparency, an alicyclic epoxy having a cyclohexane skeleton Resins are particularly preferred. These epoxy resins can be used in combination as one kind or a mixture of two or more kinds as required, such as imparting heat resistance.

Details of the curing agent (B) and the curing accelerator (C) used in the present invention will be described.
As the curing agent (B), amine compounds, acid anhydride compounds, carboxylic acid compounds, amide compounds, phenol compounds, and the like can be used without particular limitation. Specifically, polyamide resin synthesized from diamine of diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine compound, linolenic acid and ethylenediamine, Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hydrogenated nadic acid anhydride, hydrogenated methyl nadic acid anhydride, Methyl nadic acid anhydride, hexahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride, 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid Phosphoric acid, methylhexahydrophthalic acid, trimellitic acid, cyclohexanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene , Dihydroxynaphthalene, etc.) and polycondensates of various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, or bismethoxymethylbiphenyl and naphthols or phenols. Examples include condensates, biphenols and modified products thereof, imidazole, boron trifluoride-amine complexes, guanidine derivatives, and the like. Among these, an acid anhydride compound and a carboxylic acid compound are particularly preferable from the viewpoint of an appropriate pot life when mixed with an epoxy resin to obtain a resin composition, and transparency of the cured product, and hexahydrophthalic acid. Particularly preferred are anhydride, methylhexahydrophthalic anhydride, 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride, hydrogenated nadic acid anhydride, and hydrogenated methyl nadic acid anhydride.
The amount of the curing agent (B) used is preferably about 0.2 to 1.5 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins combined with the siloxane compound (A) or other epoxy resin in the composition, About 0.3 to 1.2 equivalents are particularly preferable. In particular, when a tertiary amine such as benzyldimethylamine is used as the curing agent (B), the curing agent is used in an amount of 0.3 to 20% by weight based on the epoxy group-containing compound in the composition. It is preferably 0.5 to 10% by weight.

  Examples of the curing accelerator (C) include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-me Tyrimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Various imidazoles such as imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole; and imidazoles and phthalic acid, isophthalic acid, Salts with polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and succinic acid; amides such as dicyandiamide; 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as -7; Salts such as nylborate and phenol novolac; salts with the above polycarboxylic acids or phosphinic acids; ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, cetyltrimethylammonium hydroxide, trioctylmethylammonium bromide; triphenyl Phosphines such as phosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethyl phosphate, and phosphonium compounds; phenols such as 2,4,6-trisaminomethylphenol; amine adducts ; For example, as a commercial item, U-CAT 18X (trade name: manufactured by San Apro Co., Ltd.) and the like can be mentioned. These curing accelerators may be microencapsulated. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. The curing accelerator is usually 0.001 to 15 parts by weight, preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the block type siloxane compound (A) having a reactive functional group or other epoxy resin. Is used, more preferably 0.05 to 1 part by weight.

In the curable resin composition of the present invention, an inorganic filler, a colorant, a silicone resin, a leveling agent, a lubricant, a coupling agent, a leveling agent, a lubricant, a light stabilizer, depending on the purpose, as long as transparency is not impaired. Antioxidants, phosphors, and the like can be added as appropriate.
The inorganic filler is not particularly limited, and examples thereof include crystalline or amorphous silica, talc, silicon nitride, boron nitride, alumina, silica / titania mixed melt, and the like.
There are no particular restrictions on the colorant, and phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine-based organic dyes, titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium Inorganic pigments such as vermilion, valve shell, cobalt violet, bitumen, ultramarine, carbon black, chrome green, chromium oxide, cobalt green and the like can be mentioned.
Examples of the silicone resin include dimethyl silicone, phenylmethyl silicone, epoxy-modified silicone, polyether-modified silicone, amine-modified silicone, vinyl-modified silicone, and silyl-modified silicone.

  Leveling agents include acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like, oligomers having a molecular weight of 4,000 to 12,000, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil, titanium-based cups A ring agent etc. are mentioned.

  Lubricants such as paraffin wax, microwax, polyethylene wax, etc .; higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid; stearylamide, palmitylamide, oleyl Higher fatty acid amide-based lubricants such as amide, methylene bisstearamide, ethylene bisstearamide; hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or tetra-) Higher fatty acid ester lubricants such as stearate; alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol; lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behe Acid, ricinoleic acid, metal soaps are magnesium, calcium, Kadonyuumu, Baryuumu, zinc, metal salts such as lead naphthenate acid;, carnauba wax, candelilla wax, beeswax, natural waxes such as montan; and the like.

  As coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrime Silane coupling agents such as xysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neoalkoxy tri Titanium coupling agents such as (p-N- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxy tris neodecanoyl zirconate , Neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zircoate Nitrate, zirconium such as ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate, and aluminum coupling agents.

  As the light stabilizer, a hindered amine light stabilizer (HALS) is suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-pentamethyl-4- Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.

Examples of the antioxidant include phenol-based, sulfur-based, and phosphorus-based antioxidants.
Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t- Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t- Butyl-4-hydroxybenzyl phosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methyl Enyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bisphenols such as bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1 , 3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc. Molecular type phenols are exemplified.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2 , 4-di-tert-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. Fights; 9,10-jihi Rho-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene Examples thereof include oxaphosphaphenanthrene oxides such as -10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part with respect to the resin component in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part. It is.

When using the curable resin composition of this invention for an optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substances, the addition amount is 1 to 80 parts by weight, and preferably 5 to 60 parts by weight with respect to 100 parts by weight of the resin component.

The preferable curable resin composition of the present invention is as follows.
(I) The reactive functional group-containing siloxane compound according to any one of (i) to (xix) (hereinafter referred to as the siloxane compound (A) of the present invention or the siloxane compound (A)), and optionally The total amount of the epoxy compound other than the siloxane compound (A) (hereinafter also referred to as O-EPO) may be 30 to 90% by weight based on the whole composition (hereinafter, unless otherwise specified, the weight) %), And the balance is a curing agent (B).
(II) The curable resin composition according to (I), wherein the curing agent (B) is contained in a range of 0.2 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the siloxane compound (A).
(III) Curability as described in (I) or (II) above, comprising 50 to 90% of the total amount of the siloxane compound (A) and optionally O-EPO, based on the total composition Resin composition.
(IV) Any one of the above (I) to (III), wherein the ratio of the siloxane compound (A) to the total amount of the siloxane compound (A) and optionally O-EPO is 50 to 100% The curable resin composition described in 1.
(V) The ratio of the siloxane compound (A) to the total amount of the siloxane compound (A) and optionally O-EPO is 30 to 90%, and any one of the above (I) to (IV) The curable resin composition described in 1.
(VI) Furthermore, the curing accelerator is contained in any one of the above (I) to (V) containing 0.001 to 15 parts by weight with respect to 10 parts by weight of the siloxane compound (A). Curable resin composition.
(VII) The curable resin composition according to any one of (I) to (VI) above, wherein the curing agent (B) is an acid anhydride compound or a carboxylic acid compound.
Said curable resin composition of this invention can be obtained by mixing said raw material uniformly by arbitrary methods.

  The curable resin composition of the present invention includes a siloxane compound (A) having a reactive functional group, a curing agent (B), and a curing accelerator (C) as necessary, and the curable resin. If necessary, the composition may further contain other optional ingredients. Examples of other optional components include inorganic fillers, colorants, silicone resins, leveling agents, lubricants, coupling agents, light stabilizers, antioxidants, and phosphors. These other compounding components can be appropriately added in the range of 0 to 500 parts by weight, preferably about 0 to 100 parts by weight, with respect to 100 parts by weight of the total amount of the siloxane compound (A) and the curing agent (B). is there. If these blended ingredients are solid, they are mixed using a blender such as a Henschel mixer or Nauta mixer, then kneaded at 80-120 ° C using a kneader, extruder, or heated roll and cooled. Thereafter, it can be pulverized to obtain a powder. On the other hand, when the blended material is liquid, it can be uniformly dispersed using a planetary mixer or the like to obtain the curable resin composition of the present invention containing these other blended components.

In order to obtain an optical semiconductor of the present invention by sealing an optical semiconductor such as an LED, a photosensor, or a transceiver using the composition of the present invention thus obtained, a transfer mold, a compression mold, an injection mold, a dispensing method, printing What is necessary is just to shape | mold by the conventional shaping | molding methods, such as a method.
In addition, the heating method for curing the resin composition for sealing an optical semiconductor after molding is not particularly limited, and a conventionally known method such as hot air circulation heating, infrared heating, high frequency heating or the like can be adopted. . The curing condition is usually performed by heating at about 80 to 250 ° C. for 30 seconds to 15 hours, but the conditions may be changed as appropriate. A preferable condition is 110 to 200 ° C., for example, a method of first curing at 100 to 140 ° C. and then performing a final curing at 130 to 200 ° C. is preferable.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical property value in an Example was measured with the following method.
(1) Molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by gel permeation chromatography (GPC) method.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
(2) Epoxy equivalent: measured by the method described in JIS K-7236.
(3) Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. In the synthesis examples and examples, “part” means part by weight, and “%” means% by weight. Moreover, as for the alkoxy equivalent and the silanol equivalent, as for the thing in which the unit is not described, the unit is g / eq.
Example 1
(Example in which an alkoxy group is reacted at 5.3 equivalents with respect to 1 equivalent of silanol groups)
First stage reaction: Silanol-terminated dimethylsilicone oil having 197.1 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1 g / eq) and weight average molecular weight 1060 (measured by GPC) 237. 4 parts (silanol equivalent 530 g / eq), 21.3 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.11 parts as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. It was. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
The silanol equivalent 530 g / eq was calculated as a half of the weight average molecular weight 1060 measured using GPC, assuming that the molecular weight of the silicone oil is two silanol groups per molecule. Also in the following examples, the silanol equivalent of the silanol-terminated silicone oil (b) was determined in the same manner.
Second stage reaction: 305 parts of methanol was added to the reaction solution obtained above, 86.4 parts of 50% distilled water in methanol was added dropwise over 60 minutes, and then reacted at 75 ° C. under reflux for 8 hours. It was. After completion of the reaction, the reaction solution was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. After adding 380 parts of methyl isobutyl ketone (MIBK) to the remaining reaction solution, washing with water was repeated three times. Next, after separating the organic phase, the solvent was removed therefrom at 100 ° C. under reduced pressure to obtain 344 parts of a block type siloxane compound (A-1) having a reactive functional group. The epoxy equivalent of the obtained compound was 457 g / eq, the weight average molecular weight was 3,700, the viscosity was 600 mPa · s, and the appearance was colorless and transparent.
Further, the ratio of silicon atoms belonging to the silsesquioxane segment (ratio of silicon atoms bonded to three oxygen atoms calculated from the ratio of charged raw materials to all silicon atoms) was 19.6 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 80.4 mol%.

Example 2
(Example in which an alkoxy group is reacted at a rate of 30.8 equivalents with respect to 1 equivalent of a silanol group)
First stage reaction: 237.4 parts of silanol-terminated dimethyl silicone oil having 197.1 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average molecular weight of 6120 (measured by GPC) (Silanol equivalent 3060), 20.0 parts of a 0.5% KOH methanol solution (0.1 parts as the number of KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
As the second stage reaction, 260 parts of methanol was added, 86.4 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 380 parts of MIBK was added, and washing with water was repeated three times. Subsequently, 360 parts of block type siloxane compounds (A-2) which have a reactive functional group were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The epoxy equivalent of the obtained compound was 468 g / eq, the weight average molecular weight was 4160, the viscosity was 481 mPa · s, and the appearance was colorless and transparent.
Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 19.6 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 80.4 mol%.

Example 3
(Example in which an alkoxy group is reacted at a rate of 80.1 equivalents per 1 equivalent of a silanol group)
First stage reaction: 118.7 parts of silanol-terminated dimethylsilicone oil having 98.6 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average molecular weight of 15800 (measured by GPC). (Silanol equivalent 7900) and 10.0 parts of a 0.5% KOH methanol solution (0.05 parts as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
Second stage reaction: After 142 parts of methanol was added, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 191 parts of MIBK was added, and washing with water was repeated three times. Subsequently, the organic phase was removed at 100 ° C. under reduced pressure to obtain 169 parts of a block type siloxane compound (A-3) having a reactive functional group. The epoxy equivalent of the obtained compound was 447 g / eq, the weight average molecular weight was 4130, the viscosity was 710 mPa · s, and the appearance was colorless and transparent.
Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 19.6 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 80.4 mol%.

Example 4
(Example in which alkoxy group is reacted at a ratio of 8.6 equivalent to 1 equivalent of silanol group)
First stage reaction: β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 49.3 parts (alkoxy group equivalent 82.1), phenyltrimethoxysilane 39.7 parts (alkoxy group equivalent 66.1), weight A reaction vessel was charged with 118.7 parts of silanol-terminated methylphenyl silicone oil having an average molecular weight of 1700 (GPC measurement value) (silanol equivalent: 850) and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts). The liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
Second stage reaction: After adding 123 parts of methanol, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 191 parts of MIBK was added, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 168 parts of a block type siloxane compound (A-4) having a reactive functional group. The epoxy equivalent of the obtained compound was 874 g / eq, the weight average molecular weight was 2630, the viscosity was 4600 mPa · s, and the appearance was colorless and transparent.
The proportion of silicon atoms belonging to the silsesquioxane segment was 22.5 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 77.5 mol%.

Example 5
(Example in which alkoxy group is reacted at a ratio of 8.6 equivalent to 1 equivalent of silanol group)
First stage reaction: β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 49.3 parts (alkoxy group equivalent 82.1), methyltrimethoxysilane 27.2 parts (alkoxy group equivalent 45.4), weight A reaction vessel was charged with 118.7 parts of silanol-terminated methylphenyl silicone oil having an average molecular weight of 1700 (GPC measurement value) (silanol equivalent: 850) and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts). The liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
Second stage reaction: After adding 123 parts of methanol, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 166 parts of MIBK was added, and washing with water was repeated three times. Subsequently, 151 parts of block type siloxane compounds (A-5) which have a reactive functional group were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The epoxy equivalent of the obtained compound was 832 g / eq, the weight average molecular weight was 5850, the viscosity was 4610 mPa · s, and the appearance was colorless and transparent.
Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 20.0 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 80.0 mol%.

Comparative Example 1
(Example in which alkoxy group is reacted at a ratio of 1.4 equivalent to 1 equivalent of silanol group: Example of gelation in first stage reaction)
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 37.0 parts (alkoxy group equivalent 82.1), weight average molecular weight 1060 (GPC measurement value) silanol-terminated dimethyl silicone oil 170.9 parts (silanol equivalent 530) Then, 12.3 parts of 0.5% KOH methanol solution (0.06 parts as KOH parts) was put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the mixture was reacted at 75 ° C. under reflux for 4 hours. The reaction product became a solvent-insoluble gelled product (A-6).

Reference example 1
(Example in which alkoxy group is reacted in the presence of water at a ratio of 5.5 equivalent to 1 equivalent of silanol group)
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 98.6 parts (alkoxy group equivalent 82.1), weight average molecular weight 1060 (GPC measurement value) silanol-terminated dimethyl silicone oil 118.7 parts (silanol equivalent 530) 131 parts of methanol and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After the temperature increase, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 191 parts of MIBK was added, and washing with water was repeated three times. Subsequently, 176 parts of siloxane compounds (A-7) which have a reactive functional group were obtained by removing a solvent at 100 degreeC under pressure reduction of the organic phase. The obtained compound had an epoxy equivalent of 459 g / eq, a weight average molecular weight of 3300, and the appearance was cloudy and could not be used as a composition for optical semiconductor encapsulants.

Reference example 2
(Example in which alkoxy group is reacted in the presence of water at a ratio of 30.7 equivalent to 1 equivalent of silanol group)
In the same manner as the synthesis method in Patent Document 1, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 45.4 parts (alkoxy group equivalent 82.1), weight average molecular weight 6120 (GPC measurement value) silanol terminal Dimethyl silicone oil 54.6 parts (silanol equivalent 3060), triethylamine 10.0 parts and MIBK 500 parts are put in a reaction vessel, and 100 parts of distilled water is added dropwise over 30 minutes while stirring at room temperature. The reaction was performed for 6 hours. After completion of the reaction, the mixture was neutralized with a 20% aqueous solution of sodium dihydrogen phosphate and then washed with water three times. Next, when the solvent was removed from the organic phase under reduced pressure at 100 ° C., 85 parts of a cloudy liquid (A-8) was obtained, which could not be used as a composition for an optical semiconductor encapsulant.

Reference example 3
(Example in which an alkoxy group is reacted in the presence of water at a ratio of 31.0 equivalent to 1 equivalent of silanol group)
94.0 parts (silanol equivalent 3060) of silanol-terminated dimethyl silicone oil having a β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 78.8 parts (alkoxy group equivalent 82.1) and a weight average molecular weight 6120 (GPC measurement value). Then, 104 parts of methanol and 8.0 parts of 0.5% KOH methanol solution (0.04 parts as KOH parts) were put into a reaction vessel, and the liquid temperature was raised to 75 ° C. After the temperature rise, 34.6 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 152 parts of MIBK was added, and washing with water was repeated three times. Next, when the solvent was removed from the organic phase under reduced pressure at 100 ° C., 151 parts of a cloudy liquid (A-9) was obtained, which could not be used as a composition for an optical semiconductor encapsulant.

Reference example 4
(Example in which an alkoxy group is reacted in the presence of water at a ratio of 80.0 equivalent to 1 equivalent of silanol group)
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 98.6 parts (alkoxy group equivalent 82.1), weight average molecular weight 15800 (GPC measured value) silanol-terminated dimethyl silicone oil 118.7 parts (silanol equivalent 7900) Then, 142 parts of methanol and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After the temperature increase, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 191 parts of MIBK was added, and washing with water was repeated three times. Subsequently, when the solvent was removed from the organic phase under reduced pressure at 100 ° C., 189 parts of a cloudy liquid (A-10) was obtained.

Comparative Example 2
Synthesis was performed using a silicone oil having an alkoxy group at the terminal represented by the following formula (5) instead of the silanol-terminated silicone oil of the formula (2) used in Examples 1 to 5.

  β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 37.0 parts (alkoxy group equivalent 82.1), weight average molecular weight 2500 (GPC measurement value) 63.1 parts methoxy-terminated dimethyl silicone oil (alkoxy equivalent 1250) Then, 64 parts of methanol and 5.0 parts of 0.5% KOH methanol solution (0.025 parts as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After the temperature rise, 16.2 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 88 parts of MIBK was added, and washing with water was repeated three times. Next, when the solvent was removed from the organic phase under reduced pressure at 100 ° C., 80.6 parts of a cloudy liquid (A-11) was obtained, which could not be used as a composition for an optical semiconductor encapsulant.

Table 1 summarizes the properties of the resins A-1 to A-11 obtained in Examples 1 to 5, Comparative Examples 1 and 2, and Reference Examples 1 to 4.

  From the above results, Comparative Example 1 in which the compound represented by the general formula (1) and the compound represented by the general formula (2) were prepared with an alkoxy group / silanol group charge equivalent value of 1.4 was a solvent-insoluble gelled product. It was confirmed that it could not be used as an epoxy resin. Reference Example 1, Reference Example 2, Reference Example 3, and Reference Example 4 (A-) were prepared by synthesizing the compound represented by the general formula (1) and the compound represented by the general formula (2) by adding an alkali catalyst and water at once. 7, A-8, A-9, A-10) turned into a cloudy liquid, and it was confirmed that it was not suitable for optical use. Furthermore, as a chain silicone segment, A-11 (Comparative Example 2) using a compound of the formula (5) which is a silicone oil having an alkoxy group at the terminal instead of the compound represented by the general formula (2) also became cloudy. It turned out to be a liquid and not suitable for optical applications. On the other hand, Examples 1-3 (A-1, A-2, A-3) in which the compounds represented by the general formula (1) and the general formula (2) were reacted in two stages, the general formula (1), In Examples 4 and 5 (A-4 and A-5) in which the compounds represented by (2) and (3) were reacted in two stages, it was confirmed that a colorless and transparent resin was obtained and was suitable for optical use. did it.

Comparative Example 3
When dimethylsiloxane is considered as a unit structure, the following formula (Mole%) is used so that the content concentration (mol%) of the dimethylsiloxane unit structure contained in the compound is the same concentration (mol%) as in Examples 1-3. The synthesis was performed using dimethyldimethoxysilane of 6) as a raw material.

  In the same manner as in the method described in Patent Document 1, 33.9 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1), dimethyldimethoxysilane (alkoxy equivalent 60.60). 1) 10.0 parts of triethylamine and 500 parts of MIBK were charged into a reaction vessel, 100 parts of distilled water was added dropwise over 30 minutes while stirring at room temperature, and the mixture was reacted at 80 ° C. for 6 hours. After completion of the reaction, the mixture was neutralized with a 20% aqueous solution of sodium dihydrogen phosphate and then washed with water three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 60 parts of a siloxane compound (A-12) having a reactive functional group. The epoxy equivalent of the obtained compound was 459 g / eq, the weight average molecular weight was 940, and the appearance was colorless and transparent.

Example 6
(Example in which an alkoxy group is reacted at a ratio of 3.8 equivalents to 1 equivalent of a silanol group)
First stage reaction: 252.8 parts of silanol-terminated dimethyl silicone oil having 147.8 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average molecular weight of 1060 (measured by GPC) (Silanol equivalent 356) and 20.0 parts of a 0.5% KOH methanol solution (0.1 parts as the number of KOH parts) were charged into the reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
Second stage reaction: After adding 255 parts of methanol, 64.8 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 352 parts of MIBK was added, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 333 parts of a block type siloxane compound (A-13) having a reactive functional group. The epoxy equivalent of the obtained compound was 578 g / eq, the weight average molecular weight was 5250, the viscosity was 257 mPa · s, and the appearance was colorless and transparent.
Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 14.9 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 85.1 mol%.

Comparative Example 4
When dimethylsiloxane is considered as a unit structure, the following formula (6) is satisfied so that the content concentration (mol%) of the dimethylsiloxane unit structure contained in the compound is the same concentration (mol%) as in Example 6. Synthesis was performed using dimethyldimethoxysilane as a raw material.

  The synthesis was carried out in the same manner as described in Patent Document 1, 26.6 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1), 73.4 parts of dimethyldimethoxysilane ( An alkoxy equivalent of 60.1), 10.0 parts of triethylamine, and 500 parts of MIBK were charged into a reaction vessel, and 100 parts of distilled water was added dropwise over 30 minutes with stirring at room temperature, and the mixture was reacted at 80 ° C. for 6 hours. After completion of the reaction, the mixture was neutralized with a 20% aqueous solution of sodium dihydrogen phosphate and then washed with water three times. Subsequently, the organic phase was removed under reduced pressure at 100 ° C. to obtain 60 parts of a siloxane compound (A-14) having a reactive functional group. The epoxy equivalent of the obtained compound was 561 g / eq, the weight average molecular weight was 830, and the appearance was colorless and transparent.

Example 7
(Example in which an alkoxy group is reacted at a ratio of 4.8 equivalents to 1 equivalent of a silanol group)
First stage reaction: Silanol-terminated methylphenyl silicone oil 130.6 with 59.1 parts β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and weight average molecular weight 1700 (GPC measured value) Parts (silanol equivalent: 850) and 10.0 parts of a 0.5% KOH methanol solution (0.1 parts as the number of KOH parts) were charged into the reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
Second stage reaction: After adding 135 parts of methanol, 25.9 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. under reflux for 8 hours. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 170 parts of MIBK was added for washing, and washing with water was repeated three times. Subsequently, 162 parts of block type siloxane compounds (A-15) which have a reactive functional group were obtained by removing a solvent at 100 degreeC under pressure reduction of an organic phase. The epoxy equivalent of the obtained compound was 707 g / eq, the weight average molecular weight was 2680, the viscosity was 727 mPa · s, and the appearance was colorless and transparent.
Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 13.6 mol%. Similarly, the proportion of silicon atoms belonging to the chain silicone segment was 86.4 mol%.

Examples 8-13, Comparative Examples 5-7
The synthesized siloxane compound (any one of A-1 to 3 and 12 to 15) or a commercially available alicyclic epoxy resin (ERL-4221) conventionally used for optical semiconductor encapsulation, and a curing agent ( B-1 to B-3) or both the curing agent (B-3) and the curing accelerator C-1 were mixed in parts by weight shown in Table 2, 3, 4 or 5, and Example 8 of the present invention was performed. To 13 and Comparative Examples 5 to 7 were obtained.
Examples and Comparative Examples described in Table 2 are as follows.
Example 8: Composition using Compound A-1 and curing agent B-1 Example 9: Composition using Compound A-2 and curing agent B-1 Example 10: Compound A-3 and curing agent B Composition Comparative Example 5 using -1: Composition Comparative Example 6 using Compound A-12 and Curing Agent B-1: Composition using ERL-4221 and Curing Agent B-1 Implementation described in Table 3 Examples and comparative examples are as follows.
Example 11: Composition using compound A-13, curing agent B-3 and curing accelerator C-1 Comparative example 7: Using compound A-14, curing agent B-3 and curing accelerator C-1 Composition The Example and comparative example which were described in Table 4 are as follows.
Example 12: Composition using Compound A-15, Curing Agent B-3, and Curing Accelerator C-1 Examples and Comparative Examples described in Table 5 are as follows.
Example 13: Composition using compound A-13, curing agent B-3 and curing accelerator C-1 Comparative example 6: Composition using ERL-4221 and curing agent B-1

  The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were subjected to the following transmittance test, mechanical property test (dynamic viscoelasticity test), and LED lighting test, and the results are shown in Table 2. 3, 4, and 5 are shown.

(UV durability transmission test)
The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were vacuum defoamed for 20 minutes, and then gently poured into an aluminum cup having a bottom diameter of 5 cm and a height of 2 cm. The cast was placed in an oven under a predetermined curing condition and cured to obtain a test piece for permeability having a thickness of 2 mm. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) before and after ultraviolet irradiation was measured with a spectrophotometer, and the rate of change was calculated.
The ultraviolet irradiation conditions are as follows.
UV irradiation machine: Eye Super UV Tester SUV-W11
Temperature: 60 ° C
Irradiation energy: 65 mW / cm ²
Irradiation time: 100 hours

(Thermal durability transmission test)
The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were vacuum defoamed for 20 minutes, and then gently poured into an aluminum cup having a bottom diameter of 5 cm and a height of 2 cm. The cast was placed in an oven under a predetermined curing condition and cured to obtain a test piece for permeability having a thickness of 2 mm. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) before and after being left in a 150 ° C. oven for 96 hours was measured with a spectrophotometer, and the rate of change was calculated.

(Mechanical property test)
The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were vacuum degassed for 20 minutes, and then gently poured into a test piece mold having a width of 7 mm, a length of 5 cm, and a thickness of about 800 μm. Then, the lid was covered with a polyimide film from above. The cast was cured under the conditions described in Tables 2 and 3 to obtain dynamic viscoelastic test pieces. Using these test pieces, a dynamic viscoelasticity test was performed under the conditions shown below.
Measurement conditions: Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: The peak point of Tan-δ in DMA measurement was defined as Tg.
−30 ° C. Elastic modulus: The elastic modulus at −30 ° C. was measured.

(LED lighting test)
The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were vacuum degassed for 20 minutes, then filled into a syringe and mounted with a light emitting element having an emission wavelength of 375 nm using a precision discharge device. The surface mounted LED was cast. Thereafter, an LED for lighting test was obtained by curing under predetermined curing conditions. Since the lighting test is a test under accelerated conditions, a lighting test was performed at 60 mA, which is three times the specified current. Detailed conditions are shown below. As a measurement item, the illuminance before and after lighting for 100 hours was measured using an integrating sphere, and the illuminance retention rate was calculated. Furthermore, the state of the light emitting element surface after lighting for 100 hours was observed.
Detailed lighting conditions Light emission wavelength: 375 nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 20 mA)
Driving environment: 25 ° C, 65%

* Curing agent B-1: As a curing agent, 30 parts of 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride ("H-TMA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) and methylhexahydrophthalic acid in advance A mixture prepared by mixing 70 parts of “MH-700G” (manufactured by Shin Nippon Chemical Co., Ltd.), which is a mixture of anhydride and hexahydrophthalic anhydride, was used as curing agent B-1.
* Curing agent B-2: As a curing agent, 50 parts of 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride ("H-TMA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) and methylhexahydrophthalic acid in advance A mixture prepared by mixing 50 parts of “MH-700G” (manufactured by Shin Nippon Chemical Co., Ltd.), which is a mixture of anhydride and hexahydrophthalic anhydride, was used as curing agent B-2.
* ERL-4221: Dow Chemical's alicyclic epoxy resin.
* Curing conditions: 120 ° C. 2 hr + 140 ° C. 2 hr (Examples 8, 9, 10 and Comparative Examples 5 and 6)
* The unit of Tg is [° C.], and the unit of -30 ° C. elastic modulus is [MPa].

 From the above results, the curable resin compositions of Examples 8 to 10 using the siloxane compound (A) of the present invention synthesized by a two-step reaction have the same dimethylsiloxane unit structure content concentration (mol%). Compared to Comparative Example 5 using the same compound, Tg is high and excellent in heat resistance, and elastic modulus at low temperature is reduced, and it is found that heat resistance and low elastic modulus characteristics are excellent. did. Furthermore, it has confirmed that it was excellent in light resistance and the low elastic modulus characteristic rather than the comparative example 6 which is a conventional alicyclic epoxy resin.

Table 3
Example 11 Comparative Example 7
(Combination)
Compound A-13 100 −
Compound A-14-100
Curing agent B-3 28.9 29.9
Curing accelerator C-1 0.1 0.1
(Mechanical property test)
Tg 57 ° C * 2)
-30 ° C elastic modulus 1139 * 2)
No surface tack * 2)
(UV durability transmission test)
375 nm 94.6% 93.8%
Transmission retention
400 nm 99.0% 97.2%
Transmission retention 465 nm 100% 100%
Transmission retention
(Thermal durability transmission test)
375 nm 97.4% 84.0%
Transmission retention
400 nm 99.1% 89.4%
Transmission retention 465 nm 100% 96.1%
Transmission retention
(Weight change after curing) * 3)
Weight retention 95% 91%
* Curing agent B-3: A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride was used (“MH-700G” manufactured by Shin Nippon Rika Co., Ltd.)
* Curing accelerator C-1: “U-CAT 18X” (trade name) sold by Sun Apro Co., Ltd. was used as a reaction accelerator for epoxy resin and acid anhydride.
* Curing conditions: unified at 120 ° C. for 2 hrs + 140 ° C. for 2 hrs.
* 2) There was a foaming trace, and a sample suitable as a cured product for dynamic viscoelasticity could not be obtained.
* 3) Since the foaming trace of Comparative Example 7 was confirmed in * 2), the weight loss of the resin was measured and the weight retention rate was confirmed when preparing a sample for UV durability transmission test.
The weight retention was calculated by (weight of cast product after curing / weight of cast product before curing) × 100.

  In the curable resin composition of Comparative Example 7, foaming traces were generated and a cured product could not be normally prepared for dynamic viscoelasticity measurement, whereas the curable resin composition of Example 11 was tacky. It has been found that a cured product having no elasticity can be produced and a cured product having a low elastic modulus can be obtained. Further, in the curable resin composition of Comparative Example 7, as a result of measuring the resin weight loss before and after curing of the UV durability transmission test sample, the curability of Example 11 was reduced by 9%. In the resin composition, the weight loss is only about 5%, and the curable resin composition of the present invention has little weight loss before and after curing, and there are also few dents after curing of the LED package casting. The conductive resin composition was found to be suitable in this respect as an LED sealing composition. Furthermore, it was found that Example 11 was superior in transmittance UV durability and thermal durability compared to Comparative Example 7.

Table 4
Example 12
(Combination)
Compound A-15 100
Curing agent B-3 21.4
Curing accelerator C-1 0.1
(Mechanical property test)
Tg 45 ℃
-30 ° C elastic modulus 1539
No surface tack (UV durability transmission test)
375 nm 88.1%
Transmission retention
400nm 93.9%
Transmission retention 465 nm 99.2%
Transmission retention

* Curing agent B-3: A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride was used (“MH-700G” manufactured by Shin Nippon Rika Co., Ltd.)
* Curing accelerator C-1: “U-CAT 18X” (trade name) sold by Sun Apro Co., Ltd. was used as a reaction accelerator for epoxy resin and acid anhydride.
* Curing conditions: 120 ° C. 1 hr + 150 ° C. 3 hr
* The unit of Tg is [° C.], and the unit of -30 ° C. elastic modulus is [MPa].

It was found that the curable resin composition of Example 12 using the siloxane compound (A) of the present invention synthesized by a two-step reaction was a cured product having a low elastic modulus at a low temperature.

Table 5
Example 13 Comparative Example 6 Unsealed (Formulation)
Compound A-13 100 − −
ERL-4221-100
Curing agent B-2-71.8-
Curing agent B-3 29.1--
Curing accelerator C-1 0.1 − −
(UV durability transmission test)
375 nm 92.5% 72% −
Transmission retention
400 nm 96.5% 76% −
Transmission retention 465 nm 99.7% 90% −
Transmission retention (LED lighting test)
Illuminance retention 91% 21% 83%
Element surface state No color Brown Color Colorless

* In order to see the deterioration of the element itself, an LED lighting test was conducted at the same time for the unsealed resin not injected.
* Curing agent B-2: As a curing agent, 50 parts of 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride ("H-TMA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) and methylhexahydrophthalic acid in advance A mixture prepared by mixing 50 parts of “MH-700G” (manufactured by Shin Nippon Chemical Co., Ltd.), which is a mixture of anhydride and hexahydrophthalic anhydride, was used as curing agent B-2.
* Curing agent B-3: A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride was used (“MH-700G” manufactured by Shin Nippon Rika Co., Ltd.)
* Curing accelerator C-1: “U-CAT 18X” (trade name) sold by Sun Apro Co., Ltd. was used as a reaction accelerator for epoxy resin and acid anhydride.
* ERL-4221: Dow Chemical's alicyclic epoxy resin.
* Curing conditions: 110 ° C., 6 hours (Example 13)
* Curing conditions: 120 ° C. 1 hr + 150 ° C. 3 hr (Comparative Example 6)
* The unit of Tg is [° C.], and the unit of -30 ° C. elastic modulus is [MPa].

  From the above results, when the curable resin composition of Example 13 using the siloxane compound (A) of the present invention synthesized by a two-step reaction was applied to an LED sealing material, a conventional alicyclic epoxy resin was used. It was found that the illuminance retention was clearly superior to the curable resin composition of Comparative Example 6. From this, it has confirmed that the curable resin composition of this invention was suitable as an LED sealing material.

Claims (22)

 Block-type siloxane oligomer having a linear silicone segment and a hydrolytic condensation segment of tri (C1-C10) alkoxysilane having a group selected from the group consisting of a reactive functional group having an epoxy group, a methyl group and a phenyl group The reactive functional group-containing siloxane compound, wherein the at least one hydrolytic condensation segment is a segment containing a reactive functional group having at least one epoxy group.   The reactive functional group-containing siloxane compound according to claim 1, wherein the hydrolytic condensation segment is a silsesquioxane segment. As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m represents an average value of 2 to 2000, and a general formula (1)
XSi (OR ₂ ) ₃ (1)
(In the formula, X represents a reactive functional group having an epoxy group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms.)
Is reacted in the range of 1.5 to 200 equivalents of the alkoxy group equivalent of the alkoxysilane compound to 1 equivalent of the silanol group of the silanol-terminated silicone oil (b), Reactive functional group-containing product according to claim 1 or 2 obtained by condensing and then adding water to the resulting reaction solution as a second stage reaction to hydrolyze and condense the remaining alkoxy groups Siloxane compounds. The reactive functional group-containing siloxane compound according to claim 3, wherein m is 2 to 200. As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 200), and the general formula (1)
XSi (OR ₂ ) ₃ (1)
(Wherein X represents a reactive functional group having an epoxy group, R ₂ represents an alkyl group having 1 to 10 carbon atoms) and the general formula (3)
R ₄ Si (OR ₂ ) ₃ (3)
(Wherein, R ₄ is a methyl group or a phenyl group, R ₂ is Formula (may be the same or different as R ₂ in 1) each independently represent an alkyl group having 1 to 10 carbon atoms .)
Both of the alkoxysilane compounds (c) represented by formula (1) are the total equivalents of the alkoxy groups of the alkoxysilane compounds (a) and (c) with respect to 1 equivalent of silanol groups of the silanol-terminated silicone oil (b). A reaction product obtained by reacting in a range of 5 to 200 equivalents and condensing, and then adding water to the resulting reaction solution to hydrolyze and condense the remaining alkoxy group as a second stage reaction. The reactive functional group-containing siloxane compound described in 1. R _{3 in the} general formula (2) independently represents a methyl group or a phenyl group, R _{2 in the} general formula (1) independently represents a methyl group or an ethyl group, and R _{2 in the} general formula (3) is The reactive functional group-containing siloxane compound according to any one of claims 3 to 5, which may be the same as or different from R _{2 in the} general formula (1) and independently represents a methyl group or an ethyl group. .   The reactive functional group-containing siloxane compound according to any one of claims 3 to 6, wherein X in the general formula (1) is an epoxycyclohexylethyl group.   Reactive functional group containing siloxane compound as described in any one of Claims 3-6 whose weight average molecular weights (Mw) of the silanol terminal silicone oil (b) of General formula (2) are 300-18,000.   The weight average molecular weight (Mw) is 800-20,000, The reactive functional group containing siloxane compound as described in any one of Claims 1-8.  The reactive functional group-containing siloxane compound according to claim 1 or 2, wherein the substituent on the silicone in the chain silicone segment is one or both of a methyl group and a phenyl group.  The reactive functional group-containing siloxane compound according to claim 1 or 10, wherein the reactive functional group having an epoxy group in the silsesquioxane segment contains an epoxycyclohexyl group. As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same as or different from each other, and each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or 6 to 14 carbon atoms. An silanol-terminated silicone oil (b) represented by an aryl group or an alkenyl group having 2 to 10 carbon atoms, and m represents an average value of 2 to 2000, and a general formula (1)
XSi (OR ₂ ) ₃ (1)
(In the formula, X represents a reactive functional group having an epoxy group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms.)
In the range of 1.5 to 200 equivalents, the equivalent of the alkoxy group of the alkoxysilane compound (a) is equivalent to 1 equivalent of the silanol group of the silanol-terminated silicone oil (b). A reactive functional group characterized by reacting in the presence of a catalyst, condensing, and then adding water to the resulting reaction solution to hydrolyze and condense the remaining alkoxy groups as a second step reaction A method for producing a siloxane compound. The method for producing a reactive functional group-containing siloxane compound according to claim 12, wherein m is 2 to 200. As the first stage reaction, the general formula (2)

(In the formula, a plurality of R ₃ may be the same or different from each other, and each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or aryl having 6 to 14 carbon atoms. A silanol-terminated silicone oil (b) represented by a group or an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 200.
XSi (OR ₂ ) ₃ (1)
(In the formula, X represents a reactive functional group having an epoxy group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms.)
An alkoxysilane compound (a) represented by the general formula (3)
R ₄ Si (OR ₂ ) ₃ (3)
(Wherein, R ₄ is a methyl group, a phenyl group, R ₂ is Formula (may be the same or different as R ₂ in 1) each independently represent an alkyl group having 1 to 10 carbon atoms .)
The alkoxysilane compound (c) represented by the formula (1) is a total equivalent of alkoxy groups of the alkoxysilane compounds (a) and (c) with respect to 1 equivalent of silanol groups of the silanol-terminated silicone oil (b), and 1.5 to A reaction characterized in that a condensation reaction is carried out in the presence of a catalyst in the range of 200 equivalents, and then, as a second stage reaction, water is added to the resulting reaction product to hydrolyze and condense the remaining alkoxy groups. For producing a functional functional group-containing siloxane compound.  The method for producing a reactive functional group-containing siloxane compound according to any one of claims 12 to 14, wherein the first stage reaction and the second stage reaction are sequentially carried out in one pot as the production process.  The alkoxysilane compound represented by the general formula (1) is β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane or β- (3,4-epoxycyclohexyl) ethyltriethoxysilane. A process for producing a reactive functional group-containing siloxane compound as described in 1). In the silanol-terminated silicone oil (b) represented by the general formula (2), R ₃ may be the same as or different from each other, and each independently represents a methyl group or a phenyl group. The manufacturing method of the reactive functional group containing siloxane compound of description.  The alkoxysilane compound represented by the general formula (3) is at least one selected from the group consisting of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. 15. A method for producing a reactive functional group-containing siloxane compound according to 15.  A curable resin composition comprising the reactive functional group-containing siloxane compound (A) according to any one of claims 1 to 11 and a curing agent (B).  Furthermore, a hardening accelerator (C) is contained, The curable resin composition of Claim 19 characterized by the above-mentioned.  Hardened | cured material for optical semiconductors obtained by thermosetting the curable resin composition of Claim 19 or 20.  An optical semiconductor device sealed with the optical semiconductor cured product according to claim 20.