TWI437030B - Method for manufacturing siloxane containing reactive group - Google Patents

Description

Method for producing a cyclooxygen compound containing a reactive functional group

The present invention relates to a novel oxoxane compound containing a reactive functional group, a process for producing the same, and a composition thereof. More specifically, it is a curable resin composition for an optical semiconductor which is excellent in transparency, light resistance, and low modulus of elasticity at a low temperature, and an optical semiconductor element sealed by the cured product.

In the past, epoxy resin has been used as a sealing material for optical semiconductor elements such as LEDs in terms of balance between performance and economy. In particular, a bisphenol A type epoxy resin and an alicyclic epoxy resin which are excellent in heat resistance, transparency, and mechanical properties are widely used.

In recent years, as a result of the progress of the short-wavelength (360 nm to 480 nm) of the LED light-emitting wavelength and the improvement of the light-emitting intensity, it has been pointed out that the above-mentioned sealing material is colored by the influence of light, and finally the characteristics of the LED are lowered.

Among them, the review of the polyoxyxene resin was carried out for the purpose of avoiding coloring of the sealing material by light. However, the mechanical properties and adhesion of the polyoxyxene resin are inferior to those of the epoxy resin, so that only the sealed state of the gel state can be selected. Therefore, the market has pointed out that there is a problem that the surface is sticky or deformed after sealing.

In order to improve the durability of the above epoxy resin, particularly the tackiness of the above polyoxyxylene resin, Patent Document 1 discloses an epoxy group-containing decane compound and an epoxy group-free decane compound in an organic Heating is carried out in the presence of a solvent, an organic base and water to obtain a polyorganosiloxane having a weight average molecular weight of 500 to 1,000,000. From the viewpoint of light resistance, the polyorganosiloxane is higher than conventional epoxy resins. Further, with respect to the bifunctional alkoxysilane compound, the amount of introduction of the trifunctional alkoxysilane compound is increased to improve tackiness and hardness. However, in order to improve the surface tackiness and deformation, the elastic modulus of the hardened material is increased, particularly in the low temperature range (below -30 ° C). As a result, in the heat cycle test, low elastic modulus characteristics at low temperatures (-30 ° C or lower) were caused to be inferior.

The sealant cured product is one of the important characteristics in the optical semiconductor encapsulant even in the low-temperature ratio, and this improvement has become an important issue.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Re-publication Patent WO2005/100445

An object of the present invention is to provide a siloxane compound, a curable resin composition using the same, and an optical semiconductor element using the curable resin composition as a sealing material, wherein a siloxane compound is used as an LED sealing material. And a novel compound having a reactive functional group which is compatible with light resistance and low modulus at low temperature.

As a result of intensive research to solve the above problems, the inventors of the present invention have found that a polyfluorene-containing oil (anthracene compound) having a sterol end group represented by the following formula (2) and a reactive functional group containing an epoxy group are found. a chain-like polyoxyl segment and three obtained by reacting a trialkoxyalkane compound (anthracene compound) The reactive functional group-containing oxoxane compound of the hydrolyzed condensed segment of the alkoxydecane can be used to solve the above problems. In other words, the curable resin composition containing the siloxane compound is one that satisfies the above problems. Moreover, it has been further found that the decane compound can be efficiently synthesized by a two-stage reaction. The present invention has been completed by the results thereof.

Further, as described above, the oxoxane compound of the present invention is formed by a hydrolyzed condensed segment of a chain polyoxyxene segment and an alkoxysilane (preferably a silsesquioxane segment). An oligomer (polymer), and at least a portion of the hydrolyzed condensed segment contains at least one reactive functional group containing an epoxy group.

The description of the present invention is as follows.

That is, the present invention relates to the following.

[1] A reactive functional group-containing oxoxane compound having a chain polyoxynitride segment and a group having a reactive functional group selected from an epoxy group-containing reactive group, a methyl group, and a phenyl group; a block type oxane oligomer of a hydrolyzed condensed segment of a tri(C1-C10) alkoxydecane, and at least a portion of the hydrolyzed condensed segment is a chain containing at least one reactive functional group containing an epoxy group Paragraph.

[2] The hydroxyl group-containing compound having a reactive functional group according to the above [1], wherein the hydrolyzed condensed segment is a sesquioxane chain segment.

[3] The catalytic functional group-containing oxoxane compound according to [1] or [2] above, which is obtained by the following two-stage reaction, wherein the first-stage reaction system is carried out by the general formula (2) The decyl alcohol terminal polyoxyxane oil (b) is alkoxy decane compound (a) represented by the formula (1), and the sterol group is 1 equivalent with respect to the sterol terminal polyoxyxanic oil (b). The alkoxide equivalent of the compound is reacted and condensed in the range of 1.5 to 200 equivalents, and the second stage reaction thereafter is carried out by adding water to the obtained reaction liquid to hydrolyze and condense the remaining alkoxy group; (wherein a plurality of R ₃ may be mutually identical or mutually different, and represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or a carbon number of 2 to 10 alkenyl; m represents an average of 2 to 2000) 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 ).

[4] The reactive functional group-containing oxoxane compound according to [3] above, wherein m is from 2 to 200.

[5] The reactive functional group-containing oxosiloxane compound according to the above [1], which is obtained by the following two-stage reaction, wherein the first-stage reaction is carried out by the sterol terminal represented by the formula (2) Polyoxyxane oil (b), both with the alkoxydecane compound (a) represented by the formula (1) and the alkoxydecane compound (c) represented by the formula (3), at the end of the oxime 1 equivalent of the sterol group of the oil (b), the total equivalent of the alkoxylated compound (a) and the alkoxy group of (c) is reacted and condensed in the range of 1.5 to 200 equivalents, and the second stage reaction thereafter is carried out Water is added to the obtained reaction liquid to hydrolyze and condense the remaining alkoxy group; (wherein a plurality of R ₃ may be mutually identical or mutually different, and represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or a carbon number of 2 to 10 alkenyl; m represents an average of 2 to 200) 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 R ₄ Si(OR ₂ ) ₃ (3) (wherein R ₄ represents a methyl group or a phenyl group; and R ₂ may be the same as or different from R _{2 of the} formula (1), and each independently represents a carbon number of 1 To 10 alkyl).

[6] The reactive functional group-containing oxirane compound according to any one of the above [3], wherein R _{3 of the} formula (2) is independently a methyl group or a phenyl group; R _{2 of the} formula (1) is independently represented by a methyl group or an ethyl group; R _{2 of the} formula (3) may be the same as or different from R _{2 of the} formula (1), and each independently represents a methyl group or a base.

[7] The reactive functional group-containing oxirane compound according to any one of [3] to [6] wherein X of the formula (1) is an epoxycyclohexylethyl group.

[8] The reactive functional group-containing oxirane compound according to any one of the above [3] to [6] wherein the weight of the sterol terminal polyfluorene oxide (b) of the formula (2) The average molecular weight (Mw) is from 300 to 18,000.

[9] The reactive functional group-containing oxirane compound according to any one of [1] to [8] wherein the weight average molecular weight (Mw) is from 800 to 20,000.

[10] The reactive functional group-containing oxoxane compound according to [1] or [2] above, wherein the substituent on the polyfluorene oxide in the chain polyoxynoxy segment is a methyl group or a phenyl group. Either or both.

[11] The reactive functional group-containing oxoxane compound according to the above [1] or [10] wherein the reactive functional group having an epoxy group in the sesquiterpene oxide chain contains an epoxy group. Base ring base.

[12] A method for producing a reactive functional group-containing oxoxane compound, characterized in that the first-stage reaction is carried out by using a decyl alcohol-terminated polyoxyxane oil (b) represented by the formula (2), and a formula ( 1) The alkoxyoxane compound (a) is shown in an amount of from 1.5 to 200 equivalents based on 1 equivalent of the oxime group of the oxime-terminated polyoxosulfonate (b), and the alkoxylated compound (a) has an alkoxy equivalent of from 1.5 to 200 equivalents. Internally, reacting and condensing in the presence of a catalyst, and then performing the second-stage reaction by adding water to the obtained reaction liquid to hydrolyze the remaining alkoxy group.

(wherein, a plurality of R ₃ may be mutually identical or mutually different, each independently, and represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or Alkenyl with 2 to 10 carbon atoms; m means an average of 2 to 2000)

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).

[13] The method for producing a reactive functional group-containing oxoxane compound according to [12] above, wherein m is from 2 to 200.

[14] A method for producing a reactive functional group-containing oxoxane compound, comprising the following two-stage reactor, wherein the first-stage reaction system is a sterol-terminated polyoxyxene oil represented by the general formula (2) (b) And the alkoxy decane compound (a) represented by the formula (1) and the alkoxy decane compound (c) represented by the following formula (3), after the polyoxyxanthene (b) with respect to the sterol terminal 1 equivalent of the alcohol group, the total equivalent weight of the alkoxydecane compound (a) and the alkyl group of (c) is in the range of 1.5 to 200 equivalents, and the condensation reaction is carried out in the presence of a catalyst, followed by the second-stage reaction system. Water is added to the obtained reaction product to hydrolyze and condense the remaining alkoxy group;

(wherein, a plurality of R ₃ may be mutually identical or mutually different, each independently, and represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or Alkenyl having 2 to 10 carbon atoms; m means an average of 2 to 200)

XSi(OR ₂ ) ₃ (1)

(Wherein, X represents a reactive functional group having epoxy groups; R ₂ represents an alkyl group of 1 to 10 carbon atoms)

R ₄ Si(OR ₂ ) ₃ (3)

(wherein R ₄ represents a methyl group or a phenyl group; and R ₂ may be the same as or different from R _{2 of the} formula (1), and each independently represents an alkyl group having 1 to 10 carbon atoms).

[15] The method for producing a reactive functional group-containing oxoxane compound according to the above [12] to [14] wherein the production step is a first-stage reaction and a second-stage reaction in a one-pot manner. By.

[16] The method for producing a reactive functional group-containing oxoxane compound according to the above [11] to [15], wherein the alkoxydecane compound represented by the formula (1) is β-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, or β-(3,4-epoxycyclohexyl)ethyltriethoxydecane.

[17] The method for producing a reactive functional group-containing oxoxane compound according to the above [12] to [16], wherein the sterol terminal polyfluorene oxide (b) represented by the formula (2) ₃ may be mutually identical or mutually different, each being a separate methyl or phenyl group.

[18] The method for producing a reactive functional group-containing oxoxane compound according to the above [13] to [15] wherein the alkoxydecane compound represented by the formula (3) is selected from methyltrimethoxy group. At least one of a group consisting of decane, phenyltrimethoxydecane, methyltriethoxydecane, and phenyltriethoxydecane.

[19] A curable resin composition comprising the reactive functional group-containing oxirane compound (A) and the curing agent (B) according to any one of the above [1] to [11].

[20] The curable resin composition according to the above [19], which further comprises a curing accelerator (C).

[21] A cured product for an optical semiconductor obtained by thermally curing the curable resin composition according to the above [19] or [20].

[22] An optical semiconductor device which is sealed with the cured product for an optical semiconductor according to the above [20].

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

[Best Mode for Carrying Out the Invention]

The reactive functional group-containing oxane compound of the present invention (hereinafter also referred to as a oxoxane compound of the present invention) has a chain polyfluorene chain segment in one molecule and a hydrolysis condensation segment with a trialkoxy decane. (preferably a sesquioxane chain segment having a reactive functional group containing an epoxy group, and a sesquioxane chain segment having a three-dimensional network is more preferable).

The oxoxane compound of the present invention is usually a hydrolyzed condensed segment of a trialkoxy decane (referred to as a sesquioxane group having a network structure in a three-dimensional distribution). As a core, the chain polyphosphonium chain segment is extended, followed by the structure of the hydrolysis condensation segment of the trialkoxysilane (preferably a sesquioxane chain segment). This configuration imparts a balance between hardness and flexibility of the curable composition of the present invention.

The oxoxane compound of the present invention is as described above, having a hydrolyzed condensed segment of a trialkoxy decane (preferably a sesquioxane chain segment) and a chain polyoxyxene segment, which are repeated by the lines The viewpoint may also be referred to as a block type siloxane compound.

The oxoxane compound of the present invention is, for example, an alkoxy decane compound (a-1) represented by the following formula (10) (hereinafter also referred to as an alkoxy decane (a-1)), preferably a general formula (1) The alkoxysilane compound (a) (hereinafter also referred to as alkoxysilane (a)) and the polyoxyxane (b) represented by the formula (2) can be produced as a raw material, if necessary The alkoxydecane compound (a-1) (preferably as (a)) and the alkoxydecane compound (c) represented by the above formula (3) may be used together as a raw material, XSi(R ₁ )n (OR _{2 ) 3-n} (10) (wherein X represents a reactive functional group having an epoxy group; R ₁ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted carbon number of 6 to 14 An aryl group, or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms; R ₂ represents an alkyl group having 1 to 10 carbon atoms; n represents an integer of 0 to 2; when a plurality of R ₁ are present, a plurality of R ₁ can be mutually different or different),

XSi(OR ₂ ) ₃ (1)

(wherein X and R ₂ are synonymous with the above formula (10)).

The chain polyoxyxene segment in the oxoxane compound of the present invention is formed by a polyoxyxanic acid (b), and a hydrolyzed condensation segment of a trialkoxy decane (preferably a sesquioxane chain segment, It is more preferable to use a three-dimensional network of sesquiterpene oxyalkylene segments from the alkoxy decane compound (a-1), preferably (a), and to use an alkoxy decane compound (c) as needed (hereinafter also referred to as In the case of alkoxydecane (c)), it is formed by alkoxydecane (a-1), preferably (a), and alkoxydecane (c).

The hydrolysis condensation segment is preferably a segment formed by the two-stage reaction of the alkoxysilane compound (a) and, if necessary, (c), by hydrolysis and dealcoholization of the alkoxy group. By the hydrolysis condensation, the structural unit of X (required and R ₄ )SiO 3/2 is a structure in which a plurality of bonds are combined. Since the oxoxane compound formed by the structural unit is referred to as sesquiterpene oxide, the hydrolyzed condensation segment can be referred to as a sesquiterpene oxide segment.

Hereinafter, each raw material will be described in detail.

The alkoxydecane compound (a-1) represented by the above formula (10) or (1) or the X in (a) is not particularly limited as long as it is an organic group having an epoxy group. For example, a glycidyloxy group having a carbon number of 1 to 4 such as β-glycidoxyethyl group, γ-glycidoxypropyl group or γ-glycidoxybutyl group; glycidyl group; β-( 3,4-epoxycyclohexyl)ethyl, γ-(3,4-epoxycyclohexyl)propyl, β-(3,4-epoxycycloheptyl)ethyl, β-(3 , 4-epoxycyclohexyl)propyl, β-(3,4-epoxycyclohexyl)butyl, β-(3,4-epoxycyclohexyl)pentyl, etc., having an epoxy ring ( An alkyl group having 1 to 5 carbon atoms substituted by a cycloalkyl group having 5 to 8 carbon atoms of the oxirane ring). Among these, an alkyl group having 1 to 3 carbon atoms substituted by a glycidoxy group or an alkyl group having 1 to 3 carbon atoms substituted by a cycloalkyl group having 5 to 8 carbon atoms of an epoxy ring is, for example, Β-glycidoxyethyl, γ-glycidoxypropyl, β-(3,4-epoxycyclohexyl)ethyl, preferably β-(3,4-epoxycyclohexyl) Ethyl is especially good.

R ₂ in the formula (10) or (1), each independently, represents an alkyl group having 1 to 10 carbon atoms, and may be any of a linear chain, a branched chain or a cyclic chain. Examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like. From the viewpoint of reaction conditions such as compatibility and reactivity, the R ₂ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

Further, R _{1 of the} formula (10) can be directly referred to the description of each group in the description of R _{3 of the} following formula (2).

Preferable specific examples of the alkoxydecane (a-1) or (a) represented by the formula (10) or (1) include, for example, β-glycidoxyethyltrimethoxydecane and β-glycidol. Oxyethyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, β-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, with β-(3,4-epoxycyclohexyl)ethyltrimethoxynonane good. These alkoxydecane compounds (a) may be used singly or in combination of two or more kinds, and the alkoxy decane (c) represented by the following formula (3) may be used in combination.

The polyoxygenated oil (b) is a chain polyoxyxene oil having a sterol group at the terminal having a structure represented by the following formula (2).

(where R ₃ and m are the same as above)

In the formula (2), a plurality of R ₃ may be mutually the same or different from each other, and represent an 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.

The alkyl group having 1 to 10 carbon atoms may, for example, be a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group and isopropyl group. , n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, anthracene Base, base, etc. When light resistance is taken into consideration, a methyl group, an ethyl group or a cyclohexyl group is preferred.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, and a xylyl group.

The alkenyl group having 2 to 10 carbon atoms may, for example, be an alkenyl group such as a vinyl group, a 1-methylvinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group or a hexenyl group.

From the viewpoint of light resistance and heat resistance, each of R _{3 is} preferably a methyl group, a phenyl group, a cyclohexyl group or a n-propyl group, and a methyl group or a phenyl group is particularly preferred. Specific examples thereof include the case where two R ₃ of the formula (2) are a methyl group or a phenyl group, or one of them is a methyl group and the other is a phenyl group. The combination of these is generally the case where the overlapping units are all the same combination, however, as long as the effect of the present invention is achieved, different combinations can be mixed in the overlapping unit. For example, even if the respective repetitive units are different, the foreign matter can be mixed regularly or randomly.

The compound of the formula (2) has an average value of m of from 2 to 2,000, preferably from 2 to 200, more preferably from 3 to 100, still more preferably from 3 to 50. When the M value is too low, the hardened material is too hard to deteriorate the low modulus of elasticity. When the M value is too high, the cured product tends to deteriorate in mechanical properties.

The weight average molecular weight (Mw) of the polyoxygenated oil (b) is generally in the range of 300 to 50,000, preferably in the range of 300 to 30,000, and more preferably in the range of 300 to 18,000 (GPC measured value). Among these, if the elastic modulus at a low temperature is considered, it is preferably a molecular weight of 300 to 10,000. For further consideration of the compatibility in composition physicochemical, it is preferably from 300 to 5,000, especially from 500 to 3,000. good. When the weight average molecular weight is less than 300, the properties of the chain polyoxynithalic chain forging portion may not be exhibited. The molecular weight of the polyoxyxane oil (b) of the present invention is a weight average molecular weight (Mw) of converted polystyrene measured by GPC (Gel Permeation Chromatography) under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Corporation

Column: guard column SHODEX GPC LF-G LF-804 (3)

Flow rate: 1.0ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

The dynamic viscosity of the polyoxygenated oil (b) is preferably in the range of 10 to 200 cSt, and more preferably 30 to 90 cSt. When the viscosity is too low, the viscosity of the target oxirane compound of the present invention is also low and it is not suitable for the case of the optical semiconductor encapsulant. On the contrary, when the viscosity is too high, the viscosity of the block type siloxane compound (A) is increased. There is a tendency to hinder the operability.

Specific examples of the polyoxynoxy terminated dimethylpolyphthalic acid oil in which R ₃ of the polyoxyxane oil (b) is a methyl group include the following product names. For example: Dongli Dao Kang Ning Poly Oxide (shares) products are PRX413, BY16-873; Shin-Etsu Chemical Industry Co., Ltd. products are X-21-5841, KF-9701; Momentive (shares) products have XC96-723, TSR160, YR3370, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XF3905; Gelest products are 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 polyoxonium-terminated methylphenyl polyfluorene oxide in which R ₃ of the polyoxyxane oil (b) is a methyl group and a phenyl group include the following product names. For example, the products of Momentive (shares) are YF3804; the products of Gelest (shares) are PDS-0332, PDS-1615 and so on.

As the polyoxynoxy-terminated diphenylpolyoxyl oil wherein R ₃ of the polyoxygenated oil (b) is a phenyl group, PDS-9931 such as Gelest can be cited as a specific example of a preferred product name. In the above specific examples, from the viewpoints of molecular weight and dynamic viscosity, it is preferably PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS. -S15, DMS-S21, PDS-1615. Among these, since it is characterized by the flexibility of polyoxyl chain forging, X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight. These polyoxygenated oils (b) may be used singly or in combination of two or more.

Next, the alkoxydecane compound (c) will be described in detail.

The alkoxydecane compound (c) has a structure of the following formula (3).

R ₄ Si(OR ₂ ) ₃ (3)

R ₄ in the formula (3) represents a methyl group or a phenyl group.

General formula R (3) R ₂ in the general formula (10) or (1) ₂ may be the same or different, each independently lines, represents an alkyl group of 1 to 10 carbon atoms, may be linear, branched, or Any of the rings. Specifically, it contains a preferred group and a more preferred group, and is the same as exemplified in the description of R ₂ of the above formula (10) or (1).

Preferable specific examples of the alkoxydecane compound (c) include methyltrimethoxydecane, phenyltrimethoxydecane, methyltriethoxydecane, and phenyltriethoxydecane. Among the above, methyltrimethoxydecane or phenyltrimethoxydecane is preferred.

In the present invention, in order to adjust the molecular weight of the block type siloxane compound (A), the compatibility at the time of forming a composition, and the heat resistance, light resistance, low permeability, low gas permeability, etc. of the cured product, the alkoxydecane The compound (c) may be used in combination with the alkoxydecane compound (a-1), preferably (a).

With respect to the sum of the alkoxydecane compounds ((a-1), preferably the sum of (a) and (c)), the alkoxydecane compound (c) is used in an amount of from 0 to 70 mol%, from 0 to 55% of the moles is preferred, preferably from 0 to 40% by mole. When the alkoxydecane compound (c) is used in combination with the alkoxydecane compound (a), the alkoxydecane compound (c) is preferably used in an amount of from 5 to 70 mol%, based on the total of the alkoxydecane compound. It is better to 50% by mole, and particularly preferably 10 to 40% by mole.

Hereinafter, a method for producing a oxoxane compound of the present invention will be described.

The alkoxyalkyl compound of the present invention may be the alkoxydecane compound (a-1) (hereinafter also referred to as alkoxydecane (a-1)) as an alkoxysilane (a) (hereinafter also referred to as alkoxysilane (a). ()) is preferably produced by using the above polyoxyxane oil (b) as a raw material, and the alkoxylated oxane compound (c) described above may be used in combination as needed.

In the production of the oxoxane compound of the present invention, the oxirane compound of the present invention having the above two segments can be produced, and any method can be employed.

The most suitable method is as described above, and the first-stage reaction is carried out by the following two-stage reaction system, which is a sterol-terminated polyoxyxane oil (b) or an alkoxydecane (a-1) (preferably (a)). And the alkoxyoxane (c) as required, reacting in an amount of from 1.5 to 200 equivalents based on 1 equivalent of the decyl alcohol group of the oxime-terminated polyoxyxanic oil (b) The condensation is carried out, and the second stage reaction is carried out by adding water to the obtained reaction liquid to hydrolyze and condense the remaining alkoxy group (one-pot method).

In the above first-stage reaction, in the absence of water, it is preferably carried out in the presence of an acid catalyst or an alkali catalyst (preferably a base catalyst).

The alkoxynonane (a-1) of the above first-stage reaction, preferably the above alkoxydecane in the reaction of (a) (corresponding to the use of the alkoxydecane (c) in combination with the polyoxyxane oil (b) The ratio of the compound to the polyoxyxane (b) is generally 1 equivalent to the decyl group of the polyoxyxanic oil (b), and the alkoxydecane (a-1) is preferably (a) [according to the need And the alkoxy equivalent of alkoxyoxane (c) is used together (in the case of alkoxysilane (c), alkoxydecane (a-1), preferably (a), and alkoxylate of alkoxydecane (c) The total equivalent weight of the base is from 1.5 to 200 equivalents, preferably from 2 to 200 equivalents, more preferably from 2 to 150 equivalents, still more preferably from 2 to 100 equivalents. Further, the ratio is 1 equivalent to the decyl group of the polyoxyxane oil (b), and the alkoxy oxirane compound may have an alkoxy equivalent of 3 to 100 equivalents, preferably 4 to 100 equivalents, and 5 to 100 equivalents. Better.

When the amount of the alkoxydecane compound is substantially outside the above upper limit range, the resultant may lose the preferred physical properties of the alkoxysilane compound of the present invention.

It is disclosed in Patent Document 1 (WO2005/100445) that a decyl compound having an epoxy group and a decane compound having no epoxy group are simultaneously hydrolyzed in the presence of water without using a sterol terminal polyoxyxanic oil (b). condensation. In the synthesis of a sesquiterpene having a functional group, in the same manner as in Patent Document 1, the alkoxysilane compound having a functional group and the alkoxysilane compound having no functional group are simultaneously subjected to hydrolysis condensation in the presence of water.

However, according to the present invention, in addition to the alkoxydecane (a-1), (a) is preferred [in response to the desired alkoxyoxane (c)], and polyoxyxane (b) is also used as a raw material, The raw materials are reacted together in the presence of a catalyst and water. The alkoxyoxane (a-1) is preferably (a) [in response to the hydrolysis of the alkoxy group of the alkoxyoxane (c) required) The condensation reaction proceeds preferentially, and the formed sesquiterpene oxide compound and the unreacted polyoxyxane oil (b) may remain incompatible with each other, and tend to cause uneven white turbidity compounds. Such a white turbid organopolysiloxane is not suitable for optical use.

Further, even if the transparency is not impaired, the synthesized compound tends to have a reduced molecular weight, and heat resistance is lowered and "stickiness" occurs, and it is difficult to obtain a preferred oxoxane compound of the present invention.

Including the above-described optimum method, the method for producing a reactive functional group-containing oxoxane compound of the present invention is preferably a production step shown by the following (i) and (ii).

Manufacturing step (i): alkoxysilane is subjected to alkoxysilane modification by a dealcoholization condensation of a decyl alcohol-terminated polyoxyxane oil (b) with the above alkoxysilane to form an alkoxysilane modified body ( Step d) (chain polyoxyl segment formation step), production step (ii): performing alkoxydecane modified body (d) and alkoxy group in the alkoxydecane compound in the presence of water Hydrolysis ‧ condensation to form a hydrolyzed condensed segment of the alkoxy decane (preferably a sesquioxane chain segment).

The production steps (i) and (ii) may be carried out by each step, regardless of the order.

Further, depending on the case, the sterol terminal polyoxyxane oil (b) may be reacted with the alkoxy decane compound by a method such as dropping water in sequence, and the reaction of the above production steps (i) and (ii) may be carried out in one step. .

Further, in (i), when a silsesquioxane having two or more alkoxy groups which are separately synthesized is used instead of the alkoxydecane, the oxygen of the present invention can be obtained only by the production step (i). Alkane compound.

A preferred manufacturing method includes the above-described optimum method, and specifically, the following three manufacturing methods are exemplified:

<Manufacturing method (A)>

First, a manufacturing step (i) is carried out: a dealcoholization condensation reaction of a polyoxyxanic acid (b) having a sterol group at the end with an alkoxysilane (a) [which can be used in combination with an alkoxydecane (c) as required), The alkoxydecane modified body (d) can be obtained by converting the end of the polyoxyxane oil to an alkoxysilane.

Next, the production step (ii) is preferably carried out in the coexistence of the alkoxysilane (a) [which can be used in combination with the alkoxysilane (c)] to produce the polyoxyl oil obtained in the step (i). Between the alkoxy groups of the oxoxane modified substance (d) or the alkoxy oxane modified substance (d) and the alkoxy group of the alkoxy decane compound in the presence of the alkoxy decane compound, in water In the presence of a hydrolytic condensation reaction, a chain polyfluorene chain segment is formed (usually represented by -(OSi(R ₃ ) ₂ ) _m - (R ₃ represents synonymous with formula (2)) and an alkoxy group. A method of hydrolyzing a condensed segment of decane (preferably a sesquioxane chain segment) in the form of a block of the present invention.

<Manufacturing method (B)>

First, the following steps are carried out: alkoxyoxane (a) [may be used in combination with alkoxydecane (c) in the presence of water] to carry out a hydrolysis condensation reaction between alkoxy groups to obtain an alkoxy group in the molecule. A hydrolysis condensate of alkoxyoxane (preferably sesquioxane (e)).

Next, a preferred manufacturing method is to separate the alkoxydecane hydrolyzed condensate synthesized above (preferably sesquioxane (e)), and further, it is preferred to have a sterol group at the terminal in the absence of water. The hydrolyzed condensate of the oxirane oil (b) and the alkoxy oxane obtained above (preferably sesquioxane (e) is preferred) is subjected to a dealcoholization condensation reaction to obtain a oxoxane compound of the present invention.

<Manufacturing Method (C)>

First, the manufacturing step (i) is carried out: in the absence of water, in the presence of the above alkoxysilane, the polyoxyxanthene (b) having a sterol group at the end and the alkoxysilane (a) The alkoxysilane (e) is subjected to a dealcoholization condensation reaction to form the alkoxydecane modified body (d), followed by a production step (ii): in the presence of water, via residual alkoxylation矽 ( (a) [when alkoxy decane (c) is used in combination, the residual alkoxy oxane (a) and (c)] and the alkoxy group of the alkoxy oxane modified substance (d) are The hydrolytic condensation reaction produces a pot method of the oxoxane compound of the present invention.

In the present invention, from the viewpoint of shortening the production step, it is preferred to carry out the second-stage reaction directly without separating the first-stage reactant, and sequentially carry out the reaction in a one-pot manner.

Hereinafter, a specific production method (C) (the above-described preferred production method) will be further described.

In the one-pot type, the production step (i) is used as the first-stage reaction, and the production step (ii) is used as the second-stage reaction. First, in the first-stage reaction (manufacturing step (i)), the polyoxygenated oil is carried out. (b) a dealuol condensation of alkoxyoxane (a) [corresponding to the desired alkoxyoxane (c)] to reform the hydrogen atom of the sterol group at the end of the polyoxyxanic oil (b) to an alkoxydecane, An alkoxydecane modified body (d) is obtained. In the first-stage reaction, it is preferred to carry out the hydrolysis without condensing, so that no hydrolysis condensation occurs between the alkoxy groups, and when the reaction is carried out using an alkoxy group of 3 equivalent or more with respect to 1 equivalent of the decyl group, the alkane is considered to be an alkane. The oxoxane modified body (d) is present in a structure represented by the following formula (4), and it is considered that after such a modified body (d) is formed, it is preferred to carry out hydrolysis and condensation between alkoxy groups. Therefore, the reaction is preferably one of the reaction using 3 equivalents to 200 equivalents of the alkoxy group with respect to 1 equivalent of the decyl alcohol group of the polyoxyxane oil (b).

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

In the first-stage reaction, when the alkoxy group is reacted in an amount of less than 1.0 equivalent with respect to 1 equivalent of the sterol group, the alkoxy group is not present at the end of the first-stage reaction, and the second stage cannot be reached. a reaction, and, if the alkoxy group is reacted between 1.0 and 1.5 equivalents, the alkoxyoxane (a) [in response to the desired alkoxyoxane (c)] (b) The sterol group reacts, and at the end of the first stage reaction, gelation occurs due to excessive formation of a polymer. Therefore, it is necessary to react with 1.5 equivalents or more of the alkoxy group with respect to 1 equivalent of the sterol group. From the viewpoint of controlling the reaction, it is preferably 2.0 equivalent or more.

The hydrolyzed condensed segment of the alkoxysilane is preferably 3 equivalents or more, and 4 equivalents or more, based on 1 equivalent of the decyl alcohol group, from the viewpoint of forming a preferred sesquiterpene gas chain segment. Good, more than 5 equivalents.

Meanwhile, the sesquiterpene oxide segment in the present invention may be any structure of a so-called ladder type, a partial ring opener of a cage type, or a random type, and is generally considered to be such a mixed type.

After completion of the first-stage reaction, water is directly added to the reaction liquid to carry out a second-stage reaction (manufacturing step (ii)) in which hydrolysis and condensation between alkoxy groups are carried out.

The amount of water added is about 0.5 equivalent to 100 equivalents per equivalent of the alkoxy group of the alkoxysilane compound used as the above raw material. The theoretical amount of water required for the hydrolytic condensation of the residual alkoxy group after the end of the first-stage reaction is preferably from about 1 to 10 times (more preferably from about 1 to 5 times).

It is considered that the reaction of the following (I) to (III) is caused in the second-stage reaction.

(I): a hydrolysis condensation reaction between alkoxy groups of alkoxyoxane (a) remaining in the system (and alkoxydecane (c) when used in combination).

(II): Hydrolysis condensation between the alkoxyoxane modified product (d) obtained in the first stage reaction and the alkoxy group of the alkoxydecane (a) (and the alkoxydecane (c) when used in combination) reaction.

(III): alkoxy oxane (a) formed by the reaction of the alkoxy oxane modified product (d) obtained in the first stage reaction with the above (I) (and alkoxy decane (c) when used in combination a condensation reaction between alkoxy groups of the hydrolysis condensate.

In the second-stage reaction described above, the above reaction occurs in combination, and at the same time, the formation of the above-mentioned hydrolysis condensation segment (preferably a sesquioxane chain segment) and the chain derived from the polyoxyxane oil (b) are carried out. Condensation of a polyoxylated segment.

The block type siloxane compound of the present invention produced by the first-stage reaction and the second-stage reaction is excellent in transparency and transparency and low modulus of elasticity of the cured product obtained by using the resin composition of the compound. Excellent.

The production of the block type siloxane compound having a reactive functional group of the present invention can be carried out without a catalyst, but the reaction proceeds slowly without a catalyst, and the reaction time is shortened in the presence of a catalyst. The performer is better. As the catalyst which can be used, any compound which exhibits acidity or alkalinity 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 the alkaline catalyst include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide-based alkali metal hydroxides; alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. An inorganic base such as salt or ammonia; an organic base such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine or tetramethylammonium hydroxide. Among these, in particular, from the viewpoint of easiness of removing the catalyst from the product, an inorganic base is preferred, and sodium hydroxide or potassium hydroxide is more preferred. The amount of the catalyst added is generally from 0.001 to 7.5% by weight, based on the total weight of the alkoxydecane (a) (which may be used in combination with the alkoxysilane (c)), in an amount of from 0.01 to 5% by weight. good. Also, the amount added may be about 0.01 to 1% by weight.

The method of adding the catalyst is directly added or used in a state of being dissolved in a soluble solvent or the like. Among them, it is preferred to add the catalyst in advance in the form of an alcohol such as methanol, ethanol, propanol or butanol. In this case, when it is added by using an aqueous solution of water or the like, the condensation of the alkoxydecane (a) (alkoxy alkane (c) which is used in combination as needed) is unilaterally carried out as described above, and the sesquiterpene thus produced is obtained. The oxyalkylene oligomer and the polyoxygenated oil (b) are mutually miscible and may be cloudy.

The production of the reactive functional group-containing oxirane compound of the present invention can be carried out without a solvent or in a solvent. It is also possible to add a solvent to the middle of the manufacturing process. The solvent is preferably a solvent which can dissolve the alkoxysilane compound (a), the polyoxyxane oil (b) (and alkoxysilane (c) if necessary), and the alkoxysilane modified body (d). Examples of such a solvent include, for example, an aprotic polar solvent such as dimethylformamide, dimethylacetamide or tetrahydrofuran; and a ketone such as methyl ethyl ketone, methyl isobutyl ketone or cyclopentanone. Ethyl acetate, butyl acetate, ethyl lactate, isopropyl butyrate and other esters; such as methanol, ethanol, propanol, butanol and other alcohols; such as hexane, cyclohexane, toluene, xylene, etc. Hydrocarbons, etc. In the present invention, it is preferred to carry out the reaction in an alcohol from the viewpoint of reaction control, and it is more preferable to use methanol and/or ethanol. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and the alkoxydecane compound (a) (alkoxydecane (c) may be used in combination as needed) and the polyoxygenated oil (b) The total weight of 100 parts is generally about 0 to 900 parts by weight. The reaction temperature varies depending on the amount of the catalyst, but it is usually from 20 to 160 ° C, preferably from 40 to 140 ° C, more preferably from 50 to 150 ° C. Further, the reaction time is usually from 1 to 40 hours in each of the production steps, preferably from 5 to 30 hours.

After the reaction is completed, the catalyst is removed by neutralization and/or water washing as needed. When washing with water, it is preferred to add a solvent which can be separated from water depending on the type of solvent to be used. Examples of preferred solvents include, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butyrate; Such as hexane, cyclohexane, toluene, xylene and other hydrocarbons.

In this reaction, the catalyst may be removed only by washing with water. However, since the reaction is carried out under acidic or basic conditions or under any of the conditions, the mixture is washed with water after neutralization, or after the adsorbent is adsorbed by the adsorbent. It is preferred to remove the adsorbent by filtration. When the adsorbent is used, the adsorbent is added to the reaction liquid, and the mixture is stirred, heated, and the like. After the catalyst is adsorbed, the adsorbent is filtered, and the residue is washed with water, whereby the catalyst and the adsorbent can be removed.

A compound which exhibits acidity or basicity can be used for neutralization.

Examples of the acidic compound 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 the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide; alkali metals such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. a carbonate; an inorganic base such as an alkali phosphate such as disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid or sodium tripolyphosphate; or ammonia, triethylamine, diethylenetriamine, n-butylamine, or dimethyl An organic base such as arylaminoethanol, triethanolamine or tetramethylammonium hydroxide. Among these, in particular, from the viewpoint of being easily removed from the intended product, an inorganic base or an inorganic acid compound is preferred, and more preferably, the pH is adjusted to a neutral sodium dihydrogen phosphate or Phosphates such as the above basic phosphates.

Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic/organic synthetic adsorbent, ion exchange resin, and the like. Specific examples thereof include the following products.

Examples of activated clays include, for example, Dongxin Chemicals Co., Ltd.: activated clay (SA35, SA1, T, R-15 or E), or Nicolette (G-36, G-153 or G-168); Products of Mizusawa Chemical Industry Co., Ltd.: Galleon Earth, or Mizuka Ace ^RTM (superscript RTM stands for registered trademark. The same applies below).

Examples of the activated carbon include, for example, Ajinomoto Fine Chemicals Co., Ltd.: CL-H, Y-10S or Y-10SF; Futamura Chemical Co., Ltd.: S, Y, FC, DP, SA1000, K , A, KA, M, CW130BR, CW130AR or GM130A.

Examples of the zeolite include, for example, products of Union Showa (stock): Molecular Sieve 3A, 4A, 5A or 13X.

Examples of the synthetic adsorbent include, for example, Kyowa ^RTM 100, 200, 300, 400, 500, 600, 700, 1000, 2000; and Rohm and Haas (stock) products: Amberlyst ^RTM 15JWET , 15DRY, 16WET, 31WET, A21, Amberlite ^RTM IRA40, 0JC1, IRA403BLC1, IRA404JC1; and Dow Chemical (stock) products: DOWEX ^RTM 66, HCR-S, HCRW2 or MAC-3.

After the completion of the reaction or after the neutralization, it can be purified by other conventional separation and purification means which are washed with water and filtered. Examples of the purification means include column chromatography, concentration under reduced pressure, distillation, and extraction. These purification means may be carried out singly or in combination of plural kinds.

When a solvent mixed with water is used as a reaction solvent, it is preferred to remove the reaction solvent mixed with water from the reaction system by distillation or concentration under reduced pressure after neutralization, and then add the reaction system to the reaction system. The solvent for water separation is obtained by dissolving the desired reaction product and then washing it with water.

After washing with water, the solvent used above is removed by concentration under reduced pressure or the like to obtain a reactive functional group-containing oxoxane compound of the present invention.

The appearance of the oxirane compound of the present invention is generally a colorless, transparent liquid having a fluidity at 25 °C.

The oxoxane compound of the present invention obtained in the above reaction is a block type siloxane compound having a reactive functional group as described above, which is characterized in that it is composed of a chain-like polyoxygen segment, preferably a -Si R ₃ ) ₂ O) _m - [R ₃ and m represent a chain polyoxynized segment represented by the above formula (2), and (R ₆ SiO _3/2 ) _nx [R ₆ as a structural unit) Synonymous with the above formula (4); nx represents a sesquiterpene oxide segment having an average value of 2 to 20], and at least a portion of the sesquiterpene oxide segment has at least one epoxy group-containing reaction. Sexual functional base.

In the sesquiterpene oxide segment, the number of reactive functional groups having an epoxy group represented by X derived from the alkoxydecane compound (a) is relative to one halogen atom in the sesquiterpene oxide segment. The average ratio is preferably from 0.3 to 1, preferably from 0.45 to 1, and from 0.6 to 1. Further, the group represented by R ₄ derived from the alkoxydecane (c) is preferably in an amount of from 0 to 0.7 on average, and in a ratio of from 0 to 0.55, based on one atom of the sesquioxane group. More preferably, it is particularly good at a ratio of 0 to 0.4.

The preferred molecular weight of the oxoxane compound of the present invention is a weight average molecular weight of about 500 to 20,000 as measured by GPC, preferably about 800 to 20,000, more preferably about 1,000 to 10,000, and about 1,500 to 6,000. good. When the weight average molecular weight is too low, the heat resistance is lowered, and when the viscosity is too high, the viscosity is increased and the operation is disadvantageous.

The weight average molecular weight is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Manufacturing Co., Ltd.

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 pieces)

Flow rate: 1.0ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

The epoxy equivalent of the oxirane compound of the present invention (determined by the method described in JIS K-7236) is preferably from 300 to 1600 g/eq, more preferably from 400 to 1000 g/eq, and further from 450 to 900 g/eq. It is especially good. When the epoxy equivalent is too small, the hardened material is too hard and has low inelasticity, and when it is too large, the mechanical properties of the cured product are deteriorated.

The viscosity of the oxirane compound of the present invention (E-type viscosity meter, measured at 25 ° C) is generally about 50 to 20,000 mPa ‧ S, preferably about 150 to 10,000 mPa ‧ S, and about 200 to 10000 mPa ‧ s Good, and the best is about 200 to 5000 mPa‧S. Moreover, it is sometimes better to use 500 to 10000 mPa‧S, and more preferably 800 to 5000 mPa‧S.

a hydrazine atom bonded to three oxygen atoms in a hydrolyzed condensed segment of an alkoxy decane which is a oxoxane compound of the present invention (preferably a sesquioxane chain segment), relative to all ruthenium atoms The ratio may be about 5 to 95 mol%, preferably 5 to 50 mol% for the sealing of the optical semiconductor element, more preferably 8 to 30 mol%, and 10 to 25 mol%. good. The remainder is the proportion of deuterium atoms belonging to the chain polyoxyl segment. The above "all germanium atoms" means all of the germanium atoms in the halogenated alkane compound of the present invention. a ruthenium atom bonded to three oxygen atoms belonging to the sesquioxane chain segment, and the ratio of the chain polyphosphonium chain is strongly exhibited when the ratio is less than 5 mol% with respect to all of the ruthenium atoms. When used as a component of the curable resin composition described below, the cured product of the resin composition tends to be too soft, and the surface is sticky or damaged. On the other hand, when it is more than 50% by mole, the characteristics of the sesquiterpene oxide segment are strongly exhibited, and when used as a component of the following curable resin composition, the cured product of the resin composition is too hard to be low in elasticity. The rate characteristics are inferior and the results of the thermal cycle test tend to deteriorate.

The oxoxane compound of the present invention is characterized in that it has a chain polyoxy oxymethylene segment and a hydrolyzed condensed segment of the alkoxy decane (preferably a sesquioxane chain segment), the latter chain It is also a feature that the reactive functional group having an epoxy group in the segment, particularly the azide oxide compound of the present invention which increases the proportion of the chain polyoxynoxy segment, is suitable for the sealing of the optical semiconductor. For example, as described above, the ratio of the ruthenium atoms belonging to the hydrolyzed condensation segment (preferably a sesquioxane chain segment) of the above alkoxydecane is 5 with respect to all the ruthenium atoms in the oxoxane compound of the present invention. At 50 mol%, the proportion of deuterium atoms belonging to the chain polyoxyl segment is 50 to 95 mol%. A preferred ratio of the ruthenium atoms belonging to the chain polyoxynene segment is from 70 to 92 mol%, preferably from 75 to 90 mol%.

The proportion of the ruthenium atom in the two segments of the oxoxane compound of the present invention can be calculated from the feed ratio of the raw material, and can also be subjected to ¹ H NMR, ²⁹ Si NMR, elemental analysis, etc. of the oxoxane compound of the present invention. Find out.

The naphthenic compound of the present invention is as follows.

(i) a reactive functional group-containing oxoxane compound having a chain polyoxynized segment and a group having a reactive functional group selected from an epoxy group, a methyl group, and a phenyl group. a block type oxane oligomer of a hydrolyzed condensed segment of a tris(C1-C10) alkoxydecane, and at least a portion of the hydrolyzed condensed segment contains at least one reactive functional group containing an epoxy group Chain segment.

(ii) The reactive functional group-containing oxirane compound according to the above (i), wherein the chain polyoxynized segment is a segment represented by the following formula (2A), -(Si(R ₃ ) ₂ O)m- (2A) (wherein R ₃ may be mutually identical or mutually different, and represents 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; m represents an average value of 2 to 2000).

(iii) The reactive functional group-containing oxirane compound according to the above (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 oxirane compound according to any one of the above (i) to (iii), wherein R ₃ is a methyl group.

(v) The reactive functional group-containing oxirane compound according to any one of the above (i) to (iv), wherein the reactive functional group having an epoxy group is a carbon number having an epoxy group A cycloalkyl group of 5 to 8 is substituted with an alkyl group having 1 to 3 carbon atoms.

(vi) The reactive functional group-containing oxirane compound according to any one of the above (i) to (iv), which has a reactive functional group selected from an epoxy group, a methyl group, and a phenyl group. The tri(C1-C10) alkoxydecane group of the group is a tris(C1-C10) having an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms of an epoxy group. Alkoxydecane.

(vii) The reactive functional group-containing oxoxane compound according to the above (vi), which has a cycloalkyl group having 5 to 8 carbon atoms and having an epoxy group A tri(C1-C10) alkoxydecane having an alkyl group having 1 to 3 carbon atoms is β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

(viii) The reactive functional group-containing oxirane compound according to any one of the above (i) to (vii), which has a reactive functional group selected from an epoxy group, a methyl group, and a phenyl group. The tris(C1-C10) alkoxydecane group of the group is a tri(C1-C10) alkoxydecane having a reactive functional group containing an epoxy group, and having a selected from a methyl group and a phenyl group. Both of the three (C1-C10) alkoxydecane groups in the group.

(1) The reactive functional group-containing oxoxane compound according to the above (viii), wherein the tri(C1-C10) alkoxy decane having a group selected from the group consisting of a methyl group and a phenyl group is a (C1-C10) alkoxy decane system Phenyltrimethoxydecane or methyltrimethoxydecane.

(a) The reactive functional group-containing oxirane compound according to any one of the above (i) to (ix), wherein the weight average molecular weight measured by GPC is from 500 to 20,000.

(xi) The reactive functional group-containing oxoxane compound according to any one of the above (i) to (x), which is obtained by the following two-stage reaction, and the first-stage reaction system is a general formula ( 2) the sterol-terminated polyoxyxane oil (b) and the alkoxy decane compound (a) represented by the formula (1) are 1 equivalent to the sterol group of the fluorene-terminated oxy-acid (b). The alkoxyoxane compound is reacted and condensed in an amount of from 1.5 to 200 equivalents, and the second stage reaction thereafter is carried out by adding water to the obtained reaction liquid to hydrolyze and condense the remaining alkoxy group;

(wherein a plurality of R ₃ may be mutually identical or mutually different, and represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or a carbon number of 2 to 10 alkenyl; m means an average of 2 to 2000)

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).

(xii) The oxime compound having a reactive functional group as described in the above (xi), wherein the sterol terminal polyfluorene oxide represented by the formula (2) is measured by GPC (gel permeation chromatography) The weight average molecular weight of (b) is from 300 to 30,000.

(xiii) The reactive functional group-containing oxoxane compound as described in the above (xi) or (xii), wherein the oxime group is equivalent to 1 equivalent of the sterol-terminated polyoxyxanic oil (b), 1) The alkoxy group of the alkoxydecane compound (a) shown has an equivalent weight of 2 to 100 equivalents.

(Xiv) The reactive functional group-containing oxirane compound according to any one of the above (xi) to (xiii), wherein the sterol terminal polyfluorene oxide (b) represented by the formula (2) is A sterol terminal dimethylpolyphthalic acid oil or a sterol terminal methyl phenyl phthalate oil.

(a) a reactive functional group-containing oxoxane compound according to any one of the above (xi) to (xiv), wherein the alkoxydecane compound (a) represented by the formula (1) is a β-shrinkage Glyceryloxyethyltrimethoxydecane, β-glycidoxyethyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane , β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane or β-(3,4-epoxycyclohexyl)ethyltriethoxydecane.

(Xvi) The reactive functional group-containing oxirane compound according to any one of the above (i) to (x), wherein the first-stage reaction is carried out by polymerizing the sterol terminal of the formula (2) The oxy-oil (b), both the alkoxy decane compound (a) represented by the formula (1) and the alkoxy decane compound (c) represented by the formula (3), are condensed with respect to the sterol-terminated polyoxyxene oil ( b) the sterol group is 1 equivalent, the alkoxy decane compound (a) and the total alkoxy group equivalent of (c) are reacted and condensed in the range of 1.5 to 200 equivalents, and the second stage reaction thereafter is carried out by adding water. In the resulting reaction solution, the remaining alkoxy groups are hydrolyzed and condensed:

(wherein a plurality of R ₃ may be mutually identical or mutually different, and represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms or a carbon number of 2 to 10 alkenyl; m means an average of 2 to 200),

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),

R ₄ Si(OR ₂ ) ₃ (3)

(wherein R ₄ represents a methyl group or a phenyl group; and R ₂ may be the same as or different from R _{2 of the} formula (1), and each independently, and represents an alkyl group having 1 to 10 carbon atoms).

(xvii) The reactive functional group-containing oxirane compound according to the above (xvi), wherein the sterol terminal polyfluorene oxide (b) represented by the formula (2) is the above (xii) or (xiv) The polyoxyl oil described.

(a) The alkoxysilane compound having a reactive functional group as described in the above (xvi) or (xvii), wherein the alkoxysilane compound (a) represented by the formula (1) is as described in the above (xv) Compound.

(1) The reactive functional group-containing oxoxane compound according to any one of the above (xvi) to (xviii), wherein the alkoxy decane compound (c) represented by the formula (3) is a methyl trimethyl group. Oxydecane or phenyltrimethoxydecane.

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 "the oxoxane compound (A) of the present invention" or simply "the siloxane compound (A)" in the description of the curable resin composition. In this case, the oxoxane compound (A) may be a reactive functional group-containing oxoxane compound as described in any one of the above (i) to (xix), and may also include all combinations with the oxoxane compound. .

The curable resin composition of the present invention contains the oxirane compound (A) of the present invention as an epoxy resin component, and further contains a curing agent (B). Further, an epoxy resin other than the siloxane compound (A) or a curing accelerator may be further contained as needed. The other epoxy resin does not lose the characteristics of the oxirane compound (A) of the present invention (for example, as a property of a cured product when used in a curable resin composition, specifically, transparency, heat resistance, light resistance, and low temperature) It can be used in combination within the range of low modulus of elasticity, non-stickiness, thermal cycle resistance, and hardness. Such other epoxy resins may improve the cured properties of the curable resin composition, as the case may be. The ratio of the oxoxane 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, depending on the aspect of use. It is preferably from 60 to 100% by weight, or from 70 to 100% by weight, more preferably from 80 to 100% by weight.

When used in combination, in combination with the epoxy resin compound (A) of the present invention and the other epoxy resin, the proportion of the oxoxane compound of the present invention is preferably 20 to 90% by weight, and preferably 30. Up to 90% by weight is particularly preferred.

Further, in the curable resin composition of the present invention, the ratio of the oxirane compound (A) of the present invention, alone or in combination with the epoxy resin of the present invention, the total epoxy resin of the oxirane compound (A) and other epoxy resins, It is preferably from 30 to 90% by weight, more preferably from 40 to 90% by weight, still more preferably from 50 to 90% by weight, based on the total mass of the composition. Further, depending on the embodiment, it is preferably 40 to 80% by weight, more preferably 50 to 80% by weight.

Specific examples of the other epoxy resin include polyfunctional epoxy resins of glycidyl ether compounds of polyphenol compounds, polyfunctional epoxy resins of glycidyl ether compounds of various phenol resins, and nuclear hydrogenation of aromatic epoxy resins ( Hydrogenated), alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, halogenated phenol glycidylated epoxy resin, glycidylation Polyoxyl resin, etc.

Examples of the polyphenol compound used in the above polyfunctional epoxy resin include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethylbisphenol A, and dimethyl bisphenol A. , tetramethylbisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'- Bisphenol, 1-(4-hydroxyphenyl)-2-[4-(1,1-bis-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylene-double (4-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), tris(hydroxyphenyl)methane, isophthalic acid Phenols, hydroquinones, pyrogallols, phenols having a diisopropylidene skeleton, 1,1-di-4-hydroxyphenylhydrazine, etc., phenols having an anthracene skeleton, phenolated polybutadiene Polyphenolic compounds. Therefore, as the polyfunctional epoxy resin of the glycidyl ether compound of the above polyphenol compound, specifically, a glycidyl ether compound of the above polyphenol compound can be mentioned.

Examples of the phenolic resin used in the above polyfunctional epoxy resin include phenolic resins obtained by using various phenols as raw materials, and various phenols as raw materials include phenol, cresol, ethyl phenol, and butyl phenol. a phenolic resin containing octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthols as raw materials; a phenolic phenolic resin containing a benzene dimethyl skeleton; and a dicyclopentadiene skeleton Phenolic phenolic resin; phenolic phenolic resin containing a biphenyl skeleton; various phenolic resins such as a phenolic phenolic resin containing an anthracene skeleton. Therefore, specific examples of the polyfunctional epoxy resin of the glycidyl ether compound of various phenol resins include glycidyl ether compounds of the phenol resins.

The nuclear hydride of the aromatic epoxy resin may, for example, be a nuclear hydrogenated product of a glycidyl ether compound of a phenol resin using a phenol resin as a raw material of the above various phenols, and specifically, various phenols (for example, bisphenol A, a glycidyl ether compound of a phenol compound such as bisphenol F, bisphenol S or 4,4'-biphenol, or phenol, cresol, ethyl phenol, butyl phenol, octyl phenol, bisphenol A, A nuclear hydride of a glycidyl ether compound of a phenol resin as a raw material of bisphenol F, bisphenol S, and naphthol.

The alicyclic epoxy resin may, for example, be 2,2'-bis(4-glycidoxycyclohexyl)propane or 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl Ester, vinyl cyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxin An alicyclic epoxy resin having an aliphatic skeleton such as an alkane, a bis(3,4-epoxycyclohexyl) adipate or the like, and a cyclohexane.

The aliphatic epoxy resin is a glycidyl ether of a polyhydric alcohol, and examples thereof include 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, and benzenedimethanol. A glycidyl ether or the like of a polyhydric alcohol such as a derivative.

Examples of the heterocyclic epoxy resin include a heterocyclic epoxy resin having a hetero ring such as an isocyanuric ring or an intramethylene urea ring.

Examples of the glycidyl ester-based epoxy resin include an epoxy resin composed of a glycidyl carboxylic acid such as hexahydrophthalic acid diglycidyl ester or tetrahydrophthalic acid diglycidyl ester.

Examples of the glycidylamine-based epoxy resin include glycidation of amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminotoluene derivative. Epoxy resin, etc.

The halogenated phenolic glycidylated epoxy resin may, for example, be brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, A halogenated phenol such as bisphenol A or a glycidylated epoxy resin.

These epoxy resins are not particularly limited in use, and from the viewpoint of transparency, those having less coloring properties are preferred. Generally applicable are 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, tris(hydroxyphenyl)methane, resorcinol, 2,6-di-t-butyl hydroquinone a polyfunctional epoxy resin having a diisopropylidene skeleton phenol or a glycidyl compound having an anthracene skeleton such as 1,1-di-4-hydroxyphenylhydrazine; a phenol or a cresol a phenolic resin containing various phenols such as bisphenol A, bisphenol S and naphthol, a phenolic phenolic resin containing a dicyclopentadiene skeleton, a phenolic phenolic resin containing a biphenyl skeleton, and a phenolic phenolic resin containing an anthracene skeleton Glycidyl etherate of various phenolic resins; glycidyl etherate of phenolic compounds such as bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, or phenol, cresol, ethylphenol a nuclear hydride of glycidyl etherate of a phenolic resin of various phenols such as butyl phenols, octyl phenols, bisphenol A, bisphenol F, bisphenol S and naphthols; 3', 4'- Ethylene cyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester or the like having cyclohexane bone Epoxy epoxy resin; glycidyl ether of 1,6-hexanediol, polyethylene glycol, polypropylene glycol; or triglycidyl isocyanurate or hexahydrophthalic acid diglycidyl ester Wait. From the viewpoint of heat-resistant transparency and light-resistant transparency, an alicyclic epoxy resin having a cyclohexane skeleton is particularly preferable. These epoxy resins may be used alone or in combination of two or more kinds depending on the heat resistance and the like.

The contents of the curing agent (B) and the curing accelerator (C) used in the present invention will be described.

As the curing agent (B), an amine compound, an acid anhydride compound, a carboxylic acid compound, a guanamine compound, a phenol compound, or the like can be used without particular limitation. Specific examples thereof include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophoronediamine, dicyandiamide, and tetra-strand Ethylpentamine, dimethylbenzylamine, ketimine compound, polyamine resin synthesized from dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride , maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hydrogenated nadic anhydride, hydrogenated methyl nadic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, A Hexahydrophthalic anhydride, 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride; phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl six Hydrogen phthalic acid, trimellitic acid, cyclohexanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid; bisphenols, phenols (phenols, alkyl-substituted phenols, naphthols, alkanes) Polycondensate of various substituted aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylols, or dimethoxy base Biphenyl condensates of a phenol or naphthol and the like, as well as those modified with phenols of substance, imidazoles, boron trifluoride - amine complexes, and guanidine derivatives. Among these, an acid anhydride-based compound or a carboxylic acid-based compound is particularly useful in terms of an appropriate usable time (or operation time; Pot Life) and transparency of a cured product when the resin composition is mixed with an epoxy resin. The compound is preferably hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride, hydrogenated nadic anhydride, hydrogenated The kinadic anhydride is the best.

The hardener (B) is preferably used in an amount of from 0.2 to 1.5 equivalents per equivalent of the epoxy group of all the epoxy resins combined with the oxirane compound (A) or other epoxy resin in the composition. It is particularly preferably from about 0.3 to 1.2 equivalents. Further, in particular, the amount of the hardener used when a tertiary amine such as benzyldimethylamine is used as the hardener (B) is preferably used in an amount of 0.3 to 20 by weight based on the epoxy group-containing compound contained in the composition. % is particularly preferably from 0.5 to 10% by weight.

Examples of the hardening accelerator (C) include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4-methylimidazole. , 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'-methylimidazolium (1')) ethyl-s-three 2,4-Diamino-6(2'-undecylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-ethyl, 4-methylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-s-three ‧Isocyanuric acid adduct, 2:3 adduct of 2-methylimidazoisocyanuric acid, 2-phenylimidazoisocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole And various imidazoles such as 2-phenyl-4-hydroxymethyl-5-methylimidazole and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole; a salt of the imidazoles and a polycarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid or oxalic acid; a diazonium compound such as dicyandiamide; a diaza compound such as 1,8-diaza-bicyclo(5.4.0) undecen-7; and a salt of such tetraphenylborate or phenol novolac a salt formed with the above polycarboxylic acid or phosphonic acid; tetrabutylammonium bromide, cetyltrimethylammonium bromide, cetyltrimethylammonium hydroxide, trioctyl bromide Ammonium salts such as ammonium chloride; phosphines such as triphenylphosphine, tris(tolyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethyl phosphate or a hydrazine compound; a phenol such as 2,4,6-tris(aminomethyl)phenol; an amine adduct. For example, U-CAT 18X (trade name: manufactured by San-Apro Co., Ltd.) of a commercial item, etc. The hardening accelerators can be microencapsulated. Which of these hardening accelerators is used can be suitably selected, for example, according to the characteristics required for the transparent resin composition which can obtain transparency, a hardening speed, and operating conditions. The hardening accelerator is generally used in an amount of from 0.005 to 5 parts by weight, based on 100 parts by weight of the block type siloxane compound having a reactive functional group or with other epoxy resins. Preferably, it is particularly preferably 0.05 to 1 part by weight.

In the curable resin composition of the present invention, an inorganic filler, a colorant, a polyoxyxylene resin, a leveling agent, a lubricant, a coupling agent, and a leveling agent may be appropriately added depending on the purpose in the range of non-destructiveness and transparency. Agents, lubricants, light stabilizers, antioxidants, and phosphors.

The inorganic filler is not particularly limited, and examples thereof include crystalline or amorphous cerium oxide, talc, cerium nitride, boron nitride, aluminum oxide, cerium oxide, and titanium oxide mixed solution.

The coloring agent is not particularly limited, and examples thereof include phthalocyanine, azo, disazo, quinacridone, anthracene, flavanone, purple ring ketone, hydrazine, and dioxins. , condensed azo, azodimethine, various organic pigments, titanium oxide, lead sulfate, chrome yellow, zinc yellow, molybdenum orange, iron oxide, cobalt violet, Prussian blue, ultramarine blue, carbon black, chrome green, An inorganic pigment such as chromium oxide or cobalt green.

The polyoxynoxy resin may, for example, be dimethyl polyfluorene oxide, phenylmethyl polyfluorene oxide, epoxy modified polyfluorene oxide, polyether modified polyfluorene oxide, amine modified polyoxyl oxide, vinyl modified Poly-oxygen, decyl-modified polyoxyl, and the like.

The leveling agent may, for example, be an acrylate having a molecular weight of 4000 to 12000 composed of an acrylate such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; an epoxidized soybean fatty acid; an epoxidized rosin alcohol; Hydrogenated castor oil; titanium-based coupling agent.

Examples of the lubricant include hydrocarbon-based lubricants such as paraffin wax, microcrystalline wax, and polyethylene wax; and higher fatty acid-based lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; a high-grade fatty amide-based lubricant such as stearylamine, palm amide, ceramide, methylenebisstearylamine or ethyl bis-stearamide; hardened castor oil, butyl stearate, a higher fatty acid ester-based lubricant such as ethylene glycol monostearate or pentaerythritol (mono, di-, tri- or tetra) stearate; cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerin, etc. Alcohol-based lubricant; metal salts of magnesium, calcium, cadmium, strontium, zinc, lead, etc. of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid, etc. Metal soaps; natural waxes such as carnauba wax, rehearsal wax, beeswax, and montan wax (also known as montan wax).

The coupling agent may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinyl Benzylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3 a decane-based coupling agent such as chloropropylmethyltrimethoxydecane; (N-ethylaminoethylamino) isopropyl titanate, isopropyl triisostearate isopropyl titanate, and di(II) Octyl pyroylphosphonium oxyacetate, tetraisopropylbis(dioctylphosphite) titanate, neoalkoxytris(pN-(β-aminoethyl)aminophenyl) Titanium coupling agent such as titanate; zirconium acetonate, zirconium methacrylate, zirconium propionate, neoalkoxy zirconate, new Oxygen tridecyl zirconate, neoalkoxytris(taudecyl)benzenesulfonium zirconate, neoalkoxytris(ethylenediamineethyl)zirconate, neoalkoxy III A zirconium or aluminum-based coupling agent such as (m-aminophenyl) zirconate, ammonium zirconium carbonate, aluminum acetonate, aluminum methacrylate or aluminum propionate.

The light stabilizer is suitably a hindered amine light stabilizer (HALS). HALS is not particularly limited, but can be listed as: dibutylamine ‧1,3,5-three ‧N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and N-(2,2,6,6-tetramethyl-4 Polycondensate of -piperidinyl)butylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, poly[ {6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imido}], bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethyl) 4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2, 2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacic acid Ester, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidin Pyridyl) ester and the like. HALS can be used alone or in combination of two or more types.

Examples of the antioxidant include a phenol type, a sulfur type, and a phosphorus type antioxidant.

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and stearin. Benzyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Ester, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-three Monophenols such as 2,4-bis[(octylthio)methyl]o-cresol; 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2, 2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'- Butylene bis(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 Third butyl-4-hydroxy hydrogenated cinnamylamine), 2,2'-thio-diethylidene bis[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- Tributyl-4-hydroxy-5-tolyl)propoxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di a bisphenol such as calcium tributyl-4-hydroxybenzylsulfonate; 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, tetra-[methylene-3-(3',5 '-Di-tert-butyl-4'-hydroxyphenyl)propionate] methane, double [3,3' - bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]diol, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanuramide Acid ester, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-three -2,4,6-(1H,3H,5H) triols, tea phenols and other polymeric phenols.

Specific examples of the sulfur-based antioxidant are: 3,3'-dilaurate of thiodipropionate, 3,3'-thiodipropionate dimyristate, 3,3'-thiodipropionic acid Stearyl ester and the like.

Specific examples of the phosphorus-based antioxidant are: triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diiso Indole pentaerythritol phosphite, tris(2,4-di-t-butylphenyl)phosphite, cyclopentanetetraylbis(octadecyl)phosphite, cyclopentane tetrakis 2,4-di-t-butylphenyl)phosphite, cyclopentanetetraylbis(2,4-di-t-butyl-4-methylphenyl)phosphite, double [2- a phosphite such as tributyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite; 9,10-dihydro-9-oxa -10-phosphinophen-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphinophen-10 An oxaphosphonium phenanthrene oxide such as an oxide or a 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

These antioxidants may be used alone or in combination of two or more. In particular, in the present invention, a phosphorus-based antioxidant is preferred. The antioxidant is used in an amount of usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component in the curable resin composition of the present invention.

When the curable resin composition of the present invention is used in a photo-semiconductor encapsulant, a phosphor can be added as needed. The fluorescent system emits white light having a wavelength converted by, for example, absorbing a portion of the blue light emitted by the blue LED element. After the phosphor is previously dispersed in the curable resin composition, the photo-semiconductor is sealed. The phosphor is not particularly limited, and conventionally used phosphors can be used, and examples thereof include an aluminate of a rare earth element, a thiogallate, and a protoporate. More specifically, examples thereof include a phosphor such as a YAG phosphor, a TAG phosphor, a protonate phosphor, a thiogallate phosphor, or a sulfide phosphor, and for example: 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 so on. The particle diameter of the phosphor may be a particle diameter conventionally known in the art, and the average particle diameter is from 1 to 250 μm, preferably from 2 to 50 μm. When these phosphors are used, the amount thereof is from 1 to 80 parts by weight, preferably from 5 to 60 parts by weight, per 100 parts by weight of the resin component.

The preferred curable resin composition of the present invention is as follows.

(I) A curable resin composition containing the reactive functional group-containing oxirane compound (hereinafter referred to as the oxoxane compound (A) of the present invention or the above-mentioned (i) to (xix) The oxoxane compound (A)) and an epoxy compound (hereinafter also referred to as O-EPO) other than the siloxane compound (A) which is optionally contained, the total amount thereof being 30 to 90 by weight based on the entire composition. % (hereinafter, unless otherwise specified, the weight %), and the rest is the hardener (B).

(II) The curable resin composition according to the above (I), wherein the hardener (B) is contained in an amount of from 0.2 to 1.5 equivalents per equivalent of the epoxy group of the siloxane compound (A).

(III) The curable resin composition according to the above (I) or (II), wherein the total amount of the oxirane compound (A) and optionally O-EPO is the same as the total amount of the composition. 50 to 90%.

(IV) The curable resin composition according to any one of the above-mentioned (I) to (III), wherein the oxy-oxygen compound (A) and the total amount of O-EPO which may be optionally contained are oxidized. The ratio of the alkane compound (A) is from 50 to 100%.

(V) The curable resin composition according to any one of the above-mentioned (I) to (IV), wherein the oxy-oxygen compound (A) and the total amount of O-EPO which may be optionally contained are oxidized. The ratio of the alkane compound (A) is from 30 to 90%.

The curable resin composition according to any one of the above-mentioned (1), wherein the hardening resin is contained in an amount of 0.001 to 15 parts by weight based on 10 parts by weight of the siloxane compound (A). Promoter.

(VII) The curable resin composition according to any one of the above (1), wherein the curing agent (B) is an acid anhydride compound or a carboxylic acid compound.

The curable resin composition of the present invention described above can be obtained by uniformly mixing the above raw materials by any method.

The curable resin composition of the present invention contains a reactive functional group-containing oxirane compound (A), a curing agent (B), and a curing-promoting (C) agent required for the curing, and the curable resin composition In addition, if there is further need, other optional ingredients can be adjusted. Other optional ingredients may be, for example, inorganic fillers, colorants, polyoxyxides, leveling agents, lubricants, coupling agents, photosensitizers, antioxidants, and phosphors. The other compounding component may be appropriately added in an amount of from 0 to 500 parts by weight, based on 100 parts by weight of the total amount of the siloxane compound (A) and the curing agent (B), and is from about 0 to 100 parts by weight. good. For the preparation of these other ingredients, in a solid state, use a mixer such as a Henschel mixer or a Nauta mixer, and then use a kneader, an extruder, and a heating roller at 80 to 120. After kneading at °C and cooling, the powder is obtained by pulverization. On the other hand, when the blender is in a liquid state, it is uniformly dispersed by using a planetary mixer or the like, and the curable resin composition of the present invention containing the other blending components may be used.

When the optical semiconductor of the present invention is obtained by sealing the optical semiconductor such as an LED, a photoreceptor or a transceiver by using the composition of the present invention thus obtained, transfer molding and compression molding can be used. Forming by a conventional molding method such as injection molding, dispensing, and printing. Further, after the molding, the heating method for curing the resin composition for sealing the optical semiconductor is not particularly limited, and conventional conventional methods such as hot air circulation heating, infrared heating, and high frequency heating can be employed. The hardening conditions are generally heated at about 80 to 250 ° C for a period of from 30 seconds to 15 hours, but the conditions may be appropriately changed. Preferred conditions are from 110 to 200 ° C, preferably such as: first hardening at 100 to 140 ° C, followed by final hardening at 130 to 200 ° C.

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. Meanwhile, the present invention is not limited to the above-described synthesis examples and examples. Further, each physical property value in the examples was measured by the following method.

(1) Molecular weight: A polystyrene-equivalent weight average molecular weight determined by a gel permeation chromatography (GPC) method under the following conditions.

Various conditions of GPC

Manufacturer: Shimadzu Corporation

Pipe column: protection column SHODEX GPC LF-G LF-804 (3 pieces)

Flow rate: 1.0ml/min.

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Detector: RI (differential refraction detector)

(2) Epoxy equivalent: Measured according to the method described in JIS K-7236.

(3) Viscosity: It was measured at 25 ° C using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.

[Examples]

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples. Meanwhile, the "parts" and "%" in the synthesis examples and the examples are "parts by weight" and "% by weight", respectively. Further, although the alkoxy equivalent and the decyl alcohol equivalent are not described, the units are all g/eq.

Example 1 (Example of reacting at a ratio of 5.3 equivalents per equivalent of alkoxy group to sterol group)

Phase 1 reaction: 197.1 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1 g/eq), weight average molecular weight 1060 (GPC measured value) of the sterol end 237.4 parts of dimethylpolysiloxane (sterol equivalent 530g/eq), 21.3 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.11 parts of KOH) were charged into the reaction vessel, and the liquid temperature was raised. To 75 ° C. After the temperature was raised, the reaction was carried out at 75 ° C for 8 hours under reflux. The sterol equivalent weight 530 g/eq is a molecular weight molecular weight of 1060 measured by GPC as the molecular weight of the polyoxygenated oil, and since it has two sterol groups per molecule, half of the value is calculated. In the following examples, the sterol equivalent of the sterol terminal polyoxyxane oil (b) was also determined in the same manner.

The second-stage reaction: 305 parts of methanol was added to the reaction liquid obtained above, and 86.4 parts of a methanol solution of 50% distilled water was added dropwise thereto over 60 minutes, followed by a reaction at 75 ° C for 8 hours under reflux. After completion of the reaction, the reaction solution was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. After adding 380 parts of methyl isobutyl ketone (MIBK) to the remaining reaction liquid, water washing was repeated three times. After the organic phase was separated, the solvent was removed under reduced pressure at 100 ° C to obtain 344 parts of a block type siloxane compound (A-1) having a reactive functional group. The obtained compound had an epoxy equivalent of 457 g/eq, a weight average molecular weight of 3,700, a viscosity of 600 mPa·s, and a colorless and transparent appearance.

The proportion of ruthenium atoms belonging to the sesquioxane chain segment (the ratio of the ruthenium atoms combined with the three oxygen atoms calculated from the feedstock ratio to the total ruthenium atom) was 19.6 mol%. Similarly, the proportion of germanium atoms belonging to the chain polyoxynene segment was 80.4 mol%. Example 2

(Example of reacting with a ratio of 1 equivalent of alkoxy group to 30.8 equivalents of a sterol group)

Phase 1 reaction: 197.1 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), weight average molecular weight 6120 (GPC measured value) of sterol terminal dimethyl 237.4 parts of polyoxygenated oil (sterol equivalent of 3060) and 20.0 parts of a 0.5% KOH methanol solution (0.1 part by weight of KOH) were placed in a reaction vessel, and the liquid temperature was raised to 75 °C. After the temperature was raised, the mixture was reacted at 75 ° C for 8 hours under reflux.

In the second-stage reaction, after adding 260 parts of methanol, 86.4 parts of a methanol solution of 50% distilled water was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 380 parts of MIBK were added and washed three times. Next, the organic phase was subjected to a solvent under reduced pressure at 100 ° C to obtain 360 parts of a block type siloxane compound (A-2) having a reactive functional group. The obtained compound had an epoxy equivalent of 468 g/eq, a weight average molecular weight of 4,160, a viscosity of 481 mPa·s, and a colorless and transparent appearance.

The proportion of ruthenium atoms belonging to the sesquioxane chain segment was 19.6 mol%. Similarly, the proportion of germanium atoms belonging to the chain polyoxynene segment was 80.4 mol%. Example 3

(Example of reacting at a ratio of 1 equivalent of alkoxy group to 1 equivalent of sterol group)

Phase 1 reaction: 98.6 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), weight average molecular weight 15800 (GPC measured value) of sterol terminal dimethyl 118.7 parts of polyoxygenated oil (sterol equivalent of 7900) and 10.0 parts of a 0.5% KOH methanol solution (0.05 parts of KOH fraction) were placed in a reaction vessel to raise the liquid temperature to 75 °C. After the temperature was raised, the mixture was reacted at 75 ° C for 8 hours under reflux.

The second-stage reaction: After adding 142 parts of methanol, 43.2 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 191 parts of MIBK were added, and the washing was repeated three times. Next, the organic phase was subjected to a solvent under reduced pressure at 100 ° C to obtain 169 parts of a block type siloxane compound (A-3) having a reactive functional group. The obtained compound had an epoxy equivalent of 477 g/eq, a weight average molecular weight of 4130, a viscosity of 710 mPa·s, and a colorless transparency.

The proportion of ruthenium atoms belonging to the sesquioxane chain segment was 19.6 mol%. Similarly, the proportion of germanium atoms belonging to the chain polyoxynene segment was 80.4 mol%. Example 4

(Example of reacting at a ratio of 8.6 equivalents per 1 equivalent of the alkoxy group to the sterol group)

Stage 1 reaction: 49.3 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), 39.7 parts of phenyltrimethoxydecane (alkoxy equivalent 66.1), weight 118.7 parts (sterol equivalent weight 850) of sterol-terminated methylphenyl polyfluorene oxide having an average molecular weight of 1,700 (GPC measured value), and 10.0 parts of a 0.5% KOH methanol solution (0.05 parts of KOH) were placed in a reaction vessel. The liquid temperature was raised to 75 °C. After the temperature was raised, the mixture was reacted at 75 ° C for 8 hours under reflux.

In the second-stage reaction, after adding 123 parts of methanol, 43.2 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 191 parts of MIBK were added, and the washing was repeated three times. Next, the organic phase was subjected to a solvent under reduced pressure at 100 ° C to obtain 168 parts of a block type siloxane compound (A-4) having a reactive functional group. The obtained compound had an epoxy equivalent of 874 g/eq, a weight average molecular weight of 2,630, a viscosity of 4,600 mPa·s, and a colorless and transparent appearance.

The proportion of ruthenium atoms belonging to the sesquioxane chain segment was 22.5 mol%. Similarly, the proportion of germanium atoms belonging to the chain polyoxynene segment was 77.5 mol%. Example 5

(Example of reacting at a ratio of 8.6 equivalents per 1 equivalent of the alkoxy group to the sterol group)

Stage 1 reaction: 49.3 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), methyl 3-methoxydecane 27.2 parts (alkoxy equivalent: 45.4), weight 118.7 parts (sterol equivalent weight 850) of sterol-terminated methylphenyl polyfluorene oxide having an average molecular weight of 1,700 (GPC measured value), and 10.0 parts of a 0.5% KOH methanol solution (0.05 parts of KOH) were placed in a reaction vessel. The liquid temperature was raised to 75 °C. After the temperature was raised, the mixture was reacted at 75 ° C for 8 hours under reflux.

In the second-stage reaction, after adding 123 parts of methanol, 43.2 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 166 parts of MIBK were added and washed three times in succession. Next, the organic phase was subjected to a solvent under reduced pressure at 100 ° C to obtain 151 parts of a block type siloxane compound (A-5) having a reactive functional group. The obtained compound had an epoxy equivalent of 832 g/eq, a weight average molecular weight of 5,850, a viscosity of 4610 mPa·s, and a colorless and transparent appearance.

The proportion of ruthenium atoms belonging to the sesquioxane chain segment was 20.0 mol%. Similarly, the proportion of germanium atoms belonging to the chain polyoxynene segment was 80.0 mol%.

Comparative example 1 (Example in which a reaction is carried out at a ratio of 1.4 equivalents per equivalent of the sterol group to 1.4 equivalents: an example of gelation in the first stage reaction)

37.0 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), weight average molecular weight 1060 (GPC measured value) of decyl alcohol terminal dimethyl polyfluorene oxide 170.9 A portion (sterol equivalent 530), 12.3 parts of a 0.5% KOH methanol solution (0.06 parts of KOH fraction) was placed in a reaction vessel, and the liquid temperature was raised to 75 °C. After the temperature was raised, the reaction was carried out at 75 ° C for 4 hours under reflux, and the reaction product became a solvent-insoluble gel (A-6).

Reference example 1 (Example of making a ratio of 5.5 equivalents to 1 equivalent of alkoxy group relative to a sterol group and reacting in the presence of water)

98.6 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxynonane (alkoxy equivalent: 82.1), weight average molecular weight 1060 (GPC measured value) of decyl alcohol terminal dimethyl polyfluorene oxide 118.7 A portion (sterol equivalent of 530), 131 parts of methanol, and 10.0 parts of a 0.5% KOH methanol solution (0.05 parts of KOH) were placed in a reaction vessel to raise the liquid temperature to 75 °C. After the temperature was raised, 43.2 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 191 parts of MIBK were added, and the washing was repeated three times. Next, the organic phase was subjected to a solvent under reduced pressure at 100 ° C to obtain 176 parts of a oxoxane compound (A-7) having a reactive functional group. The obtained compound had an epoxy equivalent of 459 g/eq and a weight average molecular weight of 3,300. The appearance of white turbidity occurred and it could not be used as a composition for an optical semiconductor sealing material.

Reference example 2 (Example in which 1 equivalent of alkoxy group relative to a sterol group is 30.7 equivalents and reacted in the presence of water)

In the same manner as in the synthesis method of Patent Document 1, 45.4 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1) and a weight average molecular weight of 6120 (GPC measured value) were obtained. 54.6 parts of an alcohol terminal dimethylpolyfluorene oxide (sterol equivalent of 3060), 10.0 parts of triethylamine, and 500 parts of MIBK were placed in a reaction vessel, and stirred at room temperature, and 100 parts of distilled water was added dropwise over 30 minutes. The temperature was raised to 80 ° C and the reaction was allowed to proceed 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. Then, the organic phase was removed under reduced pressure at 100 ° C to obtain 85 parts of a white turbid liquid (A-8), which was not used as a composition for an optical semiconductor sealing material.

Reference example 3 (Example of making the ratio of alkoxy group of 1 equivalent of sterol group to 31.0 equivalents and reacting in the presence of water)

78.8 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), weight average molecular weight 6120 (GPC measured value) of decyl alcohol terminal dimethyl polyoxyl oil 94.0 A portion (sterol equivalent of 3060), 104 parts of methanol, and 8.0 parts of a 0.5% KOH methanol solution (0.04 parts of KOH fraction) were placed in a reaction vessel to raise the liquid temperature to 75 °C. After the temperature was raised, 34.6 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 152 parts of MIBK were added, and the washing was repeated three times. Then, the organic phase was removed under reduced pressure at 100 ° C to obtain 151 parts of a white turbid liquid (A-9), which was not used as a composition for an optical semiconductor sealing material.

Reference example 4 (Example in which 1 equivalent of alkoxy group relative to a sterol group is made to be 80.0 equivalents and reacted in the presence of water)

98.6 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1) and a weight average molecular weight of 15800 (GPC measured value) of decyl alcohol terminal dimethyl polyfluorene oxide 118.7 A portion (sterol equivalent of 7900), 142 parts of methanol, and 10.0 parts of a 0.5% KOH methanol solution (0.05 parts of KOH) were placed in a reaction vessel to raise the liquid temperature to 75 °C. After the temperature was raised, 43.2 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 191 parts of MIBK were added, and the washing was repeated three times. Next, the organic phase was subjected to removal of the solvent under reduced pressure at 100 ° C to obtain 189 parts of a white turbid liquid (A-10).

Comparative example 2

The alkoxy-terminated polyoxyxene oil represented by the following formula (5) is used in place of the decyl alcohol-terminated polyoxygenated oil of the formula (2) used in Examples 1 to 5 to carry out the synthesis.

37.0 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), weight average molecular weight 2500 (GPC measured value) of methoxy-terminated dimethyl polyfluorene oxide 63.1 parts (alkoxy equivalent of 1250), 64 parts of methanol, 5.0 parts of a 0.5% KOH methanol solution (0.025 parts of KOH) were placed in a reaction vessel to raise the temperature of the liquid to 75 °C. After the temperature was raised, 16.2 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 88 parts of MIBK were added and washed three times with repeated washing. Then, the organic phase was removed under reduced pressure at 100 ° C to obtain 80.6 parts of a white turbid liquid (A-11), which was not used as a composition for an optical semiconductor sealing material.

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

From the above results, it was confirmed that Comparative Example 1 in which the alkoxy group/sterol group of the compound represented by the formula (1) and the alkoxy group/sterol group of the compound represented by the formula (2) were fed was made into a solvent-insoluble coagulation. Glue cannot be used as an epoxy resin. Further, Reference Example 1, Reference Example 2, Reference Example 3, and Reference Example 4 (A-7, A) in which a compound represented by the formula (1) and a compound represented by the formula (2) are added with a base catalyst and water at a time. -8, A-9, A-10) become a turbid liquid, and it is confirmed that it is not suitable for optical use. Further, A-11 (Comparative Example 2) in which a compound of the formula (2) is substituted with a compound of the formula (2) using a polyoxyphthalic acid having an alkoxy group at the end as a chain polyoxynized group also becomes a cloudy liquid. , the judgment is not applicable for optical use. On the other hand, the compounds of the formula (1) and the formula (2) are subjected to the two-stage reaction of Examples 1 to 3 (A-1, A-2, A-3) and the formula (1), The compounds shown in (2) and (3) were obtained as colorless and transparent resins in Examples 4 and 5 (A-4, A-5) in a two-stage reaction, and were confirmed to be suitable for optical use.

Comparative example 3

When dimethyl methoxy oxane is used as a unit, the dimethyl dimethoxy decane of the following formula (6) is used as a raw material, and the content of the dimethyl methoxy siloxane unit contained in the compound is determined. The concentration (% by mole) was synthesized in the same concentration (mol%) as in the above Examples 1 to 3.

The synthesis system was operated in the same manner as in the method described in Patent Document 1, and 33.9 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1) and dimethyldimethoxydecane ( The alkoxy equivalent of 60.1), the triethylamine (10.0 parts), and the MIBK 500 parts were placed in a reaction container, and the mixture was stirred at room temperature, and 100 parts of distilled water was added dropwise thereto for 30 minutes, and the temperature was raised to 80 ° C, and the reaction was allowed to proceed 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 subjected to removal of the solvent under reduced pressure at 100 ° C to obtain 60 parts of a oxoxane compound (A-12) having a reactive functional group. The obtained compound had an epoxy equivalent of 459 g/eq, a weight average molecular weight of 940, and a colorless and transparent appearance.

Example 6 (Example of reacting with a ratio of 3.8 equivalents per equivalent of alkoxy group of a sterol group)

Phase 1 reaction: 147.8 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), weight average molecular weight 1060 (GPC measured value) of sterol terminal dimethyl 252.8 parts of polyoxygenated oil (sterol equivalent 356), 20.0 parts of a 0.5% KOH methanol solution (0.1 part by weight of KOH) were placed in a reaction vessel, and the liquid temperature was raised to 75 °C. After the temperature was raised, the mixture was reacted at 75 ° C for 8 hours under reflux.

The second-stage reaction: After adding 255 parts of methanol, 64.8 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. 352 parts of MIBK were added, and the washing was repeated three times. Next, the organic phase was subjected to a solvent under reduced pressure at 100 ° C to obtain 333 parts of a block type oxoxane compound (A-13) having a reactive functional group. The obtained compound had an epoxy equivalent of 578 g/eq, a weight average molecular weight of 5,250, a viscosity of 257 mPa·s, and a colorless and transparent appearance.

The proportion of ruthenium atoms belonging to the sesquioxane chain segment was 14.9 mol%. Similarly, the proportion of germanium atoms belonging to the chain polyoxynene segment was 85.1 mol%.

Comparative example 4

When considering the structure of dimethyl methoxy oxane as a unit, the dimethyl dimethoxy decane of the following formula (6) is used as a raw material, and the concentration of the dimethyl methoxy siloxane unit contained in the compound is determined. (Mole %) was synthesized in the same concentration (mol%) as in Example 6 above.

The synthesis system was operated in the same manner as in the method described in Patent Document 1, and 26.6 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), dimethyldimethoxydecane 73.4. A portion (alkoxy equivalent of 60.1), 10.0 parts of triethylamine, and 500 parts of MIBK were placed in a reaction vessel, and stirred at room temperature. 100 parts of distilled water was added dropwise thereto over 30 minutes, and the temperature was raised to 80 ° C, and the reaction was allowed to proceed 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 subjected to removal of the solvent under reduced pressure at 100 ° C to obtain 60 parts of a oxoxane compound (A-14) having a reactive functional group. The obtained compound had an epoxy equivalent of 561 g/eq, a weight average molecular weight of 830, and was colorless and transparent in appearance.

Example 7

(Example of reacting with a ratio of 4.8 equivalents per equivalent of alkoxy group of a sterol group)

Phase 1 reaction: 59.1 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (alkoxy equivalent: 82.1), weight average molecular weight 1700 (GPC measured value) of sterol terminal methylbenzene A solution of 130.6 parts of a polyoxyl oleate (sterol equivalent 850) and 10.0 parts of a 0.5% KOH methanol solution (0.1 part by weight of KOH) was placed in a reaction vessel to raise the temperature of the liquid to 75 °C. After the temperature was raised, the mixture was reacted at 75 ° C for 8 hours under reflux.

Second-stage reaction: After adding 135 parts of methanol, 25.9 parts of a 50% distilled water methanol solution was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous sodium dihydrogen phosphate solution, and then methanol was distilled off at 80 °C. Thereafter, 170 parts of MIBK was added for washing, and water washing was repeated three times. Next, the organic phase was subjected to a solvent under reduced pressure at 100 ° C to obtain 162 parts of a block type siloxane compound (A-15) having a reactive functional group. The obtained compound had an epoxy equivalent of 707 g/eq, a weight average molecular weight of 2,680, a viscosity of 727 mPa·s, and a colorless and transparent appearance.

The proportion of germanium atoms belonging to the sesquioxane chain segment was 13.6 mol%. Similarly, the proportion of germanium atoms belonging to the chain polyoxynene segment was 86.4 mol%.

Examples 8 to 13, Comparative Examples 5 to 7

The commercially available oxirane epoxy resin (ERL-4221) and the hardener (for any of the above-mentioned synthesized alkoxylate compounds (A-1 to 3, 12 to 15) or conventional optical semiconductor sealing materials ( B-1 to B-3) or both the hardener (B-3) and the hardening accelerator C-1 are mixed in parts by weight shown in Tables 2, 3, 4 or 5 to give Example 8 of the present invention. 13 and the compositions of Comparative Examples 5 to 7.

The examples and comparative examples described in Table 2 are as follows.

Example 8: Composition using Compound A-1 and Hardener B-1

Example 9: Composition using Compound A-2 and Hardener B-1

Example 10: Composition using Compound A-3 and Hardener B-1

Comparative Example 5: Composition using Compound A-12 and Hardener B-1

Comparative Example 6: Composition using ERL-4221 and hardener B-1

The examples and comparative examples described in Table 3 are as follows.

Example 11: Composition using Compound A-13, Hardener B-3, and Hardening Accelerator C-1

Comparative Example 7: Composition using Compound A-14, Hardener B-3, and Hardening Accelerator C-1

The examples described in Table 4 are as follows.

Example 12: Composition using Compound A-15, Hardener B-3, and Hardening Accelerator C-1

The examples and comparative examples described in Table 5 are as follows.

Example 13: Composition using Compound A-13, Hardener B-3, and Hardening Accelerator C-1

Comparative Example 6: Composition using ERL-4221 and hardener 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 illumination test, and the results are shown in Tables 2 and 3. 4, 5.

(UV durability penetration test)

The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were subjected to vacuum defoaming for 20 minutes, and then gently poured into an aluminum foil cup having a bottom surface diameter of 5 cm and a height of 2 cm. The cast product was placed in an oven under predetermined hardening conditions to be hardened to obtain a test piece for penetration of 2 mm in thickness. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) before and after ultraviolet irradiation was measured by 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: 65mW/cm ²

Irradiation time: 100 hours

(thermal durability penetration test)

The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were subjected to vacuum defoaming for 20 minutes, and then gently poured into an aluminum foil cup having a bottom surface diameter of 5 cm and a height of 2 cm. The cast product was placed in an oven under predetermined hardening conditions to be hardened to obtain a test piece for penetration of 2 mm in thickness. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) was measured by a spectrophotometer in an oven at 150 ° C for 96 hours, and the rate of change was calculated.

(Mechanical characteristics test)

The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were subjected to vacuum defoaming for 20 minutes, and then a test piece having a width of 7 mm, a length of 5 cm, and a thickness of about 800 μm was gently poured into a mold, and then Covered with a polyimide film from above. The cast product was cured under the curing conditions described in Tables 2 and 3 to obtain a test piece for dynamic viscoelasticity. Using these test pieces, a dynamic viscoelasticity test was carried out under the following conditions.

Measuring condition

Dynamic viscoelasticity tester: TA-instrument, DMA-2980

Measuring temperature range: -30 ° C to 280 ° C

Heating rate: 2 ° C / min

Test piece size: those cut into 5 mm × 50 mm (thickness: about 800 μm) were used.

Analysis conditions:

Tg: The Tan-δ peak point measured by DMA is Tg.

-30 ° C modulus: the modulus of elasticity 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 subjected to vacuum defoaming for 20 minutes, and then filled in a syringe and mounted on a surface mount type LED having a light-emitting element having an emission wavelength of 375 nm, using a precision discharge device. Casting in. Thereafter, it was hardened under predetermined hardening conditions to obtain an LED for illumination test. In the lighting test, an illumination test was performed at 60 mA which is three times the predetermined current in order to perform the test under the accelerated condition. The detailed conditions are as follows. In the measurement item, the illuminance before and after the illumination for 100 hours was measured using an integrating sphere, and the illuminance retention rate was calculated. After further lighting for 100 hours, the surface state of the light-emitting element was observed.

[Detailed conditions of lighting]

Light emission wavelength: 375nm

Drive mode: constant current mode, 60mA (the specified current of the light-emitting component is 20mA)

Drive environment: 25 ° C, 65%

* Hardener B-1: Hardener is prepared by preliminarily preparing 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride ("H-TMA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) and methyl group. "MH-700G" (manufactured by Shin Nippon Chemical & Chemical Co., Ltd.) of a mixture of hexahydrophthalic anhydride and hexahydrophthalic anhydride was used as a hardener B-1.

* Hardener B-2: Hardener is prepared by pre-preparing 50 parts of methyl 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride ("H-TMA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) "MH-700G" (manufactured by Shin Nippon Chemical & Chemical Co., Ltd.) of a mixture of hexahydrophthalic anhydride and hexahydrophthalic anhydride was used as a hardener B-2.

*ERL-4221: An alicyclic epoxy resin manufactured by The Dow Chemical Company.

* Hardening conditions: 120 ° C 2 hr + 140 ° C 2 hr (Examples 8, 9, 10, Comparative Examples 5, 6)

* The unit of Tg is [°C], and the unit of modulus of elasticity at -30 °C is [MPa].

From the above results, it is understood that the curable resin compositions of Examples 8 to 10 using the oxoxane compound (A) of the present invention synthesized in a two-stage reaction are compared with the content of the dimethyl methoxy siloxane unit structure. In Comparative Example 5 in which the concentration (mol%) was the same, the Tg was high and the heat resistance was excellent, and the elastic modulus at a low temperature was lowered, and the heat resistance and the low modulus property were excellent. Further, in Comparative Example 6 of the conventional alicyclic epoxy resin, it was confirmed that the light resistance and the low modulus of elasticity were superior.

* Hardener B-3: A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride ("MH-700G" manufactured by Nippon Chemical and Chemical Co., Ltd.) was used.

* Hardening accelerator C-1: A reaction accelerator for an epoxy resin and an acid anhydride is "U-CAT 18X" (trade name) sold by San-apro Co., Ltd.

* Hardening conditions: unified to 120 ° C 2hr + 140 ° C 2hr

* The unit of Tg is [°C], and the unit of modulus of elasticity at -30 °C is [MPa].

*2) There is a foaming mark, and a suitable sample cannot be obtained as a cured material for dynamic viscoelasticity.

*3) Since the foaming trace of Comparative Example 7 in *2) was confirmed, when the sample for UV durability penetration test was produced, the amount of reduction of the resin was measured to confirm the weight retention ratio.

Further, the weight maintenance ratio was calculated by (weight of the cast product after hardening/weight of the cast product before hardening) × 100.

In the curable resin composition of Comparative Example 7, a foaming mark was generated and it was not possible to form a normal cured product for dynamic viscoelasticity measurement. On the other hand, it was found that the curable resin composition of Example 11 can be made non-tacky. Hardened and cured as a low modulus of elasticity. Further, in the curable resin composition of Comparative Example 7, the amount of reduction of the resin before and after curing of the sample for UV durability penetration test was measured to be 9% by weight, whereas the curable resin of Example 11 was used. The amount of the composition to be reduced is about 5%, and the curable resin composition of the present invention has a small amount of reduction before and after curing, and the cast product for LED encapsulation has less depression after hardening, so that the curability of the present invention can be confirmed. The resin composition is also suitable as a composition for LED sealing at this point. Further, as compared with Comparative Example 7, it was also found that the UV durability and heat resistance of the transmittance of Example 11 were also excellent.

* Hardener B-3: A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride ("MH-700G" manufactured by Nippon Chemical and Chemical Co., Ltd.) was used.

* Hardening accelerator C-1: A reaction accelerator for an epoxy resin and an acid anhydride is "U-CAT 18X" (trade name) sold by San-apro Co., Ltd.

* Hardening conditions: 120 ° C 1 hr + 150 ° C 3 hr

* The unit of Tg is [°C], and the unit of modulus of elasticity at -30 °C is [MPa].

The curable resin composition of Example 12 of the oxirane compound (A) of the present invention synthesized by the two-stage reaction was found to be a cured product having a low modulus at a low temperature.

* In order to check the deterioration of the component itself, the unsealed person who did not inject the resin simultaneously performed the LED illumination test.

* Hardener B-2: Hardener is prepared by pre-preparing 50 parts of methyl 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride ("H-TMA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) "MH-700G" (manufactured by Shin Nippon Chemical & Chemical Co., Ltd.) of a mixture of hexahydrophthalic anhydride and hexahydrophthalic anhydride was used as a hardener B-2.

* Hardener B-3: "MH-700G" (manufactured by Shin Nippon Chemical & Chemical Co., Ltd.) using a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride.

* Hardening accelerator C-1: A reaction accelerator for an epoxy resin and an acid anhydride is "U-CAT 18X" (trade name) sold by San-apro Co., Ltd.

*ERL-4221: An alicyclic epoxy resin manufactured by The Dow Chemical Company.

* Hardening conditions: 110 ° C 6 hr (Example 13)

* Hardening conditions: 120 ° C 1 hr + 150 ° C 3 hr (Comparative Example 6)

* The unit of Tg is [°C], and the unit of modulus of elasticity at -30 °C is [MPa].

From the above results, it was found that when the curable resin composition of Example 13 using the oxirane compound (A) of the present invention synthesized by the two-stage reaction is used in an LED sealing material, the alicyclic type is used in comparison with the conventional one. The curable resin composition of Comparative Example 6 of the epoxy resin was remarkably excellent in the illuminance maintenance ratio. From this, it was confirmed that the curable resin composition of the present invention is suitably used as an LED sealing material.

Claims (12)

A method for producing a reactive functional group-containing oxoxane compound, characterized by comprising the following two-stage reaction; the first-stage reaction is a sterol-terminated polyoxyxene oil (b) represented by the formula (2), With the alkoxydecane compound (a) represented by the formula (1), the alkoxy group of the alkoxystane compound (a) is 1.5 equivalent to 1 equivalent of the decyl alcohol group of the polyoxyxanthene oil (b). In the range of 200 equivalents, it is reacted and condensed in the presence of a catalyst, and the second stage reaction thereafter is carried out by adding water to the obtained reaction liquid to hydrolyze the remaining alkoxy group. (wherein, a plurality of R ₃ may be mutually identical or mutually different, each independently, and represent 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; m represents an average value of 2 to 2000) XSi(OR ₂ ) ₃ (1) (wherein X represents a reactive functional group having an epoxy group; and R ₂ represents a carbon number of 1 to 10 alkyl). A method for producing a reactive functional group-containing oxoxane compound, which comprises the following two-stage reaction, wherein the first-stage reaction is carried out by using a sterol-terminated polyoxyxene oil (b) represented by the formula (2). And the alkoxydecane compound (a) represented by the formula (1) and the alkoxydecane compound (c) represented by the formula (3), 1 equivalent of the decyl group relative to the oxime terminal polyoxyxanic oil (b) The alkoxyoxane compound (a) and the total alkoxy group of (c) have a total equivalent weight of from 1.5 to 200 equivalents, and a condensation reaction is carried out in the presence of a catalyst, and then the second stage reaction is carried out by adding water thereto. In the obtained reaction product, the remaining alkoxy group is hydrolyzed and condensed; (wherein, a plurality of R ₃ may be mutually identical or mutually different, each independently, and represent 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; m represents an average value of 2 to 200) XSi(OR ₂ ) ₃ (1) (wherein X represents a reactive functional group having an epoxy group; and R ₂ represents a carbon number of 1 to 10 alkyl)R ₄ Si(OR ₂ ) ₃ (3) (wherein R ₄ represents a methyl group or a phenyl group; and R ₂ may be the same as or different from R _{2 of the} formula (1), and each independently. Represents an alkyl group having 1 to 10 carbon atoms). A method for producing a reactive functional group-containing aziridine compound according to the first aspect of the invention, wherein m is from 2 to 200. A method for producing a reactive functional group-containing alkane compound according to claim 2, wherein m is from 2 to 200. The method for producing a reactive functional group-containing oxoxane compound according to any one of claims 1 to 4, wherein the manufacturing step is a first-stage reaction and a second-stage reaction in a one-pot manner. Responder. The method for producing a reactive functional group-containing oxoxane compound according to any one of claims 1 to 4, wherein the alkoxy decane compound represented by the formula (1) is β-(3, 4) -Epoxycyclohexyl)ethyltrimethoxydecane, or β-(3,4-epoxycyclohexyl)ethyltriethoxydecane. A method for producing a reactive functional group-containing alkane compound according to claim 5, wherein the alkoxydecane compound represented by the formula (1) is β-(3,4-epoxycyclohexyl)B. Tris-methoxydecane, or β-(3,4-epoxycyclohexyl)ethyltriethoxydecane. The method for producing a reactive functional group-containing oxoxane compound according to any one of claims 1 to 4, wherein the sterol terminal polyfluorene oxide (b) represented by the formula (2) R ₃ may be the same or different from each other and are each independently a methyl group or a phenyl group. The method of manufacturing a siloxane compound containing silicon patent range, Paragraph 5 of the reactive functional group, wherein the general formula (2) shown in an alcohol terminated poly silicon oxide silicon oil (b) R ₃ may be mutually the same or mutually different , each is a separate methyl or phenyl group. The method of manufacturing a siloxane compound containing a range of silicon patent, Paragraph 6 of the reactive functional group, wherein the general formula (2) shown in an alcohol terminated poly silicon oxide silicon oil (b) R ₃ may be mutually the same or mutually different , each is a separate methyl or phenyl group. The method of manufacturing a siloxane compound containing silicon patent scope of Paragraph 7 of reactive functional group, wherein the general formula (2) shown in an alcohol terminated poly silicon oxide silicon oil (b) R ₃ may be mutually the same or mutually different , each is a separate methyl or phenyl group. The method for producing a reactive functional group-containing oxoxane compound according to the second aspect of the invention, wherein the alkoxy decane compound represented by the formula (3) is selected from the group consisting of methyltrimethoxydecane and phenyltrimethoxy. Decane, methyl three At least one of a group consisting of ethoxy decane and phenyl triethoxy decane.