WO2010026714A1 - シロキサン化合物、硬化性樹脂組成物、その硬化物及び光半導体素子 - Google Patents

シロキサン化合物、硬化性樹脂組成物、その硬化物及び光半導体素子 Download PDF

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WO2010026714A1
WO2010026714A1 PCT/JP2009/004150 JP2009004150W WO2010026714A1 WO 2010026714 A1 WO2010026714 A1 WO 2010026714A1 JP 2009004150 W JP2009004150 W JP 2009004150W WO 2010026714 A1 WO2010026714 A1 WO 2010026714A1
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group
reactive functional
siloxane compound
functional group
silanol
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PCT/JP2009/004150
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English (en)
French (fr)
Japanese (ja)
Inventor
宮川直房
川田義浩
中西政隆
佐々木智江
窪木健一
青木静
鈴木瑞観
正人 鎗田
小柳敬夫
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日本化薬株式会社
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Priority to JP2010527669A priority Critical patent/JP5453276B2/ja
Priority to CN200980134516.2A priority patent/CN102143986B/zh
Publication of WO2010026714A1 publication Critical patent/WO2010026714A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a novel reactive functional group-containing siloxane compound, a production method thereof and a composition thereof. More specifically, the present invention relates to a curable resin composition for optical semiconductors excellent in transparency, light resistance, and low elastic modulus characteristics at low temperature, and an optical semiconductor element sealed with the cured product.
  • epoxy resin has been adopted as a sealing material for optical semiconductor elements such as LEDs in terms of a balance between performance and economy.
  • bisphenol A type epoxy resins, alicyclic epoxy resins, and the like that are excellent in the balance of heat resistance, transparency, and mechanical properties have been widely used.
  • the sealing material is colored by the influence of light and ultimately the characteristics of the LED are deteriorated. ing.
  • silicone resins have been studied for the purpose of avoiding coloring of the sealing material by light.
  • Patent Document 1 a silane compound having an epoxy group and a silane compound having no epoxy group are combined with an organic solvent, an organic base and water.
  • the polyorganosiloxane having a weight average of 500 to 1,000,000 is obtained by heating in the presence.
  • the polyorganosiloxane is improved from the conventional epoxy resin in terms of light resistance.
  • tackiness and hardness are improved by increasing the amount of the trifunctional alkoxysilane compound introduced relative to the bifunctional alkoxysilane compound.
  • the elastic modulus is increased particularly in a low temperature region (a level of ⁇ 30 ° C. or lower).
  • the low elastic modulus characteristic is lowered at a low temperature ( ⁇ 30 ° C. or lower).
  • the present invention relates to a siloxane compound having a novel reactive functional group having both light resistance and low elastic modulus at low temperature as an LED sealing material, a curable resin composition using the same, and the curable resin composition.
  • An object is to provide an optical semiconductor element used as a sealing material.
  • the inventors of the present invention have a silanol-terminated silicone oil (silicon compound) represented by the following general formula (2) and a reactive functional group-containing trialkoxysilane containing an epoxy group. It has been found that a reactive functional group-containing siloxane compound having a chain-like silicone segment obtained by reaction with a compound (silicon compound) and a trialkoxysilane hydrolytic condensation segment is useful for solving the above-mentioned problems. That is, it has been found that a curable resin composition containing the siloxane compound satisfies the above-mentioned problems.
  • the siloxane compound of the present invention is an oligomer (polymer) composed of a hydrolytic condensation segment (preferably a silsesquioxane segment) of a linear silicone segment and an alkoxysilane, and at least the hydrolytic condensation segment.
  • a hydrolytic condensation segment preferably a silsesquioxane segment
  • alkoxysilane preferably a silsesquioxane segment
  • One part of contains a reactive functional group having at least one epoxy group.
  • the present invention (1) A block type having a linear silicone segment and a hydrolytic condensation segment of tri (C1-C10) alkoxysilane having a group selected from the group consisting of a reactive functional group having an epoxy group, a methyl group and a phenyl group A reactive functional group-containing siloxane compound, wherein the at least one hydrolytic condensation segment is a segment containing a reactive functional group having at least one epoxy group, (2) The reactive functional group-containing siloxane compound according to (1), wherein the hydrolysis-condensation segment is a silsesquioxane segment, (3) As the first stage reaction, the general formula (2)
  • a plurality of R 3 may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 2000), and a general formula (1) XSi (OR 2 ) 3 (1) (Wherein X represents a reactive functional group having an epoxy group, and R 2 represents an alkyl group having 1 to 10 carbon atoms) Is reacted with 1 equivalent of silanol groups of the silanol-terminated silicone oil (b) in the range of 1.5 to 200 equivalents of equivalents of alkoxy groups of the alkoxysilane compound, Reactive functional group-containing product according to claim 1 or 2 obtained by condensing and then adding water to the resulting reaction solution as a second step reaction to hydrolyze and condense the remaining alk
  • a plurality of R 3 may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 200, and a compound represented by the general formula (1) XSi (OR 2 ) 3 (1) (Wherein X represents a reactive functional group having an epoxy group, and R 2 represents an alkyl group having 1 to 10 carbon atoms) and the general formula (3) R 4 Si (OR 2 ) 3 (3) (Wherein, R 4 is a methyl group or a phenyl group, R 2 is Formula (may be the same or different as R 2 in 1) each independently represent an alkyl group having 1 to 10 carbon atoms .) Both of the alkoxysilane compounds (c) represented by formula (1) are the total equivalents of the alkoxysi
  • Reactive functional group-containing siloxane compound according to (6) R 3 in the general formula (2) independently represents a methyl group or a phenyl group, R 2 in the general formula (1) independently represents a methyl group or an ethyl group, and R in the general formula (3) 2 may be the same as or different from R 2 in the general formula (1), and each independently represents a methyl group or an ethyl group, according to any one of the above (3) to (5) Reactive functional group-containing siloxane compounds, (7) The reactive functional group-containing siloxane compound according to any one of (3) to (6), wherein X in the general formula (1) is an epoxycyclohexylethyl group, (8) The reactive functional group according to any one of (3) to (6) above, wherein the weight average molecular weight (Mw)
  • a plurality of R 3 may be the same or different from each other, and each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an aryl group or an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 2000), and a general formula (1) XSi (OR 2 ) 3 (1)
  • X represents a reactive functional group having an epoxy group
  • R 2 represents an alkyl group having 1 to 10 carbon atoms.
  • the equivalent of the alkoxy group of the alkoxysilane compound (a) to the equivalent of the silanol group of the silanol-terminated silicone oil (b) A reactive functional group characterized by reacting in the presence of a catalyst, condensing, and then adding water to the resulting reaction solution to hydrolyze and condense
  • R 3 s may be the same or different from each other, and each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, aryl having 6 to 14 carbon atoms
  • XSi (OR 2 ) 3 (1)
  • X represents a reactive functional group having an epoxy group
  • R 2 represents an alkyl group having 1 to 10 carbon atoms.
  • R 4 is a methyl group, a phenyl group
  • R 2 is Formula (may be the same or different as R 2 in 1), an alkyl group having 1 to 10 carbon atoms independently.
  • the alkoxysilane compound (c) represented by the formula (1) is a total equivalent of the alkoxy groups of the alkoxysilane compounds (a) and (c), 1.5 to A reaction characterized in that a condensation reaction is carried out in the presence of a catalyst in the range of 200 equivalents, and then, as a second stage reaction, water is added to the obtained reaction product to hydrolyze and condense the remaining alkoxy groups.
  • alkoxysilane compound represented by the general formula (1) is ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane or ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane.
  • R 3 may be the same as or different from each other, and each independently represents a methyl group or a phenyl group (12 )
  • the alkoxysilane compound represented by the general formula (3) is at least one selected from the group consisting of methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane (13)
  • the cured product of the curable resin composition containing the siloxane compound of the present invention has no tackiness or deformation, and is excellent in transparency, light resistance, and low elastic modulus characteristics at low temperatures. Therefore, the curable resin composition of the present invention is extremely useful as an optical semiconductor sealing material.
  • the reactive functional group-containing siloxane compound of the present invention (hereinafter also simply referred to as the siloxane compound of the present invention) comprises a chain-like silicone segment and a hydrolysis-condensation segment of trialkoxysilane, preferably a reactive functional group having an epoxy group.
  • the silsesquioxane segment to be contained, more preferably, the three-dimensional network silsesquioxane segment is contained in one molecule.
  • the siloxane compound of the present invention is usually a hydrolytic condensation segment of trialkoxysilane, preferably a silsesquioxane segment having a three-dimensional network structure called silsesquioxane, which is a chain-like structure.
  • the structure is such that the silicone segment extends and is linked to the next hydrolysis-condensation segment of trialkoxysilane, preferably the silsesquioxane segment.
  • This structure provides a balance between hardness and flexibility in the cured product of the curable composition of the present invention.
  • the siloxane compound of the present invention has a hydrolysis-condensation segment of trialkoxysilane, preferably a silsesquioxane segment and a chain-like silicone segment, and is called a block-type siloxane compound because they are repeated. You can also.
  • the siloxane compound of the present invention includes, for example, the following general formula (10) XSi (R 1 ) n (OR 2 ) 3-n (10) (Wherein X is a reactive functional group having an epoxy group, R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, or a substituted or unsubstituted group.
  • alkoxysilane compound (a-1) (hereinafter also referred to as alkoxysilane (a-1)), preferably represented by the following general formula (1) XSi (OR 2 ) 3 (1) (Wherein X and R 2 represent the same meaning as in formula (10)).
  • the silicone oil (b) represented by the general formula (2) can be produced as raw materials, and if necessary, the above-described alkoxysilane compound (a) (hereinafter also referred to as alkoxysilane (a))
  • the alkoxysilane (a-1), preferably (a) can be used together with the alkoxysilane compound (c) represented by the general formula (3) as a raw material.
  • the chain silicone segment in the siloxane compound of the present invention is formed from silicone oil (b), and is a hydrolysis-condensation segment of trialkoxysilane, preferably a silsesquioxane segment, more preferably a three-dimensional network of silsesquioxane.
  • the sun segment is an alkoxysilane compound (a-1), preferably (a) (if used together with an alkoxysilane compound (c) (hereinafter also referred to as alkoxysilane (c)), the alkoxysilane (a-1 ), Preferably (a) and alkoxysilane (c) ⁇ .
  • the hydrolysis-condensation segment is preferably a segment in which the alkoxysilane (a) and optionally (c) are formed by a two-stage reaction of hydrolysis of the alkoxy group and dealcoholization condensation. By the hydrolysis condensation, a structure in which a plurality of structural units of X (if necessary and R 4 ) SiO 3/2 are bonded is obtained. Since the siloxane compound formed from the structural unit is called silsesquioxane, the hydrolytic condensation segment can be called a silsesquioxane segment.
  • X in the alkoxysilane compound (a-1) or (a) represented by the general formula (10) or (1) is not particularly limited as long as it is an organic group having an epoxy group.
  • ⁇ -glycidoxyethyl, ⁇ -glycidoxypropyl, ⁇ -glycidoxybutyl and the like glycidoxy having 1 to 4 carbon atoms; glycidyl group; ⁇ - (3,4-epoxycyclohexyl) ethyl group, ⁇ -(3,4-epoxycyclohexyl) propyl group, ⁇ - (3,4-epoxycycloheptyl) ethyl group, ⁇ - (3,4-epoxycyclohexyl) propyl group, ⁇ - (3,4-epoxycyclohexyl) butyl group
  • an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy ring such as ⁇ - A glycidoxyethyl group, a ⁇ -glycidoxypropyl group, and a ⁇ - (3,4-epoxycyclohexyl) ethyl group are preferable, and a ⁇ - (3,4-epoxycyclohexyl) ethyl group is particularly preferable.
  • R 2 in the general formula (10) or (1) independently represents an alkyl group having 1 to 10 carbon atoms, and may be linear, branched or cyclic.
  • R 2 is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • alkoxysilane (a-1) or (a) represented by the general formula (10) or (1) include ⁇ -glycidoxyethyltrimethoxysilane and ⁇ -glycidoxyethyltriethoxysilane.
  • alkoxysilane compounds (a) may be used independently, may use 2 or more types, and can also be used together with the alkoxysilane (c) represented by General formula (3) mentioned later.
  • Silicone oil (b) has the following formula (2)
  • R 3 and m are the same as above
  • a plurality of R 3 may be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 to 10 carbon atoms. Represents an alkenyl group.
  • alkyl group having 1 to 10 carbon atoms examples include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like.
  • a methyl group, an ethyl group, or a cyclohexyl group is preferable.
  • the aryl group having 6 to 14 carbon atoms include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group and the like.
  • the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group and hexenyl group.
  • R 3 is independently preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group, and particularly preferably a methyl group or a phenyl group.
  • R 3 in the general formula (2) are methyl or phenyl, one is methyl and the other is phenyl.
  • these combinations are usually the same in all repeating units.
  • different combinations may be included in the repeating units. For example, they may be different for each repeating unit, or different ones may be mixed regularly or randomly.
  • m is an average value of 2 to 2000, preferably 2 to 200, more preferably 3 to 100, and particularly preferably 3 to 50. If m is too low, the cured product becomes too hard and the low elastic modulus characteristics are deteriorated. If m is too high, the mechanical properties of the cured product tend to deteriorate.
  • the weight average molecular weight (Mw) of the silicone oil (b) is usually in the range of 300 to 50,000, preferably in the range of 300 to 30,000, more preferably 300 to 18,000 (GPC measurement). Value).
  • Mw weight average molecular weight
  • those having a molecular weight of 300 to 10,000 are more preferable in consideration of the elastic modulus at a low temperature
  • those having a molecular weight of 300 to 5,000 are more preferable in consideration of compatibility at the time of forming the composition.
  • Those of 3,000 are preferred.
  • the weight average molecular weight is less than 300, the properties of the chain silicone segment portion may be difficult to be obtained.
  • the kinematic viscosity of the silicone oil (b) is preferably in the range of 10 to 200 cSt, more preferably 30 to 90 cSt. If the viscosity is too low, the viscosity of the target siloxane compound of the present invention will be low, which may not be suitable as an optical semiconductor sealing agent, and if it is too high, the viscosity of the block type siloxane compound (A) will increase. There is a tendency for the workability to be adversely affected.
  • silicone-terminated dimethyl silicone oil in which R 3 of the silicone oil (b) is a methyl group include the following product names.
  • products of Toray Dow Corning Silicone Co., Ltd. PRX413, BY16-873, as products of Shin-Etsu Chemical Co., Ltd., X-21-5841, KF-9701, as products of Momentive Co., Ltd., XC96-723 , TSR160, YR3370, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XF3905, products of Gelest Co., Ltd.
  • silicone-terminated methylphenyl silicone oil in which R 3 of the silicone oil (b) is a methyl group and a phenyl group include the following product names.
  • a product of Momentive Co., Ltd., YF3804, and as a product of Gelest Co., Ltd. there are PDS-0332, PDS-1615, and the like.
  • R 3 of the silicone oil (b) is a phenyl group, as the silicone-terminal diphenyl silicone oil, can be mentioned as specific examples of the PDS-9931 is preferably the product name, for example, Gelest Corporation.
  • X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight in order to give the silicone segment flexibility characteristics.
  • These silicone oils (b) may be used alone or in combination of two or more.
  • the alkoxysilane compound (c) has a structure of the following formula (3).
  • R 4 in the general formula (3) represents a methyl group or a phenyl group.
  • R 2 in the general formula (3) has the general formula (10) or may be the same or different as R 2 (1), each independently, represent an alkyl group having 1 to 10 carbon atoms, straight It may be any of a chain, a branch, or a ring. Specifically, including a preferable group and a more preferable group, it is the same as illustrated in the description of R 2 in the general formula (10) or (1).
  • preferable alkoxysilane compound (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Among the above, methyltrimethoxysilane or phenyltrimethoxysilane is preferable.
  • the alkoxysilane compound (c) adjusts the molecular weight of the block type siloxane compound (A), the compatibility with the composition, the heat resistance of the cured product, the light resistance, the low moisture permeability, the low gas permeability, and the like. Therefore, it can be used in combination with the alkoxysilane compound (a-1), preferably (a).
  • the amount of the alkoxysilane compound (c) used is 0 to 70 mol%, preferably 0 to 70 mol%, based on the total of the alkoxysilane compounds ((a-1), preferably the total of (a) and (c)). It is 55 mol%, more preferably 0 to 40 mol%.
  • the alkoxysilane compound (c) is preferably used in the range of 5 to 70 mol% with respect to the total of alkoxysilane compounds. % Is more preferable, and 10 to 40 mol% is particularly preferable.
  • the siloxane compound of the present invention is an alkoxysilane compound (a-1) (hereinafter also referred to as alkoxysilane (a-1)), preferably an alkoxysilane compound (a) (hereinafter also referred to as alkoxysilane (a)). )
  • the silicone oil (b) can be produced as raw materials, and the alkoxysilane compound (c) can be used together as a raw material if necessary.
  • any method can be adopted as long as the siloxane compound of the present invention having the two segments can be produced.
  • the most suitable method is that the silanol-terminated silicone oil (b), the alkoxysilane (a-1), preferably (a), and, if necessary, the alkoxysilane (c) as With respect to 1 equivalent of the silanol group of the silicone oil (b), the reaction is conducted in the range of 1.5 to 200 equivalents of the alkoxy group equivalent of the alkoxysilane compound, followed by condensation. In this method, water is added to the resulting reaction solution to hydrolyze and condense the remaining alkoxy groups (one-pot method).
  • the first stage reaction is preferably carried out in the absence of water in the presence of an acid or base catalyst, preferably a base catalyst.
  • the alkoxysilane compound and the silicone oil (a) in the reaction of the alkoxysilane (a-1) in the first stage reaction preferably (a) (along with alkoxysilane (c) if necessary) and the silicone oil (b)
  • the proportion of b) is usually within alkoxysilane (a-1), preferably (a) (along with alkoxysilane (c) if necessary) with respect to 1 equivalent of silanol group of silicone oil (b).
  • alkoxysilane (c) when alkoxysilane (c) is used in combination, alkoxysilane (a-1), preferably the total alkoxy equivalent of (a) and alkoxysilane (c)), 1.5 to 200 equivalents,
  • the amount is preferably 2 to 200 equivalents, more preferably 2 to 150 equivalents, still more preferably 2 to 100 equivalents.
  • the ratio may be 3 to 100 equivalents, preferably 4 to 100 equivalents, with respect to 1 equivalent of silanol groups of the silicone oil (b), as an alkoxy equivalent of the above alkoxysilane compound. More preferably, it may be 5 to 100 equivalents.
  • Patent Document 1 (WO2005 / 100445) does not use a silanol-terminated silicone oil (b), and hydrolyzes a silane compound having an epoxy group and a silane compound having no epoxy group at a time in the presence of water. It is what is condensed.
  • silicone oil (b) is used as a raw material in addition to alkoxysilane (a-1), preferably (a) (optionally alkoxysilane (c)) as in the present invention
  • those When the raw materials are reacted together in the presence of a catalyst and water, hydrolysis / condensation reaction between the alkoxy groups of the alkoxysilane (a-1), preferably (a) (optionally alkoxysilane (c)) is performed. Since the process proceeds with priority, in some cases, the formed silsesquioxane compound and the unreacted silicone oil (b) remain, and they are not compatible with each other.
  • Such cloudy polyorganosiloxane is not suitable for optical applications.
  • the manufacturing method of the reactive functional group containing siloxane compound of this invention including said optimal method passes through the manufacturing process shown by the following (i) and (ii).
  • the silanol-terminated silicone oil (b) and the alkoxysilane compound are reacted with each other by a method such as dropwise addition of water, and the reaction in the production steps (i) and (ii) described above is performed. You may carry out in one process. Furthermore, when using silsesquioxane having two or more alkoxy substitutions synthesized separately instead of the alkoxysilane in (i), the siloxane compound of the present invention can be obtained only in the production step (i). it can.
  • ⁇ Manufacturing method (I)> As a production step (i), by a dealcoholization condensation reaction between a silicone oil having a silanol group at the terminal (b) and an alkoxysilane (a) (alkoxysilane (c) may be used in combination as necessary), A step of obtaining a modified alkoxysilane (d) is performed by changing the terminal of the silicone oil to alkoxysilane.
  • the alkoxysilane-modified product of the silicone oil obtained in the production step (i) (d) in the presence of alkoxysilane (a) (along with alkoxysilane (c) if necessary) (d) In the presence of water between the alkoxy groups of the modified alkoxysilane (d) and the alkoxysilane compound, in the presence of water.
  • a linear silicone segment ⁇ usually represented by-(OSi (R 3 ) 2 ) m- (R 3 represents the same meaning as in formula (2)) ⁇ and an alkoxysilane hydrolytic condensation segment
  • a method for producing a block-type siloxane compound of the present invention preferably having a silsesquioxane segment.
  • ⁇ Manufacturing method (b)> First, a hydrolysis condensation reaction between alkoxy groups in the presence of water of alkoxysilane (a) (along with alkoxysilane (c) if necessary) is carried out to hydrolyze alkoxysilane having an alkoxy group in the molecule.
  • a step of obtaining a decomposition condensate, preferably silsesquioxane (e) is performed.
  • the hydrolyzed condensate of alkoxysilane synthesized above, preferably silsesquioxane (e) is isolated and preferably in the absence of water, a silicone oil having a silanol group at the terminal.
  • a method for producing the siloxane compound of the present invention by subjecting (b) to a hydrolytic condensate of the alkoxysilane obtained above, preferably a silsesquioxane (e), to carry out a dealcohol condensation reaction.
  • a dealcoholization condensation reaction between a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) (along with an alkoxysilane (c) if necessary) is preferably water.
  • an alkoxysilane (a) (along with an alkoxysilane (c) if necessary) is preferably water.
  • the alkoxysilane-modified product (d) is formed.
  • the remaining alkoxysilane ( a) When alkoxysilane (c) is used in combination as necessary, the remaining alkoxysilanes (a) and (c)) and the hydrolytic condensation reaction between the alkoxy groups of the modified alkoxysilane (d) are performed.
  • a one-pot method for producing the siloxane compound of the present invention is performed.
  • the production method (c) in which the second-stage reaction is directly performed without isolating the first-stage reactant and the reaction is sequentially performed in one pot.
  • the production method (c) (the aforementioned most preferred production method) will be described more specifically.
  • the production process (i) in the one-pot is the first stage reaction and the production process (ii) is the second stage reaction
  • the dealcohol condensation of silane (a) (alkoxysilane (c) if necessary) is performed, and the hydrogen atom of the terminal silanol group of silicone oil (b) is modified to alkoxysilyl to obtain a modified alkoxysilane (d).
  • the alkoxysilane-modified product (d) is considered to exist in the structure represented by the following formula (4). After the formation of such a modified product (d), hydrolysis of the next alkoxy groups is performed. It may be preferable to perform the condensation. Therefore, an embodiment in which the reaction is carried out using 3 to 200 equivalents of alkoxy groups per 1 equivalent of silanol groups of silicone oil (b) is one of the preferred embodiments.
  • R 2 , R 3 , and m have the same meaning as described above, and R 6 may be the same or different, and each independently represents X and / or R 4 .
  • the process cannot proceed to the second stage reaction.
  • the alkoxy group is reacted in an amount of 1.0 to 1.5 equivalents, two or more alkoxy groups in the alkoxysilane (a) (optionally alkoxysilane (c)) are converted into silanol of the silicone oil (b). It will react with the group, and at the end of the first stage reaction, it becomes a polymer and gelation occurs.
  • the alkoxy group is 3 equivalents or more, preferably 4 equivalents or more, more preferably 5 equivalents or more, per 1 equivalent of silanol group. It is preferable to use it.
  • the silsesquioxane segment in the present invention may be a general ladder type, a partially ring-opened structure of a saddle type, or a structure called a random type, and usually a mixture thereof. Conceivable.
  • the second stage reaction (production process (ii)) in which water is added to the reaction solution as it is to carry out hydrolysis condensation between alkoxy groups is performed.
  • the amount of water added is about 0.5 to 100 equivalents with respect to 1 equivalent of the alkoxy group of the alkoxysilane compound used as the raw material.
  • water is used in an amount of about 1 to 10 times, preferably about 1 to 5 times the theoretical amount of water required for the hydrolytic condensation of the remaining alkoxy group after completion of the first stage reaction.
  • the following reactions (I) to (III) are considered to occur.
  • the block-type siloxane compound of the present invention produced through the above first-stage reaction and second-stage reaction is excellent in transparency, and the cured product obtained from the resin composition using the block-type siloxane compound has transparency and low elastic modulus. Excellent in properties.
  • the production of the block type siloxane compound having a reactive functional group of the present invention can be carried out without a catalyst. However, when no catalyst is used, the progress of the reaction is slow.
  • the catalyst that can be used any compound that exhibits acidity or basicity can be used.
  • the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid.
  • Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.
  • Inorganic bases such as alkali metal carbonates and ammonia
  • organic bases such as triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide
  • an inorganic base is particularly preferable in terms of easy removal of the catalyst from the product, and sodium hydroxide and potassium hydroxide are particularly preferable.
  • the addition amount of the catalyst is usually 0.001 to 7.5% by weight, preferably based on the total weight of the alkoxysilane (a) in the reaction system (the alkoxysilane (c) may be used in combination if necessary) Is 0.01 to 5% by weight.
  • the amount added may be about 0.01 to 1% by weight.
  • a method for adding the catalyst it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol.
  • alcohols such as methanol, ethanol, propanol and butanol.
  • the reactive functional group-containing siloxane compound of the present invention can be produced without a solvent or in a solvent. Moreover, a solvent can also be added in the middle of a manufacturing process. As a solvent, the solvent which melt
  • solvents examples include aprotic polar solvents such as dimethylformamide, dimethylacetamide, and tetrahydrofuran, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and butanoic acid.
  • aprotic polar solvents such as dimethylformamide, dimethylacetamide, and tetrahydrofuran
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, ethyl acetate, butyl acetate, ethyl lactate, and butanoic acid.
  • esters such as isopropyl, alcohols such as methanol, ethanol, propanol and butanol, hydrocarbons such as hexane, cyclohexane, tolu
  • the reaction in alcohols is preferable from the viewpoint of reaction control, and methanol or / and ethanol are more preferable.
  • the amount of the solvent used is not particularly limited as long as the reaction proceeds smoothly, and alkoxysilane (a) (alkoxysilane (c) may be used in combination as necessary) and silicone oil (b), Usually, about 0 to 900 parts by weight is used with respect to 100 parts by weight.
  • the reaction temperature is usually 20 to 160 ° C., preferably 40 to 140 ° C., particularly preferably 50 to 150 ° C., depending on the amount of catalyst.
  • the reaction time is usually 1 to 40 hours, preferably 5 to 30 hours, in each production step.
  • the catalyst is removed by neutralization and / or washing with water as necessary.
  • a solvent that can be separated from water.
  • Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.
  • the catalyst may be removed only by washing with water, but since the reaction is carried out under acidic or basic conditions, either neutralization is followed by washing with water, or the catalyst is removed using an adsorbent. It is preferable to remove the adsorbent by filtration after adsorption.
  • an adsorbent add the adsorbent to the reaction solution, stir, heat, etc., adsorb the catalyst, filter the adsorbent, and wash the residue with water to remove the catalyst and adsorbent. be able to.
  • a compound showing acidity or basicity can be used for neutralization.
  • Examples of the compound exhibiting acidity include inorganic acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sodium dihydrogen phosphate, and organic acids such as formic acid, acetic acid, and oxalic acid.
  • inorganic acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sodium dihydrogen phosphate
  • organic acids such as formic acid, acetic acid, and oxalic acid.
  • Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide; sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate Such as alkali metal carbonates; basic phosphates such as disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid, sodium tripolyphosphate; inorganic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylamino Organic bases such as ethanol, triethanolamine, tetramethylammonium hydroxide can be used.
  • alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide
  • alkali metal carbonates such as alkali metal carbonates
  • basic phosphates such as disodium hydrogen phosphate, trisodium phosphate, polyphosphoric acid,
  • an inorganic base or an inorganic acid compound is preferable in that it can be easily removed from the target product, and more preferably, sodium dihydrogen phosphate or the above base, which is easier to adjust the pH to near neutrality.
  • Phosphates such as soluble phosphates.
  • Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
  • activated clay for example, products of Toshin Kasei Co., Ltd .: activated clay (SA35, SA1, T, R-15, or E), or nikkanite (G-36, G-153, or G-168), Products of Mizusawa Chemical Co., Ltd .: Galeon Earth, or Mizuka Ace RTM (superscript RTM represents a registered trademark; the same applies hereinafter).
  • the activated carbon for example, products of Ajinomoto Fine Techno Co., Ltd .: CL-H, Y-10S or Y-10SF, products of Phutamura Chemical Co., Ltd .: S, Y, FC, DP, SA1000, K, A, KA, M , CW130BR, CW130AR, or GM130A.
  • the zeolite include Union Showa Co., Ltd. products: Molecular Sieve 3A, 4A, 5A, or 13X.
  • Synthetic adsorbents include, for example, products of Kyowa Chemical Co., Ltd .: Kyoward RTM 100, 200, 300, 400, 500, 600, 700, 1000, 2000, and products of Rohm and Haas Co., Ltd .: Amberlyst RTM 15JWET, 15DRY, 16WET, 31WET, A21, Amberlite RTM IRA400JCl, IRA403BLCl, IRA404JCl, and products of Dow Chemical Co., Ltd .: Dowex RTM 66, HCR-S, HCR-W2 or MAC-3.
  • the soot reaction or after neutralization After completion of the soot reaction or after neutralization, it can be purified by conventional separation and purification means other than water washing and filtration.
  • the purification means include column chromatography, vacuum concentration, distillation, extraction and the like. These purification means may be performed singly or in combination.
  • the reactive functional group-containing siloxane compound of the present invention can be obtained by removing the solvent used above by vacuum concentration or the like.
  • the appearance of the siloxane compound of the present invention is usually colorless and transparent and is a liquid having fluidity at 25 ° C.
  • the siloxane compound of the present invention obtained by the above reaction is a linear silicone segment as described above, preferably-(Si (R 3 ) 2 O) m- (R 3 and m have the same meaning as in the above formula (2).
  • Reactive functional group-containing block-type siloxane characterized in that at least one part of the silsesquioxane segment has a reactive functional group having at least one epoxy group A compound.
  • the number of reactive functional groups having an epoxy group represented by X derived from the alkoxysilane (a) is on average with respect to one silicon atom in the silsesquioxane segment.
  • a ratio of 0.3 to 1 is preferable, a ratio of 0.45 to 1 is more preferable, and a ratio of 0.6 to 1 is particularly preferable.
  • the group represented by R 4 derived from the alkoxysilane (c) preferably has an average ratio of 0 to 0.7 with respect to one silicon atom in the silsesquioxane segment, A ratio of 0 to 0.55 is more preferable, and a ratio of 0 to 0.4 is particularly preferable.
  • the preferred molecular weight of the siloxane compound of the present invention is about 500 to 20,000, more preferably about 800 to 20,000, still more preferably about 1,000 to 10,000, particularly as the weight average molecular weight measured by GPC. Preferably, it is about 1,500 to 6,000. If the weight average molecular weight is too low, the heat resistance may be lowered. If it is too high, the viscosity will increase and the workability will be adversely affected.
  • the weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured under the following conditions using GPC (gel permeation chromatography).
  • the epoxy equivalent (measured by the method described in JIS K-7236) of the siloxane compound of the present invention is preferably from 300 to 1,600 g / eq, more preferably from 400 to 1,000 g / eq, particularly from 450 to 900 g. / Eq is preferred. If the epoxy equivalent is too small, the cured product will be too hard and the low elastic modulus may be inferior. If it is too large, the mechanical properties of the cured product will deteriorate.
  • the viscosity of the siloxane compound of the present invention is usually about 50 to 20,000 mPa ⁇ s, preferably about 150 to 10,000 mPa ⁇ s, preferably 200 to 10,000 mPa ⁇ s. More preferable is about s, and most preferable is about 200 to 5000 mPa ⁇ s. Further, in some cases, those of 500 to 10,000 mPa ⁇ s are more preferred, and those of 800 to 5,000 mPa ⁇ s are particularly preferred.
  • the ratio of silicon atoms bonded to three oxygens belonging to the hydrolysis-condensation segment, preferably the silsesquioxane segment, of alkoxysilane is about 5 to 95 mol%. However, it is preferably 5 to 50 mol%, more preferably 8 to 30 mol%, and particularly preferably 10 to 25 mol% for sealing an optical semiconductor element.
  • the balance is the proportion of silicon atoms belonging to the chain silicone segment.
  • total silicon atoms means all silicon atoms in the siloxane compound of the present invention.
  • the ratio of the silicon atoms belonging to the silsesquioxane segment to the total silicon atoms in the three oxygen bonds is less than 5 mol%, the characteristics of the chain silicone segment are strongly enhanced, and as a result, the curable resin composition described later When used as a component, the cured product of the resin composition tends to be too soft, and there is a concern of surface tack and scratches. Moreover, when it exceeds 50 mol%, as a result of the strong characteristics of the silsesquioxane segment, when used as a component of a curable resin composition to be described later, the cured product of the resin composition becomes too hard and the low elastic modulus characteristics deteriorate. However, the result of the heat cycle test tends to deteriorate.
  • the siloxane compound of the present invention has a linear silicone segment and a hydrolysis-condensation segment (preferably a silsesquioxane segment) of the alkoxysilane, and the latter segment has a reactive functional group having an epoxy group.
  • the siloxane compound of the present invention in which the proportion of the chain silicone segment is increased is also a great feature in that it is suitable for optical semiconductor encapsulation.
  • the ratio of silicon atoms belonging to the hydrolysis-condensation segment (preferably silsesquioxane segment) of the alkoxysilane to the total silicon atoms in the siloxane compound of the present invention is 5 to 50 mol%
  • the proportion of silicon atoms belonging to the chain silicone segment is 50 to 95 mol%.
  • the preferred proportion of silicon atoms belonging to the chain silicone segment is 70 to 92 mol%, more preferably 75 to 90 mol%.
  • the proportion of silicon atoms in the two segments in the siloxane compound of the present invention may be calculated from the raw material charge ratio, or determined by 1 H NMR, 29 Si NMR, elemental analysis, etc. of the obtained siloxane compound of the present invention. You can also.
  • siloxane compounds of the present invention are summarized as follows.
  • the chain silicone segment is represented by the following formula (2A) -(Si (R 3 ) 2 O) m- (2A) (Wherein R 3 may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 carbon atoms) Represents an alkenyl group of ⁇ 10, and m represents an average value of 2 to 2,000)
  • the reactive functional group containing siloxane compound as described in said (i) which is a segment represented by these.
  • a tri (C1-C10) alkoxysilane having a reactive functional group having an epoxy group a group selected from the group consisting of a methyl group and a phenyl group is substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group
  • Tri (C1-C10) alkoxysilane having an alkyl group having 1 to 3 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an epoxy group is ⁇ - (3,4 epoxy cyclohexyl) ethyl
  • (Viii) a tri (C1-C10) alkoxysilane having a reactive functional group having an epoxy group, a group selected from the group consisting of a methyl group and a phenyl group, The reactivity according to any one of (i) to (vii) above, which is both C10) alkoxysilane and tri (C1-C10) alkoxysilane having a group selected from the group consisting of a methyl group and a phenyl group.
  • Functional group-containing siloxane compound is any one of (i) to (vii) above, which is both C10) alkoxysilane and tri (C1-C10) alkoxysilane having a group selected from the group consisting of a methyl group and a phenyl group.
  • (Ix) Reactive functional group-containing siloxane according to (viii) above, wherein the tri (C1-C10) alkoxysilane having a group selected from the group consisting of a methyl group and a phenyl group is phenyltrimethoxysilane or methyltrimethoxysilane Compound.
  • (X) The reactive functional group-containing siloxane compound according to any one of (i) to (ix) above, wherein the weight average molecular weight measured by GPC is 500 to 20,000.
  • X represents a reactive functional group having an epoxy group
  • R 2 represents an alkyl group having 1 to 10 carbon atoms.
  • a silanol-terminated silicone oil (b) represented by: General formula (1) XSi (OR 2 ) 3 (1)
  • X represents a reactive functional group having an epoxy group
  • R 2 represents an alkyl group having 1 to 10 carbon atoms.
  • silanol-terminated silicone oil (b) represented by the general formula (2) measured by GPC (gel permeation chromatography) has a weight average molecular weight of 300 to 30,000.
  • (Xiii) The above (xi) or (xi) wherein the alkoxy group equivalent of the alkoxysilane compound (a) represented by the general formula (1) is 2 to 100 equivalents relative to 1 equivalent of the silanol group of the silanol-terminated silicone oil (b) A reactive functional group-containing siloxane compound as described in xii).
  • the silanol-terminated silicone oil (b) represented by the general formula (2) is a silanol-terminated dimethylsilicone oil or a silanol-terminated methylphenylsilicone oil according to any one of (xi) to (xiii) Reactive functional group-containing siloxane compound.
  • the alkoxysilane compound (a) represented by the general formula (1) is ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ Any one of (xi) to (xiv) which is glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane or ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane
  • the reactive functional group-containing siloxane compound according to one item.
  • a plurality of R 3 may be the same as or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or A silanol-terminated silicone oil (b) represented by an alkenyl group having 2 to 10 carbon atoms, and m is an average value of 2 to 200, and a compound represented by the general formula (1) XSi (OR 2 ) 3 (1) (Wherein X represents a reactive functional group having an epoxy group, and R 2 represents an alkyl group having 1 to 10 carbon atoms) and the general formula (3) R 4 Si (OR 2 ) 3 (3) (Wherein, R 4 is a methyl group or a phenyl group, R 2 is Formula (may be the same or different as R 2 in 1) each independently represent an alkyl group having 1 to 10 carbon atoms .) Both of the alkoxysilane compounds (c) represented by formula (1) are the total equivalents of the alkoxysi
  • the above (i) obtained by reacting in the range of 5 to 200 equivalents and condensing, then adding water to the resulting reaction solution to hydrolyze and condense the remaining alkoxy groups as the second stage reaction.
  • (Xvii) The reactive functional group-containing siloxane compound according to (xvi), wherein the silanol-terminated silicone oil (b) represented by the general formula (2) is the silicone oil according to (xii) or (xiv) .
  • the reactive functional group-containing siloxane compound according to (xvi) or (xvii), wherein the alkoxysilane compound (a) represented by the general formula (1) is the compound described in (xv) above.
  • the siloxane compound of the present invention can be used as a component of a curable resin composition.
  • the siloxane compound of the present invention is referred to as “siloxane compound (A) of the present invention” or simply “siloxane compound (A)” in the description of the curable resin composition.
  • the siloxane compound (A) may be any reactive functional group-containing siloxane compound described in any one of (i) to (xix) above, and includes all combinations with the siloxane compound.
  • the curable resin composition of the present invention contains the siloxane compound (A) of the present invention as an epoxy resin component, and further contains a curing agent (B).
  • the other epoxy resin is a property of the siloxane compound (A) of the present invention, for example, a property as a cured product when used in a curable resin composition, specifically, transparency, heat resistance / light resistance, low temperature. It can be used in combination as long as the low elastic modulus characteristics, non-tack property, heat cycle resistance, hardness and the like are not lost. In some cases, the other epoxy resin improves the physical properties of the cured product of the curable resin composition.
  • the ratio of the siloxane compound (A) of the present invention to the entire epoxy resin component is 20 to 100% by weight, preferably 30 to 100% by weight, more preferably 50 to 100% by weight. It may be 100% by weight, or 70 to 100% by weight, and further 80 to 100% by weight.
  • the proportion of the siloxane compound of the present invention in the total epoxy resin including the siloxane compound (A) of the present invention and other epoxy resins is preferably 20 to 90% by weight, particularly 30 to 90% by weight. % Is preferred.
  • the ratio of the total epoxy resin obtained by combining the siloxane compound (A) of the present invention alone or the siloxane compound (A) of the present invention and another epoxy resin is the composition.
  • epoxy resins include polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds, polyfunctional epoxy resins that are glycidyl etherified products of various novolak resins, nuclear hydrides of aromatic epoxy resins, and alicyclic epoxies.
  • Examples thereof include resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and glycidylated silicone resins.
  • Polyphenol compounds used in the above polyfunctional epoxy resins include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, and tetramethyl.
  • Bisphenol S dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4 -Hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), Trishydroxyphenyl Tan, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having fluorene skeleton such as 1,1-di-4-hydroxyphenyl fluorene, may be mentioned a polyphenol compound of phenolic polybutadiene or the like.
  • various novolak resins used in the polyfunctional epoxy resin include novolac resins using various phenols as raw materials.
  • Examples of the various raw phenols include phenol, cresols, ethylphenols, butylphenols, Novolak resin, xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, fluorene skeleton
  • Various novolak resins such as a phenol novolak resin can be given.
  • specific examples of the polyfunctional epoxy resin that is a glycidyl etherified product of various novolak resins include glycidyl etherified products of these novolak resins.
  • nuclear hydride of the aromatic epoxy resin examples include a hydride of a glycidyl etherified product of a novolak resin using the above-mentioned novolac resin as a raw material, specifically, various phenols such as bisphenol A and bisphenol.
  • Raw materials such as F, bisphenol S, glycidyl etherified products of phenol compounds such as 4,4'-biphenol, or phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.
  • a nuclear hydride of a glycidyl etherified product of a novolak resin examples include a hydride of a glycidyl etherified product of a novolak resin using the above-mentioned novolac resin as a raw material, specifically, various phenols such as bisphenol A and bisphenol.
  • Raw materials such as F, bisphenol
  • alicyclic epoxy resins examples include 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2- (3 , 4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, and the like, an alicyclic ring having an aliphatic skeleton such as cyclohexane An epoxy resin can be mentioned.
  • Aliphatic epoxy resins include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, xylylene glycol derivatives and the like. Examples thereof include glycidyl ethers.
  • the heterocyclic epoxy resin include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.
  • Examples of the glycidyl ester-based epoxy resin include epoxy resins composed of glycidyl esters of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
  • Examples of the glycidylamine-based epoxy resins include epoxy resins obtained by glycidylation of amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivatives, and diaminomethylbenzene derivatives.
  • Halogenated phenols such as brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A are used as epoxy resins obtained by glycidylation of halogenated phenols. Examples thereof include epoxy resins obtained by glycidylation of phenols.
  • epoxy resins there are no particular restrictions on the use of these epoxy resins, but those with less colorability are more preferred from the viewpoint of transparency.
  • Polyfunctional epoxy resins that are glycidylated phenols having a fluorene skeleton such as: Novolak resins made from various phenols such as phenol, cresols, bisphenol A, bisphenol S, naphthols, and phenol novolacs containing dicyclopenta
  • an alicyclic epoxy having a cyclohexane skeleton Resins are particularly preferred. These epoxy resins can be used in combination as one kind or a mixture of two or more kinds as required, such as imparting heat resistance.
  • curing agent (B) and the curing accelerator (C) used in the present invention Details of the curing agent (B) and the curing accelerator (C) used in the present invention will be described.
  • the curing agent (B) amine compounds, acid anhydride compounds, carboxylic acid compounds, amide compounds, phenol compounds, and the like can be used without particular limitation.
  • an acid anhydride compound and a carboxylic acid compound are particularly preferable from the viewpoint of an appropriate pot life when mixed with an epoxy resin to obtain a resin composition, and transparency of a cured product, and hexahydrophthalic acid.
  • Particularly preferred are anhydride, methylhexahydrophthalic anhydride, 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride, hydrogenated nadic acid anhydride, and hydrogenated methyl nadic acid anhydride.
  • the amount of the curing agent (B) used is preferably about 0.2 to 1.5 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins combined with the siloxane compound (A) or other epoxy resin in the composition, About 0.3 to 1.2 equivalents are particularly preferred.
  • the curing agent (B) when a tertiary amine such as benzyldimethylamine is used as the curing agent (B), the curing agent is used in an amount of 0.3 to 20% by weight based on the epoxy group-containing compound in the composition. It is preferably 0.5 to 10% by weight.
  • curing accelerator (C) examples include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole.
  • curing accelerators may be microencapsulated. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions.
  • the curing accelerator is usually 0.001 to 15 parts by weight, preferably 0.005 to 5 parts by weight based on 100 parts by weight of the block type siloxane compound (A) having a reactive functional group or other epoxy resin. And more preferably 0.05 to 1 part by weight.
  • an inorganic filler In the curable resin composition of the present invention, an inorganic filler, a colorant, a silicone resin, a leveling agent, a lubricant, a coupling agent, a leveling agent, a lubricant, a light stabilizer, depending on the purpose, as long as transparency is not impaired. Antioxidants, phosphors and the like can be added as appropriate.
  • the inorganic filler is not particularly limited, and examples thereof include crystalline or amorphous silica, talc, silicon nitride, boron nitride, alumina, silica / titania mixed melt, and the like.
  • the colorant there is no particular limitation on the colorant, and phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine-based various organic dyes, titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium Inorganic pigments such as vermilion, valve shell, cobalt violet, bitumen, ultramarine, carbon black, chrome green, chromium oxide, cobalt green and the like can be mentioned.
  • the silicone resin include dimethyl silicone, phenylmethyl silicone, epoxy-modified silicone, polyether-modified silicone, amine-modified silicone, vinyl-modified silicone, and silyl-modified silicone.
  • Leveling agents include oligomers composed of acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil, titanium-based cup A ring agent etc. are mentioned.
  • Lubricants such as paraffin wax, microwax, polyethylene wax, etc .; higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid; stearylamide, palmitylamide, oleyl Higher fatty acid amide type lubricants such as amide, methylene bisstearamide, ethylene bisstearamide; hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or tetra-) Higher fatty acid ester lubricants such as stearate; Alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol; lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, Phosphate, ricinoleic acid, magnesium such as naphthenic acid
  • HALS hindered amine light stabilizer
  • HALS is not particularly limited, but typical examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ], bis (1,2,2, 6,6-pentamethyl-4-
  • antioxidants examples include phenol-based, sulfur-based, and phosphorus-based antioxidants.
  • phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-but
  • sulfur antioxidant examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyll-3,3′-thiodipropionate, and the like. .
  • phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2 , 4-di-tert-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- ⁇ 2- (octa
  • antioxidants can be used alone, but two or more of them may be used in combination.
  • a phosphorus-based antioxidant is particularly preferable.
  • the amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component in the curable resin composition of the present invention. It is.
  • a fluorescent substance can be added as needed.
  • the phosphor has, for example, a function of forming white light by absorbing a part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed.
  • fluorescent substance A conventionally well-known fluorescent substance can be used, For example, the rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated.
  • phosphors such as YAG phosphors, TAG phosphors, orthosilicate phosphors, thiogallate phosphors, sulfide phosphors, and the like can be mentioned.
  • YAlO 3 Ce, Y 3 Al 5 O 12 : Ce, Y 4 Al 2 O 9 : Ce, Y 2 O 2 S: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, (SrEu) O.Al 2 O 3 and the like are exemplified.
  • the particle diameter of the phosphor those known in this field are used, and the average particle diameter is preferably 1 to 250 ⁇ m, particularly preferably 2 to 50 ⁇ m. When these phosphors are used, the addition amount thereof is 1 to 80 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of the resin component.
  • Preferred curable resin compositions of the present invention are as follows.
  • the total amount of the epoxy compound other than the siloxane compound (A) (hereinafter also referred to as O-EPO) may be 30 to 90% by weight (hereinafter, unless otherwise specified) %), And the balance is a curing agent (B).
  • the curable resin composition of the present invention includes a siloxane compound (A) having a reactive functional group, a curing agent (B), and a curing accelerator (C) as necessary, and the curable resin.
  • the composition may further contain other optional ingredients.
  • other optional components include inorganic fillers, colorants, silicone resins, leveling agents, lubricants, coupling agents, light stabilizers, antioxidants, and phosphors.
  • These other compounding components can be appropriately added in the range of 0 to 500 parts by weight, preferably about 0 to 100 parts by weight, with respect to 100 parts by weight of the total amount of the siloxane compound (A) and the curing agent (B). is there.
  • these other ingredients are mixed, if they are solid, they are mixed using a blender such as a Henschel mixer or Nauter mixer, then kneaded at 80-120 ° C using a kneader, extruder, or heated roll and cooled. Thereafter, it can be pulverized to obtain a powder.
  • a blender such as a Henschel mixer or Nauter mixer
  • the blended material is liquid, it can be uniformly dispersed using a planetary mixer or the like to obtain the curable resin composition of the present invention containing these other blended components.
  • an optical semiconductor of the present invention by sealing an optical semiconductor such as an LED, a photosensor or a transceiver using the composition of the present invention thus obtained, a transfer mold, a compression mold, an injection mold, a dispensing method, printing What is necessary is just to shape
  • the heating method for curing the resin composition for sealing an optical semiconductor after molding is not particularly limited, and conventionally known methods such as hot air circulation heating, infrared heating, and high frequency heating can be employed. .
  • the curing conditions are usually performed by heating at about 80 to 250 ° C. for 30 seconds to 15 hours, but the conditions may be changed as appropriate. Preferable conditions are 110 to 200 ° C., for example, a method of first curing at 100 to 140 ° C. and then final curing at 130 to 200 ° C. is preferable.
  • the present invention will be described in more detail with reference to synthesis examples and examples.
  • “part” means part by weight
  • “%” means% by weight.
  • the unit whose unit is not described is a unit of g / eq.
  • Example 1 (Example in which an alkoxy group is reacted at 5.3 equivalents with respect to 1 equivalent of silanol groups)
  • First stage reaction Silanol-terminated dimethylsilicone oil having 197.1 parts of ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1 g / eq) and weight average molecular weight 1060 (measured by GPC) 237. 4 parts (silanol equivalent 530 g / eq), 21.3 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.11 part as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. It was.
  • KOH potassium hydroxide
  • silanol equivalent of 530 g / eq was calculated as half of the weight average molecular weight of 1060 measured using GPC, assuming that the molecular weight of the silicone oil is two silanol groups per molecule. Also in the following examples, the silanol equivalent of the silanol-terminated silicone oil (b) was determined in the same manner.
  • Second stage reaction 305 parts of methanol was added to the reaction solution obtained above, 86.4 parts of 50% distilled water in methanol was added dropwise over 60 minutes, and then reacted at 75 ° C. under reflux for 8 hours. It was.
  • reaction solution was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C.
  • MIBK methyl isobutyl ketone
  • washing with water was repeated three times.
  • solvent was removed therefrom at 100 ° C. under reduced pressure to obtain 344 parts of a block type siloxane compound (A-1) having a reactive functional group.
  • the epoxy equivalent of the obtained compound was 457 g / eq, the weight average molecular weight was 3,700, the viscosity was 600 mPa ⁇ s, and the appearance was colorless and transparent.
  • the ratio of silicon atoms belonging to the silsesquioxane segment was 19.6 mol%.
  • the ratio of silicon atoms belonging to the chain silicone segment was 80.4 mol%.
  • Example 2 (Example in which an alkoxy group is reacted at a rate of 30.8 equivalents with respect to 1 equivalent of a silanol group)
  • First stage reaction 237.4 parts of silanol-terminated dimethylsilicone oil having 197.1 parts of ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average molecular weight of 6120 (measured by GPC) (Silanol equivalent 3060), 20.0 parts of a 0.5% KOH methanol solution (0.1 parts as the number of KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C.
  • silanol-terminated dimethylsilicone oil having 197.1 parts of ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average molecular weight of 6120 (measured by GPC) (S
  • the epoxy equivalent of the obtained compound was 468 g / eq, the weight average molecular weight was 4160, the viscosity was 481 mPa ⁇ s, and the appearance was colorless and transparent. Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 19.6 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 80.4 mol%.
  • Example 3 (Example in which an alkoxy group is reacted at a rate of 80.1 equivalents per 1 equivalent of a silanol group)
  • First stage reaction 118.7 parts of silanol-terminated dimethyl silicone oil having 98.6 parts of ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average molecular weight of 15800 (measured by GPC).
  • Silanol equivalent 7900 and 10.0 parts of a 0.5% KOH methanol solution (0.05 parts as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C.
  • Second stage reaction After 142 parts of methanol was added, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. under reflux for 8 hours. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 191 parts of MIBK was added, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 169 parts of a block type siloxane compound (A-3) having a reactive functional group.
  • A-3 block type siloxane compound having a reactive functional group.
  • the epoxy equivalent of the obtained compound was 447 g / eq, the weight average molecular weight was 4130, the viscosity was 710 mPa ⁇ s, and the appearance was colorless and transparent. Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 19.6 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 80.4 mol%.
  • Example 4 (Example in which an alkoxy group is reacted at a ratio of 8.6 equivalents to 1 equivalent of a silanol group)
  • First stage reaction ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane 49.3 parts (alkoxy group equivalent 82.1), phenyltrimethoxysilane 39.7 parts (alkoxy group equivalent 66.1), weight
  • a reaction vessel was charged with 118.7 parts of silanol-terminated methylphenyl silicone oil having an average molecular weight of 1700 (GPC measured value) (silanol equivalent: 850) and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts).
  • the liquid temperature was raised to 75 ° C.
  • Second stage reaction After adding 123 parts of methanol, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. under reflux for 8 hours. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 191 parts of MIBK was added, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 168 parts of a block type siloxane compound (A-4) having a reactive functional group.
  • A-4 block type siloxane compound having a reactive functional group.
  • the epoxy equivalent of the obtained compound was 874 g / eq, the weight average molecular weight was 2630, the viscosity was 4600 mPa ⁇ s, and the appearance was colorless and transparent.
  • the proportion of silicon atoms belonging to the silsesquioxane segment was 22.5 mol%.
  • the ratio of silicon atoms belonging to the chain silicone segment was 77.5 mol%.
  • Example 5 (Example in which an alkoxy group is reacted at a ratio of 8.6 equivalents to 1 equivalent of a silanol group)
  • First stage reaction ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane 49.3 parts (alkoxy group equivalent 82.1), methyltrimethoxysilane 27.2 parts (alkoxy group equivalent 45.4), weight
  • a reaction vessel was charged with 118.7 parts of silanol-terminated methylphenyl silicone oil having an average molecular weight of 1700 (GPC measured value) (silanol equivalent: 850) and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts).
  • the liquid temperature was raised to 75 ° C.
  • Second stage reaction After adding 123 parts of methanol, 43.2 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. under reflux for 8 hours. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 166 parts of MIBK was added, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 151 parts of a block type siloxane compound (A-5) having a reactive functional group.
  • A-5 block type siloxane compound having a reactive functional group.
  • the epoxy equivalent of the obtained compound was 832 g / eq, the weight average molecular weight was 5850, the viscosity was 4610 mPa ⁇ s, and the appearance was colorless and transparent. Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 20.0 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 80.0 mol%.
  • Comparative Example 1 Example in which alkoxy group is reacted at a ratio of 1.4 equivalent to 1 equivalent of silanol group: Example of gelation in first stage reaction) ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane 37.0 parts (alkoxy group equivalent 82.1), weight average molecular weight 1060 (GPC measured value) silanol-terminated dimethyl silicone oil 170.9 parts (silanol equivalent 530) Then, 12.3 parts of 0.5% KOH methanol solution (0.06 parts as KOH parts) was put in a reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the mixture was reacted at 75 ° C. for 4 hours under reflux. As a result, the reaction product became a solvent-insoluble gel (A-6).
  • Reference example 1 Example in which alkoxy group is reacted in the presence of water at a ratio of 5.5 equivalent to 1 equivalent of silanol group
  • ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane 98.6 parts (alkoxy group equivalent 82.1), weight average molecular weight 1060 (GPC measured value) silanol-terminated dimethyl silicone oil 118.7 parts (silanol equivalent 530)
  • 131 parts of methanol and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts) were put into a reaction vessel, and the liquid temperature was raised to 75 ° C.
  • Reference example 2 Example in which an alkoxy group is reacted in the presence of water at a ratio of 30.7 equivalent to 1 equivalent of silanol group
  • ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane 45.4 parts (alkoxy group equivalent 82.1)
  • weight average molecular weight 6120 (GPC measurement value) silanol terminal Dimethyl silicone oil 54.6 parts (silanol equivalent 3060), triethylamine 10.0 parts, and MIBK 500 parts are put into a reaction vessel, and 100 parts of distilled water are added dropwise over 30 minutes while stirring at room temperature. The reaction was performed for 6 hours.
  • Reference example 3 Example in which an alkoxy group is reacted in the presence of water at a ratio of 31.0 equivalent to 1 equivalent of silanol group
  • 94.0 parts silanol equivalent 3060 of silanol-terminated dimethylsilicone oil having 78.8 parts of ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and weight average molecular weight 6120 (GPC measurement value)
  • 104 parts of methanol and 8.0 parts of 0.5% KOH methanol solution (0.04 parts as KOH parts) were put into a reaction vessel, and the liquid temperature was raised to 75 ° C.
  • Reference example 4 Example in which an alkoxy group is reacted in the presence of water at a ratio of 80.0 equivalent to 1 equivalent of silanol group) ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane 98.6 parts (alkoxy group equivalent 82.1), weight average molecular weight 15800 (GPC measured value) silanol-terminated dimethyl silicone oil 118.7 parts (silanol equivalent 7900) Then, 142 parts of methanol and 10.0 parts of 0.5% KOH methanol solution (0.05 parts as KOH parts) were put in a reaction vessel, and the liquid temperature was raised to 75 ° C.
  • Comparative Example 2 Synthesis was performed using a silicone oil having an alkoxy group at the terminal represented by the following formula (5) instead of the silanol-terminated silicone oil of the formula (2) used in Examples 1 to 5.
  • reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 88 parts of MIBK was added, and washing with water was repeated three times.
  • solvent was removed from the organic phase under reduced pressure at 100 ° C., 80.6 parts of a cloudy liquid (A-11) was obtained, which could not be used as a composition for an optical semiconductor encapsulant.
  • Table 1 summarizes the properties of the resins A-1 to A-11 obtained in Examples 1 to 5, Comparative Examples 1 and 2, and Reference Examples 1 to 4.
  • Comparative Example 1 in which the compound represented by the general formula (1) and the compound represented by the general formula (2) were prepared with an alkoxy group / silanol group charge equivalent value of 1.4 was a solvent-insoluble gelled product. It was confirmed that it could not be used as an epoxy resin. Further, Reference Example 1, Reference Example 2, Reference Example 3, Reference Example 4 (A-) were prepared by synthesizing the compound represented by the general formula (1) and the compound represented by the general formula (2) by adding an alkali catalyst and water at once. 7, A-8, A-9, and A-10) became white turbid liquids, and it was confirmed that they were not suitable for optical use.
  • A-11 (Comparative Example 2) using a compound of the formula (5) which is a silicone oil having an alkoxy group at the terminal instead of the compound represented by the general formula (2) as the chain silicone segment also became cloudy. It turned out to be a liquid and not suitable for optical applications.
  • Examples 1 to 3 (A-1, A-2, A-3) in which the compounds represented by the general formula (1) and the general formula (2) were reacted in two steps, the general formula (1), In Examples 4 and 5 (A-4 and A-5), in which the compounds represented by (2) and (3) were reacted in two stages, it was confirmed that a colorless and transparent resin was obtained and was suitable for optical use. did it.
  • Example 6 (Example in which an alkoxy group is reacted at a ratio of 3.8 equivalents to 1 equivalent of silanol groups)
  • First stage reaction 252.8 parts of silanol-terminated dimethyl silicone oil having 147.8 parts of ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average molecular weight of 1060 (measured by GPC) (Silanol equivalent 356) and 20.0 parts of a 0.5% KOH methanol solution (0.1 parts as the number of KOH parts) were charged into the reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C. under reflux for 8 hours.
  • silanol-terminated dimethyl silicone oil having 147.8 parts of ⁇ - (3,4 epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and a weight average mo
  • Second stage reaction After adding 255 parts of methanol, 64.8 parts of 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 352 parts of MIBK was added, and washing with water was repeated three times. Next, the organic phase was removed under reduced pressure at 100 ° C. to obtain 333 parts of a block type siloxane compound (A-13) having a reactive functional group.
  • A-13 block type siloxane compound having a reactive functional group.
  • the epoxy equivalent of the obtained compound was 578 g / eq, the weight average molecular weight was 5250, the viscosity was 257 mPa ⁇ s, and the appearance was colorless and transparent. Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 14.9 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 85.1 mol%.
  • Comparative Example 4 When dimethylsiloxane is considered as a unit structure, the following formula (6) is used so that the content concentration (mol%) of the dimethylsiloxane unit structure contained in the compound is the same concentration (mol%) as in Example 6. Synthesis was performed using dimethyldimethoxysilane as a raw material.
  • the organic phase was removed under reduced pressure at 100 ° C. to obtain 60 parts of a siloxane compound (A-14) having a reactive functional group.
  • the epoxy equivalent of the obtained compound was 561 g / eq, the weight average molecular weight was 830, and the appearance was colorless and transparent.
  • Example 7 (Example in which an alkoxy group is reacted at a ratio of 4.8 equivalents to 1 equivalent of a silanol group)
  • First stage reaction Silanol-terminated methylphenylsilicone oil 130.6 having 59.1 parts ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane (alkoxy group equivalent 82.1) and weight average molecular weight 1700 (measured by GPC) Parts (silanol equivalent 850) and 10.0 parts of 0.5% KOH methanol solution (0.1 parts as KOH parts) were charged into the reaction vessel, and the liquid temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out at 75 ° C.
  • Second stage reaction After adding 135 parts of methanol, 25.9 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, for washing, 170 parts of MIBK was added, and washing with water was repeated three times. Subsequently, the organic phase was removed under reduced pressure at 100 ° C. to obtain 162 parts of a block type siloxane compound (A-15) having a reactive functional group.
  • A-15 block type siloxane compound having a reactive functional group.
  • the epoxy equivalent of the obtained compound was 707 g / eq, the weight average molecular weight was 2680, the viscosity was 727 mPa ⁇ s, and the appearance was colorless and transparent. Moreover, the ratio of the silicon atom which belongs to a silsesquioxane segment was 13.6 mol%. Similarly, the ratio of silicon atoms belonging to the chain silicone segment was 86.4 mol%.
  • Examples 8 to 13, Comparative Examples 5 to 7 The synthesized siloxane compound (any one of A-1 to 3, 12 to 15) or a commercially available alicyclic epoxy resin (ERL-4221) conventionally used for optical semiconductor encapsulation, and a curing agent ( B-1 to B-3) or both the curing agent (B-3) and the curing accelerator C-1 were mixed in the parts by weight shown in Table 2, 3, 4 or 5, and Example 8 of the present invention was performed. To 13 and Comparative Examples 5 to 7 were obtained. Examples and Comparative Examples described in Table 2 are as follows.
  • Example 8 Composition using Compound A-1 and curing agent B-1
  • Example 9 Composition using Compound A-2 and curing agent B-1
  • Example 10 Compound A-3 and curing agent B
  • Composition Comparative Example 5 using -1 Composition Comparative Example 6 using Compound A-12 and Curing Agent B-1: Composition using ERL-4221 and Curing Agent B-1 Implementation described in Table 3
  • Example 11 Composition using Compound A-13, Curing Agent B-3 and Curing Accelerator C-1 Comparative Example 7: Using Compound A-14, Curing Agent B-3 and Curing Accelerator C-1 Composition
  • the Example and comparative example which were described in Table 4 are as follows.
  • Example 12 Composition using Compound A-15, Curing Agent B-3 and Curing Accelerator C-1 Examples and Comparative Examples described in Table 5 are as follows.
  • Example 13 Composition using Compound A-13, Curing Agent B-3 and Curing Accelerator C-1 Comparative
  • Example 6 Composition using ERL-4221 and Curing Agent B-1
  • UV durability transmission test The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were vacuum defoamed for 20 minutes, and then gently poured into an aluminum cup having a bottom diameter of 5 cm and a height of 2 cm. The cast was placed in an oven and cured under a predetermined curing condition to obtain a test piece for permeability having a thickness of 2 mm. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) before and after ultraviolet irradiation was measured with a spectrophotometer, and the rate of change was calculated.
  • the ultraviolet irradiation conditions are as follows. UV irradiation machine: Eye Super UV Tester SUV-W11 Temperature: 60 ° C Irradiation energy: 65 mW / cm 2 Irradiation time: 100 hours
  • Thermal durability transmission test The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were vacuum defoamed for 20 minutes, and then gently poured into an aluminum cup having a bottom diameter of 5 cm and a height of 2 cm. The cast was placed in an oven and cured under a predetermined curing condition to obtain a test piece for permeability having a thickness of 2 mm. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) before and after being left in a 150 ° C. oven for 96 hours was measured with a spectrophotometer, and the rate of change was calculated.
  • Dynamic viscoelasticity measuring device manufactured by TA-instruments, DMA-2980 Measurement temperature range: -30 ° C to 280 ° C Temperature rate: 2 ° C./min Test piece size: 5 mm ⁇ 50 mm cut out (thickness is about 800 ⁇ m). Analysis condition Tg: The peak point of Tan- ⁇ in DMA measurement was defined as Tg. ⁇ 30 ° C. Elastic modulus: The elastic modulus at ⁇ 30 ° C. was measured.
  • LED lighting test The curable resin compositions obtained in Examples 8 to 13 and Comparative Examples 5 to 7 were vacuum degassed for 20 minutes, then filled into a syringe and mounted with a light emitting element having an emission wavelength of 375 nm using a precision discharge device. The surface mounted LED was cast. Then, the LED for lighting test was obtained by making it harden
  • Curing agent B-1 As a curing agent, 30 parts of 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride (“H-TMA” manufactured by Mitsubishi Gas Chemical Co., Ltd.) and methylhexahydrophthalic acid in advance A mixture obtained by mixing 70 parts of “MH-700G” (manufactured by Shin Nippon Rika Co., Ltd.), which is a mixture of anhydride and hexahydrophthalic anhydride, was prepared as curing agent B-1.
  • H-TMA 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride
  • MH-700G manufactured by Shin Nippon Rika Co., Ltd.
  • Curing agent B-2 As a curing agent, 50 parts of 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride (“H-TMA” manufactured by Mitsubishi Gas Chemical Co., Ltd.) and methylhexahydrophthalic acid in advance A mixture obtained by mixing 50 parts of “MH-700G” (manufactured by Shin Nippon Rika Co., Ltd.), which is a mixture of anhydride and hexahydrophthalic anhydride, was prepared as curing agent B-2.
  • ERL-4221 Dow Chemical's alicyclic epoxy resin.
  • Curing conditions 120 ° C. 2 hr + 140 ° C. 2 hr (Examples 8, 9, 10 and Comparative Examples 5 and 6) * The unit of Tg is [° C.], and the unit of -30 ° C. elastic modulus is [MPa].
  • the curable resin compositions of Examples 8 to 10 using the siloxane compound (A) of the present invention synthesized by a two-step reaction have the same dimethylsiloxane unit structure content concentration (mol%).
  • Tg is high and excellent in heat resistance, and elastic modulus at low temperature is reduced, and it is found that heat resistance and low elastic modulus characteristics are excellent. did.
  • Example 11 In the curable resin composition of Comparative Example 7, foaming traces were generated and a cured product could not be normally prepared for dynamic viscoelasticity measurement, whereas the curable resin composition of Example 11 was tacky. It has been found that a cured product having no elasticity can be produced and a cured product having a low elastic modulus can be obtained. Further, in the curable resin composition of Comparative Example 7, as a result of measuring the resin weight loss before and after curing of the UV durability transmission test sample, the curability of Example 11 was reduced by 9%. In the resin composition, the weight loss is only about 5%, and the curable resin composition of the present invention has little weight loss before and after curing, and there are also few dents after curing of the LED package casting. The conductive resin composition was found to be suitable in this respect as an LED sealing composition. Furthermore, it was found that Example 11 was superior in transmittance UV durability and thermal durability compared to Comparative Example 7.
  • Curing agent B-3 A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride was used (“MH-700G” manufactured by Shin Nippon Rika Co., Ltd.)
  • Curing accelerator C-1 “U-CAT 18X” (trade name) sold by San Apro Co., Ltd. was used as a reaction accelerator for epoxy resin and acid anhydride.
  • Curing conditions 120 ° C. 1 hr + 150 ° C. 3 hr * The unit of Tg is [° C.], and the unit of -30 ° C. elastic modulus is [MPa]. It was found that the curable resin composition of Example 12 using the siloxane compound (A) of the present invention synthesized by a two-step reaction was a cured product having a low elastic modulus at a low temperature.
  • Curing agent B-2 As a curing agent, 50 parts of 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride (“H-TMA” manufactured by Mitsubishi Gas Chemical Co., Ltd.) and methylhexahydrophthalic acid in advance A mixture obtained by mixing 50 parts of “MH-700G” (manufactured by Shin Nippon Rika Co., Ltd.), which is a mixture of anhydride and hexahydrophthalic anhydride, was prepared as curing agent B-2.
  • H-TMA 1,3,4-cyclohexanetricarboxylic acid-3,4-anhydride
  • MH-700G manufactured by Shin Nippon Rika Co., Ltd.
  • Curing agent B-3 A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride was used (“MH-700G” manufactured by Shin Nippon Rika Co., Ltd.) * Curing accelerator C-1: “U-CAT 18X” (trade name) sold by San Apro Co., Ltd. was used as a reaction accelerator for epoxy resin and acid anhydride. * ERL-4221: Dow Chemical's alicyclic epoxy resin. * Curing conditions: 110 ° C., 6 hours (Example 13) * Curing conditions: 120 ° C. 1 hr + 150 ° C. 3 hr (Comparative Example 6) * The unit of Tg is [° C.], and the unit of -30 ° C. elastic modulus is [MPa].

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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JP2011111585A (ja) * 2009-11-30 2011-06-09 Nippon Kayaku Co Ltd エポキシ樹脂組成物、硬化性樹脂組成物
WO2011108516A1 (ja) * 2010-03-02 2011-09-09 日本化薬株式会社 オルガノポリシロキサンの製造方法、該製造方法により得られるオルガノポリシロキサン、該オルガノポリシロキサンを含有する組成物
WO2011108588A1 (ja) * 2010-03-02 2011-09-09 日本化薬株式会社 硬化性樹脂組成物、及びその硬化物
JP2012233110A (ja) * 2011-05-06 2012-11-29 Shin-Etsu Chemical Co Ltd 末端アルコキシ変性オルガノポリシロキサン及びその製造方法
JP2012255125A (ja) * 2011-05-17 2012-12-27 Mitsubishi Chemicals Corp 熱硬化性樹脂組成物、半導体デバイス用部材、及びそれを用いた半導体デバイス
JP2013057001A (ja) * 2011-09-08 2013-03-28 Mitsubishi Chemicals Corp 熱硬化性樹脂組成物、半導体デバイス用部材、及びそれを用いた半導体デバイス
CN103608408A (zh) * 2011-06-17 2014-02-26 Lg化学株式会社 可固化组合物
JP2014185263A (ja) * 2013-03-25 2014-10-02 Nippon Kayaku Co Ltd エポキシ基含有シリコーン樹脂、エポキシ基含有シリコーン樹脂組成物、及びその硬化物
WO2014208619A1 (ja) * 2013-06-26 2014-12-31 日本化薬株式会社 エポキシ基含有ポリオルガノシロキサンおよびそれを含有する硬化性樹脂組成物
US10658554B2 (en) 2014-06-19 2020-05-19 Inkron Oy LED lamp with siloxane particle material
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011063799A (ja) * 2009-08-21 2011-03-31 Jsr Corp 光半導体封止用組成物
JP2011111585A (ja) * 2009-11-30 2011-06-09 Nippon Kayaku Co Ltd エポキシ樹脂組成物、硬化性樹脂組成物
JPWO2011108588A1 (ja) * 2010-03-02 2013-06-27 日本化薬株式会社 硬化性樹脂組成物、及びその硬化物
WO2011108516A1 (ja) * 2010-03-02 2011-09-09 日本化薬株式会社 オルガノポリシロキサンの製造方法、該製造方法により得られるオルガノポリシロキサン、該オルガノポリシロキサンを含有する組成物
WO2011108588A1 (ja) * 2010-03-02 2011-09-09 日本化薬株式会社 硬化性樹脂組成物、及びその硬化物
JP5878862B2 (ja) * 2010-03-02 2016-03-08 日本化薬株式会社 硬化性樹脂組成物、及びその硬化物
JP2012233110A (ja) * 2011-05-06 2012-11-29 Shin-Etsu Chemical Co Ltd 末端アルコキシ変性オルガノポリシロキサン及びその製造方法
JP2012255125A (ja) * 2011-05-17 2012-12-27 Mitsubishi Chemicals Corp 熱硬化性樹脂組成物、半導体デバイス用部材、及びそれを用いた半導体デバイス
CN103608408A (zh) * 2011-06-17 2014-02-26 Lg化学株式会社 可固化组合物
US9123647B2 (en) 2011-06-17 2015-09-01 Lg Chem, Ltd. Curable composition
CN103608408B (zh) * 2011-06-17 2016-04-13 Lg化学株式会社 可固化组合物
JP2013057001A (ja) * 2011-09-08 2013-03-28 Mitsubishi Chemicals Corp 熱硬化性樹脂組成物、半導体デバイス用部材、及びそれを用いた半導体デバイス
JP2014185263A (ja) * 2013-03-25 2014-10-02 Nippon Kayaku Co Ltd エポキシ基含有シリコーン樹脂、エポキシ基含有シリコーン樹脂組成物、及びその硬化物
WO2014208619A1 (ja) * 2013-06-26 2014-12-31 日本化薬株式会社 エポキシ基含有ポリオルガノシロキサンおよびそれを含有する硬化性樹脂組成物
JPWO2014208619A1 (ja) * 2013-06-26 2017-02-23 日本化薬株式会社 エポキシ基含有ポリオルガノシロキサンおよびそれを含有する硬化性樹脂組成物
US10658554B2 (en) 2014-06-19 2020-05-19 Inkron Oy LED lamp with siloxane particle material
CN114222779A (zh) * 2019-08-27 2022-03-22 三菱化学株式会社 含有环氧基的聚有机硅氧烷、包含含有环氧基的聚有机硅氧烷的固化性树脂组合物及其固化物

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