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WO2014208619A1 - Polyorganosiloxane contenant un groupe époxy et composition de résine durcissable le contenant - Google Patents

Polyorganosiloxane contenant un groupe époxy et composition de résine durcissable le contenant Download PDF

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Publication number
WO2014208619A1
WO2014208619A1 PCT/JP2014/066888 JP2014066888W WO2014208619A1 WO 2014208619 A1 WO2014208619 A1 WO 2014208619A1 JP 2014066888 W JP2014066888 W JP 2014066888W WO 2014208619 A1 WO2014208619 A1 WO 2014208619A1
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Prior art keywords
group
component
epoxy
compound
carbon atoms
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English (en)
Japanese (ja)
Inventor
直房 宮川
直佑 谷口
窪木　健一
智江 佐々木
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2015524095A priority Critical patent/JP6239616B2/ja
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    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups

Definitions

  • the present invention relates to an epoxy group-containing polyorganosiloxane suitable for use in a portion requiring high transparency, particularly for optical semiconductor sealing, and a curable resin composition containing the epoxy group.
  • the curable resin composition is a thermosetting resin composition that has excellent workability and excellent electrical properties, heat resistance, adhesion, moisture resistance, etc. It is widely used in such fields.
  • curable resin compositions have been used as resins for encapsulating optical semiconductors such as red and green colored LEDs (light emitting diodes).
  • red and green colored LEDs light emitting diodes
  • Resin sealing materials have been used (see Patent Document 1).
  • the present invention relates to an epoxy group-containing polyorganosiloxane that provides a cured product having excellent heat-resistant transparency, excellent sulfidation resistance, and low tack, and a method for producing the same, and a curable resin containing the epoxy group-containing polyorganosiloxane.
  • An object is to provide a composition.
  • the present inventors have found that an epoxy group-containing polyorganosiloxane having a specific structure or an epoxy group-containing polyorganosiloxane produced using a specific compound as a raw material and a curability containing the same
  • the present inventors have found that a resin composition solves the above problems and have completed the present invention. That is, the present invention relates to the following (1) to (14).
  • L represents an integer greater than or equal to 2.
  • * represents a bond to a silicon atom of the silicone resin structure (A) or the silicone oil structure (C));
  • Silicone resin (component a) represented by average formula (1); epoxy group-containing silicon compound (component b) represented by formula (2); and silanol-terminated silicone represented by formula (3) A method for producing an epoxy group-containing polyorganosiloxane produced using oil (component c) as a raw material, comprising the following two-stage production steps: [Manufacturing step I] A step of dealcoholizing the silanol groups of component a and c and the alkoxy group of component b in the presence of an inorganic base compound [Manufacturing step II] After manufacturing step I, water is added to remain. The step of condensing the alkoxy groups together:
  • R 7 has a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • An aryl group, R 8 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, e represents 0, 1 or 2, and f represents (3-e));
  • Silicone resin represented by average formula (1) (component a); epoxy group-containing silicon compound represented by formula (2) (component b); and silanol-terminated silicone represented by formula (3) A method for producing an epoxy group-containing polyorganosiloxane produced from oil (component c) as a raw material, comprising the following three steps: [Manufacturing step 1] A step of dealcoholizing a silanol group of component a and an alkoxy group of component b in the presence of an inorganic base compound. [Manufacturing step 2] A step of adding a component c after the manufacturing step 1 and performing dealcoholization condensation between the alkoxy group remaining after the manufacturing step 1 and silanol of the component c. [Manufacturing step 3] After manufacturing step 2, water is added to condense the remaining alkoxy groups:
  • R 7 has a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • An aryl group, R 8 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, e represents 0, 1 or 2, and f represents (3-e));
  • a plurality of R 9 s may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms, and g represents an average value of 2 to 2000. Show).
  • a curable resin composition comprising the epoxy group-containing polyorganosiloxane according to any one of (1) to (4) and an epoxy resin curing agent.
  • the polycarboxylic acid compound is a carbinol-modified silicone oil (d) at both terminals, a polyhydric alcohol compound (e) having two or more hydroxyl groups in the molecule, and one carboxylic acid anhydride in the molecule.
  • an epoxy group-containing polyorganosiloxane having a specific structure or an epoxy group-containing polyorganosiloxane produced using a specific compound as a raw material and a curable resin composition containing the epoxy group-containing polyorganosiloxane have heat resistant transparency, In order to give a cured product having excellent sulfidity and low tackiness, it is extremely useful as a sealing resin for materials that require high transparency and low tackiness, particularly optical semiconductors (LEDs, etc.).
  • the silicone resin (component a) in the present invention is a silicone resin represented by the following average formula (1). It is a component for introducing a phenyl group into the epoxy group-containing siloxane of the present invention without excessively increasing the viscosity and improving the sulfidation resistance of the cured product for optical semiconductor encapsulation of the present invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are monovalent hydrocarbon groups or hydroxyl groups, preferably linear or branched having 1 to 10 carbon atoms in total. Alternatively, it is a cyclic alkyl group or an aryl group having an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • a plurality of R 1 to R 6 present in the formula may be the same or different, but when R 1 to R 6 in the molecule is 100 mol%, a hydroxyl group (silanol group, Si—OH) is present. 5 to 50 mol%, and the phenyl group is 30 to 95 mol%.
  • R 1 to R 6 other than hydroxyl group and phenyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, and n-pentyl group. N-hexyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, hydroxyl group and the like. Among these, a methyl group and an n-propyl group are preferable from the viewpoints of compatibility and heat-resistant transparency of the cured product.
  • the hydroxyl group is preferably 20 to 45 mol%, particularly preferably 25 to 40 mol%.
  • the phenyl group is preferably 35 to 95 mol%, more preferably 40 to 90 mol%, and particularly preferably 50 to 85 mol%.
  • the a structure is preferably 0.2 to 0.7, and particularly preferably 0.3 to 0.6.
  • the b structure is preferably from 0.3 to 0.7, particularly preferably from 0.4 to 0.7.
  • the weight average molecular weight (Mw) of the silicone resin (component a) is preferably in the range of 400 to 10,000 (GPC). If the weight average molecular weight is less than 400, the cured product may have poor sulfidation resistance, and if it exceeds 10,000, the epoxy group-containing polyorganosiloxane may have too high a viscosity and poor workability.
  • the weight average molecular weight (Mw) is more preferably 1000 to 5000, and particularly preferably 1500 to 3000.
  • Silicone resin (component a) includes, for example, tetraalkoxysilane, tetrachlorosilane, phenyltrialkoxysilane, phenyltrichlorosilane, diphenyl dialkoxysilane, diphenyldichlorosilane, alkyltrialkoxysilane having 1 to 10 carbon atoms, 1 to carbon atoms It can be obtained by hydrolytic condensation of a hydrolyzable silane compound such as 10 alkyltrichlorosilanes.
  • preferable silicone resin include the following product names.
  • Z-6018, 217FLAKE, FCA-107, 220FLAKE, 233FLAKE, 249FLAKE are manufactured by Toray Dow Corning
  • SILRES 603, SILRES 604, SILRES 605, SILRES H44, SILRES4 SY300, SILRES4 SY300, SILRES4 SY300, SILRES4 SY300 , SILRES4 SY300 , SILRES IC836, manufactured by Momentive, Inc. include TSR160.
  • Z-6018, 217FLAKE, FCA-107, 233FLAKE, SILRES603, and SILRES604 are preferable from the viewpoint of compatibility, molecular weight, and sulfidation resistance of the cured product.
  • These silicone resins (component a) may be used alone or in combination of two or more.
  • the epoxy group-containing silicon compound (component b) in the present invention is an alkoxysilicon compound represented by the formula (2).
  • the epoxy group-containing silicon compound (component b) is a compound for introducing an epoxy group into the epoxy group-containing polyorganosiloxane of the present invention.
  • An epoxy group is introduced by dealcohol condensation with a silanol group (Si—OH group) of the silanol-terminated silicone oil (component c).
  • X is not particularly limited as long as X is a reactive functional group having an epoxy group.
  • an alkyl group having 1 to 4 carbon atoms substituted with a glycidoxy group such as ⁇ -glycidoxyethyl, ⁇ -glycidoxypropyl, ⁇ -glycidoxybutyl, glycidyl group, ⁇ - (3,4-epoxy Cyclohexyl) ethyl group, ⁇ - (3,4-epoxycyclohexyl) propyl group, ⁇ - (3,4-epoxycycloheptyl) ethyl group, 4- (3,4-epoxycyclohexyl) butyl group, 5- (3 And an alkyl group having 1 to 5 carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as 4-epoxycyclohexyl) pentyl group.
  • a glycidoxy group
  • R 8 in the formula (2) represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
  • E in the formula (2) is an integer representing 0, 1, 2 and f represents (3-e), respectively. From the viewpoint of the viscosity of the epoxy group-containing polyorganosiloxane and the mechanical strength of the cured product, e is preferably 0 or 1.
  • preferable epoxy group-containing silicon compounds include ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycid.
  • 2- (3,4-epoxycyclohexyl) is particularly preferable.
  • Ethyltrimethoxysilane is preferred.
  • These epoxy group-containing silicon compounds (component b) may be used alone or in combination of two or more, and may also be used in combination with the following alkoxysilicon compounds (component g).
  • an alkoxy silicon compound (g component) represented by the following formula (4) can be used together with the epoxy group-containing silicon compound (component b).
  • the alkoxysilicon compound (g component) By using the alkoxysilicon compound (g component) in combination, the viscosity, refractive index and the like of the epoxy group-containing polyorganosiloxane of the present invention can be adjusted.
  • R 7 and R 8 are the same as described above, h is an integer, 0, 1, 2, 3 and i is (4-h).
  • the silanol-terminated silicone oil (component c) refers to a silicone resin represented by the following formula (3) and having silanol groups at both ends.
  • g represents an average value of 2 to 2000, preferably 3 to 200, more preferably 3 to 100, and further preferably 3 to 50.
  • g is less than 3, the cured product becomes too hard, and the heat cycle resistance may be inferior. If g exceeds 200, the mechanical strength of the cured product tends to decrease, such being undesirable.
  • the weight average molecular weight (Mw) of the silanol-terminated silicone oil (component c) is preferably in the range of 400 to 3000 (GPC).
  • the weight average molecular weight of the silanol-terminated silicone oil (component c) is a weight average molecular weight (calculated in terms of polystyrene) based on values measured under the following conditions using GPC (gel permeation chromatography). Mw).
  • Silanol-terminated silicone oil (component c) can be produced, for example, by hydrolyzing and condensing dimethyl dialkoxysilane and dimethyldichlorosilane.
  • preferable silanol-terminated silicone oil include the following product names.
  • PRX413, BY16-873 manufactured by Toray Dow Corning Co., Ltd. X-21-5841, KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd., XC96-723, TSR160, YR3370, YF3800, manufactured by Momentive XF3905, YF3057, YF3807, YF3802, YF3897, XF3905, YF3804, Asahi Kasei Wacker Silicone, FINISH WS 62M, CT 601M, CT 5000M, Gelest, DMS-S12, DMS-S14, DMS-S15 , DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-
  • PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, FINISH WS 62 M, DMS-S12, DMS-S14, DMS-S15, DMS-S21 and PDS-1615 are preferred.
  • X-21-5841, XC96-723, YF3800, FINISH WS 62 M, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight.
  • These silanol-terminated silicone oils (component c) may be used alone or in combination of two or more.
  • the epoxy group-containing silicon compound (component b) for the total amount of silanol groups in the silicone resin (component a) and silanol-terminated silicone oil (component c) 1 equivalent
  • the alkoxy group of the alkoxy silicon compound (g component) is reacted in an amount smaller than 1.5 equivalents to give an epoxy group-containing silicon compound (component b) (and if necessary, the alkoxy silicon compound (g Two or more alkoxy groups in the component)) will react with the silanol groups of the silicone resin (component a) and / or the silanol-terminated silicone oil (component c), resulting in too much polymer during production and gelation. There is a risk of it. For this reason, it is preferable to make an alkoxy group react with 1.5 equivalent or more with respect to 1 equivalent of silanol groups. From the viewpoint of reaction control, 2.0 equivalents or
  • the epoxy group-containing polyorganosiloxane of the present invention can be obtained through the production steps I and II or the production steps 1 to 3.
  • Silanol group of silicone resin (component a) and silanol-terminated silicone oil (component c), and alkoxy of epoxy group-containing silicon compound (component b) (and alkoxy silicon compound (g) as required) A step of subjecting a group to dealcohol condensation in the presence of an inorganic base compound
  • [Production Step II] A step of adding water after the production step I to condense the remaining alkoxy groups.
  • the silanol group and the alkoxy group are surely reacted to obtain a modified silicone resin and a modified silicone oil, and then the remaining alkoxy groups are dealcoholized and hydrolyzed and condensed to achieve uniform stability. Product can be obtained.
  • the polymerization of the epoxy group-containing silicon compound (component b) (and the alkoxy silicon compound (component g as necessary)) is caused by the condensation reaction between the silanol group and the alkoxy group. May progress further, become an excessively high molecular weight body and become a solvent-insoluble component (gelation).
  • Examples of primary alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, nonane alcohol, decane alcohol, propylene glycol and the like
  • examples of secondary alcohols include isopropanol, cyclohexanol, propylene glycol. Etc. From the viewpoint of subsequent removal performance, a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol is preferable. These alcohols may be used as a mixture.
  • the amount of primary alcohol is preferably 5% by weight or more, more preferably 8% by weight or more of the total alcohol amount.
  • the amount of alcohol used is silicone resin (a component), silanol-terminated silicone oil (c component) and epoxy group-containing silicon compound (b component) (and alkoxy silicon compound (g component) if necessary). It is preferable to contain 2% by weight or more based on the total weight. It is more preferably 2 to 100% by weight, further preferably 3 to 50% by weight, particularly preferably 4 to 40% by weight. When the amount exceeds 100% by weight, the progress of the reaction may be extremely slow. When the amount is less than 2% by weight, the reaction other than the target reaction proceeds, the molecular weight increases, gelation, increase in viscosity, and curing. There may be a problem such as an increase in elastic modulus that makes it difficult to use as an object.
  • solvents may be used in combination as necessary.
  • solvents that can be used in combination include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butanoate, hexane, hydrocarbons such as cyclohexane, toluene, and xylene. it can.
  • silicone resins (component a) used in this reaction are in a solid state, it is desirable to use a solvent that dissolves the silicone resin (component a).
  • methyl isobutyl ketone, butyl acetate, and toluene are preferable from the viewpoint of workability such as the solubility, versatility, and boiling point of the silicone resin (component a) are not too low.
  • the stability of the epoxy group-containing organopolysiloxane is preferred. From the viewpoint of transparency, methyl isobutyl ketone and toluene are particularly preferable.
  • an inorganic base compound By using an inorganic base compound, not only can the reaction sufficiently proceed, but it can be easily removed from the product.
  • the inorganic base compound include alkali metal inorganic salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or alkaline earth metal inorganic salts, and hydroxides are particularly preferable.
  • potassium hydroxide is particularly preferable from the viewpoint of catalytic ability and solubility in alcohol.
  • the addition method of an inorganic base compound is used in the state added directly or in the state melt
  • the allowable range of moisture at this time is the total of silicone resin (a component), silanol-terminated silicone oil (c component) and epoxy group-containing silicon compound (b component) (and alkoxy silicon compound (g component) if necessary) It is preferably 0.5% by weight or less, more preferably 0.3% by weight or less, and more preferably no water as much as possible.
  • the reaction temperature in the production step I is usually preferably 20 to 160 ° C., more preferably 40 to 100 ° C., particularly preferably 50 to 95 ° C., although it depends on the amount of inorganic base compound added and the solvent used.
  • the reaction time is usually preferably 1 to 20 hours, more preferably 3 to 12 hours.
  • the polymerization reactions (1) to (8) are considered to proceed simultaneously in parallel.
  • the basic inorganic compound is necessary as a catalyst, and the necessary amount may be added in the production process I first.
  • alcohol is preferably used as the solvent in the production process II.
  • examples of alcohols that can be used include alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, nonane alcohol, decane alcohol, cyclohexanol, and cyclopentanol. Etc.
  • primary alcohols and secondary alcohols are particularly preferred, and primary alcohols are particularly preferred.
  • a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol is preferable. These alcohols may be used as a mixture. The presence of these alcohols can contribute to molecular weight control and stability.
  • the silicone resin (a component) charged in the production process I, the silicon compound (b component) containing an epoxy group (and the alkoxy silicon compound (g component) if necessary), and a silanol-terminated silicone oil are used. It is preferably 20 to 200% by weight, more preferably 20 to 150% by weight, and particularly preferably 30 to 120% by weight based on the total weight of the component (c).
  • the molecular weight control is not effective, and the molecular weight may be higher than necessary. Furthermore, there is a possibility of inhibiting the stability of the epoxy group-containing polyorganosiloxane.
  • the reaction temperature in the production step II is preferably 20 to 160 ° C., more preferably 40 to 100 ° C., particularly preferably 50 to 95 ° C., although it depends on the amount of catalyst and the solvent used.
  • the reaction time is usually 1 to 20 hours, preferably 3 to 12 hours.
  • the catalyst can be removed by quenching and / or washing with water as necessary.
  • a solvent that can be separated from water.
  • preferable 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. it can.
  • the catalyst may be removed only by washing with water.
  • the catalyst is adsorbed by using an adsorbent after washing with water after quenching by a neutralization reaction. It is preferable to remove the adsorbent later by filtration.
  • Any compound that exhibits acidity can be used for the neutralization reaction.
  • the compound exhibiting acidity include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid.
  • an inorganic acid is preferable because it can be easily removed from the product, and phosphates and the like that can more easily adjust the pH to near neutral are more preferable.
  • adsorbent examples 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, manufactured by Toshin Kasei Co., Ltd., activated clay, SA35, SA1, T, R-15, E, Nikkanite (trade names) G-36, G-153, G-168, Mizusawa Chemical Industries
  • Galeon Earth trade name
  • Mizuka Ace trade name
  • the activated carbon for example, CL-H, Y-10S, Y-10SF manufactured by Ajinomoto Fine Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like.
  • the zeolite include, for example, molecular sieves (trade names) 3A, 4A, 5A, and 13X manufactured by Union Showa.
  • the synthetic adsorbent include Kyowa Chemical Co., Ltd., Kyoward (trade name) 100, 200, 300, 400, 500, 600, 700, 1000, 2000, and Rohm and Haas Co., Ltd.
  • the reaction After completion of the reaction or after quenching, 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.
  • reaction solvent mixed with water is removed from the system by distillation or vacuum concentration after quenching, and then washed with a solvent that can be separated from water. It is preferable.
  • the epoxy group-containing polyorganosiloxane of the present invention can be obtained by removing the solvent by vacuum concentration or the like.
  • a silanol group and an alkoxy group of the silicone resin (component a) having relatively low reactivity in the production process 1 are surely reacted to obtain a modified silicone resin, and then the production process 2
  • the silanol-terminated silicone oil (component c) is added and the silanol group of the relatively highly reactive silanol-terminated silicone oil (component c) is reacted with the alkoxy group to obtain a modified silicone oil.
  • the remaining alkoxy group can be dealcoholized and hydrolyzed to obtain a uniform and stable product.
  • the condensation reaction between the silanol group and the alkoxy group and the polymerization reaction between the alkoxysilanes become a competitive reaction, resulting in a difference in the reaction rate between the products and the compatibility of the products. Due to the difference, a heterogeneous compound can be obtained, or a large amount of silicone resin (a component) or silanol-terminated silicone oil (c component) having no epoxy group can be adversely affected.
  • Examples of primary alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, nonane alcohol, decane alcohol, propylene glycol, and the like.
  • Examples of secondary alcohols include isopropanol, cyclohexanol, propylene glycol. Etc.
  • a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol and t-butanol is preferred. These alcohols may be used as a mixture.
  • the solubility of the catalyst described later is excellent.
  • the amount of primary alcohol is preferably 5% by weight or more, more preferably 10% by weight or more of the total alcohol amount.
  • the amount of change in the weight average molecular weight per unit time in the reaction system of production process 1 is smaller than when only the primary alcohol is used, so the reaction is more easily controlled. It is.
  • the combined use of secondary alcohols is particularly important for large-scale reactions such as industrial production from the viewpoint of reaction control. Useful for.
  • solvents may be used in combination as necessary.
  • solvents that can be used in combination include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate, and isopropyl butanoate, hexane, cyclohexane, toluene, and xylene hydrocarbons. It can be illustrated.
  • silicone resins (component a) used in this reaction are in a solid state, it is desirable to dissolve them in the initial stage of production process 1.
  • an epoxy group-containing silicon compound (component b) (and an alkoxysilicon compound (component g as necessary)) that is usually liquid may be used, or the above-described solvents that can be used in combination may be used.
  • methyl isobutyl ketone, butyl acetate, and toluene are preferable from the viewpoint of workability such as the solubility, versatility, and boiling point of the silicone resin (component a) are not too low.
  • epoxy group-containing organopolysiloxanes are preferred. Methyl isobutyl ketone and toluene are particularly preferable from the viewpoints of stability and transparency.
  • the reaction in the production step 1 of the present invention is performed in the presence of an inorganic base compound.
  • the inorganic base compound acts as a catalyst for the reaction.
  • the reaction progress is slow and the reaction efficiency is remarkably poor.
  • an organic base such as triethylamine
  • the basicity is weak
  • the reaction efficiency is poor
  • the viscosity of the resulting epoxy resin is too low
  • the hardness of the cured product is insufficient, and the reaction proceeds depending on the reaction temperature. Sometimes it doesn't.
  • an inorganic base compound By using an inorganic base compound, not only can the reaction sufficiently proceed, but it can be easily removed from the product.
  • the inorganic base compound include alkali metal salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or alkaline earth metal salts, and hydroxides are particularly preferable.
  • potassium hydroxide is particularly preferable from the viewpoint of catalytic ability and solubility in alcohol.
  • the addition method of an inorganic base compound is used in the state added directly or in the state melt
  • the allowable range of moisture is silicone resin (component a), silanol-terminated silicone oil (component c) and epoxy group-containing silicon compound (component b) (and alkoxy silicon compound (component g) as required) ) Is preferably 0.5% by weight or less, more preferably 0.3% by weight or less, and more preferably as little water as possible.
  • the amount of the inorganic base compound that can be used in the production process 1 of the present invention includes the silicone resin (a component), silanol-terminated silicone oil (c component) and epoxy group-containing silicon compound (b component) used in the reaction (and necessary Accordingly, it is usually preferably 0.001 to 5% by weight, more preferably 0.01 to 2% by weight, based on the total weight of the alkoxysilicon compound (component g).
  • silanol-terminated silicone oil (component c) is added after production step 1, silanol groups of silanol-terminated silicone oil (component c), and epoxy group-containing silicon compound (component b) (and necessary) Depending on the case, dealcohol condensation with the alkoxy group of the alkoxysilicon compound (g component) is carried out.
  • the silicone resin (component a) and the silanol-terminated silicone oil (component c) are condensed with an epoxy group-containing silicon compound (component b) (and, if necessary, an alkoxy silicon compound (component g)).
  • a modified silicone resin and a modified silicone oil can be obtained.
  • the reaction in the production process 2 of the present invention is performed in the presence of an inorganic base compound for the same reason as in the production process 1.
  • the inorganic base compound used in the production process 2 is used within the range of the kind and addition amount exemplified in the production process 1 described above, but a new inorganic base compound may be added in the production process 2.
  • the reaction in the production process 2 of the present invention can be carried out without a solvent as in the production process 1, but it is preferably carried out in the presence of a solvent.
  • the solvent used in the manufacturing process 2 can be used within the range of the kind and addition amount exemplified in the manufacturing process 1 described above.
  • the reaction temperature in the production step 2 is usually preferably 20 to 160 ° C., more preferably 40 to 100 ° C., and particularly preferably 50 to 95 ° C., although it depends on the amount of inorganic base compound added and the solvent used.
  • the reaction time is usually preferably 1 to 20 hours, more preferably 2 to 12 hours.
  • the manufacturing process 3 After completion of the reaction in the production process 2, water is added, and the alkoxy group remaining in the modified silicone resin and modified silicone oil obtained in the production processes 1 and 2 and the epoxy group remaining unreacted are contained. Hydrolytic dealcohol condensation of the alkoxy group of the silicon compound (component b) (and the alkoxysilicon compound (component g) if necessary) is performed. At this time, if necessary, the above-mentioned epoxy compound-containing silicon compound (component b) (and, if necessary, an alkoxysilicon compound (component g)) and an inorganic base compound are added within the aforementioned amounts. It doesn't matter.
  • This reaction is carried out by using (1) modified silicone resins and / or (2) modified silicone oils and / or (3) silicon compounds containing epoxy groups (component b). And alkoxy silicon compound (component g)) and / or (4) between modified silicone resin and modified silicone oil and / or (5) silicon compound containing modified silicone resin and epoxy group (b) Component) (and alkoxy silicon compound (g component) if used) and / or (6) silicon compound containing modified silicone oil and epoxy group (b component) (and if used) And / or (7) a silicon compound containing an epoxy group (b component).
  • a low molecular weight alcohol having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, and t-butanol is preferable. These alcohols may be used as a mixture. The presence of these alcohols can contribute to molecular weight control and stability.
  • the silicone resin (a component) charged in the production steps 1 and 2 the silicon compound containing epoxy group (b component) (and the alkoxy silicon compound (g component) if necessary) and the silanol terminal It is preferably 20 to 200% by weight, more preferably 20 to 150% by weight, and particularly preferably 30 to 120% by weight based on the total weight with the silicone oil (component c).
  • water is added (ion exchange water, distilled water, or clean water can be used).
  • the amount of water used is preferably 0.5 to 8.0 equivalents, more preferably 0.6 to 5.0 equivalents, particularly preferably 0.65 to 2.0 equivalents relative to the amount of remaining alkoxy groups. is there.
  • the amount of water is less than 0.5 equivalent, the progress of the reaction is slowed, and the silicon compound containing the epoxy group (component b) (and the alkoxy silicon compound (component g) if necessary) does not react. There is a possibility that a problem such as remaining may occur, a sufficient network may not be formed, and a curing failure may occur even after curing after a subsequent curable resin composition.
  • the molecular weight control is not effective, and the molecular weight may be higher than necessary. Furthermore, there is a possibility of inhibiting the stability of the epoxy group-containing polyorganosiloxane.
  • the reaction temperature in production step 3 is usually preferably 20 to 160 ° C., more preferably 40 to 100 ° C., and particularly preferably 50 to 95 ° C., although it depends on the amount of inorganic base compound added and the solvent used.
  • the reaction time is usually preferably 1 to 20 hours, more preferably 3 to 12 hours.
  • the epoxy equivalent (measured by the method described in JIS K-7236) of the epoxy group-containing polyorganosiloxane of the present invention is 300 to 1500 g / eq.
  • the epoxy equivalent is less than 300 g / eq, the cured product tends to be too hard, and when it exceeds 1500 g / eq, the mechanical properties of the cured product tend to deteriorate.
  • the epoxy group-containing polyorganosiloxane may be a single epoxy group-containing polyorganosiloxane or a mixture of two or more epoxy group-containing polyorganosiloxanes.
  • the epoxy resin is a mixture of two or more epoxy group-containing polyorganosiloxanes, it is specified if it is a single epoxy group-containing polyorganosiloxane.
  • the epoxy equivalent of the sum of the epoxy equivalent of the epoxy group-containing polyorganosiloxane x is 300 to 1500 g / eq. It is preferably 350 to 1000 g / eq.
  • the viscosity of the epoxy group-containing polyorganosiloxane is preferably 50 to 40,000 mPa ⁇ s, more preferably 500 to 20,000 mPa ⁇ s, particularly 800 to 15, 000 mPa ⁇ s is preferred. If the viscosity is less than 50 mPa ⁇ s, the viscosity may be too low to be suitable for use as an optical semiconductor encapsulant, and if it exceeds 40,000 mPa ⁇ s, the viscosity may be too high and workability may be poor. is there.
  • the ratio of silicon atoms to which three oxygen atoms are bonded to the total silicon atoms is preferably 3 to 50 mol%, more preferably 5 to 40 mol%, and particularly preferably 6 to 35 mol%. . If the ratio of silicon atoms bonded to three oxygen atoms to the total silicon atoms is less than 3 mol%, the cured product tends to be too soft, and there is a concern of surface tack and scratches. Moreover, when it exceeds 50 mol%, hardened
  • the proportion of silicon atoms present can be determined by 1 H NMR, 29 Si NMR, elemental analysis, etc. of the epoxy group-containing polyorganosiloxane.
  • R ′ 1 , R ′ 2 , R ′ 3 , R ′ 4 , R ′ 5 , R ′ 6 may be the same as or different from each other, and may be a monovalent hydrocarbon group or a hydroxyl group.
  • L represents an integer greater than or equal to 2.
  • * represents a bond to a silicon atom of the silicone resin structure (A) or the silicone oil structure (C));
  • a plurality of R 9 s may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms, and g represents an average value of 2 to 2000.
  • * Represents a bond to the oxygen atom of the epoxy group-containing silsesquioxane structure (B).
  • the silicone resin (component a) and the silanol-terminated silicone oil (component c) that can be obtained through the production steps I and II or the production steps 1 to 3, which are preferred embodiments of the epoxy group-containing polyorganosiloxane in the present invention.
  • the condensate of the silanol group and the silicon compound containing the epoxy group (component b) (and, if necessary, the alkoxysilicon compound (component g)) has been described.
  • the resin composition for encapsulating an optical semiconductor of the present invention may be used by mixing an epoxy resin in addition to the epoxy group-containing organopolysiloxane obtained through the production steps I and II or the production steps 1 to 3 described above. it can.
  • Other epoxy resins that can be used include epoxy resins that are glycidyl etherified products of phenolic compounds, epoxy resins that are glycidyl etherified products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, Glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds having an epoxy group and other polymerizable unsaturated compounds, etc. Can be mentioned.
  • Examples of the epoxy resin that is a glycidyl etherified product of the phenol compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3 -Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, Dimethylbisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) Ethyl) phenyl] propane, 2,2'-me Ren-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-ter
  • novolac resins such as a novolak resin, a phenol novolac resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolac resin containing a fluorene skeleton.
  • Examples of the alicyclic epoxy resin include alicyclic rings having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.
  • An epoxy resin is mentioned.
  • Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
  • heterocyclic epoxy resin examples 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 made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
  • examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
  • epoxy resins obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like.
  • An epoxy resin obtained by glycidylating any of the halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like.
  • copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound other than the above As a product available from the market, Marproof (trade name) G-0115S, G-0130S, G-0250S, G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation) and the like.
  • polymerizable unsaturated compounds having an epoxy group include glycidyl acrylate, methacrylic acid, and the like. Examples thereof include glycidyl acid and 4-vinyl-1-cyclohexene-1,2-epoxide.
  • Examples of other polymerizable unsaturated compound copolymers include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinylcyclohexane.
  • the above epoxy resins may be used alone or in combination of two or more.
  • an alicyclic epoxy resin a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
  • these epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc.
  • the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane.
  • Diols Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane And the like.
  • carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
  • epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to them (reference: review epoxy resin basic edition I p76-85, the entire contents of which are incorporated herein by reference).
  • the ratio of the epoxy group-containing organopolysiloxane to the total epoxy resin is preferably 60 to 99 parts by weight, preferably 90 to 97 parts by weight. Is particularly preferred. If the amount is less than 60 parts by weight, the light resistance (UV resistance) of the cured product may be inferior.
  • the blending ratio of the total epoxy resin containing the epoxy group-containing organopolysiloxane and the epoxy resin curing agent is 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. It is preferable to use a curing agent. When less than 0.5 equivalent or more than 1.2 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.
  • the epoxy resin curing agent examples include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and polyvalent carboxylic acid compounds.
  • the epoxy resin curing agent is particularly preferably an acid anhydride compound or a polyvalent carboxylic acid compound from the viewpoints of hardness, workability (being liquid at room temperature), and transparency of the cured product.
  • acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, glutaric anhydride, 2,4-diethyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane- Acids such as 2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Anhydrides are mentioned.
  • the polyvalent carboxylic acid compound is a compound having at least two carboxyl groups.
  • the polyvalent carboxylic acid is preferably a bi- to hexafunctional carboxylic acid, such as butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, malic acid, etc.
  • Linear alkyl diacids, alkyl tricarboxylic acids such as 1,3,5-pentanetricarboxylic acid, citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid
  • An aliphatic cyclic polycarboxylic acid such as acid, nadic acid and methyl nadic acid; a multimer of unsaturated fatty acids such as linolenic acid and oleic acid; and dimer acids which are reduced products thereof; Examples include compounds obtained by reaction with acid anhydrides, bifunctional to hexafunctional polyhydric alcohols and acid anhydrides Compounds obtained by the reaction of, heat resistance, and more preferable from the viewpoint of workability.
  • the polyhydric carboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid
  • the bi- to hexafunctional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol.
  • Preferred polyhydric alcohols are alcohols having 5 or more carbon atoms, such as 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2,4 Compounds such as diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol are preferred, and 2-ethyl-2-butyl-1,3 is particularly preferred Alcohols having a branched chain structure or a cyclic structure such as propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol, Preferred from the viewpoint of transparency In particular, tricyclodecan
  • the conditions for the addition reaction can be used without any particular limitation as long as they are known methods.
  • Specific reaction conditions include, for example, acid anhydrides and polyhydric alcohols in the absence of a catalyst and in the absence of a solvent.
  • a method of reacting at 150 ° C. and heating, and taking it out as it is after completion of the reaction can be mentioned.
  • the epoxy resin curing agent in the present invention is particularly an acid anhydride (C1), a polyvalent carboxylic acid (C2) having at least two carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton from the viewpoint of heat resistance. Or a polyhydric alcohol compound (E) having two or more hydroxyl groups in the molecule, a compound (f) having one carboxylic acid anhydride group in the molecule, and optionally two or more in the molecule.
  • the polyvalent carboxylic acid resin (C3) obtained by addition reaction with the compound (h) having a carboxylic acid anhydride group is preferred.
  • both ends carbinol-modified silicone oil (d) and other polyhydric alcohol compounds having two or more hydroxyl groups in the molecule A polycarboxylic acid resin (C3) containing e) is more preferred.
  • the acid anhydride (C1) include succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, phthalic anhydride, naphthalenedicarboxylic anhydride, trimellit Acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, bicyclo [ 2.2.1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3, 4-anhydride, pentanedioic anhydride,
  • the polyvalent carboxylic acid (C2) is a compound having at least two carboxyl groups.
  • the polyvalent carboxylic acid is preferably a bi- to hexafunctional carboxylic acid, such as butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, malic acid, etc.
  • Linear alkyl diacids such as 1,3,5-pentanetricarboxylic acid, alkyltricarboxylic acids such as citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid
  • alkyltricarboxylic acids such as citric acid, phthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanetricarboxylic acid
  • aliphatic cyclic polycarboxylic acids such as acid, nadic acid, and methyl nadic acid, multimers of unsaturated fatty acids such as linolenic acid and oleic acid, and dimer acids that are reduced products thereof, and the above acid anhydrides
  • the polyvalent carboxylic acid resin (C3) preferred as an epoxy resin curing agent used in the curable resin composition of the present invention is an alcoholic hydroxyl group of a polyhydric alcohol compound (E) having two or more hydroxyl groups in the molecule described below.
  • the acid anhydride group of the compound (f) having one carboxylic anhydride group in the molecule (and optionally the compound (h) having two or more carboxylic anhydride groups in the molecule) undergoes an addition reaction. This compound is obtained by having two or more carboxylic acids in the molecule as functional groups.
  • both ends carbinol-modified silicone oil (d) and the other polyhydric alcohol compound (e) having two or more hydroxyl groups in the molecule It is preferable to use together.
  • polyhydric alcohol compound (E) having two or more hydroxyl groups in the molecule examples include those having 1 to 10 carbon atoms such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol.
  • polycyclic polyphenol compound is a compound having two or more six-membered rings and having two or more phenolic hydroxyl groups.
  • an alcohol compound (e6), a terminal alcohol polyester compound (e7), and a terminal alcohol polycarbonate compound (e8) in which one or more aromatic rings having a hydroxyl group are hydrogenated, and selected from these groups At least one polyhydric alcohol compound can be used, and two or more kinds can be used in combination.
  • Both terminal carbinol-modified silicone oil (d) is a silicone compound having alcoholic hydroxyl groups at both ends represented by the following formula (7).
  • R 10 examples include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, heptylene, octylene and other alkylene groups, ethoxyethylene group, propoxyethylene group propoxy
  • Examples include an alkylene group having an ether bond such as a propylene group and an ethoxypropylene group. Particularly preferred are propoxyethylene group and ethoxypropylene group.
  • R 9 represents an alkyl group having 1 to 3 carbon atoms, such as a methyl group, or a phenyl group, and may be the same or different.
  • a methyl group is preferred compared to a phenyl group.
  • v is an average value of 1 to 100, preferably 2 to 80, more preferably 5 to 30.
  • X-22-160AS, KF6001, KF6002, KF6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-201, BY16-004 are used as the both-end carbinol-modified silicone oil (d) represented by the formula (7).
  • SF8427 both manufactured by Toray Dow Corning Co., Ltd.
  • XF42-B0970, XF42-C3294 both manufactured by Momentive Performance Materials Japan GK
  • Silaplane trade names
  • FM-4411, FM-4421, FM-4425 (both manufactured by JNC Co., Ltd.) and the like, and all are available from the market.
  • These two terminal carbinol-modified silicone oils can be used alone or in combination.
  • X-22-160AS, KF6001, KF6002, BY16-201, XF42-B0970, and FM-4411 are preferable.
  • the chain alkylene diol (e2) having a branched structure which is a polyhydric alcohol compound will be described.
  • Specific examples of the branched alkylene diol (e2) having a branched structure include, for example, neopentyl glycol, 2-ethyl-2-butylpropylene-1,3-diol, 2,4-diethylpentane-1,5-diol, Examples include, but are not limited to, dimethylbutanediol, dimethylpentanediol, diethylpropanediol, dimethylhexanediol, diethylbutanediol, dimethylheptanediol, diethylpentanediol, dimethyloctanediol, diethylhexanediol, and ethylbutylpropanediol. There is nothing. These may be used alone or
  • the polyhydric alcohol (e3) which has an alicyclic structure which is a polyhydric alcohol compound is demonstrated.
  • Specific examples of the polyhydric alcohol having an alicyclic structure which is a particularly preferred polyhydric alcohol compound include cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, tricyclodecanediol, pentacyclodecane dimethanol, norbornanediol, norbornanedi. Examples thereof include, but are not limited to, methanol, dioxane glycol, and spiro glycol. These may be used alone or in combination of two or more. It is preferable to apply a polyhydric alcohol having an alicyclic structure because gas permeability resistance is improved in the cured product.
  • polyhydric alcohol (e4) having three or more hydroxyl groups in the molecule which is a polyhydric alcohol compound
  • polyhydric alcohols having three or more hydroxyl groups in the molecule which are particularly preferred polyhydric alcohol compounds, include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, and tris (2-hydroxyethyl) isocyanurate.
  • Pentaerythritol, ditrimethylolpropane, diglycerol, dipentaerythritol and the like but are not limited thereto. These may be used alone or in combination of two or more. It is preferable to apply a polyhydric alcohol having three or more hydroxyl groups in the molecule because the hardness of the cured product is increased.
  • a polyhydric alcohol (e5) obtained by ring-opening addition polymerization of a lactone having 2 to 8 carbon atoms to a polyhydric alcohol having two or more hydroxyl groups in the molecule which is a polyhydric alcohol compound
  • a polyhydric alcohol-modified lactone polymer obtained by ring-opening addition polymerization of a lactone having 2 to 8 carbon atoms to a polyhydric alcohol having two or more hydroxyl groups in the molecule which is a particularly preferred polyhydric alcohol.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and other alkylene diols having 1 to 10 carbon atoms, EO (ethylene oxide) modification Bisphenol A, EO-modified bisphenol F, EO-modified bisphenol E, EO-modified naphthalene diol, PO (propylene oxide) -modified bisphenol A, a branched alkylene diol having a branched structure, neopentyl glycol, 2-ethyl-2-butyl group Pyrene-1,3-diol, 2,4-diethylpentane-1,5-diol, dimethylbutanediol, dimethylpentanediol, diethylpropanedio
  • Terminals represented by formula (3) such as glycerin, trimethylolpropane, isocyanuric acid tris (2-hydroxyethyl), pentaerythritol, ditrimethylolpropane, diglycerol, dipentaerythritol, etc., which are polyhydric alcohols having a hydroxyl group above Examples include alcohol polyester compounds, but are not limited thereto.
  • alkylene oxide modified bisphenol A such as EO modified bisphenol A
  • alkylene oxide modified bisphenol F such as EO modified bisphenol F
  • polyhydric alcohol having an alicyclic structure and chain alkylene diol having a branched structure are preferable. These may be used alone or in combination of two or more.
  • the lactones used for obtaining the polyhydric alcohol-modified lactone polymer are lactones having 4 to 8 carbon atoms. Specific examples include ⁇ -butyrolactone, ⁇ -methylpropiolactone, ⁇ -valerolactone, ⁇ -Caprolactone, 3-methylcaprolactone, 4-methylcaprolactone, trimethylcaprolactone, ⁇ -methyl- ⁇ -caprolactone and the like.
  • the polyhydric alcohol-modified lactone polymer usually contains lactones in the range of 0.1 to 10 mol, preferably 0.2 to 5 mol, more preferably 0.3 to 2 mol, per mol of the hydroxyl group of the polyhydric alcohol.
  • a catalyst such as an alkali metal compound, a tin compound, a titanium compound, a zinc compound, a molybdenum compound, an aluminum compound, or a tungsten compound is usually used at 80 to 230 ° C., preferably 100 to 200 ° C., more preferably 120 to 160 ° C. It is obtained by making it react.
  • an alcohol compound (e6) in which one or more aromatic rings having a hydroxyl group of a polycyclic polyhydric phenol compound which is a polyhydric alcohol compound is hydrogenated will be described.
  • 1 having a hydroxyl group of a polycyclic polyphenol compound a polycyclic polyphenol compound is a compound having two or more six-membered rings and having two or more phenolic hydroxyl groups.
  • Ethane hydrogenated bisphenol E
  • 4,4′-bicyclohexanol hydrogenated biphenol
  • methylene biscyclohexanol Hydrogenated bisphenol F
  • 4,4 ′, 4 ′′ -methylidenetriscyclohexanol 4,4 ′-[(4-hydroxycyclohexyl) Methylene] bis (2-methylhexanol)
  • the terminal alcohol polyester compound (e7) is a polyester compound having a hydroxyl group at the terminal represented by the following formula (8).
  • R 11 and R 12 each independently represents an alkylene group having 1 to 10 carbon atoms, and n represents an average value of 1 to 100
  • R 11 examples include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isopropylene, ethylbutylpropylene, isobutylene, Examples thereof include an alkylene group having a branched chain of 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and an alkylene group having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene.
  • an alkylene group having a branched chain having 1 to 10 carbon atoms or an alkylene group having a cyclic structure is preferable, and in particular, ethylbutylpropylene, isobutylene, neopentylene, diethylpentylene, and cyclohexanedimethylene are the heat-resistant transparency of the cured product. It is preferable from the viewpoint.
  • R 12 examples include linear alkylene groups having 1 to 10 carbon atoms such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isopropylene, ethylbutylpropylene, isobutylene, Examples thereof include an alkylene group having a branched chain having 1 to 10 carbon atoms such as isopentylene, neopentylene and diethylpentylene, and an alkylene group having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene.
  • a linear alkylene group having 1 to 10 carbon atoms is preferable, and propylene, butylene, pentylene, and hexylene are particularly preferable from the viewpoint of adhesion of a cured product to a substrate.
  • n is an average value of 1 to 100, preferably 2 to 40, more preferably 3 to 30.
  • the weight average molecular weight (Mw) of the terminal alcohol polyester (e7) is preferably 500 to 20000, more preferably 500 to 5000, and still more preferably 500 to 3000. If the weight average molecular weight is less than 500, the cured product hardness of the curable resin composition of the present invention is too high, and there is a concern that cracks may occur in a heat cycle test or the like. If the weight average molecular weight is more than 20000, the cured product becomes sticky. There is a concern that will occur.
  • a weight average molecular weight means the weight average molecular weight (Mw) calculated in polystyrene conversion based on the value measured on condition of the following using GPC (gel permeation chromatography).
  • polyester polyols having an alcoholic hydroxyl group at the terminal include polyester polyols having an alcoholic hydroxyl group at the terminal.
  • polyester polyols such as Kyowapol (trade name) 1000PA, 2000PA, 3000PA, 2000BA (all manufactured by Kyowa Hakko Chemical Co., Ltd.); Adeka New Ace (trade name) Y9-10, YT-101 (both manufactured by ADEKA); Plaxel (trade name) 220EB, 220EC (both manufactured by Daicel Chemical Industries); Polylite (trade name) OD-X-286, OD-X- 102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2554, OD-X-2108, OD-X-2376 OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2 23, OD-X-2555 (all manufactured by DIC
  • terminal alcohol polycarbonate compound (e8) will be described. Although it does not specifically limit as a terminal alcohol polycarbonate compound, For example, the polycarbonate compound etc. which have a hydroxyl group at the terminal shown by following formula (9) are mentioned.
  • R 14 represents an alkylene group having 1 to 10 carbon atoms, and j represents an average value of 1 to 100
  • R 14 examples include linear alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, isopropylene, ethylbutylpropylene, Examples thereof include alkylene groups having a branched chain of 1 to 10 carbon atoms such as isobutylene, isopentylene, neopentylene, diethylpentylene, and the like, and alkylene groups having a cyclic structure such as cyclopentanedimethylene and cyclohexanedimethylene.
  • linear alkylene groups having 4 to 7 carbon atoms such as butylene, pentylene, hexylene and heptylene are preferable from the viewpoint of workability because the viscosity of the terminal alcohol polycarbonate compound is not too high.
  • a plurality of R 14 present in the formula (9) may be the same or different.
  • j is an average value of 1 to 100, preferably 2 to 40, more preferably 3 to 30.
  • the weight average molecular weight (Mw) of the terminal alcohol polycarbonate compound is preferably 500 to 20000, more preferably 500 to 5000, and still more preferably 500 to 3000. If the weight average molecular weight is 500 or more, the cured product hardness of the curable resin composition does not become excessively high, and there is no fear of cracking in a heat cycle test or the like, which is preferable. Moreover, if a weight average molecular weight is 20000 or less, there is no fear that stickiness of hardened
  • a weight average molecular weight means the weight average molecular weight (Mw) calculated in polystyrene conversion based on the value measured on condition of the following using GPC (gel permeation chromatography).
  • both ends carbinol-modified silicone oil (d) and other polyhydric alcohol (e) are used in combination as the polyhydric alcohol
  • the other polyhydric alcohol (e) is used in the amount of both ends carbinol-modified silicone oil.
  • the amount is preferably 0.5 to 200 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 10 to 30 parts by weight with respect to 100 parts by weight. If the amount is less than 0.5 parts by weight, the mechanical strength of the cured product may be inferior, and if it exceeds 200 parts by weight, the heat resistant transparency of the cured product may be inferior.
  • the compound (h) having two or more carboxylic acid anhydride groups in the molecule is, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetra.
  • the compound (h) having two or more carboxylic acid anhydride groups in the molecule can be used alone or in combination.
  • 1,2,3,4-butanetetracarboxylic dianhydride, 1,2 4,5-cyclohexanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is preferred
  • 1,2,3,4-butanetetracarboxylic dianhydride is preferred.
  • the compound (f) having one carboxylic acid anhydride group in the molecule is, for example, succinic anhydride, methyl succinic anhydride, ethyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, phthalic anhydride.
  • the compound (f) having one carboxylic anhydride group in the molecule can be used alone or in combination.
  • a cured product obtained by curing a polyvalent carboxylic acid resin and an epoxy resin is excellent, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, norbornane-2 3-dicarboxylic acid anhydride, methylnorbornane-2, 3-dicarboxylic acid anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and 2,4-diethylpentanedioic acid anhydride are preferred.
  • methylhexahydrophthalic anhydride 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 2,4-diethylpentanedioic anhydride, and particularly preferred is methylhexahydrophthalic anhydride. It is a thing.
  • the amount of compound (f) having one carboxylic anhydride group in the molecule is 100% of (h) when compound (h) having two or more carboxylic anhydride groups in the molecule is used.
  • the amount is preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, still more preferably 50 to 300 parts by weight with respect to parts by weight. If the amount is less than 5 parts by weight, the polyvalent carboxylic acid resin (C3) may be too high in molecular weight and workability may be inferior, and if it is more than 300 parts by weight, the mechanical strength of the cured product may be inferior.
  • the amount of the polyhydric alcohol compound (E), the compound (h) having two or more carboxylic anhydride groups in the molecule, and the compound (f) having one carboxylic anhydride group in the molecule is Compound (h) having two or more carboxylic anhydride groups in the molecule and compound (f) having one carboxylic anhydride group in the molecule with respect to 1 equivalent of the total alcoholic hydroxyl group of the alcohol compound (E)
  • the total carboxylic acid anhydride group is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents. If it is less than 0.5 equivalent, the mechanical strength of the cured product may be inferior, and if it is more than 2.0, a large amount of acid anhydride groups may remain, resulting in poor storage stability.
  • the production of the polyvalent carboxylic acid resin can be performed with or without a solvent.
  • the solvent does not react with the polyhydric alcohol compound (E), the compound (h) having two or more carboxylic anhydride groups in the molecule, and the compound (f) having one carboxylic anhydride group in the molecule.
  • Any solvent can be used without particular limitation.
  • solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone and methyl isobutyl ketone, toluene and xylene.
  • an aromatic hydrocarbon and ketones are preferable.
  • These solvents may be used alone or in combination of two or more.
  • the amount used is the polyhydric alcohol compound (E), the compound (h) having two or more carboxylic anhydride groups in the molecule, and the compound having one carboxylic anhydride group in the molecule. 0.5 to 300 parts by weight is preferable with respect to 100 parts by weight of the total of (f).
  • the polyvalent carboxylic acid resin (C3) can be produced without a catalyst or with a catalyst.
  • usable catalysts are hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, water Metal hydroxides such as calcium oxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, Heterocyclic compounds such as imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
  • a catalyst When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.
  • the amount used thereof is a polyhydric alcohol compound (E), a compound (h) having two or more carboxylic anhydride groups in the molecule, and a compound having one carboxylic anhydride group in the molecule. 0.05 to 10 parts by weight is preferable with respect to 100 parts by weight in total of (f).
  • a method for adding the catalyst it is added directly or used in a state dissolved in a soluble solvent or the like.
  • an alcoholic solvent such as methanol or ethanol or water means that an unreacted compound (h) having two or more carboxylic acid anhydride groups in the molecule or one carboxylic acid anhydride in the molecule. Since it reacts with the compound (f) having a physical group, it is preferable to avoid it.
  • the reaction temperature during the production of the polyvalent carboxylic acid resin (C3) depends on the amount of catalyst and the solvent used, but is usually preferably 20 to 160 ° C, more preferably 50 to 150 ° C, particularly preferably 60 to 145 ° C. is there.
  • the total reaction time is usually preferably 1 to 20 hours, more preferably 3 to 12 hours.
  • the reaction may be carried out in two or more stages. For example, the reaction may be carried out at 20 to 100 ° C. for 1 to 8 hours and then at 100 to 160 ° C. for 1 to 12 hours.
  • the compound (f) having one carboxylic acid anhydride group in the molecule is often highly volatile. When such a compound is used, the compound (f) is reacted at 20 to 100 ° C.
  • the catalyst can be removed by quenching and / or washing with water as necessary, but it is left as it is and used as a curing accelerator for the curable resin composition of the present invention.
  • 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.
  • 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.
  • the polycarboxylic acid resin (C3) thus obtained is usually a liquid having fluidity at 25 ° C.
  • the molecular weight is preferably from 800 to 80,000, more preferably from 1,000 to 10,000, and particularly preferably from 1500 to 8,000 as the weight average molecular weight measured by GPC.
  • the weight average molecular weight is less than 800, the fluidity at 25 ° C. may decrease, and when it exceeds 80,000, when a curable resin composition using the same is used, the compatibility with the epoxy resin described later is low. May be inferior.
  • the weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.
  • the acid value (measured by the method described in JIS K-2501) of the produced polycarboxylic acid resin (C3) is preferably 35 to 200 mgKOH / g, more preferably 50 to 180 mgKOH / g, particularly 60-150 mgKOH / g is preferred.
  • the functional group equivalent is less than 35 mgKOH / g, the mechanical properties of the cured product tend to deteriorate, and when it exceeds 150 mgKOH / g, the cured product tends to be hard and the elastic modulus tends to be too high.
  • the viscosity of the polycarboxylic acid resin (C3) (E-type viscometer, measured at 25 ° C.) is preferably from 50 to 800,000 mPa ⁇ s, more preferably from 500 to 100,000 mPa ⁇ s, particularly from 800 to The thing of 30,000 mPa * s is preferable.
  • the viscosity is less than 50 mPa ⁇ s, the viscosity is too low and may not be suitable when used as a sealing material or the like, and when it exceeds 800,000 mPa ⁇ s, the viscosity is too high or the sealing material or the like. May be inferior in workability.
  • two or more of acid anhydride (C1), polyvalent carboxylic acid (C2), and polyvalent carboxylic acid resin (C3) are used in combination as an epoxy resin curing agent. You can also.
  • solid polyvalent carboxylic acid (C2) is used in applications such as an optical semiconductor encapsulant that requires liquid at room temperature (25 ° C.)
  • liquid acid anhydride (C1) and / or polyvalent carboxylic acid It is desirable to use the resin (C3) in combination and use it as a liquid mixture.
  • the acid anhydride (C1) and / or the polyvalent carboxylic acid resin (C3) can be used in a proportion of 0.5 to 99.5% by weight of the total epoxy resin curing agent.
  • the curing agent other than the above-mentioned acid anhydride and / or polyvalent carboxylic acid resin and / or polyvalent carboxylic acid resin is used in combination as the epoxy resin curing agent
  • the acid anhydride and / or polyvalent carboxylic acid and / or polyhydric carboxylic acid are used.
  • the proportion of the total amount of the polyvalent carboxylic acid resin in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.
  • the curing agent that can be used in combination include amine compounds, amide compounds, phenol compounds, and the like.
  • curing agents that can be used include amines and polyamide compounds (such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and polyamide resins synthesized from linolenic acid dimer and ethylenediamine).
  • amines and polyamide compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and polyamide resins synthesized from linolenic acid dimer and ethylenediamine).
  • Polyphenols bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, fe (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyaceto
  • the curing accelerator any epoxy group-containing polyorganosiloxane (and an epoxy resin when used in combination) and an epoxy resin curing agent capable of accelerating the curing reaction can be used.
  • examples include ammonium salt curing accelerators, phosphonium salt curing accelerators, metal soap curing accelerators, imidazole curing accelerators, amine curing accelerators, phosphine curing accelerators, and phosphite curing accelerators. Agents, Lewis acid curing accelerators and the like.
  • the curing accelerator is preferably used in an amount of 0.001 to 15 parts by weight of the curing accelerator with respect to 100 parts by weight of the curable resin composition.
  • another curing catalyst (curing accelerator) can be used in combination as necessary.
  • the curing catalyst that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole) (1 ′)) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-diamino-6 (2′-di
  • Diaza compounds such as undecene-7 and the like Salts such as tetraphenylborate and phenol novolak, salts with the above polycarboxylic acids, or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide and other ammonium salts, triphenylphosphine, triphenylphosphine (Toluyl) phosphines such as phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, etc.
  • Salts such as tetraphenylborate and phenol novolak, salts with the above polycarboxylic acids, or
  • microcapsule type curing accelerator obtained by making these curing accelerators into microcapsules. 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 preferably used in the range of usually 0.001 to 15 parts by weight per 100 parts by weight of the epoxy resin.
  • the metal soap curing accelerator is excellent, and among the metal soap curing accelerators, a zinc carboxylate compound is particularly preferable.
  • the metal soap type curing accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, potassium octylate, calcium stearate, zinc stearate, magnesium stearate, stearin Aluminum oxide, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxyphosphate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, 12-hydroxystearic acid Barium, lithium 12-hydroxystearate, sodium 12-hydroxystearate, calcium montanate, zinc montanate, mon Magnesium phosphate, aluminum montanate, lithium montanate, lithium montanate, lithium montan
  • Carbons such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate, and zinc palmitate are used to obtain cured products with excellent transparency and sulfidation resistance.
  • Zinc salts composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as zinc carbonate of several tens to thirty and zinc 12-hydroxystearate can be preferably used.
  • a zinc salt composed of a monocarboxylic acid compound having 10 to 20 carbon atoms such as zinc stearate and zinc undecylenate, and a hydroxyl group such as zinc 12-hydroxystearate.
  • a zinc salt composed of a monocarboxylic acid compound having 15 to 20 carbon atoms can be preferably used, more preferably zinc stearate, zinc undecylenate and zinc 12-hydroxystearate, particularly preferably zinc stearate, 12- Zinc hydroxystearate can be used.
  • ammonium salt curing accelerator examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide.
  • Trimethylcetylammonium hydroxide Trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate and the like.
  • the phosphonium salt curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium diethylphosphate, and the like.
  • ammonium salt-based curing accelerators phosphonium salt-based curing accelerators, metal soap-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, and heterocyclic compound-based curing accelerators.
  • a phosphine-based curing accelerator, a phosphite-based curing accelerator, a Lewis acid-based curing accelerator, or the like can be used.
  • the curing accelerator described above can be used as a solid compound or a liquid compound at room temperature (25 ° C.).
  • a solid compound when used as a curing accelerator at room temperature (25 ° C.), it can be used by dissolving it in a resin in advance.
  • coupling agent in the curable resin composition of the present invention as necessary, it is possible to supplement the viscosity adjustment of the composition and the hardness of the cured product.
  • coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl.
  • Trimethoxysilane N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate
  • the curable resin composition of the present invention it is possible to supplement mechanical strength without impairing transparency by using a nano-order level inorganic filler as necessary.
  • the standard for the nano-order level is preferably an average particle diameter of 500 nm or less, and particularly preferably a filler having an average particle diameter of 200 nm or less from the viewpoint of transparency.
  • inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
  • the present invention is not limited to these.
  • These fillers may be used alone or in combination of two or more.
  • the content of these inorganic fillers is preferably such that it accounts for 0 to 95% by weight in the curable resin composition of the present invention.
  • a phosphor can be added to the curable resin composition of the present invention as necessary.
  • the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light.
  • the optical semiconductor is sealed.
  • fluorescent substance A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated.
  • phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO 3 : Ce, Y 3 Al 5 O 12 : Ce, Y 4 Al 2 O 9 : Ce, Y 2 O 2 S: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, (SrEu) O.Al 2 O 3 and the like are exemplified.
  • the particle size of such a phosphor those known in this field are used, and the average particle size is preferably 1 to 250 ⁇ m, particularly preferably 2 to 50 ⁇ m.
  • the addition amount is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight with respect to 100 parts by weight of the resin component.
  • a thixotropic imparting agent such as fine silica powder (also referred to as “aerosil” or “aerosol”) can be added for the purpose of preventing sedimentation of various phosphors during curing.
  • silica fine powder examples include Aerosil (trade name) 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974, AerosilR974. Aerosil R812S, Aerosil R805, RY200, RX200 (manufactured by Nippon Aerosil Co., Ltd.) and the like.
  • the curable resin composition of the present invention may contain an amine compound as a light stabilizer or a phosphorus compound and a phenol compound as an antioxidant.
  • the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (2,2,6) decanedioate , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-t
  • the following commercially available products can be used as the amine compound that is the light stabilizer.
  • the commercially available amine compound is not particularly limited.
  • TINUVIN trade name 765
  • TINUVIN 770DF TINUVIN 144
  • TINUVIN 123 TINUVIN 622LD
  • TINUVIN 152 and CHIMASSORB (trade name) 944 are manufactured by Ciba Specialty Chemicals.
  • ADEKA LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like can be mentioned.
  • the phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-
  • the commercially available phosphorus compounds are not particularly limited.
  • ADK STAB (trade name) PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A and the like.
  • the phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.
  • IRGANOX (trade name) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX manufactured by Ciba Specialty Chemicals 1098, IRGANOX 1520L, manufactured by Adeka
  • Adeka Stub (trade name) AO-20, Adeka Stub AO-30, Adeka Stub AO-40, Adeka Stub AO-50, Adeka Stub AO-60, Adeka Stub AO-70, Adeka Stub AO-80, Adeka Stub AO-90, ADK STAB AO-330, manufactured by Sumitomo Chemical Co., Ltd., Sumilizer (trade name) GA- 0, Sumilizer MDP-S, Sumilizer B
  • THINUVIN (trade name) 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB (trade name) 2020FDL, CHIMASSORB 119FL and the like can be cited as products manufactured by Ciba Specialty Chemicals.
  • the amount of the compound is not particularly limited, but with respect to the total weight of the curable resin composition of the present invention, A range of 0.005 to 5.0% by weight is preferred.
  • the curable resin composition of the present invention can be obtained by uniformly mixing the above components at room temperature or under heating. For example, mix thoroughly until uniform using an extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. Prepared.
  • the curable resin composition of the present invention is obtained by thoroughly mixing additives such as an epoxy group-containing polyorganosiloxane, an epoxy resin curing agent, a curing accelerator, an antioxidant, and a light stabilizer. It can be prepared and used as a sealing material.
  • additives such as an epoxy group-containing polyorganosiloxane, an epoxy resin curing agent, a curing accelerator, an antioxidant, and a light stabilizer. It can be prepared and used as a sealing material.
  • mixing method can be performed at room temperature or by heating using a kneader, a triple roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, or the like.
  • Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like.
  • Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material).
  • a wire such as a gold wire is connected to pass an electric current.
  • the semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens.
  • the curable resin composition of this invention can be used for this sealing material.
  • an injection method in which the sealing material is injected into the mold frame in which the optical semiconductor element is fixed is inserted and then heat-cured and then molded, and the sealing material is injected on the mold in advance.
  • a compression molding method is used in which an optical semiconductor element fixed on a substrate is immersed therein and heat-cured and then released from a mold.
  • the injection method include a dispenser.
  • methods such as hot air circulation, infrared rays and high frequency can be used.
  • the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours.
  • For the purpose of reducing internal stress generated during heat-curing for example, after pre-curing at 80 to 120 ° C.
  • X to Y indicates a range from X to Y, and the range includes X and Y.
  • Example 1 Synthesis of an epoxy group-containing polyorganosiloxane through production steps I and II (production step I) In a 500 ml four-necked flask made of glass, FCA107 (manufactured by Dow Corning Toray Co., Ltd., weight average molecular weight 1750, silanol equivalent 283 g / eq, 61.9 mol% phenyl group and 38.1 hydroxyl group in the above formula (1).
  • FCA107 manufactured by Dow Corning Toray Co., Ltd., weight average molecular weight 1750, silanol equivalent 283 g / eq, 61.9 mol% phenyl group and 38.1 hydroxyl group in the above formula (1).
  • the epoxy equivalent of the obtained compound was 437 g / eq
  • the weight average molecular weight was 3,800
  • the viscosity was 9651 mPa ⁇ s
  • the appearance was a colorless transparent liquid.
  • Example 2 Synthesis of an epoxy group-containing polyorganosiloxane through production steps I and II (production step I) In a 500 ml four-necked flask made of glass, 21.5 parts of FCA107 (silicone resin manufactured by Toray Dow Corning, Inc.), 82.0 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, FINISH WS62M (described above) Asahi Kasei Wacker's silanol-terminated silicone oil) 86.5 parts, 0.8% by weight KOH methanol solution, 7.3 parts of isopropyl alcohol, 124 parts of toluene, and Jimroth condenser, sales expansion device, thermometer installed And the flask was immersed in a water bath. The water bath was heated, the internal temperature was kept at 72 ° C., and the reaction was performed for 6 hours.
  • FCA107 silicone resin manufactured by Toray Dow Corning, Inc.
  • the epoxy equivalent of the obtained compound was 496 g / eq, the weight average molecular weight was 4444, the viscosity was 1731 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Example 3 Production Example of Epoxy Group-Containing Polysiloxane via Production Processes 1 to 3 (Production Process 1)
  • FCA 107 silicone resin manufactured by Toray Dow Corning Co., Ltd.
  • 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 95.4 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane
  • isopropyl alcohol The Dimroth condenser, the sales expansion device and the thermometer were installed, and the flask was immersed in a water bath.
  • the epoxy equivalent of the obtained compound was 432 g / eq, the weight average molecular weight was 5051, the viscosity was 6533 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Example 4 Production Example of Epoxy Group-Containing Polysiloxane via Production Processes 1 to 3 (Production Process 1)
  • FCA107 the above-mentioned silicone resin manufactured by Toray Dow Corning
  • 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 95.4 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane
  • isopropyl alcohol The Dimroth condenser, the sales expansion device and the thermometer were installed, and the flask was immersed in a water bath.
  • the epoxy equivalent of the obtained compound was 426 g / eq
  • the weight average molecular weight was 6094
  • the viscosity was 9216 mPa ⁇ s
  • the appearance was a colorless transparent liquid.
  • Example 5 Production Example of Epoxy Group-Containing Polysiloxane after Production Process I / II (Production Process I) In a 500 ml four-necked flask made of glass, SILRES 604 (manufactured by Asahi Kasei Wacker Co., Ltd., weight average molecular weight 2176, silanol equivalent 485 g / eq, 40.6 mol% phenyl group in the above formula (1), 27.4 mol% hydroxyl group.
  • SILRES 604 manufactured by Asahi Kasei Wacker Co., Ltd., weight average molecular weight 2176, silanol equivalent 485 g / eq, 40.6 mol% phenyl group in the above formula (1), 27.4 mol% hydroxyl group.
  • the epoxy equivalent of the obtained compound was 410 g / eq, the weight average molecular weight was 4267, the viscosity was 5328 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Example 6 Production Example of Epoxy Group-Containing Polysiloxane via Production Steps I and II (Production Step I) To a 500 ml four-necked flask made of glass, 33.8 parts of SILRES 604 (the above-mentioned silicone resin manufactured by Asahi Kasei Wacker), 106.0 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, FINISH WS62M (described above, Asahi Kasei Wacker's silanol-terminated silicone oil) 70.2 parts, 0.9 parts by weight of KOH methanol solution, 8.1 parts of isopropyl alcohol, 105 parts of methyl isobutyl ketone, Jimroth condenser, sales expansion equipment, thermometer installed And the flask was immersed in a water bath. The water bath was heated, the internal temperature was kept at 72 ° C., and the reaction was performed for 6 hours.
  • SILRES 604
  • the epoxy equivalent of the obtained compound was 422 g / eq, the weight average molecular weight was 5204, the viscosity was 36600 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Example 7 Production Example of Epoxy Group-Containing Polysiloxane after Production Process I / II (Production Process I) In a glass 500 ml four-necked flask, 36.4 parts of SILRES 604 (the aforementioned silicone resin manufactured by Asahi Kasei Wacker), 91.2 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, FINISH WS62M (described above, Asahi Kasei Wacker Co., Ltd.
  • SILRES 604 the aforementioned silicone resin manufactured by Asahi Kasei Wacker
  • 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane FINISH WS62M (described above, Asahi Kasei Wacker Co., Ltd.
  • Silanol-terminated silicone oil 82.4 parts, 0.9 parts by weight of 5% by weight KOH methanol solution, 8.1 parts of isopropyl alcohol, 105 parts of methyl isobutyl ketone, charged with Jimroth condenser, sales expansion device and thermometer And the flask was immersed in a water bath. The water bath was heated, the internal temperature was kept at 72 ° C., and the reaction was performed for 6 hours.
  • the epoxy equivalent of the obtained compound was 499 g / eq
  • the weight average molecular weight was 5476
  • the viscosity was 10033 mPa ⁇ s
  • the appearance was a colorless transparent liquid.
  • Example 8 Production Example of Epoxy Group-Containing Polysiloxane after Production Process I / II (Production Process I)
  • SILRES 604 the aforementioned silicone resin manufactured by Asahi Kasei Wacker
  • 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane FINISH WS62M (described above, Asahi Kasei Wacker's Silanol-terminated silicone oil) 98.2 parts, 0.9 parts of 5 wt% KOH methanol solution, 8.1 parts of isopropyl alcohol, 116 parts of methyl isobutyl ketone, and Jimroth condenser, sales expansion device, thermometer installed
  • the flask was immersed in a water bath. The water bath was heated, the internal temperature was kept at 72 ° C., and the reaction was performed for 6 hours.
  • the epoxy equivalent of the obtained compound was 482 g / eq, the weight average molecular weight was 5181, the viscosity was 2458 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Example 9 Production example of epoxy group-containing polysiloxane through production steps 1 to 3 (production step 1)
  • FCA107 the above-mentioned silicone resin manufactured by Toray Dow Corning
  • 84.1 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 7. 3 parts were charged, a Jimroth condenser, a sales expansion device and a thermometer were installed, and the flask was immersed in a water bath.
  • the epoxy equivalent of the obtained compound was 474 g / eq, the weight average molecular weight was 6009, the viscosity was 1454 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Example 10 Production example of epoxy group-containing polysiloxane after production steps 1 to 3 (production step 1)
  • FCA107 the above-mentioned silicone resin manufactured by Toray Dow Corning Co., Ltd.
  • 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane isopropyl alcohol 7. 3 parts were charged, a Jimroth condenser, a sales expansion device and a thermometer were installed, and the flask was immersed in a water bath.
  • the epoxy equivalent of the obtained compound was 566 g / eq
  • the weight average molecular weight was 10158
  • the viscosity was 1910 mPa ⁇ s
  • the appearance was a colorless transparent liquid.
  • Example 13 Production Example of Epoxy Group-Containing Polysiloxane after Production Process I / II (Production Process I)
  • SILRES 603 manufactured by Asahi Kasei Wacker, weight average molecular weight 1500, silanol equivalent 567 g / eq, in the above formula (1), the phenyl group is 83.7 mol%, the hydroxyl group is 16.3 mol%.
  • SILRES 603 was dissolved in 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane while maintaining the internal temperature at 60 ° C. and stirring for 30 minutes. Thereafter, X-21-5841 (manufactured by Shin-Etsu Chemical Co., Ltd., silanol-terminated silicone oil having a weight average molecular weight of 1000 and a silanol equivalent of 500 g / eq) 80.1 parts, 0.9 parts of 5 wt% KOH methanol solution, isopropyl alcohol 8. 1 part was charged, the water bath was heated, the internal temperature was kept at 72 ° C., and the reaction was carried out for 8 hours.
  • X-21-5841 manufactured by Shin-Etsu Chemical Co., Ltd., silanol-terminated silicone oil having a weight average molecular weight of 1000 and a silanol equivalent of 500 g / eq
  • the epoxy equivalent of the obtained compound was 463 g / eq, the weight average molecular weight was 7445, the viscosity was 6835 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Comparative Example 1 Example using an organic base compound as a catalyst (Production Process 1) In a glass 500 ml four-necked flask, 20 parts of FCA107 (the above-mentioned silicone resin manufactured by Toray Dow Corning), 95.4 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 7.3 parts of isopropyl alcohol The Dimroth condenser, the sales expansion device and the thermometer were installed, and the flask was immersed in a water bath. The water bath was heated and the internal temperature was kept at 60 ° C.
  • FCA107 the above-mentioned silicone resin manufactured by Toray Dow Corning
  • 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 7.3 parts of isopropyl alcohol
  • the Dimroth condenser, the sales expansion device and the thermometer were installed, and the flask was immersed in a water bath. The water bath was heated and the internal temperature was kept
  • Silicone resin FCA107 manufactured by Toray Dow Corning a-2
  • Silicone resin SILRES604 manufactured by Asahi Kasei Wacker a-3
  • Silicone resin SILRES603 manufactured by Asahi Kasei Wacker b-1
  • 2- 3-,4-epoxycyclohexyl) ethyltrimethoxysilane c-1
  • silicone oil from Asahi Kasei Wacker, FINISH WS62M c-2 Silicone oil XC96-723 manufactured by Momentive c-3: Silicone oil X-21-5841 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Examples 1 to 10 and 13 are all obtained with a colorless and transparent liquid resin, and can be obtained with appropriate epoxy equivalent, viscosity, and weight average molecular weight, and are particularly suitable as a liquid epoxy resin for optical applications. It could be confirmed.
  • Synthesis Example 1 Production Example of Epoxy Group-Containing Polysiloxane Using Silicone Resin through Production Process I / II (Production Process I)
  • a glass 500 ml four-necked flask 86.9 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, XC96-723 (the aforementioned Silanol-terminated silicone oil made by Momentive) 103.8 parts, 5% by weight
  • a KOH methanol solution 0.8 part and isopropyl alcohol 7.3 parts were charged, a Dimroth condenser, a sales expansion device, and a thermometer were installed, and the flask was immersed in a water bath. The water bath was heated, the internal temperature was kept at 72 ° C., and the reaction was carried out for 10 hours.
  • an epoxy group-containing polyorganosiloxane (A-11) containing no silicone resin was obtained 154 parts of an epoxy group-containing polyorganosiloxane (A-11) containing no silicone resin.
  • the epoxy equivalent of the obtained compound was 473 g / eq, the weight average molecular weight was 6511, the viscosity was 845 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Synthesis Example 2 Production Example of Epoxy Group-Containing Polysiloxane Using Silanol-Terminated Silicone Oil Containing Phenyl Group as Silanol-Terminated Silicone Oil without Using Silicone Resin through Production Process I / II (Production Process I)
  • the organic layer contains an epoxy group using a silanol-terminated silicone oil containing a phenyl group as a silanol-terminated silicone oil without using a silicone resin that has undergone production steps I and II.
  • 731 parts of polysiloxane (A-12) were obtained.
  • the epoxy equivalent of the obtained compound was 491 g / eq, the weight average molecular weight was 2090, the viscosity was 3328 mPa ⁇ s, and the appearance was a colorless transparent liquid.
  • Synthesis Example 3 Carbinol-modified silicone oil (d) at both ends, terminal alcohol polyester compound (i), compound (h) having two or more carboxylic anhydride groups in the molecule, and one in the molecule
  • polyvalent carboxylic acid resin which is epoxy resin curing agent (B) obtained by addition reaction with compound (f) having carboxylic anhydride group Glass equipped with stirrer, Dimroth condenser and thermometer
  • 47.1 parts of both-end carbinol-modified silicone X22-160AS manufactured by Shin-Etsu Chemical Co., Ltd.
  • Adeka New Ace Y9-10 made by ADEKA Corporation
  • a polyester polyol the above formula (6 polyester polyol) 11.8 parts R 12 is butyl and R 11 is neopentyl group in), RIKACID BT-10 (1,2,3,4-butanetetracarboxylic dianhydride, manufactured by Shin Nippon Rika Co.,
  • Example 11 100 parts of the epoxy group-containing polyorganosiloxane (A-2) obtained in Example 2, 63.2 parts of the polyvalent carboxylic acid resin (B-1) obtained in Synthesis Example 3, and a curing accelerator As described above, 0.5 part of zinc 2-ethylhexanoate was placed in a polypropylene container, mixed and degassed for 5 minutes to obtain a curable resin composition for sealing an optical semiconductor of the present invention.
  • Example 12 100 parts of the epoxy group-containing polyorganosiloxane (A-9) obtained in Example 9, 66.7 parts of the polyvalent carboxylic acid resin (B-1) obtained in Synthesis Example 3, and a curing accelerator As described above, 0.5 part of zinc 2-ethylhexanoate was placed in a polypropylene container, mixed and degassed for 5 minutes to obtain a curable resin composition for sealing an optical semiconductor of the present invention.
  • Comparative Example 2 100 parts of an epoxy group-containing polyorganosiloxane (A-11) not using the silicone resin obtained in Synthesis Example 1 as a raw material, and the polyvalent carboxylic acid resin (B-1) 66 obtained in Synthesis Example 3 .8 parts and 0.5 parts of zinc 2-ethylhexanoate as a curing accelerator were placed in a polypropylene container, mixed and degassed for 5 minutes to obtain a curable resin composition for optical semiconductor encapsulation.
  • Table 2 shows the blending ratios of the curable resin compositions for sealing an optical semiconductor obtained in Examples 11 to 12 and Comparative Examples 2 to 3, and the results of hardness, transmittance, sulfidation resistance, and tack test of the cured products. Shown in The test in Table 2 was performed as follows.
  • the durometer A hardness was measured by the method described in JIS K-7215.
  • (2) Cured product transmittance and cured post-heat cured product transmittance The curable resin composition for sealing an optical semiconductor obtained in Examples 11 to 12 and Comparative Examples 2 to 3 was vacuum degassed for 5 minutes, and then 30 mm ⁇ The mold was gently cast on a glass substrate on which a dam was created with a heat-resistant tape so that the height was 20 mm and the height was 0.8 mm. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained specimen was measured for light transmittance at 400 nm under the following conditions.
  • Spectrophotometer measurement conditions Manufacturer Hitachi High-Technologies Corporation Model: U-3300 Slit width: 2.0nm Scan speed: 120 nm / min
  • 120mm x 180mm x 36mmt polypropylene made from a sealed surface-mount LED with two glass containers (open lid) with an opening diameter of 0.6cm and a height of 3.5cm containing 1ml of 20% ammonium sulfide aqueous solution It put into the airtight container and left to stand in a 25 degreeC thermostat. The discoloration of the silver-plated portion on the bottom surface was visually confirmed every 2 hours. The time when it was confirmed that the silver plating on the bottom surface was severely discolored was entered.
  • the LED-A after sealing is fixed to a 1 g aluminum plate using double-sided tape so that the opening is on top, and the LED-B is placed on the LED-A so that the respective openings are in contact with each other.
  • the LED-B was pressed for 5 seconds. After that, when only LED-B is lifted with tweezers, the sample lifted with 1 g of aluminum metal plate makes a judgment (D) that there is tack (stickiness), and LED-B peels off from LED-A.
  • the sample which raised only B was judged (A) without tack (stickiness).
  • A-2, A-9, A-11, A-12, and B-1 represent the compounds obtained in the above Examples and Comparative Examples.
  • Comparative Example 2 using an epoxy group-containing polysiloxane that does not use a silicone resin as a raw material is suitable for optical semiconductor sealing applications in terms of viscosity, hardness, and cured product transmittance after mixing.
  • Comparative Example 3 the viscosity and hardness after mixing and the cured product transmittance are suitable for optical semiconductor sealing applications, but they are excellent in sulfidation resistance but inferior in tackiness.
  • Examples 11 to 12 In addition to its appropriate physical properties, it has excellent sulfidation resistance and tackiness.
  • the epoxy group-containing polyorganosiloxane of the present invention and the curable resin composition containing the epoxy group are excellent in heat-resistant transparency and sulfidation resistance, and further provide a low-tack cured product. Therefore, it can be suitably used as a sealing resin for optical semiconductors (such as LEDs).

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne un polyorganosiloxane contenant un groupe époxy dans lequel une structure de résine de silicone (A) présentant une structure spécifique, une structure de silasesquioxanes contenant un groupe époxy (B) présentant une structure spécifique, et une structure d'huile de silicone (C) présentant une structure spécifique sont liées, les terminaisons étant un groupe alcoxy possédant de 1 à 10 atomes de carbone et/ou un groupe silanol.
PCT/JP2014/066888 2013-06-26 2014-06-25 Polyorganosiloxane contenant un groupe époxy et composition de résine durcissable le contenant Ceased WO2014208619A1 (fr)

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JP2017001900A (ja) * 2015-06-05 2017-01-05 信越化学工業株式会社 ナノ粒子、ナノ粒子の製造方法、付加硬化型シリコーン樹脂組成物、及び半導体装置
KR20180103115A (ko) * 2016-01-15 2018-09-18 페르녹스 가부시키가이샤 축합반응형 실리콘 조성물 및 경화물

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CN108892776A (zh) * 2018-04-13 2018-11-27 湖北航泰科技有限公司 一种有机硅改性的环氧树脂及其制备方法
JP7021046B2 (ja) * 2018-10-22 2022-02-16 信越化学工業株式会社 付加硬化型シリコーン組成物、シリコーン硬化物、及び、光学素子

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KR102081074B1 (ko) 2016-01-15 2020-02-25 페르녹스 가부시키가이샤 축합반응형 실리콘 조성물 및 경화물

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