WO2010001992A1 - Composition de résine modifiée, son procédé de fabrication de celle-ci et composition de résine durcissable la contenant - Google Patents

Composition de résine modifiée, son procédé de fabrication de celle-ci et composition de résine durcissable la contenant Download PDF

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Publication number
WO2010001992A1
WO2010001992A1 PCT/JP2009/062201 JP2009062201W WO2010001992A1 WO 2010001992 A1 WO2010001992 A1 WO 2010001992A1 JP 2009062201 W JP2009062201 W JP 2009062201W WO 2010001992 A1 WO2010001992 A1 WO 2010001992A1
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resin composition
group
alkoxysilane compound
modified resin
composition according
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PCT/JP2009/062201
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English (en)
Japanese (ja)
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光代 秋元
光武 中村
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旭化成ケミカルズ株式会社
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Priority to CN2009801247757A priority Critical patent/CN102076734B/zh
Publication of WO2010001992A1 publication Critical patent/WO2010001992A1/fr

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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45147—Copper (Cu) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a modified resin composition obtained by reacting an epoxy resin and an alkoxysilane compound, a method for producing the same, a curable resin composition containing the composition, and a use thereof.
  • an epoxy resin composition using an acid anhydride-based curing agent gives a transparent cured product and has high heat resistance and adhesiveness. Therefore, a light emitting diode (hereinafter abbreviated as LED) and a photodiode are used. It has been suitably used as an encapsulating resin for optical semiconductors.
  • a resin for LED sealing in addition to the conventionally required good transparency and high heat resistance and adhesiveness, in addition to heat discoloration, light resistance, and thermal cycle
  • a cured product having excellent crack resistance and having no surface tack is desired, and a composition comprising a conventionally used epoxy resin such as a bisphenol A epoxy resin or a bisphenol F epoxy resin is used.
  • the modified resin composition has not only the excellent transparency and heat resistance of the epoxy resin, and a cured product having no surface tackiness, but also the light resistance and oxidation resistance of the cured product of silicone. Furthermore, it is expected to have flexibility.
  • Patent Document 1 contains a T structure as an essential repeating unit, and contains an epoxy group-containing organic group in a range of 0.1 to 40 mol% with respect to all organic groups bonded to a silicon atom in one molecule.
  • a modified resin composition has been proposed.
  • Patent Document 2 describes a composition containing a silicone compound having a molecular weight in a specific range and having at least two epoxy groups in one molecule and its use for an optical semiconductor sealing material.
  • Patent Documents 3 to 5 disclose resin compositions obtained by mixing an epoxy resin and a precondensed silicone resin.
  • Patent Documents 6 to 11 disclose resin compositions obtained by mixing an epoxy resin and alkoxysilanes or a partial condensate thereof and then subjecting to a dealcoholization reaction.
  • Patent Document 12 discloses a resin composition consisting of a modified phenoxy resin and an epoxy resin containing an alkoxy group twice the number of Si atoms in the molecule.
  • the resin compositions described in Patent Documents 1 and 2 have insufficient light resistance, and are not yet satisfactory in terms of crack resistance and adhesiveness. Furthermore, the modified resin composition described above has low storage stability in some cases, and the viscosity of the resin tends to increase remarkably during storage, so it cannot be said that it has sufficient practicality.
  • the composition obtained by mixing a silicone resin precondensed in the absence of an epoxy resin with an epoxy resin described in Patent Documents 3 to 5 has low storage stability, and the composition of the resin during storage is low. Viscosity tends to increase significantly. Furthermore, in some cases, it cannot be said that the epoxy resin and the silicone resin are sufficiently practical, for example, the epoxy resin and the silicone resin cannot be mixed uniformly.
  • the present invention can form a cured product having good transparency, excellent heat resistance, heat discoloration, light resistance, and crack resistance in thermal cycle, and good.
  • An object is to provide a modified resin composition having storage stability.
  • the present invention has excellent light-emitting components such as LEDs, excellent adhesion to elements and package materials, no cracks, and little decrease in luminance over a long period of time, and can be injection-molded and hardened after curing. It is an object of the present invention to provide an optical lens having excellent step stability and light resistance, and a semiconductor device using the light emitting component and / or the optical lens.
  • Another object of the present invention is to provide a photosensitive composition that can suppress inhibition of polymerization due to oxygen and has excellent adhesion, a coating agent containing the composition, and a coating film obtained by curing the coating agent.
  • Another object of the present invention is to provide a fluorescent resin composition excellent in dispersion stability of a phosphor and a phosphorescent material using the fluorescent resin composition.
  • Another object of the present invention is to provide a conductive resin composition that is excellent in fluidity, conductivity, and adhesiveness and does not generate voids.
  • Another object of the present invention is to provide an insulating resin composition that is excellent in fluidity, insulation, and adhesiveness and that does not generate voids.
  • the present inventor is a modified resin composition obtained by reacting an epoxy resin and a specific alkoxysilane compound at a specific ratio, wherein the resin composition It has been found that the above problems can be solved by adjusting the amount of residual alkoxy groups in the product to a specific range, and the present invention has been completed.
  • a modified resin composition obtained by reacting an epoxy resin (A) with an alkoxysilane compound represented by the following general formula (1), (R 1 ) n —Si— (OR 2 ) 4-n (1)
  • R 1 represents an integer of 0 or more and 3 or less.
  • each R 1 is independently selected from a hydrogen atom, a) a structure group consisting of an unsubstituted or substituted chain, branched, and cyclic structure.
  • each R 2 independently has a hydrogen atom, d) an unsubstituted or substituted aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of a chain, a branch, and a ring.
  • One or more organic groups selected from the group consisting of monovalent organic groups having 1 to 8 carbon atoms are shown.
  • the content (mol%) of the component (C) in the alkoxysilane compound is shown.) And the modified resin composition whose residual alkoxy group amount in the said modified resin composition is 5% or less.
  • the content (mol%) of the compound is shown, and 0 ⁇ ⁇ ( ⁇ n0) / ( ⁇ n0 + ⁇ n1 + ⁇ n2) ⁇ ⁇ 0.1.
  • n represents an integer of 0 or more and 3 or less.
  • each R 1 is independently selected from a hydrogen atom, a) a structure group consisting of an unsubstituted or substituted chain, branched, and cyclic structure.
  • each R 2 independently has a hydrogen atom, d) an unsubstituted or substituted aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of a chain, a branch, and a ring.
  • One or more organic groups selected from the group consisting of monovalent organic groups having 1 to 8 carbon atoms are shown.
  • (B) n 1 or 2 and at least one alkoxysilane compound having at least one cyclic ether group as R 1 .
  • (C) n 1 or 2, and at least one alkoxysilane compound having at least one aromatic organic group as R 1 .
  • n represents an integer of 0 or more and 3 or less.
  • each R 1 is independently selected from a hydrogen atom, a) a structure group consisting of an unsubstituted or substituted chain, branched, and cyclic structure.
  • each R 2 independently has a hydrogen atom, d) an unsubstituted or substituted aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of a chain, a branch, and a ring.
  • One or more organic groups selected from the group consisting of monovalent organic groups having 1 to 8 carbon atoms are shown.
  • (B) n 1 or 2 and at least one alkoxysilane compound having at least one cyclic ether group as R 1 .
  • (C) n 1 or 2, and at least one alkoxysilane compound having at least one aromatic organic group as R 1 .
  • the content (mol%) of the compound is shown, and 0 ⁇ ⁇ ( ⁇ n0) / ( ⁇ n0 + ⁇ n1 + ⁇ n2) ⁇ ⁇ 0.1.
  • a semiconductor device comprising the light-emitting component according to [26] and / or the optical lens according to [27].
  • a curable resin composition obtained by further adding a curing accelerator (I) to the resin composition according to any one of the above [20] to [22].
  • a photosensitive resin composition obtained by further adding a photoacid generator (J) to the resin composition according to any one of the above [20] to [22].
  • a modified resin composition capable of forming a cured product having excellent light resistance and thermal shock resistance (crack resistance in a thermal cycle) and having good storage stability. It becomes possible to do.
  • a cross-sectional view of a bullet-type LED is shown.
  • a cross-sectional view of an SMD type LED is shown.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. This invention is not limited to the form shown below.
  • the modified resin composition in the present embodiment is a modified resin composition obtained by reacting an epoxy resin (A) with an alkoxysilane compound represented by the following general formula (1), (R 1 ) n —Si— (OR 2 ) 4-n (1) (Here, n represents an integer of 0 or more and 3 or less.
  • each R 1 is independently selected from a hydrogen atom, a) a structure group consisting of an unsubstituted or substituted chain, branched, and cyclic structure.
  • each R 2 independently has a hydrogen atom, d) an unsubstituted or substituted aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of a chain, a branch, and a ring.
  • One or more organic groups selected from the group consisting of monovalent organic groups having 1 to 8 carbon atoms are shown.
  • the epoxy resin (A) used in the present embodiment is not particularly limited.
  • an alicyclic epoxy resin an aliphatic epoxy resin, a polyfunctional epoxy resin composed of a glycidyl ether product of a polyphenol compound, or a glycidyl ether of a novolac resin.
  • polyfunctional epoxy resins aromatic epoxy resin nuclear hydrides, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and the like. These epoxy resins may be used alone or in combination.
  • the alicyclic epoxy resin that can be used in the present embodiment is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include a cyclohexene oxide group, a tricyclodecene oxide group, and a cyclopentene.
  • An epoxy resin having an oxide group or the like can be given.
  • Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate as monofunctional alicyclic epoxy compounds.
  • bifunctional alicyclic epoxy compound examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di
  • polyfunctional alicyclic epoxy compound examples include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Furthermore, as what is marketed as a polyfunctional alicyclic epoxy compound, Epolide GT401, EHPE3150 (made by Daicel Chemical Industries Ltd.), etc. are mentioned.
  • the aliphatic epoxy resin that can be used in the present embodiment is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, penta Examples thereof include glycidyl ethers of polyhydric alcohols such as erythritol and xylylene glycol derivatives.
  • the polyfunctional epoxy resin comprising a glycidyl etherified product of a polyphenol compound that can be used in the present embodiment is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′- Biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1 -(4-Hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol ), 4, '-Butylidene-bis (3-methyl-6-t-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t
  • a typical example of a polyfunctional epoxy resin that is a glycidyl etherified product of phenols having a bisphenol skeleton is shown below.
  • these repeating units are not particularly limited, but preferably 0 or more and 50 It is less than the range. If the number of repeating units is 50 or more, the fluidity is lowered, which may cause a practical problem. From the viewpoint of increasing the reactivity with the alkoxysilane compounds and further from the viewpoint of increasing the fluidity of the resulting modified resin composition, the range of the repeating unit is preferably in the range of 0.001 to 10, more preferably 0.00. The range is from 01 to 2.
  • the polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol.
  • Glycidyl etherified products of various novolac resins such as novolak resins made from various phenols such as chlorophenols, phenol novolak resins containing xylylene skeleton, phenol novolac resins containing dicyclopentadiene skeleton, biphenyl skeleton containing phenol novolac resins, fluorene skeleton containing phenol novolac resins Etc.
  • polyfunctional epoxy resins that are glycidyl etherified products of novolak resins.
  • the nuclear hydride of the aromatic epoxy resin that can be used in the present embodiment is not particularly limited, and for example, a glycidyl etherified product of a phenol compound (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.). Or a nuclear hydride of an aromatic ring of various phenols (phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.), a nucleid hydride of a glycidyl etherified product of a novolac resin Etc.
  • a nuclear hydride of an aromatic ring of various phenols phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.
  • heterocyclic epoxy resin there is no limitation in particular as a heterocyclic epoxy resin,
  • the heterocyclic epoxy resin etc. which have heterocyclic rings, such as an isocyanuric ring and a hydantoin ring, are mentioned.
  • the glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins made of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
  • the glycidylamine-based epoxy resin is not particularly limited, and examples thereof include an epoxy resin obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. It is done.
  • Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited.
  • brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as chlorinated bisphenol A.
  • a cured product obtained by curing the target modified resin composition of the present embodiment which is easily obtained, has excellent transparency, heat resistance, heat discoloration resistance, light resistance, and thermal cycle time. Therefore, polyfunctional epoxy resins composed of alicyclic epoxy resins, aliphatic epoxy resins, and glycidyl ethers of polyphenol compounds are preferred, and alicyclic epoxy resins and glycidyl ethers of polyphenol compounds are preferred. More preferred is a polyfunctional epoxy resin made of glycidyl etherified product of a polyphenol compound, still more preferred is a bisphenol A type epoxy resin.
  • the viscosity at 25 ° C. of the epoxy resin (A) used in the present embodiment is not particularly limited. However, since the fluidity as a liquid is ensured and the compatibility with the alkoxysilane compound tends to be improved,
  • the liquid is preferably 1000 Pa ⁇ s or less, more preferably 500 Pa ⁇ s or less, still more preferably 300 Pa ⁇ s or less, and particularly preferably 100 Pa ⁇ s or less.
  • the epoxy equivalent (WPE) of the epoxy resin (A) used in the present embodiment is not particularly limited, but is preferably 100 g / eq or more from the viewpoint of enhancing the storage stability of the modified resin composition of the present embodiment. From the viewpoint of improving crack resistance of a cured product obtained by curing the modified resin composition of the present embodiment, it is preferably 700 g / eq or less, more preferably in the range of 100 g / eq to 500 g / eq, The range of 100 g / eq or more and 300 g / eq or less is more preferable.
  • the alkoxysilane compound that can be used in this embodiment refers to a silicon compound having 1 to 4 alkoxyl groups, and is represented by the following general formula (1).
  • (R 1 ) n —Si— (OR 2 ) 4-n (1) (Here, n represents an integer of 0 or more and 3 or less.
  • each R 1 is independently selected from a hydrogen atom, a) a structure group consisting of an unsubstituted or substituted chain, branched, and cyclic structure.
  • each R 2 independently has a hydrogen atom, d) an unsubstituted or substituted aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of a chain, a branch, and a ring.
  • One or more organic groups selected from the group consisting of monovalent organic groups having 1 to 8 carbon atoms are shown.
  • the cyclic ether group in this embodiment refers to an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered cyclic ether group is particularly preferable.
  • each R 1 is independently a hydrogen atom, a) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more structures selected from a chain, branched, or cyclic structure group An organic group containing a cyclic ether group having 4 or more and 24 or less carbon atoms and 1 or more and 5 or less oxygen atoms, and b) an unsubstituted or substituted structural group consisting of a chain, a branched, and a ring A monovalent aliphatic organic group having an aliphatic hydrocarbon unit of at least one selected structure and having 1 to 24 carbon atoms and 0 to 5 oxygen atoms, c) an unsubstituted or substituted fragrance Carbon group having an aliphatic hydrocarbon unit having one or more types of structures selected from the group consisting of a chain, a branched chain and a ring, which is an aromatic hydrocarbon unit, which is unsubstituted
  • Examples of the organic group containing a cyclic ether group consisting of 1 to 5 include oxyglycidyl groups having 4 or less carbon atoms such as ⁇ -glycidoxyethyl, ⁇ -glycidoxypropyl, ⁇ -glycidoxybutyl, etc.
  • Glycidoxyalkyl group glycidyl group, ⁇ - (3,4-epoxycyclohexyl) ethyl group, ⁇ - (3,4-epoxycyclohexyl) propyl group, ⁇ - (3,4-epoxycycloheptyl) ethyl group ⁇ - (3,4-epoxycyclohexyl) propyl group, ⁇ - (3,4-epoxycyclohexyl) butyl group, ⁇ - (3,4-epoxycyclohexyl) pentyl Alkyl group substituted with a cycloalkyl group having a carbon number of 5-8 having an oxirane group and the like.
  • the monovalent aliphatic organic group in which is 0 or more and 5 or less include: (B-1) Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n- Chains composed of aliphatic hydrocarbons such as hexyl, n-heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa
  • the monovalent aromatic organic group having an aliphatic hydrocarbon unit and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms include, for example, phenyl group, tolyl group, xylyl group, benzyl group, ⁇ -Methylstyryl group, 3-methylstyryl group, 4-methylstyryl group and the like.
  • the alkoxysilane compound may be a mixture of two or more different organic groups as described in a) to c) above.
  • the organic group is a hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, halogen atom such as fluorine or chlorine, or ester bond. Furthermore, it may contain heteroatoms such as nitrogen, phosphorus and sulfur excluding oxygen and silicon atoms. Further, the above a) to c) may be an organic group in which one kind or two or more kinds are mixed.
  • the light resistance of the cured product obtained by curing the modified resin composition of the present embodiment tends to be good, or the stability during storage tends to increase, so the total of all Si units Hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, halogen atom such as fluorine or chlorine, or ester bond, and nitrogen, phosphorus other than oxygen atom and silicon atom, phosphorus,
  • the total number of moles of silicon atoms to which an organic group containing a hetero atom such as sulfur is bonded is preferably 10% or less, more preferably 1% or less, and still more preferably not contained at all.
  • the total number of monovalent aliphatic organic groups such as vinyl group, allyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group and hexenyl group is preferably 10% or less, and preferably 5% More preferably, it is more preferably 1% or less, and particularly preferably not contained at all.
  • the organic group R 1 of the general formula (1) in the present embodiment includes the above a), b-1), b-2) and c) are preferably selected from the group consisting of a) and carbon such as ⁇ -glycidoxyethyl, ⁇ -glycidoxypropyl, ⁇ -glycidoxybutyl, etc.
  • a glycidoxyalkyl group glycidyl group, ⁇ - (3,4-epoxycyclohexyl) ethyl group, ⁇ - (3,4-epoxycyclohexyl) propyl group, ⁇ - (3,4 -Epoxycycloheptyl) ethyl group, ⁇ - (3,4-epoxycyclohexyl) propyl group, ⁇ - (3,4-epoxycyclohexyl) butyl group, ⁇ - (3,4-epoxycyclohexyl) pentyl A group, an organic group selected from the group consisting of 1 to 8 carbon atoms in b-1) and b-2) and an oxygen number of 0, and a group selected from the group consisting of a phenyl group and a benzyl group.
  • a) is a glycidoxyalkyl group, glycidyl group, ⁇ -glycidoxyethyl, ⁇ -glycidoxypropyl, ⁇ -glycidoxybutyl, or the like having an oxyglycidyl group having 4 or less carbon atoms bonded thereto.
  • each R 2 is independently a hydrogen atom, d) an unsubstituted or substituted aliphatic hydrocarbon unit having at least one structure selected from a chain, branched, or cyclic structure group.
  • Examples of the monovalent organic group having 1 to 8 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, sec- Butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl Chain organic groups composed of aliphatic hydrocarbons such as heptadecyl group and octadecyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methyl Examples thereof include organic groups composed of hydrocarbons containing cyclic units such as a
  • the alkoxysilane compound may be a mixture of two or more different organic groups in d). These may be organic groups in which one kind or two or more kinds are mixed.
  • a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable, and a methyl group and an ethyl group are more preferable because the reactivity of the alkoxysilane compound tends to increase.
  • component (B) used in the present embodiment include, for example, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl ( Methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) Dimethoxysilane, 2,3-epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysila ,
  • component (C) used in the present embodiment include, for example, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, Examples thereof include diphenyldiethoxysilane and phenyltrimethoxysilane. These can be used as one kind or a mixture of two or more kinds.
  • n 0, which indicates the number of R 1 in the general formula (1), specifically, as other components.
  • alkoxysilane compound in which four (OR 2 ) are bonded examples include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. These can be used as one kind or a mixture of two or more kinds.
  • the mixing index ⁇ is 0.001 or more for ensuring the fluidity and storage stability of the modified resin composition, while the flowability of the modified resin composition and the resistance of the cured product are In order to ensure cracking properties, it is necessary to set the range to 19 or less.
  • the value of ⁇ is more preferably in the range of 0.2 to 5, more preferably 0.3 to 2.
  • the amount of residual alkoxy groups in the composition is 5% or less. If the residual alkoxy group exceeds 5%, the cured product obtained by curing the composition has insufficient crack resistance and adhesiveness during thermal cycling.
  • the amount of residual alkoxy groups in the modified resin composition is more preferably 3% or less, further preferably 1% or less, still more preferably 0.5% or less, and particularly preferably not contained at all.
  • the quantitative value of the amount of residual alkoxy groups was calculated by calculating the area ratio between the internal standard peak obtained by H-NMR measurement using 1,1,2,2-tetrabromoethane as the internal standard substance and the peak derived from the residual alkoxy group. Can be obtained. Specifically, it can be determined by the following method and analysis method.
  • ⁇ H-NMR measurement> 10 mg of the modified resin composition, 20 mg of an internal standard substance (1,1,2,2-tetrabromoethane; Tokyo Chemical Industry), and 970 mg of deuterated chloroform are uniformly mixed to obtain an H-NMR measurement solution. .
  • the H-NMR spectrum of the above solution (1) is measured under the following conditions. Equipment: “ ⁇ -400” manufactured by JEOL Ltd.
  • the liquid is preferably 1,000 Pa ⁇ s or less, more preferably 500 Pa ⁇ s or less, still more preferably 300 Pa ⁇ s or less, and further preferably 100 Pa ⁇ s or less. It is particularly preferred that it is s or less.
  • the mixing index ⁇ used in the present embodiment will be described.
  • Mixing index ⁇ ⁇ ( ⁇ n2) / ( ⁇ n0 + ⁇ n1) ⁇ (3)
  • the content (mol%) of the compound is shown, and 0 ⁇ ⁇ ( ⁇ n0) / ( ⁇ n0 + ⁇ n1 + ⁇ n2) ⁇ ⁇ 0.1.
  • the mixing index ⁇ is obtained by curing the modified resin composition on the other hand, 0.01 or more because the fluidity of the modified resin composition is improved and the handleability tends to be improved. Since it tends to increase the crack resistance of the cured product, it is preferably 1.4 or less, more preferably in the range of 0.03 or more and 1.2 or less, and 0.05 or more and 1.0 or less. More preferably, it is in the range.
  • Mixing index ⁇ ( ⁇ a) / ( ⁇ s) (4)
  • ⁇ a is the mass (g) of the epoxy resin (A)
  • the mixing index ⁇ is 0.02 or more because there is a tendency that the crack resistance at the thermal cycle of the cured product obtained by curing the modified resin composition is increased.
  • the range of 15 or less is preferable, the range of 0.04 or more and 7 or less is more preferable, and the range of 0.08 or more and 5 or less is more preferable because the light resistance of the cured product obtained by curing tends to be improved.
  • the condensation rate of the alkoxysilane compound is 80% or more from the viewpoint of improving the storage stability of the modified resin composition, that is, suppressing the viscosity of the resin during storage and improving the handleability.
  • it is 82% or more, more preferably 85% or more, and particularly preferably 88% or more.
  • condensation rate of the alkoxysilane compound of this embodiment exists in the modified resin composition with respect to the number of moles (U) of the (OR 2 ) group contained in the alkoxysilane compound represented by the general formula (1). It is shown as a mole fraction represented by the following formula (5) using the number of moles (V) of the (OR 2 ) group in the silicone component.
  • Alkoxysilane compound condensation rate (%) [(U ⁇ V) / U] ⁇ 100 (5)
  • the modified resin composition of this embodiment includes at least (B) and (C) represented by the following general formula (1) in the presence of the epoxy resin (A), and is represented by the following general formula (2).
  • the alkoxysilane compound having a mixing index ⁇ of 0.001 or more and 19 or less can be produced by reacting with the following [Production Method 1] or [Production Method 2].
  • (R 1 ) n —Si— (OR 2 ) 4-n (1) (Here, n represents an integer of 0 or more and 3 or less.
  • each R 1 is independently selected from a hydrogen atom, a) a structure group consisting of an unsubstituted or substituted chain, branched, and cyclic structure.
  • each R 2 independently has a hydrogen atom, d) an unsubstituted or substituted aliphatic hydrocarbon unit consisting of one or more structures selected from a chain, branched, or cyclic structure group.
  • a monovalent organic group having 1 to 8 carbon atoms, and one or more organic groups selected from the group consisting of: ) (B) n 1 or 2 and at least one alkoxysilane compound having at least one cyclic ether group as R 1 .
  • (C) n 1 or 2, and at least one alkoxysilane compound having at least one aromatic organic group as R 1 .
  • Mixing index ⁇ ( ⁇ c) / ( ⁇ b) (2) (Here, in the formula (2), ⁇ b represents the content (mol%) of the component (B), and ⁇ c represents the content (mol%) of the component (C).)
  • Step (a) In the presence of the epoxy resin (A), the alkoxysilane compound containing at least the above (B) and (C) represented by the general formula (1) is cohydrolyzed by a reflux step without dehydration. Manufacturing the intermediate.
  • Step (c) A step of producing an intermediate by cohydrolyzing an alkoxysilane compound containing at least the above (B) and (C) represented by the general formula (1) by a reflux step without dehydration.
  • Step (d) A step in which the epoxy resin (A) is allowed to coexist with the intermediate produced in the step (c) to perform a dehydration condensation reaction.
  • “Process for producing an intermediate by co-hydrolysis by a reflux process without dehydration” means water and solvent blended for co-hydrolysis, and water and solvent derived from alkoxysilane compound generated during the reaction. Is a step of performing the reaction while returning to the reaction solution.
  • the reaction mode is not particularly limited, and can be carried out by one or a combination of two or more of various reaction modes such as batch, semi-batch, or continuous.
  • a cooling tube is attached to the upper part of the reaction vessel and the reaction is performed while refluxing the generated water or solvent, or the reaction solution is stirred and / or circulated in a sealed vessel. And the like.
  • the “step of dehydrating condensation reaction” is a step of performing the condensation reaction while removing the added water and solvent and the water and solvent generated in the above “refluxing step without dehydration”.
  • rotary evaporators vertical stirring tanks equipped with distillation tubes, surface renewal stirring tanks, thin film evaporators, surface renewal biaxial kneaders, biaxial horizontal stirrers, wet wall reactors, free fall types
  • One type or two or more types of devices such as a perforated plate reactor, a reactor in which a volatile component is distilled off while dropping a compound along a support, and the like can be used.
  • the modified resin composition of the present embodiment can be produced by any of the above [Production Method 1] and [Production Method 2].
  • There is no particular limitation on the reaction method of the alkoxysilane compound in producing the modified resin composition of the present embodiment and it is possible to react by batch conversion in the initial stage, and it is also possible to react sequentially or continuously. It is also possible to add to the system and react.
  • the epoxy resin (A) can be added at once or dividedly and sequentially added in any of [Production Method 1] and [Production Method 2].
  • the step (a) and the step (b) may be performed continuously, or after the reaction mixture obtained in the step (a) is separated or recovered, the step (b) Can also be done.
  • the step (c) and the step (d) are performed continuously, or the step (d) is performed after the reaction mixture obtained in the step (c) is recovered. You can also.
  • examples of the epoxy resin (A) and the alkoxysilane compound used in [Production Method 1] and [Production Method 2] include the same epoxy resins (A) and alkoxysilane compounds listed above.
  • the preferred range of the mixing index ⁇ to ⁇ of the alkoxysilane compound in [Production Method 1] and [Production Method 2] is the same as described above.
  • the condensation rate of the intermediate at the end of the step of producing an intermediate by cohydrolysis by a reflux step without dehydration is 78% or more. Is preferable, 80% or more is more preferable, and 83% or more is still more preferable.
  • the condensation rate of the intermediate is less than 78%, a lot of OH groups derived from silicone remain in the produced resin composition even after the subsequent dehydration condensation step. Condensation causes remarkable thickening and gelation of the resin composition and tends to deteriorate storage stability.
  • the condensation rate of the alkoxysilane compound is 80 from the viewpoint of improving the storage stability of the modified resin composition, that is, suppressing the viscosity of the resin during storage and improving the handleability. % Or more, more preferably 82% or more, still more preferably 85% or more, and particularly preferably 88% or more.
  • the amount of residual alkoxy groups in the resulting modified resin composition is set to 5% or less.
  • the amount of residual alkoxy groups in the resulting modified resin composition is preferably 3% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably not contained at all.
  • step (a) or step (c) of this embodiment water is allowed to coexist in the reaction system in order to hydrolyze the alkoxysilane compound.
  • the main purpose of adding water is to hydrolyze the alkoxysilane compound.
  • the timing of adding water is not particularly limited, and it may be added until the end of the step of producing an intermediate by co-hydrolysis, a method of batch addition at the initial stage of the reaction, a method of successive points during the reaction Alternatively, any method of adding continuously during the reaction may be used. Among these, the method of adding all at the beginning of the reaction is preferably used.
  • the ratio of the amount of water to be added (number of moles) and the amount (number of moles) of (OR 2 ) in the above formula (1) is defined as a mixing index ⁇ represented by the following formula (7).
  • Mixing index ⁇ ( ⁇ w) / ( ⁇ s) (7) (Here, in formula (7), ⁇ w represents the amount of water added (mol number), while ⁇ s represents the amount (mol number) of (OR 2 ) in general formula (1)).
  • the mixing index ⁇ is preferably in the range of 0.1 to 5, more preferably in the range of 0.2 to 3, and still more preferably in the range of 0.3 to 1.5. If the mixing index ⁇ is less than 0.1, the hydrolysis reaction may not proceed. If it exceeds 5, the storage stability of the modified resin composition may be reduced.
  • the step (a) or the step (c) described above can be performed without a solvent or in a solvent.
  • a solvent a known one can be used as long as it is an organic solvent that can dissolve the epoxy resin and the alkoxysilane compound and is inactive to them.
  • Solvents used include dimethyl ether, diethyl ether, diisopropyl ether, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, anisole and the like.
  • Ether solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as hexane, cyclohexane, heptane, octane and isooctane; Toluene, o-xylene, m-xylene, p-xylene and ethylbenzene Aromatic hydrogen solvents such as: Ester solvents such as ethyl acetate and butyl acetate; Methanol, ethanol, butanol, isopropanol Lumpur, n- butanol, butyl cellosolve, alcohol-based solvents such as butyl carbitol.
  • solvents can be used as one kind or a mixture of two or more kinds.
  • an ether solvent, a ketone solvent, an aliphatic hydrocarbon solvent, and an aromatic hydrocarbon solvent are preferable, and the ether solvent is 50% by mass or more. More preferably a solvent containing at least one solvent selected from the group consisting of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and propylene glycol dimethyl ether, more preferably 1,4-dioxane and tetrahydrofuran. preferable.
  • the amount of the solvent added is the epoxy resin (A) and the alkoxysilane compound that are added up to the end of the step of producing the intermediate by cohydrolysis by the reflux step without dehydration.
  • the amount of the alkoxysilane compound added by the end of the step of producing the intermediate by cohydrolysis by the reflux step without dehydration is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and still more preferably 0.03 to 10 times.
  • the molecular weight of the resin composition of the present embodiment can be controlled by the addition amount of the solvent, by setting the addition amount of the solvent within the above range, a resin composition having an appropriate molecular weight and, therefore, an appropriate viscosity tends to be obtained.
  • the reaction temperature in the step (a) or the step (c) is usually in the range of 0 ° C. or higher and 200 ° C. or lower. If it is lower than 0 ° C., water may solidify. On the other hand, if it exceeds 200 ° C., the resin composition may be colored. From the viewpoint of increasing the reaction rate and suppressing the modification of the resin such as ring opening of the epoxy group, the reaction temperature is preferably in the range of 20 ° C. or higher and 150 ° C. or lower, more preferably in the range of 40 ° C. or higher and 120 ° C. or lower, and 50 ° C. The range of 100 ° C. or lower is more preferable. The reaction temperature need not be constant as long as it is within the above range, and may be changed during the reaction.
  • step (a) or step (c) improves the reaction rate of (OR 2) in the formula (1), from the viewpoint of suppressing denaturation of the resin, 0.1 A range of not less than 100 hours is preferable, a range of not less than 1 hour and less than 80 hours is more preferable, a range of not less than 3 hours and less than 60 hours is further preferable, and a range of not less than 5 hours and less than 50 hours is particularly preferable.
  • the reaction temperature in the step (b) or the step (d) is usually in the range of 0 ° C. or more and 200 ° C. or less.
  • the reaction rate may decrease and the reaction time may be long.
  • the resin composition may be colored.
  • the reaction temperature is preferably in the range of 20 ° C. or higher and 150 ° C. or lower, more preferably in the range of 40 ° C. or higher and 120 ° C. or lower, and 50 ° C.
  • the range of 100 ° C. or lower is more preferable.
  • the reaction temperature does not need to be constant as long as it is within the above range, and may be changed at the initial stage of the reaction or during the reaction.
  • the reaction time of the step (b) or the step (d) is not particularly limited, but from the viewpoint of improving the reaction rate and suppressing the denaturation of the resin, a range of 0.1 hour or more and less than 100 hours is preferable. More preferably, the range is 5 hours or more and less than 80 hours, more preferably 1 hour or more and less than 50 hours, and particularly preferably 3 hours or more and less than 50 hours.
  • the modified resin composition of the present embodiment can be produced in an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon, or in the air.
  • an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon is preferable, and nitrogen, helium, neon, argon, Krypton, xenon and carbon dioxide are more preferred, nitrogen and helium are more preferred, and nitrogen is particularly preferred.
  • the steps (a) to (d) for producing the modified resin composition of the present embodiment can be performed under the above-mentioned gas atmosphere, under the above-mentioned gas flow, under reduced pressure, under pressure, or a combination thereof.
  • the pressure need not be constant and may be changed during the reaction.
  • the step (a) and the step (c) are industrially easy reaction solutions of water and solvents blended for cohydrolysis and water and solvents derived from alkoxysilane compounds generated during the reaction. Therefore, the reaction is preferably performed under an atmospheric pressure atmosphere and / or under pressure.
  • step (b) and step (d) remove the water and solvent added in step (a) or step (c) and the water and solvent generated in the above “refluxing step without dehydration”. Therefore, it is preferable to carry out the condensation reaction and / or under reduced pressure.
  • a hydrolysis condensation catalyst may be added during the co-hydrolysis of the above-described (A) epoxy resin and alkoxysilane compound.
  • the hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction.
  • a metal lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc.
  • organic metals lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.
  • inorganic salts Magnnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium
  • organic tin refers to one in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, and tetraorganotin.
  • organic tin examples include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyl
  • alkali organic metals that exhibit alkalinity when a ligand is liberated are suitable.
  • an alkali organic metal as the hydrolysis-condensation catalyst, the storage stability of the modified resin composition of the present embodiment tends to be good.
  • the condensation reaction tends to progress rapidly by using an alkali organic metal, it is very useful for obtaining a resin composition having an intermediate condensation ratio of 78% or more.
  • alkali organic tin is preferable, and alkoxide organic tin is particularly preferable.
  • alkoxide-based organic tin include dibutyltin dimethoxide, dibutyltin diethyloxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethyloxide, dioctyltin dibutoxide, and the like.
  • the above-mentioned hydrolysis-condensation catalyst may be used alone or in combination of two or more.
  • organic acid tin and alkaline organic tin may be used in combination, or may be treated with an inorganic base after reacting with an organic acid salt such as tin.
  • the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide.
  • the preferable addition amount is obtained from the following mixing index ⁇ which is a ratio to (OR 2 ) in the above formula (1).
  • the mixing index ⁇ is represented by the following formula (8).
  • Mixing index ⁇ ( ⁇ e) / ( ⁇ s) (8) (Here, in formula (8), ⁇ e represents the addition amount (number of moles) of the hydrolysis-condensation catalyst, and ⁇ s represents the amount (number of moles) of (OR 2 ) in formula (1)).
  • the mixing index ⁇ is preferably in the range of 0.0005 or more and 5 or less, more preferably in the range of 0.001 or more and 1 or less, and still more preferably in the range of 0.005 or more and 0.5 or less.
  • the mixing index ⁇ is less than 0.0005, it may be difficult to obtain the effect of promoting hydrolysis condensation. If it exceeds 5, the ring opening of the cyclic ether group is promoted. Or the storage stability may be deteriorated.
  • the modified resin composition of the present embodiment has a good storage stability and can form a cured product having excellent transparency, heat resistance, heat discoloration resistance, light resistance, and crack resistance in thermal cycle.
  • Raw resin composition such as light-emitting element sealing material, optical lens, photosensitive resin, fluorescent resin, conductive resin, insulating resin, etc. It can be suitably used as a product.
  • the modified resin composition of the present embodiment includes an oxetane compound (D), a phosphor (E), a conductive metal powder (F), an insulating powder (G), an epoxy resin (A ′), a curing agent ( H), curing accelerator (I), photoacid generator (J), and if necessary, cationic polymerization catalyst, modifier, vinyl ether compound, organic resin other than epoxy resin (A ′), silane coupling agent It is also possible to blend.
  • the oxetane compound (D) is not particularly limited as long as it is a compound containing an oxetane ring.
  • the oxetane compound (D) is not particularly limited as long as it is a compound containing an oxetane ring.
  • the polymerization rate tends to increase, and the viscosity of the composition tends to decrease.
  • Typical examples of oxetane compounds are shown below.
  • an appropriate combination of an oxetane compound having an aromatic ring is combined with a resin composition using an epoxy resin having a bisphenol skeleton as a raw material. Choosing a combination is a common practice.
  • the phosphor (E) in the present embodiment is a substance that emits fluorescence, that is, absorbs energy such as an electron beam, X-rays, ultraviolet rays, and an electric field, and converts a part of the absorbed energy into visible light relatively efficiently. It is not particularly limited as long as it is a substance that emits (emits light), and any inorganic or organic substance can be used. Of these, inorganic phosphors that generally exhibit excellent light-emitting properties are preferred.
  • the size of the inorganic phosphor that can be used in the present embodiment is not particularly limited, but usually a powder having a particle size of 1 to several tens of ⁇ m is used.
  • a compound A called an activator (emission center) introduced into a compound A called a matrix is generally used. : Activator B ”.
  • the fluorescent resin composition when used as an LED sealing material, it is preferable to use a cerium-activated yttrium aluminate phosphor (YAG: Ce phosphor) for the reason described later.
  • YAG Ce phosphor
  • a phosphorescent phosphor When used, it is preferable to use a phosphorescent phosphor. These may be used alone or in combination of two or more.
  • the blending amount is less than 95: 5, the phosphor as the phosphor The function may be insufficient.
  • the matrix A and the activator B are not particularly limited, and examples of the matrix A include oxide phosphors and nitride phosphors.
  • examples of the activator B include rare earth elements such as europium (Eu) and cerium (Ce).
  • YAG: Ce phosphor in which the base A is yttrium aluminate (Y3Al5O12: hereinafter referred to as YAG) and the activator B is cerium (Ce) is well known.
  • YAG yttrium aluminate
  • Ce cerium
  • the emission peak position is obtained by changing the structure of the matrix A by substituting a part of Y of “Y3Al5O12” with another Gd, Tb, or the like, or substituting a part of Al with Ga or the like. Can be shifted to the long wavelength side or the short wavelength side, which is very useful.
  • the “YAG: Ce phosphor” means that the base A is YAG, or a part of Y is replaced with other Gd, Tb or the like, or a part of Al is replaced with Ga or the like.
  • the activator B is a phosphor of Ce. Specific examples thereof include “Y3Al5O12: Ce3 +” and “(Y3, Gd0.9) Al5O12: Ce3 +”.
  • the base A is strontium barium silicate (Sr, Ba) 2 SiO 4 and europium (Eu) is introduced as the activator B, “(Sr, Ba) 2 SiO 4: Eu fluorescence. "Body” is known. In this system, the emission color can be adjusted from green to orange by changing the composition ratio of Sr and Ba.
  • ⁇ -Sialon phosphor Base A is a crystal in which a metal ion such as Ca, aluminum, and oxygen are dissolved in an ⁇ -type silicon nitride crystal, “(Mp (Si, Al) 12 (O, N) 16
  • M represents a metal ion
  • p represents a solid solution amount.
  • Cap (Si, Al) 12 (O, N) 16: Eu” and the like can be mentioned.
  • ⁇ -sialon phosphor Base A is represented by a composition of “Si6-qALqOqN8-q” in which aluminum and oxygen are dissolved in ⁇ -type silicon nitride crystal.
  • q represents the amount of solid solution.
  • Specific examples include “Si6-qALqOqN8-q: Eu”.
  • CaAlSiN3 phosphor The base A is a nitride crystal obtained by reacting calcium nitride, aluminum nitride, and silicon nitride at a high temperature of 1800 ° C., and specifically includes “CaAlSiN3: Eu”.
  • the inorganic phosphor include, for example, “6MgO.As2O5: Mn4 +, Y (PV) O4: Eu”, “CaLa0.1Eu0.9Ga3O7”, “BaY0. 9Sm0.1Ga3O7 “,” Ca (Y0.5Eu0.5) (Ga0.5In0.5) 3O7 "," Y3O3: Eu, YVO4: Eu “,” Y2O2: Eu “,” 3.5MgO.0.5MgF2GeO2: Mn4 + " And “(Y ⁇ Cd) BO2: Eu”.
  • blue light-emitting colors include “(Ba, Ca, Mg) 5 (PO 4) 3 Cl: Eu 2+”, “(Ba, Mg) 2 Al 16 O 27: Eu 2+”, “Ba 3 MgSi 2 O 8: Eu 2+”, “BaMg 2 Al 16 O 27: “Eu2 +", “(Sr, Ca) 10 (PO4) 6Cl2: Eu2 +", “(Sr, Ca) 10 (PO4) 6Cl2 / nB2O3: Eu2 +", “Sr10 (PO4) 6Cl2: Eu2 +", “(Sr, Ba , Ca) 5 (PO4) 3Cl: Eu2 + ”,“ Sr2P2O7: Eu ”,“ Sr5 (PO4) 3Cl: Eu ”,“ (Sr, Ca, Ba) 3 (PO4) 6Cl: Eu ”,“ SrO ⁇ P2O5 ⁇ B2O5: Eu “,” (BaCa) 5 (PO4) 3Cl: Eu “,” Sr
  • green light emitting colors include “Y3Al5O12: Ce3 + (YAG)”, “Y2SiO5: Ce3 +, Tb3 +”, “Sr2Si3O8 ⁇ 2SrCl2: Eu”, “BaMg2Al16O27: Eu2 +, Mn2 +”, “ZnSiO4: Mn”.
  • YVO4 Dy having a white emission color
  • CaLu0.5Dy0.5Ga3O7 having a yellow emission color
  • organic phosphor examples include, for example, 1,4-bis (2-methylstyryl) benzene (Bis-MSB), trans-4,4′-diphenylstilbene (DPS) having a blue emission color.
  • stilbene dyes such as 7-hydroxy-4-methylcoumarin (coumarin 4).
  • Examples of commercially available products having yellow to green fluorescent colors include Brilliantsulfoflavine FF, Basic yellow HG, SINLOIHI COLOR FZ-5005 (manufactured by SINLOIHI), and the like.
  • Examples of commercially available products having yellow to red fluorescent colors include Eosine, Rhodamine 6G, and Rhodamine B.
  • phosphors when light or an electron beam, which is an irradiation excitation source, is cut off, light emission is immediately attenuated and disappears.
  • a phosphorescent phosphor there is a phosphor exhibiting afterglow for several seconds to several tens of hours after the excitation source is cut off, and this is called a phosphorescent phosphor.
  • the type is not particularly limited as long as it exhibits this property.
  • the manufacturing method of the fluorescent resin composition of the present embodiment is not particularly limited, for example, the modified resin composition and the phosphor are stirred simultaneously or separately with a mixing device described later while heating as necessary.
  • examples thereof include a method of mixing and dispersing, a method of performing defoaming treatment under reduced pressure, if necessary, following the above method.
  • the mixing apparatus is not particularly limited, and examples thereof include a lykai machine, a three-roll mill, a ball mill, a planetary mixer, a line mixer, a homogenizer, and a homodisper.
  • the conductive metal powder (F) that can be used in the present embodiment is not particularly limited as long as it is a metal powder containing silver, and may be not only silver powder but also metal powder having silver adhered or coated on its surface.
  • the metal powder herein include metal elements such as aluminum, silicon, boron, carbon, magnesium, nickel, copper, graphite, gold, and palladium, and powders of metal oxides and metal nitrides thereof. Among these, aluminum, nickel, gold, and palladium are preferable from the viewpoint of conductivity.
  • metal oxide and the metal nitride include alumina, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, fused silica, crystalline silica, magnesium silicate, aluminum and silicon composite metal oxide, aluminum and Examples include magnesium composite metal oxides.
  • the conductive metal powder may be surface-coated with a polymer such as polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethyleneoxide moiety.
  • a polymer such as polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethyleneoxide moiety.
  • the entire conductive metal powder particles are not silver. Both can also be used with metal powder having silver deposited or coated on its surface.
  • the shape of the silver powder is not particularly limited, and examples thereof include scaly, spherical, and dendritic shapes.
  • the scale-like silver powder has many silver powder contacts and is excellent in conductivity, and when it is made into a conductive resin composition from its orientation, it tends to be excellent in workability because it exhibits thixotropy. On the other hand, when used for a precise member, there may be a problem of poor electrical connection due to the orientation.
  • the size is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 1 to 20 ⁇ m, as an average particle size obtained with a laser diffraction particle size distribution analyzer. Such an average particle size is preferable because the possibility of poor electrical connection is reduced even when used for precision electronic components.
  • the spherical silver powder Since the spherical silver powder has almost no orientation, it is difficult to cause a problem in electrical joining. However, since the particles are in point contact, the conductivity tends to be inferior.
  • the size is not particularly limited, but the average particle size is preferably 20 ⁇ m or less, more preferably 5 ⁇ m or less. When the average particle size exceeds 20 ⁇ m, the conductivity tends to be low. Furthermore, when using together with scale-like silver powder and using also for the purpose of aiming at electroconductivity by filling the clearance gap, it is preferable to select a thing of 5 micrometers or less. Although dendritic silver powder has a large specific surface area and excellent conductivity, the quality may be unstable due to its specific shape.
  • the size is not particularly limited, but the average particle size is preferably 30 ⁇ m or less, more preferably 5 ⁇ m or less. This average particle size is preferable because it tends to be excellent in handling. In the present embodiment, it is preferable to use silver powder having different shapes in combination in view of these properties depending on the purpose and application.
  • the preferable blending amount of the conductive metal powder with respect to the resin composition is 60 to 85% by mass, more preferably 70 to 80% by mass.
  • the blending amount is 60% by mass or more, the conductivity tends to be further improved, and when it is 85% by mass or less, the bleeding phenomenon tends to be prevented.
  • an insulating resin composition obtained by further adding an insulating powder (G) to the modified resin composition of the present embodiment will be described.
  • Specific examples of the insulating powder (G) that can be used in this embodiment include non-oxide ceramic powders such as carbon, boron carbide, boron nitride, aluminum nitride, and titanium nitride; beryllium, magnesium, aluminum, titanium, and the like.
  • Oxide powder silicon oxide, silicon nitride, fused silica, crystalline silica, and other fillers containing silicon; magnesium silicate, aluminum and silicon composite metal oxide, aluminum and magnesium composite metal oxide; muscovite, Examples include powders such as phlogopite, micanite, steatite, alumina, soda glass, borosilicate glass, quartz glass, and wood; and resin powders such as silicon rubber and Teflon (registered trademark). These may be used alone or in combination. Can be used. Among these, silicon oxide, silicon nitride, fused silica, crystalline silica, and other fillers containing silicon are preferable from the viewpoints of insulation and availability.
  • the insulating powder may be surface-coated with a polymer such as a silane compound, polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethyleneoxide moiety.
  • a polymer such as a silane compound, polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, or a copolymer having a polyethyleneimine moiety and a polyethyleneoxide moiety.
  • the preferable blending amount of the insulating powder with respect to the resin composition is 5 to 50% by mass, more preferably 10 to 30% by mass.
  • the blending amount is 5% by mass or more, the insulating property tends to be further improved, and when it is 50% by mass or less, the reliability of the semiconductor device tends to be improved due to the stress relaxation effect.
  • an epoxy resin (A ′) other than the epoxy resin (A) contained in the modified resin composition of the present embodiment can be further blended in the modified resin composition of the present embodiment.
  • organic resins such as silicone resin, acrylic resin, urea resin, and imide resin can be blended as the organic resin other than the epoxy resin (A ′).
  • the modified resin composition of the present embodiment can be further added with a curing agent (H) and / or a curing accelerator (I) to obtain a curable resin composition.
  • curing agent (H) is a substance used in order to harden a resin composition, and is not specifically limited.
  • the curing agent for example, acid anhydride compounds, amine compounds, amide compounds, phenol compounds and the like can be used, and in particular, aromatic acid anhydrides, cycloaliphatic acid anhydrides, aliphatic acid anhydrides, etc.
  • An acid anhydride compound is preferable, and a carboxylic acid anhydride is more preferable.
  • the acid anhydride compound includes an alicyclic acid anhydride, and among the carboxylic acid anhydrides, alicyclic carboxylic acid anhydrides are preferable. These hardened
  • cured materials may be used individually or may be used in combination of 2 or more type.
  • the curing agent examples include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride.
  • curing agents (H) since the light resistance of a cured product obtained by curing the modified resin composition of the present embodiment tends to increase, two alicyclic acid anhydrides per molecule. More preferred are silicones having the above acid anhydride-containing functional group as a substituent, such as methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic acid. An acid anhydride is more preferable. These curing agents can be used as one kind or a mixture of two or more kinds.
  • the addition amount of the curing agent (H) is determined from the mixing index ⁇ which is the ratio to the cyclic ether group contained in the above-described epoxy resin and alkoxysilane compound.
  • the mixing index ⁇ is expressed by the following formula (9).
  • Mixing index ⁇ ( ⁇ f) / ( ⁇ k) (9) (Here, in formula (9), ⁇ f: addition amount (mol number) of curing agent (H), ⁇ k: amount (mol number) of cyclic ether group contained in epoxy resin and alkoxysilane compound. )
  • the mixing index ⁇ is preferably in the range of 0.1 to 1.5, more preferably in the range of 0.2 to 1.3, and still more preferably in the range of 0.3 to 1.3.
  • the mixing index ⁇ is less than 0.1, the curing rate may be reduced, and when it exceeds 1.5, the moisture resistance as a cured product may be deteriorated.
  • Curing accelerator (I) is a curing catalyst used for the purpose of promoting the curing reaction.
  • the curing accelerator tertiary amines and salts thereof are preferable. Specific examples of the curing accelerator include the following.
  • Tertiary amines benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine and the like.
  • Imidazoles 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-pheny
  • Organophosphorous compounds diphenylphosphine, triphenylphosphine, triphenyl phosphite and the like.
  • Quaternary phosphonium salts benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide Tetraphenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, ethyl triphenyl phosphonium acetate, tetra-n-butyl phosphonium o, o-diethyl phosphodithionate, tetra-n-butyl phosphonate Nitrobenzotriazolate, Tetra-n-butylphosphonium tetrafluoroborate, Tetra-n-buty
  • Diazabicycloalkenes 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof.
  • Organometallic compounds zinc octylate, tin actylate, aluminum acetylacetone complex, etc.
  • Quaternary ammonium salts tetraethylammonium bromide, tetra-n-butylammonium bromide and the like.
  • Metal halide compounds Boron compounds such as boron trifluoride and triphenyl borate; zinc chloride, stannic chloride and the like.
  • the addition amount of hardening accelerator (I) is calculated
  • the mixing index ⁇ is represented by the following formula (10).
  • Mixing index ⁇ ( ⁇ g) / ( ⁇ k) (10) (Here, in formula (10), ⁇ g: mass (g) of curing accelerator (I), ⁇ k: mass of epoxy resin and alkoxysilane compound (g)).
  • the mixing index ⁇ is preferably in the range of 0.01 to 5, more preferably in the range of 0.05 to 3, and still more preferably in the range of 0.1 to 1. If the mixing index ⁇ is less than 0.01, curing may not proceed well, and if it exceeds 5, the cured product may be colored.
  • a photosensitive resin composition obtained by further adding a photoacid generator (J) to the modified resin composition of the present embodiment will be described.
  • the photoacid generator (J) that can be used in the present embodiment is not particularly limited as long as it is a compound that releases an acid when irradiated with light and initiates polymerization.
  • an onium salt is preferable.
  • Specific examples include, for example, diazonium salts, iodonium salts, sulfonium salts, and the like, in which the cation portion is aromatic diazonium, aromatic iodonium, aromatic sulfonium, respectively, and the anion portion is BF4 ⁇ , PF6 ⁇ , SbF6. - , [BX4] - (wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups) and the like.
  • Typical examples of the photoacid generator are shown below.
  • More specific examples include boron difluoride aryldiazonium salts, phosphorus hexafluoride triarylsulfonium salts, phosphorus hexafluoride diaryliodonium salts, antimony hexafluoride triarylphosphonium salts, antimony hexafluoride.
  • Diaryl iodonium salt arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride tri-4-methylphenylsulfonium salt, tetrakis (pentafluorophenyl) borate triarylsulfonium salt, tetrakis (pentafluoro Phenyl) borate diaryl iodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, and the like.
  • CD-1012 manufactured by SARTOMER
  • PCI-019 manufactured by Nippon Kayaku Co., Ltd.
  • PCI-021 manufactured by Nippon Kayaku Co., Ltd.
  • Optmer SP-150 manufactured by ADEKA Corporation
  • UVI-6990 UVI-6974 (manufactured by Dow Chemical Co., Ltd.)
  • CPI-100P CPI-100A
  • CPI-100L manufactured by Sun Apro
  • TEPBI-S manufactured by Nippon Shokubai Co., Ltd.
  • Rhodorsil 2074 manufactured by Rhodia
  • these can be used alone or in combination of two or more.
  • sulfonium salts and iodonium salts are preferable from the viewpoint that the cured product is less colored, and sulfonium salts are particularly preferable in view of curability.
  • vinyl ether compounds can be blended with the photosensitive resin composition as necessary.
  • these compounds include vinyl ether compounds that do not contain a hydroxyl group.
  • ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane diol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol A divinyl ether etc. can be mentioned.
  • a conventionally well-known cationic polymerization catalyst can also be mix
  • the cationic polymerization catalyst that can be used include Lewis acid catalysts typified by BF 3 ⁇ amine complexes, PF 5 , BF 3 , AsF 5 , SbF 5 , phosphonium salts, quaternary ammonium salts, sulfonium salts, benzylammonium.
  • thermosetting cationic polymerization catalyst represented by amine imide, diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate
  • UV curable cationic polymerization catalysts represented by the above.
  • a thermosetting cationic polymerization catalyst is preferably used because it has a high glass transition temperature and tends to obtain a transparent cured product having excellent solder heat resistance and adhesion and little coloring.
  • thermosetting cationic polymerization catalysts include, for example, SI-100L, SI-60L (manufactured by Sanshin Chemical Industry), CP-66, CP-, which are sulfonium salt cationic polymerization initiators. 77 (manufactured by Asahi Denka Kogyo Co., Ltd.).
  • the modified resin composition obtained by the present embodiment may contain a modifier as necessary from the viewpoint of imparting flexibility to the cured product and improving the peel adhesion.
  • the modifying agent used include polyols containing two or more hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, Propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,4-butanediol, neopentyl glycol, glycerin, erythritol, trimethylolpropane, 1,2,4-butanetriol, etc.
  • Aliphatic polyols, polycarbonate diols, and silicones having a silanol group at the terminal are preferably used. These modifiers can be used as one kind or a mixture of two or more kinds.
  • the residual alkoxy group in the modified resin composition needs to be 5% or less. If the residual alkoxy group exceeds 5%, the cured product obtained by curing the composition has insufficient crack resistance and adhesiveness during thermal cycling.
  • Suitable silane coupling agents for the modified resin composition of the present embodiment include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N-
  • inorganic fillers other than those described above, colorants, leveling agents, lubricants, surfactants, antioxidants, as long as their functions are not impaired.
  • a light stabilizer or the like can be appropriately added.
  • plasticizers, flame retardants, stabilizers, antistatic agents, impact strengthening agents, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, and crosslinks that are generally used as additives for resins An agent or the like can be blended.
  • the inorganic filler examples include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.), silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, Barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon Examples thereof include fibers and molybdenum disulfide.
  • silicas calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate and the like are preferable, and silicas are more preferable in consideration of physical properties of the cured product.
  • These inorganic fillers may be used alone or in combination of two or more.
  • the colorant is not particularly limited as long as it is a substance used for the purpose of coloring.
  • the leveling agent is not particularly limited, and examples thereof include oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, Examples include hydrogenated castor oil and titanium-based coupling agents. These leveling agents may be used alone or in combination of two or more.
  • the lubricant is not particularly limited.
  • hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid.
  • Higher fatty acid amide type lubricants such as stearylamide, palmitylamide, oleylamide, methylenebisstearamide, ethylenebisstearamide; hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono- , Di-, tri-, or tetra-) stearate and other higher fatty acid ester lubricants; cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol and other alcohol lubricants; lauric acid, myristic acid, palmi Metal soaps that are metal salts such as magnesium, calcium, cadmium, barium, zinc, lead such as acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid; natural such as carnauba wax, candelilla wax, beeswax, montan wax Examples thereof include waxes. These lubricants may be used alone
  • the surfactant is an amphipathic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent.
  • the type of the surfactant is not particularly limited, and examples thereof include silicone surfactants and fluorine surfactants. Surfactants may be used alone or in combination of two or more.
  • the antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite; organic sulfur type such as distearyl-3,3′-thiodipropinate. Antioxidants; phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol and the like.
  • the light stabilizer is not particularly limited, and examples thereof include ultraviolet absorbers such as benzotriazole, benzophenone, salicylate, cyanoacrylate, nickel, and triazine, hindered amine light stabilizers, and the like.
  • the curable resin composition containing an organic resin other than) and a silane coupling agent can be cured by a known method.
  • the method of hardening by heating or the method of hardening by irradiating light is a method generally used as a hardening method of an epoxy resin, and can be illustrated as a preferable method in this embodiment.
  • the temperature for curing by heating is not particularly limited because it depends on the epoxy resin and the curing agent used, but is usually in the range of 20 to 200 ° C.
  • the light used for curing by irradiating light is preferably ultraviolet light or visible light, and more preferably ultraviolet light.
  • the light source include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser,
  • the light source include a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, and a plasma light source.
  • the above curing reaction can be performed in the air, or in an inert gas atmosphere such as nitrogen, helium, or argon as necessary.
  • the modified resin composition of the present embodiment includes, for example, a) a modified resin composition of the present embodiment, b) a resin composition obtained by further adding an oxetane compound (D) to the modified resin composition of the present embodiment, c ) A fluorescent resin composition obtained by further adding the phosphor (E) to the modified resin composition of the present embodiment, or a resin composition obtained by further adding a curing agent (H) to the above a) to c).
  • Is an excellent light-emitting element sealing material that has excellent adhesion to elements and package materials, does not generate cracks, and has little decrease in luminance over a long period of time, or can be injection-molded.
  • a curable resin composition for producing an optical lens having excellent stability and light resistance.
  • a curable resin composition obtained by further adding a curing accelerator (I) to the resin composition obtained by further adding a curing agent (H) to the above a) to c), or the above a) to c The photosensitive resin composition obtained by further adding a photoacid generator (J) to the above light-emitting element sealing material, or a curable resin composition or a photosensitive resin composition for producing an optical lens. It can be usefully used as a product.
  • a light emitting component such as a light emitting diode can be manufactured by sealing a light emitting element using a curable resin composition containing the modified resin composition of the present embodiment.
  • the above light emitting diode and / or the above optical lens include, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal light, an indicator light, and a display. It can be suitably used as a semiconductor device such as a device, a light source of a planar light emitter, a display, a decoration, and various lights.
  • the emission wavelength of the light emitting device sealed using the sealing material for light emitting device comprising the curable resin composition containing the modified resin composition of the present embodiment is from infrared to red, green, blue, purple, and ultraviolet. It can be used widely, and light having a wavelength of 250 nm to 550 nm, which is deteriorated due to insufficient light resistance with conventional sealing materials, can be practically used. As a result, a white light-emitting diode having a long life, high energy efficiency, and high color reproducibility can be obtained.
  • the emission wavelength refers to the main emission peak wavelength.
  • the light emitting element used for example, a light emitting element formed by stacking semiconductor materials on a substrate can be exemplified.
  • the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.
  • the substrate examples include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. If necessary, a buffer layer may be formed between the substrate and the semiconductor material. Examples of these buffer layers include GaN and AlN.
  • the method for laminating the semiconductor material on the substrate is not particularly limited, and for example, MOCVD method, HDVPE method, liquid phase growth method and the like are used.
  • Examples of the structure of the light emitting element include a MIS junction, a PN junction, a homojunction having a PIN junction, a heterojunction, and a double heterostructure.
  • a single or multiple quantum well structure may also be used.
  • a light emitting diode can be manufactured by sealing a light emitting element using a light emitting element sealing material comprising a curable resin composition containing the modified resin composition of the present embodiment.
  • the light-emitting element can be sealed only with the light-emitting element sealing material, but it is also possible to use another sealing material in combination.
  • other sealing materials include epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, and glass.
  • a light emitting element sealing material is previously injected into a mold mold, and the light emitting element is injected there. And a method of curing after immersing a lead frame or the like to which the light emitting element is fixed, a method of injecting a light emitting element sealing material into a mold frame in which the light emitting element is inserted, and a method of curing.
  • examples of the method for injecting the light-emitting element sealing material include injection by a dispenser, transfer molding, injection molding, and the like.
  • sealing methods include a method in which a light emitting device sealing material is dropped onto the light emitting device, and stencil printing, screen printing, or a method of applying and curing through a mask, a cup in which the light emitting device is disposed in the lower part, etc.
  • a method of injecting a light-emitting element sealing material with a dispenser or the like and curing it For example, a method of injecting a light-emitting element sealing material with a dispenser or the like and curing it.
  • the curable resin composition containing the modified resin composition of this embodiment can also be used as a die bond material for fixing a light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.
  • Examples of the shape of the sealing portion include a bullet-shaped lens shape, a plate shape, and a thin film shape.
  • the performance of the light-emitting diode obtained using the modified resin composition of the present embodiment can be improved by a conventionally known method.
  • a method for improving the performance for example, a method of providing a light reflecting layer or a light collecting layer on the back surface of the light emitting element, a method of forming a complementary colored portion on the bottom, and a layer that absorbs light having a wavelength shorter than the main emission peak is emitted.
  • the light-emitting diode obtained using the modified resin composition of the present embodiment includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal light, an indicator light, It is useful as a light emitting component such as a display device, a light source of a planar light emitter, a display, a decoration, and various lights.
  • a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal light, an indicator light
  • a light emitting component such as a display device, a light source of a planar light emitter, a display, a decoration, and various lights.
  • a curable resin composition obtained by further adding a curing agent (H) to a fluorescent resin composition obtained by further adding a phosphor (E) to the modified resin composition of the present embodiment, or the present embodiment By curing the photosensitive resin composition obtained by further adding the photoacid generator (J) to the modified resin composition in the form, a phosphorescent material having excellent light-emitting properties can be produced.
  • a phosphorescent material is excited by light stimulation such as sunlight, fluorescent light, ultraviolet light, etc., energy is converted to emit light, and light is gradually emitted even after the excitation stop by the above light stimulation, for a long time.
  • light stimulation such as sunlight, fluorescent light, ultraviolet light, etc.
  • the use of the phosphorescent material using the modified resin composition of the present embodiment is not particularly limited, for example, indications at night / power outage, disaster prevention / safety sign, clock, wallpaper, electric switch, signboard, Examples include clothing, shoes, reflectors for bicycles and motorcycles, adhesive tapes, fishing gear such as fishing hooks and floats, exercise equipment, accessories, toys, and the like.
  • a conductive resin composition obtained by further adding a conductive metal powder (F) to the modified resin composition of the present embodiment is excellent in fluidity, conductivity and adhesiveness, and has voids.
  • a raw material for a curable conductive resin composition that suppresses generation e) an insulating resin composition obtained by further adding an insulating powder (G) to the modified resin composition of the present embodiment, f) the present present The insulating resin composition obtained by adding the epoxy resin (A ′) and the insulating powder (G) to the modified resin composition of the embodiment, or the above-mentioned d) to f), and further a curing agent (H) Is useful as a curable insulating resin composition raw material that is excellent in insulation and adhesiveness and suppresses the generation of voids.
  • a curable resin composition obtained by further adding a curing accelerator (I) to a resin composition obtained by further adding a curing agent (H) to the above d) to f), or the above d) to f ) And a photoacid generator (J) can be used as the above curable conductive resin composition or curable insulating resin composition, respectively.
  • the use of the conductive resin composition using the modified resin composition of the present embodiment is not particularly limited.
  • the application of the insulating resin composition using the modified resin composition of the present embodiment is not particularly limited. For example, mounting of a semiconductor chip in a semiconductor device; semiconductor chip (IC, LSI, etc.), ceramic A die bond agent, an adhesive agent, etc. for joining to a case, a lead frame, a board
  • a highly heat-insulating insulating material such as an interposer for semiconductor packages, a printed circuit board, a display, a solar cell, a generator / motor board, an automobile board, and the like.
  • a) a modified resin composition of the present embodiment b) a resin composition obtained by further adding an oxetane compound (D) to the modified resin composition of the present embodiment, and c) a modified resin composition of the present embodiment.
  • Insulating resin composition comprising epoxy resin (A ′) and insulating powder (G) added to d) to f
  • the product can be usefully used as a coating agent that is less susceptible to polymerization inhibition by oxygen.
  • the coating agent in the present embodiment is not particularly limited as long as it is a material for forming and coating a coating film on the surface of a substance, and its main use purpose is as follows, and if necessary It is also possible to mix pigments, pigments and the like with the coating agent and use them as paints and inks.
  • Glossiness imparted to coatings and substrates (3) Water-repellent treatments to coatings and substrates (4) Non-slip processing for flooring, etc. (5) Sealing and insulation of electronic components
  • an epoxy compound has a fast polymerization start, but a subsequent polymerization reaction is not fast.
  • the present inventors have surprisingly been able to accelerate the polymerization rate by blending an oxetane compound with the resin composition having an epoxy group, and are a photosensitive resin composition excellent in photocurability and adhesiveness. It was found that can be obtained. Furthermore, depending on the selection of the oxetane compound, it is possible to reduce the viscosity of the resin composition.
  • the viscosity of the photosensitive resin composition of the present embodiment is preferably 1000 Pa ⁇ s or less, more preferably 0.05 to 50 Pa ⁇ s, and still more preferably 0.2 to 30 Pa in terms of fluidity. -It is the range below s. When the viscosity of the photosensitive resin composition exceeds 1000 Pa ⁇ s, the fluidity is impaired and may not be suitable for practical use.
  • the coating agent of this embodiment can be applied by a conventionally known method, and then cured to form a coating film.
  • the application methods include brush coating, roller coating, spray coating, bar coater, roll coater, baking coating, dip coating, electrodeposition coating, electrostatic coating, powder coating, vapor deposition, plating, and other coating techniques.
  • Printing techniques such as inkjet, laser printing, rotary printing, gravure printing, and screen printing, on the other hand, as a method of forming a coating film, a method of curing by heating, or a method of curing by irradiating light, Each is preferably used.
  • the coating agent and the coating film of the present embodiment is not particularly limited.
  • the coating agent (painting, resin, plastic, metal, steel pipe, automobile, building, optical fiber application, etc.), optical disc (DVD) , CD, Blu-ray disc, etc.) coating and adhesion, ink (inkjet printer, gravure printing, flexographic printing, resist for printed wiring board, UV printing, etc.), printing plate making materials (PS flat plate, photosensitive resin relief plate, screen plate) Photosensitive materials, etc.), photoresists (semiconductor resists, printed wiring board resists, photofabrication resists, etc.), printed wiring boards, pattern formation of various electronic parts including IC, LSI, liquid crystal and PDP displays Color filter forming materials, seals for liquid crystals and organic EL , Semiconductor / LED peripheral materials (encapsulant, lens material, substrate material, die bond material, chip coating material, laminated plate, optical fiber, optical waveguide, optical filter, adhesive for electronic components, coating material, sealing material, insulating material,
  • Aircraft / automobile / plastic molding jigs resin molds such as press molds, stretched dies, matched dies, vacuum molding / blow molding molds, master models, casting patterns, laminated jigs, various inspection jigs, etc.
  • It can be used as a modifier / stabilizer (fiber resin processing, stabilizer for polyvinyl chloride, additive to synthetic rubber, etc.) and the like. Among these, it is useful for coating agents, paints, adhesives, and optical modeling resin applications.
  • the mixing index ⁇ was calculated from the following general formula (2).
  • Mixing index ⁇ ( ⁇ c) / ( ⁇ b) (2) here, ⁇ b: (B)
  • n 1 or 2
  • R 1 is mol% of an alkoxysilane compound having at least one cyclic ether group
  • ⁇ c (C)
  • n 1 or 2
  • R 1 is mol% of an alkoxysilane compound having at least one aromatic organic group.
  • the mixing index ⁇ was calculated from the following general formula (3).
  • the mixing index ⁇ was calculated from the following general formula (4).
  • the mixing index ⁇ was calculated from the following general formula (5).
  • Mixing index ⁇ ( ⁇ e) / ( ⁇ s) (5) here, ⁇ e: addition amount of hydrolytic condensation catalyst (mol number), ⁇ s: the amount (mol number) of (OR 2 ) in the general formula (1).
  • the mixing index ⁇ was calculated from the following general formula (6).
  • Mixing index ⁇ ( ⁇ w) / ( ⁇ s) (6) here, ⁇ w: amount of water added (in mol), .epsilon.s: The amount of the general formula (1) (OR 2) ( mol number).
  • the mixing index ⁇ was calculated from the following general formula (7).
  • Mixing index ⁇ ( ⁇ f) / ( ⁇ k) (7) here, ⁇ f: addition amount (number of moles) of curing agent, ⁇ k: The amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.
  • the mixing index ⁇ was calculated from the following general formula (8).
  • Mixing index ⁇ ( ⁇ g) / ( ⁇ k) ⁇ 100 (8) here, ⁇ g: mass (g) of curing accelerator, ⁇ k: mass (g) of epoxy resin and alkoxysilane compound.
  • Storage stability index ⁇ (storage viscosity) / (starting viscosity) (9)
  • the container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”. When the resin composition was fluid (viscosity was 1000 Pa ⁇ s or less) and the storage stability index ⁇ was 4 or less, it was judged to have storage stability.
  • the area value of the residual alkoxy group-derived peak in the present embodiment is the sum of the areas of the plurality of residual alkoxy group-derived peaks.
  • the peak derived from the residual alkoxy group is a composite peak> From the point of slope 0 surrounded by the peak derived from the residual alkoxy group and the peak derived from other than the residual alkoxy group, a tangent line is drawn so that the area of the peak derived from the residual alkoxy group is minimized.
  • the area surrounded by the tangent line and the peak derived from the residual alkoxy group was defined as the area value of the peak derived from the residual alkoxy group.
  • the peak derived from the residual alkoxy group is the main component of the peak, and there is no point where the slope becomes zero between the peak derived from the residual alkoxy group and the peak derived from other than the residual alkoxy group
  • the peak derived from other than the residual alkoxy group was not regarded as a peak, and all the peaks were regarded as the residual alkoxy group-derived peak.
  • the peak derived from other than the residual alkoxy group is the main component of the peak, and there is no point where the slope is 0 between the peak derived from the residual alkoxy group and the peak derived from other than the residual alkoxy group
  • the peak derived from the residual alkoxy group was not regarded as a peak.
  • the light resistance of the cured product was evaluated by the following method. (1) The cured product solution prepared by the method described later was cured to prepare a cured product of 20 mm ⁇ 10 mm ⁇ thickness 3 mm. (2) The cured product was covered with a black mask of 25 mm ⁇ 15 mm ⁇ thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test. (3) A UV irradiation device (USHIO Inc., “Spot Cure SP7-250DB”) is set up so that the above sample in a constant temperature incubator kept constant at 50 ° C. can be irradiated with UV light via an optical fiber. Got ready.
  • USHIO Inc. “Spot Cure SP7-250DB”
  • the thermal shock resistance of the cured product was evaluated by the following method.
  • Silicon chip (2) A solution for cured product prepared by the method described later is poured into the substrate, and 10 silicon chips are prepared and cured. A sample for a thermal shock test was used.
  • Epoxy resin (1-1) Epoxy resin A1: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A1 epoxy resin) ⁇ Product name: “AER2600”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows. Epoxy equivalent (WPE): 187 g / eq Viscosity (25 ° C.): 14.3 Pa ⁇ s
  • Epoxy resin A2 Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A2 epoxy resin) ⁇ Product name: “AER2500” manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows. Epoxy equivalent (WPE): 186 g / eq Viscosity (25 ° C.): 10.2 Pa ⁇ s
  • Epoxy resin A3 Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A3 epoxy resin) ⁇ Product name: “AER6071” manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) measured by the above-mentioned method was as follows. However, since this epoxy resin A3 was solid at 25 ° C., the viscosity could not be measured. Epoxy equivalent (WPE): 470 g / eq
  • Epoxy resin B 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (hereinafter referred to as alicyclic epoxy resin) -Product name: “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.
  • the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • DMDMS Dimethyldimethoxysilane
  • Alkoxysilane Compound K Tetraethoxysilane (hereinafter referred to as TEOS) ⁇ Product name: “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd. (2-5) Alkoxysilane compound L: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as ECETMS) ⁇ Product name: “KBM-303”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • TEOS Tetraethoxysilane
  • ECETMS 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • DBTDL Dibutyltin dilaurate: Wako Pure Chemical Industries, Ltd.
  • DBTDA Dibutyltin diacetate: manufactured by Tokyo Chemical Industry Co., Ltd.
  • DOTDA Dioctyltin diacetate “Neostan U-820” manufactured by Nitto Kasei Co., Ltd.
  • Curing accelerator Amine-based curing agent-Trade name: "U-CAT 18X” manufactured by San Apro Co., Ltd.
  • Silicone resin “SCR-1012 (liquid A and liquid B)” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Inorganic filler colloidal silica-Product name: “Methanol silica sol” (SiO2: 30%, particle size: 10-20 nm), manufactured by Nissan Chemical Industries, Ltd. (10) Internal standard substance 1,1,2,2-tetrabromoethane: manufactured by Tokyo Chemical Industry Co., Ltd.
  • Example 1 A resin composition was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) In accordance with the composition ratio in Table 1, Bis-A1 epoxy resin, alkoxysilane compound and THF were placed in a flask containing a stirrer in an atmosphere at 25 ° C., mixed and stirred, and further hydrolyzed with water. The condensation catalyst was added and mixed and stirred. (3) Subsequently, a cooling tube was set in the flask, and the flask was immediately immersed in an oil bath at 80 ° C.
  • the epoxy equivalent (WPE), the starting viscosity, and the storage viscosity of the resin composition obtained in the above (6) were measured. Furthermore, the storage stability index ⁇ 1 was obtained and shown in Table 3.
  • a cured product was produced and evaluated by the following procedure.
  • (10) Under an atmosphere of 25 ° C., the above resin composition, curing agent and curing accelerator were mixed and stirred according to the composition ratios in Table 2, and deaerated under vacuum to obtain a cured product solution.
  • (11) A 3 mm thick, U-shaped silicon rubber was sandwiched between two stainless steel plates coated with a release agent to prepare a molding jig.
  • (12) The cured product solution was poured into the molding jig and the 10 thermal shock test substrates, and one silicon chip was placed on each substrate.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 1 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 2 1.44 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.3 ⁇ 13, which is an index of the light resistance test of the cured product, and it was judged to have light resistance.
  • the number of times of the thermal shock test was 500 times or more and ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 2 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 3 1.45 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 9.2 ⁇ 13, which is an index of the light resistance test of the cured product, and it was determined that the cured product has light resistance.
  • the number of times of the thermal shock test was 500 times or more and ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 3 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 4 1.43 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.7 ⁇ 13 which is an index of a light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 4 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • Example 5 In the same manner as in Example 1, a resin composition and a cured product were prepared according to Tables 1 and 2. Table 3 shows the results of evaluation by the same method as in Example 1, the mixing indices ⁇ 5 to ⁇ 5, and the storage stability index ⁇ 5. In addition, it was confirmed that (OR 2 ) in the above formula (1) of the intermediate was hydrolyzed to (OH). The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance was 0% ⁇ 5%. As shown in Table 3, this resin composition had an epoxy equivalent (WPE) of 245 g / eq and showed an appropriate value.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 5 1.42 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.5 ⁇ 13, which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 250 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 5 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 6 1.46 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.1 ⁇ 13, which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 350 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 6 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 7 1.41 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.3 ⁇ 13, which is an index of the light resistance test of the cured product, and it was judged to have light resistance.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 7 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 8 1.45 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 7.6 ⁇ 13, which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 150 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 8 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 9 1.03 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.0 ⁇ 13, which is an index of the light resistance test of the cured product, and it was determined that it had light resistance.
  • the number of times of the thermal shock test was 350 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 9 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 10 1.04 ⁇ 4, indicating that the resin composition has storage stability.
  • YI 7.8 ⁇ 13 which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 10 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 11 1.60 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 7.5 ⁇ 13, which is an index of the light resistance test of the cured product, and it was judged that the cured product had light resistance.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 11 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 12 1.44 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 9.8 ⁇ 13, which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 12 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 13 1.48 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 9.9 ⁇ 13, which is an index of the light resistance test of the cured product, and it was judged that the cured product has light resistance.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 13 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • Example 14 Resin composition according to Tables 1 and 2 in the same manner as in Example 1 except that the curing temperature of (12) in Example 1 was changed to 110 ° C. for 4 hours and further to 150 ° C. for 1 hour. A cured product was prepared. Table 3 shows the results of evaluation by the same method as in Example 1, the mixing indices ⁇ 14 to ⁇ 14, and the storage stability index ⁇ 14. In addition, it was confirmed that (OR 2 ) in the above formula (1) of the intermediate was hydrolyzed to (OH). The amount of residual alkoxy groups calculated from the resin composition and the internal standard substance was 0% ⁇ 5%.
  • the storage stability index ⁇ 14 1.74 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 5.2 ⁇ 13, which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 150 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 14 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • Example 15 A resin composition and a cured product were prepared according to Tables 1 and 2 in the same manner as in Example 1, except that the curing temperature of (13) in Example 1 was changed to 110 ° C. for 4 hours.
  • Table 3 shows the results of evaluation by the same method as in Example 1, the mixing indices ⁇ 15 to ⁇ 15, and the storage stability index ⁇ 15.
  • (OR 2 ) in the above formula (1) of the intermediate was hydrolyzed to (OH).
  • the amount of residual alkoxy groups calculated from the resin composition and the internal standard substance was 0% ⁇ 5%.
  • the storage stability index ⁇ 15 1.92 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.8 ⁇ 13, which is an index of the light resistance test of the cured product, and it was determined that the cured product has light resistance.
  • the number of times of the thermal shock test was 250 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 15 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 16 1.21 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 12.4 ⁇ 13, which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 450 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 16 has fluidity and storage stability, and the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 17 1.53 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 7.2 ⁇ 13 which is an index of a light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 150 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 17 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 23 1.68 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 7.9 ⁇ 13, which is an index of the light resistance test of the cured product, and it was determined that the cured product has light resistance.
  • the number of times of the thermal shock test was 150 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 18 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 24 1.50 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 7.3 ⁇ 13, which is an index of the light resistance test of the cured product, and it was judged to have light resistance.
  • the number of times of the thermal shock test was 150 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 19 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the resin composition had storage stability.
  • YI 7.8 ⁇ 13 which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 50 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 20 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the storage stability index ⁇ 21 3.7 ⁇ 4, and it was found that the resin composition had storage stability.
  • YI 8.4 ⁇ 13, which is an index of the light resistance test of the cured product, and it was judged that the cured product has light resistance.
  • the number of times of the thermal shock test was 50 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 21 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance. It was judged that.
  • WPE epoxy equivalent
  • the resin composition has storage stability.
  • YI 8.2 ⁇ 13, which is an index of the light resistance test of the cured product, and it was judged to have light resistance.
  • the number of times of the thermal shock test was 50 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 22 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance. It was judged that.
  • WPE epoxy equivalent
  • Example 24 A resin composition was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio in Table 1, in an atmosphere of 25 ° C., the alkoxysilane compound and THF are placed in a flask containing a stirrer and mixed and stirred, and then water and a hydrolysis condensation catalyst are added. The mixture was stirred. (3) Subsequently, a cooling tube was set in the flask, and the flask was immediately immersed in an oil bath at 80 ° C.
  • WPE epoxy equivalent
  • a resin composition and a cured product were produced in the same manner as in Example 1 according to Table 2.
  • YI 8.3 ⁇ 13 which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 500 times or more and ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 24 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and thermal shock resistance, and therefore passes as a comprehensive judgment. It was judged that.
  • Example 25 A resin composition was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio in Table 1, in an atmosphere of 25 ° C., a mass equivalent to half the amount of Bis-A1 epoxy resin, an alkoxysilane compound and THF were placed in a flask containing a stirrer and mixed and stirred. Water and a hydrolysis condensation catalyst were added and mixed and stirred. (3) Subsequently, a cooling tube was set in the flask, and the flask was immediately immersed in an oil bath at 80 ° C.
  • the storage stability index ⁇ 25 1.42 ⁇ 4, and it was found that the resin composition had storage stability.
  • a resin composition and a cured product were produced in the same manner as in Example 1 according to Table 2.
  • YI 8.3 ⁇ 13 which is an index of the light resistance test of the cured product, and had light resistance.
  • the number of times of the thermal shock test was 500 times or more and ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, since the resin composition of Example 25 has fluidity and storage stability, and the cured product of the resin composition has light resistance and cold shock resistance, it passes as a comprehensive judgment. It was judged that.
  • Example 26 A resin composition was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) Except for the P-MS component, the Bis-A1 epoxy resin, the alkoxysilane compound and the THF component were mixed in a flask containing a stirrer in an atmosphere of 25 ° C. according to the composition ratio shown in Table 1. After the stirring, water and a hydrolysis condensation catalyst were further added and mixed and stirred. (3) Subsequently, a cooling tube was set in the flask, and the flask was immediately immersed in an oil bath at 80 ° C.
  • a resin composition and a cured product were produced in the same manner as in Example 1 according to Table 2.
  • YI 10.6 ⁇ 13 which is an index of the light resistance test of the cured product, and it had light resistance.
  • the number of times of the thermal shock test was 50 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 26 has fluidity and storage stability, and further, the cured product of the resin composition has light resistance and cold shock resistance. It was judged that.
  • WPE epoxy equivalent
  • WPE epoxy equivalent
  • Example 3 A resin composition was prepared in the same manner as in Example 1 according to Table 1.
  • Table 3 shows the results of evaluation by the same method as in Example 1, the mixing indices ⁇ 29 to ⁇ 29, and the storage stability index ⁇ 29.
  • WPE epoxy equivalent
  • the starting viscosity was 3.8 Pa ⁇ s ⁇ 1000 Pa ⁇ s and the storage viscosity was> 1000 Pa ⁇ s, indicating no fluidity.
  • the storage stability index ⁇ 28 263 or more> 4, and there was no storage stability.
  • Example 4 A resin composition was prepared in the same manner as in Example 1 according to Table 1.
  • Table 3 shows the results of evaluation by the same method as in Example 1, the mixing indices ⁇ 30 to ⁇ 30, and the storage stability index ⁇ 30.
  • WPE epoxy equivalent
  • the starting viscosity was 10.5 Pa ⁇ s ⁇ 1000 Pa ⁇ s and the storage viscosity was> 1000 Pa ⁇ s, indicating no fluidity.
  • the storage stability index ⁇ 30 95 or higher was> 4, and it was found that there was no storage stability.
  • Example 5 A resin composition was prepared in the same manner as in Example 1 according to Table 1.
  • Table 3 shows the results of evaluation by the same method as in Example 1, the mixing indices ⁇ 31 to ⁇ 31, and the storage stability index ⁇ 31.
  • the epoxy equivalent (WPE) of the resin composition of Comparative Example 5 was not measurable.
  • the starting viscosity was 24.0 Pa ⁇ s ⁇ 1000 Pa ⁇ s and the storage viscosity was> 1000 Pa ⁇ s, indicating no fluidity.
  • the storage stability index ⁇ 30 41 or more was> 4, and it was found that there was no storage stability.
  • Example 6 A cured product was produced in the same manner as in Example 1 according to Table 2.
  • Example 7 A solution for a cured product was prepared in the same manner as in Example 1 in accordance with Table 2 by mixing and stirring the above-described silicone resin A liquid and B liquid at a mass ratio of 1: 1.
  • the above-mentioned curing solution is poured into the molding jig and the above-described 10 thermal shock test substrates, and a silicon chip is further formed on each substrate. Were added one by one.
  • the molding jig and the thermal shock test substrate were placed in an oven and cured at 70 ° C. for 1 hour and further at 150 ° C. for 5 hours to produce a cured product.
  • Table 3 shows the results of evaluation performed in the same manner as in Example 1.
  • Epoxy equivalent (WPE) of the resin composition of Comparative Example 8 was 282 g / eq, which was a suitable value.
  • a cured product was prepared and evaluated in the same manner as in Example 1.
  • the cured product of Comparative Example 8 had a thermal shock test number of 0 ⁇ 50 times, and the thermal shock resistance was 0. It turns out that there is no sex.
  • minute cracks were generated and measurement was not possible. From the above results, the cured product of Comparative Example 8 was determined to be unacceptable as a comprehensive judgment.
  • Example 9 A resin composition was prepared in the same manner as in Example 1 according to Table 1.
  • Table 3 shows the evaluation results obtained in the same manner as in Example 1 and the mixing indices ⁇ 33 to ⁇ 33.
  • many intermediates in which (OR 2 ) in formula (1) was not hydrolyzed remained, and the hydrolysis reaction did not proceed normally. For this reason, a normal resin composition was not obtained, and it was judged as unacceptable.
  • the amount of residual alkoxy groups calculated from this resin composition and the internal standard material was 100% or more and> 5%.
  • condensation rate of the alkoxysilane and the condensation rate of the intermediate of the modified resin composition will be specifically described with reference to Examples and Comparative Examples.
  • evaluation methods of physical properties in Examples 27 to 35 and Comparative Examples 10 to 14 are shown below.
  • the residual alkoxy amount, epoxy equivalent (WPE), viscosity, and mixing indices ⁇ to ⁇ of the modified resin composition were determined according to the same method as described above.
  • the condensation rate of the intermediate was determined by the following procedure from the Si-NMR measurement result of the sample solution (intermediate) collected after the refluxing step.
  • (2) The sample solution after completion of the reflux process of 200 mg was weighed into a sample bottle, and the Cr solution was added to adjust to 1 g.
  • (3) The solution of (2) above was transferred to an NMR tube having a diameter of 5 mm ⁇ , and Si-NMR was measured under the following conditions.
  • R is arbitrary organic groups or H.
  • R is arbitrary organic groups or H.
  • R is arbitrary organic groups or H.
  • R is arbitrary organic groups or H.
  • the condensation rate of the alkoxysilane compound of the modified resin composition is determined as the condensation rate L (%) by the same method as the intermediate condensation rate calculation method from the Si-NMR measurement results of the sample solution collected after completion of the dehydration condensation process. It was.
  • Storage stability index ⁇ (storage viscosity) / (starting viscosity) (9)
  • the container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 60 ° C. for 16.5 days. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”.
  • the resin composition has fluidity (viscosity is 1000 Pa ⁇ s or less) and the storage stability index ⁇ is 6 or less, it was determined that the resin composition had storage stability and was determined as follows. 0 ⁇ ⁇ ⁇ 4 ⁇ 4 ⁇ ⁇ 6 ⁇
  • the light resistance of the cured product of the resin composition was evaluated by the following method.
  • (1) The cured product solution prepared by the method described later was cured to prepare a cured product of 20 mm ⁇ 10 mm ⁇ thickness 3 mm.
  • (2) The cured product was covered with a black mask of 25 mm ⁇ 15 mm ⁇ thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
  • a UV irradiation device USHIO Inc., “Spot Cure SP7-250DB” is set up so that the above sample in a constant temperature incubator kept constant at 50 ° C. can be irradiated with UV light via an optical fiber. Got ready.
  • Silicon chip (having a recess of 10 mm in diameter and 1.2 mm in depth at the center of a flat plate of 15 mm ⁇ 15 mm ⁇ thickness 2 mm)
  • Silicon chip (1-2) Silicon chip (: A commercially available silicon wafer cut to 5 mm ⁇ 5 mm ⁇ thickness 200 ⁇ m) (2) A solution for a cured product produced by the method described later was poured into the substrate, and 10 pieces of the silicon chip placed therein were produced and cured to obtain a thermal shock test sample. (3) The above sample is set in a thermal shock apparatus (“TSE-11-A” manufactured by ESPEC Corporation), and “( ⁇ 40 ° C. to 120 ° C.) / Cycle: exposure time of 14 minutes, heating / cooling time of 1 minute. The sample was heat cycled.
  • TSE-11-A manufactured by ESPEC Corporation
  • Epoxy resin (1-1) Epoxy resin A: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A epoxy resin) ⁇ Product name: “AER2600”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • Alkoxysilane compound H 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as GPTMS) ⁇ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound I phenyltrimethoxysilane (hereinafter referred to as PTMS) ⁇ Product name: “KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound J Dimethyldimethoxysilane (hereinafter referred to as DMDMS) ⁇ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound K tetraethoxysilane (hereinafter referred to as TEOS) ⁇ Product name: “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.
  • DBTDM Dibutyltin dimethoxide
  • DOTDA Dioctyltin diacetate
  • DBTDL Dibutyltin dilaurate
  • Curing accelerator Amine-based compound-Product name: "U-CAT 18X” manufactured by Sun Apro Co., Ltd.
  • a resin composition was prepared by the following steps. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio shown in Table 4 below, the Bis-A epoxy resin, the alkoxysilane compound, and THF are mixed and stirred in a flask containing a stirrer in an atmosphere at 25 ° C. Water and a hydrolysis condensation catalyst were added and mixed and stirred. (3) Subsequently, a cooling tube was set in the flask, and the flask was quickly immersed in an oil bath at 80 ° C.
  • the epoxy equivalent (WPE), the starting viscosity and the storage viscosity of the resin composition obtained in the above (6) were measured. Further, a storage stability index ⁇ 34 was determined and these are shown in Table 6.
  • a cured product was produced and evaluated by the following procedure.
  • (11) Under the atmosphere at 25 ° C., the above resin composition, curing agent and curing accelerator were mixed and stirred according to the composition ratio shown in Table 5 below, and deaerated under vacuum to obtain a cured product solution.
  • (12) A U-shaped silicon rubber having a thickness of 3 mm is sandwiched between two stainless steel plates coated with a release agent, and a cured product produced by this molding jig is about 50 mm ⁇ about 20 mm ⁇ thickness 3 mm. Thus, a molding jig was produced.
  • Example 28 A resin composition and a cured product thereof were prepared according to the following Table 4 and Table 5 by the same method as in Example 27 described above. About this resin composition and its hardened
  • cured material, it evaluated by the method similar to Example 27 mentioned above. The evaluation results, mixing indices ⁇ 35 to ⁇ 35, and storage stability index ⁇ 35 are shown in Table 6 below. Intermediate condensation ratio K2 (%) 78.2% ⁇ 78%. The condensation rate L2 (%) of the modified resin composition was 81.8% ⁇ 80%. The residual alkoxy content of the modified resin composition was 0% ⁇ 5%. As shown in Table 6 below, the resin composition of Example 28 had an epoxy equivalent (WPE) of 233 g / eq, and showed an appropriate value.
  • WPE epoxy equivalent
  • YI 8.1 ⁇ 13 which is an index of the light resistance test of the cured product, and that the light resistance was practically sufficient.
  • the number of times of the thermal shock test was 250 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was practically sufficient. From the above results, the resin composition of Example 28 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.
  • Example 29 A resin composition and a cured product thereof were prepared according to the following Table 4 and Table 5 by the same method as in Example 27 described above. About this resin composition and its hardened
  • WPE epoxy equivalent
  • Example 30 A resin composition and a cured product thereof were prepared according to the following Table 4 and Table 5 by the same method as in Example 27 described above. About this resin composition and its hardened
  • WPE epoxy equivalent
  • YI 8.8 ⁇ 13, which is an index of the light resistance test of this cured product, and it was judged that the light resistance was practically sufficient.
  • the number of times of the thermal shock test was 150 times ⁇ 50 times, and it was judged to have practically sufficient cold thermal shock resistance. From the above results, the resin composition of Example 30 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.
  • Example 31 In the same manner as in Example 27 described above, a resin composition and a cured product thereof were produced according to Tables 4 and 5 below. About this resin composition and its hardened
  • WPE epoxy equivalent
  • YI 8.2 ⁇ 13, which is an index of the light resistance test of this cured product, and it was judged that the light resistance was practically sufficient.
  • the number of times of the thermal shock test was 150 times ⁇ 50 times, and it was judged to have practically sufficient cold thermal shock resistance. From the above results, the resin composition of Example 31 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.
  • Example 32 In the same manner as in Example 27 described above, a resin composition and a cured product thereof were produced according to Tables 4 and 5 below. About this resin composition and its hardened
  • WPE epoxy equivalent
  • Example 33 In the same manner as in Example 27 described above, a resin composition and a cured product thereof were produced according to Tables 4 and 5 below. About this resin composition and its hardened
  • WPE epoxy equivalent
  • YI 7.5 ⁇ 13, which is an index of the light resistance test of the cured product, and it was determined that the cured product has sufficient light resistance.
  • the number of times of the thermal shock test was 350 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was practically sufficient. From the above results, the resin composition of Example 33 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.
  • WPE epoxy equivalent
  • WPE epoxy equivalent
  • the number of times of the thermal shock test was 250 times ⁇ 50 times, and it was judged that the thermal thermal shock resistance was provided. From the above results, the resin composition of Example 35 has excellent fluidity and improved storage stability, and the cured product of the resin composition has practically sufficient light resistance and cold thermal shock resistance. Since it has property, it was judged that it was a pass as comprehensive judgment.
  • the condensation ratio L10 (%) of the modified resin composition was 75.4.0% ⁇ 80%.
  • the residual alkoxy content of the modified resin composition was 21%> 5%.
  • the onset viscosity was 11.7 Pa ⁇ s ⁇ 1000 Pa ⁇ s.
  • the storage viscosity was> 1000 Pa ⁇ s, the fluidity was not exhibited, and the storage stability index ⁇ 43> 85 and the storage stability was poor.
  • the light resistance and the thermal shock resistance of the cured product using the resin composition of Comparative Example 10 were good, but the storage stability of the resin composition was poor, and it was not good as a comprehensive judgment. Judged to pass.
  • silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., “SCR-1012 (liquid A and liquid B)”
  • a cured product solution was prepared in the same manner as in Example 26.
  • the curing solution was poured into the molding jig and the above-mentioned 10 thermal shock test substrates, and the silicon chip was put on each substrate. I put them one by one.
  • the molding jig and the thermal shock test substrate were placed in an oven and cured at 70 ° C. for 1 hour and further at 150 ° C. for 5 hours to produce a cured product.
  • the onset viscosity was 15.2 Pa ⁇ s ⁇ 1000 Pa ⁇ s. However, storage viscosity> 1000 Pa ⁇ s, fluidity was not exhibited, storage stability index ⁇ 44> 66, storage stability was poor, and it was judged as unacceptable as a comprehensive judgment. From the above, even if the time for performing the dehydration condensation process is extended, the storage stability of the resin composition does not reach the pass line, and the characteristics of the resin composition are the condensation rate of the intermediate in the reflux process (chemical structure) It turned out to depend greatly on.
  • WPE epoxy equivalent
  • the onset viscosity was 16.4 Pa ⁇ s ⁇ 1000 Pa ⁇ s. However, storage viscosity> 1000 Pa ⁇ s, fluidity was not exhibited, storage stability index ⁇ 44> 61 and storage stability was poor, and it was judged as unacceptable as a comprehensive judgment.
  • an epoxy resin and a specific alkoxysilane compound are mixed at a specific ratio to specify the condensation rate of the intermediate in the reflux step of the cohydrolysis condensation, and then dehydration condensation is performed.
  • the resin compositions of Examples 27 to 35 prepared by specifying the condensation rate of the modified resin composition have excellent fluidity and storage stability, and cured products of these resin compositions. Were found to have excellent light resistance and thermal shock resistance.
  • the light resistance of the cured product was evaluated by the following method. (1) The cured product solution prepared by the method described later was cured to prepare a cured product of 20 mm ⁇ 10 mm ⁇ thickness 3 mm. (2) The cured product was covered with a black mask of 25 mm ⁇ 15 mm ⁇ thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test. (3) A UV irradiation device (USHIO Inc., “Spot Cure SP7-250DB”) is set up so that the above sample in a constant temperature incubator kept constant at 50 ° C. can be irradiated with UV light via an optical fiber. Got ready.
  • USHIO Inc. “Spot Cure SP7-250DB”
  • ⁇ Crack test of cured product The presence or absence of cracks in the cured product was evaluated by the following method.
  • substrate shown below was prepared.
  • Five of the cured product solutions prepared by the method described below were poured into the substrate, and the cured products were used as crack test samples.
  • ⁇ Surface tackiness test of cured product> The surface tackiness of the cured product was evaluated by the following method. (1) The cured product solution prepared by the method described later was cured to prepare a cured product of 20 mm ⁇ 10 mm ⁇ thickness 3 mm. (2) The surface of the obtained cured product was lightly pressed with a thumb wearing latex gloves, and when no stickiness was observed, it was judged that the surface tackiness was good.
  • Epoxy resin (1-1) Epoxy resin A: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A epoxy resin) ⁇ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • Alkoxysilane compound H 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as GPTMS) ⁇ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound I phenyltrimethoxysilane (hereinafter referred to as PTMS) ⁇ Product name: “KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound J Dimethyldimethoxysilane (hereinafter referred to as DMDMS) ⁇ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound K tetraethoxysilane (hereinafter referred to as TEOS) ⁇ Product name: “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.
  • DBTDL dibutyltin dilaurate
  • Oxetane compound 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane (manufactured by Toagosei Co., Ltd., “Aron Oxetane OXT-221”)
  • Curing accelerator Amine compound-Product name: "U-CAT 18X” manufactured by Sun Apro Co., Ltd.
  • Resin composition A was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio in Table 7, in an atmosphere of 25 ° C., the alicyclic epoxy resin, the alkoxysilane compound and THF are placed in a flask containing a stirrer, mixed and stirred, and further hydrolyzed with water. A condensation catalyst was added and mixed and stirred. (3) Subsequently, a cooling tube was set on the flask, and it was immediately immersed in an oil bath at 80 ° C.
  • Resin Composition B Resin Composition B was synthesized and evaluated in the same manner as in Synthesis Example 1 according to the composition ratio in Table 7. Table 9 shows the mixing indices ⁇ 47 to ⁇ 47.
  • the epoxy equivalent (WPE) of the resin composition B was 163 g / eq, which was an appropriate value.
  • Resin composition C Resin composition C was synthesized and evaluated in the same manner as in Synthesis Example 1 in accordance with the composition ratio in Table 7. Table 9 shows the mixing indexes ⁇ 48 to ⁇ 48.
  • the epoxy equivalent (WPE) of the resin composition C was 160 g / eq, which was an appropriate value.
  • Composition 1 was prepared and evaluated according to the following procedure. (1) Composition 1 was obtained by mixing and stirring 75% by mass of resin composition A of Synthesis Example 1 and 25% by mass of an oxetane compound, and further degassing under vacuum. The viscosity of composition 1 was 1.82 Pa ⁇ s, and it was a liquid excellent in fluidity. (2) 0.8% by mass of a cationic polymerization initiator was added to and mixed with 99.2% by mass of Composition 1, and degassing treatment was performed under the same conditions as in (1) to prepare a cured product solution. .
  • Composition 2 was produced and evaluated by the following procedure. (1) 70% by mass of the resin composition B of Synthesis Example 2 and 30% by mass of an oxetane compound were mixed and stirred, and degassed by the same method as in Example 36 to obtain Composition 2. The viscosity of the composition 2 was 2.78 Pa ⁇ s, and it was a liquid excellent in fluidity. (2) 0.6% by weight of cationic polymerization initiator was added to and mixed with 99.4% by weight of composition 2, and degassing was performed under the same conditions as in (1) to prepare a cured product solution. . (3) Using the solution for a cured product, a curing treatment was performed in the same manner as in Example 36 to prepare a cured product.
  • YI 7.9 ⁇ 11, which is an index of the light resistance test of this cured product, and it was judged that it had light resistance. Further, no cracks were generated in all of the 5/5 samples, and it was judged that the samples had crack resistance. Furthermore, no stickiness was observed and the surface tackiness was good. From the above results, the composition 2 of Example 35 has fluidity, and the cured product of the composition has light resistance and crack resistance, and also has good surface tackiness. It was judged that the test was acceptable.
  • Example 38 Composition 3 was produced and evaluated by the following procedure. (1) 80% by mass of the resin composition C of Synthesis Example 3 and 20% by mass of an oxetane compound were mixed and stirred, and degassed by the same method as in Example 36 to obtain Composition 3. The viscosity of the composition 3 was 2.27 Pa ⁇ s, and it was a liquid excellent in fluidity. (2) 0.7% by mass of a cationic polymerization initiator was added to and mixed with 99.3% by mass of Composition 3, and deaeration treatment was performed under the same conditions as in (1) to prepare a cured product solution. . (3) Using the solution for a cured product, a curing treatment was performed in the same manner as in Example 36 to prepare a cured product.
  • YI 8.8 ⁇ 11, which is an index of the light resistance test of the cured product, and it was determined that the cured product has light resistance. Further, no cracks were generated in 4/5 samples, and it was judged to have crack resistance. Furthermore, no stickiness was observed and the surface tackiness was good. From the above results, the composition 3 of Example 38 has fluidity, and the cured product of the composition has light resistance and crack resistance, and also has good surface tackiness. It was judged that the test was acceptable.
  • a resin composition obtained by mixing an epoxy resin and a specific alkoxysilane compound at a specific ratio and cohydrolyzing and condensing, and a resin containing an oxetane compound The composition was excellent in fluidity. Moreover, the hardened
  • the photosensitive resin composition obtained by adding a photoacid generator to the modified resin composition of the present embodiment will be specifically described with reference to Examples and Comparative Examples.
  • the epoxy equivalent (WPE), viscosity, and mixing indices ⁇ to ⁇ were determined according to the same method as described above.
  • the physical properties of Examples 39 to 41 and Comparative Examples 17 to 19 were evaluated as follows.
  • a coating film was produced in air under conditions of an air temperature of 23 ° C. and a humidity of 55% RH.
  • the following substrates were prepared, and each surface was wiped dry with ethanol (Wako Pure Chemical Industries, Ltd., 99.5%).
  • Substrate Polyethylene terephthalate resin (hereinafter referred to as PET)
  • PET Polyethylene terephthalate resin
  • PC Polycarbonate resin
  • PMMA Polymethyl methacrylate resin
  • the substrate was set in a UV curing device (manufactured by Fusion UV Systems Japan Co., Ltd.), and the following conditions were repeated three times for curing.
  • Light source and light intensity High pressure mercury lamp (120W / cm2)
  • Belt conveyor speed 10 m / min (4)
  • the substrate was heat-treated at 100 ° C. for 1 hour to be post-cured.
  • ⁇ Preparation method b of coating film> a coating film was produced in air under conditions of an air temperature of 23 ° C. and a humidity of 55% RH.
  • the following substrates were prepared, and each surface was wiped dry with ethanol (Wako Pure Chemical Industries, Ltd., 99.5%).
  • the photosensitive composition of an Example or the composition of a comparative example was apply
  • the substrate was set in a UV curing device (manufactured by Fusion UV Systems Japan Co., Ltd.), and the following conditions were repeated 5 times and cured.
  • Light source and light intensity High pressure mercury lamp (120W / cm2)
  • Belt conveyor speed 5m / min
  • Epoxy resin (1-1) Epoxy resin A: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A epoxy resin) ⁇ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • Alkoxysilane compound H 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as GPTMS) ⁇ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound I phenyltrimethoxysilane (hereinafter referred to as PTMS) ⁇ Product name: “KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound J Dimethyldimethoxysilane (hereinafter referred to as DMDMS) ⁇ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound K tetraethoxysilane (hereinafter referred to as TEOS) ⁇ Product name: “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.
  • DBTDL Dibutyltin dilaurate
  • Photoacid generator (8-1) Hexafluorophosphate mixture of triallylsulfonium ⁇ Product name: “UVI-6990” (hereinafter referred to as UVI-6900) manufactured by Union Carbide.
  • (8-2) Hexafluoroantimonate of aromatic sulfonium • Product name: “SAN-AID SI-80L” (hereinafter referred to as SI-80L), manufactured by Sanshin Chemical Industry Co., Ltd.
  • Resin composition D Resin composition D was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) In accordance with the composition ratio in Table 10, in an atmosphere of 25 ° C., the alicyclic epoxy resin, the alkoxysilane compound, and THF are placed in a flask containing a stirrer, mixed and stirred, and then further hydrolyzed with water. A condensation catalyst was added and mixed and stirred. (3) Subsequently, a cooling tube was set on the flask, and it was immediately immersed in an oil bath at 80 ° C.
  • Resin composition E was synthesized and evaluated in the same manner as in Synthesis Example 4 according to the composition ratio in Table 10. Table 12 shows the mixing indices ⁇ 50 to ⁇ 50.
  • the epoxy equivalent (WPE) of the resin composition E was 152 g / eq, which was an appropriate value. Further, the viscosity was 0.93 Pa ⁇ s ⁇ 1000 Pa ⁇ s, indicating good fluidity.
  • the photosensitive resin composition 1 and its coating film were manufactured and evaluated by the following procedures.
  • the photosensitive resin composition 1 was obtained by using the resin composition D of Synthesis Example 4 above, mixing and stirring in accordance with the formulation of Table 11, and degassing under vacuum.
  • the viscosity of the photosensitive resin composition 1 was 12.6 Pa ⁇ s ⁇ 1000 Pa ⁇ s, and the liquid was excellent in fluidity.
  • Photosensitive resin composition 2 was produced in the same manner as in Example 39 according to the formulation in Table 11. However, the belt conveyor speed of the UV curing device was set to 10 m / min. The evaluation results are shown in Table 12. The viscosity of the photosensitive resin composition 2 was 3.2 Pa ⁇ s ⁇ 1000 Pa ⁇ s, and the liquid was excellent in fluidity. As shown above, the photosensitive resin composition 2 is excellent in fluidity, has good photocurability of the coating film, and has better adhesiveness than the comparative example 17, which is a reference. Judged that there was.
  • Photosensitive resin composition 3 was produced according to the formulation shown in Table 11 and evaluated in the same manner as in Example 39.
  • the viscosity of the photosensitive resin composition 3 was 1.0 Pa ⁇ s ⁇ 1000 Pa ⁇ s, and the liquid was excellent in fluidity.
  • the photosensitive resin composition 3 was used and PET was used as a substrate to produce a coating film according to the above-described “coating film production method b”.
  • the results are shown in Table 12.
  • the photosensitive resin composition 3 is excellent in fluidity, has good photocurability of the coating film, and has better adhesiveness than the comparative example 19 as a reference. Judged that there was.
  • Photosensitive resin composition 4 was produced in the same manner as in Example 39 according to the formulation in Table 11. The evaluation results are shown in Table 12. The viscosity of the photosensitive resin composition 4 was 13.8 Pa ⁇ s ⁇ 1000 Pa ⁇ s, and the liquid was excellent in fluidity. However, as shown in Table 12, although the photosensitive resin composition 4 was excellent in fluidity, it was judged to be unacceptable as a comprehensive judgment because the adhesiveness of the coating film was poor.
  • Photosensitive resin composition 5 was produced in the same manner as in Example 39 according to the formulation in Table 11. GPTMS was used as the silane coupling agent. The evaluation results are shown in Table 12. The viscosity of the photosensitive resin composition 5 was 12.1 Pa ⁇ s ⁇ 1000 Pa ⁇ s, and the liquid was excellent in fluidity. However, as shown in Table 12, although the photosensitive resin composition 5 was excellent in fluidity, the effect of improving the adhesiveness of the coating film was not seen, and it was judged as unacceptable as a comprehensive judgment.
  • Photosensitive resin composition 6 was produced in the same manner as in Example 39 according to the formulation in Table 11. The evaluation results are shown in Table 12. The viscosity of the photosensitive resin composition 6 was 0.3 Pa ⁇ s ⁇ 1000 Pa ⁇ s, and the liquid was excellent in fluidity. However, as shown in Table 12, although the photosensitive resin composition 6 was excellent in fluidity, the adhesiveness of the coating film was poor.
  • a photosensitive resin containing a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound, and a photoacid generator The composition was excellent in fluidity, and the coating agent and coating film using these photosensitive resin compositions were excellent in photocurability and adhesiveness.
  • Examples 42 to 44 and Comparative Examples 20 to 23 were evaluated as follows.
  • the epoxy equivalent (WPE), viscosity, and mixing indices ⁇ to ⁇ were determined according to the same method as described above.
  • Storage stability index ⁇ (storage viscosity) / (starting viscosity) (9)
  • the container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”. When the resin composition was fluid (viscosity was 1000 Pa ⁇ s or less) and the storage stability index ⁇ was 4 or less, it was judged to have storage stability.
  • ⁇ Light resistance test of cured product (cured product of resin composition)> A cured product in which a solid (phosphor) is dispersed has a large variation in yellowness (YI). Therefore, a cured product was prepared from a resin composition to which no phosphor was added by the following method, and the evaluation result was regarded as light resistance evaluation.
  • the cured product solution prepared by the method described later was cured to prepare a cured product of 20 mm ⁇ 10 mm ⁇ thickness 3 mm.
  • the cured product was covered with a black mask of 25 mm ⁇ 15 mm ⁇ thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
  • a UV irradiation device (USHIO Inc., “Spot Cure SP7-250DB”) is set up so that the above sample in a constant temperature incubator kept constant at 50 ° C. can be irradiated with UV light via an optical fiber. Got ready.
  • the sample was set in a constant temperature incubator at 50 ° C. with the black mask on top.
  • UV light of 2 W / cm 2 was irradiated for 96 hours from the top of the black mask so that UV light could be irradiated to a hole with a diameter of 5.5 mm.
  • ⁇ Luminescence test of phosphorescent material (afterglow time measurement)> The sample was irradiated with a conventional light source fluorescent lamp D65 as defined in “JIS Z9107: 2008 Safety Sign—Performance Classification, Performance Criteria and Test Method” at 200 lux for 20 minutes. After irradiation, the afterglow brightness was measured with a luminance meter, and the time until it reached 0.3 mcd / m 2 or less was defined as the afterglow time. When the afterglow time was 120 minutes or more, the light emission was judged to be acceptable.
  • ⁇ LED reliability test (1) (continuous operation test: hereinafter referred to as “L test”)> Ten LEDs are connected to “MIL-STD-750E (TEST METHODS FOR SEMICONDUCTOR DEVICES)”, METHOD 1026.5 (STEADY-STATE OPERATION LIFE), and “MIL-STD-883G (MICROCIRMEITS.5)”.
  • MIL-STD-750E TEST METHODS FOR SEMICONDUCTOR DEVICES
  • METHOD 1026.5 STEADY-STATE OPERATION LIFE
  • MIL-STD-883G MICROCIRMEITS.5
  • total luminous flux maintenance factor (%) (total luminous flux after lighting) / (total luminous flux before lighting) ⁇ 100” is obtained, and the minimum value of the total luminous flux maintenance factor (%) of all LEDs is 90. When it was more than%, it was judged as passing.
  • thermo shock test hereinafter referred to as “TS test”.
  • Ten LEDs were evaluated under the following conditions in accordance with test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). “-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” is one cycle, and after 100 cycles of thermal shock, the lighting of the LEDs was confirmed. .
  • TC test temperature cycle test: hereinafter referred to as “TC” test
  • Ten LEDs were evaluated under the following conditions in accordance with Test Method 105 (Temperature Cycle Test) of “EIAJ ED-4701 / 100 (Semiconductor Device Environment and Durability Test Method (Life Test I)”). “-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle. When all 10 were turned on, it was judged as passing.
  • Epoxy resin (1-1) Epoxy resin A: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “Bis-A epoxy resin”) ⁇ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • Alkoxysilane compound (2-1) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”) ⁇ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd. (2-2) Alkoxysilane Compound I: Phenyltrimethoxysilane (hereinafter referred to as “PTMS”) ⁇ Product name: “KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • GTMS 3-glycidoxypropyltrimethoxysilane
  • PTMS Phenyltrimethoxysilane
  • THF Tetrahydrofuran (Wako Pure Chemical Industries, Ltd., stabilizer-free type)
  • DBTDL dibutyltin dilaurate
  • Curing accelerator Amine-based compound-Trade name: "U-CAT 18X” manufactured by Sun Apro Co., Ltd.
  • Reactive diluent “1,2: 8,9 diepoxy limonene” ⁇ Product name: “Celoxide 3000”, manufactured by Daicel Chemical Industries, Ltd.
  • the resin composition was manufactured by the following process. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio shown in Table 13 below, the Bis-A1 epoxy resin, alkoxysilane compound, and THF were placed in a flask containing a stirrer and mixed and stirred in an atmosphere at 25 ° C. Water and a hydrolysis condensation catalyst were added and mixed and stirred. (3) Subsequently, a cooling tube was set on the flask, and the flask was immediately immersed in an oil bath at 80 ° C.
  • the epoxy equivalent (WPE), the starting viscosity and the storage viscosity of the resin composition obtained in the above (6) were measured. Furthermore, the storage stability index ⁇ 51 was determined and these are shown in Table 16.
  • Example 42 A cured product was produced using the resin composition of Synthesis Example 6 described above, which was stored at 25 ° C. for 2 weeks, and a light resistance test was performed. The results are shown in Table 16.
  • (1) In an atmosphere of 25 ° C., the above-described resin composition, curing agent, and curing accelerator were mixed and stirred according to the composition ratio in Table 14, and deaerated under vacuum to obtain a cured product solution.
  • (2) A 3 mm thick, U-shaped silicon rubber was sandwiched between two stainless steel plates coated with a release agent to prepare a molding jig.
  • the above-mentioned solution for cured product was poured into this molding jig and subjected to curing treatment at 120 ° C.
  • a shell-type LED was manufactured according to the following procedure, and reliability tests (1) to (3) were performed. The results are shown in Table 16.
  • This bullet-type LED has two lead frames, and a cup portion for mounting an LED chip is formed on one upper end of the lead frame.
  • the fluorescent resin composition, the curing agent, and the curing accelerator were mixed and stirred according to the composition ratio in Table 15, and degassed under vacuum to obtain an LED sealing material.
  • the LED sealing material (9) was injected into the cup portion of a bullet-shaped mold frame having a diameter of 5 mm.
  • the fluorescent resin composition of Example 42 passed all of the dispersion stability test, light resistance test, light emission test, and reliability test (1) to (3). Judged to pass.
  • Example 44 A phosphor resin composition was prepared and evaluated by blending 60% by mass of the phosphor B with 40% by mass of the resin composition of Synthesis Example 7 in the same manner as in Example 42. When the dispersion stability test of the fluorescent resin composition of Example 44 was carried out, no precipitation was observed, and the product was uniform and judged to be acceptable. Then, the fluorescent resin composition, the reaction diluent and the polymerization initiator are mixed at the ratio shown in Table 17, defoamed under vacuum, and further, in the air, at an air temperature of 23 ° C. and a humidity of 55% RH. Under the conditions, a phosphorescent material (coating film) was produced.
  • Example 44 A slide glass having a size of 5 cm ⁇ 5 cm was prepared, and the surface was wiped with ethanol (99.5%, manufactured by Wako Pure Chemical Industries, Ltd.) and dried. (2) The fluorescent resin composition was applied onto the slide glass using a bar coater (# 3). (3) The slide glass was cured at 140 ° C. for 10 minutes to form a coating film. When the afterglow time was measured by the above-mentioned method as a luminous test of the phosphorescent material (coating film), it was 600 minutes or more, and it was judged to be acceptable. From the above results, the fluorescent resin composition of Example 44 passed the dispersion stability test and the light emission test, and was judged to be acceptable as a comprehensive judgment. The results are shown in Table 18.
  • Table 16 shows the results of producing and evaluating a fluorescent resin composition using an alicyclic epoxy resin instead of the resin composition of Synthesis Example 6.
  • the fluorescent resin composition of Comparative Example 20 was stored at 25 ° C. for 5 hours, the phosphor was precipitated, was non-uniform, and the dispersion stability was judged to be unacceptable. And since the normal fluorescent resin composition was not able to be produced, preparation and evaluation of hardened
  • the fluorescent resin compositions of Examples 42 and 43 were excellent in dispersion stability, and the cured product was excellent in light resistance.
  • the LED using the fluorescent resin composition of Examples 42 and 43 as a sealing material had a good light emission test and an excellent reliability test.
  • the fluorescent resin composition of Example 44 was excellent in dispersion stability, and the phosphorescent material had a good light emission test.
  • Comparative Examples 20 and 23 had poor dispersion stability of the fluorescent resin composition.
  • at least one of the light resistance when used as the cured product and the light emission test and reliability test of the LED used as the sealing material was defective. From the above, it was shown that the fluorescent resin composition of the present embodiment is excellent in dispersion stability, the sealing material using it is excellent in reliability, and the phosphorescent material is excellent in luminescent properties. .
  • an insulating resin composition obtained by adding insulating powder to the modified resin composition of the present embodiment will be specifically described with reference to examples and comparative examples.
  • Examples 45 to 48 and Comparative Examples 24 to 25 were evaluated as follows.
  • the epoxy equivalent (WPE), viscosity, and mixing indices ⁇ to ⁇ were determined according to the same method as described above.
  • ⁇ Adhesive strength measurement and adhesive evaluation of insulating resin composition The adhesive strength before and after the moisture absorption treatment was measured according to the following procedure. (1) The insulating resin composition was applied to the die pad portion (9 mm ⁇ 9 mm) of the copper lead frame. (2) Next, a silicon chip (8 mm ⁇ 16 mm) was mounted on the die pad portion and heated in an oven at 200 ° C. for 1 hour. (Sample before moisture absorption treatment) (3) The sample prepared in (2) was absorbed for 72 hours in a thermo-hygrostat set to a temperature of 85 ° C. and a humidity of 85%.
  • ⁇ Void evaluation of insulating resin composition The insulating resin composition was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually checked for the presence of voids under a magnifier. About the insulating resin composition of an Example and a comparative example, when insulation and adhesiveness were favorable and generation
  • Epoxy resin (1-1) Epoxy resin A: bisphenol A type epoxy resin (hereinafter referred to as Bis-A epoxy resin) ⁇ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows. Epoxy equivalent (WPE): 187 g / eq Viscosity (25 ° C.): 14.3 Pa ⁇ s (1-2) Epoxy resin F: Bisphenol F type epoxy resin (hereinafter referred to as “Bis-F epoxy resin”) ⁇ Product name: “JER807” manufactured by Japan Epoxy Resin Co., Ltd.
  • Epoxy equivalent (WPE) 169 g / eq Viscosity (25 ° C.): 3.2 Pa ⁇ s
  • Alkoxysilane compound H 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”) ⁇ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane Compound I Phenyltrimethoxysilane (hereinafter referred to as “PTMS”) ⁇ Product name: “KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound J Dimethyldimethoxysilane (hereinafter referred to as “DMDMS”) ⁇ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound K tetraethoxysilane (hereinafter referred to as “TEOS”) ⁇ Product name: “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Insulating powder (10-1) Fused silica (manufactured by Toshin Kasei Co., Ltd., average particle size 6.1 ⁇ m) (10-2) Hydrophobic silica (Asahi Kasei Wacker Silicone Co., Ltd., “H18”)
  • Resin composition F was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio in Table 19, in an atmosphere of 25 ° C., the epoxy resin, the alkoxysilane compound, and THF are placed in a flask containing a stirrer, mixed and stirred, and then water and a hydrolysis condensation catalyst are further added. Added and mixed and stirred. (3) Subsequently, a cooling tube was set on the flask, and immediately, it was immersed in an oil bath at 80 ° C.
  • the epoxy equivalent (WPE) of the resin composition F obtained in the above (6) was measured.
  • the viscosity was 12.7 Pa ⁇ s and a fluid liquid.
  • Resin Composition G was synthesized and evaluated in the same manner as in Synthesis Example 8 according to the composition ratio in Table 19. Table 21 shows the mixing indices ⁇ 55 to ⁇ 55.
  • the viscosity was 13.8 Pa ⁇ s and a fluid liquid.
  • Resin Composition H Resin Composition H was synthesized and evaluated in the same manner as in Synthesis Example 8 according to the composition ratio in Table 19. Table 21 shows the mixing indices ⁇ 56 to ⁇ 56.
  • the viscosity was 18.2 Pa ⁇ s and a fluid liquid.
  • Resin Composition I Resin Composition I was synthesized and evaluated in the same manner as in Synthesis Example 8 according to the composition ratio in Table 19. Table 21 shows the mixing indices ⁇ 57 to ⁇ 57.
  • the viscosity was 10.2 Pa ⁇ s, and it was a fluid liquid.
  • Insulating resin composition 1 was produced and evaluated by the following procedure. Table 21 shows the evaluation results and mixing indices ⁇ 54 to ⁇ 54. Using the resin composition F of Synthesis Example 8 above, the raw materials were blended according to the composition of Table 20, and kneaded uniformly with a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd.). Furthermore, what was degassed at 400 Pa for 30 minutes using a vacuum chamber was designated as Insulating Composition 1. What applied the insulating resin composition 1 to the slide glass so that it might be set to 40 micrometers in thickness with a bar coater was heated at 200 degreeC for 60 minutes, and the coating film was formed.
  • the adhesive strength remaining rate of the insulating resin composition 1 was determined by the following procedure. (1) Four points were produced by applying the insulating resin composition 1 to the die pad portion (9 mm ⁇ 9 mm) of the copper lead frame. (2) Next, a silicon chip (8 mm ⁇ 16 mm) was mounted on the die pad portion and heated in an oven at 200 ° C. for 1 hour. (3) Of the samples prepared in (2), two points were designated as “samples before moisture absorption treatment”.
  • sample after moisture absorption treatment A sample obtained by absorbing the remaining two points of the sample prepared in (2) for 72 hours in a thermo-hygrostat set to a temperature of 85 ° C. and a humidity of 85% was designated as “sample after moisture absorption treatment”.
  • the insulating resin composition 1 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour.
  • Example 46 Insulating resin composition 2 was produced and evaluated in the same manner as in Example 45 using the above-described resin composition G according to the composition of Table 20. The evaluation results and mixing indexes ⁇ 55 to ⁇ 55 are shown in Table 21.
  • the volume resistivity of the insulating resin composition 2 was 1 ⁇ 10 10 ⁇ ⁇ cm or more, and it was determined that the insulating property was good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “hygroscopic treatment sample” of the insulating resin composition 2 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • Example 47 The insulating resin composition 3 was produced and evaluated in the same manner as in Example 45 using the resin composition H described above according to the composition of Table 20. Table 21 shows the evaluation results and mixing indices ⁇ 56 to ⁇ 56.
  • the volume resistivity of the insulating resin composition 3 was 1 ⁇ 10 10 ⁇ ⁇ cm or more, and it was determined that the insulating property was good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the insulating resin composition 3 was substituted into the following formula to determine the adhesive strength residual ratio, and the adhesiveness was evaluated.
  • Example 48 Insulating resin composition 4 was produced and evaluated in the same manner as in Example 43 using resin composition I described above according to the composition of Table 20. Table 21 shows the evaluation results and mixing indices ⁇ 57 to ⁇ 57.
  • the volume resistivity of the insulating resin composition 4 was 1 ⁇ 10 10 ⁇ ⁇ cm or more, and it was determined that the insulating property was good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the insulating resin composition 4 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • the insulating resin composition 4 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually confirmed under a magnifying glass, but no void was generated. From said result, since the insulating resin composition 4 was excellent in insulation and adhesiveness, and also there was no generation
  • Insulating resin composition 5 was produced in the same manner as in Example 45, using Bis-A epoxy resin and Bis-F epoxy resin instead of resin composition F according to the composition of Table 20, and evaluated. did. The results are shown in Table 21.
  • the volume resistivity of the insulating resin composition 5 was 1 ⁇ 10 10 ⁇ ⁇ cm or more, and it was determined that the insulating property was good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the insulating resin composition 5 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • Insulating resin composition 6 was produced and evaluated in the same manner as in Example 43 using Bis-A epoxy resin, GPTMS and PTMS instead of resin composition F according to the composition of Table 20. The results are shown in Table 21.
  • the volume resistivity of the insulating resin composition 6 was 1 ⁇ 10 10 ⁇ ⁇ cm or more, and it was determined that the insulating property was good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the insulating resin composition 6 was substituted into the following equation to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • Examples 49 to 58 and Comparative Examples 26 to 30 were evaluated as follows.
  • the epoxy equivalent (WPE), viscosity, and mixing indices ⁇ to ⁇ were determined according to the same method as described above.
  • Storage stability index ⁇ (storage viscosity) / (starting viscosity) (9)
  • the container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”. When the resin composition was fluid (viscosity was 1000 Pa ⁇ s or less) and the storage stability index ⁇ was 4 or less, it was judged to have storage stability.
  • the cured product solution prepared by the method described later was cured to prepare a cured product of 20 mm ⁇ 10 mm ⁇ thickness 3 mm.
  • the cured product was covered with a black mask of 25 mm ⁇ 15 mm ⁇ thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
  • a UV irradiation device (USHIO Inc., “Spot Cure SP7-250DB”) is set up so that the above sample in a constant temperature incubator kept constant at 50 ° C. can be irradiated with UV light via an optical fiber. Got ready.
  • the sample was set in a constant temperature incubator at 50 ° C. with the black mask on top.
  • UV light of 2 W / cm 2 was irradiated for 96 hours from the top of the black mask so that UV light could be irradiated to a hole with a diameter of 5.5 mm.
  • IF forward current
  • Ta ambient temperature
  • 960 hours the total luminous flux
  • total luminous flux maintenance rate (%) (total luminous flux after lighting) / (total luminous flux before lighting) ⁇ 100” is obtained, and the minimum value of the total luminous flux maintenance rate (%) of all LEDs is When it was 90% or more, it was judged to be acceptable.
  • thermo shock test hereinafter referred to as “TS test”.
  • Ten LEDs were evaluated under the following conditions in accordance with test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Assuming that “-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” is one cycle, lighting of the LEDs was confirmed after applying 100 cycles of thermal shock.
  • ⁇ LED reliability test (3) (temperature cycle test: hereinafter referred to as “TC test”)> Ten LEDs were evaluated under the following conditions in accordance with Test Method 105 (Temperature Cycle Test) of “EIAJ ED-4701 / 100 (Semiconductor Device Environment and Durability Test Method (Life Test I)”). “-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle. When all 10 lights were turned on, it was judged as passing. In the evaluation of the LED, when all of the light resistance and reliability tests (1) to (3) were acceptable, it was judged as acceptable as a comprehensive judgment.
  • Epoxy resin (1-1) Epoxy resin A1: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “Bis-A1 epoxy resin”) ⁇ Product name: “AER2600”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • Epoxy resin A3 poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “Bis-A3 epoxy resin”) ⁇ Product name: “AER6071” manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) measured by the above-mentioned method was as follows. However, since this epoxy resin A3 was solid at 25 ° C., the viscosity could not be measured.
  • Alkoxysilane compound H 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”) ⁇ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound L 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as “ECETMS”) ⁇ Product name: “KBM-303”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound I phenyltrimethoxysilane (hereinafter referred to as “PTMS”) ⁇ Product name: “KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound J Dimethyldimethoxysilane (hereinafter referred to as “DMDMS”) ⁇ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound K tetraethoxysilane (hereinafter referred to as “TEOS”) ⁇ Product name: “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.
  • DBTDL Dibutyltin dilaurate
  • DBTDM Dibutyltin dimethoxide
  • Curing accelerator Amine compound-Product name: "U-CAT 18X”, manufactured by Sun Apro Co., Ltd.
  • Silicone resin ⁇ Product name: “EG6301 (liquid A / liquid B)” manufactured by Toray Dow Corning Co., Ltd.
  • the resin composition was manufactured by the following process. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio shown in Table 22 below, the Bis-A1 epoxy resin, alkoxysilane compound, and THF were placed in a flask containing a stirrer and mixed and stirred in an atmosphere at 25 ° C. Water and a hydrolysis condensation catalyst were added and mixed and stirred. (3) Subsequently, a cooling tube was set on the flask, and the flask was immediately immersed in an oil bath at 80 ° C.
  • the epoxy equivalent (WPE), the starting viscosity and the storage viscosity of the resin composition obtained in the above (6) were measured. Further, a storage stability index ⁇ 58 was obtained and these are shown in Table 24.
  • the starting viscosity was 1.89 Pa ⁇ s ⁇ 1000 Pa ⁇ s
  • the storage viscosity was 2.03 Pa ⁇ s ⁇ 1000 Pa ⁇ s, both of which were fluid liquids.
  • the storage stability index ⁇ 70 1.07 ⁇ 4, indicating that the resin composition has storage stability.
  • Example 49 A cured product was produced using the resin composition of Synthesis Example 12 stored at 25 ° C. for 2 weeks, and a light resistance test was performed. The results are shown in Table 24.
  • the above-mentioned resin composition, curing agent, and curing accelerator were mixed and stirred in a 25 ° C. atmosphere according to the composition ratio in Table 23, and deaerated under vacuum to obtain a cured product solution.
  • a 3 mm thick, U-shaped silicon rubber was sandwiched between two stainless steel plates coated with a release agent to prepare a molding jig.
  • the above-mentioned solution for cured product was poured into this molding jig and subjected to curing treatment at 120 ° C. for 1 hour and further at 150 ° C.
  • a bullet-type LED having the structure shown in FIG. 1 was manufactured according to the following procedure, and reliability tests (1) to (3) were performed. The results are shown in Table 24.
  • the cured product solution of (1) was injected as a sealing resin into the cup part of a bullet-shaped mold frame having a diameter of 5 mm.
  • An LED chip having an emission wavelength of 400 nm was die-bonded with a silver paste, and a lead frame connected with a bonding wire (gold wire) was immersed therein.
  • curing treatment was performed at 90 ° C. for 1 hour and further at 110 ° C. for 5 hours.
  • Example 59 Using the resin composition of Synthesis Example 13, an SMD type LED having a size of 2.5 mm ⁇ 2.5 mm and having the structure shown in FIG. (1) On the glass epoxy board
  • Comparative Example 27 Using the resin composition of Comparative Synthesis Example 2 instead of the resin composition of Synthesis Example 12, a cured product and an LED were produced in the same manner as in Example 49, and a light resistance test and a reliability test ( Attempts were made to implement 1) to (3), but the storage stability of the resin composition was poor, and it was impossible to produce cured products and LEDs. Therefore, it judged that it was unacceptable as comprehensive judgment.
  • Storage stability index ⁇ (storage viscosity) / (starting viscosity) (9)
  • the container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”. When the resin composition was fluid (viscosity was 1000 Pa ⁇ s or less) and the storage stability index ⁇ was 4 or less, it was judged to have storage stability.
  • a cured product was prepared by the following method, and the evaluation result was used as a light resistance evaluation of the optical lens.
  • the cured product solution prepared by the method described later was cured to prepare a cured product of 20 mm ⁇ 10 mm ⁇ thickness 3 mm.
  • the cured product was covered with a black mask of 25 mm ⁇ 15 mm ⁇ thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
  • a device that can irradiate UV light from the UV irradiation device (USHIO Inc., “Spot Cure SP7-250DB”) to the sample in a constant temperature incubator made constant at 50 ° C. via an optical fiber. Prepared.
  • the sample was set in a constant temperature incubator at 50 ° C. with the black mask on top.
  • UV light of 2 W / cm 2 was irradiated for 96 hours from the top of the black mask so that UV light could be irradiated to a hole with a diameter of 5.5 mm.
  • Epoxy resin (1-1) Epoxy resin A: poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A epoxy resin) ⁇ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • TEOS Tetrae
  • THF Tetrahydrofuran (Wako Pure Chemical Industries, Ltd., stabilizer-free type)
  • Curing accelerator Amine-based compound-Trade name: "U-CAT 18X” manufactured by Sun Apro Co., Ltd.
  • the resin composition was manufactured by the following process. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) According to the composition ratio shown in Table 25 below, the Bis-A1 epoxy resin, alkoxysilane compound, and THF were placed in a flask containing a stirrer and mixed and stirred in an atmosphere at 25 ° C. Water and a hydrolysis condensation catalyst were added and mixed and stirred. (3) Subsequently, a cooling tube was set on the flask, and the flask was immediately immersed in an oil bath at 80 ° C.
  • Example 60 A cured product was produced by the following steps using the resin composition of Synthesis Example 22 stored at 25 ° C. for 2 weeks, and a light resistance test was performed. The results are shown in Table 27.
  • the above-mentioned solution for cured product was poured into this molding jig and subjected to curing treatment at 120 ° C. for 1 hour and further at 150 ° C.
  • the number of thermal shock tests was 400 times ⁇ 200 times, and the thermal thermal shock resistance was judged to be acceptable.
  • the surface tack test by the above-mentioned method
  • no stickiness was observed, and it was judged to be acceptable.
  • the void property test by the above-mentioned method
  • no void was confirmed, and it was judged as passing. From the above results, the optical lens of Example 60 passed all of the light resistance test, the thermal shock test, the surface tack test, and the void test, and was determined to be acceptable as a comprehensive judgment.
  • Example 61 As a result of performing the void property test by the above-mentioned method, no void was confirmed, and it was judged as passing. From the above results, the optical lens of Example 61 passed all of the light resistance test, the thermal shock test, the surface tack test, and the void test, and was determined to be acceptable as a comprehensive judgment.
  • Example 62 As a result of performing the void property test by the above-mentioned method, no void was confirmed, and it was judged as passing. From the above results, the optical lens of Example 62 passed all of the light resistance test, the thermal shock test, the surface tack test, and the void test, and was determined to be acceptable as a comprehensive judgment.
  • Example 63 passed all of the light resistance test, the thermal shock test, the surface tack test, and the void test, and was determined to be acceptable as a comprehensive judgment.
  • Comparative Example 32 Using the resin composition of Comparative Synthesis Example 5 instead of the resin composition of Synthesis Example 22, a cured product and an optical lens were produced in the same manner as in Example 60, and the light resistance test and the thermal shock test were conducted. Attempts were made to carry out a surface tack test and a void test, but the storage stability of the resin composition was poor, and it was impossible to produce cured products and optical lenses. Therefore, it judged that it was unacceptable as comprehensive judgment.
  • Examples 64-67 and Comparative Examples 36-38 were evaluated as follows.
  • the epoxy equivalent (WPE), viscosity, and mixing indices ⁇ to ⁇ were determined according to the same method as described above.
  • ⁇ Void evaluation of conductive resin composition The conductive resin composition was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually checked for the presence of voids under a magnifier. About the resin composition of an Example and a comparative example, when fluidity
  • Epoxy resin (1-1) Epoxy resin A: bisphenol A type epoxy resin (hereinafter referred to as “Bis-A epoxy resin”) ⁇ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • Epoxy resin F Bisphenol F type epoxy resin (hereinafter referred to as “Bis-F epoxy resin”) ⁇ Product name: “JER807” manufactured by Japan Epoxy Resin Co., Ltd.
  • the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
  • Alkoxysilane compound H 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”) ⁇ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane Compound I Phenyltrimethoxysilane (hereinafter referred to as “PTMS”) ⁇ Product name: “KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound J Dimethyldimethoxysilane (hereinafter referred to as “DMDMS”) ⁇ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Alkoxysilane compound K tetraethoxysilane (hereinafter referred to as “TEOS”) ⁇ Product name: “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Resin composition J was produced and evaluated by the following procedure. (1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer. (2) In accordance with the composition ratio in Table 28, in an atmosphere of 25 ° C., the epoxy resin, alkoxysilane compound and THF are placed in a flask containing a stirrer, mixed and stirred, and then water and a hydrolysis condensation catalyst are added. Then, the mixture was stirred. (3) Subsequently, a cooling tube was set on the flask, and immediately, it was immersed in an oil bath at 80 ° C.
  • the epoxy equivalent (WPE) of the resin composition J obtained in the above (6) was measured.
  • Resin composition K Resin composition K was synthesized and evaluated in the same manner as in Synthesis Example 26 according to the composition ratios in Table 28. Table 30 shows the mixing indexes ⁇ 78 to ⁇ 78.
  • Resin composition L Resin composition L was synthesized and evaluated in the same manner as in Synthesis Example 26 according to the composition ratio in Table 28. Table 30 shows the mixing indices ⁇ 79 to ⁇ 79.
  • Resin composition M Resin composition M was synthesized and evaluated in the same manner as in Synthesis Example 26 according to the composition ratio in Table 28. Table 30 shows the mixing indexes ⁇ 80 to ⁇ 80.
  • the viscosity was 10.2 Pa ⁇ s, and it was a fluid liquid.
  • Conductive resin composition 1 was produced and evaluated by the following procedure. Table 30 shows the evaluation results and mixing indexes ⁇ 77 to ⁇ 77. Using the resin composition J of Synthesis Example 26, the raw materials were blended according to the composition shown in Table 29, and uniformly kneaded with a three-roll mill (manufactured by Inoue Seisakusho Co., Ltd.). Furthermore, what was defoamed at 400 Pa for 30 minutes using a vacuum chamber was designated as conductive resin composition 1. The viscosity of the conductive resin composition 1 was 21.5 Pa ⁇ s, and the liquid was excellent in fluidity.
  • the adhesive strength residual rate of the conductive resin composition 1 was determined by the following procedure. (1) Four points were produced by applying the conductive resin composition 1 to the die pad portion (9 mm ⁇ 9 mm) of the copper lead frame.
  • sample before moisture absorption treatment a sample obtained by absorbing the remaining two points of the sample prepared in (2) for 72 hours in a thermo-hygrostat set to a temperature of 85 ° C. and a humidity of 85% was designated as “sample after moisture absorption treatment”.
  • sample after moisture absorption treatment a sample obtained by absorbing the remaining two points of the sample prepared in (2) for 72 hours in a thermo-hygrostat set to a temperature of 85 ° C. and a humidity of 85% was designated as “sample after moisture absorption treatment”.
  • sample after moisture absorption treatment Using the “sample before moisture absorption treatment” and “sample after moisture absorption treatment”, with the silicon chip down, heat on a hot plate at 250 ° C.
  • the adhesiveness of the product 1 was judged to be good.
  • the conductive resin composition 1 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually confirmed under a magnifying glass, but no void was generated. From said result, since the conductive resin composition 1 was excellent in fluidity
  • Example 65 The conductive resin composition 2 was produced and evaluated in the same manner as in Example 64 using the resin composition K described above according to the composition of Table 29. Table 30 shows the evaluation results and mixing indices ⁇ 78 to ⁇ 78.
  • the viscosity of the conductive resin composition 2 was 23.7 Pa ⁇ s, and it was a liquid excellent in fluidity.
  • the volume resistivity of the conductive resin composition 2 was 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the electrical conductivity was judged to be good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the conductive resin composition 2 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • the adhesiveness of the product 2 was judged to be good.
  • the conductive resin composition 2 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually confirmed under a magnifying glass, but no void was generated. From said result, since the conductive resin composition 2 was excellent in fluidity
  • Example 66 The conductive resin composition 3 was produced and evaluated in the same manner as in Example 64 using the resin composition L described above according to the composition of Table 29. Table 30 shows the evaluation results and mixing indexes ⁇ 79 to ⁇ 79.
  • the viscosity of the conductive resin composition 3 was 28.2 Pa ⁇ s, and it was a liquid excellent in fluidity.
  • the volume resistivity of the conductive resin composition 3 was 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the electrical conductivity was judged to be good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the conductive resin composition 3 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • the adhesiveness of the object 3 was judged to be good.
  • it shows the adhesiveness superior to the conductive resin composition 4 of Example 65 manufactured by the same composition except having changed the ratio of NP resin and DBU it is synergistic by combined use of 2 types of hardening
  • the conductive resin composition 3 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually confirmed under a magnifying glass, but no void was generated. From said result, since the conductive resin composition 3 was excellent in fluidity
  • Example 67 Conductive resin composition 4 was produced and evaluated in the same manner as in Example 64 using the above-described resin composition M according to the composition of Table 29. Table 30 shows the evaluation results and mixing indexes ⁇ 80 to ⁇ 80.
  • the viscosity of the conductive resin composition 4 was 19.1 Pa ⁇ s, and the liquid was excellent in fluidity.
  • the volume resistivity of the conductive resin composition 4 was 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the electrical conductivity was judged to be good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and “post-moisture treatment sample” of the conductive resin composition 4 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • the adhesiveness of the product 4 was judged to be good.
  • the conductive resin composition 4 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually confirmed under a magnifying glass, but no void was generated. From said result, since the conductive resin composition 4 was excellent in fluidity
  • Conductive resin composition 5 was produced in the same manner as in Example 64, using Bis-A epoxy resin and Bis-F epoxy resin instead of resin composition J in accordance with the composition of Table 29, and evaluated. did. The results are shown in Table 30.
  • the viscosity of the conductive resin composition 5 was 26.4 Pa ⁇ s, and the liquid was excellent in fluidity.
  • the volume resistivity of the conductive resin composition 5 was 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the electrical conductivity was judged to be good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the conductive resin composition 5 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • the conductive resin composition 5 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. This sample was visually confirmed under a magnifying glass, but no void was generated. From the above results, the conductive resin composition 5 was judged to be unacceptable as a comprehensive judgment because the fluidity and conductivity were good and there was no void, but the adhesiveness was poor.
  • Conductive resin composition 6 was produced and evaluated in the same manner as in Example 1 using Bis-A epoxy resin, GPTMS, and PTMS instead of resin composition J according to the composition of Table 29. The results are shown in Table 30.
  • the viscosity of the conductive resin composition 6 was 18.2 Pa ⁇ s, and it was a liquid excellent in fluidity.
  • the volume resistivity of the conductive resin composition 6 was 42 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the conductivity was judged to be poor.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the conductive resin composition 6 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • the adhesiveness of the product 6 was good.
  • the conductive resin composition 6 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. When this sample was visually confirmed under a magnifying glass, generation of voids was confirmed. From the above results, although the conductive resin composition 6 has good fluidity and adhesiveness, it was determined that it was unacceptable as a comprehensive judgment because the conductivity was poor and the occurrence of voids was also confirmed. did.
  • Conductive resin composition 7 was produced in the same manner as in Example 62 using Bis-A epoxy resin, Bis-F epoxy resin, and TEOS instead of resin composition J according to the composition of Table 29. ,evaluated. The results are shown in Table 30.
  • the viscosity of the conductive resin composition 7 was 16.3 Pa ⁇ s, and the liquid was excellent in fluidity.
  • the volume resistivity of the conductive resin composition 7 was 3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the electrical conductivity was judged to be good.
  • the average value of the adhesive strength of the “pre-moisture treatment sample” and the “post-moisture treatment sample” of the conductive resin composition 7 was substituted into the following formula to determine the adhesive strength residual rate, and the adhesiveness was evaluated.
  • the adhesiveness of the product 7 was good.
  • the conductive resin composition 7 was applied to the die pad portion of the copper lead frame, a glass chip (8 mm ⁇ 8 mm) was mounted, and heated in an oven at 200 ° C. for 1 hour. When this sample was visually confirmed under a magnifying glass, generation of voids was confirmed. From the above results, although the conductive resin composition 7 had good fluidity, conductivity, and adhesiveness, it was determined that the generation of voids was rejected as a comprehensive judgment because of the occurrence of voids.
  • a resin composition obtained by mixing an epoxy resin and a specific alkoxysilane compound at a specific ratio in the present embodiment and cohydrolyzing and condensing, and a conductive property The conductive resin composition containing metal powder and a curing agent was excellent in fluidity. Moreover, the conductive resin composition of the present embodiment was excellent in conductivity and adhesiveness, and no void was generated.
  • a cured product having good transparency, excellent heat resistance, heat discoloration resistance, light resistance, and thermal shock resistance can be formed, and has good storage stability. It becomes possible to provide a modified resin composition. Furthermore, by using the modified resin composition of the present invention, ⁇ a> excellent light-emitting components such as LEDs, excellent adhesion to the element and package material, no cracks, and little decrease in luminance over a long period of time; An optical lens that can be injection-molded, is hard after curing, has excellent step stability, and has light resistance, and a semiconductor device using the light-emitting component and / or optical lens, ⁇ b>, oxygen A photosensitive composition that can suppress the inhibition of polymerization due to the above, and has excellent adhesion, a coating agent containing the composition, a coating film obtained by curing the coating agent, and ⁇ c> fluorescence excellent in dispersion stability of the phosphor A resin composition, a phosphorescent material using the fluorescent resin composition, ⁇ d> a conductive resin composition
  • LED 10a Light emitting diode (LED) 10a, 20a: LED chip 10A, 20A: Anode electrode 10C, 20C: Cathode electrode 12, 22: Sealing material 14, 24: Bonding wire 16: Outer layer resin 18: Lead frame 26: Package substrate 28: Reflecting plate

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Abstract

L'invention porte sur une composition de résine modifiée obtenue par réaction d'une résine époxy (A) et d'un composé alcoxysilane représenté par la formule générale (1) : (R1)n-Si-(OR2)4-n. Le composé alcoxysilane contient (B) au moins une sorte d'un composé alcoxysilane dans lequel n vaut 1 ou 2 et au moins un groupe éther cyclique est contenu en tant que R1 et (C) au moins une sorte d'un composé alcoxysilane dans lequel n vaut 1 ou 2 et au moins un groupe organique aromatique est contenu en tant que R1. L'indice de mélange α du composé alcoxysilane, qui est représenté par la formule générale suivante (2) : indice de mélange α = (αc)/(αb), n'est pas inférieur à 0,001 mais non supérieur à 19, et la quantité de groupes alcoxy restants dans la composition de résine modifiée n'est pas supérieure à 5 %.
PCT/JP2009/062201 2008-07-03 2009-07-03 Composition de résine modifiée, son procédé de fabrication de celle-ci et composition de résine durcissable la contenant WO2010001992A1 (fr)

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JP2010229216A (ja) * 2009-03-26 2010-10-14 Asahi Kasei Chemicals Corp 蛍光樹脂組成物、それを用いた封止材及び蓄光材料
JP2011208094A (ja) * 2010-03-30 2011-10-20 Asahi Kasei Chemicals Corp ポリオルガノシロキサン及びその製造方法、並びに、それを含む硬化性樹脂組成物とその用途
JP2013522888A (ja) * 2010-03-12 2013-06-13 シチュアン サンフォー ライト カンパニー リミテッド 白色光ｌｅｄ照明装置
JP2013526006A (ja) * 2010-03-12 2013-06-20 シチュアン サンフォー ライト カンパニー リミテッド パルス電流駆動の白色光ｌｅｄ照明装置
WO2014031404A1 (fr) * 2012-08-22 2014-02-27 The Walman Optical Company Composition et procédé de revêtement
EP2799509A4 (fr) * 2011-12-28 2015-09-02 Posco Composition adhésive isolante pour un stratifié plaqué cuivre à base métallique (mccl), plaque métallique revêtue l'utilisant et son procédé de fabrication
CN109874702A (zh) * 2019-04-12 2019-06-14 云南农业大学 一种利用温度脱模的环氧树脂巢房模型制作方法
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JP2014102348A (ja) * 2012-11-19 2014-06-05 Nitto Denko Corp 光導波路形成用樹脂組成物およびそれを用いた光導波路ならびに光伝送用フレキシブルプリント基板、およびその光導波路の製法
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JP6907773B2 (ja) * 2016-09-05 2021-07-21 住友ベークライト株式会社 エポキシ樹脂組成物および半導体装置
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JP2010229216A (ja) * 2009-03-26 2010-10-14 Asahi Kasei Chemicals Corp 蛍光樹脂組成物、それを用いた封止材及び蓄光材料
JP2013522888A (ja) * 2010-03-12 2013-06-13 シチュアン サンフォー ライト カンパニー リミテッド 白色光ｌｅｄ照明装置
JP2013526006A (ja) * 2010-03-12 2013-06-20 シチュアン サンフォー ライト カンパニー リミテッド パルス電流駆動の白色光ｌｅｄ照明装置
JP2011208094A (ja) * 2010-03-30 2011-10-20 Asahi Kasei Chemicals Corp ポリオルガノシロキサン及びその製造方法、並びに、それを含む硬化性樹脂組成物とその用途
EP2799509A4 (fr) * 2011-12-28 2015-09-02 Posco Composition adhésive isolante pour un stratifié plaqué cuivre à base métallique (mccl), plaque métallique revêtue l'utilisant et son procédé de fabrication
WO2014031404A1 (fr) * 2012-08-22 2014-02-27 The Walman Optical Company Composition et procédé de revêtement
US11198795B2 (en) 2015-02-17 2021-12-14 The Walman Optical Company Glycidyl ether based optical coating compositions
CN109874702A (zh) * 2019-04-12 2019-06-14 云南农业大学 一种利用温度脱模的环氧树脂巢房模型制作方法
CN109874702B (zh) * 2019-04-12 2021-09-10 云南农业大学 一种利用温度脱模的环氧树脂巢房模型制作方法

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