WO2018135557A1 - 硬化性エポキシ樹脂組成物 - Google Patents

硬化性エポキシ樹脂組成物 Download PDF

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WO2018135557A1
WO2018135557A1 PCT/JP2018/001302 JP2018001302W WO2018135557A1 WO 2018135557 A1 WO2018135557 A1 WO 2018135557A1 JP 2018001302 W JP2018001302 W JP 2018001302W WO 2018135557 A1 WO2018135557 A1 WO 2018135557A1
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group
resin composition
epoxy resin
curable epoxy
compound
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PCT/JP2018/001302
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English (en)
French (fr)
Japanese (ja)
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鈴木弘世
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株式会社ダイセル
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Priority to KR1020197024267A priority Critical patent/KR102489346B1/ko
Priority to JP2018562416A priority patent/JP7146643B2/ja
Publication of WO2018135557A1 publication Critical patent/WO2018135557A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C08G59/5086—Triazines; Melamines; Guanamines
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/26—Di-epoxy compounds heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • 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 curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, and an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition.
  • a sealing agent for forming a sealing material having high heat resistance for example, a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known (see Patent Document 1).
  • a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin is known (see Patent Document 1).
  • Patent Document 1 a composition containing monoallyl diglycidyl isocyanurate and a bisphenol A type epoxy resin.
  • the coloring of the sealant progresses depending on light and heat emitted from the optical semiconductor element and high humidity conditions.
  • the light to be output is absorbed, and as a result, there is a problem that the luminous intensity of the light output from the optical semiconductor device decreases with time.
  • -Liquid alicyclic epoxy resins having an alicyclic skeleton such as an adduct of epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and ⁇ -caprolactone and 1,2,8,9-diepoxylimonene are known. ing.
  • the cured products of these alicyclic epoxy resins are susceptible to various stresses, and cracks are generated when a thermal shock such as a cooling cycle (repeating heating and cooling periodically) is applied. Etc. had occurred.
  • an optical semiconductor device for example, a surface-mount type optical semiconductor device
  • a reflow process for joining the electrodes of the optical semiconductor device to a wiring board by soldering.
  • lead-free solder having a high melting point has been used as a solder as a bonding material, and the heat treatment in the reflow process has become a higher temperature (for example, the peak temperature is 240 to 260 ° C.).
  • the peak temperature is 240 to 260 ° C.
  • the sealing material in the optical semiconductor device has high heat resistance and light resistance, and also has a characteristic that cracks are not easily generated when a thermal shock is applied (sometimes referred to as “thermal shock resistance”), and
  • thermal shock resistance sometimes referred to as “thermal shock resistance”
  • reflow resistance characteristics that are less likely to cause cracking or peeling even when heat-treated in the reflow process.
  • the optical semiconductor device is kept under high humidity conditions for a certain time (for example, 192 hours under conditions of 30 ° C. and 60% RH; 60 ° C., 60% RH).
  • an object of the present invention is to have high heat resistance, light resistance, thermal shock resistance, and reflow resistance, and in particular, to improve the current-carrying characteristics and moisture absorption reflow resistance of optical semiconductor devices at high temperatures and high humidity. It is providing the curable epoxy resin composition which can form a possible hardened
  • cured material. Another object of the present invention is to have high heat resistance, light resistance, thermal shock resistance and reflow resistance, and in particular, to improve the current-carrying characteristics and moisture absorption reflow resistance of optical semiconductor devices at high temperatures and high humidity. It is in providing the hardened
  • another object of the present invention is excellent in current-carrying characteristics at high temperature and high humidity, and further suppressed deterioration such as a decrease in luminous intensity when heat-treated in a reflow process after being stored under high humidity conditions. Another object is to provide a high-quality optical semiconductor device.
  • a curable epoxy resin composition containing an alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and a stress relaxation agent has high heat resistance
  • a cured product having light resistance, thermal shock resistance, and reflow resistance can be formed, and in particular, a cured product capable of improving current-carrying characteristics and moisture absorption reflow resistance at high temperatures and high humidity of an optical semiconductor device can be formed.
  • the present invention relates to an alicyclic epoxy compound (A) and the following formula (1).
  • R 1 and R 2 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the curable epoxy resin composition characterized by including the monoallyl diglycidyl isocyanurate compound (B) represented by these, and a stress relaxation agent (C) is provided.
  • the stress relaxation agent (C) may be at least one selected from the group consisting of silicone rubber particles (C1) and silicone oil (C2).
  • the silicone rubber particles (C1) may be cross-linked polydimethylsiloxane having a silicone resin on the surface.
  • the silicone oil (C2) may be a polyalkylene ether-modified silicone compound having a structure represented by the following formula (2) having an epoxy equivalent of 3000 to 15000.
  • x is an integer from 80 to 140
  • y is an integer from 1 to 5
  • z is an integer from 5 to 20.
  • R 3 is an alkylene group having 2 or 3 carbon atoms.
  • A is a polyalkylene ether group having a structure represented by the following formula (2a). (In the formula, a and b are each independently an integer of 0 to 40.
  • B is a hydrogen atom or a methyl group.)]
  • the alicyclic epoxy compound (A) may be a compound having a cyclohexene oxide group.
  • the alicyclic epoxy compound (A) has the following formula (I-1): The compound represented by these may be sufficient.
  • the curable epoxy resin composition may further contain rubber particles other than silicone rubber particles.
  • the curable epoxy resin composition may further contain a curing agent (D) and a curing accelerator (E).
  • the curable epoxy resin composition may further contain a curing catalyst (F).
  • the present invention also provides a cured product of the curable epoxy resin composition.
  • the curable epoxy resin composition may be an optical semiconductor sealing resin composition.
  • the present invention also provides an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition.
  • the curable epoxy resin composition of the present invention Since the curable epoxy resin composition of the present invention has the above-described configuration, by curing the resin composition, it has high heat resistance, light resistance, thermal shock resistance, and reflow resistance. A cured product capable of improving the current-carrying characteristics and moisture absorption reflow resistance at high temperatures and high humidity can be formed. For this reason, when the curable epoxy resin composition of the present invention is used as a resin composition for sealing an optical semiconductor, deterioration such as a decrease in luminous intensity is unlikely to occur particularly under severe conditions of high temperature and high humidity. In addition, it is possible to obtain a highly durable and high quality optical semiconductor device that is less susceptible to deterioration such as a decrease in luminous intensity even when heat treatment is performed in a reflow process after storage under high humidity conditions.
  • FIG. 1 It is the schematic which shows one Embodiment of the optical semiconductor device by which the optical semiconductor element was sealed with the hardened
  • the left figure (a) is a perspective view
  • the right figure (b) is a sectional view. It is an example of the surface temperature profile (temperature profile in one heat processing among two heat processing) of the optical semiconductor device in the solder heat resistance test of an Example.
  • the curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A) and a monoallyl diglycidyl isocyanurate compound (B) represented by the following formula (1) (“monoallyl diglycidyl isocyanurate compound ( B) ”) and a stress relaxation agent (C) as essential components (curable composition).
  • the alicyclic epoxy compound (alicyclic epoxy resin) (A) in the curable epoxy resin composition of the present invention has an alicyclic (aliphatic ring) structure and an epoxy group (oxiranyl group) in the molecule (in one molecule). And a compound having at least In the curable epoxy resin composition of the present invention, a known or commonly used alicyclic epoxy compound can be used.
  • alicyclic epoxy compound (A) specifically, (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, (Ii) A compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and the like.
  • the compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i) has at least one alicyclic epoxy group in the molecule. Any known or commonly used compound can be used without any particular limitation. Especially, as said alicyclic epoxy group, a cyclohexene oxide group is preferable.
  • a compound having a cyclohexene oxide group is preferable from the viewpoint of transparency and heat resistance.
  • a compound (alicyclic epoxy compound) represented by the following formula (I) is preferable.
  • X represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. And a group in which a plurality of are connected.
  • a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (I).
  • Examples of the compound in which X in the above formula (I) is a single bond include (3,4,3 ′, 4′-diepoxy) bicyclohexane and the like.
  • Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.
  • alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like.
  • the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
  • the linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation.
  • Representative examples of the alicyclic epoxy compounds represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10), bis (3,4-epoxycyclohexylmethyl) ) Ether, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2 -Bis (3,4-epoxycyclohexane-1-yl) propane and the like.
  • l and m each represents an integer of 1 to 30.
  • R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and is a methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene.
  • linear or branched alkylene groups such as a group, a heptylene group, and an octylene group.
  • linear or branched alkylene groups having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group are preferable.
  • N1 to n6 in the following formulas (I-9) and (I-10) each represents an integer of 1 to 30.
  • Examples of the compound (ii) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).
  • R 4 represents a p-valent organic group.
  • p represents an integer of 1 to 20.
  • Examples of the p-valent organic group include a p-valent organic group having a structure formed by removing p hydroxy groups from the structural formula of an organic compound having p hydroxy groups described later.
  • q represents an integer of 1 to 50.
  • p is an integer greater than or equal to 2
  • several q may be the same and may differ.
  • the sum (total) of q in the formula (II) is an integer of 3 to 100.
  • R 5 is a substituent on the cyclohexane ring shown in the formula, and represents any of the groups represented by the following formulas (IIa) to (IIc).
  • the bonding position of R 5 on the cyclohexane ring is not particularly limited. Usually, when the positions of the two carbon atoms of the cyclohexane ring bonded to the oxygen atom are the 1st and 2nd positions, the carbon atom at the 4th or 5th position It is.
  • the bonding positions of R 5 in each cyclohexane ring may be the same or different.
  • At least one R 5 in the formula (II) is a group (epoxy group) represented by the formula (IIa).
  • a plurality of R 5 s may be the same or different.
  • R 6 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.
  • alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl. Examples thereof include straight-chain or branched alkyl groups having 1 to 20 carbon atoms.
  • alkylcarbonyl group examples include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl.
  • alkylcarbonyl group examples include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl.
  • alkylcarbonyl group examples include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, iso
  • arylcarbonyl group examples include arylcarbonyl groups having 6 to 20 carbon atoms such as a phenylcarbonyl group (benzoyl group), 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, and the like.
  • Examples of the substituent that the above-described alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include a substituent having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms).
  • Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C 1-6 alkoxy group, more preferably C 1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C 2-6 alkenyloxy group, more preferably C 2-4 alkenyloxy group)
  • An acyloxy group such as an acetyloxy group, a propionyloxy group and a (meth) acryloyloxy group (preferably a C 1-12
  • examples of the substituent that the above-described arylcarbonyl group may have include the above-described substituted or unsubstituted alkyl group and the above-described substituted or unsubstituted alkylcarbonyl group.
  • the ratio of the group (epoxy group) represented by formula (IIa) to the total amount (100 mol%) of R 5 in the compound represented by formula (II) is not particularly limited, but is 40 mol% or more (for example, 40 to 100 mol%) is preferable, more preferably 60 mol% or more, and still more preferably 80 mol% or more. There exists a tendency for the heat resistance of a hardened
  • the above ratio can be calculated by, for example, 1 H-NMR spectrum measurement, oxirane oxygen concentration measurement, or the like.
  • the compound represented by the formula (II) is not particularly limited.
  • an organic compound [R 4 (OH) p ] having p hydroxy groups in the molecule is used as an initiator (that is, the hydroxy group of the compound). (Starting with active hydrogen)), 1,2-epoxy-4-vinylcyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) is subjected to ring-opening polymerization (cationic polymerization), and then Manufactured by epoxidation with an oxidizing agent.
  • Examples of the organic compound [R 4 (OH) p ] having p hydroxy groups in the molecule include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol; ethylene glycol, diethylene glycol , Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, neopentyl glycol ester, cyclohexanedi Methanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, water Polyhydric alcohol such as bisphenol S; polyviny
  • the 1,2-epoxy-4-vinylcyclohexane can be produced by a known or commonly used method, and is not particularly limited.
  • 4-vinylcyclohexene obtained by dimerization reaction of butadiene is replaced with an oxidizing agent such as peracetic acid. Obtained by partial epoxidation using.
  • 1,2-epoxy-4-vinylcyclohexane a commercially available product can be used.
  • the oxidant may be a known or conventional oxidant such as hydrogen peroxide or organic peracid, and is not particularly limited.
  • the organic peracid include performic acid, peracetic acid, peroxygen. Examples include benzoic acid and trifluoroperacetic acid. Among them, peracetic acid is preferable because it is industrially available at low cost and has high stability.
  • the standard polystyrene equivalent weight average molecular weight of the compound represented by the formula (II) is not particularly limited, but is preferably 300 to 100,000, more preferably 1,000 to 10,000.
  • the weight average molecular weight is 300 or more, the mechanical strength, heat resistance, and light resistance of the cured product tend to be further improved.
  • the weight average molecular weight is 100,000 or less, the viscosity does not become too high and the fluidity during molding tends to be maintained low.
  • the weight average molecular weight is measured by a gel permeation chromatography (GPC) method.
  • the equivalent (epoxy equivalent) of the epoxy group of the compound represented by the formula (II) is not particularly limited, but is preferably 50 to 1000, more preferably 100 to 500.
  • the epoxy equivalent is 50 or more, the cured product tends not to be brittle.
  • the epoxy equivalent is 1000 or less, the mechanical strength of the cured product tends to be improved.
  • the epoxy equivalent is measured according to JIS K7236: 2001.
  • the alicyclic epoxy compound (A) can be used singly or in combination of two or more.
  • commercially available products such as trade names “Celoxide 2021P”, “Celoxide 2081”, “EHPE3150” (manufactured by Daicel Corporation) can be used.
  • Examples of the alicyclic epoxy compound (A) include compounds represented by the above formula (I-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; for example, trade name “Celoxide 2021P”. (Daicel Co., Ltd.) etc. are particularly preferred.
  • the content (blending amount) of the alicyclic epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is 10 with respect to the total amount (100% by weight) of the curable epoxy resin composition. It is preferably -95% by weight, more preferably 15-90% by weight, and still more preferably 20-90% by weight.
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) is Although not particularly limited, it is preferably 20 to 99% by weight, more preferably 30 to 95% by weight, and still more preferably 40 to 95% by weight.
  • the ratio of the alicyclic epoxy compound (A) is 20% by weight or more, the curability of the curable epoxy resin composition tends to be further improved, and the heat resistance of the cured product tends to be further improved.
  • the ratio of the alicyclic epoxy compound (A) is 99% by weight or less, the thermal shock resistance of the cured product tends to be further improved.
  • the monoallyl diglycidyl isocyanurate compound (B) in the curable epoxy resin composition of the present invention is a compound represented by the above formula (1).
  • R 1 and R 2 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group.
  • R 1 and R 2 in the above formula (1) are particularly preferably hydrogen atoms.
  • monoallyl diglycidyl isocyanurate compound (B) examples include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methyl And propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate, and the like.
  • monoallyl diglycidyl isocyanurate compound (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the monoallyl diglycidyl isocyanurate compound (B) may be modified in advance by adding a compound that reacts with an epoxy group (oxiranyl group) such as alcohol or acid anhydride.
  • an epoxy group oxiranyl group
  • content (blending amount) of the monoallyl diglycidyl isocyanurate compound (B) in the curable epoxy resin composition of the present invention is not particularly limited, it is 5 with respect to 100 parts by weight of the alicyclic epoxy compound (A). Is preferably 120 parts by weight, more preferably 5 to 110 parts by weight, and still more preferably 5 to 105 parts by weight.
  • the curability of the curable epoxy resin composition is further improved, and the heat resistance and mechanical strength of the cured product are further improved. There is a tendency to improve.
  • Monoallyl diglycidyl isocyanurate compound (100% by weight) with respect to the total amount (100% by weight) of alicyclic epoxy compound (A) and monoallyl diglycidyl isocyanurate compound (B) contained in the curable epoxy resin composition of the present invention (
  • the proportion of B) is not particularly limited, but is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, and still more preferably 7 to 55% by weight.
  • the curability of the curable epoxy resin composition is further improved, and the heat resistance and mechanical strength of the cured product are further improved. Tend to.
  • the stress relaxation agent (C) in the curable epoxy resin composition of the present invention is a compound that can relieve internal stress in the cured product.
  • the curable epoxy resin composition of the present invention contains the stress relaxation agent (C)
  • the heat resistance, light resistance, thermal shock resistance, and reflow resistance of the cured product are improved.
  • a cured product capable of improving current-carrying characteristics and moisture absorption reflow resistance at high humidity can be formed.
  • the stress relaxation agent (C) is not particularly limited.
  • silicone rubber particles (C1) silicone oil (C2), liquid rubber component (C3), inorganic filler (C4), thermoplastic resin (C5), and the like. Is mentioned.
  • the silicone rubber particles (C1) are not particularly limited, and examples thereof include those composed of polysiloxanes such as polydimethylsiloxane and polymethylphenylsiloxane. Moreover, it is preferable that the polysiloxane which comprises a silicone rubber particle (C1) is bridge
  • the crosslinked polysiloxane is not particularly limited. For example, it is crosslinked by a condensation reaction such as a silanol group, a radical reaction between a mercaptosilyl group and a vinylsilyl group, or an addition reaction between a vinylsilyl group and a hydrosilyl group (SiH group). In terms of reactivity and reaction process, polysiloxane crosslinked by addition reaction of vinyl group-containing organopolysiloxane and organohydrogenpolysiloxane in the presence of a platinum-based catalyst. Is preferred.
  • the silicone rubber particles (C1) may be surface-treated from the viewpoint of familiarity with the epoxy resin composition, improvement of dispersibility, and adjustment of the viscosity of the epoxy resin composition after dispersion.
  • the aspect of the surface treatment is not particularly limited, and examples thereof include silicone rubber particles coated with methyl methacrylate, silicone rubber particles coated with silicone resin, and the like.
  • the average particle diameter (d 50 ) of the silicone rubber particles (C1) is not particularly limited, but is preferably 0.1 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m.
  • the maximum particle size of the silicone rubber particles (C1) is not particularly limited, but is preferably 0.1 to 250 ⁇ m, more preferably 0.1 to 150 ⁇ m. When the average particle size is 100 ⁇ m or less (or the maximum particle size is 250 ⁇ m or less), the crack resistance of the cured product tends to be further improved. On the other hand, when the average particle size is 0.1 ⁇ m or more (or the maximum particle size is 0.1 ⁇ m or more), the dispersibility of the silicone rubber particles (C1) tends to be further improved.
  • the shape of the silicone rubber particles (C1) is not particularly limited, but is preferably spherical from the viewpoint of improving workability.
  • the silicone rubber particles (C1) have high heat resistance, light resistance, thermal shock resistance, and reflow resistance, and in particular, improve energization characteristics and moisture absorption reflow resistance at high temperatures and high humidity of optical semiconductor devices. From the standpoint that a cured product that can be formed can be formed, those composed of a crosslinked polysiloxane or those whose surfaces are coated with a silicone resin are preferable. Among them, an epoxy resin component and silicone rubber particles are preferable. In view of the compatibility of (C1), it is particularly preferred that the surface of the crosslinked polydimethylsiloxane is coated with a silicone resin.
  • the silicone rubber particles (C1) can be used alone or in combination of two or more.
  • the silicone rubber particles (C1) can be produced by a known or conventional method.
  • the silicone rubber particles produced by the method described in JP-A-7-196815 can be used.
  • Commercially available products such as “ ⁇ 594”, “X-52-875”, “KMP-590”, “KMP-701” (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.
  • the silicone oil (C2) is not particularly limited, and examples thereof include non-modified silicone oil and modified silicone oil.
  • the non-modified silicone oil is not particularly limited, and examples thereof include a polydimethylsiloxane type, a polymethylhydrogensiloxane type, and a polymethylphenylsiloxane type.
  • the modified silicone oil is not particularly limited, and for example, either a reactive silicone oil that is reactive with an epoxy resin or a non-reactive silicone oil that is not reactive with an epoxy resin may be used.
  • the reactive silicone oil include amino-modified type, epoxy-modified type, carboxyl-modified type, carbinol-modified type, methacryl-modified type, mercapto-modified type, and phenol-modified type.
  • non-reactive silicone oils include polyalkylene ether-modified types, methylstyryl-modified types, alkyl-modified types, fatty acid ester-modified types, alkoxy-modified types, and fluorine-modified types.
  • the reactive silicone oil may have a non-reactive modifying group, and examples thereof include polyalkylene ether-amino modified silicone oil and polyalkylene ether-epoxy modified silicone oil.
  • Polyalkylene ether-epoxy modified silicone oils that have reactivity with the product and can be controlled in fluidity and viscosity are preferred.
  • the silicone oil (C2) has high heat resistance, light resistance, thermal shock resistance, and reflow resistance, and in particular, improves the current-carrying characteristics and moisture absorption reflow resistance of the optical semiconductor device at high temperature and high humidity.
  • a polyalkylene ether-epoxy modified silicone oil is preferable, and in particular, a polyalkylene ether modified having a structure represented by the following formula (2) having an epoxy equivalent of 3000 to 15000:
  • a silicone compound hereinafter sometimes referred to as “polyalkylene ether-modified silicone compound (2)” is preferred.
  • R 3 is an alkylene group having 2 or 3 carbon atoms.
  • alkylene group having 2 or 3 carbon atoms include a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, and a trimethylene group is preferable.
  • x represents an integer of 80 to 140.
  • y represents an integer of 1 to 5.
  • z represents an integer of 5 to 20. Note that the structures in parentheses to which z is attached may be the same or different.
  • A is a polyalkylene ether group having a structure represented by the following formula (2a).
  • a and b are each independently an integer of 0 to 40.
  • a is 40 or less, the water resistance of the cured product tends to be improved.
  • b is 40 or less, the fluidity of the curable epoxy resin composition tends to be improved.
  • the total of a and b is not particularly limited, but is preferably an integer of 1 to 80. When the sum of a and b is in the range, it becomes easy to control the water resistance of the cured product and the fluidity of the curable epoxy resin composition.
  • B is a hydrogen atom or a methyl group. From the viewpoint of water resistance of the cured product, B is preferably a methyl group.
  • each structural unit in the above formula (2) may be a random type or a block type as long as two trimethylsilyl groups in the formula (2) are present at both ends. Further, the addition form of each structural unit in the above formula (2a) may be a random type or a block type as long as B is present at the terminal. Further, the order of arrangement of the structural units in the above formulas (2) and (2a) is not particularly limited.
  • the epoxy equivalent of the polyalkylene ether-modified silicone compound (2) is from 3000 to 15000, preferably from 4000 to 15000, more preferably from 5000 to 13000.
  • the epoxy equivalent is 3000 or more, the stress relaxation inside the cured product tends to be further improved.
  • the epoxy equivalent is 15000 or less, the compatibility with the resin tends to be further improved.
  • the epoxy equivalent of the polyalkylene ether-modified silicone compound (2) can be measured in accordance with JIS K 7236: 2001.
  • the silicone oil (C2) can be used alone or in combination of two or more.
  • the silicone oil (C2) can be produced by a known or conventional method.
  • the silicone oil (C2) produced by the method described in JP-A-2008-201904 is used.
  • a commercial product such as “SF8421” (made by Toray Dow Corning Co., Ltd.) or “Y-19268” (made by Momentive Performance Materials Japan). You can also.
  • the liquid rubber component (C3) is not particularly limited.
  • polybutadiene maleated polybutadiene, acrylated polybutadiene, methacrylated polybutadiene, epoxidized polybutadiene, acrylonitrile butadiene rubber, carboxy terminal acrylonitrile butadiene rubber, amino terminal acrylonitrile butadiene rubber.
  • the said liquid rubber component (C3) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the inorganic filler (C4) is not particularly limited.
  • fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia examples include zirconia, zircon, fosterite, steatite, spinel, mullite, titania and the like.
  • These inorganic fillers can be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the average particle diameter (d 50 ) of the inorganic filler (C4) is not particularly limited, but is usually 1 to 50 ⁇ m, preferably 1 to 25 ⁇ m, more preferably 1 to 10 ⁇ m.
  • the inorganic filler (C4) preferably further contains a coupling agent from the viewpoint of improving the dispersibility by increasing the affinity between the epoxy resin component and the inorganic filler (C4).
  • the coupling agent is not particularly limited, and known ones can be used, but various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, titanium compound, and aluminum chelates. Aluminum / zirconium compounds are preferred.
  • vinyltrichlorosilane vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, and ⁇ -acryloxypropyltrimethoxy.
  • the amount of the coupling agent is not particularly limited, but is preferably 0.05 to 5% by mass, more preferably 0.1 to 2.5% by mass with respect to the inorganic filler (C4).
  • the dispersibility improvement effect of an inorganic filler (C4) can be acquired, and by making it 5 mass% or less, the void in a hardened
  • thermoplastic resin (C5) is not particularly limited.
  • thermoplastic resins can be used singly or in combination of two or more.
  • the glass transition temperature (Tg) of the thermoplastic resin (C5) is not particularly limited, but is preferably 200 ° C. or lower.
  • the said stress relaxation agent (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the stress relaxation agent (C) has high heat resistance, light resistance, thermal shock resistance, and reflow resistance, and in particular, improves the current-carrying characteristics and moisture absorption reflow resistance of optical semiconductor devices at high temperatures and high humidity.
  • at least one selected from the group consisting of silicone rubber particles (C1) and silicone oils (C2) is preferable, and in particular, as silicone rubber particles (C1) Is preferably a crosslinked polydimethylsiloxane having a silicone resin on its surface, and the silicone oil (C2) is preferably a polyalkylene ether-modified silicone compound (2).
  • the content (blending amount) of the stress relaxation agent (C) of the present invention is not particularly limited, but is preferably 0.1 to 100 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). Is 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight.
  • the content of the stress relaxation agent (C) is 100 parts by weight or less, the curability of the curable epoxy resin composition tends to be further improved.
  • Content of stress relaxation agent (C) with respect to total amount (100 parts by weight) of alicyclic epoxy compound (A) and monoallyl diglycidyl isocyanurate compound (B) contained in curable epoxy resin composition of the present invention Is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 18 parts by weight, and still more preferably 0.5 to 15 parts by weight.
  • the content of the stress relaxation agent (C) is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 18 parts by weight, and still more preferably 0.5 to 15 parts by weight.
  • the curable epoxy resin composition of the present invention may further contain a curing agent (D).
  • the curing agent (D) is a compound having an epoxy group (oxiranyl group) such as an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B), and an epoxy-modified silicone oil as a stress relaxation agent (C). It is a compound which has a function which hardens a curable epoxy resin composition by reacting with.
  • a known or conventional curing agent can be used as a curing agent for epoxy resin, and is not particularly limited.
  • acid anhydrides (acid anhydride curing agents), amines ( Amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, etc.
  • acid anhydrides (acid anhydride curing agents)
  • amines Amine curing agents
  • polyamide resins imidazoles (imidazole curing agents)
  • polymercaptans polymercaptan curing agents
  • phenols phenolic curing agents
  • polycarboxylic acids dicyandiamides
  • organic acid hydrazides etc.
  • acid anhydrides as the curing agent (D)
  • known or commonly used acid anhydride curing agents can be used, and are not particularly limited.
  • methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.
  • methylhexahydrophthalic anhydride such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride
  • dodecenyl succinic anhydride methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic
  • acid anhydrides for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.
  • a solid acid anhydride at 25 ° C. for example, by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture, the curing agent (D in the curable epoxy resin composition of the present invention (D ) Tends to be improved.
  • saturated monocyclic hydrocarbon dicarboxylic acid anhydrides (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable from the viewpoint of heat resistance and transparency of the cured product.
  • amines (amine-based curing agent) as the curing agent (D) a known or conventional amine-based curing agent can be used, and is not particularly limited.
  • ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-amino Cycloaliphatic polyamines such as ethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylenediamine, p-phenylenediamine, Len-2
  • phenols phenolic curing agents
  • known or conventional phenolic curing agents can be used, and are not particularly limited.
  • novolac type phenol resins novolac type cresol resins
  • paraxylylene-modified phenols examples thereof include aralkyl resins such as resins, paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.
  • Examples of the polyamide resin as the curing agent (D) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.
  • imidazole (imidazole curing agent) as the curing agent (D), a known or conventional imidazole curing agent can be used, and is not particularly limited.
  • Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (D) include liquid polymercaptan and polysulfide resin.
  • polycarboxylic acids examples include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and the like.
  • the curing agent (D) acid anhydrides (acid anhydride curing agents) are preferable from the viewpoint of heat resistance and transparency of the cured product.
  • curing agent (D) can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type.
  • a commercial item can also be used as a hardening
  • commercially available acid anhydrides include trade names “Licacid MH-700” and “Licacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.); trade name “HN-5500” (Hitachi Chemical Industries). Etc.).
  • the content (blending amount) of the curing agent (D) in the curable epoxy resin composition of the present invention is not particularly limited, but is 100 parts by weight based on the total amount of compounds having an epoxy group contained in the curable epoxy resin composition.
  • the amount is preferably 50 to 200 parts by weight, more preferably 80 to 150 parts by weight. More specifically, when acid anhydrides are used as the curing agent (D), 0.5 equivalent per 1 epoxy group equivalent in the compound having all epoxy groups contained in the curable epoxy resin composition of the present invention. It is preferable to use at a ratio of ⁇ 1.5 equivalent.
  • the curing accelerator (E) is a compound having a function of accelerating the reaction rate when a compound having an epoxy group (oxiranyl group) reacts with the curing agent (D).
  • the curing accelerator (E) may be a known or conventional curing accelerator, and is not particularly limited.
  • 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, , Phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (for example, phenol Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc.
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • DBN 1,5-diazabicyclo [4.3.0] nonene-5
  • DBN 1,5-diazabicyclo [4.3.0] nonen
  • Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole
  • Phosphate compounds such as triphenylphosphine and tris (dimethoxy) phosphine
  • Phosphonium compounds such as tetraphenylphosphonium tetra (p-tolyl) borate
  • Organometallic salts such as zinc octylate, tin octylate, and zinc stearate; Examples thereof include metal chelates such as aluminum acetylacetone complex.
  • a hardening accelerator (E) can also be used individually by 1 type in the curable epoxy resin composition of this invention, and can also be used in combination of 2 or more type.
  • the curing accelerator (E) trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X”, “U-CAT 12XD” ( (Developed product) (San Apro Co., Ltd.); Trade names “TPP-K”, “TPP-MK” (Hokuko Chemical Co., Ltd.); Trade name “PX-4ET” (Nippon Chemical Industry ( It is also possible to use a commercial product such as a product manufactured by Co. Ltd.
  • the content (blending amount) of the curing accelerator (E) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of compounds having epoxy groups contained in the curable epoxy resin composition is 100 parts by weight. On the other hand, it is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, still more preferably 0.03 to 2 parts by weight.
  • the content of the curing accelerator (E) is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, still more preferably 0.03 to 2 parts by weight.
  • the curable epoxy resin composition of the present invention may further contain a curing catalyst (F) (for example, instead of the curing agent (D)).
  • the curing catalyst (F) is a curing reaction (polymerization) of a cation curable compound such as an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B), or an epoxy-modified silicone oil as a stress relaxation agent (C). It is a compound having the function of curing the curable epoxy resin composition by initiating and / or promoting reaction.
  • the curing catalyst (F) is not particularly limited.
  • a cationic polymerization initiator photo cationic polymerization initiator, thermal cationic polymerization
  • a cationic polymerization initiator that initiates polymerization by generating cationic species by performing light irradiation, heat treatment, or the like.
  • Initiators, etc. Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.
  • Examples of the photocationic polymerization initiator as the curing catalyst (F) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically.
  • triarylsulfonium hexafluorophosphate eg, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate
  • sulfonium salts such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salts)
  • diaryl iodonium hexafluorophosphate Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodine Iodonium salts such as nium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridinium salts such as N-he
  • cationic photopolymerization initiator examples include, for example, trade names “UVACURE 1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States).
  • Commercial products such as Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.
  • thermal cationic polymerization initiator as the curing catalyst (F) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”.
  • thermal cationic polymerization initiator a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone
  • a compound of a chelate compound with a phenol and a phenol such as bisphenol S.
  • Lewis acid / amine complex as the curing catalyst (F), a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
  • a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
  • Bronsted acid salts as the curing catalyst (F), known or commonly used Bronsted acid salts can be used, and are not particularly limited.
  • imidazole as the curing catalyst (F), known or conventional imidazoles can be used, and are not particularly limited.
  • the curing catalyst (F) can be used alone or in combination of two or more.
  • a commercial item can also be used as a curing catalyst (F).
  • the content (blending amount) of the curing catalyst (F) in the curable epoxy resin composition of the present invention is not particularly limited, but is 100 parts by weight based on the total amount of the compounds having an epoxy group contained in the curable epoxy resin composition.
  • the amount is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, and still more preferably 0.03 to 2 parts by weight.
  • the curable epoxy resin composition of the present invention may further contain rubber particles other than silicone rubber particles (hereinafter sometimes simply referred to as “rubber particles”).
  • rubber particles known and commonly used rubber particles can be used without particular limitation as long as they are other than silicone rubber particles.
  • particulate NBR acrylonitrile-butadiene rubber
  • CTBN reactive terminal carboxy group NBR
  • metal-free NBR metal-free NBR
  • particulate SBR styrene-butadiene rubber
  • the rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion.
  • the rubber particles are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) on the surface.
  • Rubber particles having a hydroxy group and / or a carboxy group (either one or both of a hydroxy group and a carboxy group) as a group are preferred. If neither the hydroxy group nor the carboxy group is present on the surface of the rubber particles, the cured product becomes cloudy due to a thermal shock such as a cold cycle, and the transparency tends to decrease, which is not preferable.
  • the polymer constituting the core part having rubber elasticity in the rubber particles is not particularly limited as long as it is other than a silicone compound, but such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.
  • a polymer containing (meth) acrylic acid ester as an essential monomer component is preferred.
  • the polymer constituting the core part having rubber elasticity includes, for example, aromatic vinyl such as styrene and ⁇ -methylstyrene; nitrile such as acrylonitrile and methacrylonitrile; conjugated diene such as butadiene and isoprene; ethylene, propylene, An ⁇ -olefin such as isobutene may be included as a monomer component.
  • the polymer constituting the core portion having rubber elasticity is combined with one or more selected from the group consisting of aromatic vinyl, nitrile, and conjugated diene together with (meth) acrylic acid ester as a monomer component. It is preferable to include. That is, as the polymer constituting the core portion, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers, (meth) acrylic acid ester / aromatic And terpolymers such as group vinyl / conjugated dienes.
  • the polymer constituting the core part includes, as other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc.
  • a reactive crosslinking monomer having two or more reactive functional groups in the molecule may be contained.
  • the core part of the rubber particles is, among other things, a (meth) acrylate / aromatic vinyl binary copolymer (particularly butyl acrylate / styrene) or (meth) acrylate / aromatic vinyl / others.
  • a core portion composed of a terpolymer of monomers (particularly butyl acrylate / styrene / divinylbenzene) is preferable in that the refractive index of the rubber particles can be easily adjusted.
  • the glass transition temperature of the polymer constituting the core part of the rubber particles is not particularly limited, but is preferably less than 60 ° C. (eg, ⁇ 150 ° C. or more and less than 60 ° C.), more preferably ⁇ 150 to 15 ° C., and even more preferably. Is -100 to 0 ° C.
  • the glass transition temperature of the polymer which comprises the said core part means the calculated value calculated by the formula of the following Fox (refer Bull. Am. Phys. Soc., 1 (3) 123 (1956)).
  • Tg glass transition temperature (unit: K) of the polymer constituting the core portion indicates, W i is the weight fraction of the monomer i for the monomer total amount constituting the polymer constituting the core portion Indicates the rate. Further, Tg i is the glass transition temperature of the homopolymer of monomer i (unit: K) shows a.
  • the glass transition temperature of the homopolymer values described in various documents can be adopted, for example, values described in “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.) can be adopted. In addition, about the thing which is not described in literature, the value of the glass transition temperature measured by DSC method of the homopolymer obtained by superposing
  • the core portion of the rubber particles can be manufactured by a commonly used method, for example, by a method of polymerizing the monomer by an emulsion polymerization method.
  • the whole amount of the monomer may be charged all at once and polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently for polymerization.
  • a polymerization method using seed particles may be used.
  • the polymer constituting the shell layer of the rubber particles is preferably a polymer different from the polymer constituting the core portion (polymer having a different monomer composition).
  • the shell layer preferably has a hydroxy group and / or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A).
  • the polymer constituting the shell layer is preferably a polymer containing (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate as an essential monomer component.
  • (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate
  • (meth) acrylic acid esters other than butyl acrylate for example, ( (Meth) methyl acrylate, ethyl (meth) acrylate, butyl methacrylate, etc.
  • Examples of the monomer component that may be contained in addition to the (meth) acrylic acid ester include aromatic vinyl such as styrene and ⁇ -methylstyrene; nitrile such as acrylonitrile and methacrylonitrile.
  • aromatic vinyl such as styrene and ⁇ -methylstyrene
  • nitrile such as acrylonitrile and methacrylonitrile.
  • the rubber particles as a monomer component constituting the shell layer, it is preferable to contain the monomer alone or in combination of two or more together with (meth) acrylic acid ester, and in particular, at least contain aromatic vinyl. Is preferable in that the refractive index of the rubber particles can be easily adjusted.
  • the polymer constituting the shell layer forms a hydroxy group and / or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component.
  • Hydroxy group-containing monomers eg, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate
  • carboxy group-containing monomers eg, ⁇ , ⁇ -unsaturated acids such as (meth) acrylic acid; ⁇ , ⁇ -unsaturated acid anhydrides such as maleic anhydride
  • the polymer constituting the shell layer in the rubber particles preferably contains one or two or more kinds selected from the monomers together with (meth) acrylic acid ester as a monomer component. That is, the shell layer is composed of, for example, a ternary copolymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / ⁇ , ⁇ -unsaturated acid.
  • a shell layer composed of a polymer or the like is preferable.
  • the polymer constituting the shell layer includes, as the other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, trimethyl, as well as the above-described monomer.
  • a reactive crosslinking monomer having two or more reactive functional groups may be contained in the molecule such as allyl cyanurate, diallyl phthalate, butylene glycol diacrylate.
  • the glass transition temperature of the polymer constituting the shell layer of the rubber particles is not particularly limited, but is preferably 60 to 120 ° C., more preferably 70 to 115 ° C.
  • the heat resistance of the cured product tends to be further improved.
  • cured material tends to improve more by making the glass transition temperature of the said polymer into 120 degrees C or less.
  • the glass transition temperature of the polymer which comprises the said shell layer means the calculated value computed by the said Formula of Fox, For example, it can measure similarly to the glass transition temperature of the polymer which comprises the above-mentioned core.
  • the rubber particles can be obtained by covering the core portion with a shell layer.
  • the method for coating the core part with the shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a polymer constituting the shell layer; Examples thereof include a graft polymerization method in which the core portion having rubber elasticity is a trunk component and each component constituting the shell layer is a branch component.
  • the average particle diameter of the rubber particles is not particularly limited, but is preferably 10 to 500 nm, more preferably 20 to 400 nm.
  • the maximum particle size of the rubber particles is not particularly limited, but is preferably 50 to 1000 nm, more preferably 100 to 800 nm.
  • the average particle size is 500 nm or less (or the maximum particle size is 1000 nm or less)
  • the dispersibility of the rubber particles in the cured product is improved, and the crack resistance tends to be further improved.
  • the average particle diameter is 10 nm or more (or the maximum particle diameter is 50 nm or more)
  • the crack resistance of the cured product tends to be further improved.
  • the refractive index of the rubber particles is not particularly limited, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.58.
  • the difference between the refractive index of the rubber particles and the refractive index of the cured product obtained by curing the curable epoxy resin composition containing the rubber particles (the curable epoxy resin composition of the present invention) is ⁇ 0.03. Is preferably within. By setting the difference in refractive index within ⁇ 0.03, excellent transparency of the cured product is secured, and the optical intensity of the optical semiconductor device tends to be kept high.
  • the refractive index of the rubber particles is, for example, by casting 1 g of rubber particles into a mold and compression molding at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. From the obtained flat plate, a test piece of 20 mm length ⁇ 6 mm width And using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, It can be determined by measuring the refractive index at 20 ° C. and sodium D line.
  • DR-M2 multi-wavelength Abbe refractometer
  • the refractive index of the cured product of the curable epoxy resin composition of the present invention is, for example, a test piece having a length of 20 mm ⁇ width of 6 mm ⁇ thickness of 1 mm from a cured product obtained by the heat curing method described in the section of cured product below. And using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, It can be determined by measuring the refractive index at 20 ° C. and sodium D line.
  • DR-M2 multi-wavelength Abbe refractometer
  • the content (blending amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable epoxy resin composition,
  • the amount is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight.
  • the curable epoxy resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention.
  • a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin
  • the reaction can be allowed to proceed slowly.
  • silicone and fluorine antifoaming agents, leveling agents, and silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, as long as the viscosity and transparency are not impaired.
  • Surfactants inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors (eg YAG phosphor fine particles, silicate phosphors) Inorganic phosphor fine particles such as fine particles) and conventional additives such as mold release agents can be used.
  • inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors (eg YAG phosphor fine particles, silicate phosphors)
  • phosphors eg YAG phosphor fine particles, silicate phosphors
  • Inorganic phosphor fine particles such as fine particles
  • conventional additives such as mold release agents
  • the curable epoxy resin composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components in a heated state as necessary.
  • the curable epoxy resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more stored separately.
  • These components can also be used as a multi-liquid composition (for example, a two-liquid system) that is used by mixing them at a predetermined ratio before use.
  • the stirring / mixing method is not particularly limited, and for example, known or commonly used stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
  • stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
  • the rubber particles are prepared by dispersing the rubber particles in the alicyclic epoxy compound (A) in advance (the composition is referred to as “rubber”). It is preferable to blend in a state of “sometimes referred to as a“ particle-dispersed epoxy compound ””. That is, when rubber particles are blended in the curable epoxy resin composition of the present invention, the curable epoxy resin composition of the present invention contains the rubber particle-dispersed epoxy compound, the monoallyl diglycidyl isocyanurate compound (B), It is preferable to prepare by mixing the stress relaxation agent (C) and other components as necessary. Such a preparation method can particularly improve the dispersibility of the rubber particles in the curable epoxy resin composition.
  • the blending method of the rubber particles is not limited to the above method, and may be a method of blending alone.
  • the rubber particle-dispersed epoxy compound is obtained by dispersing the rubber particles in the alicyclic epoxy compound (A).
  • the alicyclic epoxy compound (A) in the rubber particle-dispersed epoxy compound may be the total amount of the alicyclic epoxy compound (A) constituting the curable epoxy resin composition, or may be a partial amount. There may be.
  • the rubber particles in the rubber particle-dispersed epoxy compound may be the total amount of rubber particles constituting the curable epoxy resin composition, or may be a partial amount.
  • the viscosity of the rubber particle-dispersed epoxy compound can be adjusted, for example, by using a reactive diluent together (that is, the rubber particle-dispersed epoxy compound may further contain a reactive diluent).
  • a reactive diluent for example, an aliphatic polyglycidyl ether having a viscosity at room temperature (25 ° C.) of 200 mPa ⁇ s or less can be preferably used.
  • Examples of the aliphatic polyglycidyl ether having a viscosity (25 ° C.) of 200 mPa ⁇ s or less include cyclohexane dimethanol diglycidyl ether, cyclohexane diol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
  • the usage-amount of the said reactive diluent can be adjusted suitably, and is not specifically limited.
  • the method for producing the rubber particle-dispersed epoxy compound is not particularly limited, and a well-known and commonly used method can be used. For example, after the rubber particles are dehydrated and dried to form powder, the rubber particles are mixed and dispersed in the alicyclic epoxy compound (A), or the emulsion of rubber particles and the alicyclic epoxy compound (A) are directly mixed. Subsequently, a method of dehydrating and the like can be mentioned.
  • the curable epoxy resin composition of the present invention is preferably liquid at 25 ° C.
  • the viscosity at 25 ° C. of the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 100 to 10,000 mPa ⁇ s, more preferably 200 to 9000 mPa ⁇ s, and still more preferably 300 to 8000 mPa ⁇ s.
  • the viscosity of the curable epoxy resin composition at 25 ° C. is, for example, using a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ ⁇ R24, temperature : Measured under conditions of 25 ° C. and rotation speed: 0.5 to 10 rpm.
  • the curable epoxy resin composition of the present invention By curing the curable epoxy resin composition of the present invention, it has high transparency, heat resistance, light resistance, and reflow resistance, excellent thermal shock resistance, especially at high temperatures and high humidity of optical semiconductor devices.
  • a cured product capable of improving current-carrying characteristics and moisture absorption reflow resistance (a cured product obtained by curing the curable epoxy resin composition of the present invention may be referred to as “cured product of the present invention”). be able to.
  • the curing means known or conventional means such as heat treatment or light irradiation treatment can be used.
  • the temperature for curing by heating is not particularly limited, but is preferably 45 to 200 ° C, more preferably 50 to 190 ° C, and still more preferably 55 to 180 ° C.
  • the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and further preferably 60 to 480 minutes.
  • the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient.
  • the curing temperature and the curing time are higher than the upper limit value in the above range, the resin component may be decomposed.
  • the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased.
  • hardening can also be performed in one step and can also be performed in two or more steps.
  • the curable epoxy resin composition of the present invention is a resin composition for sealing an optical semiconductor element in an optical semiconductor device, that is, an optical semiconductor sealing resin composition (an optical semiconductor element sealing agent in an optical semiconductor device). ) Can be preferably used.
  • an optical semiconductor sealing resin composition an optical semiconductor element sealing agent in an optical semiconductor device.
  • the curable epoxy resin composition of the present invention has high transparency, heat resistance, light resistance, and reflow resistance, excellent thermal shock resistance, especially light
  • An optical semiconductor device in which an optical semiconductor element is sealed with a cured product capable of improving current-carrying characteristics and moisture absorption reflow resistance at high temperatures and high humidity of the semiconductor device is obtained.
  • the above optical semiconductor device is less likely to decrease in light intensity even when subjected to thermal shock, high temperature heat or high humidity conditions, and when it is subjected to heat treatment in a reflow process after absorbing moisture for a certain period of time under high humidity conditions In addition, cracks and peeling are unlikely to occur, and durability is high.
  • the optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention.
  • the optical semiconductor element can be sealed, for example, by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heat-curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened
  • the curing temperature and the curing time can be appropriately set within the same range as when the cured product is prepared.
  • the curable epoxy resin composition of the present invention is not limited to the above-described optical semiconductor element sealing application, and includes, for example, an optical pickup sensor, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, and a resist.
  • Composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc. can do.
  • Production Example 1 Manufacture of rubber particles
  • 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream.
  • a monomer mixture composed of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion of the rubber particles.
  • the obtained latex was frozen at ⁇ 30 ° C., dehydrated and washed with a suction filter, and then blown and dried at 60 ° C. overnight to obtain rubber particles.
  • the resulting rubber particles had an average particle size of 254 nm and a maximum particle size of 486 nm.
  • the average particle size and the maximum particle size of the rubber particles are determined based on a nanotrac TM particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0 The maximum particle size at the time of exceeding 0.000 was defined as the maximum particle size.
  • a nanotrac TM particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0
  • Production Example 2 (Manufacture of rubber particle-dispersed epoxy compounds) 10 parts by weight of the rubber particles obtained in Production Example 1 were dispersed in 70 parts by weight of a trade name “Celoxide 2021P” (manufactured by Daicel Corporation) using a dissolver while being heated to 60 ° C. in a nitrogen stream. (1000 rpm, 60 minutes) and vacuum degassing to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 1356 mPa ⁇ s). The viscosity at 25 ° C.
  • Example 1 First, the product name “Celoxide 2021P” (manufactured by Daicel Corporation), the product name “MA-DGIC” (manufactured by Shikoku Kasei Kogyo Co., Ltd.), The name “KMP-600” (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed evenly using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.) Defoaming was performed to produce an epoxy resin. The above mixing was carried out with stirring at 80 ° C. for 1 hour in order to dissolve MA-DGIC.
  • the revolution ratio stirrer (trade name “Awatori”) was prepared by combining the epoxy resin obtained above and the epoxy curing agent obtained in Production Example 3 so that the blending ratio (unit: parts by weight) shown in Table 1 was obtained.
  • the mixture was uniformly mixed and defoamed to obtain a curable epoxy resin composition.
  • the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm ⁇ 2.8 mm) shown in FIG. 1, and then in an oven (resin curing oven) at 120 ° C.
  • FIG. 1 100 is a reflector (light reflecting resin composition), 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).
  • Example 2 to 9 Comparative Examples 1 to 6 A curable epoxy resin composition was prepared in the same manner as in Example 1 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 1.
  • Example 9 the rubber particle-dispersed epoxy compound obtained in Production Example 2 was used as a constituent component of the epoxy resin. Further, in the same manner as in Example 1, an optical semiconductor device in which an optical semiconductor element was sealed with a cured product was produced.
  • Example 10 First, the product name “Celoxide 2021P” (manufactured by Daicel Corporation), the product name “MA-DGIC” (manufactured by Shikoku Kasei Kogyo Co., Ltd.), The name “KMP-600” (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed evenly using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.) Defoaming was performed to produce an epoxy resin. In addition, the said mixing was implemented by stirring at 80 degreeC for 1 hour.
  • the epoxy resin obtained above and the trade name “Sun-Aid SI-100L” (manufactured by Sanshin Chemical Industry Co., Ltd.) were revolved so that the blending ratio (unit: parts by weight) shown in Table 2 was obtained.
  • a curable epoxy resin composition was obtained by uniformly mixing and defoaming using an agitator (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.). Further, the curable epoxy resin composition obtained above was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm ⁇ 2.8 mm) shown in FIG. 1, and then in an oven (resin curing oven) at 120 ° C. By curing by heating for 5 hours, an optical semiconductor device in which an optical semiconductor element was sealed with a cured product of the curable epoxy resin composition was obtained.
  • Example 11 to 18, Comparative Examples 7 to 12 A curable epoxy resin composition was prepared in the same manner as in Example 10 except that the composition of the curable epoxy resin composition was changed to the composition shown in Table 2.
  • Example 18 the rubber particle-dispersed epoxy compound obtained in Production Example 2 was used as a constituent component of the epoxy resin. Further, in the same manner as in Example 10, an optical semiconductor device in which an optical semiconductor element was sealed with a cured product was produced.
  • Luminance retention [%] heat resistance test
  • Luminance retention [%] heat resistance and humidity resistance test
  • ⁇ Luminance retention [%] (heat resistance test) ⁇ ⁇ Total luminous flux after 100 hours (heat resistance test) (lm) ⁇ / ⁇ total luminous flux for 0 hour (lm) ⁇ ⁇ 100
  • ⁇ Luminance retention [%] (heat and humidity resistance test) ⁇ ⁇ Total luminous flux after 100 hours (heat and humidity resistance test) (lm) ⁇ / ⁇ total luminous flux for 0 hour (lm) ⁇ ⁇ 100
  • FIG. 2 shows an example of a surface temperature profile (temperature profile in one of the two heat treatments) of the optical semiconductor device when heated by the reflow furnace. Thereafter, the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Co., Ltd.), whether or not a crack having a length of 90 ⁇ m or more occurred in the cured product, and It was evaluated whether or not electrode peeling (peeling of the cured product from the electrode surface) occurred.
  • the number of optical semiconductor devices in which a crack having a length of 90 ⁇ m or more occurred in the cured product is shown in the column of “Solder heat resistance test [number of cracks]” in Tables 1 and 2.
  • the number of the generated optical semiconductor devices is shown in the column of “Solder heat resistance test [electrode peeling number]” in Tables 1 and 2.
  • Thermal shock test The optical semiconductor devices obtained in Examples and Comparative Examples (5 were used for each curable epoxy resin composition) were exposed in an atmosphere of ⁇ 40 ° C. for 30 minutes, and subsequently in an atmosphere of 150 ° C. A thermal shock with one cycle of exposure to 30 minutes was applied for 200 cycles using a thermal shock tester. Thereafter, the length of cracks generated in the cured product in the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), and among the five optical semiconductor devices, The number of optical semiconductor devices in which cracks having a length of 90 ⁇ m or more occurred in the cured product was measured. The results are shown in the column of “thermal shock test [number of cracks]” in Tables 1 and 2.
  • Conductivity test luminous intensity retention rate (heat resistance test) is 85% or more
  • Conductivity test luminous intensity retention rate (heat resistance and humidity resistance test) is 85% or more
  • Solder heat resistance test 90 ⁇ m in length on the cured product The number of optical semiconductor devices in which the above cracks occurred was zero
  • Solder heat resistance test the number of optical semiconductor devices in which electrode peeling occurred was zero
  • Thermal shock test 90 ⁇ m or more in length on the cured product The number of the optical semiconductor devices in which the cracks occurred is 0. The results are shown in the “Comprehensive judgment” column of Tables 1 and 2.
  • Example and the comparative example is as follows.
  • MA-DGIC Trade name “MA-DGIC” [monoallyl diglycidyl Isocyanurate], Shikoku Kasei Kogyo Co., Ltd.
  • YD-128 trade name “YD-128” [bisphenol A type epoxy resin], manufactured by Nippon Steel Chemical Co., Ltd.
  • KMP-600 trade name “KMP-600” [crosslinked polydimethylsiloxane with silicone resin on the surface], manufactured by Shin-Etsu Chemical Co., Ltd.
  • KMP-602 trade name “KMP-602” [silicone resin on the surface Prepared cross-linked polydimethylsiloxane], manufactured by Shin-Etsu Chemical Co., Ltd.
  • SF8421 trade name “SF8421” [polyalkylene ether-modified silicone compound represented by formula (2)], manufactured by Toray Dow Corning Co., Ltd.
  • Test equipment Resin curing oven Espec Co., Ltd. GPHH-201 -Thermostatic chamber ESPEC Co., Ltd. Small high temperature chamber ST-120B1 ⁇ Total luminous flux measuring machine Optronic Laboratories Multi-spectral Radiation Measurement System OL771 ⁇ Thermal shock tester Espec Co., Ltd. Small thermal shock device TSE-11-A ⁇ Reflow furnace manufactured by Nippon Antom Co., Ltd., UNI-5016F
  • Alicyclic epoxy compound (A) and the following formula (1) [Wherein, R 1 and R 2 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom).
  • the curable epoxy resin composition characterized by including the monoallyl diglycidyl isocyanurate compound (B) represented by these, and a stress relaxation agent (C).
  • the alicyclic epoxy compound (A) has (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and (ii) ) The curable epoxy resin composition according to the above [1], comprising at least one selected from the group consisting of compounds in which an epoxy group is directly bonded to the alicyclic ring with a single bond. [3] The curable epoxy resin composition according to the above [1] or [2], wherein the alicyclic epoxy compound (A) includes a compound having a cyclohexene oxide group.
  • the linking group is a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or these
  • the curable epoxy resin composition according to the above [4], wherein is a group in which a plurality of are connected.
  • the alicyclic epoxy compound represented by the formula (I) is a compound represented by the following formulas (I-1) to (I-10), bis (3,4-epoxycyclohexylmethyl) ether, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, and 2,2-bis
  • the curable epoxy resin composition according to the above [4] or [5] which is at least one selected from the group consisting of (3,4-epoxycyclohexane-1-yl) propane.
  • R in the above formula (I-5) is an alkylene group having 1 to 8 carbon atoms (preferably a linear or branched alkylene group having 1 to 3 carbon atoms).
  • n1 to n6 each represents an integer of 1 to 30.
  • the alicyclic epoxy compound (A) is represented by the following formula (I-1)
  • R 4 represents a p-valent organic group.
  • p represents an integer of 1 to 20.
  • q represents an integer of 1 to 50. When p is an integer greater than or equal to 2, several q may be the same and may differ.
  • the sum (total) of q in the formula (II) is an integer of 3 to 100.
  • R 5 represents any one of groups represented by the following formulas (IIa) to (IIc). At least one of R 5 is a group represented by the formula (IIa).
  • R 6 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.)] [9]
  • the ratio of the group represented by the formula (IIa) to the total amount (100 mol%) of R 5 in the compound represented by the formula (II) is 40 mol% or more (preferably 60 mol% or more, more
  • Composition. [11] In any one of the above [8] to [10], the epoxy group equivalent (epoxy equivalent) of the compound represented by the formula (II) is 50 to 1000 (preferably 100 to 500).
  • the content (blending amount) of the alicyclic epoxy compound (A) is 10 to 95% by weight (preferably 15 to 90% by weight) with respect to the total amount (100% by weight) of the curable epoxy resin composition.
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) is 20 to 99% by weight (preferably The curable epoxy resin composition according to any one of [1] to [12] above, which is 30 to 95% by weight, more preferably 40 to 95% by weight.
  • the content (blending amount) of the monoallyl diglycidyl isocyanurate compound (B) is 5 to 120 parts by weight (preferably 5 to 110 parts by weight) with respect to 100 parts by weight of the alicyclic epoxy compound (A).
  • the curable epoxy resin composition according to any one of [1] to [13] above, more preferably 5 to 105 parts by weight.
  • the ratio of the monoallyl diglycidyl isocyanurate compound (B) to the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) is 1 to 60
  • the stress relaxation agent (C) is selected from the group consisting of silicone rubber particles (C1), silicone oil (C2), liquid rubber component (C3), inorganic filler (C4), and thermoplastic resin (C5).
  • the stress relaxation agent (C) is at least one selected from the group consisting of silicone rubber particles (C1) and silicone oil (C2).
  • a polyalkylene ether-modified silicone compound (hereinafter referred to as “polyalkylene ether-modified silicone compound (2)”) wherein the silicone oil (C2) has a structure represented by the following formula (2) having an epoxy equivalent of 3000 to 15000:
  • the curable epoxy resin composition according to any one of [16] to [20] above.
  • x is an integer from 80 to 140
  • y is an integer from 1 to 5
  • z is an integer from 5 to 20.
  • R 3 is an alkylene group having 2 or 3 carbon atoms (preferably a trimethylene group).
  • A is a polyalkylene ether group having a structure represented by the following formula (2a). (Wherein, a and b are each independently an integer of 0 to 40.
  • the content (blending amount) of the stress relaxation agent (C) is 0.1 to 100 parts by weight (preferably 0.1 to 50 parts by weight) with respect to 100 parts by weight of the alicyclic epoxy compound (A).
  • the content of the stress relaxation agent (C) relative to the total amount (100 parts by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) is 0.1 to 20 parts by weight
  • the curing agent (D) is an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including those having a substituent such as an alkyl group bonded to the ring).
  • the curable epoxy resin composition according to one.
  • the content (blending amount) of the curing agent (D) is 50 to 200 parts by weight (preferably 80 to 200 parts by weight based on 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable epoxy resin composition). 150 parts by weight), the curable epoxy resin composition according to any one of the above [26] to [29].
  • the content (blending amount) of the curing accelerator (E) is 0.01 to 5 parts by weight (preferably with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable epoxy resin composition). Is 0.02 to 3 parts by weight, more preferably 0.03 to 2 parts by weight).
  • the curable epoxy resin composition according to any one of [26] to [30] above.
  • the content (blending amount) of the curing catalyst (F) is 0.01 to 5 parts by weight (preferably with respect to 100 parts by weight of the total amount of compounds having epoxy groups contained in the curable epoxy resin composition).
  • the rubber particles other than silicone rubber particles are rubber particles having a multilayer structure (core-shell structure) composed of a core portion having rubber elasticity and at least one shell layer covering the core portion. 34].
  • the refractive index of the rubber particles other than the silicone rubber particles is 1.40 to 1.60 (preferably 1.42 to 1.58).
  • the difference between the refractive index of rubber particles other than silicone rubber particles and the refractive index of a cured product obtained by curing a curable epoxy resin composition containing the rubber particles is within ⁇ 0.03.
  • the content (blending amount) of rubber particles other than silicone rubber particles is 0.5 to 30 parts by weight with respect to 100 parts by weight of the total amount of compounds having epoxy groups contained in the curable epoxy resin composition (
  • the curable resin composition of the present invention can be preferably used as a material (sealing agent) for forming a sealing material for an optical semiconductor element (LED element) in an optical semiconductor device.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2018/001302 2017-01-23 2018-01-18 硬化性エポキシ樹脂組成物 WO2018135557A1 (ja)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111969133A (zh) * 2020-06-16 2020-11-20 深圳信达新能源科技有限公司 一种电池的制备方法及制得的电池
JP2021042337A (ja) * 2019-09-13 2021-03-18 味の素株式会社 樹脂組成物
JP2021528503A (ja) * 2019-05-30 2021-10-21 天津徳高化成新材料股▲ふん▼有限公司Ｔｅｃｏｒｅ Ｓｙｎｃｈｅｍ Ｉｎｃ Ｌｅｄディスプレイの表面実装式ディスクリートデバイス用の封止樹脂組成物及びその用途
WO2022148103A1 (zh) * 2021-01-07 2022-07-14 天津德高化成光电科技有限责任公司 一种预聚体、含有该预聚体的封装树脂及封装树脂的应用
CN115772374A (zh) * 2022-12-20 2023-03-10 武汉市三选科技有限公司 一种液态模封胶及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013018921A (ja) * 2011-07-13 2013-01-31 Daicel Corp 硬化性エポキシ樹脂組成物
JP2013203865A (ja) * 2012-03-28 2013-10-07 Kyocera Chemical Corp 半導体封止用樹脂組成物および半導体装置
JP2014133807A (ja) * 2013-01-09 2014-07-24 Daicel Corp 硬化性エポキシ樹脂組成物
JP5708486B2 (ja) * 2009-06-03 2015-04-30 住友ベークライト株式会社 半導体封止用樹脂組成物及び半導体装置
JP2015098586A (ja) * 2013-10-16 2015-05-28 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2016040383A (ja) * 2015-12-07 2016-03-24 日立化成株式会社 電子部品封止用エポキシ樹脂組成物およびそれを用いた電子部品装置
JP2016050221A (ja) * 2014-08-28 2016-04-11 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2016065146A (ja) * 2014-09-25 2016-04-28 京セラケミカル株式会社 熱硬化性樹脂組成物、半導体装置及び電気・電子部品
JP2016113525A (ja) * 2014-12-12 2016-06-23 ナミックス株式会社 液状エポキシ樹脂組成物、半導体封止剤、半導体装置、および液状エポキシ樹脂組成物の製造方法
WO2017138491A1 (ja) * 2016-02-12 2017-08-17 株式会社ダイセル 光反射用硬化性樹脂組成物及びその硬化物、並びに光半導体装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3477111B2 (ja) 1999-06-01 2003-12-10 四国化成工業株式会社 熱硬化性エポキシ樹脂組成物
JP5968137B2 (ja) * 2012-07-20 2016-08-10 ナミックス株式会社 液状封止材、それを用いた電子部品
TWI618728B (zh) * 2013-08-07 2018-03-21 日立化成股份有限公司 環氧樹脂組成物及電子零件裝置

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5708486B2 (ja) * 2009-06-03 2015-04-30 住友ベークライト株式会社 半導体封止用樹脂組成物及び半導体装置
JP2013018921A (ja) * 2011-07-13 2013-01-31 Daicel Corp 硬化性エポキシ樹脂組成物
JP2013203865A (ja) * 2012-03-28 2013-10-07 Kyocera Chemical Corp 半導体封止用樹脂組成物および半導体装置
JP2014133807A (ja) * 2013-01-09 2014-07-24 Daicel Corp 硬化性エポキシ樹脂組成物
JP2015098586A (ja) * 2013-10-16 2015-05-28 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2016050221A (ja) * 2014-08-28 2016-04-11 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2016065146A (ja) * 2014-09-25 2016-04-28 京セラケミカル株式会社 熱硬化性樹脂組成物、半導体装置及び電気・電子部品
JP2016113525A (ja) * 2014-12-12 2016-06-23 ナミックス株式会社 液状エポキシ樹脂組成物、半導体封止剤、半導体装置、および液状エポキシ樹脂組成物の製造方法
JP2016040383A (ja) * 2015-12-07 2016-03-24 日立化成株式会社 電子部品封止用エポキシ樹脂組成物およびそれを用いた電子部品装置
WO2017138491A1 (ja) * 2016-02-12 2017-08-17 株式会社ダイセル 光反射用硬化性樹脂組成物及びその硬化物、並びに光半導体装置

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021528503A (ja) * 2019-05-30 2021-10-21 天津徳高化成新材料股▲ふん▼有限公司Ｔｅｃｏｒｅ Ｓｙｎｃｈｅｍ Ｉｎｃ Ｌｅｄディスプレイの表面実装式ディスクリートデバイス用の封止樹脂組成物及びその用途
JP7017636B2 (ja) 2019-05-30 2022-02-08 天津徳高化成新材料股▲ふん▼有限公司 Ｌｅｄディスプレイの表面実装式ディスクリートデバイス用の封止樹脂組成物及びその用途
JP2021042337A (ja) * 2019-09-13 2021-03-18 味の素株式会社 樹脂組成物
JP7184002B2 (ja) 2019-09-13 2022-12-06 味の素株式会社 樹脂組成物
JP2023024463A (ja) * 2019-09-13 2023-02-16 味の素株式会社 樹脂組成物
JP7396443B2 (ja) 2019-09-13 2023-12-12 味の素株式会社 樹脂組成物
CN111969133A (zh) * 2020-06-16 2020-11-20 深圳信达新能源科技有限公司 一种电池的制备方法及制得的电池
WO2022148103A1 (zh) * 2021-01-07 2022-07-14 天津德高化成光电科技有限责任公司 一种预聚体、含有该预聚体的封装树脂及封装树脂的应用
CN115772374A (zh) * 2022-12-20 2023-03-10 武汉市三选科技有限公司 一种液态模封胶及其制备方法
CN115772374B (zh) * 2022-12-20 2023-08-18 武汉市三选科技有限公司 一种液态模封胶及其制备方法

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