WO2011105192A1 - Resin composition for sealing an optical semiconductor and optical semiconductor device using said resin composition - Google Patents

Resin composition for sealing an optical semiconductor and optical semiconductor device using said resin composition Download PDF

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Publication number
WO2011105192A1
WO2011105192A1 PCT/JP2011/052347 JP2011052347W WO2011105192A1 WO 2011105192 A1 WO2011105192 A1 WO 2011105192A1 JP 2011052347 W JP2011052347 W JP 2011052347W WO 2011105192 A1 WO2011105192 A1 WO 2011105192A1
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WIPO (PCT)
Prior art keywords
optical semiconductor
resin composition
group
epoxy
sealing
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PCT/JP2011/052347
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French (fr)
Japanese (ja)
Inventor
木村伯子
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ダイセル化学工業株式会社
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Application filed by ダイセル化学工業株式会社 filed Critical ダイセル化学工業株式会社
Priority to CN201180008555.5A priority Critical patent/CN102782000B/en
Publication of WO2011105192A1 publication Critical patent/WO2011105192A1/en

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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
    • C08G59/68—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 catalysts used
    • C08G59/688—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 catalysts used containing phosphorus
    • 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
    • C08G59/40—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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a resin composition for sealing an optical semiconductor, a cured product obtained by curing the resin composition, and an optical semiconductor device using the same.
  • Patent Document 1 contains an epoxy-modified ester compound that is excellent in solubility in an organic solvent and can be easily mixed with an epoxy resin as an epoxy resin curing agent, and has low hygroscopicity, low dielectric constant, low dielectric loss tangent, etc.
  • curing agent (B), and a hardening accelerator (C) is disclosed.
  • Patent Document 3 hydrogenation is performed for the purpose of providing an epoxy resin composition that exhibits excellent translucency and ultraviolet resistance, does not discolor even when heated for a long time, and has low hygroscopicity.
  • An epoxy resin composition contained therein in an amount of 0.01 to 5% by weight is disclosed.
  • JP 2004-217869 A JP 2007-320974 A Japanese Patent Laid-Open No. 2005-126662
  • the objective of this invention is providing the resin composition for optical semiconductor sealing which can obtain the hardened
  • Another object of the present invention is to provide a cured product obtained by curing the above-mentioned resin composition for encapsulating an optical semiconductor and imparting excellent luminance stability while maintaining high heat resistance and transparency. It is in.
  • the other object of this invention is to provide the optical semiconductor device which sealed the optical semiconductor element using the said resin composition for optical semiconductor sealing.
  • a resin composition containing a specific structure alicyclic epoxy resin and using a specific curing accelerator has a high heat resistance.
  • it In the reliability test of the optical semiconductor device using transparency and its cured product, it has excellent luminance stability with small luminance fluctuation, and is useful as a resin composition for optical semiconductor encapsulation.
  • the inventors have found that the luminance stability has a causal relationship with the adhesion between the sealing resin and the frame, and have reached the present invention.
  • the present invention is an optical semiconductor sealing resin composition containing an epoxy resin, a curing agent (B), and a curing accelerator (C),
  • the alicyclic epoxy resin (A) (A1) the following formula (I) [In Formula (I), X represents a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked]
  • A2 a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond
  • the curing agent (B) is an acid anhydride curing agent
  • the curing accelerator (C) the following formula (1) [R 1 , R 2 , R 3 , and R 4 in the formula (1) each represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other].
  • An optical semiconductor encapsulating resin composition comprising an ionic combination of a phosphonium ion and a halogen anion capable of forming an ion pair with the phosphonium ion is provided.
  • the halogen anion is preferably bromine ion or iodine ion.
  • this invention provides the hardened
  • an optical semiconductor device that has high heat resistance and transparency, and has excellent luminance stability with small luminance fluctuations in a reliability test of an optical semiconductor device using the cured product.
  • the resin composition for optical semiconductor sealing obtained can be provided.
  • a cured product obtained by curing the resin composition for optical semiconductor encapsulation of the present invention has high heat resistance and transparency, and in a reliability test of an optical semiconductor device using the cured product, Luminance fluctuation is small and luminance stability is excellent.
  • an optical semiconductor device having high heat resistance and transparency, small luminance fluctuation, and excellent luminance stability can be obtained.
  • the resin composition for optical semiconductor encapsulation of the present invention is an optical semiconductor encapsulation resin composition containing an epoxy resin, a curing agent (B), and a curing accelerator (C), and an alicyclic epoxy resin ( As A), (A1) the following formula (I) [In Formula (I), X represents a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked] (A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring.
  • A1 the following formula (I) [In Formula (I), X represents a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbon
  • the curing agent (B) is an acid anhydride curing agent
  • the curing accelerator (C) the following formula (1) [R 1 , R 2 , R 3 , and R 4 in Formula (1) each represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other] And an ion conjugate of a halogen anion capable of forming an ion pair with the phosphonium ion. Since the resin composition for sealing an optical semiconductor of the present invention contains an epoxy resin, it has high heat resistance and transparency.
  • the epoxy resin contained in the resin composition for encapsulating an optical semiconductor of the present invention is (A1) represented by the following formula (I) as the alicyclic epoxy resin (A).
  • X represents a linking group, represented by a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked].
  • (A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. At least one compound selected from the group consisting of the above compounds is contained in an amount of 55 to 100 wt% with respect to the total amount of the epoxy resin.
  • the alicyclic epoxy resin (A) contained in the resin composition for sealing an optical semiconductor of the present invention is (A1) represented by the following formula (I): [In formula (I), X represents a linking group, represented by a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked].
  • (A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. It is at least one compound selected from the group consisting of the compounds as described above.
  • the divalent hydrocarbon group represented as the linking group X is a linear or branched alkylene group having 1 to 18 carbon atoms, divalent And an alicyclic hydrocarbon group (particularly a divalent cycloalkylene group).
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1, And divalent cycloalkylene groups (including cycloalkylidene groups) such as 4-cyclohexylene and cyclohexylidene groups.
  • Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-7).
  • commercially available products such as Celoxide 2021P and Celoxide 2081 (manufactured by Daicel Chemical Industries, Ltd.) can also be used, where m represents an integer of 1 to 30.
  • Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formulas (I-8) and (I-9).
  • Examples of the compound (A3) having 3 or more epoxy groups composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring are represented by the following formulas (I-10) and (I-11). The compound which is made is mentioned.
  • R is a group obtained by dividing q-OH from q-valent alcohol, and represents an alkyl group having about 2 to 18 carbon atoms, which may be linear or branched, and cyclic. A skeleton may be included.
  • Q and n represent natural numbers.
  • Examples of the q-valent alcohol [R— (OH) q ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (such as alcohols having 1 to 15 carbon atoms).
  • q is preferably 1 to 6, and p is preferably 1 to 30. When q is 2 or more, p in each group in () may be the same or different.
  • the compound (I-8) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, EHPE3150 (Daicel Chemical). Kogyo Co., Ltd.).
  • a, b, c, d, e, and f are integers from 0 to 30.
  • the compounds (A1) to (A3) used as the alicyclic epoxy resin (A) can be used alone or in combination of two or more.
  • Celoxide 2021P, Celoxide 2081, EHPE3150, EHPE3150CE (Daicel) Commercial products such as Chemical Industry Co., Ltd. can be used.
  • the epoxy resin contained in the resin composition for encapsulating an optical semiconductor of the present invention may contain an epoxy resin other than the alicyclic epoxy resin (A).
  • epoxy resins include glycidyl type epoxy resins such as bisphenol A type and F type having a liquid aromatic ring, and glycidyl type epoxy resins represented by the following formula.
  • the content of the alicyclic epoxy resin (A) relative to the total amount of the epoxy resin (compound having all epoxy groups) in the optical semiconductor sealing resin composition is 55 to 100 wt%, preferably 60 to 100 wt%, More preferably, it can be 70 to 100 wt%.
  • the content of the alicyclic epoxy resin (A) with respect to the total amount of the epoxy resin is less than 55%, the effect of the present application cannot be obtained.
  • the blending amount of the glycidyl type epoxy resin having an aromatic ring exceeds 30% by weight of the compound having all epoxy groups, desired performance cannot be obtained.
  • the content of the epoxy resin in the resin composition for sealing an optical semiconductor of the present invention is preferably 30 to 99.9 wt%.
  • the curing agent (B) contained in the optical semiconductor sealing resin composition of the present invention is an acid anhydride curing agent.
  • the acid anhydride curing agent can be arbitrarily selected from those generally used as curing agents for epoxy resins. Among these, those which are liquid at normal temperature are preferable, and specific examples include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like.
  • acid anhydrides that are solid at room temperature such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride, are dissolved in a liquid acid anhydride at room temperature to form a liquid mixture. Therefore, it can be used as the curing agent of the present invention.
  • the curing agent (B) commercially available products such as Jamaicacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd.) and HN-5500 (manufactured by Hitachi Chemical Co., Ltd.) can also be used. .
  • the amount of the curing agent (B) used is, for example, 50 to 200 parts by weight, preferably 100 to 145 parts by weight with respect to 100 parts by weight of the compound having all epoxy groups contained in the resin composition for optical semiconductor encapsulation. Part, more specifically, it should be used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy group in the compound having all epoxy groups contained in the resin composition for optical semiconductor encapsulation. Is preferred.
  • the amount of the curing agent (B) used is less than 50 parts by weight, the effect becomes insufficient and the toughness of the cured product (B) tends to decrease, while the amount of the curing agent (B) used is 200 weights. When it exceeds the part, the cured product may be colored to deteriorate the hue.
  • the curing accelerator (C) contained in the optical semiconductor sealing resin composition of the present invention is represented by the following formula (1).
  • R 1 , R 2 , R 3 , and R 4 in Formula (1) each represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other]
  • the ionic combination (quaternary organic phosphonium salt) of a phosphonium ion and a halogen anion represented by the above formula (1) is one in which the phosphonium ion and the halogen anion form at least one ion pair.
  • the ionic bond is quickly dissociated at the time of curing exposed to a high temperature, and phosphonium ions have a function of promoting curing. For this reason, when an optical semiconductor device is manufactured, it is considered that the halogen anion in the sealing material has an effect of improving luminance stability by lowering the adhesion with the lead frame.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms in R 1 , R 2 , R 3 , and R 4 represented by the hydrocarbon group having 1 to 20 carbon atoms in the formula (1) include, for example, 1 to And an alkyl group having 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl, methylcyclohexyl, heptyl, octyl, isooctyl, nonyl, isononyl, Examples include linear, branched or cyclic alkyl groups such as decyl and isodecyl groups.
  • Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, methylbenzyl, ethylbenzyl, dimethylbenzyl, diethylbenzyl, phenethyl, methylphenethyl, ethylphenethyl, methylphenethyl, ethylphenethyl, and aryl groups having 6 to 20 carbon atoms. Examples thereof include a phenyl group; a substituted phenyl group such as methylphenyl, dimethylphenyl, and ethylphenyl; a naphthyl group, and the like.
  • alkyl groups having 2 to 4 carbon atoms such as ethyl, propyl and butyl
  • aralkyl groups having 7 to 10 carbon atoms such as benzyl, ethylbenzyl, phenethyl and ethylphenethyl groups
  • carbons such as phenyl and methylphenyl groups
  • An aryl group of 6 to 8 is preferable, and a phenyl group, a butyl group, and an ethyl group are particularly preferable.
  • halogen anion capable of forming an ion pair with the phosphonium ion represented by the above formula (1) examples include chlorine ion, bromine ion and iodine ion. Of these, bromine ion and iodine ion are preferable.
  • the phosphonium compound as an ion conjugate of the phosphonium ion represented by the above formula (1) and the halogen anion capable of forming an ion pair with the phosphonium ion include, for example, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide , Tetrabutylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, propyltriphenylphosphonium chloride, propyltriphenyl Phenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride,
  • tetraethyl phosphonium bromide tetraethyl phosphonium bromide.
  • tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium iodide, and ethyltriphenylphosphonium iodide are preferable.
  • a commercial product such as U-CAT 5003 (manufactured by Sun Apro Co., Ltd.) can also be used as the curing accelerator (C).
  • the blending amount of these phosphonium compounds is such that the bromine or iodine content contained in the optical semiconductor sealing resin composition is 200 mg / kg or more (for example, 200 to 8000 mg / kg), preferably 200 to 5000 mg / kg, more preferably. Is preferably blended so as to be 300 to 4000 mg / kg. If the bromine or iodine content is less than 200 mg / kg, luminance stability is difficult to obtain.
  • the curing accelerator may be a phosphonium compound alone or a mixture with a commonly used amine-based curing accelerator or phosphorus-based curing accelerator.
  • amine curing accelerator examples include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine and the like.
  • phosphorus curing accelerator include phosphines such as phosphate esters and triphenylphosphine.
  • the amount of the curing accelerator (C) used is, for example, 0.05 to 5 parts by weight, preferably 0 with respect to 100 parts by weight of the compound having all epoxy groups contained in the optical semiconductor sealing resin composition. .About.1 to 3 parts by weight, particularly preferably about 0.2 to 3 parts by weight, and most preferably about 0.25 to 2.5 parts by weight.
  • the amount of the curing accelerator (C) used is less than 0.05 parts by weight, the curing acceleration effect may be insufficient.
  • the amount of the curing accelerator (C) used exceeds 5 parts by weight, The cured product may be colored to deteriorate the hue.
  • the resin composition for optical semiconductor encapsulation of the present invention may contain a solvent.
  • the solvent include glycol (ethylene glycol; polyalkylene glycol; neopentyl alcohol, etc.), ether (diethyl ether; ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether, propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl.
  • Ether dipropylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether Chain ethers such as glycol ethers such as glycerin mono, di or trialkyl ethers; Tetrahydrofuran, and cyclic ethers such as dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, C 5-6 cycloalkanediol mono or diacetate, carboxylic acid esters such as C 5-6 cycloalkane dimethanol mono or diacetate;
  • the resin composition for optical semiconductor sealing concerning this invention can use various additives in the range which does not impair the effect of this invention besides the above.
  • a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin
  • the reaction can be allowed to proceed slowly.
  • Conventional additives such as inorganic fillers, organic rubber particles, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents and the like can be used. .
  • the resin composition for encapsulating an optical semiconductor of the present invention has a temperature of 45 to 200 ° C., preferably 100 to 190 ° C., more preferably 100 to 180 ° C., and a curing time of 30 to 600 minutes, preferably 45 to 540. Minutes, more preferably 60 to 480 minutes.
  • the curing temperature and the curing time are lower than the lower limit of the range, curing is insufficient, and when the curing temperature and the curing time are higher than the upper limit of the range, the resin component may be decomposed.
  • the curing conditions depend on various conditions, when the curing temperature is high, the curing time is short, and when the curing temperature is low, the curing time is long and can be adjusted as appropriate.
  • the optical semiconductor device of the present invention can be obtained by sealing an optical semiconductor element with the resin composition for optical semiconductor encapsulation of the present invention.
  • the optical semiconductor element is sealed by injecting the resin composition for optical semiconductor sealing prepared by the above-described method into a predetermined mold and heating and curing under predetermined conditions.
  • an optical semiconductor device excellent in various physical properties such as luminance stability, heat resistance, and transparency, in which the optical semiconductor element is sealed with the resin composition for optical semiconductor sealing, is obtained.
  • the curing temperature and the curing time can be the same as described above.
  • Example 1 As an alicyclic epoxy resin, 50 parts by weight of Daicel Chemical Industries, trade name “Celoxide 2021P”, 50 parts by weight of Daicel Chemical Industries, trade name “EHPE3150CE” were used.
  • the curing agent is 100 parts by weight of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name “Licacid MH-700”), and the curing accelerator is tetraphenylphosphonium bromide (Wako Pure Chemical Industries, Ltd.) 1 part by weight was used. Furthermore, 1.5 parts by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was used. These were uniformly mixed (2000 rpm, 5 minutes) using “Awatori Rentaro” manufactured by Shinky Corp. to obtain a resin composition for optical semiconductor encapsulation.
  • Example 2 Except for using 0.5 parts by weight of ethyltriphenylphosphonium iodide (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts by weight of triphenylphosphine (manufactured by Kishida Chemical Co., Ltd.) as a curing accelerator. In the same manner as in Example 1, a resin composition for sealing an optical semiconductor was obtained.
  • ethyltriphenylphosphonium iodide manufactured by Wako Pure Chemical Industries, Ltd.
  • triphenylphosphine manufactured by Kishida Chemical Co., Ltd.
  • Example 3 Example 1 except that 70 parts by weight of Daicel Chemical Industries, Ltd., trade name “EHPE3150CE”, and 30 parts by weight of trade name “YD-128”, manufactured by Toto Kasei Co., Ltd. were used as the epoxy resin. Similarly, a resin composition for optical semiconductor encapsulation was obtained.
  • Comparative Example 1 For sealing an optical semiconductor in the same manner as in Example 1, except that tetrabutylphosphonium diethyl phosphorodithioate (trade name “Hishicolin PX-4ET” manufactured by Nippon Chemical Industry Co., Ltd.) was used as a curing accelerator. A resin composition was obtained.
  • tetrabutylphosphonium diethyl phosphorodithioate trade name “Hishicolin PX-4ET” manufactured by Nippon Chemical Industry Co., Ltd.
  • Comparative Example 2 Example 1 except that Daicel Chemical Industries, Ltd., trade name “EHPE3150CE” 50 parts by weight and Toto Kasei Co., Ltd., trade name “YD-128” 50 parts by weight were used as the epoxy resin. Similarly, a resin composition for optical semiconductor encapsulation was obtained.
  • Comparative Example 3 A resin composition for encapsulating an optical semiconductor was obtained in the same manner as in Example 1 except that 100 parts by weight of a trade name “YD-128” manufactured by Toto Kasei Co., Ltd. was used as the epoxy resin.
  • the resin compositions for sealing an optical semiconductor obtained in Examples and Comparative Examples were heated at 110 ° C. for 2 hours, and then heated at 130 ° C. for 3 hours to obtain a cured product.
  • the obtained resin composition for encapsulating an optical semiconductor was evaluated by the following method. In the following evaluation tests, the optical semiconductor sealing resin composition was cured under the same conditions as described above.
  • the obtained resin composition for encapsulating an optical semiconductor was cast into a lead frame with an optical semiconductor element (InGaN) and cured by heating to produce an optical semiconductor device.
  • the manufactured optical semiconductor device was subjected to low-temperature energization ( ⁇ 40 ° C./20 mA) and normal temperature energization (23 ° C./60 mA), and the current-carrying luminance stability under each condition was measured using the following measuring device.
  • Measuring apparatus OL771 manufactured by OPTRONIC LABORATORIES
  • the luminance after 150, 300, 500, and 1000 hours was measured, and the luminance retention rate from the initial (100%) was calculated.
  • the variation rate of the luminance retention rate indicates the maximum width from the initial stage.
  • the luminance after 300 hours was measured, and the luminance retention rate from the initial (100%) was calculated. The results are shown in Table 2.
  • the low-temperature energization characteristics were evaluated as ⁇ when the variation rate of the luminance retention rate was ⁇ 3% or more: x, and less than ⁇ 3%: ⁇ .
  • the normal temperature energization characteristics were evaluated as “X” when the luminance deterioration rate (brightness reduction rate from the initial stage) was 20% or more: “X”, and less than 20%: “ ⁇ ”.
  • X luminance deterioration rate
  • Epoxy resin Celoxide 2021P 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, manufactured by Daicel Chemical Industries, Ltd.
  • EHPE3150CE 1,2-bis (hydroxymethyl) -1-butanol 2-epoxy-4- (2-oxiranyl) cyclosexane adduct and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, manufactured by Daicel Chemical Industries, Ltd.
  • YD-128 Bisphenol A type Epoxy resin, hardener (B) manufactured by Tohto Kasei Co., Ltd.
  • a lower adhesiveness between the cured product of the resin composition for encapsulating an optical semiconductor and the lead frame according to the present invention is preferable in terms of luminance stability, and an adhesive strength is 18 N / mm 2 or less (for example, 0 to 18 N / mm). 2 ), preferably 15 N / mm 2 or less (for example, 0 to 15 N / mm 2 ), more preferably 7 N / mm 2 or less (for example, 0 to 7 N / mm 2 ). is there. Note that there is no problem even if the adhesive strength is zero.
  • an optical semiconductor device that has high heat resistance and transparency, and has excellent luminance stability with small luminance fluctuations in a reliability test of an optical semiconductor device using the cured product.
  • the resin composition for optical semiconductor sealing obtained can be provided.

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Abstract

Disclosed is a resin composition for sealing an optical semiconductor, said resin composition containing an epoxy resin, a hardener, and a hardening accelerator. Between 55% and 100% of the total weight of the epoxy resin in the disclosed resin composition is an alicyclic epoxy resin (A) consisting of at least one compound selected from among: compounds represented by formula (I); compounds in which an epoxy group is bonded to an alicycle via a direct single bond; and compounds having at least three epoxy groups each comprising adjacent two carbon atoms and an oxygen atom that are part of an alicycle. The hardener in the disclosed resin composition is an acid anhydride hardener, and the hardening accelerator is an ionic conjugate of the phosphonium ion represented by formula (1) with a halogen anion capable of forming an ion pair with the phosphonium ion.

Description

光半導体封止用樹脂組成物とこれを使用した光半導体装置Resin composition for optical semiconductor sealing and optical semiconductor device using the same
　本発明は、光半導体封止用樹脂組成物、それを硬化してなる硬化物、ならびにそれを使用した光半導体装置に関する。 The present invention relates to a resin composition for sealing an optical semiconductor, a cured product obtained by curing the resin composition, and an optical semiconductor device using the same.
　光半導体素子封止用樹脂組成物として、エポキシ樹脂、硬化剤、及び硬化促進剤からなるエポキシ樹脂組成物が多数報告されている。例えば、特許文献１では、有機溶剤への溶解性に優れ、エポキシ樹脂との混合が容易なエポキシ変性エステル化合物をエポキシ樹脂硬化剤として含有し、低吸湿性および低誘電率、低誘電正接などの電気的特性に優れた、１分子中に２個以上のエポキシ基を有するエポキシ樹脂（Ａ）と、エポキシ樹脂硬化剤（Ｂ）と、硬化促進剤（Ｃ）とを含有するエポキシ樹脂組成物が開示されている。 A large number of epoxy resin compositions comprising an epoxy resin, a curing agent, and a curing accelerator have been reported as an optical semiconductor element sealing resin composition. For example, Patent Document 1 contains an epoxy-modified ester compound that is excellent in solubility in an organic solvent and can be easily mixed with an epoxy resin as an epoxy resin curing agent, and has low hygroscopicity, low dielectric constant, low dielectric loss tangent, etc. An epoxy resin composition containing an epoxy resin (A) having two or more epoxy groups in one molecule, an epoxy resin curing agent (B), and a curing accelerator (C) having excellent electrical characteristics. It is disclosed.
　また、特許文献２では、低曲げ弾性率、高曲げ強度であり強靱性に優れ、ガラス転移温度及び透明性が高い、光半導体封止用樹脂組成物を提供することを目的として、分子内に環状脂肪族骨格と２個以上のエポキシ基を有する脂環式エポキシ化合物（ａ）からなる溶媒および脂環エポキシ基を有する（メタ）アクリル酸エステルモノマー及び／又は該モノマーをモノマー成分として含む重合体（ｂ）を含有する熱硬化性エポキシ樹脂組成物（Ａ）、硬化剤（Ｂ）および硬化促進剤（Ｃ）を含む樹脂組成物が開示されている。 Moreover, in patent document 2, it is in a molecule | numerator in order to provide the resin composition for optical semiconductor sealing which is a low bending elastic modulus, high bending strength, is excellent in toughness, and has high glass transition temperature and transparency. A solvent comprising a cycloaliphatic skeleton and an alicyclic epoxy compound (a) having two or more epoxy groups, a (meth) acrylate monomer having an alicyclic epoxy group, and / or a polymer containing the monomer as a monomer component The resin composition containing the thermosetting epoxy resin composition (A) containing (b), a hardening | curing agent (B), and a hardening accelerator (C) is disclosed.
　また、特許文献３では、優れた透光性と耐紫外線性を示し、長時間にわたり加熱しても変色せず、かつ低い吸湿性を有するエポキシ樹脂組成物を提供することを目的として、水素化エポキシ樹脂と、硬化剤と、硬化促進剤とを含み、硬化剤の活性水素当量が、エポキシ樹脂成分のエポキシ当量の０．７～１３倍であり、かつ、硬化促進剤が該エポキシ樹脂組成物中に０．０１～５重量％となる量で含有されているエポキシ樹脂組成物が開示されている。 Further, in Patent Document 3, hydrogenation is performed for the purpose of providing an epoxy resin composition that exhibits excellent translucency and ultraviolet resistance, does not discolor even when heated for a long time, and has low hygroscopicity. An epoxy resin, a curing agent, and a curing accelerator, wherein the active hydrogen equivalent of the curing agent is 0.7 to 13 times the epoxy equivalent of the epoxy resin component, and the curing accelerator is the epoxy resin composition An epoxy resin composition contained therein in an amount of 0.01 to 5% by weight is disclosed.
　一方、ＬＥＤの信頼性評価のひとつに輝度安定性の評価があり、従来の封止材では、通電試験中に輝度が上昇又は低下する現象がみられ、輝度安定性が悪いという問題点が指摘されている。しかしながら、輝度変動の小さい輝度安定性に優れたエポキシ樹脂組成物はこれまで得られていなかった。 On the other hand, there is evaluation of luminance stability as one of the reliability evaluations of LEDs, and with conventional sealing materials, the phenomenon that the luminance increases or decreases during the energization test is pointed out, and the problem is that the luminance stability is poor. Has been. However, an epoxy resin composition excellent in luminance stability with small luminance fluctuation has not been obtained so far.
特開２００４－２１７８６９号公報JP 2004-217869 A 特開２００７－３２０９７４号公報JP 2007-320974 A 特開２００５－１２６６６２号公報Japanese Patent Laid-Open No. 2005-126662
　本発明の目的は、高い耐熱性および透明性を維持しつつ、優れた輝度安定性を付与した硬化物を得ることができる光半導体封止用樹脂組成物を提供することにある。
　また、本発明の他の目的は、上記光半導体封止用樹脂組成物を硬化してなる、高い耐熱性および透明性を維持しつつ、優れた輝度安定性を付与した硬化物を提供することにある。
　さらに、本発明の他の目的は、上記光半導体封止用樹脂組成物を使用して光半導体素子を封止した光半導体装置を提供することにある。 The objective of this invention is providing the resin composition for optical semiconductor sealing which can obtain the hardened | cured material which provided the outstanding brightness | luminance stability, maintaining high heat resistance and transparency.
Another object of the present invention is to provide a cured product obtained by curing the above-mentioned resin composition for encapsulating an optical semiconductor and imparting excellent luminance stability while maintaining high heat resistance and transparency. It is in.
Furthermore, the other object of this invention is to provide the optical semiconductor device which sealed the optical semiconductor element using the said resin composition for optical semiconductor sealing.
　本発明者らは、上記課題を解決するため鋭意検討した結果、特定構造の脂環式エポキシ樹脂を含有し、且つ特定の硬化促進剤を用いた樹脂組成物は、その硬化物が高い耐熱性・透明性を有し、かつその硬化物を用いた光半導体装置の信頼性試験において、輝度変動の小さい輝度安定性に優れており、光半導体封止用樹脂組成物として有用であること、また、輝度安定性は封止樹脂とフレーム間の密着性に因果関係があることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a specific structure alicyclic epoxy resin and using a specific curing accelerator has a high heat resistance. In the reliability test of the optical semiconductor device using transparency and its cured product, it has excellent luminance stability with small luminance fluctuation, and is useful as a resin composition for optical semiconductor encapsulation. The inventors have found that the luminance stability has a causal relationship with the adhesion between the sealing resin and the frame, and have reached the present invention.
　すなわち、本発明は、エポキシ樹脂、硬化剤（Ｂ）、及び硬化促進剤（Ｃ）を含有する光半導体封止用樹脂組成物であって、
　脂環式エポキシ樹脂（Ａ）として、（Ａ１）下記式（Ｉ）
Figure JPOXMLDOC01-appb-C000003
 ［式（Ｉ）中、Ｘは連結基を示し、単結合、２価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド結合、及びこれらが複数個連結した基］
で表される化合物、（Ａ２）脂環にエポキシ基が直接単結合で結合している化合物、及び（Ａ３）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を３以上有する化合物からなる群から選択される少なくとも１種の化合物を、該エポキシ樹脂の全量に対して５５～１００ｗｔ％含有し、硬化剤（Ｂ）が酸無水物系硬化剤であり、且つ硬化促進剤（Ｃ）として、下記式（１）
Figure JPOXMLDOC01-appb-C000004
 ［式（１）中のＲl，Ｒ2，Ｒ3，及びＲ4は、それぞれ、炭素数１～２０の炭化水素基を表し、相互に同じであっても異なっていてもよい］で表されるホスホニウムイオンと該ホスホニウムイオンとイオン対を形成しうるハロゲンアニオンとのイオン結合体を含有することを特徴とする光半導体封止用樹脂組成物を提供する。
　前記ハロゲンアニオンは、臭素イオンもしくはヨウ素イオンであることが好ましい。
　また、本発明は、上記光半導体封止用樹脂組成物を硬化してなる硬化物を提供する。
　さらに、本発明は、上記光半導体封止用樹脂組成物によって光半導体素子が封止されてなる光半導体装置を提供する。 That is, the present invention is an optical semiconductor sealing resin composition containing an epoxy resin, a curing agent (B), and a curing accelerator (C),
As the alicyclic epoxy resin (A), (A1) the following formula (I)
Figure JPOXMLDOC01-appb-C000003
 [In Formula (I), X represents a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked]
(A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. And at least one compound selected from the group consisting of compounds having 3 or more of the compound is contained in an amount of 55 to 100 wt% based on the total amount of the epoxy resin, the curing agent (B) is an acid anhydride curing agent, and As the curing accelerator (C), the following formula (1)
Figure JPOXMLDOC01-appb-C000004
 [R 1 , R 2 , R 3 , and R 4 in the formula (1) each represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other]. An optical semiconductor encapsulating resin composition comprising an ionic combination of a phosphonium ion and a halogen anion capable of forming an ion pair with the phosphonium ion is provided.
The halogen anion is preferably bromine ion or iodine ion.
Moreover, this invention provides the hardened | cured material formed by hardening | curing the said resin composition for optical semiconductor sealing.
Furthermore, this invention provides the optical semiconductor device by which an optical semiconductor element is sealed with the said resin composition for optical semiconductor sealing.
　本発明によれば、その硬化物が高い耐熱性・透明性を有し、かつその硬化物を用いた光半導体装置の信頼性試験において、輝度変動の小さい輝度安定性に優れた光半導体装置が得られる光半導体封止用樹脂組成物を提供することができる。また、本発明の、上記光半導体封止用樹脂組成物を硬化してなる硬化物は、高い耐熱性・透明性を有し、かつその硬化物を用いた光半導体装置の信頼性試験において、輝度変動が小さく、輝度安定性に優れている。さらに、本発明によれば、高い耐熱性・透明性を有し、輝度変動が小さく、輝度安定性に優れた光半導体装置が得られる。 According to the present invention, there is provided an optical semiconductor device that has high heat resistance and transparency, and has excellent luminance stability with small luminance fluctuations in a reliability test of an optical semiconductor device using the cured product. The resin composition for optical semiconductor sealing obtained can be provided. In addition, a cured product obtained by curing the resin composition for optical semiconductor encapsulation of the present invention has high heat resistance and transparency, and in a reliability test of an optical semiconductor device using the cured product, Luminance fluctuation is small and luminance stability is excellent. Furthermore, according to the present invention, an optical semiconductor device having high heat resistance and transparency, small luminance fluctuation, and excellent luminance stability can be obtained.
　＜光半導体封止用樹脂組成物＞
　本発明の光半導体封止用樹脂組成物は、エポキシ樹脂、硬化剤（Ｂ）、及び硬化促進剤（Ｃ）を含有する光半導体封止用樹脂組成物であって、脂環式エポキシ樹脂（Ａ）として、（Ａ１）下記式（Ｉ）
Figure JPOXMLDOC01-appb-C000005
 ［式（Ｉ）中、Ｘは連結基を示し、単結合、２価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド結合、及びこれらが複数個連結した基］
で表される化合物、（Ａ２）脂環にエポキシ基が直接単結合で結合している化合物、及び（Ａ３）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を３以上有する化合物からなる群から選択される少なくとも１種の化合物を、該エポキシ樹脂の全量に対して５５～１００ｗｔ％含有し、硬化剤（Ｂ）が酸無水物系硬化剤であり、且つ硬化促進剤（Ｃ）として、下記式（１）
Figure JPOXMLDOC01-appb-C000006
 ［式（１）中のＲl，Ｒ2，Ｒ3，及びＲ4は、それぞれ、炭素数１～２０の炭化水素基を表し、相互に同じであっても異なっていてもよい］
で表されるホスホニウムイオンと該ホスホニウムイオンとイオン対を形成しうるハロゲンアニオンとのイオン結合体を含有することを特徴とする。本発明の光半導体封止用樹脂組成物は、エポキシ樹脂を含有するため、高い耐熱性および透明性を有している。 <Resin composition for optical semiconductor encapsulation>
The resin composition for optical semiconductor encapsulation of the present invention is an optical semiconductor encapsulation resin composition containing an epoxy resin, a curing agent (B), and a curing accelerator (C), and an alicyclic epoxy resin ( As A), (A1) the following formula (I)
Figure JPOXMLDOC01-appb-C000005
 [In Formula (I), X represents a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked]
(A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. And at least one compound selected from the group consisting of compounds having 3 or more of the compound is contained in an amount of 55 to 100 wt% based on the total amount of the epoxy resin, the curing agent (B) is an acid anhydride curing agent, and As the curing accelerator (C), the following formula (1)
Figure JPOXMLDOC01-appb-C000006
 [R 1 , R 2 , R 3 , and R 4 in Formula (1) each represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other]
And an ion conjugate of a halogen anion capable of forming an ion pair with the phosphonium ion. Since the resin composition for sealing an optical semiconductor of the present invention contains an epoxy resin, it has high heat resistance and transparency.
　＜エポキシ樹脂＞
　本発明の光半導体封止用樹脂組成物に含有されているエポキシ樹脂は、脂環式エポキシ樹脂（Ａ）として、（Ａ１）下記式（Ｉ）
Figure JPOXMLDOC01-appb-C000007
 ［式（Ｉ）中、Ｘは連結基を示し、単結合、２価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド結合、及びこれらが複数個連結した基］で表される化合物、（Ａ２）脂環にエポキシ基が直接単結合で結合している化合物、及び（Ａ３）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を３以上有する化合物からなる群から選択される少なくとも１種の化合物を、該エポキシ樹脂の全量に対して５５～１００ｗｔ％含有している。 <Epoxy resin>
The epoxy resin contained in the resin composition for encapsulating an optical semiconductor of the present invention is (A1) represented by the following formula (I) as the alicyclic epoxy resin (A).
Figure JPOXMLDOC01-appb-C000007
 [In formula (I), X represents a linking group, represented by a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked]. (A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. At least one compound selected from the group consisting of the above compounds is contained in an amount of 55 to 100 wt% with respect to the total amount of the epoxy resin.
　＜脂環式エポキシ樹脂（Ａ）＞
　本発明の光半導体封止用樹脂組成物に含有されている脂環式エポキシ樹脂（Ａ）は、（Ａ１）下記式（Ｉ）
Figure JPOXMLDOC01-appb-C000008
 ［式（Ｉ）中、Ｘは連結基を示し、単結合、２価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド結合、及びこれらが複数個連結した基］で表される化合物、（Ａ２）脂環にエポキシ基が直接単結合で結合している化合物、及び（Ａ３）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を３以上有する化合物からなる群から選択される少なくとも１種の化合物である。 <Alicyclic epoxy resin (A)>
The alicyclic epoxy resin (A) contained in the resin composition for sealing an optical semiconductor of the present invention is (A1) represented by the following formula (I):
Figure JPOXMLDOC01-appb-C000008
 [In formula (I), X represents a linking group, represented by a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked]. (A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. It is at least one compound selected from the group consisting of the compounds as described above.
　（Ａ１）上記式（Ｉ）で表される化合物において、連結基Ｘとして示される２価の炭化水素基としては、炭素数が１～１８の直鎖状又は分岐鎖状のアルキレン基、２価の脂環式炭化水素基（特に２価のシクロアルキレン基）などが好ましく例示される。炭素数が１～１８の直鎖状又は分岐鎖状のアルキレン基としては、例えば、メチレン、メチルメチレン、ジメチルメチレン、エチレン、プロピレン、トリメチレン基等が挙げられる。２価の脂環式炭化水素基としては、例えば、１，２－シクロペンチレン、１，３－シクロペンチレン、シクロペンチリデン、１，２－シクロヘキシレン、１，３－シクロヘキシレン、１，４－シクロヘキシレン、シクロヘキシリデン基等の２価のシクロアルキレン基（シクロアルキリデン基を含む）などが挙げられる。 (A1) In the compound represented by the formula (I), the divalent hydrocarbon group represented as the linking group X is a linear or branched alkylene group having 1 to 18 carbon atoms, divalent And an alicyclic hydrocarbon group (particularly a divalent cycloalkylene group). Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1, And divalent cycloalkylene groups (including cycloalkylidene groups) such as 4-cyclohexylene and cyclohexylidene groups.
　上記式（Ｉ）で表される脂環式エポキシ化合物の代表的な例としては、下記式（Ｉ－１）～（Ｉ－７）で表される化合物などが挙げられる。例えば、セロキサイド２０２１Ｐ、セロキサイド２０８１（ダイセル化学工業（株）製〉等の市販品を使用することもできる。なお、下記式中、ｍは、１～３０の整数を表す。 Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-7). For example, commercially available products such as Celoxide 2021P and Celoxide 2081 (manufactured by Daicel Chemical Industries, Ltd.) can also be used, where m represents an integer of 1 to 30.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　（Ａ２）脂環にエポキシ基が直接単結合で結合している化合物としては、例えば下記式（Ｉ－８），（Ｉ－９）で表される化合物が挙げられる。また、（Ａ３）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を３以上有する化合物としては、例えば下記式（Ｉ－１０），（Ｉ－１１）で表される化合物が挙げられる。 (A2) Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formulas (I-8) and (I-9). Examples of the compound (A3) having 3 or more epoxy groups composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring are represented by the following formulas (I-10) and (I-11). The compound which is made is mentioned.
Figure JPOXMLDOC01-appb-C000010
 上記式（Ｉ－８）中、Ｒはｑ価のアルコールからｑ個の－ＯＨを除した基であり、炭素数２～１８程度のアルキル基を表し、直鎖でも分岐鎖でもよく、また環状骨格が含まれていてもよい。；ｑ、ｎは自然数を表す。ｑ価のアルコール［Ｒ－(ＯＨ)q］としては、２，２－ビス（ヒドロキシメチル）－１－ブタノール等の多価アルコールなど（炭素数１～１５のアルコール等）が挙げられる。ｑは１～６が好ましく、ｐは１～３０が好ましい。ｑが２以上の場合、それぞれの（　）内の基におけるｐは同一でもよく異なっていてもよい。上記化合物（Ｉ－８）としては、具体的には、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物、ＥＨＰＥ３１５０（ダイセル化学工業（株）製）などが挙げられる。また、上記式（Ｉ－１０），（Ｉ－１１）中、ａ，ｂ，ｃ，ｄ，ｅ，ｆは０～３０の整数である。
Figure JPOXMLDOC01-appb-C000010
 In the above formula (I-8), R is a group obtained by dividing q-OH from q-valent alcohol, and represents an alkyl group having about 2 to 18 carbon atoms, which may be linear or branched, and cyclic. A skeleton may be included. Q and n represent natural numbers. Examples of the q-valent alcohol [R— (OH) q ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (such as alcohols having 1 to 15 carbon atoms). q is preferably 1 to 6, and p is preferably 1 to 30. When q is 2 or more, p in each group in () may be the same or different. Specific examples of the compound (I-8) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, EHPE3150 (Daicel Chemical). Kogyo Co., Ltd.). In the above formulas (I-10) and (I-11), a, b, c, d, e, and f are integers from 0 to 30.
　上記脂環式エポキシ樹脂（Ａ）として使用される化合物（Ａ１）～（Ａ３）は単独で又は２種以上を組み合わせて使用することができ、例えば、セロキサイド２０２１Ｐ、セロキサイド２０８１、ＥＨＰＥ３１５０、ＥＨＰＥ３１５０ＣＥ（ダイセル化学工業（株）製）等の市販品を使用できる。 The compounds (A1) to (A3) used as the alicyclic epoxy resin (A) can be used alone or in combination of two or more. For example, Celoxide 2021P, Celoxide 2081, EHPE3150, EHPE3150CE (Daicel) Commercial products such as Chemical Industry Co., Ltd. can be used.
　本発明の光半導体封止用樹脂組成物に含有されているエポキシ樹脂は、上記脂環式エポキシ樹脂（Ａ）以外の他のエポキシ樹脂を含んでいてもよい。他のエポキシ樹脂として、液状で芳香環を有するビスフェノールＡ型、Ｆ型などのグリシジル型エポキシ樹脂や、下記式で表されるグリシジル型エポキシ樹脂などが挙げられる。 The epoxy resin contained in the resin composition for encapsulating an optical semiconductor of the present invention may contain an epoxy resin other than the alicyclic epoxy resin (A). Examples of other epoxy resins include glycidyl type epoxy resins such as bisphenol A type and F type having a liquid aromatic ring, and glycidyl type epoxy resins represented by the following formula.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　光半導体封止用樹脂組成物中のエポキシ樹脂の全量（全エポキシ基を有する化合物）に対する上記脂環式エポキシ樹脂（Ａ）の含有量は５５～１００ｗｔ％であり、好ましくは６０～１００ｗｔ％、より好ましくは７０～１００ｗｔ％とすることができる。エポキシ樹脂の全量に対する脂環式エポキシ樹脂（Ａ）の含有量が５５％未満であると、本願の効果が得られなくなる。特に、芳香環を有するグリシジル型エポキシ樹脂の配合量が、全エポキシ基を有する化合物の３０重量％を超えると所望の性能が得られない。 The content of the alicyclic epoxy resin (A) relative to the total amount of the epoxy resin (compound having all epoxy groups) in the optical semiconductor sealing resin composition is 55 to 100 wt%, preferably 60 to 100 wt%, More preferably, it can be 70 to 100 wt%. When the content of the alicyclic epoxy resin (A) with respect to the total amount of the epoxy resin is less than 55%, the effect of the present application cannot be obtained. In particular, when the blending amount of the glycidyl type epoxy resin having an aromatic ring exceeds 30% by weight of the compound having all epoxy groups, desired performance cannot be obtained.
　本発明の光半導体封止用樹脂組成物中のエポキシ樹脂の含有量は、３０～９９．９ｗｔ％が好ましい。 The content of the epoxy resin in the resin composition for sealing an optical semiconductor of the present invention is preferably 30 to 99.9 wt%.
　＜硬化剤（Ｂ）＞
　本発明の光半導体封止用樹脂組成物に含有されている硬化剤（Ｂ）は酸無水物系硬化剤である。酸無水物系硬化剤としては、一般にエポキシ樹脂用硬化剤として慣用されているものの中から任意に選択して使用することができる。なかでも、常温で液状のものが好ましく、具体的には、例えば、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ドデセニル無水コハク酸、メチルエンドメチレンテトラヒドロ無水フタル酸などを挙げることができる。また、例えば無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルシクロヘキセンジカルボン酸無水物などの常温で固体の酸無水物は、常温で液状の酸無水物に溶解させて液状の混合物とすることで、本発明の硬化剤として使用することができる。 <Curing agent (B)>
The curing agent (B) contained in the optical semiconductor sealing resin composition of the present invention is an acid anhydride curing agent. The acid anhydride curing agent can be arbitrarily selected from those generally used as curing agents for epoxy resins. Among these, those which are liquid at normal temperature are preferable, and specific examples include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like. Also, for example, acid anhydrides that are solid at room temperature, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride, are dissolved in a liquid acid anhydride at room temperature to form a liquid mixture. Therefore, it can be used as the curing agent of the present invention.
　また、本発明においては、硬化剤（Ｂ）として、リカシッド　ＭＨ－７００（新日本理化（株）製）、ＨＮ－５５００（日立化成工業（株）製）等の市販品を使用することもできる。 In the present invention, as the curing agent (B), commercially available products such as Ricacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd.) and HN-5500 (manufactured by Hitachi Chemical Co., Ltd.) can also be used. .
　硬化剤（Ｂ）の使用量としては、例えば、光半導体封止用樹脂組成物中に含有する全エポキシ基を有する化合物１００重量部に対して、５０～２００重量部、好ましくは１００～１４５重量部、より具体的には、上記光半導体封止用樹脂組成物中に含有する全てのエポキシ基を有する化合物におけるエポキシ基１当量当たり、０．５～１．５当量となる割合で使用することが好ましい。硬化剤（Ｂ）の使用量が５０重量部を下回ると、効果が不十分となり、硬化物（Ｂ）の強靱性が低下する傾向があり、一方、硬化剤（Ｂ）の使用量が２００重量部を上回ると、硬化物が着色して色相が悪化する場合がある。 The amount of the curing agent (B) used is, for example, 50 to 200 parts by weight, preferably 100 to 145 parts by weight with respect to 100 parts by weight of the compound having all epoxy groups contained in the resin composition for optical semiconductor encapsulation. Part, more specifically, it should be used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy group in the compound having all epoxy groups contained in the resin composition for optical semiconductor encapsulation. Is preferred. When the amount of the curing agent (B) used is less than 50 parts by weight, the effect becomes insufficient and the toughness of the cured product (B) tends to decrease, while the amount of the curing agent (B) used is 200 weights. When it exceeds the part, the cured product may be colored to deteriorate the hue.
　＜硬化促進剤（Ｃ）＞
　本発明の光半導体封止用樹脂組成物に含有されている硬化促進剤（Ｃ）は、下記式（１）
Figure JPOXMLDOC01-appb-C000012
 ［式（１）中のＲl，Ｒ2，Ｒ3，及びＲ4は、それぞれ、炭素数１～２０の炭化水素基を表し、相互に同じであっても異なっていてもよい］
で表されるホスホニウムイオンと該ホスホニウムイオンとイオン対を形成しうるハロゲンアニオンとのイオン結合体を含有している。上記式（１）で表されるホスホニウムイオンとハロゲンアニオンとのイオン結合体（第４級有機ホスホニウム塩）は、ホスホニウムイオンとハロゲンアニオンが少なくとも１個のイオン対を形成したものである。この硬化促進剤は高温にさらされる硬化時にはこのイオン結合体がすみやかに解離し、ホスホニウムイオンが硬化を促進する作用を有する。このため、光半導体装置を製造した場合に、封止材中のハロゲンアニオンがリードフレームとの密着性を低くすることにより輝度安定性を向上する作用を有すると考えられる。 <Curing accelerator (C)>
The curing accelerator (C) contained in the optical semiconductor sealing resin composition of the present invention is represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000012
 [R 1 , R 2 , R 3 , and R 4 in Formula (1) each represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other]
And an ion conjugate of a halogen anion capable of forming an ion pair with the phosphonium ion. The ionic combination (quaternary organic phosphonium salt) of a phosphonium ion and a halogen anion represented by the above formula (1) is one in which the phosphonium ion and the halogen anion form at least one ion pair. In this curing accelerator, the ionic bond is quickly dissociated at the time of curing exposed to a high temperature, and phosphonium ions have a function of promoting curing. For this reason, when an optical semiconductor device is manufactured, it is considered that the halogen anion in the sealing material has an effect of improving luminance stability by lowering the adhesion with the lead frame.
　式（１）中の炭素数１～２０の炭化水素基で表されるＲl，Ｒ2，Ｒ3，及びＲ4における炭素数１～２０の炭化水素基としては、例えば、炭素数１～２０のアルキル基、炭素数７～２０のアラルキル基、炭素数６～２０のアリール基等が挙げられる。炭素数１～２０のアルキル基としては、例えば、メチル、エチル、プロピル、ブチル、イソブチル、ｓ－ブチル、ペンチル、イソペンチル、ヘキシル、イソヘキシル、シクロヘキシル、メチルシクロヘキシル、ヘプチル、オクチル、イソオクチル、ノニル、イソノニル、デシル、イソデシル基などの直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。炭素数７～２０のアラルキル基としては、ベンジル基、メチルベンジル、エチルベンジル、ジメチルベンジル、ジエチルベンジル、フェネチル、メチルフェネチル、エチルフェネチル、メチルフェネチル、エチルフェネチル、炭素数６～２０のアリール基としては、例えば、フェニル基；メチルフェニル、ジメチルフェニル、エチルフェニルなどの置換フェニル基；ナフチル基等が挙げられる。これらの中でも、エチル、プロピル、ブチルなどの炭素数２～４のアルキル基；ベンジル、エチルベンジル、フェネチル、エチルフェネチル基などの炭素数７～１０のアラルキル基；フェニル基、メチルフェニル基などの炭素数６～８のアリール基等が好ましく、フェニル基、ブチル基、エチル基が特に好ましい。 Examples of the hydrocarbon group having 1 to 20 carbon atoms in R 1 , R 2 , R 3 , and R 4 represented by the hydrocarbon group having 1 to 20 carbon atoms in the formula (1) include, for example, 1 to And an alkyl group having 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl, methylcyclohexyl, heptyl, octyl, isooctyl, nonyl, isononyl, Examples include linear, branched or cyclic alkyl groups such as decyl and isodecyl groups. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, methylbenzyl, ethylbenzyl, dimethylbenzyl, diethylbenzyl, phenethyl, methylphenethyl, ethylphenethyl, methylphenethyl, ethylphenethyl, and aryl groups having 6 to 20 carbon atoms. Examples thereof include a phenyl group; a substituted phenyl group such as methylphenyl, dimethylphenyl, and ethylphenyl; a naphthyl group, and the like. Among these, alkyl groups having 2 to 4 carbon atoms such as ethyl, propyl and butyl; aralkyl groups having 7 to 10 carbon atoms such as benzyl, ethylbenzyl, phenethyl and ethylphenethyl groups; carbons such as phenyl and methylphenyl groups An aryl group of 6 to 8 is preferable, and a phenyl group, a butyl group, and an ethyl group are particularly preferable.
　上記式（１）で表されるホスホニウムイオンとイオン対を形成しうるハロゲンアニオンとしては、塩素イオン、臭素イオン、ヨウ素イオン等が挙げられる。なかでも、臭素イオン、ヨウ素イオンが好ましい。 Examples of the halogen anion capable of forming an ion pair with the phosphonium ion represented by the above formula (1) include chlorine ion, bromine ion and iodine ion. Of these, bromine ion and iodine ion are preferable.
　上記式（１）で表されるホスホニウムイオンと該ホスホニウムイオンとイオン対を形成しうるハロゲンアニオンとのイオン結合体としてのホスホニウム化合物の具体例としては、例えば、テトラブチルホスホニウムクロリド、テトラブチルホスホニウムブロミド、テトラブチルホスホニウムヨージド、テトラフェニルホスホニウムクロリド、テトラフェニルホスホニウムブロミド、テトラフェニルホスホニウムヨージド、エチルトリフェニルホスホニウムクロリド、エチルトリフェニルホスホニウムブロミド、エチルトリフェニルホスホニウムヨージド、プロピルトリフェニルホスホニウムクロリド、プロピルトリフェニルホスホニウムブロミド、プロピルトリフェニルホスホニウムヨージド、ブチルトリフェニルホスホニウムクロリド、ブチルトリフェニルホスホニウムブロミド、ブチルトリフェニルホスホニウムヨージド、メチルトリフェニルホスホニウムブロミド、メチルトリフェニルホスホニウムヨージド、テトラメチルホスホニウムヨージド、テトラエチルホスホニウムブロミドなどが挙げられる。なかでも、テトラフェニルホスホニウムブロミド、テトラブチルホスホニウムブロミド、テトラフェニルホスホニウムヨージド、エチルトリフェニルホスホニウムヨージドが好ましい。 Specific examples of the phosphonium compound as an ion conjugate of the phosphonium ion represented by the above formula (1) and the halogen anion capable of forming an ion pair with the phosphonium ion include, for example, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide , Tetrabutylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, propyltriphenylphosphonium chloride, propyltriphenyl Phenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, Tilt Li tetraphenylphosphonium bromide, butyl triphenyl phosphonium iodide, methyl triphenyl phosphonium bromide, methyl triphenyl phosphonium iodide, tetramethyl phosphonium iodide, etc. tetraethyl phosphonium bromide. Of these, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium iodide, and ethyltriphenylphosphonium iodide are preferable.
　また、本発明においては、硬化促進剤（Ｃ）として、Ｕ－ＣＡＴ　５００３（サンアプロ（株）製）等の市販品を使用することもできる。 In the present invention, a commercial product such as U-CAT 5003 (manufactured by Sun Apro Co., Ltd.) can also be used as the curing accelerator (C).
　これらホスホニウム化合物の配合量は、光半導体封止用樹脂組成物中に含まれる臭素もしくはヨウ素含有量が２００ｍｇ／ｋｇ以上（例えば、２００～８０００ｍｇ／ｋｇ）、好ましくは２００～５０００ｍｇ／ｋｇ、より好ましくは３００～４０００ｍｇ／ｋｇとなるように配合することが好ましい。臭素もしくはヨウ素含有量が２００ｍｇ／ｋｇ未満であると輝度安定性が得られにくくなる。 The blending amount of these phosphonium compounds is such that the bromine or iodine content contained in the optical semiconductor sealing resin composition is 200 mg / kg or more (for example, 200 to 8000 mg / kg), preferably 200 to 5000 mg / kg, more preferably. Is preferably blended so as to be 300 to 4000 mg / kg. If the bromine or iodine content is less than 200 mg / kg, luminance stability is difficult to obtain.
　硬化促進剤はホスホニウム化合物単独でもよいし、慣用されているアミン系硬化促進剤やリン系硬化促進剤などとの混合物でもよい。アミン系硬化促進剤としては、ベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ－ジメチルシクロヘキシルアミンなどの３級アミンなどが挙げられる。また、リン系硬化促進剤としては、リン酸エステル、トリフェニルホスフィンなどのホスフィン類が挙げられる。 The curing accelerator may be a phosphonium compound alone or a mixture with a commonly used amine-based curing accelerator or phosphorus-based curing accelerator. Examples of the amine curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine and the like. Examples of the phosphorus curing accelerator include phosphines such as phosphate esters and triphenylphosphine.
　硬化促進剤（Ｃ）の使用量としては、例えば、光半導体封止用樹脂組成物中に含有する全エポキシ基を有する化合物１００重量部に対して、０．０５～５重量部、好ましくは０．１～３重量部、特に好ましくは０．２～３重量部、最も好ましくは０．２５～２．５重量部程度である。硬化促進剤（Ｃ）の使用量が０．０５重量部を下回ると、硬化促進効果が不十分となる場合があり、一方、硬化促進剤（Ｃ）の使用量が５重量部を上回ると、硬化物が着色して色相が悪化する場合がある。 The amount of the curing accelerator (C) used is, for example, 0.05 to 5 parts by weight, preferably 0 with respect to 100 parts by weight of the compound having all epoxy groups contained in the optical semiconductor sealing resin composition. .About.1 to 3 parts by weight, particularly preferably about 0.2 to 3 parts by weight, and most preferably about 0.25 to 2.5 parts by weight. When the amount of the curing accelerator (C) used is less than 0.05 parts by weight, the curing acceleration effect may be insufficient. On the other hand, when the amount of the curing accelerator (C) used exceeds 5 parts by weight, The cured product may be colored to deteriorate the hue.
　＜溶媒＞　　
　本発明の光半導体封止用樹脂組成物は溶媒を含んでいてもよい。溶媒として、例えば、グリコール（エチレングリコール；ポリアルキレングリコール；ネオペンチルアルコールなど）、エーテル（ジエチルエーテル；エチレングリコールモノ又はジアルキルエーテル、ジエチレングリコールモノ又はジアルキルエーテル、プロピレングリコールモノ又はジアルキルエーテル、プロピレングリコールモノ又はジアリールエーテル、ジプロピレングリコールモノ又はジアルキルエーテル、トリプロピレングリコールモノ又はジアルキルエーテル、１，３－プロパンジオールモノ又はジアルキルエーテル、１，３－ブタンジオールモノ又はジアルキルエーテル、１，４－ブタンジオールモノ又はジアルキルエーテル、グリセリンモノ，ジ又はトリアルキルエーテル等のグリコールエーテル類などの鎖状エーテル；テトラヒドロフラン、ジオキサン等の環状エーテルなど）、エステル（酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソアミル、乳酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシブチルアセテート、Ｃ5-6シクロアルカンジオールモノ又はジアセテート、Ｃ5-6シクロアルカンジメタノールモノ又はジアセテート等のカルボン酸エステル類；エチレングリコールモノアルキルエーテルアセテート、エチレングリコールモノ又はジアセテート、ジエチレングリコールモノアルキルエーテルアセテート、ジエチレングリコールモノ又はジアセテート、プロピレングリコールモノアルキルエーテルアセテート、プロピレングリコールモノ又はジアセテート、ジプロピレングリコールモノアルキルエーテルアセテート、ジプロピレングリコールモノ又はジアセテート、１，３－プロパンジオールモノアルキルエーテルアセテート、１，３－プロパンジオールモノ又はジアセテート、１，３－ブタンジオールモノアルキルエーテルアセテート、１，３－ブタンジオールモノ又はジアセテート、１，４－ブタンジオールモノアルキルエーテルアセテート、１，４－ブタンジオールモノ又はジアセテート、グリセリンモノ，ジ又はトリアセテート、グリセリンモノ又はジＣ1-4アルキルエーテルジ又はモノアセテート、トリプロピレングリコールモノアルキルエーテルアセテート、トリプロピレングリコールモノ又はジアセテート等のグリコールアセテート類又はグリコールエーテルアセテート類など）、ケトン（アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、３，５，５－トリメチル－２－シクロヘキセン－１－オンなど）、アミド（Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミドなど）、スルホキシド（ジメチルスルホキシドなど）、アルコール（メタノール、エタノール、プロパノール、３－メトキシ－１－ブタノール、Ｃ5-6シクロアルカンジオール、Ｃ5-6シクロアルカンジメタノールなど）、炭化水素（ベンゼン、トルエン、キシレン等の芳香族炭化水素、ヘキサン等の脂肪族炭化水素、シクロヘキサン等の脂環式炭化水素など）、これらの混合溶媒などが挙げられる。 <Solvent>
The resin composition for optical semiconductor encapsulation of the present invention may contain a solvent. Examples of the solvent include glycol (ethylene glycol; polyalkylene glycol; neopentyl alcohol, etc.), ether (diethyl ether; ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether, propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl. Ether, dipropylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether Chain ethers such as glycol ethers such as glycerin mono, di or trialkyl ethers; Tetrahydrofuran, and cyclic ethers such as dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, C 5-6 cycloalkanediol mono or diacetate, carboxylic acid esters such as C 5-6 cycloalkane dimethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, Diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkyl ether Acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propanediol mono or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono Or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, glycerol mono, di or triacetate, glycerol mono or di C 1-4 alkyl ether di or monoacetate, tripropylene Glycol monoalkyl ether acetate, glycol acetates such as tripropylene glycol mono- or diacetate or glycol ether acetates), ketones (acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amide (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol ( Methanol, ethanol, propanol, 3-methoxy-1-butanol, C 5-6 cycloalkanediol, C 5-6 cycloalkanedimethanol, etc., hydrocarbons (aromatic hydrocarbons such as benzene, toluene, xylene, hexane, etc.) Aliphatic hydrocarbons, cycloaliphatic hydrocarbons such as cyclohexane, and the like, and mixed solvents thereof.
　＜添加剤＞
　本発明にかかる光半導体封止用樹脂組成物は、上記以外にも、本発明の効果を損なわない範囲内で各種添加剤を使用することができる。添加剤として、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、グリセリンなどの水酸基を有する化合物を使用すると、反応を緩やかに進行させることができる。その他にも、粘度や透明性を損なわない範囲内で、シリコーン系やフッ素系消泡剤、レベリング剤、γ－グリシドキシプロピルトリメトキシシランなどのシランカップリング剤、界面活性剤、シリカ、アルミナなどの無機充填剤、有機系のゴム粒子、難燃剤、着色剤、酸化防止剤、紫外線吸収剤、イオン吸着体、顔料、蛍光体、離型剤などの慣用の添加剤を使用することができる。 <Additives>
The resin composition for optical semiconductor sealing concerning this invention can use various additives in the range which does not impair the effect of this invention besides the above. For example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is used as the additive, the reaction can be allowed to proceed slowly. In addition, silicone and fluorine antifoaming agents, leveling agents, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, surfactants, silica, alumina, as long as viscosity and transparency are not impaired Conventional additives such as inorganic fillers, organic rubber particles, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents and the like can be used. .
　＜硬化物＞
　本発明の光半導体封止用樹脂組成物は、温度４５～２００℃、好ましくは、１００～１９０℃、さらに好ましくは、１００～１８０℃で、硬化時間３０～６００分、好ましくは、４５～５４０分、さらに好ましくは、６０～４８０分で硬化させることができる。硬化温度と硬化時間が上記範囲下限値より低い場合は、硬化が不十分となり、逆に上記範囲上限値より高い場合、樹脂成分の分解が起きる場合があるので、何れも好ましくない。硬化条件は種々の条件に依存するが、硬化温度が高い場合は硬化時間は短く、硬化温度が低い場合は硬化時間は長く、適宜調整することができる。本発明の光半導体封止用樹脂組成物を硬化させることにより輝度安定性、耐熱性、透明性などの諸物性に優れた硬化物が得られる。 <Hardened product>
The resin composition for encapsulating an optical semiconductor of the present invention has a temperature of 45 to 200 ° C., preferably 100 to 190 ° C., more preferably 100 to 180 ° C., and a curing time of 30 to 600 minutes, preferably 45 to 540. Minutes, more preferably 60 to 480 minutes. When the curing temperature and the curing time are lower than the lower limit of the range, curing is insufficient, and when the curing temperature and the curing time are higher than the upper limit of the range, the resin component may be decomposed. Although the curing conditions depend on various conditions, when the curing temperature is high, the curing time is short, and when the curing temperature is low, the curing time is long and can be adjusted as appropriate. By curing the resin composition for encapsulating an optical semiconductor of the present invention, a cured product having excellent physical properties such as luminance stability, heat resistance and transparency can be obtained.
　＜光半導体装置＞
　本発明の光半導体装置は、本発明の光半導体封止用樹脂組成物で光半導体素子を封止することにより得られる。光半導体素子の封止は、前述の方法で調製された光半導体封止用樹脂組成物を所定の成形型内に注入し、所定の条件で加熱硬化して行う。これによって、光半導体封止用樹脂組成物により、光半導体素子が封止されてなる、輝度安定性、耐熱性、透明性などの諸物性に優れた光半導体装置が得られる。硬化温度と硬化時間は、上記と同様にすることができる。 <Optical semiconductor device>
The optical semiconductor device of the present invention can be obtained by sealing an optical semiconductor element with the resin composition for optical semiconductor encapsulation of the present invention. The optical semiconductor element is sealed by injecting the resin composition for optical semiconductor sealing prepared by the above-described method into a predetermined mold and heating and curing under predetermined conditions. As a result, an optical semiconductor device excellent in various physical properties such as luminance stability, heat resistance, and transparency, in which the optical semiconductor element is sealed with the resin composition for optical semiconductor sealing, is obtained. The curing temperature and the curing time can be the same as described above.
　以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
　実施例１
　脂環式エポキシ樹脂として、ダイセル化学工業（株）製、商品名「セロキサイド２０２１Ｐ」５０重量部、ダイセル化学工業（株）製、商品名「ＥＨＰＥ３１５０ＣＥ」５０重量部を用いた。
　硬化剤としては、メチルヘキサヒドロ無水フタル酸（新日本理化（株）製、商品名「リカシッドＭＨ－７００」）１００重量部、硬化促進剤としてはテトラフェニルホスホニウムブロミド（和光純薬工業（株）製）１重量部を用いた。さらに、エチレングリコール（和光純薬工業（株）製）を１．５重量部用いた。
　これらをシンキー（株）製「あわとり錬太郎」を用いて、均一に混合し（２０００ｒｐｍ、５分）、光半導体封止用樹脂組成物を得た。 Example 1
As an alicyclic epoxy resin, 50 parts by weight of Daicel Chemical Industries, trade name “Celoxide 2021P”, 50 parts by weight of Daicel Chemical Industries, trade name “EHPE3150CE” were used.
The curing agent is 100 parts by weight of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name “Licacid MH-700”), and the curing accelerator is tetraphenylphosphonium bromide (Wako Pure Chemical Industries, Ltd.) 1 part by weight was used. Furthermore, 1.5 parts by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
These were uniformly mixed (2000 rpm, 5 minutes) using “Awatori Rentaro” manufactured by Shinky Corp. to obtain a resin composition for optical semiconductor encapsulation.
　実施例２
　硬化促進剤として、エチルトリフェニルホスホニウムヨージド（和光純薬工業（株）製）０．５重量部及びトリフェニルホスフィン（キシダ化学（株）製）０．５重量部を用いた以外は、実施例１と同様にして、光半導体封止用樹脂組成物を得た。 Example 2
Except for using 0.5 parts by weight of ethyltriphenylphosphonium iodide (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts by weight of triphenylphosphine (manufactured by Kishida Chemical Co., Ltd.) as a curing accelerator. In the same manner as in Example 1, a resin composition for sealing an optical semiconductor was obtained.
　実施例３
　エポキシ樹脂として、ダイセル化学工業（株）製、商品名「ＥＨＰＥ３１５０ＣＥ」７０重量部、並びに、東都化成（株）製、商品名「ＹＤ－１２８」３０重量部を用いた以外は、実施例１と同様にして、光半導体封止用樹脂組成物を得た。 Example 3
Example 1 except that 70 parts by weight of Daicel Chemical Industries, Ltd., trade name “EHPE3150CE”, and 30 parts by weight of trade name “YD-128”, manufactured by Toto Kasei Co., Ltd. were used as the epoxy resin. Similarly, a resin composition for optical semiconductor encapsulation was obtained.
　比較例１
　硬化促進剤として、テトラブチルホスホニウムジエチルホスホロジチオエート（日本化学工業（株）製、商品名「ヒシコーリンＰＸ－４ＥＴ」）を用いた以外は、実施例１と同様にして、光半導体封止用樹脂組成物を得た。 Comparative Example 1
For sealing an optical semiconductor in the same manner as in Example 1, except that tetrabutylphosphonium diethyl phosphorodithioate (trade name “Hishicolin PX-4ET” manufactured by Nippon Chemical Industry Co., Ltd.) was used as a curing accelerator. A resin composition was obtained.
　比較例２
　エポキシ樹脂として、ダイセル化学工業（株）製、商品名「ＥＨＰＥ３１５０ＣＥ」５０重量部、並びに、東都化成（株）製、商品名「ＹＤ－１２８」５０重量部を用いた以外は、実施例１と同様にして、光半導体封止用樹脂組成物を得た。 Comparative Example 2
Example 1 except that Daicel Chemical Industries, Ltd., trade name “EHPE3150CE” 50 parts by weight and Toto Kasei Co., Ltd., trade name “YD-128” 50 parts by weight were used as the epoxy resin. Similarly, a resin composition for optical semiconductor encapsulation was obtained.
　比較例３
　エポキシ樹脂として、東都化成（株）製、商品名「ＹＤ－１２８」１００重量部を用いた以外は、実施例１と同様にして、光半導体封止用樹脂組成物を得た。 Comparative Example 3
A resin composition for encapsulating an optical semiconductor was obtained in the same manner as in Example 1 except that 100 parts by weight of a trade name “YD-128” manufactured by Toto Kasei Co., Ltd. was used as the epoxy resin.
　配合は表１に示す（数値は重量部）。 The formulation is shown in Table 1 (values are parts by weight).
　実施例、比較例で得られた光半導体封止用樹脂組成物は、１１０℃で２時間、続いて、１３０℃で３時間加熱して硬化物を得た。 The resin compositions for sealing an optical semiconductor obtained in Examples and Comparative Examples were heated at 110 ° C. for 2 hours, and then heated at 130 ° C. for 3 hours to obtain a cured product.
　得られた光半導体封止用樹脂組成物を下記方法により評価した。以下の評価試験において、光半導体封止用樹脂組成物の硬化は、上記と同様の条件で行った。 The obtained resin composition for encapsulating an optical semiconductor was evaluated by the following method. In the following evaluation tests, the optical semiconductor sealing resin composition was cured under the same conditions as described above.
　［輝度安定性］
　光半導体素子（ＩｎＧａＮ）付きリードフレームに、得られた光半導体封止用樹脂組成物を注型して加熱硬化させて光半導体装置を作製した。
　作製した光半導体装置について、低温通電（－４０℃／２０ｍＡ）、及び、常温通電（２３℃／６０ｍＡ）を行い、各条件における通電輝度安定性を下記の測定装置を用いて測定した。
　　測定装置：ＯＰＴＲＯＮＩＣ　ＬＡＢＯＲＡＴＯＲＩＥＳ社製　ＯＬ７７１ [Brightness stability]
The obtained resin composition for encapsulating an optical semiconductor was cast into a lead frame with an optical semiconductor element (InGaN) and cured by heating to produce an optical semiconductor device.
The manufactured optical semiconductor device was subjected to low-temperature energization (−40 ° C./20 mA) and normal temperature energization (23 ° C./60 mA), and the current-carrying luminance stability under each condition was measured using the following measuring device.
Measuring apparatus: OL771 manufactured by OPTRONIC LABORATORIES
　低温通電では１５０，３００，５００，１０００時間後の輝度をそれぞれ測定し、初期（１００％）からの輝度保持率を算出した。輝度保持率の変動率は初期からの最大幅を示す。また、常温通電では３００時間後の輝度を測定し、初期（１００％）からの輝度保持率を算出した。結果を表２に示す。 In low-temperature energization, the luminance after 150, 300, 500, and 1000 hours was measured, and the luminance retention rate from the initial (100%) was calculated. The variation rate of the luminance retention rate indicates the maximum width from the initial stage. In addition, at normal temperature energization, the luminance after 300 hours was measured, and the luminance retention rate from the initial (100%) was calculated. The results are shown in Table 2.
　低温通電特性は、輝度保持率の変動率が±３％以上になった場合：×、±３％未満の場合：○と評価した。また、常温通電特性は、輝度の劣化率（初期からの輝度の低下率）が２０％以上の場合：×、２０％未満の場合：○と評価した。低温通電特性と常温通電特性の両方が○であった場合に、総合判定を○、それ以外を×とした。結果を表１に示す。 The low-temperature energization characteristics were evaluated as ◯ when the variation rate of the luminance retention rate was ± 3% or more: x, and less than ± 3%: ○. In addition, the normal temperature energization characteristics were evaluated as “X” when the luminance deterioration rate (brightness reduction rate from the initial stage) was 20% or more: “X”, and less than 20%: “◯”. When both the low-temperature energization characteristics and the room-temperature energization characteristics were ◯, the comprehensive judgment was ◯, and the others were x. The results are shown in Table 1.
　［接着強度］
　銀メッキ銅板の上に、得られた光半導体封止用樹脂組成物を用いて、１．２５ｍｍ×１．２５ｍｍ×１ｍｍのシリコンウエハーを硬化・接着した。この硬化物をダイシェアテスターに供して、シリコンウエハーが銀メッキ銅板から剥がされる際にかかる接着強度を測定した。結果を表１に示す。
　　測定条件：テストスピード３００μｍ／ｓ、テスト高さ５００μｍ
　　測定装置：Ｄａｇｅ社製　Ｄａｇｅ　４０００ [Adhesive strength]
A 1.25 mm × 1.25 mm × 1 mm silicon wafer was cured and bonded onto the silver-plated copper plate using the obtained resin composition for optical semiconductor encapsulation. This cured product was subjected to a die shear tester, and the adhesive strength applied when the silicon wafer was peeled from the silver-plated copper plate was measured. The results are shown in Table 1.
Measurement conditions: test speed 300 μm / s, test height 500 μm
Measuring device: Dage 4000 manufactured by Dage
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　以下に本願で使用した化合物を示す。
　エポキシ樹脂
　セロキサイド２０２１Ｐ：３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレート、ダイセル化学工業（株）製
　ＥＨＰＥ３１５０ＣＥ：２，２－ビス(ヒドロキシメチル)-1-ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロセキサン付加物と３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレート、ダイセル化学工業（株）製
　ＹＤ－１２８：ビスフェノールＡ型エポキシ樹脂、東都化成（株）製
　硬化剤（Ｂ）
　リカシッドＭＨ－７００：４－メチルヘキサヒドロ無水フタル酸／ヘキサヒドロ無水フタル酸＝７０／３０、新日本理化（株）製
　硬化促進剤（Ｃ）
　テトラフェニルホスホニウムブロミド：和光純薬工業（株）製
　エチルトリフェニルホスホニウムヨージド：和光純薬工業（株）製
　ヒシコーリンＰＸ－４ＥＴ：テトラブチルホスホニウムジエチルホスホロジチオエート、日本化学工業（株）製
　トリフェニルホスフィン：キシダ化学（株）製
　添加剤
　エチレングリコール：和光純薬工業（株）製 The compounds used in the present application are shown below.
Epoxy resin Celoxide 2021P: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, manufactured by Daicel Chemical Industries, Ltd. EHPE3150CE: 1,2-bis (hydroxymethyl) -1-butanol 2-epoxy-4- (2-oxiranyl) cyclosexane adduct and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, manufactured by Daicel Chemical Industries, Ltd. YD-128: Bisphenol A type Epoxy resin, hardener (B) manufactured by Tohto Kasei Co., Ltd.
Rikacid MH-700: 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, curing accelerator (C) manufactured by Shin Nippon Rika Co., Ltd.
Tetraphenylphosphonium bromide: Wako Pure Chemical Industries, Ltd. Ethyltriphenylphosphonium iodide: Wako Pure Chemical Industries, Ltd. Hishicolin PX-4ET: Tetrabutylphosphonium diethyl phosphorodithioate, manufactured by Nippon Chemical Industry Co., Ltd. Phenylphosphine: manufactured by Kishida Chemical Co., Ltd. Ethylene glycol: manufactured by Wako Pure Chemical Industries, Ltd.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　本発明にかかる光半導体封止用樹脂組成物の硬化物とリードフレームとの密着性は低い方が輝度安定性の点で好ましく、接着強度が１８Ｎ／ｍｍ2以下（例えば、０～１８Ｎ／ｍｍ2）であること好ましく、なかでも１５Ｎ／ｍｍ2以下（例えば、０～１５Ｎ／ｍｍ2）であることがより好ましく、さらに好ましくは７Ｎ／ｍｍ2以下（例えば、０～７Ｎ／ｍｍ2）である。なお、接着強度については、０であっても問題ない。 A lower adhesiveness between the cured product of the resin composition for encapsulating an optical semiconductor and the lead frame according to the present invention is preferable in terms of luminance stability, and an adhesive strength is 18 N / mm 2 or less (for example, 0 to 18 N / mm). 2 ), preferably 15 N / mm 2 or less (for example, 0 to 15 N / mm 2 ), more preferably 7 N / mm 2 or less (for example, 0 to 7 N / mm 2 ). is there. Note that there is no problem even if the adhesive strength is zero.
　本発明によれば、その硬化物が高い耐熱性・透明性を有し、かつその硬化物を用いた光半導体装置の信頼性試験において、輝度変動の小さい輝度安定性に優れた光半導体装置が得られる光半導体封止用樹脂組成物を提供できる。また、本発明によれば、高い耐熱性・透明性を有し、かつ光半導体装置の信頼性試験において、輝度変動が小さく、輝度安定性に優れた硬化物を提供できる。さらに、本発明によれば、高い耐熱性・透明性を有し、輝度変動が小さく、輝度安定性に優れた光半導体装置を提供できる。 According to the present invention, there is provided an optical semiconductor device that has high heat resistance and transparency, and has excellent luminance stability with small luminance fluctuations in a reliability test of an optical semiconductor device using the cured product. The resin composition for optical semiconductor sealing obtained can be provided. Further, according to the present invention, it is possible to provide a cured product having high heat resistance and transparency and having small luminance fluctuation and excellent luminance stability in the reliability test of the optical semiconductor device. Furthermore, according to the present invention, it is possible to provide an optical semiconductor device having high heat resistance and transparency, small fluctuation in luminance, and excellent luminance stability.

Claims (4)

  1. 　エポキシ樹脂、硬化剤（Ｂ）、及び硬化促進剤（Ｃ）を含有する光半導体封止用樹脂組成物であって、
    　脂環式エポキシ樹脂（Ａ）として、（Ａ１）下記式（Ｉ）
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ｉ）中、Ｘは連結基を示し、単結合、２価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド結合、及びこれらが複数個連結した基］
    で表される化合物、（Ａ２）脂環にエポキシ基が直接単結合で結合している化合物、及び（Ａ３）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を３以上有する化合物からなる群から選択される少なくとも１種の化合物を、該エポキシ樹脂の全量に対して５５～１００ｗｔ％含有し、硬化剤（Ｂ）が酸無水物系硬化剤であり、且つ
    　硬化促進剤（Ｃ）として、下記式（１）
    Figure JPOXMLDOC01-appb-C000002
     ［式（１）中のＲl，Ｒ2，Ｒ3，及びＲ4は、それぞれ、炭素数１～２０の炭化水素基を表し、相互に同じであっても異なっていてもよい］
    で表されるホスホニウムイオンと該ホスホニウムイオンとイオン対を形成しうるハロゲンアニオンとのイオン結合体を含有することを特徴とする光半導体封止用樹脂組成物。     A resin composition for sealing an optical semiconductor containing an epoxy resin, a curing agent (B), and a curing accelerator (C),
    As the alicyclic epoxy resin (A), (A1) the following formula (I)
    Figure JPOXMLDOC01-appb-C000001
     [In Formula (I), X represents a linking group, a single bond, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked]
    (A2) a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond, and (A3) an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. And at least one compound selected from the group consisting of compounds having 3 or more of the compound is contained in an amount of 55 to 100 wt% based on the total amount of the epoxy resin, the curing agent (B) is an acid anhydride curing agent, and As the curing accelerator (C), the following formula (1)
    Figure JPOXMLDOC01-appb-C000002
     [R 1 , R 2 , R 3 , and R 4 in Formula (1) each represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other]
    A resin composition for encapsulating an optical semiconductor, comprising an ionic conjugate of a phosphonium ion represented by formula (I) and a halogen anion capable of forming an ion pair with the phosphonium ion.
  2. 　前記ハロゲンアニオンが臭素イオンもしくはヨウ素イオンである請求項１記載の光半導体封止用樹脂組成物。 The resin composition for sealing an optical semiconductor according to claim 1, wherein the halogen anion is bromine ion or iodine ion.
  3. 　請求項１又は２記載の光半導体封止用樹脂組成物を硬化してなる硬化物。 Hardened | cured material formed by hardening | curing the resin composition for optical semiconductor sealing of Claim 1 or 2.
  4. 　請求項１又は２記載の光半導体封止用樹脂組成物によって光半導体素子が封止されてなる光半導体装置。 An optical semiconductor device in which an optical semiconductor element is sealed with the optical semiconductor sealing resin composition according to claim 1.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012020625A1 (en) * 2010-08-10 2012-02-16 ダイセル化学工業株式会社 Curable resin composition and cured article thereof
JP2016191031A (en) * 2015-03-30 2016-11-10 ペルノックス株式会社 One-pack epoxy resin composition for semiconductor encapsulation, cured product, production method of semiconductor component, and semiconductor component
CN111500015A (en) * 2016-11-28 2020-08-07 联茂(无锡)电子科技有限公司 Halogen-free resin composition
EP3696231A4 (en) * 2018-01-11 2020-12-30 Lg Chem, Ltd. Epoxy resin composition for semiconductor molding, and molding film and semiconductor package using same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077257A (en) * 2010-10-06 2012-04-19 Daicel Corp Method for producing cured product, and cured product
JP6047294B2 (en) * 2012-03-30 2016-12-21 株式会社ダイセル Curable epoxy resin composition
TWI494339B (en) 2012-10-23 2015-08-01 Ind Tech Res Inst Partially esterified epoxy resin and epoxy resin composition applied with the same, and method for preparing the composition
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JP6523780B2 (en) 2014-09-29 2019-06-05 東京応化工業株式会社 Film-forming composition and method for producing cured film using the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0258530A (en) * 1988-08-23 1990-02-27 Toshiba Corp Epoxy resin composition
JP2005225964A (en) * 2004-02-12 2005-08-25 Jsr Corp Composition for optical semiconductor encapsulation
JP2005263869A (en) * 2004-03-16 2005-09-29 Nagase Chemtex Corp Resin composition for sealing optical semiconductor
JP2006083278A (en) * 2004-09-15 2006-03-30 Daicel Chem Ind Ltd Epoxy resin composition, optical semiconductor sealing agent, and optical semiconductor device
JP2006225515A (en) * 2005-02-17 2006-08-31 Jsr Corp Optical semiconductor element, sealing material therefor and sealing composition
JP2009167390A (en) * 2007-12-19 2009-07-30 Chisso Corp Thermosetting resin composition and use thereof
JP2009256604A (en) * 2008-03-28 2009-11-05 Shin Etsu Chem Co Ltd Epoxy-silicone hybrid resin composition for sealing optical semiconductor element, and tablet for transfer molding formed of the composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100513453C (en) * 2003-09-22 2009-07-15 三菱化学株式会社 Alicyclic epoxy resins, their preparation process, their compositions, epoxy resin cured product, and uses of alicyclic epoxy resin compositions
WO2005028536A1 (en) * 2003-09-22 2005-03-31 Mitsubishi Chemical Corporation Alicyclic epoxy resin, process for producing the same, composition thereof, cured epoxy resin, and use of alicyclic epoxy resin composition
EP1736500A4 (en) * 2004-04-16 2010-03-24 Jsr Corp Composition for sealing optical semiconductor, optical semiconductor sealing material, and method for producing composition for sealing optical semiconductor
US20090163652A1 (en) * 2007-12-19 2009-06-25 Chisso Corporation Thermosetting resin composition and use thereof
JP2009191217A (en) * 2008-02-18 2009-08-27 Shin Etsu Chem Co Ltd Epoxy-silicone composite resin composition and light-emitting semiconductor device
JP5669289B2 (en) * 2008-05-23 2015-02-12 新日鉄住金化学株式会社 Novel epoxy resin and method for producing the same, epoxy resin composition containing epoxy resin as essential component, and cured product containing epoxy resin as essential component
JP2010031149A (en) * 2008-07-29 2010-02-12 Shin-Etsu Chemical Co Ltd Resin composition for sealing optical semiconductor device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0258530A (en) * 1988-08-23 1990-02-27 Toshiba Corp Epoxy resin composition
JP2005225964A (en) * 2004-02-12 2005-08-25 Jsr Corp Composition for optical semiconductor encapsulation
JP2005263869A (en) * 2004-03-16 2005-09-29 Nagase Chemtex Corp Resin composition for sealing optical semiconductor
JP2006083278A (en) * 2004-09-15 2006-03-30 Daicel Chem Ind Ltd Epoxy resin composition, optical semiconductor sealing agent, and optical semiconductor device
JP2006225515A (en) * 2005-02-17 2006-08-31 Jsr Corp Optical semiconductor element, sealing material therefor and sealing composition
JP2009167390A (en) * 2007-12-19 2009-07-30 Chisso Corp Thermosetting resin composition and use thereof
JP2009256604A (en) * 2008-03-28 2009-11-05 Shin Etsu Chem Co Ltd Epoxy-silicone hybrid resin composition for sealing optical semiconductor element, and tablet for transfer molding formed of the composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012020625A1 (en) * 2010-08-10 2012-02-16 ダイセル化学工業株式会社 Curable resin composition and cured article thereof
JP2012036320A (en) * 2010-08-10 2012-02-23 Daicel Corp Curable resin composition and cured article thereof
JP2016191031A (en) * 2015-03-30 2016-11-10 ペルノックス株式会社 One-pack epoxy resin composition for semiconductor encapsulation, cured product, production method of semiconductor component, and semiconductor component
CN111500015A (en) * 2016-11-28 2020-08-07 联茂(无锡)电子科技有限公司 Halogen-free resin composition
CN111500015B (en) * 2016-11-28 2023-01-17 联茂(无锡)电子科技有限公司 Halogen-free resin composition
EP3696231A4 (en) * 2018-01-11 2020-12-30 Lg Chem, Ltd. Epoxy resin composition for semiconductor molding, and molding film and semiconductor package using same
US11702520B2 (en) 2018-01-11 2023-07-18 Lg Chem, Ltd. Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same

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