WO2012093591A1 - 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 PDFInfo
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- WO2012093591A1 WO2012093591A1 PCT/JP2011/079691 JP2011079691W WO2012093591A1 WO 2012093591 A1 WO2012093591 A1 WO 2012093591A1 JP 2011079691 W JP2011079691 W JP 2011079691W WO 2012093591 A1 WO2012093591 A1 WO 2012093591A1
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- Prior art keywords
- resin composition
- alicyclic
- epoxy resin
- curable epoxy
- compound
- Prior art date
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- CNQCVBJFEGMYDW-UHFFFAOYSA-N lawrencium atom Chemical group [Lr] CNQCVBJFEGMYDW-UHFFFAOYSA-N 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
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- TZLPVFCPHOVVII-UHFFFAOYSA-N tetrakis(4-methylphenyl)phosphanium tetraphenylphosphanium Chemical class C1(=CC=C(C=C1)[P+](C1=CC=C(C=C1)C)(C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C.C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 TZLPVFCPHOVVII-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
Definitions
- the present invention relates to a curable epoxy resin composition, a cured product obtained by curing the curable epoxy resin composition, a resin composition for optical semiconductor encapsulation comprising the curable epoxy resin composition, and the optical semiconductor encapsulation.
- the present invention relates to an optical semiconductor device in which an optical semiconductor element is sealed using a resin composition for use.
- a composition containing monoallyl diglycidyl isocyanurate and bisphenol A type epoxy resin is known as a sealing resin having high heat resistance (see Patent Document 1).
- a sealing resin having high heat resistance see Patent Document 1.
- coloring proceeds due to light and heat emitted from the optical semiconductor element, and light that should be output is absorbed.
- the luminous intensity of the light output from the optical semiconductor device decreases with time.
- a liquid alicyclic epoxy resin having an alicyclic skeleton such as an adduct of cyclohexanecarboxylate and ⁇ -caprolactone and 1,2,8,9-diepoxylimonene is known.
- the cured products of these alicyclic epoxy resins are vulnerable to various stresses, and when a thermal shock such as a cold cycle (repeating heating and cooling) is applied, cracks (cracks) occur. Had.
- an object of the present invention is to provide a curable epoxy resin composition that provides a cured product having high transparency, heat resistance, light resistance, and crack resistance. Another object of the present invention is to provide a cured product having high transparency, heat resistance, light resistance, and crack resistance obtained by curing the curable epoxy resin composition. Another object of the present invention is to provide a resin composition for encapsulating an optical semiconductor comprising the above curable epoxy resin composition, from which an optical semiconductor device in which a decrease in light intensity over time is suppressed can be obtained. Another object of the present invention is to provide high heat resistance, light resistance, transparency, and crack resistance obtained by sealing an optical semiconductor element using the above resin composition for optical semiconductor sealing. Another object of the present invention is to provide an optical semiconductor device that is sealed with a cured product and that suppresses a decrease in light intensity over time.
- the present inventor includes an alicyclic epoxy compound, a monoallyl diglycidyl isocyanurate compound, and an alicyclic polyester resin as essential components, and further includes a curing agent and a curing accelerator, Alternatively, a curable epoxy resin composition containing a curing catalyst provides a cured product having excellent heat resistance, light resistance, transparency, and crack resistance, and an optical semiconductor device in which an optical semiconductor element is sealed with the cured product Has found that the light intensity does not easily decrease with time, and has completed the present invention.
- the present invention relates to an alicyclic epoxy compound (A) and the following formula (1).
- a curable epoxy comprising a monoallyl diglycidyl isocyanurate compound (B) represented by the formula: an alicyclic polyester resin (C), a curing agent (D), and a curing accelerator (E).
- B monoallyl diglycidyl isocyanurate compound
- C alicyclic polyester resin
- D curing agent
- E curing accelerator
- the present invention provides an alicyclic epoxy compound (A) and the following formula (1): [Wherein R 1 and R 2 represent 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, an alicyclic polyester resin (C), and a curing catalyst (F) is provided.
- the curable epoxy resin composition is provided wherein the alicyclic epoxy group of the alicyclic epoxy compound (A) is a cyclohexene oxide group.
- the alicyclic epoxy compound (A) is represented by the following formula (I-1)
- the said curable epoxy resin composition which is a compound represented by these is provided.
- the curable epoxy resin composition is provided in which the alicyclic polyester resin (C) is an alicyclic polyester having an alicyclic ring in the main chain.
- the curable epoxy resin composition containing rubber particles is provided.
- the present invention also provides a cured product obtained by curing the curable epoxy resin composition.
- the present invention also provides a resin composition for sealing an optical semiconductor comprising the curable epoxy resin composition.
- the present invention also provides an optical semiconductor device in which an optical semiconductor element is sealed with the above-described resin composition for sealing an optical semiconductor.
- the curable epoxy resin composition of the present invention has the above-described configuration, a cured product having high transparency, heat resistance, light resistance, and crack resistance can be obtained by curing the resin composition. .
- an optical semiconductor device in which an optical semiconductor element is encapsulated with the curable epoxy resin composition of the present invention is less likely to decrease in light intensity over time, and can exhibit excellent quality and durability.
- the curable epoxy resin composition of the present invention can suppress a decrease in light intensity over time even when used as a sealing resin for an optical semiconductor device having an optical semiconductor element with high output and high brightness. .
- FIG. 1 It is the schematic which shows one Embodiment of the optical semiconductor device which sealed the element (optical semiconductor element) with the curable epoxy resin composition of this invention.
- the left figure (a) is a perspective view
- the right figure (b) is a sectional view.
- the curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A) and the following formula (1).
- R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- curing agent (D), and a hardening accelerator (E) are included.
- the curable epoxy resin composition of the present invention comprises an alicyclic epoxy compound (A), a monoallyl diglycidyl isocyanurate compound (B) represented by the above formula (1), and an alicyclic polyester resin ( C) and a curing catalyst (F).
- the alicyclic epoxy compound (A) used in the present invention includes (i) a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and (ii) an alicyclic ring. Includes compounds in which an epoxy group is directly bonded by a single bond.
- a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring is arbitrarily selected from known or commonly used compounds. be able to.
- the alicyclic epoxy group is preferably a cyclohexene oxide group.
- 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, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked.
- Examples of the alicyclic epoxy resin in which X in the formula (I) is a single bond include compounds represented by the following formula.
- an alicyclic epoxy resin for example, a commercially available product such as Celoxide 8000 (manufactured by Daicel Corporation) can also be used.
- 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 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.
- the linking group X is preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—; A group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like.
- divalent hydrocarbon group include those exemplified above.
- Representative examples of the alicyclic epoxy compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-8).
- commercially available products such as Celoxide 2021P and Celoxide 2081 (manufactured by Daicel Corporation) can also be used.
- l and m each represents an integer of 1 to 30.
- R is an alkylene group having 1 to 8 carbon atoms, and is a linear or branched alkylene group such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, s-butylene, pentylene, hexylene, heptylene, octylene group or the like. Can be mentioned. Of these, linear or branched alkylene groups having 1 to 3 carbon atoms such as methylene, ethylene, propylene and isopropylene groups are preferred.
- Examples of the compound in which the epoxy group is directly bonded to the alicyclic ring with a single bond include a compound represented by the following formula (II).
- R ′ is a group obtained by removing p —OH from a p-valent alcohol, and p and n represent natural numbers.
- the p-valent alcohol [R ′-(OH) p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms, etc.).
- p is preferably 1 to 6
- n is preferably 1 to 30.
- n in each () (in parentheses) may be the same or different.
- the compound examples include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, EHPE 3150 (manufactured by Daicel Corporation). Etc.
- alicyclic epoxy compounds (A) can be used alone or in combination of two or more.
- alicyclic epoxy compound (A) 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate represented by the above formula (I-1) and ceroxide 2021P are particularly preferable.
- the amount of use (content) of the alicyclic epoxy compound (A) is not particularly limited, but the total amount (100% by weight) of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B). On the other hand, it is preferably 50 to 90% by weight, more preferably 60 to 90% by weight, still more preferably 70 to 90% by weight. When the amount of the alicyclic epoxy compound (A) used is less than 50% by weight, the solubility of the monoallyl diglycidyl isocyanurate compound (B) is not sufficient, and it may be easily precipitated when placed at room temperature.
- sum of contents of alicyclic epoxy compound (A) and monoallyl diglycidyl isocyanurate compound (B) in the total amount (100% by weight) of component (A), component (B), and component (C) (total amount) ) Is not particularly limited, but is preferably 70 to 90% by weight.
- the monoallyl diglycidyl isocyanurate compound (B) used in the present invention can be represented by the following general formula (1).
- R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- alkyl group having 1 to 8 carbon atoms examples include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, and octyl groups. It is done. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl and isopropyl groups is preferred.
- 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.
- a monoallyl diglycidyl isocyanurate compound (B) can be used individually or in combination of 2 or more types.
- the monoallyl diglycidyl isocyanurate compound (B) can be arbitrarily mixed as long as it dissolves in the alicyclic epoxy compound (A), and the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B).
- the ratio of the alicyclic epoxy compound (A): monoallyl diglycidyl isocyanurate compound (B) is preferably 50:50 to 90:10 (weight ratio). Outside this range, it becomes difficult to obtain the solubility of the monoallyl diglycidyl isocyanurate compound (B).
- the monoallyl diglycidyl isocyanurate compound (B) may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
- the total amount of the alicyclic epoxy compound (A) and the monoallyl diglycidyl isocyanurate compound (B) with respect to the total amount (100% by weight) of the epoxy resin (compound having an epoxy group) is not particularly limited, From the viewpoint of improving light resistance and crack resistance, 70% by weight or more is preferable, and 80% by weight or more is particularly preferable.
- the alicyclic polyester resin (C) in the curable epoxy resin composition of the present invention plays a role of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminous intensity of the optical semiconductor device.
- the alicyclic polyester resin (C) is a polyester resin having an alicyclic structure (aliphatic ring structure).
- the alicyclic polyester resin (C) is an alicyclic polyester having an alicyclic ring (alicyclic structure) in the main chain. preferable.
- the alicyclic structure in the alicyclic polyester resin (C) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a bridged ring hydrocarbon structure (for example, a bicyclic hydrocarbon). Saturated monocyclic hydrocarbon structures and saturated bridged ring hydrocarbon structures in which all alicyclic rings are composed of carbon-carbon single bonds are preferred. Moreover, the alicyclic structure in the alicyclic polyester resin (C) may be introduced only into one of the structural unit derived from dicarboxylic acid or the structural unit derived from diol, or both are introduced. There is no particular limitation.
- the alicyclic polyester resin (C) has a structural unit derived from a monomer component having an alicyclic structure.
- the monomer having an alicyclic structure include diols and dicarboxylic acids having a known or commonly used alicyclic structure, and are not particularly limited.
- the alicyclic polyester resin (C) may have a structural unit derived from a monomer component having no alicyclic structure.
- the monomer component having no alicyclic structure include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides); adipic acid, sebacic acid, and azelain.
- Aliphatic dicarboxylic acids such as acids, succinic acid, fumaric acid and maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3 -Butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 2- Methyl-1,3-propanediol, 2,2-diethyl-1,3-propanedio Diols such as 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc.
- a monomer component having no alicyclic structure also includes those obtained by bonding an appropriate substituent (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) to the dicarboxylic acid or diol having no alicyclic structure.
- an appropriate substituent for example, an alkyl group, an alkoxy group, a halogen atom, etc.
- the ratio of the monomer unit having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin (C) is not particularly limited, but is 10 mol% or more (for example, 10 to 80 Mol%) is preferable, more preferably 25 to 70 mol%, still more preferably 40 to 60 mol%.
- the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, and crack resistance of the cured product may be lowered.
- the alicyclic polyester resin (C) is particularly preferably an alicyclic polyester containing at least one structural unit represented by the following formulas (2) to (4).
- R 3 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
- R 4 to R 7 are each independently a hydrogen atom, linear or branched, Represents a chain-like alkyl group having 1 to 4 carbon atoms, and two selected from R 4 to R 7 may be bonded to form a ring.
- R 3 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
- R 4 to R 7 are each independently a hydrogen atom, linear or branched, Represents a chain-like alkyl group having 1 to 4 carbon atoms, and may form a ring in which two members selected from R 4 to R 7 are bonded.
- R 3 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
- R 4 to R 7 are each independently a hydrogen atom, linear or branched, Represents a chain-like alkyl group having 1 to 4 carbon atoms, and may form a ring in which two members selected from R 4 to R 7 are bonded.
- Preferred specific examples of the structural units represented by the above formulas (2) to (4) include, for example, a structure derived from 4-methyl-1,2-cyclohexanedicarboxylic acid and ethylene glycol represented by the following formula (5) Units are listed.
- the alicyclic polyester resin (C) having the structural unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.
- the structural units represented by the above formulas (2) to (4) include, for example, those derived from 1,4-cyclohexanedicarboxylic acid and neopentyl glycol represented by the following formula (6):
- a structural unit is mentioned.
- the alicyclic polyester resin (C) having the structural unit can be obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.
- the total content (total content) of the structural units is not particularly limited. 20 mol% or more (for example, 20 to 100 mol%) is preferable with respect to all the structural units (100 mol%) of the cyclic polyester resin (C), more preferably 50 to 100 mol%, still more preferably 80 to 100 mol%. Mol%. If the content of the structural units represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance and crack resistance of the cured product may be lowered.
- the number average molecular weight of the alicyclic polyester resin (C) is not particularly limited, but is preferably 300 to 100,000, more preferably 300 to 30,000. If the number average molecular weight of the alicyclic polyester resin (C) is less than 300, the toughness of the cured product may not be sufficient, and crack resistance may be reduced. On the other hand, when the number average molecular weight of the alicyclic polyester resin (C) exceeds 100,000, the compatibility with the curing agent (D) is lowered, and the transparency of the cured product may be lowered. In addition, the number average molecular weight of alicyclic polyester resin (C) can be measured as a value of standard polystyrene conversion by GPC (gel permeation chromatography) method, for example.
- GPC gel permeation chromatography
- an alicyclic polyester resin (C) can be used individually by 1 type or in combination of 2 or more types.
- the alicyclic polyester resin (C) is not particularly limited and can be produced by a known or conventional method. More specifically, for example, the alicyclic polyester resin (C) may be obtained by polycondensation of the above-mentioned dicarboxylic acid and diol by a conventional method, or a derivative (acid anhydride, ester) of the above-mentioned dicarboxylic acid. , Acid halides, and the like) and diols may be obtained by polycondensation by a conventional method.
- the blending amount (content) of the alicyclic polyester resin (C) is not particularly limited, but the total amount of the alicyclic polyester resin (C) and the curing agent (D).
- the amount is preferably 1 to 60% by weight, more preferably 5 to 30% by weight with respect to (100% by weight).
- the blending amount of the alicyclic polyester resin (C) is less than 1% by weight, the crack resistance of the cured product may be lowered.
- the blending amount of the alicyclic polyester resin (C) exceeds 60% by weight, the transparency and heat resistance of the cured product may be lowered.
- the amount (content) of the alicyclic polyester resin (D) is not particularly limited, but the alicyclic polyester The content is preferably 50 to 99% by weight, more preferably 65 to 99% by weight, based on the total amount (100% by weight) of the resin (D) and the curing catalyst (F).
- cured material may fall that the compounding quantity of an alicyclic polyester resin (D) is less than 50 weight%.
- the blending amount of the alicyclic polyester resin (D) exceeds 99% by weight, the transparency and heat resistance of the cured product may be lowered.
- the curing agent (D) has a function of curing the compound having an epoxy group.
- curing agent (D) in this invention a well-known thru
- curing agent can be used as a hardening
- an acid anhydride which is liquid at 25 ° C. is preferable, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride. An acid etc. can be mentioned.
- solid acid anhydrides at room temperature such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride are liquid at room temperature (about 25 ° C.).
- the curing agent (D) in the present invention can be used as the curing agent (D) in the present invention by dissolving in an acid anhydride to form a liquid mixture.
- an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid such as an alkyl group in the ring. Including those having a substituent bonded thereto) is preferred.
- curing agent (D) can be used individually by 1 type or in combination of 2 or more types.
- the curing agent (D) 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 be used. .
- curing agent (D) It is 50 with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in the curable epoxy resin composition of this invention.
- the amount is preferably -200 parts by weight, more preferably 100-145 parts by weight. More specifically, it is preferably used at a ratio of 0.5 to 1.5 equivalents per 1 equivalent of epoxy groups in the compound having all epoxy groups contained in the curable epoxy resin composition of the present invention. .
- curing agent (D) is less than 50 weight part, hardening will become inadequate and there exists a tendency for the toughness of hardened
- curing agent (D) exceeds 200 weight part, hardened
- the curable epoxy resin composition of the present invention further contains a curing accelerator (E).
- a hardening accelerator (E) is a compound which has a function which accelerates
- the curing accelerator (E) known or conventional curing accelerators can be used.
- DBU 1,8-diazabicyclo [5.4.0] undecene-7
- salts thereof for example, Phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts
- 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and salts thereof (eg, phosphonium salts) , Sulfonium salts, quaternary ammonium salts, iodonium salts)
- tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine
- 2-ethyl-4- Imidazoles such as methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole
- phosphate ester triphenyl Phosphines such as phosphin
- U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X, 12XD developed products
- TPP-K, TPP-MK both manufactured by Hokuko Chemical Co., Ltd.
- PX-4ET manufactured by Nippon Chemical Industry Co., Ltd.
- usage-amount (content) of a hardening accelerator (E) It is 0.05 with respect to the whole quantity (100 weight part) of the compound which has an epoxy group contained in a curable epoxy resin composition. Is preferably 5 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, and particularly preferably 0.25 to 2.5 parts by weight.
- usage-amount of a hardening accelerator (E) is less than 0.05 weight part, the hardening promotion effect may become inadequate.
- a curing catalyst (F) may be used instead of the above-described curing agent (D) and curing accelerator (E). Similarly to the case of using the curing agent (D) and the curing accelerator (E), by using the curing catalyst (F), the curing reaction of the compound having an epoxy group can be advanced to obtain a cured product.
- the cationic catalyst cationic polymerization initiator which generate
- a curing catalyst (F) can be used individually by 1 type or in combination of 2 or more types.
- Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, hexafluoroarsenate salt, and the like.
- UVACURE 1590 (Daicel Cytec) (Commercially available), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer, USA), Irgacure 264 (manufactured by Ciba Japan), CIT-1682 (manufactured by Nippon Soda Co., Ltd.) Can be preferably used.
- Examples of the cation catalyst that generates cation species by heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, and the like.
- PP-33, CP-66, CP -77 manufactured by ADEKA), FC-509 (manufactured by 3M), UVE1014 (manufactured by GE), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L (Sanshin Chemical) Kogyo Co., Ltd.), CG-24-61 (Ciba Japan) and other commercial products can be preferably used.
- a chelate compound of a metal such as aluminum or titanium and a acetoacetate or diketone compound and a silanol such as triphenylsilanol or a chelate compound of a metal such as aluminum or titanium and acetoacetate or diketone and bisphenol S
- a chelate compound of a metal such as aluminum or titanium and acetoacetate or diketone and bisphenol S
- the compound with phenols, such as these may be sufficient.
- the use amount (content) of the curing catalyst (F) is not particularly limited, but is 0.01 to 0.01% with respect to the total amount (100 parts by weight) of the compound having an epoxy group contained in the curable epoxy resin composition.
- the amount is preferably 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 10 parts by weight.
- the curable epoxy resin composition of the present invention may further contain rubber particles.
- the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and 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 react with a compound having an epoxy group such as an alicyclic epoxy resin (A) on the surface.
- Rubber particles having a hydroxyl group and / or a carboxyl group (either one or both of a hydroxyl group and a carboxyl group) as the functional group to be obtained are preferred.
- the cured product becomes clouded by a thermal shock such as a cold cycle and the transparency is lowered, which is not preferable.
- the polymer constituting the core portion having rubber elasticity in the rubber particles is not particularly limited, but (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are used.
- the essential monomer component is preferred.
- the polymer constituting the core portion 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, Olefin such as isobutene may be included as a monomer component.
- the polymer which comprises the said core part which has the rubber elasticity contains 1 type, or 2 or more types selected from the group which consists of aromatic vinyl, a nitrile, and a conjugated diene with a (meth) acrylic acid ester as a monomer component. It is preferable to include it in combination. That is, as the polymer constituting the core part, 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 may contain silicone such as polydimethylsiloxane and polyphenylmethylsiloxane, polyurethane, and the like.
- 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.
- One monomer (one molecule) may contain a reactive crosslinking monomer having two or more reactive functional groups.
- the core part of the rubber particles is a core part composed of a (meth) acrylic ester / aromatic vinyl binary copolymer (particularly butyl acrylate / styrene). It is preferable in that the rate can be easily adjusted.
- 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 at once and may be polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently to polymerize,
- 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.
- the shell layer preferably has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as the alicyclic epoxy compound (A).
- the polymer constituting the shell layer preferably contains a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.
- a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.
- a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.
- a (meth) acrylate ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate
- an essential monomer component for example, when butyl acrylate is used as the (meth) acrylic acid ester in the core
- 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, and 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 particularly at least 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 hydroxyl group and / or a carboxyl 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.
- a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component.
- Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, ⁇ , ⁇ -unsaturated acids such as (meth) acrylic acid, ⁇ , ⁇ -unsaturated acid anhydrides such as maleic anhydride, etc. It is preferable to contain the monomer.
- the polymer constituting the shell layer in the rubber particles preferably contains one or more selected from the above monomers in combination 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 one monomer (one molecule) such as allyl cyanurate, diallyl phthalate, or butylene glycol diacrylate.
- the rubber particles can be obtained by covering the core portion with a shell layer.
- the method of coating the core part with a shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a copolymer constituting the shell layer, and the above method Examples thereof include a graft polymerization method in which the core portion having rubber elasticity obtained by the above is used as a trunk component, and each component constituting the shell layer is used as 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. If the average particle diameter exceeds 500 nm or the maximum particle diameter exceeds 1000 nm, the dispersibility of the rubber particles in the cured product may be reduced, and crack resistance may be reduced. On the other hand, if the average particle size is less than 10 nm or the maximum particle size is less than 50 nm, the effect of improving the crack resistance of the cured product may be difficult to obtain.
- 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 (the curable epoxy resin composition of the present invention) containing the rubber particles is ⁇ 0.00. It is preferably within 03 ( ⁇ 0.03 to 0.03).
- the difference in refractive index exceeds ⁇ 0.03 the transparency of the cured product decreases, sometimes it becomes cloudy, and the light intensity of the optical semiconductor device tends to decrease, thereby losing the function of the optical semiconductor device. There is a case.
- 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 having a length of 20 mm ⁇ width of 6 mm 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, 20 mm long ⁇ 6 mm wide ⁇ 1 mm thick from a cured product obtained by the heat curing method described in the section of the optical semiconductor device below.
- a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) with the test piece cut out and the prism and the test piece in close contact using monobromonaphthalene as an intermediate solution And it can obtain
- the content (blending amount) of the rubber particles in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount (100 parts by weight) of the compound 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 content of the rubber particles is less than 0.5 parts by weight, the crack resistance of the cured product tends to decrease.
- the content of the rubber particles exceeds 30 parts by weight, the heat resistance of the cured product tends to decrease.
- the curable epoxy resin composition of the present invention can use various additives within a range that does not impair the effects of the present invention.
- a compound having a hydroxyl 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, silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane, surfactants, silica, alumina, as long as viscosity and transparency are not impaired.
- Conventional additives such as inorganic fillers, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents and the like can be used.
- the curable epoxy resin composition of the present invention comprises the above-described alicyclic epoxy compound (A), monoallyl diglycidyl isocyanurate compound (B), alicyclic polyester resin (C), and curing agent (D). And the curing accelerator (E) or the curing catalyst (F) may be contained, and the preparation method is not particularly limited.
- an ⁇ agent containing a compound having an epoxy group such as an alicyclic epoxy compound (A) and a monoallyl diglycidyl isocyanurate compound (B) as an essential component, a curing agent (D) and a curing accelerator (E)
- a curing agent D
- a curing accelerator E
- the alicyclic polyester resin (C) may be mixed in advance as a component of the ⁇ agent and / or ⁇ agent, or when the ⁇ agent and ⁇ agent are mixed, the ⁇ agent, ⁇ You may mix
- the temperature at the time of stirring and mixing when preparing the ⁇ agent is not particularly limited, but is preferably 30 to 150 ° C, more preferably 35 to 130 ° C. Further, the temperature at the time of stirring and mixing when preparing the ⁇ agent (when composed of two or more components) is not particularly limited, but is preferably 30 to 100 ° C., more preferably 35 to 80 ° C. .
- a known apparatus such as a rotation / revolution mixer, a planetary mixer, a kneader, or a dissolver can be used.
- the alicyclic polyester resin (C) and the curing agent (D) are mixed in advance to obtain these mixtures (a mixture of the alicyclic polyester resin (C) and the curing agent (D)), and then the curing accelerator (E) and other additives are blended into the mixture. It is preferable to prepare by preparing an agent and subsequently mixing the ⁇ agent and the ⁇ agent.
- the temperature at which the alicyclic polyester resin (C) and the curing agent (D) are mixed is not particularly limited, but is preferably 60 to 130 ° C, more preferably 90 to 120 ° C.
- the mixing time is not particularly limited, but is preferably 30 to 100 minutes, and more preferably 45 to 80 minutes. Although mixing is not specifically limited, It is preferable to carry out in nitrogen atmosphere. Moreover, the above-mentioned well-known apparatus can be used for mixing.
- alicyclic polyester resin (C) Even if it performs an appropriate chemical treatment (for example, hydrogenation, terminal modification of alicyclic polyester, etc.) etc. Good.
- an appropriate chemical treatment for example, hydrogenation, terminal modification of alicyclic polyester, etc.
- a part of the curing agent (D) is an alicyclic polyester resin (C) (for example, a hydroxyl group of the alicyclic polyester). You may have reacted with.
- Examples of the mixture of the alicyclic polyester resin (C) and the curing agent (D) include “HN-7200” (manufactured by Hitachi Chemical Co., Ltd.) and “HN-5700” (manufactured by Hitachi Chemical Co., Ltd.). ) Etc. can also be used.
- the heating temperature (curing temperature) at the time of curing is not particularly limited, but is preferably 45 to 200 ° C, more preferably 100 to 190 ° C, still more preferably 100 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. When the curing temperature and the curing time are lower than the lower limit value in the above range, curing is insufficient.
- the resin component when 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, but can be appropriately adjusted by shortening the curing time when the curing temperature is increased, and increasing the curing time when the curing temperature is lowered.
- the resin composition for optical semiconductor encapsulation of the present invention comprises the curable epoxy resin composition of the present invention.
- the resin composition for sealing an optical semiconductor of the present invention the optical semiconductor element is sealed with a cured product having excellent physical properties such as transparency, heat resistance, light resistance, and crack resistance.
- An optical semiconductor device that does not easily deteriorate with time can be obtained. Even if the optical semiconductor device includes an optical semiconductor element with high output and high luminance, the light intensity is unlikely to decrease with time.
- the optical semiconductor device of the present invention is obtained by sealing an optical semiconductor element with the curable epoxy resin composition (resin composition for optical semiconductor sealing) of the present invention.
- the optical semiconductor element is sealed by injecting the curable epoxy resin composition prepared by the above-described method into a predetermined mold and heating and curing under predetermined conditions. Thereby, an optical semiconductor device in which the optical semiconductor element is sealed with the curable epoxy resin composition is obtained.
- the curing temperature and the curing time can be the same as described above.
- the curable epoxy resin composition of the present invention is not limited to the optical semiconductor (optical semiconductor element) sealing application described above, and includes, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, and a resist.
- 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 consisting 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 is added here.
- 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour for initial seed polymerization.
- 0.3 g of sodium dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid and 0.3 g of allyl methacrylate.
- the monomer mixture was continuously added over 30 minutes to perform seed polymerization. Then, it aged for 1 hour and formed the shell layer which coat
- the mixture was cooled to room temperature (25 ° C.) and filtered through a plastic mesh having an opening of 120 ⁇ m to obtain a latex containing rubber particles having a core-shell structure.
- 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
- a dissolver 1000 rpm, 60 minutes
- 10 parts by weight of the rubber particles obtained in Production Example 1 heated to 60 ° C. under a nitrogen stream
- the product name “Celoxide 2021P” (3,4-epoxy) Disperse in 70 parts by weight of cyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate manufactured by Daicel Corp.
- vacuum deaerate to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 624 mPa ⁇ s). It was.
- the viscosity (viscosity at 25 ° C.) of the rubber particle-dispersed epoxy compound obtained in Production Example 2 (10 parts by weight of rubber particles dispersed in 70 parts by weight of celoxide 2021P) is a digital viscometer (trade name) “DVU-EII type” (manufactured by Tokimec Co., Ltd.).
- Production Example 3 (Production of epoxy resin: Examples 1 to 6, Comparative Examples 2 and 3) Monoaridiglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation), obtained in Production Example 2
- a rubber particle-dispersed epoxy resin and a bisphenol A type epoxy resin (trade name “YD-128”, manufactured by Nippon Steel Chemical Co., Ltd.) are mixed according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 1.
- the monoallyl diglycidyl isocyanurate was dissolved by stirring at 80 ° C. for 1 hour to obtain an epoxy resin (mixture) (corresponding to the ⁇ agent described above). “-” In Table 1 indicates that the component was not blended, and the same applies to Table 2.
- Production Example 4 (Production of a curing agent composition containing at least a curing agent (hereinafter referred to as “K agent”): Examples 1 to 6 and Comparative Examples 1 to 3) Curing agent (acid anhydride) (trade name “Licacid MH-700”, manufactured by Shin Nippon Rika Co., Ltd.), a mixture of curing agent (acid anhydride) and alicyclic polyester resin (trade name “HN-7200”, Product name “HN-5700”, both manufactured by Hitachi Chemical Co., Ltd., curing accelerator (product name “U-CAT 18X”, manufactured by San Apro Co., Ltd.), additive (trade name “ethylene glycol”, Wako Jun) Yakuhin Kogyo Co., Ltd.) was used according to the formulation shown in Table 1 (unit: parts by weight) using a self-revolving stirrer (trade name “Awatori Nerita AR-250”, manufactured by Shinky Co., Ltd.). Were mixed uniformly and defoamed to obtain a K agent (corresponding
- Examples 1-6, Comparative Examples 1-3 Manufacture of curable epoxy resin composition
- the epoxy resin obtained in Production Example 3 and the K agent obtained in Production Example 4 were mixed with a self-revolving stirrer (trade name “Awatori Kneading” so that the blending ratio (unit: parts by weight) shown in Table 1 was obtained.
- Taro AR-250 "(manufactured by Shinky Co., Ltd.) was mixed uniformly and defoamed to obtain a curable epoxy resin composition.
- Comparative Example 1 the trade name “Celoxide 2021P” (manufactured by Daicel Corporation) was used as the epoxy resin.
- the curable epoxy resin composition obtained above is cast into a lead frame (InGaN element, 3.5 mm ⁇ 2.8 mm) of an optical semiconductor shown in FIG. 1, and then 5 in a 120 ° C. oven (resin curing oven).
- An optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product) heated for a time was obtained.
- 100 is a reflector (light reflecting resin composition)
- 101 is a metal wiring
- 102 is an optical semiconductor element
- 103 is a bonding wire
- 104 is a transparent sealing resin (cured product).
- Production Example 5 (Production of epoxy resin: Examples 7 to 12, Comparative Examples 5 and 6) Monoaridiglycidyl isocyanurate (trade name “MA-DGIC”, manufactured by Shikoku Kasei Kogyo Co., Ltd.), alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation), obtained in Production Example 2
- a rubber particle-dispersed epoxy resin and a bisphenol A type epoxy resin (trade name “YD-128”, manufactured by Nippon Steel Chemical Co., Ltd.) are mixed according to the formulation (mixing ratio) (unit: parts by weight) shown in Table 2.
- the monoallyl diglycidyl isocyanurate was dissolved by stirring at 80 ° C. for 1 hour to obtain an epoxy resin (mixture) (corresponding to the ⁇ agent described above).
- Production Example 6 (Production of alicyclic polyester resin: Examples 7 to 12)
- a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser 172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 208 weight of neopentyl glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) Part, tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 part by weight was charged, heated to 160 ° C., and further heated from 160 ° C. to 250 ° C. over 4 hours. Next, the pressure was reduced to 5 mmHg over 1 hour, further reduced to 0.3 mmHg or less, and then reacted at 250 ° C. for 1 hour to obtain an alicyclic polyester resin.
- Examples 7-12, Comparative Examples 4-6 Manufacture of curable epoxy resin composition
- the epoxy resin obtained in Production Example 5 the alicyclic polyester resin obtained in Production Example 6 and the curing catalyst (trade name “Sun-Aid SI-100L” so as to have the blending ratio (unit: parts by weight) shown in Table 2 ”, Manufactured by Sanshin Chemical Industry Co., Ltd.) using a self-revolving stirrer (trade name“ Awatori Nerita AR-250 ”, manufactured by Shinky Co., Ltd.)
- a curable epoxy resin composition was obtained.
- Comparative Example 4 the trade name “Celoxide 2021P” (manufactured by Daicel Corporation) was used as the epoxy resin.
- the curable epoxy resin composition obtained above is cast into a lead frame (InGaN element, 3.5 mm ⁇ 2.8 mm) of an optical semiconductor shown in FIG. 1, and then 5 in a 120 ° C. oven (resin curing oven). An optical semiconductor device in which the optical semiconductor element was sealed with a cured resin (cured product) heated for a time was obtained.
- Thermal shock test The optical semiconductor devices obtained in the examples and comparative examples (two used for each curable epoxy resin composition) were exposed for 30 minutes in an atmosphere of ⁇ 40 ° C., and then for 30 minutes in an atmosphere of 100 ° C. Thermal shock with one cycle of exposure was applied for 200 cycles using a thermal shock tester. Thereafter, the length of the cracks generated in the sealing resin (cured product of the curable epoxy resin) of the optical semiconductor device was observed using a digital microscope (VHX-900, manufactured by Keyence Corporation). Of the two devices, the number of optical semiconductor devices having cracks with a length of 90 ⁇ m or more was measured. The results are shown in Tables 1 and 2.
- Example and the comparative example is as follows.
- MA-DGIC monoallyl diglycidyl isocyanurate, manufactured by Shikoku Kasei Kogyo Co., Ltd.
- YD-128 Bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd.
- the curable epoxy resin composition of the present invention can be preferably used for optical semiconductor sealing applications.
- the curable epoxy resin composition of the present invention includes an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sealant, a resist, a composite material, a transparent substrate, a transparent sheet, a transparent film, an optical element, and an optical element. It can also be used for lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and the like.
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Abstract
Description
また、本発明の他の目的は、上記硬化性エポキシ樹脂組成物を硬化してなる、高い透明性、耐熱性、耐光性、及び耐クラック性を兼ね備えた硬化物を提供することにある。
また、本発明の他の目的は、経時での光度低下が抑制された光半導体装置が得られる、上記硬化性エポキシ樹脂組成物からな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用いて光半導体素子を封止することにより得られる、高い耐熱性、耐光性、透明性、及び耐クラック性を兼ね備えた硬化物により封止され、経時での光度低下が抑制された光半導体装置を提供することにある。
で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、脂環式ポリエステル樹脂(C)と、硬化剤(D)と、硬化促進剤(E)とを含むことを特徴とする硬化性エポキシ樹脂組成物を提供する。
で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、脂環式ポリエステル樹脂(C)と、硬化触媒(F)とを含むことを特徴とする硬化性エポキシ樹脂組成物を提供する。
本発明の硬化性エポキシ樹脂組成物は、脂環式エポキシ化合物(A)と、下記式(1)
で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、脂環式ポリエステル樹脂(C)と、硬化剤(D)と、硬化促進剤(E)とを含む。また、本発明の硬化性エポキシ樹脂組成物は、脂環式エポキシ化合物(A)と、上記式(1)で表されるモノアリルジグリシジルイソシアヌレート化合物(B)と、脂環式ポリエステル樹脂(C)と、硬化触媒(F)とを含む。
本発明で用いられる脂環式エポキシ化合物(A)には、(i)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有する化合物、及び(ii)脂環にエポキシ基が直接単結合で結合している化合物が含まれる。
本発明で用いられるモノアリルジグリシジルイソシアヌレート化合物(B)は、下記の一般式(1)で表すことができる。
本発明の硬化性エポキシ樹脂組成物における脂環式ポリエステル樹脂(C)は、硬化物の耐熱性、耐光性を向上させ、光半導体装置の光度低下を抑制する役割を担う。上記脂環式ポリエステル樹脂(C)は、脂環構造(脂肪族環構造)を有するポリエステル樹脂である。特に、硬化物の耐熱性、耐光性、耐クラック性向上の観点で、上記脂環式ポリエステル樹脂(C)は、主鎖に脂環(脂環構造)を有する脂環式ポリエステルであることが好ましい。
硬化剤(D)は、エポキシ基を有する化合物を硬化させる働きを有する。本発明における硬化剤(D)としては、エポキシ樹脂用硬化剤として公知乃至慣用の硬化剤を使用することができる。本発明における硬化剤(D)としては、中でも、25℃で液状の酸無水物が好ましく、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(約25℃)で固体状の酸無水物は、常温(約25℃)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、本発明における硬化剤(D)として使用することができる。本発明の硬化性エポキシ樹脂組成物における硬化剤(D)としては、耐熱性、耐光性、耐クラック性の観点で、特に、飽和単環炭化水素ジカルボン酸の無水物(環にアルキル基等の置換基が結合したものも含む)が好ましい。なお、硬化剤(D)は1種を単独で、又は2種以上を組み合わせて使用することができる。
本発明の硬化性エポキシ樹脂組成物は、さらに、硬化促進剤(E)を含む。硬化促進剤(E)は、エポキシ基を有する化合物が硬化剤により硬化する際に、硬化速度を促進する機能を有する化合物である。硬化促進剤(E)としては、公知乃至慣用の硬化促進剤を使用することができ、例えば、1,8-ジアザビシクロ[5.4.0]ウンデセン-7(DBU)、及びその塩(例えば、フェノール塩、オクチル酸塩、p-トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩);1,5-ジアザビシクロ[4.3.0]ノネン-5(DBN)、及びその塩(例えば、ホスホニウム塩、スルホニウム塩、4級アンモニウム塩、ヨードニウム塩);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;2-エチル-4-メチルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾールなどのイミダゾール;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;テトラフェニルホスホニウムテトラ(p-トリル)ボレートなどのホスホニウム化合物;オクチル酸スズ、オクチル酸亜鉛などの有機金属塩;金属キレートなどが挙げられる。これらは単独で、又は2種以上を混合して使用することができる。
本発明の硬化性エポキシ樹脂組成物においては、上述の硬化剤(D)及び硬化促進剤(E)の代わりに、硬化触媒(F)を用いてもよい。硬化剤(D)及び硬化促進剤(E)を用いた場合と同様に、硬化触媒(F)を用いることにより、エポキシ基を有する化合物の硬化反応を進行させ、硬化物を得ることができる。上記硬化触媒(F)としては、特に限定されないが、紫外線照射又は加熱処理を施すことによりカチオン種を発生して、重合を開始させるカチオン触媒(カチオン重合開始剤)を用いることができる。なお、硬化触媒(F)は1種を単独で、又は2種以上を組み合わせて使用することができる。
本発明の硬化性エポキシ樹脂組成物は、さらに、ゴム粒子を含んでいてもよい。上記ゴム粒子としては、例えば、粒子状NBR(アクリロニトリル-ブタジエンゴム)、反応性末端カルボキシル基NBR(CTBN)、メタルフリーNBR、粒子状SBR(スチレン-ブタジエンゴム)などのゴム粒子が挙げられる。上記ゴム粒子としては、ゴム弾性を有するコア部分と、該コア部分を被覆する少なくとも1層のシェル層とからなる多層構造(コアシェル構造)を有するゴム粒子が好ましい。上記ゴム粒子は、特に、(メタ)アクリル酸エステルを必須モノマー成分とするポリマー(重合体)で構成されており、表面に脂環式エポキシ樹脂(A)などのエポキシ基を有する化合物と反応し得る官能基としてヒドロキシル基及び/又はカルボキシル基(ヒドロキシル基及びカルボキシル基のいずれか一方又は両方)を有するゴム粒子が好ましい。上記ゴム粒子の表面にヒドロキシル基及び/又はカルボキシル基が存在しない場合、冷熱サイクル等の熱衝撃により硬化物が白濁して透明性が低下するため好ましくない。
本発明の硬化性エポキシ樹脂組成物は、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、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。
本発明の硬化性エポキシ樹脂組成物は、上述の脂環式エポキシ化合物(A)と、モノアリルジグリシジルイソシアヌレート化合物(B)と、脂環式ポリエステル樹脂(C)と、硬化剤(D)及び硬化促進剤(E)、又は、硬化触媒(F)とを含んでいればよく、調製方法は特に限定されない。例えば、脂環式エポキシ化合物(A)、モノアリルジグリシジルイソシアヌレート化合物(B)等のエポキシ基を有する化合物を必須成分として含むα剤と、硬化剤(D)及び硬化促進剤(E)、又は、硬化触媒(F)を必須成分として含むβ剤とを別々に調製し、当該α剤とβ剤とを所定の割合で攪拌・混合し、必要に応じて真空下で脱泡することにより調製することができる。なお、この場合、脂環式ポリエステル樹脂(C)は、あらかじめα剤及び/又はβ剤の構成成分として混合しておいてもよいし、α剤とβ剤を混合する際にα剤、β剤以外の成分として配合してもよい。
本発明の硬化性エポキシ樹脂組成物を硬化させることにより、透明性、耐熱性、耐光性、及び耐クラック性などの諸物性に優れた硬化物を得ることができる。硬化の際の加熱温度(硬化温度)としては、特に限定されないが、45~200℃が好ましく、より好ましくは100~190℃、さらに好ましくは100~180℃である。また、硬化の際に加熱する時間(硬化時間)としては、特に限定されないが、30~600分が好ましく、より好ましくは45~540分、さらに好ましくは60~480分である。硬化温度と硬化時間が上記範囲の下限値より低い場合は、硬化が不十分となり、逆に上記範囲の上限値より高い場合は、樹脂成分の分解が起きる場合があるので、いずれも好ましくない。硬化条件は種々の条件に依存するが、硬化温度を高くした場合は硬化時間を短く、硬化温度を低くした場合は硬化時間を長くする等により、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は、本発明の硬化性エポキシ樹脂組成物からなる。本発明の光半導体封止用樹脂組成物を用いることにより、透明性、耐熱性、耐光性、及び耐クラック性などの諸物性に優れた硬化物により光半導体素子が封止された、光度が経時で低下しにくい光半導体装置が得られる。上記光半導体装置は、高出力、高輝度の光半導体素子を備える場合であっても、光度が経時で低下しにくい。
本発明の光半導体装置は、本発明の硬化性エポキシ樹脂組成物(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、上述の方法で調製された硬化性エポキシ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。これにより、硬化性エポキシ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。
(ゴム粒子の製造)
還流冷却器付きの1L重合容器に、イオン交換水500g、及びジオクチルスルホコハク酸ナトリウム0.68gを仕込み、窒素気流下に撹拌しながら、80℃に昇温した。ここに、コア部分を形成するために必要とする量の約5重量%分に該当するアクリル酸ブチル9.5g、スチレン2.57g、及びジビニルベンゼン0.39gからなる単量体混合物を一括添加し、20分間撹拌して乳化させた後、ペルオキソ二硫酸カリウム9.5mgを添加し、1時間撹拌して最初のシード重合を行った。続いて、ペルオキソ二硫酸カリウム180.5mgを添加し、5分間撹拌した。ここに、コア部分を形成するために必要とする量の残り(約95重量%分)のアクリル酸ブチル180.5g、スチレン48.89g、ジビニルベンゼン7.33gにジオクチルスルホコハク酸ナトリウム0.95gを溶解させてなる単量体混合物を2時間かけて連続的に添加し、2度目のシード重合を行い、その後、1時間熟成してコア部分を得た。
次いで、ペルオキソ二硫酸カリウム60mgを添加して5分間撹拌し、ここに、メタクリル酸メチル60g、アクリル酸1.5g、及びアリルメタクリレート0.3gにジオクチルスルホコハク酸ナトリウム0.3gを溶解させてなる単量体混合物を30分かけて連続的に添加し、シード重合を行った。その後、1時間熟成し、コア部分を被覆するシェル層を形成した。
次いで、室温(25℃)まで冷却し、目開き120μmのプラスチック製網で濾過することにより、コアシェル構造を有するゴム粒子を含むラテックスを得た。得られたラテックスをマイナス30℃で凍結し、吸引濾過器で脱水洗浄した後、60℃で一昼夜送風乾燥してゴム粒子を得た。得られたゴム粒子の平均粒子径は254nm、最大粒子径は486nmであった。
(ゴム粒子分散エポキシ化合物の製造)
製造例1で得られたゴム粒子10重量部を、窒素気流下、60℃に加温した状態でディゾルバー(1000rpm、60分間)を使用して、商品名「セロキサイド2021P」(3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート、(株)ダイセル製)70重量部に分散させ、真空脱泡して、ゴム粒子分散エポキシ化合物(25℃での粘度:624mPa・s)を得た。
なお、製造例2で得られたゴム粒子分散エポキシ化合物(10重量部のゴム粒子を70重量部のセロキサイド2021Pに分散させたもの)の粘度(25℃における粘度)は、デジタル粘度計(商品名「DVU-EII型」、(株)トキメック製)を使用して測定した。
(エポキシ樹脂の製造:実施例1~6、比較例2、3)
モノアリジグリシジルイソシアヌレート(商品名「MA-DGIC」、四国化成工業(株)製)、脂環式エポキシ化合物(商品名「セロキサイド2021P」、(株)ダイセル製)、製造例2で得られたゴム粒子分散エポキシ樹脂、ビスフェノールA型エポキシ樹脂(商品名「YD-128」、新日鐵化学(株)製)を、表1に示す配合処方(配合割合)(単位:重量部)に従って混合し、80℃で1時間攪拌することでモノアリルジグリシジルイソシアヌレートを溶解させ、エポキシ樹脂(混合物)(上述のα剤にあたる)を得た。なお、表1における「-」は、当該成分の配合を行わなかったことを示し、表2においても同様である。
(硬化剤を少なくとも含む硬化剤組成物(以下、「K剤」と称する)の製造:実施例1~6、比較例1~3)
硬化剤(酸無水物)(商品名「リカシッド MH-700」、新日本理化(株)製)、硬化剤(酸無水物)と脂環式ポリエステル樹脂の混合物(商品名「HN-7200」、商品名「HN-5700」、ともに日立化成工業(株)製)、硬化促進剤(商品名「U-CAT 18X」、サンアプロ(株)製)、添加剤(商品名「エチレングリコール」、和光純薬工業(株)製)を、表1に示す配合処方(単位:重量部)に従って、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し、脱泡してK剤(上述のβ剤にあたる)を得た。
(硬化性エポキシ樹脂組成物の製造)
表1に示す配合割合(単位:重量部)となるように、製造例3で得られたエポキシ樹脂、製造例4で得られたK剤を、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し、脱泡して硬化性エポキシ樹脂組成物を得た。なお、比較例1の場合は、エポキシ樹脂として商品名「セロキサイド2021P」((株)ダイセル製)を使用した。
上記で得た硬化性エポキシ樹脂組成物を、図1に示す光半導体のリードフレーム(InGaN素子、3.5mm×2.8mm)に注型した後、120℃のオーブン(樹脂硬化オーブン)で5時間加熱し、硬化した樹脂(硬化物)で光半導体素子を封止した光半導体装置を得た。なお、図1において、100はリフレクター(光反射用樹脂組成物)、101は金属配線、102は光半導体素子、103はボンディングワイヤ、104は透明封止樹脂(硬化物)を示す。
(エポキシ樹脂の製造:実施例7~12、比較例5、6)
モノアリジグリシジルイソシアヌレート(商品名「MA-DGIC」、四国化成工業(株)製)、脂環式エポキシ化合物(商品名「セロキサイド2021P」、(株)ダイセル製)、製造例2で得られたゴム粒子分散エポキシ樹脂、ビスフェノールA型エポキシ樹脂(商品名「YD-128」、新日鐵化学(株)製)を、表2に示す配合処方(配合割合)(単位:重量部)に従って混合し、80℃で1時間攪拌することでモノアリルジグリシジルイソシアヌレートを溶解させ、エポキシ樹脂(混合物)(上述のα剤にあたる)を得た。
(脂環式ポリエステル樹脂の製造:実施例7~12)
攪拌機、温度計、及び還流冷却器を備えた反応容器に、1,4-シクロヘキサンジカルボン酸(東京化成工業(株)製)172重量部、ネオペンチルグリコール(東京化成工業(株)製)208重量部、テトラブチルチタネート(和光純薬工業(株)製)0.1重量部を仕込んで、160℃になるまで加熱し、さらに160℃から250℃まで4時間かけて昇温した。次いで、1時間かけて5mmHgまで減圧し、さらに0.3mmHg以下まで減圧してから250℃で1時間反応させ、脂環式ポリエステル樹脂を得た。
(硬化性エポキシ樹脂組成物の製造)
表2に示す配合割合(単位:重量部)となるように、製造例5で得られたエポキシ樹脂、製造例6で得られた脂環式ポリエステル樹脂、硬化触媒(商品名「サンエイド SI-100L」、三新化学工業(株)製)を、自公転式攪拌装置(商品名「あわとり練太郎AR-250」、(株)シンキー製)を使用して均一に混合し、脱泡して硬化性エポキシ樹脂組成物を得た。なお、比較例4の場合は、エポキシ樹脂として商品名「セロキサイド2021P」((株)ダイセル製)を使用した。
上記で得た硬化性エポキシ樹脂組成物を、図1に示す光半導体のリードフレーム(InGaN素子、3.5mm×2.8mm)に注型した後、120℃のオーブン(樹脂硬化オーブン)で5時間加熱し、硬化した樹脂(硬化物)で光半導体素子を封止した光半導体装置を得た。
実施例及び比較例で得られた光半導体装置について、以下の方法で評価試験を行った。
実施例及び比較例で得られた光半導体装置の全光束を全光束測定機を用いて測定した。さらに、85℃の恒温槽内で100時間、光半導体装置に60mAの電流を流した後の全光束を測定した。次式から、光度保持率を算出した。結果を表1、表2に示す。
{光度保持率(%)}
={100時間後の全光束(lm)}/{0時間の全光束(lm)}×100
実施例及び比較例で得た光半導体装置(各硬化性エポキシ樹脂組成物につき2個用いた)に、-40℃の雰囲気下に30分曝露し、続いて、100℃の雰囲気下に30分曝露することを1サイクルとした熱衝撃を、熱衝撃試験機を用いて200サイクル分与えた。その後、光半導体装置の封止樹脂(硬化性エポキシ樹脂の硬化物)に生じたクラックの長さを、デジタルマイクロスコープ(VHX-900、(株)キーエンス製)を使用して観察し、光半導体装置2個のうち長さが90μm以上のクラックを有する光半導体装置の個数を計測した。結果を表1、表2に示す。
通電試験において光度保持率が90%以上であり、なおかつ、熱衝撃試験において長さ90μm以上のクラックが生じた光半導体装置の個数が0個となったものを、総合判定○(良好)とした。これ以外のものを総合判定×(不良)とした。結果を表1、表2に示す。
[エポキシ樹脂]
CEL2021P(セロキサイド2021P):3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート、(株)ダイセル製
MA-DGIC:モノアリルジグリシジルイソシアヌレート、四国化成工業(株)製
YD-128:ビスフェノールA型エポキシ樹脂、新日鐵化学(株)製
[K剤]
MH-700(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
HN-7200:4-メチルヘキサヒドロ無水フタル酸と脂環式ポリエステルの混合物、日立化成工業(株)製
HN-5700(旧名称「DHZ-01」):4-メチルヘキサヒドロ無水フタル酸/3-メチルヘキサヒドロ無水フタル酸=70/30と脂環式ポリエステルの混合物、日立化成工業(株)製
U-CAT 18X:硬化促進剤、サンアプロ(株)製
エチレングリコール:和光純薬工業(株)製
[硬化触媒]
サンエイド SI-100L:アリールスルホニウム塩、三新化学工業(株)製
・樹脂硬化オーブン
エスペック(株)製 GPHH-201
・恒温槽
エスペック(株)製 小型高温チャンバー ST-120B1
・全光束測定機
米国オプトロニックラボラトリーズ社製 マルチ分光放射測定システム OL771
・熱衝撃試験機
エスペック(株)製 小型冷熱衝撃装置 TSE-11-A
101:金属配線
102:LED素子
103:ボンディングワイヤ
104:透明封止樹脂
Claims (9)
- 前記脂環式エポキシ化合物(A)の脂環エポキシ基がシクロヘキセンオキシド基である請求項1又は2に記載の硬化性エポキシ樹脂組成物。
- 脂環式ポリエステル樹脂(C)が、主鎖に脂環を有する脂環式ポリエステルである請求項1~4のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- さらに、ゴム粒子を含む請求項1~5のいずれか1項に記載の硬化性エポキシ樹脂組成物。
- 請求項1~6のいずれか1項に記載の硬化性エポキシ樹脂組成物を硬化してなる硬化物。
- 請求項1~6のいずれか1項に記載の硬化性エポキシ樹脂組成物からなる光半導体封止用樹脂組成物。
- 請求項8に記載の光半導体封止用樹脂組成物で光半導体素子を封止した光半導体装置。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2013035542A1 (ja) * | 2011-09-06 | 2013-03-14 | 株式会社ダイセル | 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 |
JP2014084332A (ja) * | 2012-10-19 | 2014-05-12 | Daicel Corp | 硬化性エポキシ樹脂組成物及びその硬化物、並びに光半導体装置 |
WO2014109317A1 (ja) * | 2013-01-09 | 2014-07-17 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
JP2014133806A (ja) * | 2013-01-09 | 2014-07-24 | Daicel Corp | 硬化性エポキシ樹脂組成物 |
JPWO2014038446A1 (ja) * | 2012-09-07 | 2016-08-08 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物及びその硬化物、並びに光半導体装置 |
JP2017125212A (ja) * | 2017-04-10 | 2017-07-20 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物及びその硬化物、並びに光半導体装置 |
Families Citing this family (1)
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EP3778701A4 (en) | 2018-03-28 | 2021-12-22 | Nippon Sheet Glass Company, Limited | HARDENED PRODUCT OF RESIN COMPOSITION, LAMINATE AND RESIN COMPOSITION |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2013035542A1 (ja) * | 2011-09-06 | 2013-03-14 | 株式会社ダイセル | 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 |
JPWO2014038446A1 (ja) * | 2012-09-07 | 2016-08-08 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物及びその硬化物、並びに光半導体装置 |
JP2014084332A (ja) * | 2012-10-19 | 2014-05-12 | Daicel Corp | 硬化性エポキシ樹脂組成物及びその硬化物、並びに光半導体装置 |
WO2014109317A1 (ja) * | 2013-01-09 | 2014-07-17 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物 |
JP2014133806A (ja) * | 2013-01-09 | 2014-07-24 | Daicel Corp | 硬化性エポキシ樹脂組成物 |
JP2017125212A (ja) * | 2017-04-10 | 2017-07-20 | 株式会社ダイセル | 硬化性エポキシ樹脂組成物及びその硬化物、並びに光半導体装置 |
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Publication number | Publication date |
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MY161535A (en) | 2017-04-28 |
JP5852014B2 (ja) | 2016-02-03 |
CN103154072B (zh) | 2015-11-25 |
KR20140009202A (ko) | 2014-01-22 |
KR101832537B1 (ko) | 2018-02-26 |
TW201233726A (en) | 2012-08-16 |
JPWO2012093591A1 (ja) | 2014-06-09 |
CN103154072A (zh) | 2013-06-12 |
TWI512034B (zh) | 2015-12-11 |
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