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WO2017138487A1 - Composition de résine époxy durcissable pour réflecteur blanc ainsi qu'article durci de celle-ci, substrat pour montage d'élément photo-semi-conducteur, dispositif photo-semi-conducteur, et procédés de fabrication associés - Google Patents

Composition de résine époxy durcissable pour réflecteur blanc ainsi qu'article durci de celle-ci, substrat pour montage d'élément photo-semi-conducteur, dispositif photo-semi-conducteur, et procédés de fabrication associés Download PDF

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Publication number
WO2017138487A1
WO2017138487A1 PCT/JP2017/004206 JP2017004206W WO2017138487A1 WO 2017138487 A1 WO2017138487 A1 WO 2017138487A1 JP 2017004206 W JP2017004206 W JP 2017004206W WO 2017138487 A1 WO2017138487 A1 WO 2017138487A1
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WIPO (PCT)
Prior art keywords
group
resin composition
epoxy resin
compound
white
Prior art date
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Ceased
Application number
PCT/JP2017/004206
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English (en)
Japanese (ja)
Inventor
安達良紀
大石聡司
佐藤篤志
吉田司
鈴木弘世
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Cluster Technology Co Ltd
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Cluster Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/855—Optical field-shaping means, e.g. lenses
    • H10H20/856—Reflecting means
    • 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
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a curable epoxy resin composition for a white reflector and a cured product thereof, a substrate for mounting an optical semiconductor element having a white reflector formed of the cured product, an optical semiconductor device having the substrate and the optical semiconductor element, and
  • the present invention relates to a method for producing the curable epoxy resin composition for white reflector, cured product, and the like.
  • optical semiconductor devices in various indoor or outdoor display boards, image reading light sources, traffic signals, large display units, etc., light emitting devices (optical semiconductor devices) using optical semiconductor elements (LED elements) as light sources have been increasingly adopted.
  • an optical semiconductor device in general, an optical semiconductor device in which an optical semiconductor element is mounted on a substrate (substrate for mounting an optical semiconductor element) and the optical semiconductor element is sealed with a transparent sealing material is widespread. is doing.
  • a member (white reflector) for reflecting light is formed in order to increase the extraction efficiency of light emitted from the optical semiconductor element.
  • the white reflector is required to have high light reflectivity.
  • the white reflector for example, an epoxy compound which does not have an aromatic skeleton and whose constituent atoms are only three kinds of carbon atom, oxygen atom and hydrogen atom, an acid anhydride curing agent, and titanium oxide
  • a white curable composition for optical semiconductor devices containing a filler different from titanium oxide, and a white reflector can be obtained by molding the composition using a mold such as transfer molding or compression molding. It was obtained (refer patent document 1).
  • the white reflector manufactured from the material described in Patent Document 1 described above is yellowed over time by heat generated from a semiconductor element in an optical semiconductor device using a high-power blue light semiconductor or white light semiconductor as a light source. It deteriorated and had the problem that light reflectivity fell with time. For this reason, as a material for forming a white reflector, there is currently a demand for a material with a small decrease in light reflectance due to heat (that is, a material having excellent heat resistance).
  • the white reflector is generally manufactured by subjecting a material (resin composition) for forming the white reflector to transfer molding or compression molding. For this reason, it is necessary to mold the resin composition into a tablet, and for that purpose, it is necessary to have a property capable of being pulverized (grindability) and / or a property capable of being tableted (tabletability).
  • the material described in Patent Document 1 is relatively soft after kneading of the raw materials depending on the blending of the raw materials, and thus may not be pulverized and compressed.
  • an object of the present invention is to provide a curable epoxy for a white reflector that is excellent in pulverization and / or tableting properties, is easy to handle without causing stickiness, and can form a cured product having excellent heat resistance.
  • the object is to provide a resin composition.
  • Another object of the present invention is to provide a cured product that is excellent in productivity and heat resistance and is useful as a constituent material of a white reflector.
  • Another object of the present invention is to provide a high-quality substrate for mounting an optical semiconductor element having a white reflector excellent in productivity and heat resistance.
  • Still another object of the present invention is to provide a high-quality optical semiconductor device having the optical semiconductor element mounting substrate.
  • the white reflector includes adhesion to a lead frame (for example, a silver-plated copper frame, a gold-plated copper frame, a copper electrode or a heat sink) of the substrate for mounting an optical semiconductor element, and a sealing material (for example, a silicone-based seal). It is required to be excellent in adhesiveness (hereinafter referred to as “adhesiveness” in some cases). In particular, when the adhesion to the lead frame is inferior, when the optical semiconductor device mounting substrate is molded and then punched or diced to separate the optical semiconductor device, a defect that the white resin peels off from the lead frame occurs. There is a case.
  • the optical semiconductor device becomes dark due to corrosion of the silver plating, or the encapsulant is peeled off in the hygroscopic solder reflow test or the wire is In some cases, the optical semiconductor device may fail due to disconnection or the like.
  • the white reflector is also required to have a linear expansion coefficient as low as possible in order not to cause problems such as peeling from the lead frame and warping of the lead frame as a desirable characteristic.
  • the white reflector is obtained by subjecting the material (resin composition or the like) for forming the white reflector to a molding (molding) method using a mold such as transfer molding or compression molding. Produced. For this reason, it is desirable that the material for forming the white reflector has a further property that it can be released from the mold after molding from the viewpoint of productivity in transfer molding and compression molding using a mold. It is also required to be excellent.
  • the present inventors have made at least one selected from the group consisting of an epoxy compound, an inorganic filler, and a white pigment when producing a curable epoxy resin composition for a white reflector.
  • the curable epoxy resin composition for white reflector which contains a mixture heated and mixed in advance as an essential component, is excellent in pulverization and / or tableting properties, and is easy to handle without causing stickiness. I found. Moreover, it discovered that according to the said curable epoxy resin composition, the hardened
  • the present invention is a heating mixture containing an epoxy compound (A) and at least one selected from the group consisting of an inorganic filler (B) and a white pigment (C), and the shear viscosity at 25 ° C.
  • a curable epoxy resin composition for a white reflector comprising a heated mixture of 10 to 1000 Pa ⁇ s.
  • the curable epoxy resin composition for white reflector may further contain a curing agent (D) in addition to the heating mixture.
  • the curable epoxy resin composition for white reflector is selected from the group consisting of an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′) in addition to the heating mixture. At least one kind may be included.
  • the epoxy compound (A) includes an alicyclic epoxy compound (A-1), a heterocyclic epoxy compound (A-2), and an aromatic epoxy compound (A-3). It may contain at least one selected from the group consisting of
  • the epoxy compound (A ′) includes an alicyclic epoxy compound (A-1), a heterocyclic epoxy compound (A-2), and an aromatic epoxy compound (A-3). At least one selected from the group consisting of:
  • the inorganic filler (B) and the inorganic filler (B ′) are each independently silica, zircon, calcium silicate, calcium phosphate, silicon carbide, silicon nitride, boron nitride. , Iron oxide, aluminum oxide, fosterite, steatite, spinel, clay having a refractive index of less than 1.5, dolomite, hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, and these molded bodies At least one kind selected may be included.
  • the white pigment (C) and the white pigment (C ′) are each independently glass, clay having a refractive index of 1.5 or more, mica, talc, kaolinite, halloysite. , Zeolite, acidic clay, activated clay, boehmite, inorganic oxide, metal salt, styrene resin, benzoguanamine resin, urea-formalin resin, melamine-formalin resin, amide resin, and hollow particles It may contain at least one kind.
  • the curing agent (D) is represented by the following formula (1): (In formula (1), R a represents an alkylene group having 1 to 6 carbon atoms, R b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group. In formula (1), a plurality of them are present. R a and R b may be the same or different.) The compound represented by these may be included.
  • the heated mixture is at least one selected from the group consisting of an inorganic filler (B) and a white pigment (C) with respect to 100 parts by weight of the epoxy compound (A). It may be contained in an amount of 5 to 500 parts by weight.
  • the curable epoxy resin composition for a white reflector is an alicyclic epoxy compound (A-1) having a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring (A -1-1), a compound having an epoxy group directly bonded to an alicyclic ring (A-1-2), and a compound having an alicyclic ring and a glycidyl group (A-1-3). May contain at least one kind.
  • the compound (A-1-1) may be a compound having a cyclohexene oxide group.
  • the compound (A-1-1) has the following formula (I-1): The compound represented by these may be sufficient.
  • the compound (A-1-2) has the following formula (II): [In Formula (II), R 1 represents a p-valent organic group. p represents an integer of 1 to 20. q represents an integer of 1 to 50, and the sum (total) of q in formula (II) is an integer of 3 to 100. R 2 represents any one of groups represented by the following formulas (IIa) to (IIc). However, at least one of R 2 in the formula (II) is a group represented by the formula (IIa).
  • R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. ]] The compound represented by these may be sufficient.
  • the atoms constituting the heterocyclic epoxy compound (A-2) may be carbon atoms, hydrogen atoms, oxygen atoms, and nitrogen atoms.
  • the heterocyclic epoxy compound (A-2) has the following formula (III): [Wherein, R 4 , R 5 and R 6 are the same or different and are represented by the following formula (IIIa) [Wherein R 7 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] Or a group represented by the following formula (IIIb) [Wherein R 8 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] The group represented by these is shown. However, at least one of R 4 to R 6 in the formula (III) is a group represented by the formula (IIIa). ] The compound represented by these may be sufficient.
  • the aromatic epoxy compound (A-3) includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and biphenyl type. It may contain at least one selected from the group consisting of epoxy resins.
  • the total amount of ') may be 200 to 2000 parts by weight.
  • the white pigment (C) and the white pigment (C ′) with respect to a total of 100 parts by weight of the epoxy compound (A), the epoxy compound (A ′), and the curing agent (D).
  • the total amount of may be 3 to 400 parts by weight.
  • the curing agent (D) may contain a liquid curing agent at 25 ° C.
  • the curable epoxy resin composition for white reflector may be a resin composition for transfer molding or compression molding.
  • this invention provides the hardened
  • this invention provides the manufacturing method of the curable epoxy resin composition for white reflectors including the following process (1) and (2).
  • step (2) of the method for producing the curable epoxy resin composition for white reflector the mixture further comprises an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′). At least one selected from the group may be included.
  • the present invention also provides a method for producing a cured product of a curable epoxy resin composition for a white reflector, comprising the following steps (1) to (3).
  • step (2) of the method for producing a cured product of the curable epoxy resin composition for white reflector the mixture further includes an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′ At least one selected from the group consisting of:
  • the cured product may be a white reflector for a substrate for mounting an optical semiconductor element.
  • this invention provides the manufacturing method of an optical semiconductor device including the manufacturing method of the hardened
  • the present invention relates to the following.
  • a heating mixture containing an epoxy compound (A) and at least one selected from the group consisting of an inorganic filler (B) and a white pigment (C), and having a shear viscosity of 10 to 1000 Pa at 25 ° C.
  • the curable epoxy resin composition for white reflectors containing the heating mixture which is s.
  • the composition in addition to the heated mixture, the composition further contains at least one selected from the group consisting of an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′). Or the curable epoxy resin composition for white reflectors as described in [2].
  • the epoxy compound (A) is a compound having two or more epoxy groups in the molecule (preferably 2 to 6, more preferably 2 to 4).
  • the epoxy compound (A) is at least one selected from the group consisting of an alicyclic epoxy compound (A-1), a heterocyclic epoxy compound (A-2), and an aromatic epoxy compound (A-3).
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [4], comprising:
  • the epoxy compound (A ′) is at least selected from the group consisting of an alicyclic epoxy compound (A-1), a heterocyclic epoxy compound (A-2), and an aromatic epoxy compound (A-3). Any one of the above [3] to [6], including one (preferably at least one selected from the group consisting of an alicyclic epoxy compound (A-1) and a heterocyclic epoxy compound (A-2))
  • a compound (A-1-1) having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring [5] including at least one selected from the group consisting of a compound (A-1-2) having an epoxy group directly bonded and a compound (A-1-3) having an alicyclic ring and a glycidyl group.
  • the curable epoxy resin composition for white reflectors according to any one of [7] to [7].
  • X represents a single bond or a linking group (a divalent group having one or more atoms) (preferably a divalent hydrocarbon group or a part or all of a carbon-carbon double bond is an epoxy group)
  • An alkenylene group epoxidized alkenylene group
  • a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in formula (I).
  • the linking group X is —CO—, —O—CO—O—, —COO—, —O—, —CONH—, an epoxidized alkenylene group; a group in which a plurality of these groups are linked;
  • the curable epoxy resin composition for a white reflector according to the above [10], wherein one or more of the groups and one or more of the divalent hydrocarbon groups are linked.
  • the compound represented by the above formula (I) is a compound represented by any of the following formulas (I-1) to (I-10): 2,2-bis (3,4-epoxycyclohexane-1-yl ) Propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, or bis ( The curable epoxy resin composition for a white reflector according to the above [10] or [11], comprising 3,4-epoxycyclohexylmethyl) ether. [In the formulas (I-5) and (I-7), l and m each represents an integer of 1 to 30.
  • R in the formula (I-5) is an alkylene group having 1 to 8 carbon atoms (eg, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene group).
  • a linear or branched alkylene group such as a heptylene group or an octylene group, preferably a linear or branched alkylene group having 1 to 3 carbon atoms.
  • N1 to n6 in the formulas (I-9) and (I-10) each represents an integer of 1 to 30.
  • the compound (A-1-1) is represented by the following formula (I-1)
  • the curable epoxy resin composition for a white reflector according to any one of the above [8] to [12], comprising a compound represented by:
  • the compound (A-1-2) is represented by the following formula (II) [In Formula (II), R 1 represents a p-valent organic group. p represents an integer of 1 to 20. q represents an integer of 1 to 50, and the sum (total) of q in formula (II) is an integer of 3 to 100. R 2 represents any one of groups represented by the following formulas (IIa) to (IIc). However, at least one of R 2 in the formula (II) is a group represented by the formula (IIa).
  • R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.
  • the ratio of the group (epoxy group) represented by the formula (IIa) to the total amount (100 mol%) of R 2 in the compound represented by the formula (II) is 40 mol% or more (for example, 40).
  • the curable epoxy resin composition for a white reflector according to the above [14] which is ⁇ 100 mol%, preferably 60 mol% or more, more preferably 80 mol% or more.
  • the compound (A-1-3) is converted to 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- ( 2,3-epoxypropoxy) cyclohexyl] propane, a compound obtained by hydrogenating a bisphenol A type epoxy compound (hydrogenated bisphenol A type epoxy compound), etc .; bis [2- (2,3-epoxypropoxy) cyclohexyl] Methane, [2- (2,3-epoxypropoxy) cyclohexyl] [4- (2,3-epoxypropoxy) cyclohexyl] methane, bis [4- (2,3-epoxypropoxy) cyclohexyl] Hydrogenated methane, bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane, bisphenol F type epoxy compound Hydrogenated bisphenol F type epoxy compound), etc .; hydrogenated bi
  • the heterocyclic epoxy compound (A-2) is represented by the following formula (III): [Wherein, R 4 , R 5 and R 6 are the same or different and are represented by the following formula (IIIa) [Wherein R 7 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the curable epoxy resin composition for a white reflector comprising a compound represented by: [21]
  • the heterocyclic epoxy compound (A-2) is represented by the following formula (IV): [Wherein, R 9 , R 10 , R 11 , and R 12 are the same or different and are represented by the following formula (IVa): [Wherein R 15 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] Or a group represented by the following formula (IVb) [Wherein R 16 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] The group represented by these is shown.
  • R 9 to R 12 in the formula (IV) is a group represented by the formula (IVa).
  • R 13 and R 14 are the same or different and each represents a hydrogen atom or a monovalent organic group.
  • A-3 includes at least one selected from the group consisting of bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and biphenyl type epoxy resins.
  • the inorganic filler (B) and the inorganic filler (B ′) are each independently silica (for example, fused silica, crystalline silica, high-purity synthetic silica, etc.), zircon, calcium silicate, calcium phosphate, silicon carbide.
  • silica for example, fused silica, crystalline silica, high-purity synthetic silica, etc.
  • zircon zircon, calcium silicate, calcium phosphate, silicon carbide.
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [22], comprising at least one selected from the group consisting of molded articles (preferably silica).
  • the inorganic filler (B) and the inorganic filler (B ′) are independently surface treated [for example, metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyol, silicone, etc.
  • the shapes of the inorganic filler (B) and the inorganic filler (B ′) are independently powder, spherical, crushed, fibrous, needle-like, or scaly (especially spherical, especially true spherical)
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [24], which is (for example, spherical silica having an aspect ratio of 1.2 or less).
  • the above [1] to [1] wherein the center particle sizes of the inorganic filler (B) and the inorganic filler (B ′) are each independently 0.1 to 50 ⁇ m (preferably 0.1 to 30 ⁇ m).
  • the curable epoxy resin composition for white reflectors according to any one of [25].
  • the white pigment (C) and the white pigment (C ′) are each independently a white pigment having a refractive index of 1.5 or more, according to any one of the above [1] to [26] A curable epoxy resin composition for a white reflector.
  • the white pigment (C) and the white pigment (C ′) are each independently glass, clay having a refractive index of 1.5 or more, mica, talc, kaolinite, halloysite, zeolite, acidic clay, activated clay, Including at least one selected from the group consisting of boehmite, inorganic oxides, metal salts, styrene resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amide resins, and hollow particles.
  • the curable epoxy resin composition for a white reflector according to any one of [27].
  • the white pigment (C) and the white pigment (C ′) are each independently an inorganic oxide (for example, aluminum oxide (alumina), magnesium oxide, antimony oxide, titanium oxide [for example, rutile titanium oxide, Anatase-type titanium oxide, brookite-type titanium oxide, etc.], zirconium oxide, zinc oxide, etc., particularly preferably titanium oxide), and the curable epoxy for white reflectors according to any one of the above [1] to [28] Resin composition.
  • the white pigment (C) and the white pigment (C ′) are each independently an alkaline earth metal salt (for example, magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate, magnesium hydroxide).
  • the curable epoxy resin composition for a white reflector according to any one of [1] to [29] above, which is magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, barium sulfate, or the like.
  • the white pigment (C) and the white pigment (C ′) are each independently a hollow particle (for example, inorganic glass [for example, sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.], silica Inorganic hollow particles composed of metal oxides such as alumina, metal salts such as calcium carbonate, barium carbonate, nickel carbonate and calcium silicate (including natural products such as shirasu balloon); styrene resin, acrylic Resin, silicone resin, acrylic-styrene resin, vinyl chloride resin, vinylidene chloride resin, amide resin, urethane resin, phenol resin, styrene-conjugated diene resin, acrylic-conjugated diene resin, olefin
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [30], which
  • the white pigment (C) and the white pigment (C ′) are each independently surface treated [for example, surfaces of metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyol, silicone, etc.
  • the shapes of the white pigment (C) and the white pigment (C ′) are each independently spherical, crushed, fibrous, acicular, or scaly (especially spherical titanium oxide is preferred, particularly true
  • the above [1], wherein the center particle diameters of the white pigment (C) and the white pigment (C ′) are each independently 0.1 to 50 ⁇ m (preferably 0.1 to 30 ⁇ m of titanium oxide).
  • Curable epoxy resin composition [36] The curable epoxy resin composition for a white reflector according to any one of the above [1] to [35], wherein the heating temperature in the heated mixture is 50 to 120 ° C. (preferably 60 to 100 ° C.) object.
  • the content (blending amount) of the epoxy compound (A) in the heated mixture is from 1 to 99% by weight (preferably from 10 to 95% by weight, more preferably from 100% by weight).
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [36], which is 20 to 90% by weight).
  • the ratio of the compound (A-1-1) to the total amount (100 wt%) of the epoxy compound (A) contained in the heated mixture is 5 to 100 wt% (preferably 10 to 100 wt%, more preferably Is a curable epoxy resin composition for a white reflector according to any one of the above [1] to [37].
  • the ratio of the compound (A-1-2) to the total amount (100 wt%) of the epoxy compound (A) contained in the heated mixture is 0 to 50 wt% (preferably 0 to 45 wt%, more preferably Is a curable epoxy resin composition for a white reflector according to any one of the above [1] to [38].
  • the ratio of the compound (A-1-3) to the total amount (100 wt%) of the epoxy compound (A) contained in the heated mixture is 0 to 50 wt% (preferably 0 to 45 wt%, more preferably Is a curable epoxy resin composition for a white reflector according to any one of the above [1] to [39].
  • the content (blending amount) of at least one selected from the group consisting of the inorganic filler (B) and the white pigment (C) is 1 to 99% by weight with respect to the heated mixture (100% by weight).
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [40], which is preferably 5 to 90% by weight, more preferably 10 to 80% by weight.
  • the heated mixture contains 5 to 500 parts by weight (preferably 10 parts by weight) of at least one selected from the group consisting of the inorganic filler (B) and the white pigment (C) with respect to 100 parts by weight of the epoxy compound (A).
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [41], which is contained in an amount of 400 parts by weight, more preferably 20 to 400 parts by weight.
  • the ratio of the inorganic filler (B) to the white pigment (C) (inorganic filler (B) / white pigment (C)) is 100/0 to 0/100 (preferably 99/1 to 1/99).
  • the content (blending amount) of the epoxy compound (A ′) is 1 to 10,000 parts by weight (preferably 10 to 1000 parts by weight, more preferably 10 to 500 parts by weight based on 100 parts by weight of the epoxy compound (A).
  • the total content (blending amount) of the epoxy compound (A) and the epoxy compound (A ′) is 1.5 to 15% by weight (preferably with respect to the curable epoxy resin composition (100% by weight))
  • the ratio of the compound (A-1-1) to the total amount (100 wt%) of the epoxy compound (A) and the epoxy compound (A ′) is 5 to 95 wt% (preferably 10 to 90 wt%,
  • the ratio of the compound (A-1-2) to the total amount (100 wt%) of the epoxy compound (A) and the epoxy compound (A ′) is 1 to 90 wt% (preferably 10 to 80 wt%, more
  • the ratio of the compound (A-1-3) to the total amount (100 wt%) of the epoxy compound (A) and the epoxy compound (A ′) is 0 to 90 wt% (preferably 10 to 80 wt%, more
  • the ratio of the heterocyclic epoxy compound (A-2) to the total amount (100 wt%) of the epoxy compound (A) and the epoxy compound (A ′) is 1 to 80 wt% (preferably 5 to 70 wt%)
  • the curable epoxy resin composition for a white reflector according to any one of the above [1] to [49].
  • the curing agent (D) is an acid anhydride (acid anhydride curing agent), an amine (amine curing agent), a polyamide resin, an imidazole (imidazole curing agent), or a polymercaptan (polymercaptan).
  • System curing agent phenols (phenolic curing agent), polycarboxylic acids, dicyandiamides, and at least one selected from the group consisting of organic acid hydrazides, any one of [2] to [50] above
  • the curing agent (D) includes a curing agent that is liquid (liquid) at 25 ° C.
  • the curable epoxy resin composition for white reflectors as described.
  • the curing agent (D) is represented by the following formula (1) (In formula (1), R a represents an alkylene group having 1 to 6 carbon atoms, R b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group. In formula (1), a plurality of them are present.
  • R a and R b may be the same or different.
  • the acid value (measured by the method described in JIS K-2501) of the compound represented by the above formula (1) is 150 to 415 mgKOH / g (preferably 185 to 375 mgKOH / g, more preferably 200 to 320 mgKOH).
  • the curable epoxy resin composition for white reflectors according to [53] or [54] above.
  • the functional group equivalent of the compound represented by the formula (1) is 135 to 312 g / eq (preferably 150 to 300 g / eq, more preferably 180 to 280 g / eq).
  • the curing agent (D) is at least one selected from the group consisting of the compound represented by the above formula (1) and acid anhydrides (acid anhydride curing agents) (particularly preferably, the formula (1)
  • the curable epoxy resin composition for white reflectors according to any one of [58] to [58].
  • the content (blending amount) of the curing agent (D) is 50 to 200 with respect to 100 parts by weight of the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition.
  • the curable epoxy resin composition for a white reflector according to any one of the above [2] to [59], which is by weight (preferably 75 to 180 parts by weight, more preferably 80 to 150 parts by weight).
  • the content (blending amount) of the compound represented by the formula (1) is 100 parts by weight based on the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition.
  • the curable epoxy resin for a white reflector according to any one of the above [53] to [60], which is 1 to 300 parts by weight (preferably 10 to 250 parts by weight, more preferably 20 to 200 parts by weight).
  • the ratio of the compound represented by the formula (1) to the total amount (100% by weight) of the curing agent (D) is 10% by weight or more (eg, 10 to 100% by weight, more preferably 15% by weight or more).
  • the curable epoxy resin composition for white reflectors according to any one of [53] to [61], more preferably 20% by weight or more, and particularly preferably 25% by weight or more.
  • the content (blending amount) of acid anhydrides is 0 to 1500 parts by weight (preferably 10 to 1200 parts by weight, more preferably 20 parts per 100 parts by weight of the compound represented by formula (1).
  • the curable epoxy resin composition for a white reflector according to any one of the above [59] to [62], wherein
  • a curing accelerator eg, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (eg, phenol salt, octylate, p-toluenesulfonate, formic acid) Salt, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, octylate, p-toluenesulfonate, formate, Tetraphenylborate salts, etc.); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl Imidazoles such as -2-ethyl-4-methylimidazole;
  • DBU 1,
  • Curable epoxy resin composition for white reflectors [65]
  • the content (blending amount) of the curing accelerator is 0 with respect to 100 parts by weight of the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition for white reflector.
  • the total content (blending amount) of the inorganic filler (B) and the inorganic filler (B ′) is 60 to 90% by weight (preferably with respect to the curable epoxy resin composition (100% by weight)). 60 to 75% by weight)
  • the curable epoxy resin composition for a white reflector according to any one of the above [3] to [65].
  • the total amount of inorganic filler (B) and inorganic filler (B ′) is 200 to 2000 with respect to 100 parts by weight of the total of epoxy compound (A), epoxy compound (A ′) and curing agent (D).
  • the curable epoxy resin composition for a white reflector according to any one of the above [3] to [66], which is part by weight (preferably 220 to 1500 parts by weight, more preferably 250 to 1000 parts by weight).
  • the total content (blending amount) of the white pigment (C ′) and the white pigment (C) is 2 to 40 wt% (preferably 10 to 10 wt%) with respect to the curable epoxy resin composition (100 wt%).
  • the total amount of the white pigment (C) and the white pigment (C ′) is 3 to 400 parts by weight based on 100 parts by weight of the total of the epoxy compound (A), the epoxy compound (A ′) and the curing agent (D).
  • the curable epoxy resin composition for a white reflector according to any one of the above [3] to [68], which is (preferably 5 to 350 parts by weight, more preferably 5 to 300 parts by weight).
  • the ratio of titanium oxide to the total amount (100 wt%) of the inorganic filler (B), the inorganic filler (B ′), the white pigment (C) and the white pigment (C ′) is 5 to 40 wt% (
  • the total content (blending amount) of the inorganic filler (B), the inorganic filler (B ′), the white pigment (C) and the white pigment (C ′) is an epoxy compound (A), an epoxy compound (A ') And 200 to 2,000 parts by weight (preferably 250 to 1,800 parts by weight, more preferably 300 to 1,500 parts by weight) with respect to 100 parts by weight of the total amount of the curing agent (D).
  • the curable epoxy resin composition for a white reflector as described in any one of [3] to [70] above.
  • a release agent for example, a fluorine-based release agent (fluorine atom-containing compound; for example, fluorine oil, polytetrafluoroethylene, etc.), a silicone-based release agent (silicone compound; for example, silicone oil, silicone wax) , Silicone resins, polyorganosiloxanes having polyoxyalkylene units, etc.), wax release agents (waxes; for example, plant waxes such as carnauba wax, animal waxes such as wool wax, paraffins such as paraffin wax, polyethylene Wax, oxidized polyethylene wax, etc.), higher fatty acids or salts thereof (for example, metal salts, etc.), higher fatty acid esters, higher fatty acid amides, mineral oils, etc.) as described in any one of [1] to [70] above Curable epoxy resin composition for white reflectors.
  • a fluorine-based release agent fluorine atom-containing compound; for example, fluorine oil, polytetrafluoroethylene, etc.
  • the content (blending amount) of the release agent is 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition for white reflector.
  • antioxidants for example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus antioxidants (phosphorous compounds), sulfur antioxidants
  • the antioxidant is at least one selected from a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant (preferably a phenolic antioxidant and a phosphorus antioxidant or a sulfur antioxidant)
  • the curable epoxy resin composition for a white reflector according to the above [74] which is a combined use with an inhibitor, more preferably a combined use of a phenolic antioxidant and a phosphorus antioxidant.
  • the content (blending amount) of the antioxidant is 0.00 with respect to 100 parts by weight of the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition for white reflector.
  • a method for producing a curable epoxy resin composition for a white reflector comprising the following steps (1) and (2): (1) A step of heating and mixing a mixture comprising an epoxy compound (A) and at least one selected from the group consisting of an inorganic filler (B) and a white pigment (C) to obtain a heated mixture; and (2) The process of obtaining the curable epoxy resin composition for white reflectors by mixing the said heating mixture and the mixture containing a hardening
  • the manufacturing method of the curable epoxy resin composition for white reflectors as described in said [85].
  • the manufacturing method of the curable epoxy resin composition for white reflectors as described in any one of.
  • [88] The curable epoxy for a white reflector according to any one of the above [85] to [87], wherein the heating temperature in the step (1) is 50 to 120 ° C. (preferably 60 to 100 ° C.) A method for producing a resin composition.
  • the curable epoxy for a white reflector according to any one of the above [85] to [88], wherein the rotational speed in the mixing in the step (1) is 10 to 10000 rpm (preferably 10 to 5000 rpm) A method for producing a resin composition.
  • the heating and mixing time in the step (1) is 0.5 to 24 hours (preferably 0.5 to 18 hours), according to any one of the above [85] to [89] A method for producing a curable epoxy resin composition for a white reflector.
  • a method for producing a cured product of a curable epoxy resin composition for a white reflector comprising the following steps (1) to (3): (1) A step of heating and mixing a mixture composed of an epoxy compound (A) and at least one selected from the group consisting of an inorganic filler (B) and a white pigment (C) to obtain a heated mixture; (2) a step of mixing a mixture containing the heating mixture and a curing agent (D) to obtain a curable epoxy resin composition for white reflector; and (3) a curable epoxy resin composition for white reflector. A step of heating to obtain a cured product.
  • the mixture further contains at least one selected from the group consisting of an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′).
  • a ′ an epoxy compound
  • B ′ an inorganic filler
  • C ′ a white pigment
  • the heated mixture has a shear viscosity at 25 ° C. of 10 to 1,000 Pa ⁇ s (preferably 10 to 500 Pa ⁇ s, more preferably 10 to 300 Pa ⁇ s).
  • cured material as described in any one of.
  • the curable epoxy resin composition for white reflectors of the present invention Since the curable epoxy resin composition for white reflectors of the present invention has the above-described configuration, it is excellent in grindability and / or tableting properties, and is easy to handle without causing stickiness, and also has heat resistance when cured. It is possible to form an excellent cured product. Therefore, by using the curable epoxy resin composition for white reflectors of the present invention, a high-quality (for example, highly durable) optical semiconductor element mounting having a white reflector excellent in productivity and heat resistance. A substrate is obtained. Furthermore, by using the optical semiconductor element mounting substrate as a substrate in an optical semiconductor device, a high-quality (for example, highly durable) optical semiconductor device can be obtained.
  • the left figure (a) is a perspective view
  • the right figure (b) is a sectional view.
  • It is the schematic (sectional drawing) which shows an example of the optical semiconductor device of this invention.
  • It is the schematic (sectional drawing; when it has a heat sink) which shows another example of the optical semiconductor device of this invention.
  • the left drawing (a) is a top view
  • the right drawing (b) is a cross-sectional view taken along line A-A 'in (a).
  • the curable epoxy resin composition for white reflectors of the present invention (sometimes simply referred to as “the curable epoxy resin composition of the present invention” or “the curable epoxy resin composition”) includes an epoxy compound (A) and an inorganic compound.
  • a heated mixture comprising at least one selected from the group consisting of a filler (B) and a white pigment (C), wherein the shear viscosity at 25 ° C. is 10 to 1000 Pa ⁇ s (simply referred to as “of the present invention It may be referred to as a “heated mixture”) as an essential component (curable composition).
  • the curable epoxy resin composition of the present invention may contain other components as necessary in addition to the essential components.
  • the curable epoxy resin composition of the present invention can be used as a thermosetting composition (thermosetting epoxy resin composition) that can be cured by heating and converted into a cured product.
  • Epoxy compound (A) The epoxy compound (A) in the heating mixture of the present invention is a compound having one or more epoxy groups (oxiranyl groups) in the molecule.
  • the epoxy compound (A) is preferably a compound having two or more epoxy groups (preferably 2 to 6, more preferably 2 to 4) in the molecule.
  • epoxy compound (A) known or commonly used epoxy compounds can be used, and are not particularly limited.
  • alicyclic epoxy compounds alicyclic epoxy resins
  • aliphatic epoxy compounds such as aliphatic polyglycidyl ethers ( Aliphatic epoxy resins)
  • aromatic epoxy compounds aromatic epoxy resins
  • heterocyclic epoxy compounds heterocyclic epoxy resins
  • an alicyclic epoxy compound, a heterocyclic epoxy compound, and an aromatic epoxy compound are preferable.
  • a cyclic epoxy compound or a heterocyclic epoxy compound is more preferable, and an alicyclic epoxy compound is more preferable.
  • the alicyclic epoxy compound is “alicyclic epoxy compound (A-1)”
  • the heterocyclic epoxy compound is “heterocyclic epoxy compound (A-2)”
  • the aromatic epoxy compound is “aromatic epoxy compound”. (A-3) ”may be described.
  • the alicyclic epoxy compound (A-1) is a compound having at least an alicyclic (aliphatic hydrocarbon ring) structure and an epoxy group in the molecule.
  • a known or commonly used alicyclic ring is used.
  • Formula epoxy compounds can be used. More specifically, as the alicyclic epoxy compound (A-1), for example, an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring is used.
  • the compound (A-1-1) a known or commonly used compound having one or more alicyclic epoxy groups in the molecule can be used, and it is not particularly limited.
  • the alicyclic epoxy group is preferably a cyclohexene oxide group from the viewpoints of curability of the curable epoxy resin composition, heat resistance of the cured product (white reflector), and adjustment of the heated mixture of the present invention to a predetermined viscosity.
  • the compound (A-1-1) has two or more cyclohexene oxide groups in the molecule from the viewpoint of adjusting the heat resistance of the cured product (white reflector) and adjusting the heating mixture of the present invention to a predetermined viscosity.
  • a compound is preferable, and a compound represented by the following formula (I) is more preferable.
  • X represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized (epoxidized alkenylene group), a carbonyl group, an ether bond, an ester bond, and a carbonate.
  • a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (I).
  • Examples of the compound in which X in the formula (I) is a single bond include (3,4,3 ′, 4′-diepoxy) bicyclohexyl and the like.
  • Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.
  • alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like.
  • the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
  • the linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation.
  • Representative examples of the compound represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10), 2,2-bis (3,4-epoxycyclohexane- 1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, And bis (3,4-epoxycyclohexylmethyl) ether.
  • l and m each represents an integer of 1 to 30.
  • R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and is a methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene.
  • linear or branched alkylene groups such as a group, a heptylene group, and an octylene group.
  • linear or branched alkylene groups having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group are preferable.
  • N1 to n6 in the following formulas (I-9) and (I-10) each represents an integer of 1 to 30.
  • Examples of the compound (A-1-2) include a compound (epoxy resin) represented by the following formula (II).
  • R 1 represents a p-valent organic group.
  • p represents an integer of 1 to 20.
  • Examples of the p-valent organic group include a p-valent organic group having a structure formed by removing p hydroxy groups from the structural formula of an organic compound having p hydroxy groups described later.
  • q represents an integer of 1 to 50.
  • p is an integer greater than or equal to 2
  • several q may be the same and may differ.
  • the sum (total) of q in the formula (II) is an integer of 3 to 100.
  • R 2 is a substituent on the cyclohexane ring shown in the formula, and represents any of the groups represented by the following formulas (IIa) to (IIc).
  • the bonding position of R 2 on the cyclohexane ring is not particularly limited. Usually, when the positions of the two carbon atoms of the cyclohexane ring bonded to the oxygen atom are the 1st and 2nd positions, the 4th or 5th carbon atom It is.
  • the bonding positions of R 2 in each cyclohexane ring may be the same or different.
  • At least one R 2 in the formula (II) is a group (epoxy group) represented by the formula (IIa).
  • the compound represented by the formula (II) has two or more R 2, to a plurality of R 2 may be the same or different.
  • R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group.
  • alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl. Examples thereof include straight-chain or branched alkyl groups having 1 to 20 carbon atoms.
  • alkylcarbonyl group examples include a methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl.
  • alkylcarbonyl group examples include a linear or branched alkyl-carbonyl group having 1 to 20 carbon atoms such as a carbonyl group.
  • arylcarbonyl group examples include arylcarbonyl groups having 6 to 20 carbon atoms such as a phenylcarbonyl group (benzoyl group), 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, and the like.
  • Examples of the substituent that the above-described alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include a substituent having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms).
  • Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C 1-6 alkoxy group, more preferably C 1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C 2-6 alkenyloxy group, more preferably C 2-4 alkenyloxy group)
  • An acyloxy group such as an acetyloxy group, a propionyloxy group and a (meth) acryloyloxy group (preferably a C 1-12
  • examples of the substituent that the above-described arylcarbonyl group may have include the above-described substituted or unsubstituted alkyl group and the above-described substituted or unsubstituted alkylcarbonyl group.
  • the ratio of the group (epoxy group) represented by the formula (IIa) to the total amount (100 mol%) of R 2 in the compound represented by the formula (II) is not particularly limited, but is 40 mol% or more (for example, 40 to 100 mol%) is preferable, more preferably 60 mol% or more, and still more preferably 80 mol% or more.
  • the ratio is less than 40 mol%, the heat resistance and mechanical properties of the cured product, the viscosity of the heated mixture of the present invention, and the like may be insufficient.
  • the above ratio can be calculated by, for example, 1 H-NMR spectrum measurement, oxirane oxygen concentration measurement, or the like.
  • the compound represented by the formula (II) is not particularly limited.
  • an organic compound [R 1 (OH) p ] having p hydroxy groups in the molecule is used as an initiator (ie, the hydroxy group of the compound). (Starting with active hydrogen)), 1,2-epoxy-4- (2-vinyl) cyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) ring-opening polymerization (cationic polymerization) And then epoxidized with an oxidizing agent.
  • Examples of the organic compound [R 1 (OH) p ] having p hydroxy groups in the molecule include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol; ethylene glycol, diethylene glycol , Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, neopentyl glycol ester, cyclohexanedi Methanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bisphenol F, water Polyhydric alcohols such as bisphenol S; polyvin
  • 1,2-epoxy-4- (2-vinyl) cyclohexane can be produced by a known or conventional method, and is not particularly limited.
  • 4-vinylcyclohexene obtained by dimerization reaction of butadiene is converted to peracetic acid or the like. It is obtained by partial epoxidation using an oxidizing agent.
  • 1,2-epoxy-4- (2-vinyl) cyclohexane a commercially available product can be used as 1,2-epoxy-4- (2-vinyl) cyclohexane.
  • the oxidant may be a known or conventional oxidant such as hydrogen peroxide or organic peracid, and is not particularly limited.
  • the organic peracid include performic acid, peracetic acid, peroxygen. Examples include benzoic acid and trifluoroperacetic acid. Among them, peracetic acid is preferable because it is industrially available at low cost and has high stability.
  • the standard polystyrene equivalent weight average molecular weight of the compound represented by the formula (II) is not particularly limited, but is preferably 300 to 100,000, more preferably 1,000 to 10,000.
  • the weight average molecular weight is less than 300, the mechanical strength and heat resistance of the cured product and the viscosity of the heated mixture of the present invention may be insufficient.
  • the weight average molecular weight exceeds 100,000, the viscosity becomes high and the fluidity during molding may decrease.
  • the weight average molecular weight is measured by a gel permeation chromatography (GPC) method.
  • the epoxy equivalent of the compound represented by the formula (II) is not particularly limited, but is preferably 50 to 1000, and more preferably 100 to 500. If the epoxy equivalent is less than 50, the cured product may become brittle. On the other hand, if the epoxy equivalent exceeds 1000, the mechanical strength of the cured product may be insufficient.
  • the epoxy equivalent is measured according to JIS K7236: 2001.
  • Examples of the compound (A-1-3) as the alicyclic epoxy compound (A-1) include 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2 , 2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] propane, hydrogenated bisphenol A type epoxy compound (hydrogenated bisphenol A type epoxy compound), etc .; 2- (2,3-epoxypropoxy) cyclohexyl] methane, [2- (2,3-epoxypropoxy) cyclohexyl] [4- (2,3-epoxypropoxy) cyclohexyl] methane, bis [ 4- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane Hydrogenated bisphenol F type epoxy compound (hydrogenated bisphenol F type epoxy compound), etc .; hydrogen
  • the compound (A-1) from the viewpoint of adjusting the heat resistance of the cured product (white reflector) and adjusting the heating mixture of the present invention to a predetermined viscosity, the compound (A-1-1), the compound (A -1-2) and compound (A-1-3) are preferable, and compound (A-1-1) and compound (A-1-3) are more preferable.
  • the heat resistance of the cured product (white reflector), the viscosity of the heated mixture of the present invention is further improved, and more excellent yellowing resistance (characteristic that is difficult to yellow), the pulverization property of the curable epoxy resin composition and / or
  • the compound represented by the above formula (I-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; for example, trade name “Celoxide 2021P” (( Manufactured by Daicel Co., Ltd.)], a compound represented by the above formula (II) [1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol; For example, trade name “EHPE3150” (manufactured by Daicel Corporation), etc.], hydrogenated bisphenol A type diglycidyl compound; for example, trade name “YX-8040” ( Mitsubishi Chemical Corporation)
  • heterocyclic epoxy compound (A-2) examples include heterocycles other than epoxy groups in the molecule [for example, tetrahydrofuran ring, tetrahydropyran ring, morpholine ring, chroman ring, isochroman ring, tetrahydrothiophene ring, tetrahydrothiopyran.
  • the heterocyclic epoxy compound (A-2) is preferably composed of a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom.
  • heterocyclic epoxy compound (A-2) examples include an isocyanurate having one or more epoxy groups in the molecule (hereinafter sometimes referred to as “epoxy group-containing isocyanurate”) or a glycoluril ring.
  • An epoxy compound having the same hereinafter sometimes referred to as “epoxy group-containing glycoluril” can be preferably used.
  • the number of epoxy groups in the molecule of the epoxy group-containing isocyanurate is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3.
  • the number of epoxy groups contained in the epoxy group-containing glycoluril is not particularly limited, but is preferably 1 to 6, more preferably 2 to 4.
  • epoxy group-containing isocyanurate examples include compounds represented by the following formula (III).
  • R 4 to R 6 are the same or different and each represents a hydrogen atom or a monovalent organic group. However, at least one of R 4 to R 6 is a monovalent organic group containing an epoxy group.
  • the monovalent organic group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group); a monovalent alicyclic hydrocarbon group (for example, a cycloalkyl group and a cycloalkenyl group). ); Monovalent aromatic hydrocarbon group (for example, aryl group); monovalent heterocyclic group; two or more of aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group are bonded And monovalent groups formed as above.
  • the monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom).
  • a substituent for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom.
  • Examples of the monovalent organic group containing an epoxy group include monovalent groups containing an epoxy group described later such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.
  • R 4 ⁇ R 6 in formula (III) may be the same or different, a group represented by the group or the following formula represented by the following formula (IIIa) (IIIb), the R 4 ⁇ R 6 It is preferable that at least one is a group represented by the formula (IIIa).
  • R 7 and R 8 in the above formulas (IIIa) and (IIIb) are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group.
  • R 7 and R 8 in formula (IIIa) and formula (IIIb) are particularly preferably hydrogen atoms.
  • the epoxy group-containing isocyanurate includes a compound represented by the following formula (III-1), a compound represented by the following formula (III-2), and a compound represented by the following formula (III-3). And the like.
  • R 7 and R 8 are the same or different and are the same as those in formula (IIIa) and formula (IIIb).
  • Representative examples of the compound represented by the formula (III-1) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2 -Methylpropenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate and the like.
  • Representative examples of the compound represented by the above formula (III-2) include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3-bis ( 2-methylpropenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate and the like.
  • Representative examples of the compound represented by the above formula (III-3) include triglycidyl isocyanurate, tris (2-methylepoxypropyl) isocyanurate, and the like.
  • the epoxy group-containing isocyanurate may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
  • Examples of the epoxy group-containing glycoluril include compounds represented by the following formula (IV).
  • R 9 to R 12 are the same or different and each represents a hydrogen atom or a monovalent organic group. However, at least one of R 9 to R 12 is a monovalent organic group containing an epoxy group. As said monovalent organic group, the same thing as the monovalent organic group in the above-mentioned epoxy-group-containing isocyanurate is mentioned. In addition, the monovalent organic group may have a substituent (for example, the same substituents as those exemplified as the substituent that the above-described alkyl group and alkylcarbonyl group may have).
  • R 9 to R 12 are the same or different and are preferably a monovalent organic group containing a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or an epoxy group. .
  • the monovalent organic group containing the epoxy group is an organic group containing at least one epoxy group (oxirane ring), for example, a linear or branched chain having a carbon-carbon double bond such as an alkenyl group.
  • 1,2-epoxyethyl group epoxy group
  • 1,2-epoxypropyl group 2,3-epoxypropyl group
  • 2,3-epoxy-2-methylpropyl Groups methyl glycidyl group
  • 3,4-epoxybutyl group 3-glycidyloxypropyl group, 3,4-epoxycyclohexylmethyl group, 2- (3,4-epoxycyclohexyl) ethyl group and the like.
  • a group having an epoxy group at least at the terminal is preferable, more preferably an ⁇ -epoxyalkyl group (a group in which the double bond at the terminal of the ⁇ -alkylene group is epoxidized), more preferably 2 6 is an ⁇ -epoxyalkyl group, more preferably a glycidyl group.
  • alkenyl group examples include substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group.
  • substituent examples include a halogen atom, a hydroxy group, and a carboxy group.
  • an ⁇ -alkenyl group an alkenyl group having a carbon-carbon unsaturated double bond at the terminal
  • an ⁇ -alkenyl group having 2 to 6 carbon atoms is more preferable
  • an allyl group is more preferable.
  • alkyl group examples include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl, s-butyl, and t-butyl.
  • substituent examples include a halogen atom, a hydroxy group, and a carboxy group. Of these, an alkyl group having 1 to 6 carbon atoms is preferable.
  • R 13 and R 14 are the same or different and each represents a hydrogen atom or a monovalent organic group.
  • said monovalent organic group the same thing as the monovalent organic group in the above-mentioned epoxy-group-containing isocyanurate is mentioned.
  • R 9 to R 12 in formula (IV) are the same or different and are a group represented by the following formula (IVa) or a group represented by the following formula (IVb), and R 9 to R 12 It is preferable that at least one is a group represented by the formula (IVa).
  • R 15 and R 16 in the above formulas (IVa) and (IVb) are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group.
  • R 15 and R 16 in formula (IVa) and formula (IVb) are particularly preferably a hydrogen atom.
  • the epoxy group-containing glycoluril includes a compound represented by the following formula (IV-1), a compound represented by the following formula (IV-2), and a compound represented by the following formula (IV-3).
  • R 15 and R 16 are the same or different and are the same as those in the formulas (IVa) and (IVb).
  • Representative examples of the compound represented by the above formula (IV-1) include 1,3,4,6-tetraglycidylglycoluril, 1,3,4,6-tetrakis (2-methylepoxypropyl) glycol. And uril.
  • Representative examples of the compound represented by the above formula (IV-2) include 1-allyl-3,4,6-triglycidylglycoluril, 1-allyl-3,4,6-tris (2-methyl Epoxypropyl) glycoluril, 1- (2-methylpropenyl) -3,4,6-triglycidylglycoluril, 1- (2-methylpropenyl) -3,4,6-tris (2-methylepoxypropyl) glycol And uril.
  • Representative examples of the compound represented by the above formula (IV-3) include 1,4-diallyl-3,6-diglycidyl glycoluril, 1,4-diallyl-3,6-bis (2-methyl). Epoxypropyl) glycoluril, 1,4-bis (2-methylpropenyl) -3,6-diglycidylglycoluril, 1,4-bis (2-methylpropenyl) -3,6-bis (2-methylepoxypropyl) ) Glycoluril and the like.
  • Representative examples of the compound represented by the above formula (IV-4) include 1,3-diallyl-4,6-diglycidylglycoluril, 1,3-diallyl-4,6-bis (2-methyl). Epoxypropyl) glycoluril, 1,3-bis (2-methylpropenyl) -4,6-diglycidylglycoluril, 1,3-bis (2-methylpropenyl) -4,6-bis (2-methylepoxypropyl) ) Glycoluril and the like.
  • Representative examples of the compound represented by the formula (IV-5) include 1,6-diallyl-3,4-diglycidylglycoluril, 1,6-diallyl-3,4-bis (2-methyl). Epoxypropyl) glycoluril, 1,6-bis (2-methylpropenyl) -3,4-diglycidylglycoluril, 1,6-bis (2-methylpropenyl) -3,4-bis (2-methylepoxypropyl) ) Glycoluril and the like.
  • Representative examples of the compound represented by the above formula (IV-6) include 1,3,4-triallyl-6-glycidylglycoluril, 1,3,4-triallyl-6- (2-methylepoxypropyl). ) Glycoluril, 1,3,4-tris (2-methylpropenyl) -6-glycidylglycoluril, 1,3,4-tris (2-methylpropenyl) -6- (2-methylepoxypropyl) glycoluril, etc. Is mentioned.
  • the epoxy group-containing glycoluril can be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
  • the heterocyclic epoxy compound (A-2) includes epoxy group-containing isocyanurate and epoxy group-containing glycoluril from the viewpoint of adjusting the heat resistance of the cured product (white reflector) and the heated mixture of the present invention to a predetermined viscosity.
  • an epoxy group-containing isocyanurate is more preferable.
  • the heat resistance of the cured product (white reflector), the viscosity of the heated mixture of the present invention is improved, and excellent yellowing resistance (characteristic that is difficult to yellow), and excellent crushability and / or tableting by a curable epoxy compound.
  • Triglycidyl isocyanurate for example, trade name “TEPIC-S” (manufactured by Nissan Chemical Industries)
  • monoallyl diglycidyl isocyanurate for example, trade name “MA-DGIC” (Shikoku)
  • 1,3,4,6-tetraglycidylglycoluril for example, trade name “TG-G” (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
  • monoallyl diglycidyl isocyanate Nurate is particularly preferred.
  • aromatic epoxy compound (A-3) examples include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol E type epoxy compounds, o-phenylphenol glycidyl ether, biphenyl type epoxy compounds, and phenol novolac type epoxy compounds.
  • Cresol novolak type epoxy compounds bisphenol A cresol novolak type epoxy compounds, naphthalene type epoxy compounds, epoxy compounds obtained from trisphenolmethane, and the like, and bisphenol A type epoxy compounds, Bisphenol F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, biphenyl type epoxy resin
  • bisphenol A type epoxy compounds Bisphenol F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, biphenyl type epoxy resin
  • the epoxy compound (A) can be used singly or in combination of two or more.
  • the epoxy compound (A) can also be produced by a known or conventional method.
  • trade names “Celoxide 2021P”, “Celoxide 2081”, “EHPE3150” manufactured by Daicel Corporation
  • products Commercial products such as the name “YX8040” (manufactured by Mitsubishi Chemical Corporation) can also be used.
  • the inorganic filler (B) in the curable epoxy resin composition of the present invention is mainly used to easily adjust the heated mixture of the present invention to a predetermined viscosity, and has good crushability and Or it has a function which gives tableting property and reduces the linear expansion coefficient of hardened
  • inorganic filler (B) known or conventional inorganic fillers can be used, and are not particularly limited.
  • Examples of the inorganic filler (B) include those obtained by subjecting the above-described inorganic filler to a known or conventional surface treatment. Among these, as the inorganic filler (B), silica (silica filler) is preferable from the viewpoint of adjusting the heated mixture of the present invention to a predetermined viscosity.
  • the silica is not particularly limited, and for example, known or commonly used silica such as fused silica, crystalline silica, high-purity synthetic silica or the like can be used.
  • Silica has been subjected to a known or conventional surface treatment [for example, surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone]. Can also be used.
  • the shape of the inorganic filler (B) is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, and scale shape. Among these, spherical inorganic fillers are preferable from the viewpoint of dispersibility, and spherical inorganic fillers (for example, spherical silica having an aspect ratio of 1.2 or less) are particularly preferable.
  • the center particle diameter of the inorganic filler (B) is not particularly limited, but is 0.1 to 50 ⁇ m from the viewpoint of improving the light reflectivity of the cured product (white reflector) and adjusting the heating mixture of the present invention to a predetermined viscosity. Preferably, it is 0.1 to 30 ⁇ m.
  • the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.
  • the inorganic filler (B) can be used alone or in combination of two or more.
  • the inorganic filler (B) can also be produced by a known or conventional production method.
  • FB series trade names “FB-910”, “FB-940”, “FB-950”, etc.
  • MSR-2212 trade names “MSR-25” (manufactured by Tatsumori Co., Ltd.)
  • HS-105 trade names “HS-106”
  • Commercial products such as “HS-107” (manufactured by Micron) can also be used.
  • White pigment (C) As the white pigment (C) in the heated mixture of the present invention, mainly, a high light reflectivity is imparted to the cured product (white reflector), the linear expansion coefficient is reduced, and the heated mixture of the present invention is used. It has the function of easily adjusting to a predetermined viscosity. As the white pigment (C), it is preferable to use a white pigment having a high refractive index in order to increase the reflectance of the reflector. For example, a white pigment having a refractive index of 1.5 or more is preferable.
  • the shell portion may be made of a material having a refractive index lower than 1.5.
  • the white pigment (C) may be a known or commonly used white pigment, and is not particularly limited. Examples thereof include glass, clay having a refractive index of 1.5 or more, mica, talc, kaolinite (kaolin), halloysite.
  • Inorganic white pigments such as zeolite, acid clay, activated clay, boehmite, pseudoboehmite, inorganic oxides, metal salts [for example, alkaline earth metal salts]; styrene resins, benzoguanamine resins, urea-formalin resins, Examples thereof include organic white pigments (plastic pigments and the like) such as resin pigments such as melamine-formalin resins and amide resins; hollow particles having a hollow structure (balloon structure), and the like.
  • Examples of the inorganic oxide include aluminum oxide (alumina), magnesium oxide, antimony oxide, titanium oxide [eg, rutile titanium oxide, anatase titanium oxide, brookite titanium oxide, etc.], zirconium oxide, zinc oxide, and the like. Can be mentioned.
  • Examples of the alkaline earth metal salt include magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, magnesium sulfate, calcium sulfate, and sulfuric acid. Barium etc. are mentioned.
  • Examples of the metal salt other than the alkaline earth metal salt include aluminum silicate, aluminum hydroxide, and zinc sulfide.
  • inorganic glass For example, silicate glass, aluminum silicate glass, sodium borosilicate glass, quartz, etc.], metal oxides, such as silica and alumina, calcium carbonate, barium carbonate, Inorganic hollow particles composed of inorganic materials such as nickel carbonate, calcium silicate and other metal salts (including natural products such as shirasu balloon); styrene resins, acrylic resins, silicone resins, acrylic-styrene resins, vinyl chloride -Based resins, vinylidene chloride-based resins, amide-based resins, urethane-based resins, phenol-based resins, styrene-conjugated diene-based resins, acrylic-conjugated diene-based resins, olefin-based polymers (including cross-linked products of these polymers), etc.
  • silicate glass aluminum silicate glass, sodium borosilicate glass, quartz, etc.
  • metal oxides such as silica and alumina, calcium
  • the said hollow particle may be comprised from the single material, and may be comprised from 2 or more types of materials.
  • the hollow portion of the hollow particles (the space inside the hollow particles) may be in a vacuum state or may be filled with a medium.
  • a medium for example, an inert gas such as nitrogen or argon or air
  • the white pigment (C) is subjected to a known or conventional surface treatment [for example, a surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone]. It may be what was done. By performing such a surface treatment, the compatibility and dispersibility with other components in the heated mixture of the present invention may be improved.
  • a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone.
  • the white pigment (C) an inorganic oxide is used from the viewpoint of adjusting the high reflectance of the cured product (white reflector) and the increase in light reflectivity with respect to the addition amount, and the heating mixture of the present invention to a predetermined viscosity. Titanium oxide is more preferable.
  • the shape of the white pigment (C) is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fibrous shape, a needle shape, and a scale shape.
  • spherical titanium oxide is preferable from the viewpoint of dispersibility, and spherical titanium oxide (for example, spherical titanium oxide having an aspect ratio of 1.2 or less) is particularly preferable.
  • the center particle diameter of the white pigment (C) is not particularly limited, but is preferably 0.1 to 50 ⁇ m from the viewpoint of improving the light reflectivity of the cured product (white reflector) and adjusting the heating mixture of the present invention to a predetermined viscosity.
  • the center particle diameter of the titanium oxide is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m.
  • the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.
  • the white pigment (C) can be used alone or in combination of two or more.
  • the white pigment (C) can also be produced by a known or conventional method.
  • the white pigment (C) in particular, from the viewpoint of adjusting the light reflectivity and yellowing resistance of a cured product (white reflector) and adjusting the heating mixture of the present invention to a predetermined viscosity, the trade name “R-62N”, “CR-60”, “DCF-T-17007", “DCF-T-17008", “DCF-T-17050”, “FTR-700” are preferable.
  • the heating mixture which comprises the curable epoxy resin composition of this invention is a heating mixture which consists of an epoxy compound (A) and at least 1 type selected from the group which consists of an inorganic filler (B) and a white pigment (C). And a shear viscosity at 25 ° C. of 10 to 1000 Pa ⁇ s.
  • the curable epoxy resin composition of the present invention contains a heated mixture having such characteristics, the curable epoxy resin composition is imparted with good crushability and / or tableting properties, and has a stickiness. It has the function of suppressing generation and facilitating handling and improving the heat resistance of the cured product (white reflector).
  • the shear viscosity of the heated mixture of the present invention at 25 ° C. is 10 to 1,000 Pa ⁇ s, preferably 10 to 500 Pa ⁇ s, and more preferably 10 to 300 Pa ⁇ s.
  • the shear viscosity at 25 ° C. of the heated mixture of the present invention is 10 Pa ⁇ s or more, it becomes easy to adjust the viscosity of the curable epoxy resin composition, the pulverization property and / or tableting property is improved, and the stickiness is increased. Occurrence can be easily suppressed.
  • the shear viscosity at 25 ° C. in the heated mixture of the present invention is adjusted by adjusting the blending ratio of the epoxy compound (A), the inorganic filler (B) and the white pigment (C), the heating / mixing conditions described later, and the like. Can be set to a range.
  • the shear viscosity at 25 ° C. in the heated mixture of the present invention can be measured on a parallel plate at 25 ° C. using a rheometer (for example, rheometer MCR302, manufactured by Anton Paar).
  • the heating mixture of the present invention uses a mixture of an epoxy compound (A) and at least one selected from the group consisting of an inorganic filler (B) and a white pigment (C), and heats and mixes the mixture. Is obtained.
  • the mixture may contain other additives such as a curing agent, a curing accelerator, and an antioxidant. However, in order for the heated mixture to be adjusted to the above-described shear viscosity range, other additives may be used. It is preferable not to contain.
  • a known apparatus such as a rotation / revolution mixer, a single or multi-screw extruder, a planetary mixer, a kneader, or a dissolver can be used without limitation.
  • the heating temperature is not particularly limited, but is usually preferably 50 to 120 ° C, more preferably 60 to 100 ° C. By setting the heating temperature within this range, it becomes easy to adjust the shear viscosity at 25 ° C. to a desired range.
  • the heating temperature may be adjusted to a constant temperature within the above range during heating and mixing, or may be varied within the above range.
  • the rotation speed in mixing is not particularly limited, but is usually preferably 10 to 10,000 rpm, more preferably 10 to 5000 rpm.
  • the rotation speed may be adjusted to a constant rotation speed within the above range during heating and mixing, or may be varied within the above range.
  • the heating / mixing time varies depending on the heating temperature and the rotation speed and is not particularly limited, but is usually preferably 0.5 to 24 hours, more preferably 0.5 to 18 hours. By setting the heating / mixing time within this range, it becomes easy to adjust the shear viscosity at 25 ° C. to a desired range.
  • the shear viscosity at 25 ° C. of the heated mixture can be adjusted to a predetermined range by the above heating and mixing is that the oxirane ring of the epoxy compound (A) is selected from the group consisting of inorganic filler (B) and white pigment (C)
  • the oxirane ring of the epoxy compound (A) is selected from the group consisting of inorganic filler (B) and white pigment (C)
  • a polar group for example, OH group
  • the heating mixture of the present invention contains the epoxy compound (A), it becomes easy to appropriately adjust the shear viscosity of the heating mixture at 25 ° C., and consequently, the pulverization property and / or tableting property of the curable epoxy resin composition is improved. There is a tendency to improve.
  • the content (blending amount) of the epoxy compound (A) in the heated mixture of the present invention is not particularly limited, but is preferably 1 to 99% by weight, more preferably based on the heated mixture (100% by weight) of the present invention. It is 10 to 95% by weight, more preferably 20 to 90% by weight.
  • the content of the epoxy compound (A) is 99% by weight or less, the pulverization property and / or tableting property of the curable epoxy resin composition tends to be improved.
  • the ratio of the compound (A-1-1) to the total amount (100 wt%) of the epoxy compound (A) contained in the heated mixture of the present invention is not particularly limited, but is preferably 5 to 100 wt%, more preferably 10 -100% by weight, more preferably 20-100% by weight.
  • the heated mixture of the present invention tends to be easily adjusted to a predetermined viscosity.
  • the ratio of the compound (A-1-2) to the total amount (100 wt%) of the epoxy compound (A) contained in the heated mixture of the present invention is not particularly limited, but is preferably 0 to 50 wt%, more preferably 0 To 45% by weight, more preferably 0 to 40% by weight.
  • the ratio of the compound (A-1-2) is 50% by weight or less, the heated mixture of the present invention tends to be easily adjusted to a predetermined viscosity.
  • the ratio of the compound (A-1-3) to the total amount (100 wt%) of the epoxy compound (A) contained in the heated mixture of the present invention is not particularly limited, but is preferably 0 to 50 wt%, more preferably 0 To 45% by weight, more preferably 0 to 40% by weight.
  • the ratio of the compound (A-1-3) is 50% by weight or less, the heated mixture of the present invention tends to be easily adjusted to a predetermined viscosity.
  • the heating mixture of the present invention contains the inorganic filler (B) and / or the white pigment (C), it becomes easy to appropriately adjust the shear viscosity of the heating mixture of the present invention at 25 ° C., and thus a curable epoxy resin. There exists a tendency for the grindability and / or tableting property of a composition to improve.
  • the heating mixture of the present invention may contain only the inorganic filler (B), may contain only the white pigment (C), or contains both the inorganic filler (B) and the white pigment (C). Also good.
  • the content (blending amount) of at least one selected from the group consisting of the inorganic filler (B) and the white pigment (C) in the heated mixture of the present invention is: Although not particularly limited, it is preferably 1 to 99% by weight, more preferably 5 to 90% by weight, and still more preferably 10 to 80% by weight with respect to the heated mixture (100% by weight) of the present invention.
  • the content of the inorganic filler or the like is 1% by weight or more, the pulverization property and / or tableting property of the curable epoxy resin composition tends to be improved.
  • the content of the inorganic filler or the like is 99% by weight or less, the shear viscosity of the heated mixture at 25 ° C. tends to be easily adjusted.
  • the content (blending amount) of the inorganic filler and the like with respect to the epoxy compound (A) in the heated mixture of the present invention is not particularly limited, but is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the epoxy compound (A), More preferred is 10 to 400 parts by weight, and still more preferred is 20 to 400 parts by weight.
  • the ratio (inorganic filler (B) / white pigment (C)) is not particularly limited, but is 100 / It may be appropriately selected from the range of 0 to 0/100, preferably 99/1 to 1/99, more preferably 95/5 to 5/95.
  • the curable epoxy resin composition of the present invention further includes an epoxy compound (A ′), an inorganic filler (B ′), a white pigment (C ′), a curing agent (D), a curing agent, in addition to the above heated mixture. Accelerators, antioxidants, mold release agents, and other components may be included. It is preferable that the curable epoxy resin composition of this invention contains a hardening
  • the curable epoxy resin composition of the present invention contains at least one selected from the group consisting of an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′) as necessary. It is also preferable to include.
  • the curable epoxy resin composition of the present invention contains at least one selected from the group consisting of an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′)
  • Heat resistance, yellowing resistance characteristics that are difficult to yellow
  • light reflectivity can be improved, and linear expansion coefficient can be reduced.
  • Epoxy compound (A ') As the epoxy compound (A ′) which may be contained in the curable epoxy resin composition of the present invention, a known or commonly used epoxy compound can be used, and is not particularly limited. For example, in the above-described epoxy compound (A), Epoxy compounds similar to those exemplified are exemplified. As the epoxy compound (A ′), the same epoxy compound as the above-described epoxy compound (A) may be used, or an epoxy compound different from the epoxy compound (A) may be used.
  • epoxy compound (A) is a mixture of two or more types of epoxy compounds
  • the epoxy compound (A ′) (1) a mixture having the same composition as the epoxy compound (A), (2) epoxy compound It may be any of a mixture having a composition different from (A), (3) a single epoxy compound constituting the epoxy compound (A), and (4) a single epoxy compound not constituting the epoxy compound (A).
  • Examples of the epoxy compound (A ′) include an alicyclic epoxy compound (A-1), a heterocyclic epoxy compound (A-2), and an aromatic epoxy from the viewpoint of heat resistance and light resistance of a cured product (white reflector).
  • the compound (A-3) is preferable, and the alicyclic epoxy compound (A-1) or the heterocyclic epoxy compound (A-2) is more preferable.
  • the compound (A-1-1) and the compound (A-1-2) Is more preferable, and the compound (A-1-2) is more preferable.
  • the compound [3, represented by the above formula (I-1) is more preferable in that the heat resistance of the cured product (white reflector) is further improved and more excellent yellowing resistance (characteristic that is difficult to yellow) is exhibited.
  • the curable epoxy resin composition of the present invention contains an epoxy compound (A ′), one kind can be used alone, or two or more kinds can be used in combination.
  • the epoxy compound (A ′) can also be produced by a known or conventional method.
  • the trade names “Celoxide 2021P”, “Celoxide 2081”, “EHPE3150” above, manufactured by Daicel Corporation
  • Commercial products such as trade name “TEPIC-S” (manufactured by Nissan Chemical Industries, Ltd.), trade names “MA-DGIC”, “TG-G” (manufactured by Shikoku Kasei Kogyo Co., Ltd.) can also be used.
  • the content (blending amount) of the epoxy compound (A ′) with respect to the epoxy compound (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy compound (A).
  • the amount is preferably 10,000 parts by weight, more preferably 10 to 1000 parts by weight, and still more preferably 10 to 500 parts by weight.
  • the linear expansion coefficient of the cured product (white reflector) is reduced, and problems such as warping of the lead frame on the substrate for mounting an optical semiconductor element are reduced. Occurrence tends to be more suppressed.
  • the total content (blending amount) of the epoxy compound (A) and the epoxy compound (A ′) in the curable epoxy resin composition of the present invention is not particularly limited, but is relative to the curable epoxy resin composition (100 wt%).
  • the content is preferably 1.5 to 15% by weight, more preferably 2 to 13% by weight, and still more preferably 2.5 to 10% by weight.
  • the heat resistance (particularly yellowing resistance) of the cured product (white reflector) tends to be further improved.
  • the total content 15% by weight or less the linear expansion coefficient of the cured product (white reflector) is reduced, and the occurrence of defects such as warping of the lead frame in the optical semiconductor element mounting substrate is further suppressed. There is a tendency to.
  • the ratio of the compound (A-1-1) to the total amount (100% by weight) of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition of the present invention is not particularly limited. It is preferably -95% by weight, more preferably 10-90% by weight, and more preferably 20-80% by weight.
  • the ratio of the compound (A-1-1) is 5% by weight or more, the heat resistance and light resistance of the cured product (white reflector) tend to be further improved.
  • the ratio of the compound (A-1-1) is 95% by weight or less, the pulverization property and / or tableting property of the curable epoxy resin composition tends to be secured at a high level.
  • the ratio of the compound (A-1-2) to the total amount (100% by weight) of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition of the present invention is not particularly limited. It is preferably -90% by weight, more preferably 10-80% by weight, and more preferably 20-70% by weight.
  • the ratio of the compound (A-1-2) is 1% by weight or more, the curable epoxy resin composition tends to be ensured at a high level of grindability and / or tabletability.
  • the ratio of the compound (A-1-2) is 90% by weight or less, the heat resistance and light resistance of the cured product (white reflector) tend to be further improved.
  • the ratio of the compound (A-1-3) to the total amount (100 wt%) of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition of the present invention is not particularly limited. It is preferably -90% by weight, more preferably 10-80% by weight, and more preferably 20-70% by weight. When the ratio of the compound (A-1-3) is 90% by weight or less, the heat resistance and light resistance of the cured product (white reflector) tend to be further improved.
  • the ratio of the heterocyclic epoxy compound (A-2) to the total amount (100% by weight) of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition of the present invention is not particularly limited. It is preferably 1 to 80% by weight, more preferably 5 to 70% by weight, and more preferably 10 to 60% by weight.
  • the ratio of the heterocyclic epoxy compound (A-2) is 1% by weight or more, the grindability and / or tabletability of the curable epoxy resin composition tends to be secured at a high level.
  • the ratio of the heterocyclic epoxy compound (A-2) is 95% by weight or less, the heat resistance and light resistance of the cured product (white reflector) tend to be further improved.
  • the ratio within the above range, the pulverization property and / or tableting property of the curable epoxy resin composition, the heat resistance, light resistance, and adhesion of the cured product tend to be improved in a well-balanced manner.
  • the curing agent (D) that may be contained in the curable epoxy resin composition of the present invention may be a known or commonly used curing agent for epoxy resins, and is not particularly limited.
  • acid anhydrides Acid anhydride curing agent
  • amines amine curing agent
  • polyamide resin imidazoles (imidazole curing agent)
  • polymercaptans polymercaptan curing agent
  • phenols phenol curing agent
  • Polycarboxylic acids, dicyandiamides, organic acid hydrazides and the like can be mentioned.
  • a liquid (liquid) curing agent at 25 ° C. is preferable in that a uniform curable epoxy resin composition can be efficiently prepared.
  • liquid at 25 ° C.” means a state at normal pressure.
  • acid anhydrides as the curing agent (D)
  • known or conventional acid anhydride-based curing agents can be used, and are not particularly limited.
  • methyltetrahydrophthalic anhydride Acid anhydrides such as acid, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc. at 25 ° C .
  • succinic anhydride hydrogenated pyromellitic anhydride, hydrogenated biphenyl dianhydride
  • Solid (solid) acid anhydrides at 25 ° C.
  • phthalic anhydride such as phthalic anhydride, tetrahydrophthalic anhydride (eg, 1,2,3,6-tetrahydrophthalic anhydride), hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, etc. Etc.
  • the acid anhydride curing agent for example, polyvalent carboxylic acid condensates described in JP2011-219534A can be used. Among them, it is preferable to use an acid anhydride that is liquid at 25 ° C.
  • amines (amine-based curing agent) as the curing agent (D) a known or conventional amine-based curing agent can be used, and is not particularly limited.
  • ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-amino Cycloaliphatic polyamines such as ethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylenediamine, p-phenylenediamine, Len-2
  • phenols phenolic curing agents
  • known or conventional phenolic curing agents can be used, and are not particularly limited.
  • novolac type phenol resins novolac type cresol resins
  • paraxylylene-modified phenols examples thereof include aralkyl resins such as resins, paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.
  • Examples of the polyamide resin as the curing agent (D) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.
  • imidazole (imidazole curing agent) as the curing agent (D), a known or conventional imidazole curing agent can be used, and is not particularly limited.
  • Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (D) include liquid polymercaptan and polysulfide resin.
  • Examples of the polycarboxylic acids as the curing agent (D) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and a compound represented by the following formula (1).
  • the compound represented by 1) is preferred.
  • R a represents an alkylene group having 1 to 6 carbon atoms
  • R b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carboxyl group.
  • R a and R b may be the same or different.
  • Ra include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, an isobutylene group, an isopentylene group, a neopentylene group, an isohexylene group, and a cyclohexylene group.
  • a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.
  • alkyl group having 1 to 6 carbon atoms in R b include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, A cyclopentyl group, a hexyl group, an isohexyl group, a cyclohexyl group and the like can be mentioned, and a methyl group is preferable from the viewpoint of heat-resistant transparency of the obtained cured product.
  • R b a methyl group and a carboxyl group are preferable, and the viewpoint that the viscosity at room temperature (25 ° C.) of the curable epoxy resin composition containing the curing agent (D) does not increase too much and the transparency of the resulting cured product are obtained.
  • a methyl group is preferable, and a carboxyl group is particularly preferable from the viewpoint of gas barrier properties, high glass transition temperature (Tg), and hardness of the obtained cured product.
  • a plurality of R a and R b may be the same or different from each other.
  • the curing agent (D) for example, a compound represented by the following formula (1 ′) in which R a is an ethylene group and R b is a methyl group is preferable.
  • a hardening agent (D) can also contain individually 1 type in the compound represented by Formula (1), and can also contain it in combination of 2 or more types among the compounds represented by Formula (1).
  • the compound represented by the formula (1) can be obtained by an addition reaction between a trishydroxyalkyl isocyanurate represented by the following formula (5) and a carboxylic acid anhydride compound represented by the following formula (6). it can.
  • R a are as defined above.
  • the compounds represented by the formula (5) are preferable from the viewpoint of transparency of the cured product and gas barrier properties.
  • R b represents the same meaning as described above.
  • the compounds represented by the formula (6) are particularly preferable.
  • the compound represented by formula (1) can be produced in a solvent or without a solvent.
  • the solvent any solvent that does not react with the trishydroxyalkyl compound of isocyanuric acid represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6) can be used without particular limitation.
  • solvents that can be used include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, and acetonitrile, ketones such as methyl ethyl ketone, cyclopentanone, and methyl isobutyl ketone, and toluene and xylene.
  • an aromatic hydrocarbon and ketones are preferable.
  • These solvents may be used alone or in combination of two or more.
  • the amount used in the case of using a solvent is 0. 0 with respect to a total of 100 parts by weight of the trishydroxyalkyl compound isocyanurate represented by the above formula (5) and the carboxylic anhydride compound represented by the formula (6). 5 to 300 parts by weight are preferred.
  • the compound represented by the formula (1) is often a solid at room temperature (25 ° C.), it is preferable to synthesize it in a solvent from the viewpoint of workability.
  • the compound represented by the formula (1) can be produced without a catalyst or with a catalyst.
  • usable catalysts are hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, nitric acid, trifluoroacetic acid, trichloroacetic acid and other acidic compounds, sodium hydroxide, potassium hydroxide, water Metal hydroxides such as calcium oxide and magnesium hydroxide, amine compounds such as triethylamine, tripropylamine and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, Heterocyclic compounds such as imidazole, triazole, tetrazole, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabut
  • a catalyst When using a catalyst, it can also be used 1 type or in mixture of 2 or more types.
  • the amount used in the case of using a catalyst is 0. 0 with respect to a total of 100 parts by weight of the trishydroxyalkyl compound isocyanurate represented by the above formula (5) and the carboxylic acid anhydride compound represented by the formula (6). 05 to 10 parts by weight is preferred.
  • the catalyst is added either directly or dissolved in a soluble solvent. At this time, it is preferable to avoid using an alcoholic solvent such as methanol or ethanol or water because it reacts with the unreacted carboxylic acid anhydride compound represented by the formula (6).
  • zinc carboxylate such as zinc octylate
  • calcium stearate in order to obtain a cured product having excellent transparency and resistance to sulfidation, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylate) and zinc phosphate ester ( Zinc compounds such as zinc octyl phosphate and zinc stearyl phosphate are preferably used.
  • the reaction temperature during the production of the compound represented by the formula (1) is usually 20 to 160 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 145 ° C., depending on the amount of catalyst and the solvent used.
  • the total reaction time is usually 1 to 20 hours, preferably 3 to 18 hours.
  • the reaction may be performed in two or more stages. For example, the reaction may be performed at 20 to 100 ° C. for 1 to 8 hours and then at 100 to 160 ° C. for 1 to 12 hours.
  • the carboxylic acid anhydride compound represented by the formula (6) is often highly volatile, and when such a compound is used, it is reacted at 20 to 100 ° C. and then reacted at 100 to 160 ° C. By doing so, volatilization can be suppressed. Thereby, not only the diffusion of harmful substances into the atmosphere can be suppressed, but also the compound represented by the formula (1) as designed can be obtained.
  • the catalyst can be removed by quenching and / or washing with water as necessary, but it is left as it is as a curing accelerator for the compound represented by the formula (1). It can also be used.
  • separated from water depending on the kind of solvent currently used.
  • Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone
  • esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate
  • hydrocarbons such as hexane, cyclohexane, toluene and xylene.
  • the acid value (measured by the method described in JIS K-2501) of the compound represented by the formula (1) produced is preferably 150 to 415 mgKOH / g, more preferably 185 to 375 mgKOH / g, particularly 200-320 mg KOH / g is preferred. If the acid value is 150 mgKOH / g or more, it is preferable because the mechanical properties of the cured product are improved, and if it is 415 mgKOH / g or less, the cured product does not become too hard and the elastic modulus becomes appropriate.
  • the functional group equivalent of the compound represented by the formula (1) is preferably 135 to 312 g / eq, more preferably 150 to 300 g / eq, and particularly preferably 180 to 280 g / eq.
  • the compound represented by the formula (1) preferably has a softening point of 20 to 150 ° C, more preferably 50 to 130 ° C.
  • various components can be easily stirred and mixed with a mixer, etc., and further kneaded or melt kneaded with a mixing roll, extruder, kneader, roll, extruder, etc., cooled, pulverized It becomes possible to do.
  • the curing agent (D) can be used alone or in combination of two or more.
  • the curing agent (D) compounds represented by the above formula (1), acid anhydrides (acid anhydride curing agents) and the like are preferable, and in particular, a curing agent containing a compound represented by the formula (1). (D) is preferred.
  • a curing agent (D) containing a compound having a specific structure represented by the formula (1) in the curable epoxy resin composition of the present invention excellent pulverizability to the curable epoxy resin composition. And / or tabletability is imparted, and excellent heat resistance and adhesion (particularly adhesion) and further toughness are imparted to the cured product (white reflector).
  • the curing agent (D) an embodiment including both the compound represented by the above formula (1) and acid anhydrides (acid anhydride curing agents) is also preferable.
  • the acid anhydrides are preferably liquid (liquid) acid anhydrides at 25 ° C. in that a uniform curable epoxy resin composition can be efficiently prepared.
  • acid anhydrides that are liquid at 25 ° C. are used, it is easy to mix with the compound represented by formula (1) to form a liquid mixture (curing agent composition) at 25 ° C. Productivity tends to improve.
  • the curing agent (D) can be produced by a known or conventional method.
  • trade names “Licacid MH-700”, “Licacid MH-700F”, “Licacid MH-700G”, “Licacid TH”, “ Ricacid HH, Ricacid MH-T, Ricacid HNA-100 above, Shin Nippon Rika Co., Ltd.
  • trade name “HN-5500” (Hitachi Chemical Industry Co., Ltd.)
  • trade name “H Commercially available products such as “-TMAn-S”, “H-TMAn” (manufactured by Mitsubishi Gas Chemical Co., Inc.); trade name “YH1120” (manufactured by Mitsubishi Chemical Co., Ltd.) can also be used.
  • the content (blending amount) is not particularly limited, but the epoxy compound (A) and the epoxy compound contained in the curable epoxy resin composition
  • the amount is preferably 50 to 200 parts by weight, more preferably 75 to 180 parts by weight, and still more preferably 80 to 150 parts by weight with respect to 100 parts by weight of the total amount of (A ′).
  • curing agent (D) is made into 50 weight part or more, hardening can be advanced more efficiently and there exists a tendency for the toughness of hardened
  • the content of the curing agent (D) is 200 parts by weight or less, there is a tendency that a cured product having no color (or little) and excellent in hue is easily obtained.
  • the content (blending amount) is not specifically limited, The amount is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, still more preferably 20 to 200 parts by weight, based on 100 parts by weight of the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained. .
  • the content of the compound represented by formula (1) is set to 1 part by weight or more, the pulverization property and / or tableting property of the curable epoxy resin composition, the heat resistance and adhesion of the cured product (white reflector). Tend to improve more.
  • the linear expansion coefficient of the cured product (white reflector) is further reduced, and the warpage of the lead frame in the substrate for mounting an optical semiconductor element is reduced. There is a tendency that the occurrence of defects such as these is further suppressed.
  • curing agent (D) contained in the curable epoxy resin composition of this invention contains the compound represented by Formula (1), it represents with Formula (1) with respect to the whole quantity (100 weight%) of hardening
  • the ratio of the compound to be formed is not particularly limited, but is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 15% by weight or more, still more preferably 20% by weight or more, and particularly preferably 25% by weight. That's it.
  • the ratio of the compound represented by the formula (1) By setting the ratio of the compound represented by the formula (1) to 10% by weight or more, the pulverization property and / or tableting property of the curable epoxy resin composition, the heat resistance and adhesion of the cured product (white reflector) are improved. There is a tendency to improve.
  • the content (blending amount) of the acid anhydrides in the case where the curing agent (D) of the present invention includes the compound represented by the formula (1) and the acid anhydrides is not particularly limited, but the formula (1)
  • the amount is preferably 0 to 1500 parts by weight, more preferably 10 to 1200 parts by weight, and still more preferably 20 to 1000 parts by weight with respect to 100 parts by weight of the compound represented by formula (1).
  • the curable epoxy resin composition of the present invention may contain a curing accelerator.
  • the curing accelerator is a reaction rate (curing rate) when the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition of the present invention react with a curing agent such as the curing agent (D). It is a compound which has the function which promotes.
  • a curing accelerator known or conventional curing accelerators can be used.
  • 1,8-diazabicyclo [5.4.0] undecene-7 DBU or a salt thereof (for example, a phenol salt, Octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, octylic acid) Salt, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; Imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; , Phosphines such as triphenyl
  • one type of curing accelerator can be used alone, or two or more types can be used in combination.
  • the curing accelerator can be produced by a known or conventional method.
  • trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X” are available.
  • content (blending amount) of the curing accelerator in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition.
  • the amount is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 8 parts by weight with respect to 100 parts by weight.
  • the inorganic filler (B ′) that may be contained in the curable epoxy resin composition of the present invention mainly imparts good pulverization properties and / or tabletability to the curable epoxy resin composition. Moreover, it has a function which reduces the linear expansion coefficient of hardened
  • inorganic filler (B ′) known or conventional inorganic fillers can be used, and are not particularly limited, and examples thereof include the same as the inorganic filler (B) described above.
  • silica silica filler
  • the same inorganic filler as the above-mentioned inorganic filler (B) may be used, or an inorganic filler different from the inorganic filler (B) may be used.
  • the inorganic filler (B) is a mixture of two or more kinds of inorganic fillers
  • the inorganic filler (B ′) (1) a mixture having the same composition as the inorganic filler (B), ( 2) a mixture having a composition different from that of the inorganic filler (B), (3) a single inorganic filler constituting the inorganic filler (B), and (4) a single inorganic filler not constituting the inorganic filler (B). Either may be sufficient.
  • the silica is not particularly limited, and for example, known or commonly used silica such as fused silica, crystalline silica, high-purity synthetic silica or the like can be used.
  • Silica has been subjected to a known or conventional surface treatment [for example, surface treatment with a surface treatment agent such as a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, or silicone]. Can also be used.
  • the shape of the inorganic filler (B ′) is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, and scale shape. Among these, spherical inorganic fillers are preferable from the viewpoint of dispersibility, and spherical inorganic fillers (for example, spherical silica having an aspect ratio of 1.2 or less) are particularly preferable.
  • the center particle diameter of the inorganic filler (B ′) is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m from the viewpoint of improving the light reflectivity of the cured product (white reflector). is there.
  • the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.
  • the inorganic filler (B ′) can be used alone or in combination of two or more.
  • the inorganic filler (B ′) can also be produced by a known or conventional production method.
  • FB series such as “FB-910”, “FB-940”, “FB-950”, etc. (Above, manufactured by Denki Kagaku Kogyo Co., Ltd.), trade names “MSR-2212”, “MSR-25” (above, made by Tatsumori), trade names “HS-105”, “HS-106”, Commercial products such as “HS-107” (manufactured by Micron) can also be used.
  • the curable epoxy resin composition (100% by weight) is preferably 60 to 90% by weight, more preferably 60 to 75% by weight.
  • the pulverization property and / or tableting property of the curable epoxy resin composition is further improved, and the linear expansion coefficient of the cured product (white reflector) is further reduced. Therefore, there is a tendency that problems such as warping of the lead frame in the optical semiconductor element mounting substrate are less likely to occur.
  • the curable epoxy resin composition has good fluidity, problems such as unfilling during molding (particularly transfer molding) tend to be suppressed. There is.
  • Total content of inorganic filler (B) and inorganic filler (B ′) relative to the total amount of epoxy compound (A), epoxy compound (A ′) and curing agent (D) in the curable epoxy resin composition of the present invention is not particularly limited, but is preferably 200 to 2000 parts by weight, more preferably 100 parts by weight based on the total amount of the epoxy compound (A), the epoxy compound (A ′), and the curing agent (D).
  • the amount is 220 to 1,500 parts by weight, more preferably 250 to 1,000 parts by weight.
  • the grindability and / or tabletability of the curable epoxy resin composition is further improved, There is a tendency that the linear expansion coefficient of the cured product (white reflector) becomes lower, and problems such as warping of the lead frame in the substrate for mounting an optical semiconductor element are less likely to occur.
  • the total content is set to 2000 parts by weight or less, since the curable epoxy resin composition has good fluidity, problems such as unfilling during molding (particularly transfer molding) tend to be suppressed. There is.
  • the white pigment (C ′) that may be contained in the curable epoxy resin composition of the present invention mainly imparts high light reflectivity to the cured product (white reflector), and its linear expansion coefficient. Has the function of reducing As the white pigment (C ′), a known or commonly used white pigment can be used, and is not particularly limited, but examples thereof are the same as the above-described white pigment (C ′). As the white pigment (C ′), the same white pigment as the above-mentioned white pigment (C) may be used, or a white pigment different from the white pigment (C) may be used.
  • the white pigment (C ′) includes (1) a mixture having the same composition as the white pigment (C), and (2) a white pigment.
  • the mixture may be any of a mixture having a composition different from (C), (3) a single white pigment constituting the white pigment (C), and (4) a single white pigment not constituting the white pigment (C).
  • the white pigment (C ′) is preferably an inorganic oxide, more preferably titanium oxide, from the viewpoint of the high reflectivity of the cured product (white reflector) and the increase in light reflectivity with respect to the addition amount.
  • the shape of the white pigment (C ′) is not particularly limited, and examples thereof include a spherical shape, a crushed shape, a fiber shape, a needle shape, and a scale shape.
  • spherical titanium oxide is preferable from the viewpoint of dispersibility, and spherical titanium oxide (for example, spherical titanium oxide having an aspect ratio of 1.2 or less) is particularly preferable.
  • the center particle diameter of the white pigment (C ′) is not particularly limited, but is preferably 0.1 to 50 ⁇ m from the viewpoint of improving the light reflectivity of the cured product (white reflector).
  • the center particle diameter of the titanium oxide is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 30 ⁇ m.
  • the said center particle size means the particle size (median diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction / scattering method.
  • the white pigment (C ′) can be used alone or in combination of two or more.
  • the white pigment (C ′) can also be produced by a known or conventional method.
  • trade names “SR-1”, “R-42”, “R-45M”, “R-650” , “R-32”, “R-5N”, “GTR-100”, “R-62N”, “R-7E”, “R-44”, “R-3L”, “R-11P”, “ “R-21”, “R-25”, “TCR-52”, “R-310”, “D-918”, “FTR-700” aboveve, manufactured by Sakai Chemical Industry Co., Ltd.
  • the white pigment (C ′) the trade names “R-62N”, “CR-60”, “DCF-T-” are particularly used from the viewpoint of improving light reflectivity and yellowing resistance of a cured product (white reflector). “17007”, “DCF-T-17008”, “DCF-T-17050”, “FTR-700” are preferable.
  • the total content (blending amount) of the white pigment (C ′) and the white pigment (C) in the curable epoxy resin composition of the present invention is not particularly limited, but relative to the curable epoxy resin composition (100 wt%).
  • the content is preferably 2 to 40% by weight, more preferably 10 to 30% by weight, and still more preferably 15 to 25% by weight.
  • the total content of the white pigment (C ′) and the white pigment (C) is 2% by weight or more, the light reflectivity of the cured product (white reflector) tends to be further improved.
  • the total content is 40% by weight or less, a decrease in fluidity of the curable epoxy resin composition due to the addition of the white pigment is suppressed, and workability tends to be further improved.
  • Total content of white pigment (C) and white pigment (C ′) relative to the total amount of epoxy compound (A), epoxy compound (A ′) and curing agent (D) in the curable epoxy resin composition of the present invention (formulation)
  • the amount is not particularly limited, but is preferably 3 to 400 parts by weight, more preferably 5 to 4 parts by weight with respect to 100 parts by weight of the total amount of the epoxy compound (A), the epoxy compound (A ′) and the curing agent (D). 350 parts by weight, more preferably 5 to 300 parts by weight.
  • Titanium oxide based on the total amount (100% by weight) of inorganic filler (B), inorganic filler (B ′), white pigment (C) and white pigment (C ′) contained in the curable epoxy resin composition of the present invention.
  • the ratio is not particularly limited, but is preferably 5 to 40% by weight, more preferably 10 to 35% by weight from the viewpoint of the balance between yellowing resistance and light reflectivity of the cured product (white reflector).
  • the ratio of titanium oxide 5% by weight or more the light reflectivity of the cured product (white reflector) tends to be further improved.
  • the proportion of titanium oxide is 40% by weight or less, the heat resistance (particularly yellowing resistance) of the cured product (white reflector) tends to be further improved.
  • liquidity fall of the curable epoxy resin composition by addition of a titanium oxide is suppressed, and there exists a tendency for workability
  • the total content (mixing amount) of C) and the white pigment (C ′) is not particularly limited, but is 100 parts by weight with respect to the total amount of the epoxy compound (A), the epoxy compound (A ′) and the curing agent (D).
  • the amount is preferably 200 to 2,000 parts by weight, more preferably 250 to 1,800 parts by weight, and still more preferably 300 to 1,500 parts by weight.
  • the total content of the inorganic filler (B), inorganic filler (B ′) white pigment (C) and white pigment (C ′) 200 parts by weight or more, the light reflectivity of the cured product (white reflector) Tend to improve more.
  • the total amount is 2,000 parts by weight or less, a decrease in fluidity of the curable epoxy resin composition due to the addition of the inorganic filler and the white pigment is suppressed, and workability tends to be further improved.
  • the curable epoxy resin composition of the present invention may further contain a release agent.
  • a release agent By including a release agent, continuous molding by a molding method using a mold such as transfer molding becomes easy, and a cured product (white reflector) can be produced with high productivity.
  • a known or commonly used release agent can be used, and is not particularly limited.
  • a fluorine-based release agent fluorine atom-containing compound
  • Silicone release agents silicone compounds; for example, silicone oil, silicone wax, silicone resin, polyorganosiloxane having a polyoxyalkylene unit
  • wax release agents wax release agents
  • animal waxes such as wool wax, paraffins such as paraffin wax, polyethylene wax, oxidized polyethylene wax, etc.
  • higher fatty acids or salts thereof for example, metal salts
  • higher fatty acid esters higher fatty acid amides, mineral oils, etc.
  • one type of release agent can be used alone, or two or more types can be used in combination.
  • a mold release agent can also be manufactured by a well-known thru
  • the content (blending amount) of the release agent in the curable epoxy resin composition of the present invention is not particularly limited, but is the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition.
  • the amount is preferably 1 to 12 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight.
  • the curable epoxy resin composition of the present invention may contain an antioxidant.
  • an antioxidant By containing an antioxidant, it becomes possible to produce a cured product (white reflector) having further excellent heat resistance (particularly yellowing resistance).
  • known or commonly used antioxidants can be used, and are not particularly limited. For example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus System antioxidants (phosphorus compounds), sulfur antioxidants (sulfur compounds), and the like.
  • phenolic antioxidants examples include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ - (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl- 6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl] 2,4,8,10-tetraoxa Bisphenols such as spiro [5.5] undecane; 1,1,3-tris (2-methyl-4
  • hindered amine antioxidants include bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl. ] Butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy- Examples include 2,2,6,6-tetramethylpiperidine.
  • phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (2 , 4-di-tert-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- ⁇ 2- (octade
  • sulfur-based antioxidant examples include dodecanethiol, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate Is mentioned.
  • the antioxidant can be used singly or in combination of two or more.
  • Antioxidants can also be produced by known or conventional methods. For example, trade names “Irganox 1010” (manufactured by BASF, phenolic antioxidants), trade names “AO-60”, “AO-80”.
  • a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant are preferable.
  • a phenolic antioxidant and a phosphorus antioxidant or a sulfur antioxidant are used in combination. It is preferable to use a phenol-based antioxidant and a phosphorus-based antioxidant in combination.
  • content (blending amount) of the antioxidant in the curable epoxy resin composition of the present invention is not particularly limited, the total amount of the epoxy compound (A) and the epoxy compound (A ′) contained in the curable epoxy resin composition.
  • the amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight.
  • the curable epoxy resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired in addition to the above-described components.
  • a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin
  • the reaction can be allowed to proceed slowly.
  • antifoaming agents, leveling agents, silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, surfactants, as long as the viscosity and transparency are not impaired.
  • Conventional additives such as flame retardants, colorants, ion adsorbents, and pigments can be used. The content of these additives is not particularly limited and can be appropriately selected.
  • the curable epoxy resin composition of the present invention is not particularly limited, the heated mixture of the present invention and, if necessary, an epoxy compound (A ′), an inorganic filler (B ′), a white pigment (C ′), It can prepare by mix
  • the mixing method is not particularly limited, and for example, known or commonly used mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used.
  • the curable epoxy resin composition of the present invention may be either liquid or solid, but is preferably solid at least at 30 ° C. and normal pressure.
  • the ICI cone plate viscosity is usually 0.01 to 10 Pa ⁇ s in the range of 100 to 200 ° C. By adjusting to the said range, it becomes solid at normal temperature (25 degreeC), becomes easy to shape
  • each component which has been difficult to knead because of its high crystallinity and has a high softening point or melting point, is sufficiently melted and dispersed in the curing agent.
  • the softening point of the curable epoxy resin composition of the present invention is preferably 40 to 130 ° C., more preferably 50 to 100 ° C., and particularly preferably 70 to 100 ° C. By being at such a softening point, sufficient kneading can be performed.
  • the curable epoxy resin composition of the present invention is obtained by heating and reacting a part of the heated mixture of the present invention, the epoxy compound (A ′) and the curing agent in the curable epoxy resin composition, It may be a B-stage curable epoxy resin composition (B-stage curable epoxy resin composition).
  • the curable epoxy resin composition of the present invention is excellent in grindability and / or tabletability, it can be preferably used particularly as a resin composition for transfer molding or a resin composition for compression molding. Specifically, for example, the curable epoxy resin composition of the present invention can be subjected to transfer molding or compression molding by pulverization and tableting to prepare a tablet.
  • the heating temperature (curing temperature) at the time of curing is not particularly limited, but is preferably 100 to 200 ° C, more preferably 150 to 190 ° C. Further, the heating time (curing time) during the curing is not particularly limited, but is preferably 60 to 600 seconds, more preferably 90 to 240 seconds. When the curing temperature and curing time are lower than the lower limit of the above range, the curing is insufficient. May decrease.
  • the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased. Further, the curing process may be performed in one step (for example, transfer molding only) or, for example, in multiple steps (for example, further heating in an oven or the like as post-curing (secondary curing) after transfer molding). Also good.
  • the curable epoxy resin composition of the present invention is a curable epoxy resin composition for a white reflector as described above. That is, the curable epoxy resin composition of the present invention is a molding material (gold) used for forming a white reflector (light reflecting member) of an optical semiconductor element substrate (an optical semiconductor element mounting substrate) in an optical semiconductor device. Material used for molding with a mold or the like). Accordingly, by molding (and curing) the curable epoxy resin composition of the present invention, a high-quality (for example, highly durable) optical semiconductor element mounting substrate having a white reflector excellent in heat resistance is manufactured. can do.
  • the curable epoxy resin composition of the present invention is a molding material (gold) used for forming a white reflector (light reflecting member) of an optical semiconductor element substrate (an optical semiconductor element mounting substrate) in an optical semiconductor device. Material used for molding with a mold or the like). Accordingly, by molding (and curing) the curable epoxy resin composition of the present invention, a high-quality (for example, highly durable) optical semiconductor element mounting substrate having
  • the substrate for mounting an optical semiconductor element of the present invention comprises a white reflector formed of a cured product of the curable epoxy resin composition of the present invention (cured product obtained by curing the curable epoxy resin composition of the present invention). It is a substrate having at least.
  • FIG. 1 is a schematic view showing an example of a substrate for mounting an optical semiconductor element of the present invention, where (a) is a perspective view and (b) is a cross-sectional view.
  • 100 is a white reflector
  • 101 is a metal wiring (lead frame)
  • 102 is an optical semiconductor element mounting region
  • 103 is a package substrate.
  • a metal wiring 101 and a white reflector 100 are attached to the package substrate 103, and an optical semiconductor element 107 is placed in the center (optical semiconductor element mounting region 102) and die bonded. 107 and the metal wiring 101 on the package substrate 103 are connected by wire bonding.
  • As the material of the package substrate 103 resin, ceramic, or the like is used, but it may be the same as the white reflector.
  • the upper white reflector 100 in the optical semiconductor element mounting substrate of the present invention has a concave shape that surrounds the optical semiconductor element mounting region 102 in an annular shape and is inclined so that the diameter of the ring increases upward. Have.
  • the substrate for mounting an optical semiconductor element of the present invention only needs to have at least the inner surface of the concave shape formed of a cured product of the curable epoxy resin composition of the present invention.
  • the portion surrounded by the metal wiring 101 may be the package substrate 103 or the white reflector 100 (that is, “100/103 in FIG. 1). "Means the white reflector 100 or the package substrate 103).
  • the optical semiconductor element mounting substrate of the present invention is not limited to the embodiment shown in FIG.
  • a known or conventional molding method for example, transfer molding or the like
  • a method of subjecting the conductive epoxy resin composition to various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by dispensing.
  • a white reflector (or a substrate for mounting an optical semiconductor element having the white reflector) can be manufactured.
  • the curing conditions at this time can be appropriately selected from, for example, conditions for forming the above-described cured product.
  • the optical semiconductor device of the present invention can be obtained by using the optical semiconductor element mounting substrate of the present invention as a substrate in an optical semiconductor device and mounting the optical semiconductor element on the substrate.
  • the optical semiconductor device of the present invention is an optical semiconductor device having at least the optical semiconductor element mounting substrate of the present invention and an optical semiconductor element mounted on the substrate. Since the optical semiconductor device of the present invention has a white reflector formed of a cured product of the curable epoxy resin composition of the present invention as a white reflector, it has excellent productivity, high light extraction efficiency, and brightness over time. It is also excellent in durability, such as being difficult to decrease.
  • FIG. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention. In FIG.
  • 100 is a white reflector
  • 101 is a metal wiring (lead frame)
  • 103 is a package substrate
  • 104 is a bonding wire
  • 105 is a sealing material
  • 106 is a die bonding material
  • 107 is an optical semiconductor element (LED element).
  • the light emitted from the optical semiconductor element 107 is reflected by the surface (reflecting surface) of the white reflector 100, so that the light from the optical semiconductor element 107 is extracted with high efficiency.
  • the optical semiconductor element in the optical semiconductor device of the present invention is usually sealed with a transparent sealing material (105 in FIG. 2).
  • FIGS. 3 and 4 are diagrams showing another example of the optical semiconductor device of the present invention.
  • Reference numeral 108 in FIGS. 3 and 4 denotes a heat sink (case heat sink), and by having such a heat sink 108, the heat radiation efficiency in the optical semiconductor device is improved.
  • 3 is an example in which the heat dissipation path of the heat sink is located immediately below the optical semiconductor element
  • FIG. 4 is an example in which the heat dissipation path of the heat sink is positioned in the lateral direction of the optical semiconductor device [(a) is a top view, (B) shows a cross-sectional view along AA ′ in (a)].
  • the heat sink 108 protruding from the side surface of the optical semiconductor device in FIG. 4 may be referred to as a heat radiating fin.
  • reference numeral 109 in FIG. 4 denotes a cathode mark.
  • the optical semiconductor device of the present invention is not limited to the embodiment shown in FIGS.
  • the unit of the compounding quantity of each component of the curable epoxy resin composition in Table 1 is parts by weight.
  • Synthesis example 1 [Manufacture of curing agent] Under a nitrogen atmosphere, 438.5 g of 1,3,5-tris (2-hydroxyethyl) isocyanuric acid, 440.4 g of methyl amyl ketone, and 840.0 g of methyl hexahydrophthalic anhydride were placed in a reaction vessel. During the synthesis, the reaction vessel was slowly purged with nitrogen. Next, the mixture in the reaction vessel was heated to 150 ° C. with stirring (it was confirmed that most 1,3,5-tris (2-hydroxyethyl) isocyanuric acid was dissolved at 123 ° C.). After holding at about 150 ° C. for 1 hour, the mixture was cooled to 134 ° C.
  • the nonvolatile content obtained in Synthesis Example 1 was a compound (curing agent) represented by the following formula (1 ′).
  • Synthesis example 2 [Production of heated mixture] As shown in Table 1, 20 parts by weight of an alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation) and fused silica (trade name “FB-910”, manufactured by Denki Kagaku Kogyo Co., Ltd.) 30 parts by weight were put into a planetary mixer (TK Hibismix 2P-03, manufactured by Primics Co., Ltd.), heated to 80 ° C. in a nitrogen atmosphere, stirred at 50 rpm for 1.5 hours, and heated. The mixture was obtained as a white viscous wax. The shear viscosity at 25 ° C. of the obtained heated mixture was 90 Pa ⁇ s. The shear viscosity was measured with a parallel plate at 25 ° C. using a rheometer MCR302 (manufactured by Anton Paar).
  • TK Hibismix 2P-03 manufactured by Primics Co., Ltd.
  • Example 1 As shown in Table 1, 50 parts by weight of the heating mixture prepared in Synthesis Example 2, 20 parts by weight of an alicyclic epoxy compound (trade name “EHPE3150”, manufactured by Daicel Corporation), an acid anhydride curing agent (trade name “ 45 parts by weight of Spaincid MH-700, manufactured by Shin Nippon Rika Co., Ltd., 1 part by weight of a curing accelerator (trade name “UCAT-5003”, manufactured by San Apro Co., Ltd.), a curing accelerator (trade name “PX-4ET” ”, 0.5 parts by weight of Nippon Chemical Industry Co., Ltd., 0.3 parts by weight of antioxidant (trade name“ AO-80 ”, ADEKA Co., Ltd.), antioxidant (trade name“ PEP36 ”, ADEKA Co., Ltd.) 0.3 parts by weight, release agent (trade name “Electol WEP-5”, manufactured by NOF Corporation) 2 parts by weight, white pigment (titanium oxide; trade name “DCF-T-17007) "Resino Color Industry Co.
  • the obtained curable epoxy resin composition was not sticky, and there was no blocking of the pulverized product in the pulverization step and tablet tableting step, and it was easy to handle.
  • Examples 2 to 6 A curable epoxy resin composition was obtained in the same manner as in Synthesis Example 2 and Example 1, except that the composition of the heated mixture and the composition of the curable epoxy resin composition were changed as shown in Table 1.
  • the shear viscosity at 25 ° C. of the heated mixtures obtained in Examples 2 to 6 was measured in the same manner as in Synthesis Example 2. The results are shown in Table 1.
  • the curable epoxy resin compositions obtained in Examples 2 to 6 had no stickiness, and there was no blocking of the pulverized product in the pulverization process and the tableting process, and the handling was easy.
  • Synthesis example 3 An unheated mixture was obtained in the same manner as in Synthesis Example 2 except that the mixing was performed at room temperature (25 ° C.). When the shear viscosity at 25 ° C. of the obtained mixture was measured by the same method as in Synthesis Example 2, it was 2 Pa ⁇ s. Comparative Example 1 A curable epoxy resin composition was obtained in the same manner as in Example 1 except that the unheated mixture prepared in Synthesis Example 3 was used instead of the heated mixture prepared in Synthesis Example 2. The curable epoxy resin composition obtained in Comparative Example 1 had stickiness, and the pulverized product caused blocking in the pulverization step and tablet tableting step, and was difficult to handle.
  • ⁇ Crushability When the curable epoxy resin composition is pulverized by a pulverizer, the case where no resin fusion occurs in the pulverizer is ⁇ (good pulverization), and the case where resin fusion occurs is ⁇ (pulverization) Defective).
  • ⁇ Tabletability When the curable epoxy resin composition is tableted with a tableting machine, there is no resin adhesion to the tableting machine (dies and punches) and there is no tablet deformation after tableting. The case where there was any one or both of good tabletability), resin adhesion and tablet deformation was defined as x (poor tabletability).
  • EHPE3150 (Epoxy compound (A ')) EHPE3150: Trade name “EHPE3150” (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol), MA-DGIC manufactured by Daicel Corporation Name “MA-DGIC” (monoallyl diglycidyl isocyanurate), manufactured by Shikoku Chemicals Co., Ltd.
  • MSR-2212 trade name “MSR-2212” (high purity spherical silica), manufactured by Tatsumori (white pigment (C ′))
  • DCF-T-17007 Trade name “DCF-T-17007” (titanium oxide), manufactured by Resino Color Industry Co., Ltd.
  • Rikacid MH-700 Trade name “Rikacid MH-700” (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride), manufactured by Shin Nippon Rika Co., Ltd.
  • Synthesis Example 1 Curing agent obtained in Synthesis Example 1: Compound represented by the above formula (1 ′) (curing accelerator)
  • UCAT-5003 Trade name “UCAT-5003” (quaternary phosphonium bromide), DBA / octylate manufactured by San Apro Co., Ltd .: Trade name “DBU / octylate”, San Apro Co., Ltd.
  • PX-4ET Product Name “Hishicolin PX-4ET” (tetra-n-butylphosphonium-o, o-diethylphosphorodithionate), manufactured by Nippon Chemical Industry Co., Ltd.
  • AO80 Trade name “AO-80” (phenolic antioxidant), manufactured by ADEKA Corporation
  • PEP36 Trade name “Adekastab PEP36” (phosphorous antioxidant), manufactured by ADEKA Corporation (release agent)
  • Electol WEP-5 Trade name "Electol WEP-5", manufactured by NOF Corporation
  • the curable epoxy resin composition for a white reflector of the present invention is excellent in pulverization and / or tableting properties, and is easy to handle without causing stickiness, and also has excellent heat resistance when cured. Can be formed. Therefore, the curable epoxy resin composition for a white reflector of the present invention has a high-quality (for example, highly durable) optical semiconductor element mounting substrate having a white reflector excellent in productivity and heat resistance, and the above-mentioned
  • the substrate for mounting an optical semiconductor element can be suitably used for a high-quality (for example, highly durable) optical semiconductor device having a substrate in the optical semiconductor device.
  • White reflector 101 Metal wiring (lead frame) 102: Mounting area of optical semiconductor element 103: Package substrate 104: Bonding wire 105: Sealing material for optical semiconductor element 106: Die bonding material 107: Optical semiconductor element 108: Heat sink 109: Cathode mark

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Compounds (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Abstract

L'invention a pour objet de fournir une composition de résine époxy durcissable pour moulage de réflecteur blanc qui présente d'excellentes propriétés en termes de fragibilité et/ou de pastillage, dont la manipulation est aisée sans apparition de poissage, et qui permet de former un article durci de résistance à la chaleur excellente. Plus précisément, l'invention concerne une composition de résine époxy durcissable pour réflecteur blanc qui contient un mélange chauffé contenant au moins un élément choisi dans un groupe constitué d'un composé époxy (A), d'une charge inorganique (B) et d'un pigment blanc (C), le coefficient de viscosité de cisaillement à 25°C de ce mélange étant compris entre 10 et 1000Pa.s. L'invention concerne également un article durci de cette composition, un substrat pour montage d'élément photo-semi-conducteur possédant un réflecteur blanc formé à l'aide de cet article durci, un dispositif photo-semi-conducteur possédant un élément photo-semi-conducteur monté sur ledit substrat, et des procédés de fabrication de la composition de résine époxy durcissable pour réflecteur blanc, de l'article durci, ou similaire.
PCT/JP2017/004206 2016-02-08 2017-02-06 Composition de résine époxy durcissable pour réflecteur blanc ainsi qu'article durci de celle-ci, substrat pour montage d'élément photo-semi-conducteur, dispositif photo-semi-conducteur, et procédés de fabrication associés Ceased WO2017138487A1 (fr)

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CN113573747B (zh) 2019-03-28 2023-02-24 泰尔茂株式会社 医疗器具
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