WO2017138487A1 - Curable epoxy resin composition for white reflector and cured product of same, substrate for mounting optical semiconductor element, optical semiconductor device, and manufacturing method - Google Patents

Curable epoxy resin composition for white reflector and cured product of same, substrate for mounting optical semiconductor element, optical semiconductor device, and manufacturing method 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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group
resin composition
epoxy resin
compound
white
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PCT/JP2017/004206
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French (fr)
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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クラスターテクノロジー株式会社
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Publication of WO2017138487A1 publication Critical patent/WO2017138487A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • 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

Abstract

The purpose of the present invention is to provide a curable epoxy resin composition for molding a white reflector, whereby a cured product can be formed which has excellent grinding properties and/or tableting properties, is easily handled and has no tackiness, and has excellent heat resistance as well. The present invention is: a curable epoxy resin composition for a white reflector, including a hot mix including an epoxy compound (A) and at least one species selected from the group consisting of an inorganic filler (B) and a white pigment (C), the shear viscosity thereof at 25°C being 10-1000 Pa•s; a cured product of the same; a substrate for mounting an optical semiconductor element having a white reflector formed from the cured product; an optical semiconductor device having an optical semiconductor element mounted on the substrate; and a method for manufacturing the curable epoxy resin composition for a white reflector, a cured product of the same, or the like.

Description

白色リフレクター用硬化性エポキシ樹脂組成物及びその硬化物、光半導体素子搭載用基板、光半導体装置、並びに製造方法Curable epoxy resin composition for white reflector and cured product thereof, substrate for mounting optical semiconductor element, optical semiconductor device, and manufacturing method
　本発明は、白色リフレクター用硬化性エポキシ樹脂組成物及びその硬化物、該硬化物により形成された白色リフレクターを有する光半導体素子搭載用基板、該基板と光半導体素子とを有する光半導体装置、並びに、該白色リフレクター用硬化性エポキシ樹脂組成物、硬化物等の製造方法に関する。本願は、２０１６年２月８日に日本に出願した特願２０１６－０２２１０３号の優先権を主張し、その内容をここに援用する。 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. This application claims the priority of Japanese Patent Application No. 2016-022103 for which it applied to Japan on February 8, 2016, and uses the content here.
　近年、各種の屋内又は屋外表示板、画像読み取り用光源、交通信号、大型ディスプレイ用ユニット等においては、光半導体素子（ＬＥＤ素子）を光源とする発光装置（光半導体装置）の採用が進んでいる。このような光半導体装置としては、一般に、基板（光半導体素子搭載用基板）上に光半導体素子が搭載され、さらに該光半導体素子が透明な封止材により封止された光半導体装置が普及している。このような光半導体装置における基板には、光半導体素子から発せられる光の取り出し効率を高めるため、光を反射させるための部材（白色リフレクター）が形成されている。 2. Description of the Related Art In recent years, 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. . As such 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. On the substrate in such an optical semiconductor device, a member (white reflector) for reflecting light is formed in order to increase the extraction efficiency of light emitted from the optical semiconductor element.
　上記白色リフレクターには、高い光反射性を有することが求められている。従来、上記白色リフレクターとしては、例えば、芳香族骨格を有さず、かつ構成する原子が炭素原子、酸素原子及び水素原子の３種のみであるエポキシ化合物と、酸無水物硬化剤と、酸化チタンと、酸化チタンとは異なる充填材とを含む光半導体装置用白色硬化性組成物が知られており、当該組成物をトランスファー成型、コンプレッション成型等の金型を用いて成型することによって白色リフレクターが得られていた（特許文献１参照）。 The white reflector is required to have high light reflectivity. Conventionally, as 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 And 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).
特許第５１４３９６４号公報Japanese Patent No. 5143964
　上述の特許文献１に記載の材料より作製した白色リフレクターは、高出力の青色光半導体や白色光半導体を光源とする光半導体装置において、半導体素子から発せられる熱によって経時で黄変する等して劣化し、光反射性が経時で低下するという問題を有していた。このため、白色リフレクターを形成するための材料としては、熱による光反射率の低下が少ないもの（即ち、耐熱性に優れるもの）が求められているのが現状である。 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).
　また、上記白色リフレクターは、一般に、該白色リフレクターを形成するための材料（樹脂組成物）を、トランスファー成型やコンプレッション成型に付すことによって製造される。このため、上記樹脂組成物はタブレット状に成型する必要があり、そのためには粉砕できる特性（粉砕性）及び／又は打錠できる特性（打錠性）とを兼ね備えたものである必要がある。しかしながら、上記特許文献１に記載の材料は、原料の配合によっては、原料の混練後は比較的軟らかくなるため、粉砕ができず打錠できない場合があった。また、製造工程で樹脂組成物にべとつきが発生し、取り扱いにくいという問題もあった。 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). However, 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. In addition, there is a problem that the resin composition becomes sticky during the production process and is difficult to handle.
　従って、本発明の目的は、粉砕性及び／又は打錠性に優れており、さらにべとつきが発生せず取扱いが容易であり、なおかつ耐熱性に優れた硬化物を形成でき白色リフレクター用硬化性エポキシ樹脂組成物を提供することにある。
　また、本発明の他の目的は、生産性、及び耐熱性に優れ、白色リフレクターの構成材料として有用な硬化物を提供することにある。
　さらに、本発明の他の目的は、生産性、及び耐熱性に優れた白色リフレクターを有する高品質な光半導体素子搭載用基板を提供することにある。
　さらに、本発明の他の目的は、上記光半導体素子搭載用基板を有する高品質な光半導体装置を提供することにある。 Accordingly, 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.
　なお、上記白色リフレクターには、光半導体素子搭載用基板のリードフレーム（例えば、銀メッキ銅フレーム、金メッキ銅フレーム、銅製の電極やヒートシンク等）に対する密着性や封止材（例えば、シリコーン系の封止材）に対する密着性（以下、これらの密着性を、単に「密着性」と称する場合がある）に優れることが求められる。特に、リードフレームに対する密着性に劣る場合、光半導体素子搭載用基板の成型後、光半導体装置を個片化するためにパンチングやダイシングした場合に、白色樹脂がリードフレームから剥離する不良が発生する場合がある。一方、封止材に対する密着性に劣る場合は、水分や硫黄化合物が浸入しやすくなり、銀メッキの腐食によって光半導体装置が暗くなったり、吸湿はんだリフロー試験で封止材が剥離したりワイヤーが断線したりして、光半導体装置が不灯となる等の不良が発生する場合がある。 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. On the other hand, when the adhesion to the encapsulant is inferior, moisture and sulfur compounds are likely to enter, and 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.
　また、上記白色リフレクターには、さらに有することが望ましい特性として、リードフレームからの剥離やリードフレームの反り等の不具合を生じさせないため、できるだけ線膨張係数が低いことも求められる。 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.
　さらに、上記白色リフレクターは、上述のように、該白色リフレクターを形成するための材料（樹脂組成物等）を、トランスファー成型やコンプレッション成型等の金型を用いた成型（成形）方法に付すことにより作製される。このため、上記白色リフレクターを形成するための材料には、さらに有することが望ましい特性として、金型を使用したトランスファー成型やコンプレッション成型における生産性の観点から、成型後の金型からの離型性に優れることも求められる。 Further, as described above, 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.
　本発明者らは、上記課題を解決するため鋭意検討した結果、白色リフレクター用硬化性エポキシ樹脂組成物を製造するに際して、エポキシ化合物と、無機充填剤及び白色顔料からなる群より選択される少なくとも一種とを、事前に加熱・混合した混合物を必須成分として含む白色リフレクター用硬化性エポキシ樹脂組成物が、粉砕性及び／又は打錠性に優れ、さらにはべとつきが発生せず取扱いが容易であることを見出した。また、上記硬化性エポキシ樹脂組成物によると、耐熱性に優れた硬化物を形成できることを見出した。本発明は、これらの知見に基づいて完成されたものである。 As a result of intensive studies to solve the above-mentioned problems, 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 | cured material excellent in heat resistance could be formed. The present invention has been completed based on these findings.
　すなわち、本発明は、エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とを含む加熱混合物であって、２５℃におけるずり粘度が、１０～１０００Ｐａ・ｓである加熱混合物を含む、白色リフレクター用硬化性エポキシ樹脂組成物を提供する。 That is, 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. Provided is a curable epoxy resin composition for a white reflector, comprising a heated mixture of 10 to 1000 Pa · s.
　前記白色リフレクター用硬化性エポキシ樹脂組成物は、前記加熱混合物に加えて、さらに、硬化剤（Ｄ）を含んでいてもよい。 The curable epoxy resin composition for white reflector may further contain a curing agent (D) in addition to the heating mixture.
　前記白色リフレクター用硬化性エポキシ樹脂組成物は、前記加熱混合物に加えて、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含んでいてもよい。 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、エポキシ化合物（Ａ）は、脂環式エポキシ化合物（Ａ－１）、複素環式エポキシ化合物（Ａ－２）及び芳香族エポキシ化合物（Ａ－３）からなる群より選択される少なくとも一種を含んでいてもよい。 In the curable epoxy resin composition for white reflector, 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
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、エポキシ化合物（Ａ’）は、脂環式エポキシ化合物（Ａ－１）、複素環式エポキシ化合物（Ａ－２）及び芳香族エポキシ化合物（Ａ－３）からなる群より選択される少なくとも一種を含んでいてもよい。 In the curable epoxy resin composition for white reflector, 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:
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、無機充填剤（Ｂ）及び無機充填剤（Ｂ’）は、それぞれ独立して、シリカ、ジルコン、珪酸カルシウム、リン酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、酸化鉄、酸化アルミニウム、フォステライト、ステアタイト、スピネル、屈折率１．５未満のクレー、ドロマイト、ヒドロキシアパタイト、ネフェリンサイナイト、クリストバライト、ウォラストナイト、珪藻土、及びこれらの成型体からなる群より選択される少なくとも一種を含んでいてもよい。 In the curable epoxy resin composition for white reflector, 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、白色顔料（Ｃ）及び白色顔料（Ｃ’）は、それぞれ独立して、ガラス、屈折率１．５以上のクレー、雲母、タルク、カオリナイト、ハロイサイト、ゼオライト、酸性白土、活性白土、ベーマイト、無機酸化物、金属塩、スチレン系樹脂、ベンゾグアナミン系樹脂、尿素－ホルマリン系樹脂、メラミン－ホルマリン系樹脂、アミド系樹脂、及び中空粒子からなる群より選択される少なくとも一種を含んでいてもよい。 In the curable epoxy resin composition for 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, 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、硬化剤（Ｄ）は、下記式（１）
Figure JPOXMLDOC01-appb-C000010
 （式（１）中、Ｒaは炭素数１～６のアルキレン基を、Ｒbは水素原子又は炭素数１～６のアルキル基又はカルボキシル基をそれぞれ表す。式（１）中、複数存在するＲa、Ｒbは同一であっても異なっていても構わない。）
で表される化合物を含んでいてもよい。 In the curable epoxy resin composition for white reflector, the curing agent (D) is represented by the following formula (1):
Figure JPOXMLDOC01-appb-C000010
 (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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、前記加熱混合物は、エポキシ化合物（Ａ）１００重量部に対し、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種を５～５００重量部含有していてもよい。 In the curable epoxy resin composition for a white reflector, 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物は、脂環式エポキシ化合物（Ａ－１）として、脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を有する化合物（Ａ－１－１）、脂環に直接結合しているエポキシ基を有する化合物（Ａ－１－２）、及び脂環とグリシジル基とを有する化合物（Ａ－１－３）からなる群より選択される少なくとも一種を含んでいてもよい。 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、化合物（Ａ－１－１）は、シクロヘキセンオキシド基を有する化合物であってもよい。 In the curable epoxy resin composition for white reflector, the compound (A-1-1) may be a compound having a cyclohexene oxide group.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、化合物（Ａ－１－１）は、下記式（Ｉ－１）
Figure JPOXMLDOC01-appb-C000011
 で表される化合物であってもよい。 In the curable epoxy resin composition for white reflector, the compound (A-1-1) has the following formula (I-1):
Figure JPOXMLDOC01-appb-C000011
 The compound represented by these may be sufficient.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、化合物（Ａ－１－２）は、下記式（ＩＩ）
Figure JPOXMLDOC01-appb-C000012
 ［式（ＩＩ）中、Ｒ1はｐ価の有機基を示す。ｐは、１～２０の整数を示す。ｑは、１～５０の整数を示し、式（ＩＩ）におけるｑの和（総和）は、３～１００の整数である。Ｒ2は、下記式（ＩＩａ）～（ＩＩｃ）で表される基のいずれかを示す。但し、式（ＩＩ）におけるＲ2の少なくとも１つは式（ＩＩａ）で表される基である。
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
 ［式（ＩＩｃ）中、Ｒ3は、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルキルカルボニル基、又は置換若しくは無置換のアリールカルボニル基を示す。］］
で表される化合物であってもよい。 In the curable epoxy resin composition for white reflector, the compound (A-1-2) has the following formula (II):
Figure JPOXMLDOC01-appb-C000012
 [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).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
 [In Formula (IIc), 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、複素環式エポキシ化合物（Ａ－２）を構成する原子は、炭素原子、水素原子、酸素原子、及び窒素原子であってもよい。 In the curable epoxy resin composition for white reflector, the atoms constituting the heterocyclic epoxy compound (A-2) may be carbon atoms, hydrogen atoms, oxygen atoms, and nitrogen atoms.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、複素環式エポキシ化合物（Ａ－２）は、下記式（ＩＩＩ）
Figure JPOXMLDOC01-appb-C000016
 ［式中、Ｒ4、Ｒ5、及びＲ6は、同一又は異なって、下記式（ＩＩＩａ）
Figure JPOXMLDOC01-appb-C000017
 ［式中、Ｒ7は、水素原子又は炭素数１～８のアルキル基を示す。］
で表される基、又は下記式（ＩＩＩｂ）
Figure JPOXMLDOC01-appb-C000018
 ［式中、Ｒ8は、水素原子又は炭素数１～８のアルキル基を示す。］
で表される基を示す。但し、式（ＩＩＩ）におけるＲ4～Ｒ6の少なくとも１つは式（ＩＩＩａ）で表される基である。］
で表される化合物であってもよい。 In the curable epoxy resin composition for white reflector, the heterocyclic epoxy compound (A-2) has the following formula (III):
Figure JPOXMLDOC01-appb-C000016
 [Wherein, R 4 , R 5 and R 6 are the same or different and are represented by the following formula (IIIa)
Figure JPOXMLDOC01-appb-C000017
 [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)
Figure JPOXMLDOC01-appb-C000018
 [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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、芳香族エポキシ化合物（Ａ－３）は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、及びビフェニル型エポキシ樹脂からなる群より選ばれる少なくとも１種を含んでいてもよい。 In the curable epoxy resin composition for white reflector, 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計１００重量部に対し、無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の合計量は、２００～２０００重量部であってもよい。 In the said curable epoxy resin composition for white reflectors, an inorganic filler (B) and an inorganic filler (B) 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 200 to 2000 parts by weight.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）と硬化剤（Ｄ）の合計１００重量部に対し、白色顔料（Ｃ）及び白色顔料（Ｃ’）の合計量は、３～４００重量部であってもよい。 In the curable epoxy resin composition for a white reflector, 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.
　前記白色リフレクター用硬化性エポキシ樹脂組成物において、硬化剤（Ｄ）は、２５℃で液状の硬化剤を含んでいてもよい。 In the curable epoxy resin composition for white reflector, the curing agent (D) may contain a liquid curing agent at 25 ° C.
　前記白色リフレクター用硬化性エポキシ樹脂組成物は、トランスファー成型又はコンプレッション成型用樹脂組成物であってもよい。 The curable epoxy resin composition for white reflector may be a resin composition for transfer molding or compression molding.
　また、本発明は、前記白色リフレクター用硬化性エポキシ樹脂組成物の硬化物を提供する。
　また、本発明は、前記硬化物により形成された白色リフレクターを有する光半導体素子搭載用基板を提供する。
　さらに、本発明は、前記光半導体素子搭載用基板と、該基板に搭載された光半導体素子とを有する光半導体装置を提供する。 Moreover, this invention provides the hardened | cured material of the said curable epoxy resin composition for white reflectors.
Moreover, this invention provides the board | substrate for optical semiconductor element mounting which has a white reflector formed with the said hardened | cured material.
Furthermore, the present invention provides an optical semiconductor device having the optical semiconductor element mounting substrate and an optical semiconductor element mounted on the substrate.
　また、本発明は、下記工程（１）および（２）を含む、白色リフレクター用硬化性エポキシ樹脂組成物の製造方法を提供する。
（１）エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる混合物を、加熱・混合して、加熱混合物を得る工程；及び
（２）前記加熱混合物と、硬化剤（Ｄ）とを含む混合物を混合して、白色リフレクター用硬化性エポキシ樹脂組成物を得る工程。
　前記白色リフレクター用硬化性エポキシ樹脂組成物の製造方法の工程（２）において、前記混合物は、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含んでいてもよい。 Moreover, this invention provides the manufacturing method of the curable epoxy resin composition for white reflectors including the following process (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 | curing agent (D).
In 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.
　また、本発明は、下記工程（１）～（３）を含む、白色リフレクター用硬化性エポキシ樹脂組成物の硬化物の製造方法を提供する。
（１）エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる混合物を、加熱・混合して、加熱混合物を得る工程；
（２）前記加熱混合物と、硬化剤（Ｄ）とを含む混合物を混合して、白色リフレクター用硬化性エポキシ樹脂組成物を得る工程；及び
（３）前記白色リフレクター用硬化性エポキシ樹脂組成物を加熱して、硬化物を得る工程。
　前記白色リフレクター用硬化性エポキシ樹脂組成物の硬化物の製造方法の工程（２）において、前記混合物は、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含んでいてもよい。
　前記白色リフレクター用硬化性エポキシ樹脂組成物の硬化物の製造方法において、硬化物は、光半導体素子搭載用基板用の白色リフレクターであってもよい。 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).
(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.
In 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:
In the method for producing a cured product of the curable epoxy resin composition for white reflector, the cured product may be a white reflector for a substrate for mounting an optical semiconductor element.
　さらに、本発明は、前記白色リフレクター用硬化性エポキシ樹脂組成物の硬化物の製造方法を含む、光半導体装置の製造方法を提供する。 Furthermore, this invention provides the manufacturing method of an optical semiconductor device including the manufacturing method of the hardened | cured material of the said curable epoxy resin composition for white reflectors.
　より具体的には、本発明は、以下に関する。
［１］エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とを含む加熱混合物であって、２５℃におけるずり粘度が、１０～１０００Ｐａ・ｓである加熱混合物を含む、白色リフレクター用硬化性エポキシ樹脂組成物。
［２］前記加熱混合物に加えて、さらに、硬化剤（Ｄ）を含む、上記［１］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３］前記加熱混合物に加えて、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含む、上記［１］又は［２］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 More specifically, the present invention relates to the following.
[1] 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.
[2] The curable epoxy resin composition for a white reflector according to [1], further including a curing agent (D) in addition to the heating mixture.
[3] In the above [1], 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].
［４］エポキシ化合物（Ａ）が、分子内にエポキシ基を２つ以上（好ましくは２～６つ、より好ましくは２～４つ）有する化合物である、上記［１］～［３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５］エポキシ化合物（Ａ）が、脂環式エポキシ化合物（Ａ－１）、複素環式エポキシ化合物（Ａ－２）及び芳香族エポキシ化合物（Ａ－３）からなる群より選択される少なくとも一種（好ましくは、脂環式エポキシ化合物（Ａ－１）、及び複素環式エポキシ化合物（Ａ－２）からなる群より選択される少なくとも一種、より好ましくは脂環式エポキシ化合物（Ａ－１））を含む、上記［１］～［４］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [4] Any of the above [1] to [3], wherein 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 curable epoxy resin composition for white reflectors as described in any one.
[5] 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). (Preferably, at least one selected from the group consisting of alicyclic epoxy compound (A-1) and heterocyclic epoxy compound (A-2), more preferably alicyclic epoxy compound (A-1)) The curable epoxy resin composition for a white reflector according to any one of the above [1] to [4], comprising:
［６］エポキシ化合物（Ａ’）が、分子内にエポキシ基を２つ以上（好ましくは２～６つ、より好ましくは２～４つ）有する化合物である、上記［３］～［５］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７］エポキシ化合物（Ａ’）が、脂環式エポキシ化合物（Ａ－１）、複素環式エポキシ化合物（Ａ－２）及び芳香族エポキシ化合物（Ａ－３）からなる群より選択される少なくとも一種（好ましくは、脂環式エポキシ化合物（Ａ－１）、及び複素環式エポキシ化合物（Ａ－２）からなる群より選択される少なくとも一種）を含む、上記［３］～［６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [6] The above-mentioned [3] to [5], wherein 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 curable epoxy resin composition for white reflectors as described in any one.
[7] 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)) The curable epoxy resin composition for white reflectors as described in any one.
［８］脂環式エポキシ化合物（Ａ－１）として、脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を有する化合物（Ａ－１－１）、脂環に直接結合しているエポキシ基を有する化合物（Ａ－１－２）、及び脂環とグリシジル基とを有する化合物（Ａ－１－３）からなる群より選択される少なくとも一種を含む、上記［５］～［７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［９］化合物（Ａ－１－１）が、シクロヘキセンオキシド基を有する化合物を含む、上記［８］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［１０］化合物（Ａ－１－１）が、下記式（Ｉ）で表される化合物を含む、上記［８］又は［９］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
Figure JPOXMLDOC01-appb-C000019
 ［式（Ｉ）中、Ｘは単結合又は連結基（１以上の原子を有する二価の基）（好ましくは、二価の炭化水素基、炭素－炭素二重結合の一部又は全部がエポキシ化されたアルケニレン基（エポキシ化アルケニレン基）、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド基、これらが複数個連結した基）を示す。式（Ｉ）におけるシクロヘキサン環（シクロヘキセンオキシド基）を構成する炭素原子の１以上には、アルキル基等の置換基が結合していてもよい。］
［１１］連結基Ｘが、－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯＯ－、－Ｏ－、－ＣＯＮＨ－、エポキシ化アルケニレン基；これらの基が複数個連結した基；又はこれらの基の１又は２以上と二価の炭化水素基の１又は２以上とが連結した基である、上記［１０］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［１２］上記式（Ｉ）で表される化合物が、下記式（Ｉ－１）～（Ｉ－１０）で表される化合物、２，２－ビス（３，４－エポキシシクロヘキサン－１－イル）プロパン、１，２－ビス（３，４－エポキシシクロヘキサン－１－イル）エタン、１，２－エポキシ－１，２－ビス（３，４－エポキシシクロヘキサン－１－イル）エタン、又はビス（３，４－エポキシシクロヘキシルメチル）エーテルを含む、上記［１０］又は［１１］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
 ［式（Ｉ－５）、（Ｉ－７）中のｌ、ｍは、それぞれ１～３０の整数を表す。式（Ｉ－５）中のＲは炭素数１～８のアルキレン基（例えば、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ｓ－ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基等の直鎖又は分岐鎖状のアルキレン基、好ましくは、炭素数１～３の直鎖又は分岐鎖状のアルキレン基）を示す。式（Ｉ－９）、（Ｉ－１０）中のｎ１～ｎ６は、それぞれ１～３０の整数を示す。］
［１３］化合物（Ａ－１－１）が、下記式（Ｉ－１）
Figure JPOXMLDOC01-appb-C000022
 で表される化合物を含む、上記［８］～［１２］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [8] As an alicyclic epoxy compound (A-1), 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].
[9] The curable epoxy resin composition for a white reflector as described in [8] above, wherein the compound (A-1-1) comprises a compound having a cyclohexene oxide group.
[10] The curable epoxy resin composition for a white reflector according to the above [8] or [9], wherein the compound (A-1-1) comprises a compound represented by the following formula (I).
Figure JPOXMLDOC01-appb-C000019
 [In the formula (I), 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 carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which a plurality of these are linked). 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). ]
[11] 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.
[12] 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.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
 [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. ]
[13] The compound (A-1-1) is represented by the following formula (I-1)
Figure JPOXMLDOC01-appb-C000022
 The curable epoxy resin composition for a white reflector according to any one of the above [8] to [12], comprising a compound represented by:
［１４］化合物（Ａ－１－２）が、下記式（ＩＩ）
Figure JPOXMLDOC01-appb-C000023
 ［式（ＩＩ）中、Ｒ1はｐ価の有機基を示す。ｐは、１～２０の整数を示す。ｑは、１～５０の整数を示し、式（ＩＩ）におけるｑの和（総和）は、３～１００の整数である。Ｒ2は、下記式（ＩＩａ）～（ＩＩｃ）で表される基のいずれかを示す。但し、式（ＩＩ）におけるＲ2の少なくとも１つは式（ＩＩａ）で表される基である。
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
 ［式（ＩＩｃ）中、Ｒ3は、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルキルカルボニル基、又は置換若しくは無置換のアリールカルボニル基を示す。］］
で表される化合物を含む、上記［８］～［１３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［１５］上記式（ＩＩ）で表される化合物におけるＲ2の全量（１００モル％）に対する、式（ＩＩａ）で表される基（エポキシ基）の割合が、４０モル％以上（例えば、４０～１００モル％、好ましくは６０モル％以上、さらに好ましくは８０モル％以上）である、上記［１４］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［１６］上記式（ＩＩ）で表される化合物の標準ポリスチレン換算の重量平均分子量が、３００～１０００００（好ましくは１０００～１００００）である、上記［１４］又は［１５］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［１７］上記式（ＩＩ）で表される化合物のエポキシ当量が、５０～１０００（好ましくは１００～５００）である、上記［１４］～［１６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［１８］化合物（Ａ－１－３）が、２，２－ビス［４－（２，３－エポキシプロポキシ）シクロへキシル］プロパン、２，２－ビス［３，５－ジメチル－４－（２，３－エポキシプロポキシ）シクロへキシル］プロパン、ビスフェノールＡ型エポキシ化合物を水素化した化合物（水素化ビスフェノールＡ型エポキシ化合物）等；ビス［２－（２，３－エポキシプロポキシ）シクロへキシル］メタン、［２－（２，３－エポキシプロポキシ）シクロへキシル］［４－（２，３－エポキシプロポキシ）シクロへキシル］メタン、ビス［４－（２，３－エポキシプロポキシ）シクロへキシル］メタン、ビス［３，５－ジメチル－４－（２，３－エポキシプロポキシ）シクロへキシル］メタン、ビスフェノールＦ型エポキシ化合物を水素化した化合物（水素化ビスフェノールＦ型エポキシ化合物）等；水添ビフェノール型エポキシ化合物；水添フェノールノボラック型エポキシ化合物；水添クレゾールノボラック型エポキシ化合物；ビスフェノールＡの水添クレゾールノボラック型エポキシ化合物；水添ナフタレン型エポキシ化合物；及びトリスフェノールメタンから得られるエポキシ化合物の水添エポキシ化合物等から選ばれる少なくとも１種を含む、上記［８］～［１７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［１９］複素環式エポキシ化合物（Ａ－２）を構成する原子が、炭素原子、水素原子、酸素原子、及び窒素原子である、上記［７］～［１８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２０］複素環式エポキシ化合物（Ａ－２）が、下記式（ＩＩＩ）
Figure JPOXMLDOC01-appb-C000027
 ［式中、Ｒ4、Ｒ5、及びＲ6は、同一又は異なって、下記式（ＩＩＩａ）
Figure JPOXMLDOC01-appb-C000028
 ［式中、Ｒ7は、水素原子又は炭素数１～８のアルキル基を示す。］
で表される基、又は下記式（ＩＩＩｂ）
Figure JPOXMLDOC01-appb-C000029
 ［式中、Ｒ8は、水素原子又は炭素数１～８のアルキル基を示す。］
で表される基を示す。但し、式（ＩＩＩ）におけるＲ4～Ｒ6の少なくとも１つは式（ＩＩＩａ）で表される基である。］
で表される化合物を含む、上記［７］～［１９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２１］複素環式エポキシ化合物（Ａ－２）が、下記式（ＩＶ）
Figure JPOXMLDOC01-appb-C000030
 ［式中、Ｒ9、Ｒ10、Ｒ11、及びＲ12は、同一又は異なって、下記式（ＩＶａ）
Figure JPOXMLDOC01-appb-C000031
 ［式中、Ｒ15は、水素原子又は炭素数１～８のアルキル基を示す。］
で表される基、又は下記式（ＩＶｂ）
Figure JPOXMLDOC01-appb-C000032
 ［式中、Ｒ16は、水素原子又は炭素数１～８のアルキル基を示す。］
で表される基を示す。但し、式（ＩＶ）におけるＲ9～Ｒ12の少なくとも１つは式（ＩＶａ）で表される基である。
Ｒ13及びＲ14は、同一又は異なって、水素原子又は一価の有機基を示す。］
で表される化合物を含む、上記［７］～［２０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２２］芳香族エポキシ化合物（Ａ－３）が、ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、及びビフェニル型エポキシ樹脂からなる群から選ばれる少なくとも１種を含む、上記［７］～［２１］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [14] The compound (A-1-2) is represented by the following formula (II)
Figure JPOXMLDOC01-appb-C000023
 [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).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
 [In Formula (IIc), 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 curable epoxy resin composition for a white reflector according to any one of the above [8] to [13], comprising a compound represented by:
[15] 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.
[16] For a white reflector as described in [14] or [15] above, wherein the compound represented by the formula (II) has a weight average molecular weight in terms of standard polystyrene of 300 to 100,000 (preferably 1000 to 10,000). Curable epoxy resin composition.
[17] For the white reflector according to any one of the above [14] to [16], wherein the epoxy equivalent of the compound represented by the formula (II) is 50 to 1000 (preferably 100 to 500) Curable epoxy resin composition.
[18] 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 biphenol type epoxy compound; hydrogenated phenol novolak type epoxy compound; hydrogenated cresol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound And a curable epoxy resin composition for a white reflector according to any one of the above [8] to [17], comprising at least one selected from hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane .
[19] The atoms according to any one of [7] to [18] above, wherein the atoms constituting the heterocyclic epoxy compound (A-2) are a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom. A curable epoxy resin composition for a white reflector.
[20] The heterocyclic epoxy compound (A-2) is represented by the following formula (III):
Figure JPOXMLDOC01-appb-C000027
 [Wherein, R 4 , R 5 and R 6 are the same or different and are represented by the following formula (IIIa)
Figure JPOXMLDOC01-appb-C000028
 [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)
Figure JPOXMLDOC01-appb-C000029
 [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 curable epoxy resin composition for a white reflector according to any one of the above [7] to [19], comprising a compound represented by:
[21] The heterocyclic epoxy compound (A-2) is represented by the following formula (IV):
Figure JPOXMLDOC01-appb-C000030
 [Wherein, R 9 , R 10 , R 11 , and R 12 are the same or different and are represented by the following formula (IVa):
Figure JPOXMLDOC01-appb-C000031
 [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)
Figure JPOXMLDOC01-appb-C000032
 [Wherein R 16 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 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. ]
The curable epoxy resin composition for a white reflector according to any one of the above [7] to [20], comprising a compound represented by:
[22] The above, wherein the aromatic epoxy compound (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. [7] The curable epoxy resin composition for a white reflector according to any one of [21] to [21].
［２３］無機充填剤（Ｂ）及び無機充填剤（Ｂ’）が、それぞれ独立して、シリカ（例えば、溶融シリカ、結晶シリカ、高純度合成シリカ等）、ジルコン、珪酸カルシウム、リン酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、酸化鉄、酸化アルミニウム、フォステライト、ステアタイト、スピネル、屈折率１．５未満のクレー、ドロマイト、ヒドロキシアパタイト、ネフェリンサイナイト、クリストバライト、ウォラストナイト、珪藻土、及びこれらの成型体からなる群より選択される少なくとも一種（好ましくはシリカ）を含む、上記［１］～［２２］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２４］無機充填剤（Ｂ）及び無機充填剤（Ｂ’）が、それぞれ独立して、表面処理［例えば、金属酸化物、シランカップリング剤、チタンカップリング剤、有機酸、ポリオール、シリコーン等の表面処理剤による表面処理等］が施されたものである、上記［１］～［２３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２５］無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の形状が、それぞれ独立して、粉体、球状、破砕状、繊維状、針状、又は鱗片状（中でも球状、特に真球状（例えば、アスペクト比が１．２以下の球状のシリカ）である、上記［１］～［２４］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２６］無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の中心粒径が、それぞれ独立して、０．１～５０μｍ（好ましくは０．１～３０μｍ）である、上記［１］～［２５］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [23] 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. , Silicon nitride, boron nitride, iron oxide, aluminum oxide, fosterite, steatite, spinel, clay with a refractive index of less than 1.5, dolomite, hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, and these 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).
[24] 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 curable epoxy resin composition for a white reflector according to any one of the above [1] to [23], which has been subjected to a surface treatment with a surface treatment agent or the like].
[25] 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).
[26] 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 μm (preferably 0.1 to 30 μm). [25] The curable epoxy resin composition for white reflectors according to any one of [25].
［２７］白色顔料（Ｃ）及び白色顔料（Ｃ’）が、それぞれ独立して、屈折率１．５以上の白色顔料である、上記［１］～［２６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２８］白色顔料（Ｃ）及び白色顔料（Ｃ’）が、それぞれ独立して、ガラス、屈折率１．５以上のクレー、雲母、タルク、カオリナイト、ハロイサイト、ゼオライト、酸性白土、活性白土、ベーマイト、無機酸化物、金属塩、スチレン系樹脂、ベンゾグアナミン系樹脂、尿素－ホルマリン系樹脂、メラミン－ホルマリン系樹脂、アミド系樹脂、及び中空粒子からなる群より選択される少なくとも一種を含む、上記［１］～［２７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［２９］白色顔料（Ｃ）及び白色顔料（Ｃ’）が、それぞれ独立して、無機酸化物（例えば、酸化アルミニウム（アルミナ）、酸化マグネシウム、酸化アンチモン、酸化チタン［例えば、ルチル型酸化チタン、アナターゼ型酸化チタン、ブルッカイト型酸化チタン等］、酸化ジルコニウム、酸化亜鉛等、特に好ましくは酸化チタン）である、上記［１］～［２８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３０］白色顔料（Ｃ）及び白色顔料（Ｃ’）が、それぞれ独立して、アルカリ土類金属塩（例えば、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、ケイ酸マグネシウム、ケイ酸カルシウム、水酸化マグネシウム、リン酸マグネシウム、リン酸水素マグネシウム、硫酸マグネシウム、硫酸カルシウム、硫酸バリウム等）である、上記［１］～［２９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３１］白色顔料（Ｃ）及び白色顔料（Ｃ’）が、それぞれ独立して、中空粒子（例えば、無機ガラス［例えば、珪酸ソーダガラス、アルミ珪酸ガラス、硼珪酸ソーダガラス、石英等］、シリカ、アルミナ等の金属酸化物、炭酸カルシウム、炭酸バリウム、炭酸ニッケル、珪酸カルシウム等の金属塩等の無機物により構成された無機中空粒子（シラスバルーン等の天然物も含む）；スチレン系樹脂、アクリル系樹脂、シリコーン系樹脂、アクリル－スチレン系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹脂、アミド系樹脂、ウレタン系樹脂、フェノール系樹脂、スチレン－共役ジエン系樹脂、アクリル－共役ジエン系樹脂、オレフィン系樹脂等のポリマー（これらポリマーの架橋体も含む）等の有機物により構成された有機中空粒子；無機物と有機物のハイブリッド材料により構成された無機－有機中空粒子等）である、上記［１］～［３０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３２］白色顔料（Ｃ）及び白色顔料（Ｃ’）が、それぞれ独立して、表面処理［例えば、金属酸化物、シランカップリング剤、チタンカップリング剤、有機酸、ポリオール、シリコーン等の表面処理剤による表面処理等］が施されたものである、上記［１］～［３１］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３３］白色顔料（Ｃ）及び白色顔料（Ｃ’）の形状が、それぞれ独立して、球状、破砕状、繊維状、針状、又は鱗片状（中でも、球状の酸化チタンが好ましく、特に真球状の酸化チタン（例えば、アスペクト比が１．２以下の球状の酸化チタン））である、上記［１］～［３２］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３４］白色顔料（Ｃ）及び白色顔料（Ｃ’）の中心粒径が、それぞれ独立して、０．１～５０μｍ（好ましくは０．１～３０μｍの酸化チタン）である、上記［１］～［３３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [27] 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.
[28] 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. [1] The curable epoxy resin composition for a white reflector according to any one of [27].
[29] 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.
[30] 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.
[31] 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 Organic hollow particles composed of organic substances such as polymers such as resins (including cross-linked products of these polymers); inorganic substances The curable epoxy resin composition for a white reflector according to any one of the above [1] to [30], which is an inorganic-organic hollow particle composed of a hybrid material of organic and organic matter.
[32] 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 curable epoxy resin composition for a white reflector according to any one of the above [1] to [31], which has been subjected to a surface treatment with a treating agent].
[33] 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 curable epoxy resin composition for a white reflector according to any one of the above [1] to [32], which is a spherical titanium oxide (for example, a spherical titanium oxide having an aspect ratio of 1.2 or less).
[34] 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 μm (preferably 0.1 to 30 μm of titanium oxide). The curable epoxy resin composition for a white reflector according to any one of [33].
［３５］前記加熱混合物の２５℃におけるずり粘度が、１０～５００Ｐａ・ｓ（より好ましくは１０～３００Ｐａ・ｓ）である、上記［１］～［３４］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３６］前記加熱混合物における加熱温度が、５０～１２０℃（好ましくは６０～１００℃）である、上記［１］～［３５］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３７］前記加熱混合物におけるエポキシ化合物（Ａ）の含有量（配合量）が、前記加熱混合物（１００重量％）に対して、１～９９重量％（好ましくは１０～９５重量％、さらに好ましくは２０～９０重量％）である、上記［１］～［３６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３８］前記加熱混合物に含まれるエポキシ化合物（Ａ）の全量（１００重量％）に対する化合物（Ａ－１－１）の割合が、５～１００重量％（好ましくは１０～１００重量％、より好ましくは２０～１００重量％）である、上記［１］～［３７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［３９］前記加熱混合物に含まれるエポキシ化合物（Ａ）の全量（１００重量％）に対する化合物（Ａ－１－２）の割合が、０～５０重量％（好ましくは０～４５重量％、より好ましくは０～４０重量％）である、上記［１］～［３８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４０］前記加熱混合物に含まれるエポキシ化合物（Ａ）の全量（１００重量％）に対する化合物（Ａ－１－３）の割合が、０～５０重量％（好ましくは０～４５重量％、より好ましくは０～４０重量％）である、上記［１］～［３９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４１］無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種の含有量（配合量）が、前記加熱混合物（１００重量％）に対して、１～９９重量％（好ましくは５～９０重量％、さらに好ましくは１０～８０重量％）である、上記［１］～［４０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４２］前記加熱混合物が、エポキシ化合物（Ａ）１００重量部に対し、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種を５～５００重量部（好ましくは１０～４００重量部、さらに好ましくは２０～４００重量部）含有する、上記［１］～［４１］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４３］無機充填剤（Ｂ）と白色顔料（Ｃ）の割合（無機充填剤（Ｂ）／白色顔料（Ｃ））が、１００／０～０／１００（好ましくは９９／１～１／９９、より好ましくは９５／５～５／９５）の範囲から選択される、上記［１］～［４２］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [35] The white reflector according to any one of [1] to [34], wherein the heated mixture has a shear viscosity at 25 ° C. of 10 to 500 Pa · s (more preferably 10 to 300 Pa · s). 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.
[37] 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).
[38] 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].
[39] 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].
[40] 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].
[41] 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.
[42] 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.
[43] 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 curable epoxy resin composition for a white reflector according to any one of the above [1] to [42], more preferably selected from the range of 95/5 to 5/95).
［４４］エポキシ化合物（Ａ’）の含有量（配合量）が、エポキシ化合物（Ａ）１００重量部に対して、１～１００００重量部（好ましくは１０～１０００重量部、さらに好ましくは１０～５００重量部）である、上記［３］～［４３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４５］エポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の合計含有量（配合量）が、硬化性エポキシ樹脂組成物（１００重量％）に対して、１．５～１５重量％（好ましくは２～１３重量％、さらに好ましくは２．５～１０重量％）である、上記［３］～［４４］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４６］エポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する化合物（Ａ－１－１）の割合が、５～９５重量％（好ましくは１０～９０重量％、より好ましくは２０～８０重量％である、上記［３］～［４５］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４７］エポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する化合物（Ａ－１－２）の割合が、１～９０重量％（好ましくは１０～８０重量％、より好ましくは２０～７０重量％）である、上記［３］～［４６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４８］エポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する化合物（Ａ－１－３）の割合が、０～９０重量％（好ましくは１０～８０重量％、より好ましくは２０～７０重量％）である、上記［３］～［４７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［４９］エポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する複素環式エポキシ化合物（Ａ－２）の割合が、１～８０重量％（好ましくは５～７０重量％、より好ましくは１０～６０重量％）である、上記［３］～［４８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５０］化合物（Ａ－１－１）と、化合物（Ａ－１－２）及び複素環式エポキシ化合物（Ａ－２）との重量基準の割合［＝化合物（Ａ－１－１）／化合物（Ａ－１－２）及び複素環式エポキシ化合物（Ａ－２）］が、１０／９０～９０／１０（好ましくは２０／８０～７０／３０、さらに好ましくは３０／７０～６０／４０）である、上記［１］～［４９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [44] 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 curable epoxy resin composition for a white reflector according to any one of the above [3] to [43], wherein the curable epoxy resin composition is a part by weight.
[45] 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 curable epoxy resin composition for a white reflector according to any one of the above [3] to [44], which is 2 to 13% by weight, more preferably 2.5 to 10% by weight.
[46] 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 curable epoxy resin composition for a white reflector according to any one of the above [3] to [45], which is preferably 20 to 80% by weight.
[47] 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 curable epoxy resin composition for a white reflector according to any one of the above [3] to [46], which is preferably 20 to 70% by weight).
[48] 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 curable epoxy resin composition for a white reflector according to any one of the above [3] to [47], which is preferably 20 to 70% by weight).
[49] 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 white reflectors according to any one of the above [3] to [48], more preferably 10 to 60% by weight).
[50] Weight-based ratio of compound (A-1-1) to compound (A-1-2) and heterocyclic epoxy compound (A-2) [= compound (A-1-1) / compound (A-1-2) and heterocyclic epoxy compound (A-2)] are 10/90 to 90/10 (preferably 20/80 to 70/30, more preferably 30/70 to 60/40). The curable epoxy resin composition for a white reflector according to any one of the above [1] to [49].
［５１］硬化剤（Ｄ）が、酸無水物類（酸無水物系硬化剤）、アミン類（アミン系硬化剤）、ポリアミド樹脂、イミダゾール類（イミダゾール系硬化剤）、ポリメルカプタン類（ポリメルカプタン系硬化剤）、フェノール類（フェノール系硬化剤）、ポリカルボン酸類、ジシアンジアミド類、及び有機酸ヒドラジドからなる群から選ばれる少なくとも１種である、上記［２］～［５０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５２］硬化剤（Ｄ）が、２５℃で液状（液体）の硬化剤（好ましくは、２５℃で液状の酸無水物）を含む、上記［２］～［５１］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５３］硬化剤（Ｄ）が、下記式（１）
Figure JPOXMLDOC01-appb-C000033
 （式（１）中、Ｒaは炭素数１～６のアルキレン基を、Ｒbは水素原子又は炭素数１～６のアルキル基又はカルボキシル基をそれぞれ表す。式（１）中、複数存在するＲa、Ｒbは同一であっても異なっていても構わない。）
で表される化合物を含む、上記［２］～［５２］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５４］硬化剤（Ｄ）が、下記式（１'）で表される化合物を含む、上記［２］～［５３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
Figure JPOXMLDOC01-appb-C000034
 ［５５］上記式（１）で表される化合物の酸価（ＪＩＳ　Ｋ－２５０１に記載の方法で測定）が、１５０～４１５ｍｇＫＯＨ／ｇ（好ましくは１８５～３７５ｍｇＫＯＨ／ｇ、より好ましくは２００～３２０ｍｇＫＯＨ／ｇ）である、上記［５３］又は［５４］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５６］上記式（１）で表される化合物の官能基当量が、１３５～３１２ｇ／ｅｑ（好ましくは１５０～３００ｇ／ｅｑ、より好ましくは１８０～２８０ｇ／ｅｑ）である、上記［５３］～［５５］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５７］上記式（１）で表される化合物の軟化点が、２０～１５０℃（好ましくは５０～１３０℃）である、上記［５３］～［５６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５８］硬化剤（Ｄ）が、上記式（１）で表される化合物、及び酸無水物類（酸無水物系硬化剤）からなる群から選ばれる少なくとも一種（特に好ましくは、式（１）で表される化合物を含む硬化剤（Ｄ））である、上記［２］～［５７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［５９］硬化剤（Ｄ）が、上記式（１）で表される化合物、及び酸無水物類（好ましくは、２５℃で液状の酸無水物硬化剤）の両方を含む、上記［２］～［５８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６０］硬化剤（Ｄ）の含有量（配合量）が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、５０～２００重量部（好ましくは７５～１８０重量部、さらに好ましくは８０～１５０重量部）である、上記［２］～［５９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６１］式（１）で表される化合物の含有量（配合量）が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、１～３００重量部（好ましくは１０～２５０重量部、さらに好ましくは２０～２００重量部）である、上記［５３］～［６０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６２］硬化剤（Ｄ）の全量（１００重量％）に対する式（１）で表される化合物の割合が、１０重量％以上（例えば、１０～１００重量％、より好ましくは１５重量％以上、さらに好ましくは２０重量％以上、特に好ましくは２５重量％以上）である、上記［５３］～［６１］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６３］酸無水物類の含有量（配合量）が、式（１）で表される化合物１００重量部に対して、０～１５００重量部（好ましくは１０～１２００重量部、さらに好ましくは２０～１０００重量部）である、上記［５９］～［６２］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [51] 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 curable epoxy resin composition for white reflectors described in 1.
[52] In any one of the above [2] to [51], the curing agent (D) includes a curing agent that is liquid (liquid) at 25 ° C. (preferably, an acid anhydride that is liquid at 25 ° C.). The curable epoxy resin composition for white reflectors as described.
[53] The curing agent (D) is represented by the following formula (1)
Figure JPOXMLDOC01-appb-C000033
 (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 curable epoxy resin composition for a white reflector according to any one of the above [2] to [52], comprising a compound represented by:
[54] The curable epoxy resin composition for a white reflector according to any one of the above [2] to [53], wherein the curing agent (D) comprises a compound represented by the following formula (1 ′).
Figure JPOXMLDOC01-appb-C000034
 [55] 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). / G), the curable epoxy resin composition for white reflectors according to [53] or [54] above.
[56] 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). [55] The curable epoxy resin composition for white reflectors according to any one of [55].
[57] The white color according to any one of the above [53] to [56], wherein the softening point of the compound represented by the formula (1) is 20 to 150 ° C. (preferably 50 to 130 ° C.) A curable epoxy resin composition for reflectors.
[58] 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 a white reflector according to any one of the above [2] to [57], which is a curing agent (D)) comprising a compound represented by
[59] The above [2], wherein the curing agent (D) contains both the compound represented by the above formula (1) and acid anhydrides (preferably an acid anhydride curing agent that is liquid at 25 ° C.). The curable epoxy resin composition for white reflectors according to any one of [58] to [58].
[60] 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).
[61] 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). Composition.
[62] 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.
[63] 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
［６４］さらに、硬化促進剤（例えば、１，８－ジアザビシクロ［５．４．０］ウンデセン－７（ＤＢＵ）又はその塩（例えば、フェノール塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩等）；１，５－ジアザビシクロ［４．３．０］ノネン－５（ＤＢＮ）又はその塩（例えば、フェノール塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩等）；ベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ－ジメチルシクロヘキシルアミン等の３級アミン；２－エチル－４－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール等のイミダゾール；リン酸エステル、トリフェニルホスフィン等のホスフィン類；テトラフェニルホスホニウムテトラ（ｐ－トリル）ボレート等のホスホニウム化合物；オクチル酸亜鉛やオクチル酸スズ等の有機金属塩；金属キレート等）を含む、上記［１］～［６３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６５］硬化促進剤の含有量（配合量）が、白色リフレクター用硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）のの全量１００重量部に対して、０．１～１０重量部（好ましくは０．３～８重量部）である、上記［６４］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [64] Further, 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; phosphines such as phosphate esters and triphenylphosphine A phosphonium compound such as tetraphenylphosphonium tetra (p-tolyl) borate; an organic metal salt such as zinc octylate and tin octylate; a metal chelate), and the like. 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 curable epoxy resin composition for a white reflector according to the above [64], which is 1 to 10 parts by weight (preferably 0.3 to 8 parts by weight).
［６６］無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の合計含有量（配合量）が、硬化性エポキシ樹脂組成物（１００重量％）に対して、６０～９０重量％（好ましくは６０～７５重量％）である、上記［３］～［６５］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６７］エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計１００重量部に対し、無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の合計量が２００～２０００重量部（好ましくは２２０～１５００重量部、さらに好ましくは２５０～１０００重量部）である、上記［３］～［６６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６８］白色顔料（Ｃ’）及び白色顔料（Ｃ）の合計含有量（配合量）が、硬化性エポキシ樹脂組成物（１００重量％）に対して、２～４０重量％（好ましくは１０～３０重量％、さらに好ましくは１５～２５重量％）である、上記［３］～［６７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［６９］エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）と硬化剤（Ｄ）の合計１００重量部に対し、白色顔料（Ｃ）及び白色顔料（Ｃ’）の合計量が３～４００重量部（好ましくは５～３５０重量部、さらに好ましくは５～３００重量部）である、上記［３］～［６８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７０］無機充填剤（Ｂ）、無機充填剤（Ｂ’）、白色顔料（Ｃ）と白色顔料（Ｃ’）の総量（１００重量％）に対する酸化チタンの割合が、５～４０重量％（好ましくは１０～３５重量％）である、上記［３］～［６９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７１］無機充填剤（Ｂ）、無機充填剤（Ｂ’）、白色顔料（Ｃ）と白色顔料（Ｃ’）の合計含有量（配合量）が、エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計量１００重量部に対して、２００～２，０００重量部（好ましくは２５０～１，８００重量部、さらに好ましくは３００～１，５００重量部）である、上記［３］～［７０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [66] 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].
[67] 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).
[68] 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 curable epoxy resin composition for a white reflector according to any one of the above [3] to [67], which is 30% by weight, more preferably 15 to 25% by weight.
[69] 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).
[70] 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 curable epoxy resin composition for a white reflector according to any one of the above [3] to [69], which is preferably 10 to 35% by weight).
[71] 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.
［７２］さらに、離型剤（例えば、フッ素系離型剤（フッ素原子含有化合物；例えば、フッ素オイル、ポリテトラフルオロエチレン等）、シリコーン系離型剤（シリコーン化合物；例えば、シリコーンオイル、シリコーンワックス、シリコーン樹脂、ポリオキシアルキレン単位を有するポリオルガノシロキサン等）、ワックス系離型剤（ワックス類；例えば、カルナウバワックス等の植物ロウ、羊毛ワックス等の動物ロウ、パラフィンワックス等のパラフィン類、ポリエチレンワックス、酸化ポリエチレンワックス等）、高級脂肪酸又はその塩（例えば、金属塩等）、高級脂肪酸エステル、高級脂肪酸アミド、鉱油等）を含む、上記［１］～［７０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７３］離型剤の含有量（配合量）が、白色リフレクター用硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、１～１２重量部（好ましくは２～１０重量部）である、上記［７２］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [72] Further, 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.
[73] 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. The curable epoxy resin composition for a white reflector according to the above [72], which is 12 parts by weight (preferably 2 to 10 parts by weight).
［７４］さらに、酸化防止剤（例えば、フェノール系酸化防止剤（フェノール系化合物）、ヒンダードアミン系酸化防止剤（ヒンダードアミン系化合物）、リン系酸化防止剤（リン系化合物）、イオウ系酸化防止剤（イオウ系化合物）等）を含む、上記［１］～［７３］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７５］酸化防止剤が、フェノール系酸化防止剤、リン系酸化防止剤、及びイオウ系酸化防止剤から選ばれる少なくとも１種（好ましくはフェノール系酸化防止剤とリン系酸化防止剤又はイオウ系酸化防止剤との併用、より好ましくはフェノール系酸化防止剤とリン系酸化防止剤との併用）である、上記［７４］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７６］酸化防止剤の含有量（配合量）が、白色リフレクター用硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、０．１～５重量部（好ましくは０．５～３重量部）である、上記［７４］又は［７５］に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 [74] Further, antioxidants (for example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus antioxidants (phosphorous compounds), sulfur antioxidants ( The curable epoxy resin composition for a white reflector according to any one of the above [1] to [73], comprising a sulfur compound)).
[75] 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.
[76] 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. The curable epoxy resin composition for white reflectors according to the above [74] or [75], which is 1 to 5 parts by weight (preferably 0.5 to 3 parts by weight).
［７７］硬化剤（Ｄ）が、２５℃で液状の硬化剤を含む、上記［２］～［７６］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７８］トランスファー成型又はコンプレッション成型用樹脂組成物である、上記［１］～［７７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［７９］ＩＣＩコーンプレート粘度が１００～２００℃の範囲で、０．０１～１０Ｐａ・ｓである、上記［１］～［７８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［８０］常温（２５℃）で固体とである、上記［１］～［７９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［８１］軟化点が、４０～１３０℃（好ましくは５０～１００℃、より好ましくは７０～１００℃）である、上記［１］～［８０］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物。
［８２］上記［１］～［８１］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物の硬化物。
［８３］上記［８２］に記載の硬化物により形成された白色リフレクターを有する光半導体素子搭載用基板。
［８４］上記［８３］に記載の光半導体素子搭載用基板と、該基板に搭載された光半導体素子とを有する光半導体装置。 [77] The curable epoxy resin composition for a white reflector according to any one of the above [2] to [76], wherein the curing agent (D) comprises a curing agent that is liquid at 25 ° C.
[78] The curable epoxy resin composition for a white reflector according to any one of the above [1] to [77], which is a resin composition for transfer molding or compression molding.
[79] The curable epoxy resin composition for a white reflector according to any one of the above [1] to [78], wherein the ICI cone plate viscosity is 0.01 to 10 Pa · s in the range of 100 to 200 ° C. object.
[80] The curable epoxy resin composition for a white reflector according to any one of the above [1] to [79], which is solid at normal temperature (25 ° C.).
[81] The curing for a white reflector according to any one of the above [1] to [80], wherein the softening point is 40 to 130 ° C. (preferably 50 to 100 ° C., more preferably 70 to 100 ° C.). Epoxy resin composition.
[82] A cured product of the curable epoxy resin composition for white reflectors according to any one of [1] to [81] above.
[83] An optical semiconductor element mounting substrate having a white reflector formed of the cured product according to [82].
[84] An optical semiconductor device comprising the optical semiconductor element mounting substrate according to [83] and an optical semiconductor element mounted on the substrate.
［８５］下記工程（１）および（２）を含む、白色リフレクター用硬化性エポキシ樹脂組成物の製造方法：
（１）エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる混合物を、加熱・混合して、加熱混合物を得る工程；及び
（２）前記加熱混合物と、硬化剤（Ｄ）とを含む混合物を混合して、白色リフレクター用硬化性エポキシ樹脂組成物を得る工程。
［８６］前記工程（２）において、前記混合物が、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含む、上記［８５］に記載の白色リフレクター用硬化性エポキシ樹脂組成物の製造方法。
［８７］前記加熱混合物における２５℃におけるずり粘度が、１０～１，０００Ｐａ・ｓ（好ましくは１０～５００Ｐａ・ｓ、より好ましくは１０～３００Ｐａ・ｓ）である、上記［８５］又は［８６］に記載の白色リフレクター用硬化性エポキシ樹脂組成物の製造方法。
［８８］前記工程（１）における加熱温度が、５０～１２０℃（好ましくは６０～１００℃）である、上記［８５］～［８７］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物の製造方法。
［８９］前記工程（１）の混合における回転速度が、１０～１００００ｒｐｍ（好ましくは１０～５０００ｒｐｍ）である、上記［８５］～［８８］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物の製造方法。
［９０］前記工程（１）における加熱・混合時間が、０．５～２４時間（好ましくは０．５～１８時間）である、上記［８５］～［８９］のいずれか１つに記載の白色リフレクター用硬化性エポキシ樹脂組成物の製造方法。 [85] 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 | curing agent (D).
[86] In the step (2), 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 ′). The manufacturing method of the curable epoxy resin composition for white reflectors as described in said [85].
[87] The above [85] or [86], wherein 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). 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.
[89] 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.
[90] 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.
［９１］下記工程（１）～（３）を含む、白色リフレクター用硬化性エポキシ樹脂組成物の硬化物の製造方法：
（１）エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる混合物を、加熱・混合して、加熱混合物を得る工程；
（２）前記加熱混合物と、硬化剤（Ｄ）とを含む混合物を混合して、白色リフレクター用硬化性エポキシ樹脂組成物を得る工程；及び
（３）前記白色リフレクター用硬化性エポキシ樹脂組成物を加熱して、硬化物を得る工程。
［９２］前記工程（２）において、前記混合物が、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含む、上記［９１］に記載の硬化物の製造方法。
［９３］前記加熱混合物における２５℃におけるずり粘度が、１０～１，０００Ｐａ・ｓ（好ましくは１０～５００Ｐａ・ｓ、より好ましくは１０～３００Ｐａ・ｓ）である、上記［９１］又は［９２］に記載の硬化物の製造方法。
［９４］前記工程（１）における加熱温度が、５０～１２０℃（好ましくは６０～１００℃）である、上記［９１］～［９３］のいずれか１つに記載の硬化物の製造方法。
［９５］前記工程（１）の混合における回転速度が、１０～１００００ｒｐｍ（好ましくは１０～５０００ｒｐｍ）である、上記［９１］～［９４］のいずれか１つに記載の硬化物の製造方法。
［９６］前記工程（１）における加熱・混合時間が、０．５～２４時間（好ましくは０．５～１８時間）である、上記［９１］～［９５］のいずれか１つに記載の硬化物の製造方法。
［９７］硬化物が、光半導体素子搭載用基板用の白色リフレクターである、上記［９１］～［９６］のいずれか１つに記載の硬化物の製造方法。
［９８］上記［９７］に記載の製造方法を含む、光半導体装置の製造方法。 [91] 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.
[92] In the step (2), 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 ′). The manufacturing method of the hardened | cured material as described in said [91].
[93] The above [91] or [92], wherein 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). The manufacturing method of hardened | cured material as described in any one of.
[94] The method for producing a cured product according to any one of [91] to [93] above, wherein the heating temperature in the step (1) is 50 to 120 ° C. (preferably 60 to 100 ° C.).
[95] The method for producing a cured product according to any one of [91] to [94] above, wherein the rotational speed in the mixing in the step (1) is 10 to 10,000 rpm (preferably 10 to 5000 rpm).
[96] 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 [91] to [95] A method for producing a cured product.
[97] The method for producing a cured product according to any one of [91] to [96], wherein the cured product is a white reflector for an optical semiconductor element mounting substrate.
[98] A method for manufacturing an optical semiconductor device, including the manufacturing method according to [97].
　本発明の白色リフレクター用硬化性エポキシ樹脂組成物は上記構成を有するため、粉砕性及び／又は打錠性に優れ、さらにはべとつきが発生せず取扱いが容易であり、なおかつ硬化させることによって耐熱性に優れた硬化物を形成することができる。従って、本発明の白色リフレクター用硬化性エポキシ樹脂組成物を使用することにより、生産性、及び耐熱性に優れた白色リフレクターを有する、高品質な（例えば、高耐久性の）光半導体素子搭載用基板が得られる。さらに、上記光半導体素子搭載用基板を光半導体装置における基板として使用することにより、高品質な（例えば、高耐久性の）光半導体装置が得られる。 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.
本発明の光半導体素子搭載用基板の一例を示す概略図である。左側の図（ａ）は斜視図であり、右側の図（ｂ）は断面図である。It is the schematic which shows an example of the board | substrate for optical semiconductor element mounting of this invention. The left figure (a) is a perspective view, and the right figure (b) is a sectional view. 本発明の光半導体装置の一例を示す概略図（断面図）である。It is the schematic (sectional drawing) which shows an example of the optical semiconductor device of this invention. 本発明の光半導体装置の他の一例を示す概略図（断面図；ヒートシンクを有する場合）である。It is the schematic (sectional drawing; when it has a heat sink) which shows another example of the optical semiconductor device of this invention. 本発明の光半導体装置の他の一例を示す概略図（ヒートシンク（放熱フィン）を有する場合）である。左側の図（ａ）は上面図であり、右側の図（ｂ）は（ａ）におけるＡ－Ａ’断面図である。It is the schematic (when it has a heat sink (radiation fin)) which shows another example of the optical semiconductor device of this invention. The left drawing (a) is a top view, and the right drawing (b) is a cross-sectional view taken along line A-A 'in (a).
＜白色リフレクター用硬化性エポキシ樹脂組成物＞
　本発明の白色リフレクター用硬化性エポキシ樹脂組成物（単に「本発明の硬化性エポキシ樹脂組成物」や「硬化性エポキシ樹脂組成物」と称する場合がある）は、エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる加熱混合物であって、２５℃におけるずり粘度が、１０～１０００Ｐａ・ｓである混合物（単に「本発明の加熱混合物」と称する場合がある）を必須成分として含む組成物（硬化性組成物）であることを特徴とする。本発明の硬化性エポキシ樹脂組成物は、上記必須成分以外にも、必要に応じてその他の成分を含んでいてもよい。なお、本発明の硬化性エポキシ樹脂組成物は、加熱により硬化させて硬化物へと転化可能な熱硬化性組成物（熱硬化性エポキシ樹脂組成物）として使用できる。 <Curable epoxy resin composition for white reflector>
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.
［エポキシ化合物（Ａ）］
　本発明の加熱混合物におけるエポキシ化合物（Ａ）は、分子内にエポキシ基（オキシラニル基）を１つ以上有する化合物である。中でも、エポキシ化合物（Ａ）としては、分子内にエポキシ基を２つ以上（好ましくは２～６つ、より好ましくは２～４つ）有する化合物が好ましい。 [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. Among them, 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.
　エポキシ化合物（Ａ）としては、公知乃至慣用のエポキシ化合物を使用でき、特に限定されないが、例えば、脂環式エポキシ化合物（脂環式エポキシ樹脂）；脂肪族ポリグリシジルエーテル等の脂肪族エポキシ化合物（脂肪族エポキシ樹脂）；ビスフェノールＡ型エポキシ化合物等の芳香族エポキシ化合物（芳香族エポキシ樹脂）；複素環式エポキシ化合物（複素環式エポキシ樹脂）等が挙げられる。中でも、硬化物（白色リフレクター）の耐熱性及び耐光性、本発明の加熱混合物を所定の粘度に調整する観点で、脂環式エポキシ化合物、複素環式エポキシ化合物、芳香族エポキシ化合物が好ましく、脂環式エポキシ化合物、又は複素環式エポキシ化合物がより好ましく、脂環式エポキシ化合物がさらに好ましい。以下、脂環式エポキシ化合物を「脂環式エポキシ化合物（Ａ－１）」、複素環式エポキシ化合物を「複素環式エポキシ化合物（Ａ－２）」、芳香族エポキシ化合物を「芳香族エポキシ化合物（Ａ－３）」と称して説明する場合がある。 As the epoxy compound (A), known or commonly used epoxy compounds can be used, and are not particularly limited. For example, alicyclic epoxy compounds (alicyclic epoxy resins); aliphatic epoxy compounds such as aliphatic polyglycidyl ethers ( Aliphatic epoxy resins); aromatic epoxy compounds (aromatic epoxy resins) such as bisphenol A type epoxy compounds; heterocyclic epoxy compounds (heterocyclic epoxy resins) and the like. Among these, from the viewpoint of adjusting the heat resistance and light resistance of the cured product (white reflector) and the heating mixture of the present invention to a predetermined viscosity, 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. Hereinafter, the alicyclic epoxy compound is “alicyclic epoxy compound (A-1)”, the heterocyclic epoxy compound is “heterocyclic epoxy compound (A-2)”, and the aromatic epoxy compound is “aromatic epoxy compound”. (A-3) ”may be described.
　脂環式エポキシ化合物（Ａ－１）は、分子内に脂環（脂肪族炭化水素環）構造とエポキシ基とを少なくとも有する化合物であり、本発明の加熱混合物においては、公知乃至慣用の脂環式エポキシ化合物を使用することができる。脂環式エポキシ化合物（Ａ－１）としては、より具体的には、例えば、脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基（脂環式エポキシ基）を有する化合物（「化合物（Ａ－１－１）」と称する場合がある）；脂環に直接単結合で結合しているエポキシ基を有する化合物（「化合物（Ａ－１－２）」と称する場合がある）；脂環とグリシジル基とを有する化合物（「化合物（Ａ－１－３）」と称する場合がある）等が挙げられる。 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. In the heating mixture of the present invention, 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. Compound (sometimes referred to as “Compound (A-1-1)”); Compound having an epoxy group bonded directly to the alicyclic ring with a single bond (when referred to as “Compound (A-1-2)”) And a compound having an alicyclic ring and a glycidyl group (sometimes referred to as “compound (A-1-3)”).
　上述の化合物（Ａ－１－１）としては、分子内に脂環式エポキシ基を１つ以上有する公知乃至慣用の化合物を使用することができ、特に限定されない。上記脂環式エポキシ基としては、硬化性エポキシ樹脂組成物の硬化性及び硬化物（白色リフレクター）の耐熱性、本発明の加熱混合物を所定の粘度に調整する観点で、シクロヘキセンオキシド基が好ましい。特に、化合物（Ａ－１－１）としては、硬化物（白色リフレクター）の耐熱性、本発明の加熱混合物を所定の粘度に調整する観点で、分子内に２つ以上のシクロヘキセンオキシド基を有する化合物が好ましく、より好ましくは下記式（Ｉ）で表される化合物である。 As the above-mentioned 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. In particular, 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.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（Ｉ）中、Ｘは単結合又は連結基（１以上の原子を有する二価の基）を示す。上記連結基としては、例えば、二価の炭化水素基、炭素－炭素二重結合の一部又は全部がエポキシ化されたアルケニレン基（エポキシ化アルケニレン基）、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド基、これらが複数個連結した基等が挙げられる。なお、式（Ｉ）におけるシクロヘキサン環（シクロヘキセンオキシド基）を構成する炭素原子の１以上には、アルキル基等の置換基が結合していてもよい。 In formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of 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 group, an amide group, a group in which a plurality of these groups are linked, and the like. In addition, 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).
　式（Ｉ）中のＸが単結合である化合物としては、（３，４，３’，４’－ジエポキシ）ビシクロヘキシル等が挙げられる。 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.
　上記二価の炭化水素基としては、炭素数が１～１８の直鎖又は分岐鎖状のアルキレン基、二価の脂環式炭化水素基等が挙げられる。炭素数が１～１８の直鎖又は分岐鎖状のアルキレン基としては、例えば、メチレン基、メチルメチレン基、ジメチルメチレン基、エチレン基、プロピレン基、トリメチレン基等が挙げられる。上記二価の脂環式炭化水素基としては、例えば、１，２－シクロペンチレン基、１，３－シクロペンチレン基、シクロペンチリデン基、１，２－シクロヘキシレン基、１，３－シクロヘキシレン基、１，４－シクロヘキシレン基、シクロヘキシリデン基等の二価のシクロアルキレン基（シクロアルキリデン基を含む）等が挙げられる。 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. Examples of the divalent alicyclic hydrocarbon group 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.
　上記炭素－炭素二重結合の一部又は全部がエポキシ化されたアルケニレン基（「エポキシ化アルケニレン基」と称する場合がある）におけるアルケニレン基としては、例えば、ビニレン基、プロペニレン基、１－ブテニレン基、２－ブテニレン基、ブタジエニレン基、ペンテニレン基、ヘキセニレン基、ヘプテニレン基、オクテニレン基等の炭素数２～８の直鎖又は分岐鎖状のアルケニレン基等が挙げられる。特に、上記エポキシ化アルケニレン基としては、炭素－炭素二重結合の全部がエポキシ化されたアルケニレン基が好ましく、より好ましくは炭素－炭素二重結合の全部がエポキシ化された炭素数２～４のアルケニレン基である。 Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) 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. In particular, 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.
　上記連結基Ｘとしては、特に、酸素原子を含有する連結基が好ましく、具体的には、－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯＯ－、－Ｏ－、－ＣＯＮＨ－、エポキシ化アルケニレン基；これらの基が複数個連結した基；これらの基の１又は２以上と二価の炭化水素基の１又は２以上とが連結した基等が挙げられる。二価の炭化水素基としては上記で例示したものが挙げられる。 The linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation. An alkenylene group; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.
　上記式（Ｉ）で表される化合物の代表的な例としては、下記式（Ｉ－１）～（Ｉ－１０）で表される化合物、２，２－ビス（３，４－エポキシシクロヘキサン－１－イル）プロパン、１，２－ビス（３，４－エポキシシクロヘキサン－１－イル）エタン、１，２－エポキシ－１，２－ビス（３，４－エポキシシクロヘキサン－１－イル）エタン、ビス（３，４－エポキシシクロヘキシルメチル）エーテル等が挙げられる。なお、下記式（Ｉ－５）、（Ｉ－７）中のｌ、ｍは、それぞれ１～３０の整数を表す。下記式（Ｉ－５）中のＲは炭素数１～８のアルキレン基であり、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ｓ－ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基等の直鎖又は分岐鎖状のアルキレン基が挙げられる。これらの中でも、メチレン基、エチレン基、プロピレン基、イソプロピレン基等の炭素数１～３の直鎖又は分岐鎖状のアルキレン基が好ましい。下記式（Ｉ－９）、（Ｉ－１０）中のｎ１～ｎ６は、それぞれ１～３０の整数を示す。 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. In the following formulas (I-5) and (I-7), 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. And linear or branched alkylene groups such as a group, a heptylene group, and an octylene group. Among these, 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.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　化合物（Ａ－１－２）としては、例えば、下記式（ＩＩ）で表される化合物（エポキシ樹脂）等が挙げられる。 Examples of the compound (A-1-2) include a compound (epoxy resin) represented by the following formula (II).
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　上記式（ＩＩ）中、Ｒ1はｐ価の有機基を示す。ｐは、１～２０の整数を示す。ｐ価の有機基としては、例えば、後述のｐ個のヒドロキシ基を有する有機化合物の構造式からｐ個のヒドロキシ基を除いて形成された構造を有するｐ価の有機基等が挙げられる。 In the above 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.
　式（ＩＩ）中、ｑは、１～５０の整数を示す。なお、ｐが２以上の整数の場合、複数のｑは同一であってもよいし、異なっていてもよい。式（ＩＩ）におけるｑの和（総和）は、３～１００の整数である。 In the formula (II), q represents an integer of 1 to 50. In addition, when p is an integer greater than or equal to 2, several q may be the same and may differ. The sum (total) of q in the formula (II) is an integer of 3 to 100.
　式（ＩＩ）中、Ｒ2は、式中に示されるシクロヘキサン環上の置換基であり、下記式（ＩＩａ）～（ＩＩｃ）で表される基のいずれかを示す。上記シクロヘキサン環上のＲ2の結合位置は特に限定されないが、通常、酸素原子と結合するシクロヘキサン環の２つの炭素原子の位置を１位、２位とした場合、４位又は５位の炭素原子である。また、式（ＩＩ）で表される化合物が複数のシクロヘキサン環を有する場合、それぞれのシクロヘキサン環におけるＲ2の結合位置は同一であってもよいし、異なっていてもよい。式（ＩＩ）におけるＲ2の少なくとも１つは、式（ＩＩａ）で表される基（エポキシ基）である。なお、式（ＩＩ）で表される化合物が２以上のＲ2を有する場合、複数のＲ2は同一であってもよいし、異なっていてもよい。 In the formula (II), 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. When the compound represented by the formula (II) has a plurality of cyclohexane rings, 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). In the case where 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.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　式（ＩＩｃ）中、Ｒ3は、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルキルカルボニル基、又は置換若しくは無置換のアリールカルボニル基を示す。上記アルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、２－エチルヘキシル基等の炭素数１～２０の直鎖又は分岐鎖状のアルキル基等が挙げられる。上記アルキルカルボニル基としては、例えば、メチルカルボニル基（アセチル基）、エチルカルボニル基、ｎ－プロピルカルボニル基、イソプロピルカルボニル基、ｎ－ブチルカルボニル基、イソブチルカルボニル基、ｓ－ブチルカルボニル基、ｔ－ブチルカルボニル基等の炭素数１～２０の直鎖又は分岐鎖状のアルキル－カルボニル基等が挙げられる。上記アリールカルボニル基としては、例えば、フェニルカルボニル基（ベンゾイル基）、１－ナフチルカルボニル基、２－ナフチルカルボニル基等の炭素数６～２０のアリール－カルボニル基等が挙げられる。 In formula (IIc), 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. Examples of the 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. Examples of the alkylcarbonyl group include a methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl. Examples thereof include a linear or branched alkyl-carbonyl group having 1 to 20 carbon atoms such as a carbonyl group. Examples of the arylcarbonyl group 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.
　上述のアルキル基、アルキルカルボニル基、アリールカルボニル基が有していてもよい置換基としては、例えば、炭素数０～２０（より好ましくは炭素数０～１０）の置換基等が挙げられる。上記置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；メトキシ基、エトキシ基、プロポキシ基、イソプロピルオキシ基、ブトキシ基、イソブチルオキシ基等のアルコキシ基（好ましくはＣ1-6アルコキシ基、より好ましくはＣ1-4アルコキシ基）；アリルオキシ基等のアルケニルオキシ基（好ましくはＣ2-6アルケニルオキシ基、より好ましくはＣ2-4アルケニルオキシ基）；アセチルオキシ基、プロピオニルオキシ基、（メタ）アクリロイルオキシ基等のアシルオキシ基（好ましくはＣ1-12アシルオキシ基）；メルカプト基；メチルチオ基、エチルチオ基等のアルキルチオ基（好ましくはＣ1-6アルキルチオ基、より好ましくはＣ1-4アルキルチオ基）；アリルチオ基等のアルケニルチオ基（好ましくはＣ2-6アルケニルチオ基、より好ましくはＣ2-4アルケニルチオ基）；カルボキシ基；メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基等のアルコキシカルボニル基（好ましくはＣ1-6アルコキシ－カルボニル基）；アミノ基；メチルアミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基等のモノ又はジアルキルアミノ基（好ましくはモノ又はジ－Ｃ1-6アルキルアミノ基）；アセチルアミノ基、プロピオニルアミノ基等のアシルアミノ基（好ましくはＣ1-11アシルアミノ基）；エチルオキセタニルオキシ基等のオキセタニル基含有基；アセチル基、プロピオニル基等のアシル基（好ましくはＣ1-11アシル基）；オキソ基；これらの２以上が必要に応じてＣ1-6アルキレン基を介して結合した基等が挙げられる。また、上述のアリールカルボニル基が有していてもよい置換基としては、さらに、上記置換若しくは無置換のアルキル基、上記置換若しくは無置換のアルキルカルボニル基も挙げられる。 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 acyloxy group); a mercapto group; an alkylthio group such as a methylthio group and an ethylthio group (preferably a C 1-6 alkylthio group) group, more preferably a C 1-4 alkylthio group); allyl alkenylthio such groups (Preferably C 2-6 alkenylthio group, more preferably C 2-4 alkenylthio group); carboxy; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, an alkoxycarbonyl group (preferably C such as butoxycarbonyl group 1-6 alkoxy-carbonyl group); amino group; mono- or dialkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (preferably mono- or di-C 1-6 alkylamino group); acetyl Acylamino groups such as amino groups and propionylamino groups (preferably C 1-11 acylamino groups); Oxetanyl group-containing groups such as ethyl oxetanyloxy groups; Acyl groups such as acetyl groups and propionyl groups (preferably C 1-11 acyl groups) ); An oxo group; two or more of these are optionally a C 1-6 alkylene group And the like are groups bonded through. In addition, 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.
　式（ＩＩ）で表される化合物におけるＲ2の全量（１００モル％）に対する、式（ＩＩａ）で表される基（エポキシ基）の割合は、特に限定されないが、４０モル％以上（例えば、４０～１００モル％）が好ましく、より好ましくは６０モル％以上、さらに好ましくは８０モル％以上である。上記割合が４０モル％未満であると、硬化物の耐熱性や機械特性、本発明の加熱混合物の粘度等が不十分となる場合がある。なお、上記割合は、例えば、1Ｈ－ＮＭＲスペクトル測定や、オキシラン酸素濃度測定等により算出することができる。 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. When 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.
　式（ＩＩ）で表される化合物は、特に限定されないが、例えば、分子内にｐ個のヒドロキシ基を有する有機化合物［Ｒ1（ＯＨ）p］を開始剤として（即ち、当該化合物のヒドロキシ基（活性水素）を出発点として）、１，２－エポキシ－４－（２－ビニル）シクロヘキサン（３－ビニル－７－オキサビシクロ［４．１．０］ヘプタン）を開環重合（カチオン重合）させ、その後、酸化剤によりエポキシ化することによって製造される。 The compound represented by the formula (II) is not particularly limited. For example, 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.
　上記分子内にｐ個のヒドロキシ基を有する有機化合物［Ｒ1（ＯＨ）p］としては、例えば、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、オクタノール等の脂肪族アルコール；エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、ネオペンチルグリコールエステル、シクロヘキサンジメタノール、グリセリン、ジグリセリン、ポリグリセリン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、水添ビスフェノールＡ、水添ビスフェノールＦ、水添ビスフェノールＳ等の多価アルコール；ポリビニルアルコール、ポリ酢酸ビニル部分加水分解物、デンプン、アクリルポリオール樹脂、スチレン－アリルアルコール共重合樹脂、ポリエステルポリオール、ポリカプロラクトンポリオール、ポリプロピレンポリオール、ポリテトラメチレングリコール、ポリカーボネートポリオール類、ヒドロキシ基を有するポリブタジエン、セルロース、セルロースアセテート、セルロースアセテートブチレート、ヒドロキシエチルセルロース等のセルロース系ポリマー等のヒドロキシ基を有するオリゴマー又はポリマー等が挙げられる。 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; polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, acrylic polyol resin, styrene-allyl alcohol copolymer resin, polyester polyol, polycaprolactone polyol, polypropylene polyol, polytetramethylene glycol, polycarbonate polyol Examples thereof include oligomers or polymers having a hydroxy group such as polybutadiene having a hydroxy group, cellulose, cellulose acetate, cellulose acetate butyrate, and cellulose-based polymers such as hydroxyethyl cellulose.
　上記１，２－エポキシ－４－（２－ビニル）シクロヘキサンは、公知乃至慣用の方法により製造でき、特に限定されないが、例えば、ブタジエンの二量化反応によって得られる４－ビニルシクロヘキセンを、過酢酸等の酸化剤を使用して部分エポキシ化することによって得られる。また、１，２－エポキシ－４－（２－ビニル）シクロヘキサンとしては、市販品を使用することもできる。 The above 1,2-epoxy-4- (2-vinyl) cyclohexane can be produced by a known or conventional method, and is not particularly limited. For example, 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. Moreover, as 1,2-epoxy-4- (2-vinyl) cyclohexane, a commercially available product can be used.
　また、上記酸化剤としては、過酸化水素や有機過酸等の公知乃至慣用の酸化剤を使用することができ、特に限定されないが、例えば、有機過酸としては、過ギ酸、過酢酸、過安息香酸、トリフルオロ過酢酸等が挙げられる。中でも、過酢酸は工業的に安価に入手可能であり、かつ安定度も高いため、好ましい。 The oxidant may be a known or conventional oxidant such as hydrogen peroxide or organic peracid, and is not particularly limited. Examples of 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.
　なお、上述の開環重合及びエポキシ化は、より具体的には、例えば、特開昭６０－１６１９７３号公報等に記載の周知慣用の方法に従って実施することができる。 The above ring-opening polymerization and epoxidation can be carried out more specifically according to well-known and conventional methods described in, for example, JP-A-60-161973.
　式（ＩＩ）で表される化合物の標準ポリスチレン換算の重量平均分子量は、特に限定されないが、３００～１０００００が好ましく、より好ましくは１０００～１００００である。重量平均分子量が３００未満であると、硬化物の機械強度や耐熱性、本発明の加熱混合物の粘度が不十分となる場合がある。一方、重量平均分子量が１０００００を超えると、粘度が高くなり成型時の流動性が低下する場合がある。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定される。 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. When 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. On the other hand, when 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.
　式（ＩＩ）で表される化合物のエポキシ当量は、特に限定されないが、５０～１０００が好ましく、より好ましくは１００～５００である。エポキシ当量が５０未満であると、硬化物が脆くなってしまう場合がある。一方、エポキシ当量が１０００を超えると、硬化物の機械強度が不十分となる場合がある。なお、エポキシ当量は、ＪＩＳ　Ｋ７２３６：２００１に準じて測定される。 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.
　脂環式エポキシ化合物（Ａ－１）としての上述の化合物（Ａ－１－３）としては、例えば、２，２－ビス［４－（２，３－エポキシプロポキシ）シクロへキシル］プロパン、２，２－ビス［３，５－ジメチル－４－（２，３－エポキシプロポキシ）シクロへキシル］プロパン、ビスフェノールＡ型エポキシ化合物を水素化した化合物（水素化ビスフェノールＡ型エポキシ化合物）等；ビス［２－（２，３－エポキシプロポキシ）シクロへキシル］メタン、［２－（２，３－エポキシプロポキシ）シクロへキシル］［４－（２，３－エポキシプロポキシ）シクロへキシル］メタン、ビス［４－（２，３－エポキシプロポキシ）シクロへキシル］メタン、ビス［３，５－ジメチル－４－（２，３－エポキシプロポキシ）シクロへキシル］メタン、ビスフェノールＦ型エポキシ化合物を水素化した化合物（水素化ビスフェノールＦ型エポキシ化合物）等；水添ビフェノール型エポキシ化合物；水添フェノールノボラック型エポキシ化合物；水添クレゾールノボラック型エポキシ化合物；ビスフェノールＡの水添クレゾールノボラック型エポキシ化合物；水添ナフタレン型エポキシ化合物；トリスフェノールメタンから得られるエポキシ化合物の水添エポキシ化合物等が挙げられる。 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 .; hydrogenated biphenol type epoxy compound; hydrogenated phenol novolac type epoxy compound; hydrogenated cresol novolac type epoxy compound; hydrogenated cresol of bisphenol A Examples thereof include novolak-type epoxy compounds; hydrogenated naphthalene-type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane.
　脂環式エポキシ化合物（Ａ－１）としては、硬化物（白色リフレクター）の耐熱性、本発明の加熱混合物を所定の粘度に調整する観点で、化合物（Ａ－１－１）、化合物（Ａ－１－２）、化合物（Ａ－１－３）が好ましく、化合物（Ａ－１－１）、化合物（Ａ－１－３）がより好ましい。中でも、硬化物（白色リフレクター）の耐熱性、本発明の加熱混合物の粘度をいっそう向上させ、より優れた耐黄変性（黄変しにくい特性）、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性を発現させる点で、上記式（Ｉ－１）で表される化合物［３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート；例えば、商品名「セロキサイド２０２１Ｐ」（（株）ダイセル製）等］、上記式（ＩＩ）で表される化合物［２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物；例えば、商品名「ＥＨＰＥ３１５０」（（株）ダイセル製）等］、水素化ビスフェノールＡ型ジグリシジル化合物；例えば、商品名「ＹＸ－８０４０」（三菱化学（株）製）等が特に好ましい。 As the alicyclic epoxy 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. Among them, 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) and the like are particularly preferable.
　複素環式エポキシ化合物（Ａ－２）としては、例えば、分子内にエポキシ基以外の複素環［例えば、テトラヒドロフラン環、テトラヒドロピラン環、モルホリン環、クロマン環、イソクロマン環、テトラヒドロチオフェン環、テトラヒドロチオピラン環、アジリジン環、ピロリジン環、ピペリジン環、ピペラジン環、インドリン環、２，６－ジオキサビシクロ［３．３．０］オクタン環、１，３，５－トリアザシクロヘキサン環、１，３，５－トリアザシクロヘキサ－２，４，６－トリオン環（イソシアヌル環）、ジヒドロイミダゾ［４，５－ｄ］イミダゾール－２，５－ジオン環（グリコールウリル環）等の非芳香族性複素環；チオフェン環、ピロール環、フラン環、ピリジン環等の芳香族性複素環等］と、エポキシ基とを有する化合物が挙げられる。中でも、複素環式エポキシ化合物（Ａ－２）としては、炭素原子、水素原子、酸素原子、及び窒素原子から構成されるものが好ましい。 Examples of the heterocyclic epoxy compound (A-2) include heterocycles other than epoxy groups in the molecule [for example, tetrahydrofuran ring, tetrahydropyran ring, morpholine ring, chroman ring, isochroman ring, tetrahydrothiophene ring, tetrahydrothiopyran. Ring, aziridine ring, pyrrolidine ring, piperidine ring, piperazine ring, indoline ring, 2,6-dioxabicyclo [3.3.0] octane ring, 1,3,5-triazacyclohexane ring, 1,3,5 A non-aromatic heterocyclic ring such as a triazacyclohexa-2,4,6-trione ring (isocyanuric ring), dihydroimidazo [4,5-d] imidazole-2,5-dione ring (glycoluril ring); Aromatic heterocycles such as thiophene ring, pyrrole ring, furan ring, pyridine ring, etc.] and an epoxy group And the like. Among these, the heterocyclic epoxy compound (A-2) is preferably composed of a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom.
　上記複素環式エポキシ化合物（Ａ－２）としては、例えば、分子内に１つ以上のエポキシ基を有するイソシアヌレート（以下、「エポキシ基含有イソシアヌレート」と称する場合がある）又はグリコールウリル環を有するエポキシ化合物（以下、「エポキシ基含有グリコールウリル」と称する場合がある）を好ましく使用できる。上記エポキシ基含有イソシアヌレートが分子内に有するエポキシ基の数は、特に限定されないが、１～６つが好ましく、より好ましくは１～３つである。上記エポキシ基含有グリコールウリルが分子内に有するエポキシ基の数は、特に限定されないが、１～６つが好ましく、より好ましくは２～４つである。 Examples of the heterocyclic epoxy compound (A-2) 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.
　上記エポキシ基含有イソシアヌレートとしては、例えば、下記式（ＩＩＩ）で表される化合物が挙げられる。 Examples of the epoxy group-containing isocyanurate include compounds represented by the following formula (III).
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　式（ＩＩＩ）中、Ｒ4～Ｒ6は、同一又は異なって、水素原子又は一価の有機基を示す。但し、Ｒ4～Ｒ6の少なくとも１つは、エポキシ基を含有する一価の有機基である。上記一価の有機基としては、例えば、一価の脂肪族炭化水素基（例えば、アルキル基、アルケニル基等）；一価の脂環式炭化水素基（例えば、シクロアルキル基、シクロアルケニル基等）；一価の芳香族炭化水素基（例えば、アリール基等）；一価の複素環式基；脂肪族炭化水素基、脂環式炭化水素基、及び芳香族炭化水素基の２以上が結合して形成された一価の基等が挙げられる。なお、一価の有機基は置換基（例えば、ヒドロキシ基、カルボキシ基、ハロゲン原子等の置換基）を有していてもよい。エポキシ基を含有する一価の有機基としては、例えば、エポキシ基、グリシジル基、２－メチルエポキシプロピル基、シクロヘキセンオキシド基等の後述のエポキシ基を含有する一価の基等が挙げられる。 In 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. Examples of 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). 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.
　特に、式（ＩＩＩ）におけるＲ4～Ｒ6は、同一又は異なって、下記式（ＩＩＩａ）で表される基又は下記式（ＩＩＩｂ）で表される基であって、Ｒ4～Ｒ6の少なくとも１つが式（ＩＩＩａ）で表される基であることが好ましい。 In particular, 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).
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　上記式（ＩＩＩａ）及び式（ＩＩＩｂ）中のＲ7及びＲ8は、同一又は異なって、水素原子又は炭素数１～８のアルキル基を示す。炭素数１～８のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の直鎖又は分岐鎖状のアルキル基が挙げられる。中でも、メチル基、エチル基、プロピル基、イソプロピル基等の炭素数１～３の直鎖又は分岐鎖状のアルキル基が好ましい。式（ＩＩＩａ）及び式（ＩＩＩｂ）中のＲ7及びＲ8は、水素原子であることが特に好ましい。 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. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable. R 7 and R 8 in formula (IIIa) and formula (IIIb) are particularly preferably hydrogen atoms.
　より具体的には、上記エポキシ基含有イソシアヌレートとしては、下記式（ＩＩＩ－１）で表される化合物、下記式（ＩＩＩ－２）で表される化合物、下記式（ＩＩＩ－３）で表される化合物等が挙げられる。 More specifically, 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.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　上記式（ＩＩＩ－１）～（ＩＩＩ－３）中、Ｒ7及びＲ8は、同一又は異なって、式（ＩＩＩａ）及び式（ＩＩＩｂ）におけるものと同じである。 In the above formulas (III-1) to (III-3), R 7 and R 8 are the same or different and are the same as those in formula (IIIa) and formula (IIIb).
　上記式（ＩＩＩ－１）で表される化合物の代表的な例としては、モノアリルジグリシジルイソシアヌレート、１－アリル－３，５－ビス（２－メチルエポキシプロピル）イソシアヌレート、１－（２－メチルプロペニル）－３，５－ジグリシジルイソシアヌレート、１－（２－メチルプロペニル）－３，５－ビス（２－メチルエポキシプロピル）イソシアヌレート等が挙げられる。 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.
　上記式（ＩＩＩ－２）で表される化合物の代表的な例としては、ジアリルモノグリシジルイソシアヌレート、１，３－ジアリル－５－（２－メチルエポキシプロピル）イソシアヌレート、１，３－ビス（２－メチルプロペニル）－５－グリシジルイソシアヌレート、１，３－ビス（２－メチルプロペニル）－５－（２－メチルエポキシプロピル）イソシアヌレート等が挙げられる。 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.
　上記式（ＩＩＩ－３）で表される化合物の代表的な例としては、トリグリシジルイソシアヌレート、トリス（２－メチルエポキシプロピル）イソシアヌレート等が挙げられる。 Representative examples of the compound represented by the above formula (III-3) include triglycidyl isocyanurate, tris (2-methylepoxypropyl) isocyanurate, and the like.
　なお、上記エポキシ基含有イソシアヌレートは、アルコールや酸無水物等のエポキシ基と反応する化合物を加えてあらかじめ変性して用いることもできる。 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.
　上記エポキシ基含有グリコールウリルとしては、例えば、下記式（ＩＶ）で表される化合物が挙げられる。 Examples of the epoxy group-containing glycoluril include compounds represented by the following formula (IV).
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　式（ＩＶ）中、Ｒ9～Ｒ12は、同一又は異なって、水素原子又は一価の有機基を示す。但し、Ｒ9～Ｒ12の少なくとも１つは、エポキシ基を含有する一価の有機基である。上記一価の有機基としては、上述のエポキシ基含有イソシアヌレートにおける一価の有機基と同様のものが挙げられる。なお、一価の有機基は置換基（例えば、上述のアルキル基、アルキルカルボニル基が有していてもよい置換基として例示したものと同様の置換基等）を有していてもよい。上記一価の有機基としては、中でも、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、エポキシ基を含有する一価の有機基が好ましい。従って、上記Ｒ9～Ｒ12は、同一又は異なって、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又はエポキシ基を含有する一価の有機基であることが好ましい。 In 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). As the monovalent organic group, a monovalent organic group containing a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or an epoxy group is preferable. Therefore, 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. .
　上記エポキシ基を含有する一価の有機基は、エポキシ基（オキシラン環）を少なくとも１つ含む有機基であり、例えば、アルケニル基等の炭素－炭素二重結合を有する直鎖又は分岐鎖状の炭素数２～２０の脂肪族炭化水素基が有する少なくとも１つの二重結合がエポキシ化された基や、炭素－炭素二重結合を有する環状の脂肪族炭化水素基（例えば、Ｃ3-20シクロアルケニル基；シクロヘキセニルエチル基等のＣ3-20シクロアルケニルアルキル基等）が有する少なくとも１つの二重結合がエポキシ化された基等が挙げられる。より具体的には、例えば、１，２－エポキシエチル基（エポキシ基）、１，２－エポキシプロピル基、２，３－エポキシプロピル基（グリシジル基）、２，３－エポキシ－２－メチルプロピル基（メチルグリシジル基）、３，４－エポキシブチル基、３－グリシジルオキシプロピル基、３，４－エポキシシクロヘキシルメチル基、２－（３，４－エポキシシクロヘキシル）エチル基等が挙げられる。中でも、他の成分との反応性が高く、本発明の加熱混合物を所定の粘度に調整して硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性、硬化物の耐熱性がより向上する点で、少なくとも末端にエポキシ基を有する基が好ましく、より好ましくはω－エポキシアルキル基（ω－アルキレン基の末端の二重結合がエポキシ化された基）が好ましく、さらに好ましくは炭素数２～６のω－エポキシアルキル基、さらに好ましくはグリシジル基である。 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. A group in which at least one double bond of an aliphatic hydrocarbon group having 2 to 20 carbon atoms is epoxidized, or a cyclic aliphatic hydrocarbon group having a carbon-carbon double bond (for example, C 3-20 cyclohexane) An alkenyl group; a group in which at least one double bond of a C 3-20 cycloalkenylalkyl group such as a cyclohexenylethyl group) is epoxidized, and the like. More specifically, for example, 1,2-epoxyethyl group (epoxy group), 1,2-epoxypropyl group, 2,3-epoxypropyl group (glycidyl 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. Among them, the reactivity with other components is high, and the pulverization property and / or tableting property of the curable epoxy resin composition and the heat resistance of the cured product are further improved by adjusting the heating mixture of the present invention to a predetermined viscosity. In view of this, a group having an epoxy group at least at the terminal is preferable, more preferably an ω-epoxyalkyl group (a group in which the double bond at the terminal of the ω-alkylene group is epoxidized), more preferably 2 6 is an ω-epoxyalkyl group, more preferably a glycidyl group.
　上記アルケニル基としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等の炭素数２～２０の置換又は無置換アルケニル基が挙げられる。置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基等が挙げられる。中でも、ω－アルケニル基（末端に炭素－炭素不飽和二重結合を有するアルケニル基）が好ましく、より好ましくは炭素数２～６のω－アルケニル基、さらに好ましくはアリル基である。 Examples of the alkenyl group 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. Examples of the substituent include a halogen atom, a hydroxy group, and a carboxy group. Among them, an ω-alkenyl group (an alkenyl group having a carbon-carbon unsaturated double bond at the terminal) is preferable, an ω-alkenyl group having 2 to 6 carbon atoms is more preferable, and an allyl group is more preferable.
　上記アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル、ｓ－ブチル、ｔ－ブチル等の炭素数１～２０の置換又は無置換アルキル基が挙げられる。置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基等が挙げられる。中でも、炭素数１～６のアルキル基が好ましい。 Examples of the alkyl group 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. Examples of the substituent include a halogen atom, a hydroxy group, and a carboxy group. Of these, an alkyl group having 1 to 6 carbon atoms is preferable.
　式（ＩＶ）中、Ｒ13及びＲ14は、同一又は異なって、水素原子又は一価の有機基を示す。上記一価の有機基としては、上述のエポキシ基含有イソシアヌレートにおける一価の有機基と同様のものが挙げられる。 In formula (IV), R 13 and R 14 are the same or different and each represents a hydrogen atom or a monovalent organic group. As said monovalent organic group, the same thing as the monovalent organic group in the above-mentioned epoxy-group-containing isocyanurate is mentioned.
　特に、式（ＩＶ）におけるＲ9～Ｒ12は、同一又は異なって、下記式（ＩＶａ）で表される基又は下記式（ＩＶｂ）で表される基であって、Ｒ9～Ｒ12の少なくとも１つが式（ＩＶａ）で表される基であることが好ましい。 In particular, 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).
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　上記式（ＩＶａ）及び式（ＩＶｂ）中のＲ15及びＲ16は、同一又は異なって、水素原子又は炭素数１～８のアルキル基を示す。炭素数１～８のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の直鎖又は分岐鎖状のアルキル基が挙げられる。中でも、メチル基、エチル基、プロピル基、イソプロピル基等の炭素数１～３の直鎖又は分岐鎖状のアルキル基が好ましい。式（ＩＶａ）及び式（ＩＶｂ）中のＲ15及びＲ16は、水素原子であることが特に好ましい。 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. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group. Of these, a linear or branched alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group is preferable. R 15 and R 16 in formula (IVa) and formula (IVb) are particularly preferably a hydrogen atom.
　より具体的には、上記エポキシ基含有グリコールウリルとしては、下記式（ＩＶ－１）で表される化合物、下記式（ＩＶ－２）で表される化合物、下記式（ＩＶ－３）で表される化合物、下記式（ＩＶ－４）で表される化合物、下記式（ＩＶ－５）で表される化合物、下記式（ＩＶ－６）で表される化合物等が挙げられる。 More specifically, 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). A compound represented by the following formula (IV-4), a compound represented by the following formula (IV-5), a compound represented by the following formula (IV-6), and the like.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　上記式（ＩＶ－１）～（ＩＶ－６）中、Ｒ15及びＲ16は、同一又は異なって、式（ＩＶａ）及び式（ＩＶｂ）におけるものと同じである。 In the above formulas (IV-1) to (IV-6), R 15 and R 16 are the same or different and are the same as those in the formulas (IVa) and (IVb).
　上記式（ＩＶ－１）で表される化合物の代表的な例としては、１，３，４，６－テトラグリシジルグリコールウリル、１，３，４，６－テトラキス（２－メチルエポキシプロピル）グリコールウリル等が挙げられる。 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.
　上記式（ＩＶ－２）で表される化合物の代表的な例としては、１－アリル－３，４，６－トリグリシジルグリコールウリル、１－アリル－３，４，６－トリス（２－メチルエポキシプロピル）グリコールウリル、１－（２－メチルプロペニル）－３，４，６－トリグリシジルグリコールウリル、１－（２－メチルプロペニル）－３，４，６－トリス（２－メチルエポキシプロピル）グリコールウリル等が挙げられる。 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.
　上記式（ＩＶ－３）で表される化合物の代表的な例としては、１，４－ジアリル－３，６－ジグリシジルグリコールウリル、１，４－ジアリル－３，６－ビス（２－メチルエポキシプロピル）グリコールウリル、１，４－ビス（２－メチルプロペニル）－３，６－ジグリシジルグリコールウリル、１，４－ビス（２－メチルプロペニル）－３，６－ビス（２－メチルエポキシプロピル）グリコールウリル等が挙げられる。 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.
　上記式（ＩＶ－４）で表される化合物の代表的な例としては、１，３－ジアリル－４，６－ジグリシジルグリコールウリル、１，３－ジアリル－４，６－ビス（２－メチルエポキシプロピル）グリコールウリル、１，３－ビス（２－メチルプロペニル）－４，６－ジグリシジルグリコールウリル、１，３－ビス（２－メチルプロペニル）－４，６－ビス（２－メチルエポキシプロピル）グリコールウリル等が挙げられる。 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.
　上記式（ＩＶ－５）で表される化合物の代表的な例としては、１，６－ジアリル－３，４－ジグリシジルグリコールウリル、１，６－ジアリル－３，４－ビス（２－メチルエポキシプロピル）グリコールウリル、１，６－ビス（２－メチルプロペニル）－３，４－ジグリシジルグリコールウリル、１，６－ビス（２－メチルプロペニル）－３，４－ビス（２－メチルエポキシプロピル）グリコールウリル等が挙げられる。 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.
　上記式（ＩＶ－６）で表される化合物の代表的な例としては、１，３，４－トリアリル－６－グリシジルグリコールウリル、１，３，４－トリアリル－６－（２－メチルエポキシプロピル）グリコールウリル、１，３，４－トリス（２－メチルプロペニル）－６－グリシジルグリコールウリル、１，３，４－トリス（２－メチルプロペニル）－６－（２－メチルエポキシプロピル）グリコールウリル等が挙げられる。 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.
　なお、上記エポキシ基含有グリコールウリルは、アルコールや酸無水物等のエポキシ基と反応する化合物を加えてあらかじめ変性して用いることもできる。 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.
　複素環式エポキシ化合物（Ａ－２）としては、硬化物（白色リフレクター）の耐熱性、本発明の加熱混合物を所定の粘度に調整する観点で、エポキシ基含有イソシアヌレート、エポキシ基含有グリコールウリルが好ましく、エポキシ基含有イソシアヌレートがより好ましい。中でも、硬化物（白色リフレクター）の耐熱性、本発明の加熱混合物の粘度を向上させ、優れた耐黄変性（黄変しにくい特性）、硬化性エポキシ化合物により優れた粉砕性及び／又は打錠性を発現させる点で、トリグリシジルイソシアヌレート（例えば、商品名「ＴＥＰＩＣ－Ｓ」（日産化学工業（株）製））、モノアリルジグリシジルイソシアヌレート（例えば、商品名「ＭＡ－ＤＧＩＣ」（四国化成工業（株）製））、１，３，４，６－テトラグリシジルグリコールウリル（例えば、商品名「ＴＧ－Ｇ」（四国化成工業（株）製））等が好ましく、モノアリルジグリシジルイソシアヌレートが特に好ましい。 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. Preferably, an epoxy group-containing isocyanurate is more preferable. Among them, 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) And 1,3,4,6-tetraglycidylglycoluril (for example, trade name “TG-G” (manufactured by Shikoku Kasei Kogyo Co., Ltd.)) and the like, monoallyl diglycidyl isocyanate Nurate is particularly preferred.
　上記芳香族エポキシ化合物（Ａ－３）としては、例えば、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＥ型エポキシ化合物、ｏ－フェニルフェノールグリシジルエーテル、ビフェニル型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールＡのクレゾールノボラック型エポキシ化合物、ナフタレン型エポキシ化合物、トリスフェノールメタンから得られるエポキシ化合物等の芳香族グリシジルエーテル系エポキシ化合物を挙げることができ、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビフェニル型エポキシ樹脂が好ましく、例えば、商品名「ＹＤ－１２８」（新日鐡住金化学（株）製）、商品名「ｊＥＲ１００１」（三菱化学（株）製）等の市販品を使用することができる。 Examples of the aromatic epoxy compound (A-3) 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 Preferably, for example, (manufactured by Nippon 鐡住 gold Chemical Co., Ltd.) trade name "YD-128", it is possible to use the trade name "jER1001" (manufactured by Mitsubishi Chemical Co., Ltd.) and the like commercially available.
　本発明の加熱混合物においてエポキシ化合物（Ａ）は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、エポキシ化合物（Ａ）は、公知乃至慣用の方法により製造することもできるし、例えば、商品名「セロキサイド２０２１Ｐ」、「セロキサイド２０８１」、「ＥＨＰＥ３１５０」（以上、（株）ダイセル製）、商品名「ＹＸ８０４０」（以上、三菱化学（株）製）等の市販品を使用することもできる。 In the heating mixture of the present invention, 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. For example, 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.
［無機充填剤（Ｂ）］
　本発明の硬化性エポキシ樹脂組成物における無機充填剤（Ｂ）は、主に、本発明の加熱混合物を所定の粘度に調整しやくし、硬化性エポキシ樹脂組成物に対して良好な粉砕性及び／又は打錠性を付与し、また、硬化物（白色リフレクター）の線膨張率を低減させる働きを有する。また、無機充填剤（Ｂ）の種類によっては、硬化物（白色リフレクター）に対して優れた光反射性を付与できる場合もある。 [Inorganic filler (B)]
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 | cured material (white reflector). Moreover, depending on the kind of inorganic filler (B), the light reflectivity excellent with respect to hardened | cured material (white reflector) may be provided.
　無機充填剤（Ｂ）としては、公知乃至慣用の無機充填剤を使用することができ、特に限定されないが、例えば、シリカ、ジルコン、珪酸カルシウム、リン酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、酸化鉄、酸化アルミニウム、フォステライト、ステアタイト、スピネル、屈折率１．５未満のクレー、ドロマイト、ヒドロキシアパタイト、ネフェリンサイナイト、クリストバライト、ウォラストナイト、珪藻土等の粉体、又はこれらの成型体（例えば、球形化したビーズ等）等が挙げられる。また、無機充填剤（Ｂ）としては、上述の無機充填剤に公知乃至慣用の表面処理が施されたもの等も挙げられる。中でも、無機充填剤（Ｂ）としては、本発明の加熱混合物を所定の粘度に調整する観点で、シリカ（シリカフィラー）が好ましい。 As the inorganic filler (B), known or conventional inorganic fillers can be used, and are not particularly limited. For example, silica, zircon, calcium silicate, calcium phosphate, silicon carbide, silicon nitride, boron nitride, iron oxide , Aluminum oxide, fosterite, steatite, spinel, clay with a refractive index of less than 1.5, dolomite, hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth powder, or molded products thereof (for example, Spherical beads) and the like. 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.
　シリカとしては、特に限定されず、例えば、溶融シリカ、結晶シリカ、高純度合成シリカ等の公知乃至慣用のシリカを使用できる。なお、シリカとしては、公知乃至慣用の表面処理［例えば、金属酸化物、シランカップリング剤、チタンカップリング剤、有機酸、ポリオール、シリコーン等の表面処理剤による表面処理等］が施されたものを使用することもできる。 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.
　無機充填剤（Ｂ）の形状は、特に限定されないが、例えば、粉体、球状、破砕状、繊維状、針状、鱗片状等が挙げられる。中でも、分散性の観点で、球状の無機充填剤が好ましく、特に真球状の無機充填剤（例えば、アスペクト比が１．２以下の球状のシリカ）が好ましい。 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.
　無機充填剤（Ｂ）の中心粒径は、特に限定されないが、硬化物（白色リフレクター）の光反射性向上、本発明の加熱混合物を所定の粘度に調整する観点で、０．１～５０μｍが好ましく、より好ましくは０．１～３０μｍである。なお、上記中心粒径は、レーザー回折・散乱法で測定した粒度分布における積算値５０％での粒径（メディアン径）を意味する。 The center particle diameter of the inorganic filler (B) is not particularly limited, but is 0.1 to 50 μm 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 μm. In addition, 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.
　なお、本発明の加熱混合物において無機充填剤（Ｂ）は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、無機充填剤（Ｂ）は、公知乃至慣用の製造方法により製造することもできるし、例えば、商品名「ＦＢ－９１０」、「ＦＢ－９４０」、「ＦＢ－９５０」等のＦＢシリーズ（以上、電気化学工業（株）製）、商品名「ＭＳＲ－２２１２」、「ＭＳＲ－２５」（以上、（株）龍森製）、商品名「ＨＳ－１０５」、「ＨＳ－１０６」、「ＨＳ－１０７」（以上、マイクロン社製）等の市販品を使用することもできる。 In the heating mixture of the present invention, 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. For example, FB series (trade names “FB-910”, “FB-940”, “FB-950”, etc.) As described above, manufactured by Denki Kagaku Kogyo Co., Ltd., trade names “MSR-2212”, “MSR-25” (manufactured by Tatsumori Co., Ltd.), trade names “HS-105”, “HS-106”, “ Commercial products such as “HS-107” (manufactured by Micron) can also be used.
［白色顔料（Ｃ）］
　本発明の加熱混合物における白色顔料（Ｃ）としては、主に、硬化物（白色リフレクター）に対して高い光反射性を付与し、また、その線膨張率を低減させ、本発明の加熱混合物を所定の粘度に調整しやくする働きを有する。白色顔料（Ｃ）としては、リフレクターの反射率を高くするため屈折率が高い白色顔料を使用することが好ましく、例えば、屈折率１．５以上の白色顔料が好ましい。但し、中空粒子構造を有する白色顔料は内部（コア）に低屈折率の気体を含み表面反射率が非常に大きいので、シェル部分は屈折率が１．５より低い材料で構成されていてもよい。白色顔料（Ｃ）としては、公知乃至慣用の白色顔料を使用することができ、特に限定されないが、例えば、ガラス、屈折率１．５以上のクレー、雲母、タルク、カオリナイト（カオリン）、ハロイサイト、ゼオライト、酸性白土、活性白土、ベーマイト、擬ベーマイト、無機酸化物、金属塩［例えば、アルカリ土類金属塩等］等の無機白色顔料；スチレン系樹脂、ベンゾグアナミン系樹脂、尿素－ホルマリン系樹脂、メラミン－ホルマリン系樹脂、アミド系樹脂等の樹脂顔料等の有機白色顔料（プラスチックピグメント等）；中空構造（バルーン構造）を有する中空粒子等が挙げられる。 [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. However, since the white pigment having a hollow particle structure contains a gas having a low refractive index inside (core) and has a very high surface reflectance, 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.
　上記無機酸化物としては、例えば、酸化アルミニウム（アルミナ）、酸化マグネシウム、酸化アンチモン、酸化チタン［例えば、ルチル型酸化チタン、アナターゼ型酸化チタン、ブルッカイト型酸化チタン等］、酸化ジルコニウム、酸化亜鉛等が挙げられる。また、上記アルカリ土類金属塩としては、例えば、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、ケイ酸マグネシウム、ケイ酸カルシウム、水酸化マグネシウム、リン酸マグネシウム、リン酸水素マグネシウム、硫酸マグネシウム、硫酸カルシウム、硫酸バリウム等が挙げられる。また、アルカリ土類金属塩以外の金属塩としては、例えば、ケイ酸アルミニウム、水酸化アルミニウム、硫化亜鉛等が挙げられる。 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.
　上記中空粒子としては、特に限定されないが、例えば、無機ガラス［例えば、珪酸ソーダガラス、アルミ珪酸ガラス、硼珪酸ソーダガラス、石英等］、シリカ、アルミナ等の金属酸化物、炭酸カルシウム、炭酸バリウム、炭酸ニッケル、珪酸カルシウム等の金属塩等の無機物により構成された無機中空粒子（シラスバルーン等の天然物も含む）；スチレン系樹脂、アクリル系樹脂、シリコーン系樹脂、アクリル－スチレン系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹脂、アミド系樹脂、ウレタン系樹脂、フェノール系樹脂、スチレン－共役ジエン系樹脂、アクリル－共役ジエン系樹脂、オレフィン系樹脂等のポリマー（これらポリマーの架橋体も含む）等の有機物により構成された有機中空粒子；無機物と有機物のハイブリッド材料により構成された無機－有機中空粒子等が挙げられる。なお、上記中空粒子は、単一の材料より構成されたものであってもよいし、二種以上の材料より構成されたものであってもよい。また、上記中空粒子の中空部（中空粒子の内部の空間）は、真空状態であってもよいし、媒質で満たされていてもよいが、特に、反射率向上の観点では、屈折率が低い媒質（例えば、窒素、アルゴン等の不活性ガスや空気等）で満たされた中空粒子が好ましい。 Although it does not specifically limit as said hollow particle, For example, 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. Organic hollow particles composed of organic materials; hybrid materials of inorganic and organic materials Configured inorganic Ri - organic hollow particles, and the like. In addition, the said hollow particle may be comprised from the single material, and may be comprised from 2 or more types of materials. In addition, 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. However, particularly from the viewpoint of improving the reflectance, the refractive index is low. Hollow particles filled with a medium (for example, an inert gas such as nitrogen or argon or air) are preferred.
　なお、白色顔料（Ｃ）は、公知乃至慣用の表面処理［例えば、金属酸化物、シランカップリング剤、チタンカップリング剤、有機酸、ポリオール、シリコーン等の表面処理剤による表面処理等］が施されたものであってもよい。このような表面処理を施すことにより、本発明の加熱混合物における他の成分との相溶性や分散性を向上させることができる場合がある。 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.
　中でも、白色顔料（Ｃ）としては、硬化物（白色リフレクター）の高反射率及び添加量に対する光反射性の上昇率、本発明の加熱混合物を所定の粘度に調整する観点で、無機酸化物が好ましく、より好ましくは酸化チタンである。 Among them, as 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.
　白色顔料（Ｃ）の形状は、特に限定されず、例えば、球状、破砕状、繊維状、針状、鱗片状等が挙げられる。中でも、分散性の観点で、球状の酸化チタンが好ましく、特に真球状の酸化チタン（例えば、アスペクト比が１．２以下の球状の酸化チタン）が好ましい。 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. Among them, 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.
　白色顔料（Ｃ）の中心粒径は、特に限定されないが、硬化物（白色リフレクター）の光反射性向上、本発明の加熱混合物を所定の粘度に調整する観点で、０．１～５０μｍが好ましい。特に、白色顔料（Ｃ）として酸化チタンを使用する場合、該酸化チタンの中心粒径は、特に限定されないが、０．１～５０μｍが好ましく、より好ましくは０．１～３０μｍである。なお、上記中心粒径は、レーザー回折・散乱法で測定した粒度分布における積算値５０％での粒径（メディアン径）を意味する。 The center particle diameter of the white pigment (C) is not particularly limited, but is preferably 0.1 to 50 μm 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. . In particular, when titanium oxide is used as the white pigment (C), the center particle diameter of the titanium oxide is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm. In addition, 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.
　本発明の加熱混合物において白色顔料（Ｃ）は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、白色顔料（Ｃ）は、公知乃至慣用の方法により製造することもできるし、例えば、商品名「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」（以上、堺化学工業（株）製）、商品名「タイペークＣＲ－５０」、「ＣＲ－５０－２」、「ＣＲ－６０」、「ＣＲ－６０－２」、「ＣＲ－６３」、「ＣＲ－８０」、「ＣＲ－９０」、「ＣＲ－９０－２」、「ＣＲ－９３」、「ＣＲ－９５」、「ＣＲ－９７」（以上、石原産業（株）製）、商品名「ＪＲ－３０１」、「ＪＲ－４０３」、「ＪＲ－４０５」、「ＪＲ－６００Ａ」、「ＪＲ－６０５」、「ＪＲ－６００Ｅ」、「ＪＲ－６０３」、「ＪＲ－８０５」、「ＪＲ－８０６」、「ＪＲ－７０１」、「ＪＲＮＣ」、「ＪＲ－８００」、「ＪＲ」（以上、テイカ（株）製）、商品名「ＴＲ－６００」、「ＴＲ－７００」、「ＴＲ－７５０」、「ＴＲ－８４０」、「ＴＲ－９００」（以上、富士チタン工業（株）製）、商品名「ＫＲ－３１０」、「ＫＲ－３８０」、「ＫＲ－３８０Ｎ」、「ＳＴ－４１０ＷＢ」、「ＳＴ－４５５」、「ＳＴ－４５５ＷＢ」、「ＳＴ－４５７ＳＡ」、「ＳＴ－４５７ＥＣ」、「ＳＴ－４８５ＳＡ１５」、「ＳＴ－４８６ＳＡ」、「ＳＴ－４９５Ｍ」（以上、チタン工業（株）製）等のルチル型酸化チタン；商品名「Ａ－１１０」、「ＴＣＡ－１２３Ｅ」、「Ａ－１９０」、「Ａ－１９７」、「ＳＡ－１」、「ＳＡ－１Ｌ」、「ＳＳＰシリーズ」、「ＣＳＢシリーズ」（以上、堺化学工業（株）製）、商品名「ＪＡ－１」、「ＪＡ－Ｃ」、「ＪＡ－３」（以上、テイカ（株）製）、商品名「ＫＡ－１０」、「ＫＡ－１５」、「ＫＡ－２０」、「ＳＴＴ－６５Ｃ－Ｓ」、「ＳＴＴ－３０ＥＨＪ」（以上、チタン工業（株）製）、商品名「ＤＣＦ－Ｔ－１７００７」、「ＤＣＦ－Ｔ－１７００８」、「ＤＣＦ－Ｔ－１７０５０」（以上、レジノカラー工業（株）製）等のアナターゼ型酸化チタン等の市販品を使用することもできる。 In the heating mixture of the present invention, 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. For example, 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 "(manufactured by Sakai Chemical Industry Co., Ltd.) -50 "," CR-50-2 "," CR-60 "," CR-60-2 "," CR-63 "," CR-80 "," CR-90 "," CR-90-2 " "," CR-93 "," CR-95 "," CR-97 "(manufactured by Ishihara Sangyo Co., Ltd.), trade names" JR-301 "," JR-403 " JR-405, JR-600A, JR-605, JR-600E, JR-603, JR-805, JR-806, JR-701, JRNC , "JR-800", "JR" (manufactured by Teika Co., Ltd.), trade names "TR-600", "TR-700", "TR-750", "TR-840", "TR-900 (Fuji Titanium Industry Co., Ltd.), trade names “KR-310”, “KR-380”, “KR-380N”, “ST-410WB”, “ST-455”, “ST-455WB” , “ST-457SA”, “ST-457EC”, “ST-485SA15”, “ST-486SA”, “ST-495M” (above, manufactured by Titanium Industry Co., Ltd.), etc .; A-110 "," TCA-123 " "," A-190 "," A-197 "," SA-1 "," SA-1L "," SSP series "," CSB series "(above, manufactured by Sakai Chemical Industry Co., Ltd.) "JA-1", "JA-C", "JA-3" (manufactured by Teika Co., Ltd.), trade names "KA-10", "KA-15", "KA-20", "STT-65C" -S "," STT-30EHJ "(above, manufactured by Titanium Industry Co., Ltd.), trade names" DCF-T-17007 "," DCF-T-17008 "," DCF-T-17050 "(above, Resino Color Industries) Commercial products such as anatase-type titanium oxide such as (manufactured by KK) may also be used.
　中でも、白色顔料（Ｃ）としては、特に硬化物（白色リフレクター）の光反射性及び耐黄変性向上、本発明の加熱混合物を所定の粘度に調整する観点で、商品名「Ｒ－６２Ｎ」、「ＣＲ－６０」、「ＤＣＦ－Ｔ－１７００７」、「ＤＣＦ－Ｔ－１７００８」、「ＤＣＦ－Ｔ－１７０５０」、「ＦＴＲ－７００」が好ましい。 Among them, as 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.
［加熱混合物］
　本発明の硬化性エポキシ樹脂組成物を構成する加熱混合物は、エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる加熱混合物であって、２５℃におけるずり粘度が、１０～１０００Ｐａ・ｓである混合物である。
　本発明の硬化性エポキシ樹脂組成物が、このような特徴を有する加熱混合物を含むことにより、硬化性エポキシ樹脂組成物に対して良好な粉砕性及び／又は打錠性を付与すると共に、べとつきの発生を抑制して取扱いが容易になり、また、硬化物（白色リフレクター）の耐熱性を向上させる働きを有する。 [Heating mixture]
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.
When 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).
　本発明の加熱混合物における２５℃におけるずり粘度は、上記の通り、１０～１，０００Ｐａ・ｓであり、好ましくは１０～５００Ｐａ・ｓであり、より好ましくは１０～３００Ｐａ・ｓである。本発明の加熱混合物の２５℃におけるずり粘度が１０Ｐａ・ｓ以上であることにより、硬化性エポキシ樹脂組成物の粘度を調整しやすくなり、粉砕性及び／又は打錠性が向上すると共に、べとつきの発生も抑制しやすくなる。一方、本発明の加熱混合物の２５℃におけるずり粘度が１，０００Ｐａ・ｓ以下であることにより、硬化性エポキシ樹脂組成物を混合して調製する際に、金属部品との磨耗が少なくなり、金属コンタミを抑制することで高い反射率を発現できる傾向がある。本発明の加熱混合物における２５℃におけるずり粘度は、エポキシ化合物（Ａ）、無機充填剤（Ｂ）及び白色顔料（Ｃ）の配合割合や、後述の加熱・混合条件等を調整することにより、上記範囲に設定することができる。
　なお、本発明の加熱混合物における２５℃におけるずり粘度は、レオメーター（例えば、レオメーターＭＣＲ３０２、アントンパール製）を用いて、２５℃下、パラレルプレートにて測定することができる。 As described above, 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. When 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. On the other hand, when the shear viscosity at 25 ° C. of the heated mixture of the present invention is 1,000 Pa · s or less, when it is prepared by mixing the curable epoxy resin composition, wear with metal parts is reduced, and metal There is a tendency that high reflectance can be expressed by suppressing contamination. 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).
　本発明の加熱混合物は、エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種との混合物を用いて、当該混合物を加熱・混合することにより得られる。該混合物は、硬化剤、硬化促進剤、酸化防止剤等の他の添加剤を含有していてもよいが、加熱混合物が、上記のずり粘度の範囲に調整させるためには、他の添加剤を含まないことが好ましい。 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.
　上記加熱混合物を得るための加熱・混合は、公知の装置、例えば、自転公転型ミキサー、１軸又は多軸エクストルーダー、プラネタリーミキサー、ニーダー、ディソルバー等を制限なく使用することができる。
　加熱温度は、特に限定されないが、通常、５０～１２０℃が好ましく、６０～１００℃がより好ましい。加熱温度をこの範囲内で設定することにより、２５℃におけるずり粘度を所望の範囲に調整しやすくなる。加熱温度は、加熱・混合中において上記範囲の一定の温度に調整してもよく、上記範囲内で変動させてもよい。
　混合における回転速度は、特に限定されないが、通常、１０～１００００ｒｐｍが好ましく、１０～５０００ｒｐｍがより好ましい。回転速度をこの範囲内で設定することにより、２５℃におけるずり粘度を所望の範囲に調整しやすくなる。回転速度は、加熱・混合中において上記範囲の一定の回転数に調整してもよく、上記範囲内で変動させてもよい。
　加熱・混合時間は、上記加熱温度や回転速度により変動し、特に限定されないが、通常、０．５～２４時間が好ましく、０．５～１８時間がより好ましい。加熱・混合時間をこの範囲内で設定することにより、２５℃におけるずり粘度を所望の範囲に調整しやすくなる。 For the heating / mixing to obtain the heated mixture, 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. By setting the rotation speed within this range, it becomes easy to adjust the shear viscosity at 25 ° C. to a desired range. 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.
　上記加熱混合により、加熱混合物の２５℃におけるずり粘度を所定の範囲に調整できる理由は、エポキシ化合物（Ａ）のオキシラン環が、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種の表面に存在する極性基（例えば、ＯＨ基）と化学反応した結果、粘度が上昇したものと推察される。なお、この推察は、本発明を何ら限定するものではない。 The reason why 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) As a result of a chemical reaction with a polar group (for example, OH group) present on at least one kind of surface, it is presumed that the viscosity has increased. This inference does not limit the present invention.
　本発明の加熱混合物がエポキシ化合物（Ａ）を含むことにより、加熱混合物の２５℃におけるずり粘度を適切に調整しやすくなり、ひいては、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が向上する傾向がある。
　本発明の加熱混合物におけるエポキシ化合物（Ａ）の含有量（配合量）は、特に限定されないが、本発明の加熱混合物（１００重量％）に対して、１～９９重量％が好ましく、より好ましくは１０～９５重量％、さらに好ましくは２０～９０重量％である。エポキシ化合物（Ａ）の含有量を１重量％以上とすることにより、加熱混合物の２５℃におけるずり粘度を適切に調整しやすくなる。一方、エポキシ化合物（Ａ）の含有量を９９重量％以下とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が向上する傾向がある。 When 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. By setting the content of the epoxy compound (A) to 1% by weight or more, it becomes easy to appropriately adjust the shear viscosity at 25 ° C. of the heated mixture. On the other hand, when 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.
　本発明の加熱混合物に含まれるエポキシ化合物（Ａ）の全量（１００重量％）に対する化合物（Ａ－１－１）の割合は、特に限定されないが、５～１００重量％が好ましく、より好ましくは１０～１００重量％、より好ましくは２０～１００重量％である。化合物（Ａ－１－１）の割合を５重量％以上とすることにより、本発明の加熱混合物を所定の粘度に調整しやくなる傾向がある。 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. By setting the ratio of the compound (A-1-1) to 5% by weight or more, the heated mixture of the present invention tends to be easily adjusted to a predetermined viscosity.
　本発明の加熱混合物に含まれるエポキシ化合物（Ａ）の全量（１００重量％）に対する化合物（Ａ－１－２）の割合は、特に限定されないが、０～５０重量％が好ましく、より好ましくは０～４５重量％、より好ましくは０～４０重量％である。化合物（Ａ－１－２）の割合を５０重量％以下とすることにより、本発明の加熱混合物を所定の粘度に調整しやくなる傾向がある。 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. When 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.
　本発明の加熱混合物に含まれるエポキシ化合物（Ａ）の全量（１００重量％）に対する化合物（Ａ－１－３）の割合は、特に限定されないが、０～５０重量％が好ましく、より好ましくは０～４５重量％、より好ましくは０～４０重量％である。化合物（Ａ－１－３）の割合を５０重量％以下とすることにより、本発明の加熱混合物を所定の粘度に調整しやくなる傾向がある。 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. When 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.
　本発明の加熱混合物が無機充填剤（Ｂ）及び／又は白色顔料（Ｃ）を含むことにより、本発明の加熱混合物の２５℃におけるずり粘度を適切に調整しやすくなり、ひいては、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が向上する傾向がある。
　本発明の加熱混合物は、無機充填剤（Ｂ）のみを含んでもよいし、白色顔料（Ｃ）のみを含んでもよいし、無機充填剤（Ｂ）と白色顔料（Ｃ）の両方を含んでいてもよい。 When 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.
　本発明の加熱混合物における無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種（単に「無機充填剤等」と称する場合がある）の含有量（配合量）は、特に限定されないが、本発明の加熱混合物（１００重量％）に対して、１～９９重量％が好ましく、より好ましくは５～９０重量％、さらに好ましくは１０～８０重量％である。無機充填剤等の含有量を１重量％以上とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が向上する傾向がある。一方、無機充填剤等の含有量を９９重量％以下とすることにより、加熱混合物の２５℃におけるずり粘度を適切に調整しやすくなる傾向がある。 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 (sometimes simply referred to as “inorganic filler etc.”) 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. When 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. On the other hand, when 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.
　本発明の加熱混合物におけるエポキシ化合物（Ａ）に対する無機充填剤等の含有量（配合量）は、特に限定されないが、エポキシ化合物（Ａ）１００重量部に対して、５～５００重量部が好ましく、より好ましくは１０～４００重量部、さらに好ましくは２０～４００重量部である。無機充填剤等の含有量を５重量部以上とすることにより、加熱混合物の２５℃におけるずり粘度を適切に調整しやすくなり、ひいては、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が向上する傾向がある。一方、無機充填剤等の含有量を５００重量部以下とすることにより、硬化性エポキシ樹脂組成物を混合して調製する際に、金属部品との磨耗が少なくなり、金属コンタミを抑制することで高い反射率を発現できる傾向がある。 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. By setting the content of the inorganic filler or the like to 5 parts by weight or more, it becomes easy to appropriately adjust the shear viscosity at 25 ° C. of the heated mixture, and as a result, the pulverization property and / or tableting property of the curable epoxy resin composition. Tend to improve. On the other hand, by making the content of the inorganic filler or the like 500 parts by weight or less, when mixing and preparing the curable epoxy resin composition, wear with metal parts is reduced, and metal contamination is suppressed. There is a tendency that high reflectance can be expressed.
　本発明の加熱混合物が、無機充填剤（Ｂ）と白色顔料（Ｃ）の両方を含む場合、その割合（無機充填剤（Ｂ）／白色顔料（Ｃ））は、特に限定されないが、１００／０～０／１００の範囲から適宜選択すればよく、好ましくは９９／１～１／９９、より好ましくは９５／５～５／９５の範囲から選択すればよい。 When the heated mixture of the present invention contains both the inorganic filler (B) and the white pigment (C), 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.
　本発明の硬化性エポキシ樹脂組成物は、上記の加熱混合物に加えて、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、白色顔料（Ｃ’）、硬化剤（Ｄ）、硬化促進剤、酸化防止剤、離型剤、その他の成分を含んでいてもよい。
　本発明の硬化性エポキシ樹脂組成物は、上記の加熱混合物に加えて、硬化剤（Ｄ）を含むことが好ましい。本発明の硬化性エポキシ樹脂組成物が、硬化剤（Ｄ）を含むことにより、本発明の硬化性エポキシ樹脂組成物を効率的に硬化させることができる。
　また、本発明の硬化性エポキシ樹脂組成物は、必要に応じて、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含むことも好ましい。本発明の硬化性エポキシ樹脂組成物が、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含むことにより、硬化物の耐熱性、耐黄変性（黄変しにくい特性）、光反射性を向上させたり、線膨張率を低減させることができる。 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 | curing agent (D) in addition to said heating mixture. When the curable epoxy resin composition of the present invention contains a curing agent (D), the curable epoxy resin composition of the present invention can be efficiently cured.
Moreover, 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. When 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.
［エポキシ化合物（Ａ’）］
　本発明の硬化性エポキシ樹脂組成物に含まれていてもよいエポキシ化合物（Ａ’）としては、公知乃至慣用のエポキシ化合物を使用でき、特に限定されないが、例えば、上述のエポキシ化合物（Ａ）で例示されたものと同様のエポキシ化合物が例示される。
　エポキシ化合物（Ａ’）としては、上述のエポキシ化合物（Ａ）と同一のエポキシ化合物を使用してもよく、エポキシ化合物（Ａ）と異なるエポキシ化合物を使用してもよい。
　また、上述のエポキシ化合物（Ａ）が２種以上のエポキシ化合物の混合物の場合、エポキシ化合物（Ａ’）としては、（１）エポキシ化合物（Ａ）と同一の組成の混合物、（２）エポキシ化合物（Ａ）と異なる組成の混合物、（３）エポキシ化合物（Ａ）を構成する単独のエポキシ化合物、（４）エポキシ化合物（Ａ）を構成しない単独のエポキシ化合物のいずれであってもよい。 [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.
Moreover, when the above-mentioned epoxy compound (A) is a mixture of two or more types of epoxy compounds, as 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).
　エポキシ化合物（Ａ’）としては、硬化物（白色リフレクター）の耐熱性及び耐光性の観点で、脂環式エポキシ化合物（Ａ－１）、複素環式エポキシ化合物（Ａ－２）、芳香族エポキシ化合物（Ａ－３）が好ましく、脂環式エポキシ化合物（Ａ－１）又は複素環式エポキシ化合物（Ａ－２）がより好ましい。 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.
　エポキシ化合物（Ａ’）における脂環式エポキシ化合物（Ａ－１）としては、硬化物（白色リフレクター）の耐熱性の観点で、化合物（Ａ－１－１）、化合物（Ａ－１－２）が好ましく、化合物（Ａ－１－２）がより好ましい。中でも、硬化物（白色リフレクター）の耐熱性をいっそう向上させ、より優れた耐黄変性（黄変しにくい特性）を発現させる点で、上記式（Ｉ－１）で表される化合物［３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート；例えば、商品名「セロキサイド２０２１Ｐ」（（株）ダイセル製）等］、上記式（ＩＩ）で表される化合物［２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物；例えば、商品名「ＥＨＰＥ３１５０」（（株）ダイセル製）等］が特に好ましい。 As the alicyclic epoxy compound (A-1) in the epoxy compound (A ′), from the viewpoint of heat resistance of the cured product (white reflector), the compound (A-1-1) and the compound (A-1-2) Is more preferable, and the compound (A-1-2) is more preferable. Among them, 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. 4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; for example, trade name “Celoxide 2021P” (manufactured by Daicel Co., Ltd.) and the like, and the compound represented by the above formula (II) [2,2-bis A 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of (hydroxymethyl) -1-butanol; for example, trade name “EHPE3150” (manufactured by Daicel Corporation), etc.] is particularly preferred.
　本発明の硬化性エポキシ樹脂組成物がエポキシ化合物（Ａ’）を含む場合、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、エポキシ化合物（Ａ’）は、公知乃至慣用の方法により製造することもできるし、例えば、商品名「セロキサイド２０２１Ｐ」、「セロキサイド２０８１」、「ＥＨＰＥ３１５０」（以上、（株）ダイセル製）、商品名「ＴＥＰＩＣ－Ｓ」（日産化学工業（株）製）、商品名「ＭＡ－ＤＧＩＣ」、「ＴＧ－Ｇ」（四国化成工業（株）製）等の市販品を使用することもできる。 When 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. For example, 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.
　本発明の硬化性エポキシ樹脂組成物におけるエポキシ化合物（Ａ）に対するエポキシ化合物（Ａ’）の含有量（配合量）は、特に限定されないが、エポキシ化合物（Ａ）１００重量部に対して、１～１００００重量部が好ましく、より好ましくは１０～１０００重量部、さらに好ましくは１０～５００重量部である。エポキシ化合物（Ａ’）の含有量を１重量部以上とすることにより、硬化物（白色リフレクター）の耐熱性（特に、耐黄変性）がより向上する傾向がある。一方、エポキシ化合物（Ａ’）の含有量を１００００重量部以下とすることにより、硬化物（白色リフレクター）の線膨張係数が低減され、光半導体素子搭載用基板におけるリードフレームの反り等の不具合の発生がより抑制される傾向がある。 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. By setting the content of the epoxy compound (A ′) to 1 part by weight or more, the heat resistance (particularly yellowing resistance) of the cured product (white reflector) tends to be further improved. On the other hand, by setting the content of the epoxy compound (A ′) to 10000 parts by weight or less, 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.
　本発明の硬化性エポキシ樹脂組成物におけるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の合計含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物（１００重量％）に対して、１．５～１５重量％が好ましく、より好ましくは２～１３重量％、さらに好ましくは２．５～１０重量％である。当該合計含有量を１．５重量％以上とすることにより、硬化物（白色リフレクター）の耐熱性（特に、耐黄変性）がより向上する傾向がある。一方、当該合計含有量を１５重量％以下とすることにより、硬化物（白色リフレクター）の線膨張係数が低減され、光半導体素子搭載用基板におけるリードフレームの反り等の不具合の発生がより抑制される傾向がある。 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. By setting the total content to 1.5% by weight or more, the heat resistance (particularly yellowing resistance) of the cured product (white reflector) tends to be further improved. On the other hand, by making 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.
　本発明の硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する化合物（Ａ－１－１）の割合は、特に限定されないが、５～９５重量％が好ましく、より好ましくは１０～９０重量％、より好ましくは２０～８０重量％である。化合物（Ａ－１－１）の割合を５重量％以上とすることにより、硬化物（白色リフレクター）の耐熱性及び耐光性がより向上する傾向がある。一方、化合物（Ａ－１－１）の割合を９５重量％以下とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が高いレベルで確保される傾向がある。 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. When 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. On the other hand, when 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.
　本発明の硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する化合物（Ａ－１－２）の割合は、特に限定されないが、１～９０重量％が好ましく、より好ましくは１０～８０重量％、より好ましくは２０～７０重量％である。化合物（Ａ－１－２）の割合を１重量％以上とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が高いレベルで確保される傾向がある。一方、化合物（Ａ－１－２）の割合を９０重量％以下とすることにより、硬化物（白色リフレクター）の耐熱性及び耐光性がより向上する傾向がある。 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. By setting the ratio of the compound (A-1-2) to 1% by weight or more, the curable epoxy resin composition tends to be ensured at a high level of grindability and / or tabletability. On the other hand, when 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.
　本発明の硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する化合物（Ａ－１－３）の割合は、特に限定されないが、０～９０重量％が好ましく、より好ましくは１０～８０重量％、より好ましくは２０～７０重量％である。化合物（Ａ－１－３）の割合を９０重量％以下とすることにより、硬化物（白色リフレクター）の耐熱性及び耐光性がより向上する傾向がある。 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.
　本発明の硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量（１００重量％）に対する複素環式エポキシ化合物（Ａ－２）の割合は、特に限定されないが、１～８０重量％が好ましく、より好ましくは５～７０重量％、より好ましくは１０～６０重量％である。複素環式エポキシ化合物（Ａ－２）の割合を１重量％以上とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性が高いレベルで確保される傾向がある。また、硬化物の密着性がより向上する傾向がある。一方、複素環式エポキシ化合物（Ａ－２）の割合を９５重量％以下とすることにより、硬化物（白色リフレクター）の耐熱性及び耐光性がより向上する傾向がある。 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. By setting the ratio of the heterocyclic epoxy compound (A-2) to 1% by weight or more, the grindability and / or tabletability of the curable epoxy resin composition tends to be secured at a high level. Moreover, there exists a tendency for the adhesiveness of hardened | cured material to improve more. On the other hand, when 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.
　本発明の硬化性エポキシ樹脂組成物に含まれる化合物（Ａ－１－１）と、化合物（Ａ－１－２）及び複素環式エポキシ化合物（Ａ－２）との重量基準の割合［＝化合物（Ａ－１－１）／化合物（Ａ－１－２）及び複素環式エポキシ化合物（Ａ－２）］は、特に限定されないが、１０／９０～９０／１０が好ましく、より好ましくは２０／８０～７０／３０、さらに好ましくは３０／７０～６０／４０である。上記割合を上記範囲に制御することにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性、硬化物の耐熱性、耐光性、密着性がバランス良く向上する傾向がある。 Ratio based on weight of compound (A-1-1), compound (A-1-2) and heterocyclic epoxy compound (A-2) contained in the curable epoxy resin composition of the present invention [= compound (A-1-1) / Compound (A-1-2) and Heterocyclic epoxy compound (A-2)] are not particularly limited, but are preferably 10/90 to 90/10, more preferably 20 / 80 to 70/30, more preferably 30/70 to 60/40. By controlling 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.
［硬化剤（Ｄ）］
　本発明の硬化性エポキシ樹脂組成物に含まれていてもよい硬化剤（Ｄ）は、公知乃至慣用のエポキシ樹脂用硬化剤を使用することができ、特に限定されないが、例えば、酸無水物類（酸無水物系硬化剤）、アミン類（アミン系硬化剤）、ポリアミド樹脂、イミダゾール類（イミダゾール系硬化剤）、ポリメルカプタン類（ポリメルカプタン系硬化剤）、フェノール類（フェノール系硬化剤）、ポリカルボン酸類、ジシアンジアミド類、有機酸ヒドラジド等が挙げられる。中でも、均一な硬化性エポキシ樹脂組成物を効率的に調製することができる点で、２５℃で液状（液体）の硬化剤が好ましい。なお、本明細書において「２５℃で液状」とは、常圧での状態を意味する。 [Curing agent (D)]
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. For example, 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. Among these, a liquid (liquid) curing agent at 25 ° C. is preferable in that a uniform curable epoxy resin composition can be efficiently prepared. In the present specification, “liquid at 25 ° C.” means a state at normal pressure.
　硬化剤（Ｄ）としての酸無水物類（酸無水物系硬化剤）としては、公知乃至慣用の酸無水物系硬化剤を使用することができ、特に限定されないが、例えば、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ドデセニル無水コハク酸、メチルエンドメチレンテトラヒドロ無水フタル酸等の２５℃で液状の酸無水物；無水コハク酸、水素化無水ピロメリット酸、水素化ビフェニル二無水物、無水フタル酸、テトラヒドロ無水フタル酸（例えば、１，２，３，６－テトラヒドロ無水フタル酸）、ヘキサヒドロ無水フタル酸、メチルシクロヘキセンジカルボン酸無水物等の２５℃で固体（固体状）の酸無水物等が挙げられる。また、上記酸無水物系硬化剤としては、例えば、特開２０１１－２１９５３４号公報に記載の多価カルボン酸縮合体等を使用することもできる。中でも、２５℃で液状の酸無水物を使用することが好ましい。 As the acid anhydrides (acid anhydride-based curing agents) as the curing agent (D), known or conventional acid anhydride-based curing agents can be used, and are not particularly limited. For example, 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. such as phthalic anhydride, tetrahydrophthalic anhydride (eg, 1,2,3,6-tetrahydrophthalic anhydride), hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, etc. Etc. As 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.
　硬化剤（Ｄ）としてのアミン類（アミン系硬化剤）としては、公知乃至慣用のアミン系硬化剤を使用でき、特に限定されないが、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジプロピレンジアミン、ジエチルアミノプロピルアミン、ポリプロピレントリアミン等の脂肪族ポリアミン；メンセンジアミン、イソホロンジアミン、ビス（４－アミノ－３－メチルジシクロヘキシル）メタン、ジアミノジシクロヘキシルメタン、ビス（アミノメチル）シクロヘキサン、Ｎ－アミノエチルピペラジン、３，９－ビス（３－アミノプロピル）－３，４，８，１０－テトラオキサスピロ［５，５］ウンデカン等の脂環式ポリアミン；ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、トリレン－２，４－ジアミン、トリレン－２，６－ジアミン、メシチレン－２，４－ジアミン、３，５－ジエチルトリレン－２，４－ジアミン、３，５－ジエチルトリレン－２，６－ジアミン等の単核ポリアミン、ビフェニレンジアミン、４，４－ジアミノジフェニルメタン、２，５－ナフチレンジアミン、２，６－ナフチレンジアミン等の芳香族ポリアミン等が挙げられる。 As the 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. For example, 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-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6- Examples thereof include mononuclear polyamines such as diamine, aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.
　硬化剤（Ｄ）としてのフェノール類（フェノール系硬化剤）としては、公知乃至慣用のフェノール系硬化剤を使用でき、特に限定されないが、例えば、ノボラック型フェノール樹脂、ノボラック型クレゾール樹脂、パラキシリレン変性フェノール樹脂、パラキシリレン・メタキシリレン変性フェノール樹脂等のアラルキル樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、トリフェノールプロパン等が挙げられる。 As the phenols (phenolic curing agents) as the curing agent (D), known or conventional phenolic curing agents can be used, and are not particularly limited. For example, 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.
　硬化剤（Ｄ）としてのポリアミド樹脂としては、例えば、分子内に第１級アミノ基及び第２級アミノ基のいずれか一方又は両方を有するポリアミド樹脂等が挙げられる。 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.
　硬化剤（Ｄ）としてのイミダゾール類（イミダゾール系硬化剤）としては、公知乃至慣用のイミダゾール系硬化剤を使用でき、特に限定されないが、例えば、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－フェニルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾリウムトリメリテート、１－シアノエチル－２－フェニルイミダゾリウムトリメリテート、２－メチルイミダゾリウムイソシアヌレート、２－フェニルイミダゾリウムイソシアヌレート、２，４－ジアミノ－６－［２－メチルイミダゾリル－（１）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２－エチル－４－メチルイミダゾリル－（１）］－エチル－ｓ－トリアジン等が挙げられる。 As the imidazole (imidazole curing agent) as the curing agent (D), a known or conventional imidazole curing agent can be used, and is not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanate 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]- And ethyl-s-triazine.
　硬化剤（Ｄ）としてのポリメルカプタン類（ポリメルカプタン系硬化剤）としては、例えば、液状のポリメルカプタン、ポリスルフィド樹脂等が挙げられる。 Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (D) include liquid polymercaptan and polysulfide resin.
　硬化剤（Ｄ）としてのポリカルボン酸類としては、例えば、アジピン酸、セバシン酸、テレフタル酸、トリメリット酸、カルボキシ基含有ポリエステル、下記式（１）で表される化合物等が挙げられ、式（１）で表される化合物が好ましい。 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.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
（式（１）中、Ｒaは炭素数１～６のアルキレン基を、Ｒbは水素原子又は炭素数１～６のアルキル基又はカルボキシル基をそれぞれ表す。式（１）中、複数存在するＲa、Ｒbは同一であっても異なっていても構わない。） (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.)
　以下、式（１）で表される化合物について、詳述する。
　Ｒaの具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンテレン基、ヘキシレン基、イソプロピレン基、イソブチレン基、イソペンチレン基、ネオペンチレン基、イソヘキシレン基、シクロヘキシレン基等が挙げられるが、得られる硬化物の耐熱透明性の観点からメチレン基、エチレン基、プロピレン基が好ましく、エチレン基が特に好ましい。 Hereinafter, the compound represented by Formula (1) will be described in detail.
Specific examples of 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. From the viewpoint of heat-resistant transparency of the resulting cured product, a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is particularly preferable.
　Ｒbのうち炭素数１～６のアルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、シクロペンチル基、ヘキシル基、イソヘキシル基、シクロヘキシル基等が挙げられるが、得られる硬化物の耐熱透明性の観点からメチル基が好ましい。 Specific examples of the 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.
　Ｒbの中でも、メチル基、カルボキシル基が好ましく、硬化剤（Ｄ）を含有する硬化性エポキシ樹脂組成物の室温（２５℃）での粘度が上がりすぎない観点と、得られる硬化物の透明性の観点からはメチル基が好ましく、得られる硬化物のガスバリア性、高いガラス転移温度（Ｔｇ）、硬さの観点からはカルボキシル基が特に好ましい。 Among 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. From the viewpoint of the above, 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.
　式（１）中、複数存在するＲa、Ｒbはそれぞれ互いに同一であっても異なっていても構わない。 In the formula (1), a plurality of R a and R b may be the same or different from each other.
　硬化剤（Ｄ）としては、例えば、Ｒaがエチレン基であり、Ｒbがメチル基である、下記式（１’）で表される化合物が好ましい。 As 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.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　硬化剤（Ｄ）は、式（１）で表される化合物のうち一種を単独で含むこともできるし、式（１）で表される化合物のうち二種以上を組み合わせて含むこともできる。 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).
　式（１）で表される化合物は、下記式（５）で表されるイソシアヌル酸トリスヒドロキシアルキル化合物と、下記式（６）で表されるカルボン酸無水物化合物との付加反応により得ることができる。 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.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
　式（５）中、Ｒaは前記と同じ意味を表す。 Wherein (5), R a are as defined above.
　式（５）で表される化合物の中でも、下記式（７）～（９）で表される化合物が、硬化物の透明性、ガスバリア性の観点から好ましい。 Among the compounds represented by the formula (5), the compounds represented by the following formulas (7) to (9) are preferable from the viewpoint of transparency of the cured product and gas barrier properties.
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　式（６）中、Ｒbは前記と同じ意味を表す。 In formula (6), R b represents the same meaning as described above.
　式（６）で表される化合物のうち、下記（２）～（４）で表される化合物が特に好ましい Among the compounds represented by the formula (6), the compounds represented by the following (2) to (4) are particularly preferable.
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
　式（１）で表される化合物の製造は、溶媒中でも無溶剤でも行うことができる。溶剤としては、前述の式（５）で表されるイソシアヌル酸トリスヒドロキシアルキル化合物と式（６）で表されるカルボン酸無水物化合物と反応しない溶剤であれば特に制限なく使用できる。使用しうる溶剤としては、例えばジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、テトラヒドロフラン、アセトニトリルのような非プロトン性極性溶媒、メチルエチルケトン、シクロペンタノン、メチルイソブチルケトンのようなケトン類、トルエン、キシレンのような芳香族炭化水素等が挙げられ、これらの中で、芳香族炭化水素やケトン類が好ましい。
　これらの溶剤は１種又は２種以上を混合して用いても良い。溶剤を用いる場合の使用量は、前述の式（５）で表されるイソシアヌル酸トリスヒドロキシアルキル化合物と式（６）で表されるカルボン酸無水物化合物の合計１００重量部に対して、０．５～３００重量部が好ましい。 The compound represented by formula (1) can be produced in a solvent or without a solvent. As 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. Examples of 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 etc. are mentioned, Among these, 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.
　式（１）で表される化合物は室温（２５℃）にて固体であることが多いため、溶剤中で合成することが作業性の観点から好ましい。 Since 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.
　式（１）で表される化合物は無触媒でも、触媒を用いても製造する事ができる。触媒を用いる場合、用い得る触媒は、塩酸、硫酸、メタンスルホン酸、トリフルオロメタンスルホン酸、パラトルエンスルホン酸、硝酸、トリフルオロ酢酸、トリクロロ酢酸等の酸性化合物、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウム等の金属水酸化物、トリエチルアミン、トリプロピルアミン、トリブチルアミン等のアミン化合物、ピリジン、ジメチルアミノピリジン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、イミダゾール、トリアゾール、テトラゾール等の複素環式化合物、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルエチルアンモニウムヒドロキシド、トリメチルプロピルアンモニウムヒドロキシド、トリメチルブチルアンモニウムヒドロキシド、トリメチルセチルアンモニウムヒドロキシド、トリオクチルメチルアンモニウムヒドロキシド、テトラメチルアンモニウムクロリド、テトラメチルアンモニウムブロミド、テトラメチルアンモニウムヨージド、テトラメチルアンモニウムアセテート、トリオクチルメチルアンモニウムアセテート等の４級アンモニウム塩、オルトチタン酸テトラエチル、オルトチタン酸テトラメチル等のオルトチタン酸類、オクチル酸スズ、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸マンガン、オクチル酸カルシウム、オクチル酸ナトリウム、オクチル酸カリウム等の金属石鹸類が挙げられる。 The compound represented by the formula (1) can be produced without a catalyst or with a catalyst. When a catalyst is used, 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, tetrabutylammonium hydroxide, trimethylethylammonium Roxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctyl Quaternary ammonium salts such as methylammonium acetate, orthotitanic acid such as tetraethyl orthotitanate, tetramethyl orthotitanate, tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, Examples include metal soaps such as potassium octylate.
　触媒を用いる場合、１種または２種以上を混合して用いることもできる。
　触媒を用いる場合の使用量は、前述の式（５）で表されるイソシアヌル酸トリスヒドロキシアルキル化合物と式（６）で表されるカルボン酸無水物化合物の合計１００重量部に対して、０．０５～１０重量部が好ましい。 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.
　触媒の添加方法は、直接添加するか、可溶性の溶剤等に溶解させた状態で使用する。この際、メタノール、エタノール等のアルコール性の溶媒や水を用いることは、未反応の式（６）で表されるカルボン酸無水物化合物と反応してしまうため、避けることが好ましい。 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).
　本発明においでは、得られる硬化性エポキシ樹脂組成物の硬化物において、透明性、耐熱透明性を向上させる観点からはオクチル酸亜鉛等のカルボン酸亜鉛を触媒として好ましく使用することができ、得られる硬化剤（Ｄ）又は硬化性エポキシ樹脂組成物の着色を低減させる観点からは無触媒で反応を行うことが好ましい。
　中でも、透明性、耐硫化性に優れる硬化物を得るために、特にステアリン酸カルシウム、カルボン酸亜鉛（２－エチルヘキサン酸亜鉛、ステアリン酸亜鉛、ベヘン酸亜鉛、ミスチリン酸亜鉛）やリン酸エステル亜鉛（オクチルリン酸亜鉛、ステアリルリン酸亜鉛等）等の亜鉛化合物が好ましく使用できる。 In the present invention, in the cured product of the resulting curable epoxy resin composition, zinc carboxylate such as zinc octylate can be preferably used and obtained from the viewpoint of improving transparency and heat-resistant transparency. From the viewpoint of reducing the color of the curing agent (D) or the curable epoxy resin composition, it is preferable to perform the reaction without a catalyst.
Among them, 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.
　式（１）で表される化合物の製造時の反応温度は、触媒量、使用溶剤にもよるが、通常２０～１６０℃、好ましくは５０～１５０℃、特に好ましくは６０～１４５℃である。又、反応時間の総計は通常１～２０時間、好ましくは３～１８時間である。反応は２段階以上で行なっても良く、例えば２０～１００℃で１～８時間反応させた後に、１００～１６０℃で１～１２時間などで反応させても良い。これは特に式（６）で表されるカルボン酸無水物化合物は揮発性の高いものが多く、そのようなものを用いる場合、あらかじめ２０～１００℃で反応させた後に、１００～１６０℃で反応させることで、揮発を抑えることができる。これにより、大気中への有害物質の拡散を抑制するだけでなく、設計どおりの式（１）で表される化合物を得ることができる。 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. In particular, 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.
　触媒を用いて製造を行なった場合は必要に応じてクェンチ、および／又は水洗を行なうことで触媒を除くことができるが、そのまま残存させ、式（１）で表される化合物の硬化促進剤として利用することもできる。
　水洗工程を行なう場合、使用している溶剤の種類によっては水と分離可能な溶剤を加えることが好ましい。好ましい溶剤としては例えばメチルエチルケトン、メチルイソブチルケトン、シクロペンタノンのようなケトン類、酢酸エチル、酢酸ブチル、乳酸エチル、ブタン酸イソプロピルなどのエステル類、ヘキサン、シクロヘキサン、トルエン、キシレンのような炭化水素等が例示できる。
　反応や水洗に溶剤を用いた場合、減圧濃縮などによって除くことができる。 In the case of production using a catalyst, 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.
When performing a water washing process, it is preferable to add the solvent which can be isolate | 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.
When a solvent is used for the reaction or washing with water, it can be removed by vacuum concentration or the like.
　製造された式（１）で表される化合物の酸価（ＪＩＳ　Ｋ－２５０１に記載の方法で測定）は１５０～４１５ｍｇＫＯＨ／ｇのものが好ましく、１８５～３７５ｍｇＫＯＨ／ｇのものがより好ましく、特に２００～３２０ｍｇＫＯＨ／ｇのものが好ましい。酸価が１５０ｍｇＫＯＨ／ｇ以上であれば硬化物の機械特性が向上するため好ましく、４１５ｍｇＫＯＨ／ｇ以下であれば、その硬化物が硬くなり過ぎず、弾性率が適度なものとなり好ましい。
　また、式（１）で表される化合物の官能基当量は、１３５～３１２ｇ／ｅｑのものが好ましく、１５０～３００ｇ／ｅｑのものがより好ましく、特に１８０～２８０ｇ／ｅｑが好ましい。 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.
　また、式（１）で表される化合物は、軟化点が２０～１５０℃であることが好ましく、５０～１３０℃であることがより好ましい。
　当該範囲に調整することにより、各種成分をミキサー等によって容易に撹拌、混合することができ、それをさらにミキシングロール、押出機、ニーダー、ロール、エクストルーダー等によって混練または溶融混練し、冷却、粉砕することが可能となる。 Further, the compound represented by the formula (1) preferably has a softening point of 20 to 150 ° C, more preferably 50 to 130 ° C.
By adjusting to this range, 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.
　本発明の硬化性エポキシ樹脂組成物において硬化剤（Ｄ）は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 In the curable epoxy resin composition of the present invention, the curing agent (D) can be used alone or in combination of two or more.
　硬化剤（Ｄ）としては、上記式（１）で表される化合物、酸無水物類（酸無水物系硬化剤）等が好ましく、特に、式（１）で表される化合物を含む硬化剤（Ｄ）が好ましい。本発明の硬化性エポキシ樹脂組成物において式（１）で表される特定の構造を有する化合物を含む硬化剤（Ｄ）を使用することにより、硬化性エポキシ樹脂組成物に対して優れた粉砕性及び／又は打錠性が付与され、また、硬化物（白色リフレクター）に対して優れた耐熱性及び密着性（特に密着性）、さらに優れた靭性が付与される。 As 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. By using 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).
　また、硬化剤（Ｄ）としては、上記式（１）で表される化合物と酸無水物類（酸無水物系硬化剤）の両方を含む態様も好ましい。その場合、酸無水物類としては、均一な硬化性エポキシ樹脂組成物を効率的に調製することができる点で、２５℃で液状（液体）の酸無水物類が好ましい。２５℃で液状の酸無水物類を用いた場合、式（１）で表される化合物と混合して２５℃で液状の混合物（硬化剤組成物）としやすいため、硬化性エポキシ樹脂組成物の生産性がより向上する傾向がある。 Further, as 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. In that case, the acid anhydrides are preferably liquid (liquid) acid anhydrides at 25 ° C. in that a uniform curable epoxy resin composition can be efficiently prepared. When 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.
　硬化剤（Ｄ）は公知乃至慣用の方法により製造することもできるし、例えば、商品名「リカシッドＭＨ－７００」、「リカシッドＭＨ－７００Ｆ」、「リカシッドＭＨ－７００Ｇ」、「リカシッドＴＨ」、「リカシッドＨＨ」、「リカシッドＭＨ－Ｔ」、「リカシッドＨＮＡ－１００」（以上、新日本理化（株）製）；商品名「ＨＮ－５５００」（日立化成工業（株）製）；商品名「Ｈ－ＴＭＡｎ－Ｓ」、「Ｈ－ＴＭＡｎ」（以上、三菱ガス化学（株）製）；商品名「ＹＨ１１２０」（三菱化学（株）製）等の市販品を使用することもできる。 The curing agent (D) can be produced by a known or conventional method. For example, 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.
　本発明の硬化性エポキシ樹脂組成物が硬化剤（Ｄ）を含む場合、その含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、５０～２００重量部が好ましく、より好ましくは７５～１８０重量部、さらに好ましくは８０～１５０重量部である。硬化剤（Ｄ）の含有量を５０重量部以上とすることにより、硬化をより効率的に進行させることができ、硬化物の強靱性がより向上する傾向がある。一方、硬化剤（Ｄ）の含有量を２００重量部以下とすることにより、着色の無い（又は少ない）、色相に優れた硬化物が得られやすい傾向がある。 When the curable epoxy resin composition of the present invention contains a curing agent (D), 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 ′). By making content of a hardening | curing agent (D) into 50 weight part or more, hardening can be advanced more efficiently and there exists a tendency for the toughness of hardened | cured material to improve more. On the other hand, when 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.
　本発明の硬化性エポキシ樹脂組成物における硬化剤（Ｄ）が式（１）で表される化合物を含む場合、その含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、１～３００重量部が好ましく、より好ましくは１０～２５０重量部、さらに好ましくは２０～２００重量部である。式（１）で表される化合物の含有量を１重量部以上とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性、硬化物（白色リフレクター）の耐熱性及び密着性がより向上する傾向がある。一方、式（１）で表される化合物の含有量を３００重量部以下とすることにより、硬化物（白色リフレクター）の線膨張係数がより低減され、光半導体素子搭載用基板におけるリードフレームの反り等の不具合の発生がいっそう抑制される傾向がある。 When the hardening | curing agent (D) in the curable epoxy resin composition of this invention contains the compound represented by Formula (1), 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. . By setting the content of the compound represented by formula (1) 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. On the other hand, by setting the content of the compound represented by the formula (1) to 300 parts by weight or less, 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.
　本発明の硬化性エポキシ樹脂組成物に含まれる硬化剤（Ｄ）が式（１）で表される化合物を含む場合、硬化剤（Ｄ）の全量（１００重量％）に対する式（１）で表される化合物の割合は、特に限定されないが、１０重量％以上（例えば、１０～１００重量％）が好ましく、より好ましくは１５重量％以上、さらに好ましくは２０重量％以上、特に好ましくは２５重量％以上である。式（１）で表される化合物の割合を１０重量％以上とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性、硬化物（白色リフレクター）の耐熱性及び密着性がより向上する傾向がある。 When the hardening | 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 | curing agent (D). 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. 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.
　本発明の硬化剤（Ｄ）が、式（１）で表される化合物と酸無水物類を含む場合における酸無水物類の含有量（配合量）は、特に限定されないが、式（１）で表される化合物１００重量部に対して、０～１５００重量部が好ましく、より好ましくは１０～１２００重量部、さらに好ましくは２０～１０００重量部である。酸無水物類の含有量を上記範囲とすることにより、硬化性エポキシ樹脂組成物の硬化性をより向上させることができる傾向がある。 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). By setting the content of acid anhydrides in the above range, the curability of the curable epoxy resin composition tends to be further improved.
［硬化促進剤］
　本発明の硬化性エポキシ樹脂組成物は、硬化促進剤を含んでいてもよい。硬化促進剤は、本発明の硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）が硬化剤（Ｄ）等の硬化剤と反応する際の反応速度（硬化速度）を促進する機能を有する化合物である。上記硬化促進剤としては、公知乃至慣用の硬化促進剤を使用することができ、例えば、１，８－ジアザビシクロ［５．４．０］ウンデセン－７（ＤＢＵ）又はその塩（例えば、フェノール塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩等）；１，５－ジアザビシクロ［４．３．０］ノネン－５（ＤＢＮ）又はその塩（例えば、フェノール塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩等）；ベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ－ジメチルシクロヘキシルアミン等の３級アミン；２－エチル－４－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール等のイミダゾール；リン酸エステル、トリフェニルホスフィン等のホスフィン類；テトラフェニルホスホニウムテトラ（ｐ－トリル）ボレート等のホスホニウム化合物；オクチル酸亜鉛やオクチル酸スズ等の有機金属塩；金属キレート等が挙げられる。 [Curing accelerator]
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. As the curing accelerator, known or conventional curing accelerators can be used. For example, 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 phosphine; phosphonium compounds such as tetraphenylphosphonium tetra (p- tolyl) borate, organic metal salts such as zinc octylate and tin octylate; metal chelate and the like.
　本発明の硬化性エポキシ樹脂組成物において硬化促進剤は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。 In the curable epoxy resin composition of the present invention, one type of curing accelerator can be used alone, or two or more types can be used in combination.
　硬化促進剤は、公知乃至慣用の方法により製造することもできるし、例えば、商品名「Ｕ－ＣＡＴ　ＳＡ　５０６」、「Ｕ－ＣＡＴ　ＳＡ　１０２」、「Ｕ－ＣＡＴ　５００３」、「Ｕ－ＣＡＴ　１８Ｘ」、「１２ＸＤ」（開発品）（以上、サンアプロ（株）製）；商品名「ＴＰＰ－Ｋ」、「ＴＰＰ－ＭＫ」（以上、北興化学工業（株）製）；商品名「ＰＸ－４ＥＴ」（日本化学工業（株）製）等の市販品を使用することもできる。 The curing accelerator can be produced by a known or conventional method. For example, trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT 18X” are available. ", 12XD" (developed) (San Apro Co., Ltd.); trade names "TPP-K", "TPP-MK" (Hokuko Chemical Co., Ltd.); trade names "PX-4ET" Commercial products such as “Nippon Chemical Industry Co., Ltd.” can also be used.
　本発明の硬化性エポキシ樹脂組成物における硬化促進剤の含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、０．１～１０重量部が好ましく、より好ましくは０．３～８重量部である。硬化促進剤の含有量を０．１重量部以上とすることにより、より効率的に硬化反応を進行させることができる傾向がある。一方、硬化促進剤の含有量を１０重量部以下とすることにより、硬化性エポキシ樹脂組成物の保存性がより向上したり、着色がより抑制され色相に優れた硬化物（白色リフレクター）が得られやすい傾向がある。 Although 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. By setting the content of the curing accelerator to 0.1 parts by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, by setting the content of the curing accelerator to 10 parts by weight or less, the storability of the curable epoxy resin composition is further improved, or a cured product (white reflector) that is more suppressed in coloring and excellent in hue is obtained. There is a tendency to be easily.
［無機充填剤（Ｂ’）］
　本発明の硬化性エポキシ樹脂組成物に含まれていてもよい無機充填剤（Ｂ’）は、主に、硬化性エポキシ樹脂組成物に対して良好な粉砕性及び／又は打錠性を付与し、また、硬化物（白色リフレクター）の線膨張率を低減させる働きを有する。また、無機充填剤（Ｂ’）の種類によっては、硬化物（白色リフレクター）に対して優れた光反射性を付与できる場合もある。 [Inorganic filler (B ′)]
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 | cured material (white reflector). Moreover, depending on the kind of inorganic filler (B ′), excellent light reflectivity may be imparted to the cured product (white reflector).
　無機充填剤（Ｂ’）としては、公知乃至慣用の無機充填剤を使用することができ、特に限定されないが、例えば、上述の無機充填剤（Ｂ）と同様のものが例示できる。中でも、無機充填剤（Ｂ’）としては、硬化物（白色リフレクター）の耐熱性（特に、耐黄変性）、及び流動性の観点で、シリカ（シリカフィラー）が好ましい。
　無機充填剤（Ｂ’）としては、上述の無機充填剤（Ｂ）と同一の無機充填剤を使用してもよく、無機充填剤（Ｂ）と異なる無機充填剤を使用してもよい。
　また、上述の無機充填剤（Ｂ）が２種以上の無機充填剤の混合物の場合、無機充填剤（Ｂ’）としては、（１）無機充填剤（Ｂ）と同一の組成の混合物、（２）無機充填剤（Ｂ）と異なる組成の混合物、（３）無機充填剤（Ｂ）を構成する単独の無機充填剤、（４）無機充填剤（Ｂ）を構成しない単独の無機充填剤のいずれであってもよい。 As the 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. Among these, silica (silica filler) is preferable as the inorganic filler (B ′) from the viewpoint of heat resistance (particularly yellowing resistance) of the cured product (white reflector) and fluidity.
As the inorganic filler (B ′), 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.
Moreover, when the above-mentioned inorganic filler (B) is a mixture of two or more kinds of inorganic fillers, as 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.
　シリカとしては、特に限定されず、例えば、溶融シリカ、結晶シリカ、高純度合成シリカ等の公知乃至慣用のシリカを使用できる。なお、シリカとしては、公知乃至慣用の表面処理［例えば、金属酸化物、シランカップリング剤、チタンカップリング剤、有機酸、ポリオール、シリコーン等の表面処理剤による表面処理等］が施されたものを使用することもできる。 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.
　無機充填剤（Ｂ’）の形状は、特に限定されないが、例えば、粉体、球状、破砕状、繊維状、針状、鱗片状等が挙げられる。中でも、分散性の観点で、球状の無機充填剤が好ましく、特に真球状の無機充填剤（例えば、アスペクト比が１．２以下の球状のシリカ）が好ましい。 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.
　無機充填剤（Ｂ’）の中心粒径は、特に限定されないが、硬化物（白色リフレクター）の光反射性向上の観点で、０．１～５０μｍが好ましく、より好ましくは０．１～３０μｍである。なお、上記中心粒径は、レーザー回折・散乱法で測定した粒度分布における積算値５０％での粒径（メディアン径）を意味する。 The center particle diameter of the inorganic filler (B ′) is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm from the viewpoint of improving the light reflectivity of the cured product (white reflector). is there. In addition, 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.
　なお、本発明の硬化性エポキシ樹脂組成物において無機充填剤（Ｂ’）は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、無機充填剤（Ｂ’）は、公知乃至慣用の製造方法により製造することもできるし、例えば、商品名「ＦＢ－９１０」、「ＦＢ－９４０」、「ＦＢ－９５０」等のＦＢシリーズ（以上、電気化学工業（株）製）、商品名「ＭＳＲ－２２１２」、「ＭＳＲ－２５」（以上、（株）龍森製）、商品名「ＨＳ－１０５」、「ＨＳ－１０６」、「ＨＳ－１０７」（以上、マイクロン社製）等の市販品を使用することもできる。 In the curable epoxy resin composition of the present invention, 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. For example, 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.
　本発明の硬化性エポキシ樹脂組成物における無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の合計含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物（１００重量％）に対して、６０～９０重量％が好ましく、より好ましくは６０～７５重量％である。当該合計含有量を６０重量％以上とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性がより向上し、また、硬化物（白色リフレクター）の線膨張係数がより低くなって、光半導体素子搭載用基板におけるリードフレームの反り等の不具合がいっそう生じにくくなる傾向がある。一方、当該合計含有量を９０重量％以下とすることにより、硬化性エポキシ樹脂組成物が良好な流動性を有するため、成型（特に、トランスファー成型）時の未充填等の問題が抑制される傾向がある。 Although the total content (blending amount) of the inorganic filler (B) and the inorganic filler (B ′) in the curable epoxy resin composition of the present invention is not particularly limited, the curable epoxy resin composition (100% by weight) The amount is preferably 60 to 90% by weight, more preferably 60 to 75% by weight. By making the total content 60% by weight or more, 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. On the other hand, by setting the total content to 90% 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.
　本発明の硬化性エポキシ樹脂組成物におけるエポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計量に対する無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の合計含有量（配合量）は、特に限定されないが、エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計量１００重量部に対して、２００～２０００重量部が好ましく、より好ましくは２２０～１，５００重量部、さらに好ましくは２５０～１，０００重量部である。無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の合計含有量を２００重量部以上とすることにより、硬化性エポキシ樹脂組成物の粉砕性及び／又は打錠性がより向上し、また、硬化物（白色リフレクター）の線膨張係数がより低くなって、光半導体素子搭載用基板におけるリードフレームの反り等の不具合がいっそう生じにくくなる傾向がある。一方、当該合計含有量を２０００重量部以下とすることにより、硬化性エポキシ樹脂組成物が良好な流動性を有するため、成型（特に、トランスファー成型）時の未充填等の問題が抑制される傾向がある。 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. The (blending amount) 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. By setting the total content of the inorganic filler (B) and the inorganic filler (B ′) to 200 parts by weight or more, 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. On the other hand, by setting the total content 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.
［白色顔料（Ｃ’）］
　本発明の硬化性エポキシ樹脂組成物に含まれていてもよい白色顔料（Ｃ’）は、主に、硬化物（白色リフレクター）に対して高い光反射性を付与し、また、その線膨張率を低減させる働きを有する。白色顔料（Ｃ’）としては、公知乃至慣用の白色顔料を使用することができ、特に限定されないが、上述の白色顔料（Ｃ’）と同様のものが例示される。
　白色顔料（Ｃ’）としては、上述の白色顔料（Ｃ）と同一の白色顔料を使用してもよく、白色顔料（Ｃ）と異なる白色顔料を使用してもよい。
　また、上述の白色顔料（Ｃ）が２種以上の白色顔料の混合物の場合、白色顔料（Ｃ’）としては、（１）白色顔料（Ｃ）と同一の組成の混合物、（２）白色顔料（Ｃ）と異なる組成の混合物、（３）白色顔料（Ｃ）を構成する単独の白色顔料、（４）白色顔料（Ｃ）を構成しない単独の白色顔料のいずれであってもよい。 [White pigment (C ′)]
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.
When the above-mentioned white pigment (C) is a mixture of two or more kinds of white pigments, 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).
　中でも、白色顔料（Ｃ’）としては、硬化物（白色リフレクター）の高反射率及び添加量に対する光反射性の上昇率の観点で、無機酸化物が好ましく、より好ましくは酸化チタンである。 Among them, 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.
　白色顔料（Ｃ’）の形状は、特に限定されず、例えば、球状、破砕状、繊維状、針状、鱗片状等が挙げられる。中でも、分散性の観点で、球状の酸化チタンが好ましく、特に真球状の酸化チタン（例えば、アスペクト比が１．２以下の球状の酸化チタン）が好ましい。 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. Among them, 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.
　白色顔料（Ｃ’）の中心粒径は、特に限定されないが、硬化物（白色リフレクター）の光反射性向上の観点で、０．１～５０μｍが好ましい。特に、白色顔料（Ｃ’）として酸化チタンを使用する場合、該酸化チタンの中心粒径は、特に限定されないが、０．１～５０μｍが好ましく、より好ましくは０．１～３０μｍである。なお、上記中心粒径は、レーザー回折・散乱法で測定した粒度分布における積算値５０％での粒径（メディアン径）を意味する。 The center particle diameter of the white pigment (C ′) is not particularly limited, but is preferably 0.1 to 50 μm from the viewpoint of improving the light reflectivity of the cured product (white reflector). In particular, when titanium oxide is used as the white pigment (C ′), the center particle diameter of the titanium oxide is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 30 μm. In addition, 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.
　本発明の硬化性エポキシ樹脂組成物において白色顔料（Ｃ’）は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、白色顔料（Ｃ’）は、公知乃至慣用の方法により製造することもできるし、例えば、商品名「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」（以上、堺化学工業（株）製）、商品名「タイペークＣＲ－５０」、「ＣＲ－５０－２」、「ＣＲ－６０」、「ＣＲ－６０－２」、「ＣＲ－６３」、「ＣＲ－８０」、「ＣＲ－９０」、「ＣＲ－９０－２」、「ＣＲ－９３」、「ＣＲ－９５」、「ＣＲ－９７」（以上、石原産業（株）製）、商品名「ＪＲ－３０１」、「ＪＲ－４０３」、「ＪＲ－４０５」、「ＪＲ－６００Ａ」、「ＪＲ－６０５」、「ＪＲ－６００Ｅ」、「ＪＲ－６０３」、「ＪＲ－８０５」、「ＪＲ－８０６」、「ＪＲ－７０１」、「ＪＲＮＣ」、「ＪＲ－８００」、「ＪＲ」（以上、テイカ（株）製）、商品名「ＴＲ－６００」、「ＴＲ－７００」、「ＴＲ－７５０」、「ＴＲ－８４０」、「ＴＲ－９００」（以上、富士チタン工業（株）製）、商品名「ＫＲ－３１０」、「ＫＲ－３８０」、「ＫＲ－３８０Ｎ」、「ＳＴ－４１０ＷＢ」、「ＳＴ－４５５」、「ＳＴ－４５５ＷＢ」、「ＳＴ－４５７ＳＡ」、「ＳＴ－４５７ＥＣ」、「ＳＴ－４８５ＳＡ１５」、「ＳＴ－４８６ＳＡ」、「ＳＴ－４９５Ｍ」（以上、チタン工業（株）製）等のルチル型酸化チタン；商品名「Ａ－１１０」、「ＴＣＡ－１２３Ｅ」、「Ａ－１９０」、「Ａ－１９７」、「ＳＡ－１」、「ＳＡ－１Ｌ」、「ＳＳＰシリーズ」、「ＣＳＢシリーズ」（以上、堺化学工業（株）製）、商品名「ＪＡ－１」、「ＪＡ－Ｃ」、「ＪＡ－３」（以上、テイカ（株）製）、商品名「ＫＡ－１０」、「ＫＡ－１５」、「ＫＡ－２０」、「ＳＴＴ－６５Ｃ－Ｓ」、「ＳＴＴ－３０ＥＨＪ」（以上、チタン工業（株）製）、商品名「ＤＣＦ－Ｔ－１７００７」、「ＤＣＦ－Ｔ－１７００８」、「ＤＣＦ－Ｔ－１７０５０」（以上、レジノカラー工業（株）製）等のアナターゼ型酸化チタン等の市販品を使用することもできる。 In the curable epoxy resin composition of the present invention, 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. For example, 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" (above, manufactured by Sakai Chemical Industry Co., Ltd.) “CR-50”, “CR-50-2”, “CR-60”, “CR-60-2”, “CR-63”, “CR-80”, “CR-90”, “CR-90-” 2 ”,“ CR-93 ”,“ CR-95 ”,“ CR-97 ”(above, manufactured by Ishihara Sangyo Co., Ltd.), trade names“ JR-301 ”,“ JR-403 ” “JR-405”, “JR-600A”, “JR-605”, “JR-600E”, “JR-603”, “JR-805”, “JR-806”, “JR-701”, “JRNC” ”,“ JR-800 ”,“ JR ”(manufactured by Teika Co., Ltd.), trade names“ TR-600 ”,“ TR-700 ”,“ TR-750 ”,“ TR-840 ”,“ TR- ” 900 ”(manufactured by Fuji Titanium Industry Co., Ltd.), trade names“ KR-310 ”,“ KR-380 ”,“ KR-380N ”,“ ST-410WB ”,“ ST-455 ”,“ ST-455WB ” ”,“ ST-457SA ”,“ ST-457EC ”,“ ST-485SA15 ”,“ ST-486SA ”,“ ST-495M ”(above, manufactured by Titanium Industry Co., Ltd.); “A-110”, “TCA-12” "E", "A-190", "A-197", "SA-1", "SA-1L", "SSP series", "CSB series" (above, Sakai Chemical Industry Co., Ltd.) “JA-1”, “JA-C”, “JA-3” (manufactured by Teika Co., Ltd.), trade names “KA-10”, “KA-15”, “KA-20”, “STT-” 65C-S "," STT-30EHJ "(made by Titanium Industry Co., Ltd.), trade names" DCF-T-17007 "," DCF-T-17008 "," DCF-T-17050 "(above, Resino Color) Commercial products such as anatase-type titanium oxide such as those manufactured by Kogyo Co., Ltd. can also be used.
　中でも、白色顔料（Ｃ’）としては、特に硬化物（白色リフレクター）の光反射性及び耐黄変性向上の観点で、商品名「Ｒ－６２Ｎ」、「ＣＲ－６０」、「ＤＣＦ－Ｔ－１７００７」、「ＤＣＦ－Ｔ－１７００８」、「ＤＣＦ－Ｔ－１７０５０」、「ＦＴＲ－７００」が好ましい。 Among them, as 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.
　本発明の硬化性エポキシ樹脂組成物における白色顔料（Ｃ’）及び白色顔料（Ｃ）の合計含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物（１００重量％）に対して、２～４０重量％が好ましく、より好ましくは１０～３０重量％、さらに好ましくは１５～２５重量％である。白色顔料（Ｃ’）及び白色顔料（Ｃ）の合計含有量を２重量％以上とすることにより、硬化物（白色リフレクター）の光反射性がより向上する傾向がある。一方、当該合計含有量を４０重量％以下とすることにより、白色顔料の添加による硬化性エポキシ樹脂組成物の流動性低下が抑えられ、作業性がより向上する傾向がある。 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. When 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. On the other hand, when 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.
　本発明の硬化性エポキシ樹脂組成物におけるエポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計量に対する白色顔料（Ｃ）及び白色顔料（Ｃ’）の合計含有量（配合量）は、特に限定されないが、エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計量１００重量部に対して、３～４００重量部が好ましく、より好ましくは５～３５０重量部、さらに好ましくは５～３００重量部である。白色顔料（Ｃ）及び白色顔料（Ｃ’）の合計含有量を３重量部以上とすることにより、硬化物（白色リフレクター）の光反射性がより向上する傾向がある。一方、当該合計含有量を４００重量部以下とすることにより、白色顔料（Ｃ）及び白色顔料（Ｃ’）の添加による硬化性エポキシ樹脂組成物の流動性低下が抑えられ、作業性がより向上する傾向がある。 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. By setting the total content of the white pigment (C) and the white pigment (C ′) to 3 parts by weight or more, the light reflectivity of the cured product (white reflector) tends to be further improved. On the other hand, by setting the total content to 400 parts by weight or less, a decrease in fluidity of the curable epoxy resin composition due to the addition of the white pigment (C) and the white pigment (C ′) is suppressed, and workability is further improved. Tend to.
　本発明の硬化性エポキシ樹脂組成物に含まれる無機充填剤（Ｂ）、無機充填剤（Ｂ’）、白色顔料（Ｃ）と白色顔料（Ｃ’）の総量（１００重量％）に対する酸化チタンの割合は、特に限定されないが、硬化物（白色リフレクター）の耐黄変性と光反射性のバランスの観点で、５～４０重量％が好ましく、より好ましくは１０～３５重量％である。酸化チタンの割合を５重量％以上とすることにより、硬化物（白色リフレクター）の光反射性がより向上する傾向がある。一方、酸化チタンの割合を４０重量％以下とすることにより、硬化物（白色リフレクター）の耐熱性（特に、耐黄変性）がより向上する傾向がある。また、酸化チタンの添加による硬化性エポキシ樹脂組成物の流動性低下が抑えられ、作業性がより向上する傾向がある。 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). By making the ratio of titanium oxide 5% by weight or more, the light reflectivity of the cured product (white reflector) tends to be further improved. On the other hand, when 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. Moreover, the fluidity | liquidity fall of the curable epoxy resin composition by addition of a titanium oxide is suppressed, and there exists a tendency for workability | operativity to improve more.
　本発明の硬化性エポキシ樹脂組成物におけるエポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計量に対する無機充填剤（Ｂ）、無機充填剤（Ｂ’）、白色顔料（Ｃ）と白色顔料（Ｃ’）の合計含有量（配合量）は、特に限定されないが、エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計量１００重量部に対して、２００～２，０００重量部が好ましく、より好ましくは２５０～１，８００重量部、さらに好ましくは３００～１，５００重量部である。無機充填剤（Ｂ）、無機充填剤（Ｂ’）白色顔料（Ｃ）と白色顔料（Ｃ’）の合計含有量を２００重量部以上とすることにより、硬化物（白色リフレクター）の光反射性がより向上する傾向がある。一方、当該合計量を２，０００重量部以下とすることにより、無機充填剤と白色顔料の添加による硬化性エポキシ樹脂組成物の流動性低下が抑えられ、作業性がより向上する傾向がある。 Inorganic filler (B), inorganic filler (B ′), white pigment (total amount of epoxy compound (A), epoxy compound (A ′) and curing agent (D) in the curable epoxy resin composition of the present invention 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. By making 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. On the other hand, when 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.
［離型剤］
　本発明の硬化性エポキシ樹脂組成物は、さらに、離型剤を含んでいてもよい。離型剤を含むことにより、トランスファー成型等の金型を使用した成型法による連続成型が容易となり、高い生産性で硬化物（白色リフレクター）を製造することが可能となる。離型剤としては、公知乃至慣用の離型剤を使用することができ、特に限定されないが、例えば、フッ素系離型剤（フッ素原子含有化合物；例えば、フッ素オイル、ポリテトラフルオロエチレン等）、シリコーン系離型剤（シリコーン化合物；例えば、シリコーンオイル、シリコーンワックス、シリコーン樹脂、ポリオキシアルキレン単位を有するポリオルガノシロキサン等）、ワックス系離型剤（ワックス類；例えば、カルナウバワックス等の植物ロウ、羊毛ワックス等の動物ロウ、パラフィンワックス等のパラフィン類、ポリエチレンワックス、酸化ポリエチレンワックス等）、高級脂肪酸又はその塩（例えば、金属塩等）、高級脂肪酸エステル、高級脂肪酸アミド、鉱油等が挙げられる。 [Release agent]
The curable epoxy resin composition of the present invention may further contain 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. As the release agent, a known or commonly used release agent can be used, and is not particularly limited. For example, 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 (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), higher fatty acid esters, higher fatty acid amides, mineral oils, etc. .
　なお、本発明の硬化性エポキシ樹脂組成物において離型剤は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、離型剤は、公知乃至慣用の方法によって製造することもできるし、市販品を使用することもできる。 In the curable epoxy resin composition of the present invention, one type of release agent can be used alone, or two or more types can be used in combination. Moreover, a mold release agent can also be manufactured by a well-known thru | or usual method, and a commercial item can also be used for it.
　本発明の硬化性エポキシ樹脂組成物における離型剤の含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、１～１２重量部が好ましく、より好ましくは２～１０重量部である。離型剤の含有量を１重量部以上とすることにより、硬化物（白色リフレクター）の離型性がより向上し、白色リフレクターの生産性がより向上する傾向がある。一方、離型剤の含有量を１２重量部以下とすることにより、光半導体素子搭載用基板における白色リフレクターのリードフレームに対する良好な密着性を確保できる傾向がある。 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. By making content of a mold release agent into 1 weight part or more, there exists a tendency which the mold release property of hardened | cured material (white reflector) improves more, and the productivity of a white reflector improves more. On the other hand, when the content of the release agent is 12 parts by weight or less, there is a tendency that good adhesion to the lead frame of the white reflector in the substrate for mounting an optical semiconductor element can be secured.
［酸化防止剤］
　本発明の硬化性エポキシ樹脂組成物は、酸化防止剤を含んでいてもよい。酸化防止剤を含むことにより、いっそう耐熱性（特に、耐黄変性）に優れた硬化物（白色リフレクター）を製造することが可能となる。酸化防止剤としては、公知乃至慣用の酸化防止剤を使用することができ、特に限定されないが、例えば、フェノール系酸化防止剤（フェノール系化合物）、ヒンダードアミン系酸化防止剤（ヒンダードアミン系化合物）、リン系酸化防止剤（リン系化合物）、イオウ系酸化防止剤（イオウ系化合物）等が挙げられる。 [Antioxidant]
The curable epoxy resin composition of the present invention may contain an antioxidant. By containing an antioxidant, it becomes possible to produce a cured product (white reflector) having further excellent heat resistance (particularly yellowing resistance). As the antioxidant, 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.
　フェノール系酸化防止剤としては、例えば、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－ブチル－ｐ－エチルフェノール、ステアリル－β－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート等のモノフェノール類；２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、３，９－ビス［１，１－ジメチル－２－｛β－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝エチル］２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン等のビスフェノール類；１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、テトラキス－［メチレン－３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン、ビス［３，３’－ビス－（４’－ヒドロキシ－３’－ｔ－ブチルフェニル）ブチリックアシッド］グリコールエステル、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンジル）－ｓ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）トリオン、トコフェノール等の高分子型フェノール類等が挙げられる。 Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (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- {β- (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-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl- And 4′-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, polymer type phenols such as tocophenol, and the like.
　ヒンダードアミン系酸化防止剤としては、例えば、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ブチルマロネート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート、メチル－１，２，２，６，６－ペンタメチル－４－ピペリジルセバケート、４－ベンゾイルオキシ－２，２，６，６－テトラメチルピペリジン等が挙げられる。 Examples of 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.
　リン系酸化防止剤としては、例えば、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、トリス（ノニルフェニル）ホスファイト、ジイソデシルペンタエリスリトールホスファイト、トリス（２、４－ジ－ｔ－ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（オクタデシル）ホスファイト、サイクリックネオペンタンテトライルビス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（２，４－ジ－ｔ－ブチル－４－メチルフェニル）ホスファイト、ビス［２－ｔ－ブチル－６－メチル－４－｛２－（オクタデシルオキシカルボニル）エチル｝フェニル］ヒドロゲンホスファイト等のホスファイト類；９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド、１０－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド等のオキサホスファフェナントレンオキサイド類等が挙げられる。 Examples of 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- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. Fights; 9,10- Hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene And oxaphosphaphenanthrene oxides such as -10-oxide.
　イオウ系酸化防止剤としては、例えば、ドデカンチオール、ジラウリル－３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリル－３，３’－チオジプロピオネート等が挙げられる。 Examples of the sulfur-based antioxidant include dodecanethiol, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate Is mentioned.
　本発明の硬化性エポキシ樹脂組成物において酸化防止剤は、一種を単独で使用することもできるし、二種以上を組み合わせて使用することもできる。また、酸化防止剤は、公知乃至慣用の方法により製造することもできるし、例えば、商品名「Ｉｒｇａｎｏｘ１０１０」（ＢＡＳＦ製、フェノール系酸化防止剤）、商品名「ＡＯ－６０」、「ＡＯ－８０」（（株）ＡＤＥＫＡ製、フェノール系酸化防止剤）、商品名「Ｉｒｇａｆｏｓ１６８」（ＢＡＳＦ製、リン系酸化防止剤）、商品名「アデカスタブＨＰ－１０」、「アデカスタブＰＥＰ３６」（（株）ＡＤＥＫＡ製、リン系酸化防止剤）、商品名「ＨＣＡ」（三光（株）製、リン系酸化防止剤）等の市販品を使用することもできる。 In the curable epoxy resin composition of the present invention, 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”. ”(Manufactured by ADEKA Corporation, phenolic antioxidant), trade name“ Irgafos168 ”(manufactured by BASF, phosphorous antioxidant), trade names“ Adeka Stub HP-10 ”,“ Adeka Stub PEP36 ”(manufactured by ADEKA Corporation) , Phosphorus antioxidants) and commercial names such as “HCA” (manufactured by Sanko Co., Ltd., phosphorus antioxidants) can also be used.
　中でも、酸化防止剤としては、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤が好ましく、特に、フェノール系酸化防止剤とリン系酸化防止剤又はイオウ系酸化防止剤とを併用することが好ましく、フェノール系酸化防止剤とリン系酸化防止剤とを併用することが最も好ましい。 Among them, as the antioxidant, a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant are preferable. In particular, 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.
　本発明の硬化性エポキシ樹脂組成物における酸化防止剤の含有量（配合量）は、特に限定されないが、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物（Ａ）及びエポキシ化合物（Ａ’）の全量１００重量部に対して、０．１～５重量部が好ましく、より好ましくは０．５～３重量部である。酸化防止剤の含有量を０．１重量部以上とすることにより、硬化物（白色リフレクター）の酸化が効率的に防止され、耐熱性、耐黄変性がより向上する傾向がある。一方、酸化防止剤の含有量を５重量部以下とすることにより、着色が抑制され、色相がより良好な白色リフレクターが得られやすい傾向がある。 Although 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. By making content of antioxidant into 0.1 weight part or more, there exists a tendency for the oxidation of hardened | cured material (white reflector) to be prevented efficiently and to improve heat resistance and yellowing resistance. On the other hand, when the content of the antioxidant is 5 parts by weight or less, coloring tends to be suppressed and a white reflector having a better hue tends to be obtained.
［添加剤］
　本発明の硬化性エポキシ樹脂組成物は、上述の成分以外にも、本発明の効果を損なわない範囲で各種添加剤を含有していてもよい。上記添加剤として、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、グリセリン等のヒドロキシ基を有する化合物を含有させると、反応を緩やかに進行させることができる。その他にも、粘度や透明性を損なわない範囲内で、消泡剤、レベリング剤、γ－グリシドキシプロピルトリメトキシシランや３－メルカプトプロピルトリメトキシシラン等のシランカップリング剤、界面活性剤、難燃剤、着色剤、イオン吸着体、顔料等の慣用の添加剤を使用することができる。これら添加剤の含有量は特に限定されず、適宜選択可能である。 [Additive]
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. For example, when a compound having a hydroxy group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the reaction can be allowed to proceed slowly. In addition, antifoaming agents, leveling agents, silane coupling agents such as γ-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.
　本発明の硬化性エポキシ樹脂組成物は、特に限定されないが、本発明の加熱混合物と、必要に応じて、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、白色顔料（Ｃ’）、硬化剤（Ｄ）、硬化促進剤、酸化防止剤、離型剤、その他の成分を含む混合物を、必要に応じて加熱した状態で配合及び混合することにより調製することができる。上記混合の方法は、特に限定されず、例えば、ディゾルバー、ホモジナイザー等の各種ミキサー、ニーダー、ロール、ビーズミル、自公転式撹拌装置等の公知乃至慣用の混合手段を使用できる。 Although 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 | blending and mixing the mixture containing a hardening | curing agent (D), a hardening accelerator, antioxidant, a mold release agent, and another component in the state heated as needed. 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.
　本発明の硬化性エポキシ樹脂組成物は、液体、固体のいずれであってもよいが、少なくとも３０℃、常圧において固体であることが好ましい。
　本発明の硬化性エポキシ樹脂組成物においては、通常ＩＣＩコーンプレート粘度が１００～２００℃の範囲で、０．０１～１０Ｐａ・ｓである。
　当該範囲に調整することにより、常温（２５℃）で固体となり、成型が容易となり、ボイド等の不具合を効果的に防止することができるようになるためである。また、このような低粘度の硬化性エポキシ樹脂組成物に設定することで、従来結晶性を有するため軟化点あるいは融点が高く、混練が困難であった各成分が硬化剤に十分に溶融・分散するため、結晶が崩れ、主剤となるエポキシ樹脂と十分混練されることとなり、各成分が効果的に配列し、優れた物性を有する硬化物を得ることができる。本発明の硬化性エポキシ樹脂組成物の軟化点においては、４０～１３０℃であることが好ましく、５０～１００℃であることがより好ましく、特には７０～１００℃であることが好ましい。このような軟化点にあることで、十分な混練を行うことが可能となる。 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.
In the curable epoxy resin composition of the present invention, 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 | mold, and becomes able to prevent troubles, such as a void, effectively. In addition, by setting such a low-viscosity curable epoxy resin composition, 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. Therefore, the crystals are broken and are sufficiently kneaded with the epoxy resin as the main agent, so that each component is effectively arranged and a cured product having excellent physical properties can be obtained. 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.
　なお、本発明の硬化性エポキシ樹脂組成物は、加熱して該硬化性エポキシ樹脂組成物における本発明の加熱混合物、エポキシ化合物（Ａ’）及び硬化剤の一部を反応させることによって得られる、Ｂステージ化させた硬化性エポキシ樹脂組成物（Ｂステージ状態の硬化性エポキシ樹脂組成物）であってもよい。 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).
　本発明の硬化性エポキシ樹脂組成物は粉砕性及び／又は打錠性に優れるため、特に、トランスファー成型用樹脂組成物やコンプレッション成型用樹脂組成物として好ましく使用できる。具体的には、例えば、本発明の硬化性エポキシ樹脂組成物を粉砕及び打錠に付してタブレット状に調製することによって、トランスファー成型又はコンプレッション成型に付すことができる。 Since 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.
＜硬化物＞
　本発明の硬化性エポキシ樹脂組成物を加熱によって硬化させることにより、耐熱性に優れる硬化物を得ることができる。硬化の際の加熱温度（硬化温度）は、特に限定されないが、１００～２００℃が好ましく、より好ましくは１５０～１９０℃である。また、硬化の際に加熱する時間（硬化時間）は、特に限定されないが、６０～６００秒が好ましく、より好ましくは９０～２４０秒である。硬化温度と硬化時間が上記範囲の下限値より低い場合は硬化が不十分となり、逆に上記範囲の上限値より高い場合は熱分解による黄変が発生したり、タクトタイムが長くなり生産性が低下することがある。硬化条件は種々の条件に依存するが、例えば、硬化温度を高くした場合は硬化時間を短く、硬化温度を低くした場合は硬化時間を長くする等により、適宜調整することができる。また、硬化処理は一段階（例えば、トランスファー成型のみ）で行ってもよいし、例えば、多段階（例えば、トランスファー成型後にポストキュアー（二次硬化）としてオーブン等でさらに加熱する等）で行ってもよい。 <Hardened product>
By curing the curable epoxy resin composition of the present invention by heating, a cured product having excellent heat resistance can be obtained. 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. Although 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.
　本発明の硬化性エポキシ樹脂組成物は、上述のように、白色リフレクター用硬化性エポキシ樹脂組成物である。即ち、本発明の硬化性エポキシ樹脂組成物は、光半導体装置における光半導体素子の基板（光半導体素子搭載用基板）が有する白色リフレクター（光反射部材）を形成する用途に用いられる成型材料（金型等で成型するのに使用する材料）である。従って、本発明の硬化性エポキシ樹脂組成物を成型する（かつ硬化させる）ことによって、耐熱性に優れた白色リフレクターを有する高品質な（例えば、高耐久性の）光半導体素子搭載用基板を製造することができる。 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.
＜光半導体素子搭載用基板＞
　本発明の光半導体素子搭載用基板は、本発明の硬化性エポキシ樹脂組成物の硬化物（本発明の硬化性エポキシ樹脂組成物を硬化させることにより得られる硬化物）により形成された白色リフレクターを少なくとも有する基板である。図１は、本発明の光半導体素子搭載用基板の一例を示す概略図であり、（ａ）は斜視図、（ｂ）は断面図を示す。図１における１００は白色リフレクター、１０１は金属配線（リードフレーム）、１０２は光半導体素子の搭載領域、１０３はパッケージ基板を示す。なお、パッケージ基板１０３には、金属配線１０１、さらに白色リフレクター１００が取り付けられており、その中央（光半導体素子の搭載領域１０２）に光半導体素子１０７が置かれてダイ・ボンディングされ、光半導体素子１０７とパッケージ基板１０３上の金属配線１０１の間はワイヤ・ボンディングで接続される。パッケージ基板１０３の材質としては、樹脂、セラミックなどが使用されるが、白色リフレクターと同じものであってもよい。本発明の光半導体素子搭載用基板における上側の白色リフレクター１００は、光半導体素子の搭載領域１０２の周囲を環状に取り囲み、上方に向かってその環の径が拡大するように傾斜した凹状の形状を有している。本発明の光半導体素子搭載用基板は、上記凹状の形状の内側の表面が少なくとも本発明の硬化性エポキシ樹脂組成物の硬化物により形成されていればよい。また、図１に示すように、金属配線１０１に囲まれた部分（１０２の下部）は、パッケージ基板１０３の場合もあるし、白色リフレクター１００の場合もある（即ち、図１における「１００／１０３」は、白色リフレクター１００であってもよいし、パッケージ基板１０３であってもよいことを意味する）。但し、本発明の光半導体素子搭載用基板は、図１に示す態様には限定されない。 <Optical semiconductor device mounting substrate>
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. In FIG. 1, 100 is a white reflector, 101 is a metal wiring (lead frame), 102 is an optical semiconductor element mounting region, and 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. Further, as shown in FIG. 1, the portion surrounded by the metal wiring 101 (the lower part of 102) 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). However, the optical semiconductor element mounting substrate of the present invention is not limited to the embodiment shown in FIG.
　本発明の光半導体素子搭載用基板における白色リフレクターを形成する方法としては、公知乃至慣用の成型方法（例えば、トランスファー成型等）を使用することができ、特に限定されないが、例えば、本発明の硬化性エポキシ樹脂組成物を、トランスファー成型、コンプレッション成型、インジェクション成型、ＬＩＭ成型（インジェクション成型）、ディスペンスによるダム成型等の各種成型方法に付す方法等が挙げられる。本発明の硬化性エポキシ樹脂組成物を用いてトランスファー成型によって白色リフレクターを形成する際は、具体的には、例えば、本発明の硬化性エポキシ樹脂組成物を、加圧、打錠、又は押出成形等によってタブレットを作製し、得られたタブレットをプランジャー内で加熱して溶融し、溶融された樹脂組成物を金型内に流動させて充填し、白色リフレクターの形状に成型した後、得られた成型物を硬化させることにより、白色リフレクター（又は該白色リフレクターを有する光半導体素子搭載用基板）を製造することができる。この際の硬化の条件としては、例えば、上述の硬化物を形成する際の条件等から適宜選択することができる。 As a method for forming a white reflector in the substrate for mounting an optical semiconductor element of the present invention, a known or conventional molding method (for example, transfer molding or the like) can be used, and is not particularly limited. And 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. When a white reflector is formed by transfer molding using the curable epoxy resin composition of the present invention, specifically, for example, the curable epoxy resin composition of the present invention is pressed, tableted, or extruded. It is obtained by making a tablet by, etc., heating the obtained tablet in a plunger and melting it, flowing the molten resin composition into a mold and filling it, molding it into the shape of a white reflector By curing the molded product, 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.
　本発明の光半導体素子搭載用基板を光半導体装置における基板として使用し、該基板に対して光半導体素子を搭載することによって、本発明の光半導体装置が得られる。 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.
＜光半導体装置＞
　本発明の光半導体装置は、本発明の光半導体素子搭載用基板と、該基板に搭載された光半導体素子とを少なくとも有する光半導体装置である。本発明の光半導体装置は、白色リフレクターとして本発明の硬化性エポキシ樹脂組成物の硬化物により形成された白色リフレクターを有するため、生産性に優れ、光の取り出し効率が高く、また、経時で光度が低下しにくい等、耐久性にも優れる。図２は、本発明の光半導体装置の一例を示す概略図（断面図）である。図２における１００は白色リフレクター、１０１は金属配線（リードフレーム）、１０３はパッケージ基板、１０４はボンディングワイヤ、１０５は封止材、１０６はダイボンディング材、１０７は光半導体素子（ＬＥＤ素子）を示す。図２に示す光半導体装置においては、光半導体素子１０７から発せられた光が白色リフレクター１００の表面（反射面）で反射するため、高い効率で光半導体素子１０７からの光が取り出される。なお、図２に示すように、本発明の光半導体装置における光半導体素子は、通常、透明な封止材（図２における１０５）によって封止されている。 <Optical semiconductor device>
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. 2, 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, and 107 is an optical semiconductor element (LED element). . In the optical semiconductor device shown in FIG. 2, 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. As shown in FIG. 2, 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).
　図３、４は、本発明の光半導体装置の他の一例を示す図である。図３、４における１０８は、ヒートシンク（ケースヒートシンク）を示し、このようなヒートシンク１０８を有することにより、光半導体装置における放熱効率が向上する。図３は、ヒートシンクの放熱経路が光半導体素子の直下に位置する例であり、図４は、ヒートシンクの放熱経路が光半導体装置の横方向に位置する例である［（ａ）は上面図、（ｂ）は（ａ）におけるＡ－Ａ’断面図を示す］。図４における光半導体装置の側面に突出したヒートシンク１０８は、放熱フィンと称される場合がある。また、図４における１０９は、カソードマークを示す。但し、本発明の光半導体装置は、図２～４に示される態様に限定されない。 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, and 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. Further, reference numeral 109 in FIG. 4 denotes a cathode mark. However, the optical semiconductor device of the present invention is not limited to the embodiment shown in FIGS.
　以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。なお、表１における硬化性エポキシ樹脂組成物の各成分の配合量の単位は、重量部である。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the unit of the compounding quantity of each component of the curable epoxy resin composition in Table 1 is parts by weight.
合成例１
［硬化剤の製造］
　反応容器に、窒素雰囲気下で、１，３，５－トリス（２－ヒドロキシエチル）イソシアヌル酸４３８．５ｇ、メチルアミルケトン４４０．４ｇ、及びメチルヘキサヒドロフタル酸無水物８４０．０ｇを入れた。なお、合成の間は、反応容器にゆっくり窒素パージを継続した。次に、反応容器中の混合物を攪拌しながら１５０℃に加熱した（１２３℃でほとんどの１，３，５－トリス（２－ヒドロキシエチル）イソシアヌル酸は溶解したことを確認した）。１時間の間、約１５０℃に保持した後、混合物を１３４℃まで冷却し、ｎ－ブタノール２４８．４ｇを添加した。このようにして得られた生成物は、固体成分（不揮発分）が６８．１％であり、粘度が２．７８Ｐａ・ｓであった。また、不揮発分１ｇあたりの酸価は２２４．８ｍｇＫＯＨ／ｇであった。
　合成例１で得られた不揮発分は、以下の式（１’）で表される化合物（硬化剤）であった。 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. and 248.4 g of n-butanol was added. The product thus obtained had a solid component (nonvolatile content) of 68.1% and a viscosity of 2.78 Pa · s. Moreover, the acid value per 1 g of non-volatiles was 224.8 mgKOH / g.
The nonvolatile content obtained in Synthesis Example 1 was a compound (curing agent) represented by the following formula (1 ′).
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
合成例２
［加熱混合物の製造］
　表１に示すように、脂環式エポキシ化合物（商品名「セロキサイド２０２１Ｐ」、（株）ダイセル製）２０重量部、及び溶融シリカ（商品名「ＦＢ－９１０」、電気化学工業（株）製）３０重量部を、プラネタリーミキサー（Ｔ．Ｋ．ハイビスミックス２Ｐ－０３、プライミクス（株）製）に投入し、窒素雰囲気下、８０℃に加熱して５０ｒｐｍにて１．５時間攪拌し、加熱混合物を白色の粘調なワックス状物として得た。
　得られた加熱混合物の２５℃におけるずり粘度は、９０Ｐａ・ｓであった。
　ずり粘度は、レオメーターＭＣＲ３０２（アントンパール製）を用いて、２５℃下、パラレルプレートで測定した。 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).
実施例１
　表１に示すように、合成例２で調製した加熱混合物５０重量部、脂環式エポキシ化合物（商品名「ＥＨＰＥ３１５０」、（株）ダイセル製）２０重量部、酸無水物硬化剤（商品名「リカシッドＭＨ－７００」、新日本理化（株）製）４５重量部、硬化促進剤（商品名「ＵＣＡＴ－５００３」、サンアプロ(株)製）１重量部、硬化促進剤（商品名「ＰＸ－４ＥＴ」、日本化学工業(株)製）０．５重量部、酸化防止剤（商品名「ＡＯ－８０」、ＡＤＥＫＡ(株)製）０．３重量部、酸化防止剤（商品名「ＰＥＰ３６」、ＡＤＥＫＡ（株）製）０．３重量部、離型剤（商品名「エレクトールＷＥＰ－５」、日油（株）製）２重量部、白色顔料（酸化チタン；商品名「ＤＣＦ－Ｔ－１７００７」、レジノカラー工業（株）製）１４０重量部、及びシリカフィラー（商品名「ＭＳＲ－２２１２」、龍森（株）製）４５０重量部を、プラネタリーミキサーを用いて９０℃で１０分間混合し、冷却後に粉砕することによって、粉体状の硬化性エポキシ樹脂組成物を得た。得られた硬化性エポキシ樹脂組成物にはべとつきがなく、粉砕工程とタブレット打錠工程で粉砕物のブロッキングがなく、取扱いが容易なものであった。 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 Ricacid 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., Ltd.) 140 parts by weight, and silica gel 450 parts by weight of Lara (trade name “MSR-2212”, manufactured by Tatsumori Co., Ltd.) is mixed for 10 minutes at 90 ° C. using a planetary mixer, and pulverized after cooling to form a powdery curable epoxy. A resin composition was obtained. 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.
実施例２～６
　加熱混合物の配合組成及び硬化性エポキシ樹脂組成物の配合組成を表１に示すように変更したこと以外は、合成例２、実施例１と同様にして硬化性エポキシ樹脂組成物を得た。実施例２～６で得られた加熱混合物の２５℃におけるずり粘度を合成例２と同じ方法で測定した。結果を表１に示す。
　実施例２～６で得られた硬化性エポキシ樹脂組成物にはべとつきがなく、粉砕工程とタブレット打錠工程で粉砕物のブロッキングがなく、取扱いが容易なものであった 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.
合成例３
　混合を室温下（２５℃）で行ったこと以外は、合成例２と同様にして加熱していない混合物を得た。
　得られた混合物の２５℃におけるずり粘度を合成例２と同じ方法で測定したところ、２Ｐａ・ｓであった。
比較例１
　合成例２で調製した加熱混合物の代わりに合成例３で調製した加熱していない混合物を使用したこと以外は、実施例１と同様にして硬化性エポキシ樹脂組成物を得た。比較例１で得られた硬化性エポキシ樹脂組成物にはべとつきがあり、粉砕工程とタブレット打錠工程で粉砕物はブロッキングを起こし、取扱いが困難なものであった。 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.
　＜評価＞
　実施例及び比較例で得られた硬化性エポキシ樹脂組成物及びその硬化物について、下記の評価を実施した。なお、下記の評価において用いた各試験片（硬化性エポキシ樹脂組成物の硬化物）は、トランスファー成型機を使用してトランスファー成型により作製した（硬化条件：１８０℃×１８０秒）。成型後の硬化物は１５０℃で４時間のポストキュアーを行った。 <Evaluation>
The following evaluation was implemented about the curable epoxy resin composition obtained by the Example and the comparative example, and its hardened | cured material. Each test piece (cured product of the curable epoxy resin composition) used in the following evaluation was prepared by transfer molding using a transfer molding machine (curing conditions: 180 ° C. × 180 seconds). The cured product after molding was post-cured at 150 ° C. for 4 hours.
［粉砕及び打錠の可否］
　硬化性エポキシ樹脂組成物についての粉砕性、打錠性（粉砕、打錠の可否）の評価を以下の手順で実施した。粉砕性及び打錠性の両方において○（良好）の評価が得られた場合を○（粉砕及び打錠が可能）、それ以外の場合［粉砕性及び打錠性のいずれか一方又は両方において×（不良）の評価が得られた場合］を×（粉砕及び打錠が不可）と評価した。結果を表１に示す。
・粉砕性：硬化性エポキシ樹脂組成物を粉砕機で粉砕にかけた場合、粉砕機内で樹脂融着の発生が全くない場合を○（粉砕性良好）、樹脂融着が発生した場合を×（粉砕性不良）とした。
・打錠性：硬化性エポキシ樹脂組成物を打錠機で打錠した場合、打錠機（ダイス及びパンチ）への樹脂付着がなく、かつ打錠後のタブレット変形がない場合を○（打錠性良好）、樹脂付着及びタブレット変形のいずれか一方又は両方があった場合を×（打錠性不良）とした。 [Possibility of crushing and tableting]
Evaluation of the pulverizing property and tableting property (whether pulverization and tableting are possible) of the curable epoxy resin composition was performed according to the following procedure. A case where a good (good) evaluation is obtained in both pulverization property and tableting property is ◯ (crushing and tableting is possible), and otherwise [× in either or both of pulverization property and tableting property × When (bad) evaluation was obtained] was evaluated as x (cannot be crushed and tableted). The results are shown in Table 1.
・ 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).
［初期反射率］
　硬化性エポキシ樹脂組成物を用いて長さ３０ｍｍ×幅３０ｍｍ×３ｍｍ厚の試験片（硬化物）を作製し、分光光度計（ＵＶ－３１５０、（株）島津製作所製）を用いて、上記試験片の波長４６０ｎｍの光の反射率（これを「初期反射率」とする）を測定した。結果を表１に示す。
　なお、初期反射率が９０％を超える値であれば、白色リフレクター用材料として優れていると言える。 [Initial reflectance]
A test piece (cured product) 30 mm long × 30 mm wide × 3 mm thick was prepared using the curable epoxy resin composition, and the above test was performed using a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation). The reflectance of light having a wavelength of 460 nm (this is referred to as “initial reflectance”) was measured. The results are shown in Table 1.
If the initial reflectance exceeds 90%, it can be said that the material is excellent as a white reflector material.
［１５０℃、１０００時間加熱後の反射率］
　初期反射率の評価を行った試験片（硬化物；長さ３０ｍｍ×幅３０ｍｍ×３ｍｍ厚）を用いて、当該試験片を１５０℃の乾燥機に入れて１０００時間放置する試験（耐熱試験）を行った後、波長４６０ｎｍの光の反射率を初期反射率と同様に測定した。結果を表１に示す。この耐熱試験後の反射率が高いほど、硬化物が耐熱性に優れることが示唆される。
　なお、１５０℃、１０００時間加熱後の反射率が７０％を超える値であれば、白色リフレクター用材料として耐熱性に優れていると言える。 [Reflectance after heating at 150 ° C. for 1000 hours]
Using a test piece (cured product; length 30 mm × width 30 mm × 3 mm thickness) on which the initial reflectance was evaluated, the test piece was placed in a dryer at 150 ° C. and left for 1000 hours (heat resistance test). After the measurement, the reflectance of light having a wavelength of 460 nm was measured in the same manner as the initial reflectance. The results are shown in Table 1. It is suggested that the higher the reflectivity after the heat test, the more excellent the heat resistance of the cured product.
In addition, if the reflectance after heating at 150 ° C. for 1000 hours exceeds 70%, it can be said that the material is excellent in heat resistance as a white reflector material.
Figure JPOXMLDOC01-appb-T000068
Figure JPOXMLDOC01-appb-T000068
　なお、表１に示す成分について、以下に説明する。
（エポキシ化合物（Ａ））
　セロキサイド２０２１Ｐ：商品名「セロキサイド２０２１Ｐ」（３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート）、（株）ダイセル製
　ＥＨＰＥ３１５０：商品名「ＥＨＰＥ３１５０」（２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物）、（株）ダイセル製
　ＹＸ－８０４０：商品名「ＹＸ－８０４０」（水素化ビスフェノールＡ型ジグリシジル化合物）、三菱化学（株）製
（無機充填剤（Ｂ））
　ＦＢ９１０：商品名「ＦＢ－９１０」（溶融シリカ）、電気化学工業（株）製
（白色顔料（Ｃ））
　ＤＣＦ－Ｔ－１７００７：商品名「ＤＣＦ－Ｔ－１７００７」（酸化チタン）、レジノカラー工業（株）製 In addition, the component shown in Table 1 is demonstrated below.
(Epoxy compound (A))
Celoxide 2021P: Trade name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate), manufactured by Daicel Corporation EHPE3150: Trade name “EHPE3150” (2,2-bis (hydroxymethyl) ) -1-Butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct), manufactured by Daicel Corporation YX-8040: trade name “YX-8040” (hydrogenated bisphenol A type diglycidyl compound), Made by Mitsubishi Chemical Corporation (inorganic filler (B))
FB910: Trade name “FB-910” (fused silica), manufactured by Denki Kagaku Kogyo Co., Ltd. (white pigment (C))
DCF-T-17007: Trade name “DCF-T-17007” (titanium oxide), manufactured by Resino Color Industry Co., Ltd.
（エポキシ化合物（Ａ’））
　ＥＨＰＥ３１５０：商品名「ＥＨＰＥ３１５０」（２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物）、（株）ダイセル製
　ＭＡ－ＤＧＩＣ：商品名「ＭＡ－ＤＧＩＣ」（モノアリルジグリシジルイソシアヌレート）、四国化成工業（株）製
（無機充填剤（Ｂ’））
　ＭＳＲ－２２１２：商品名「ＭＳＲ－２２１２」（高純度真球状シリカ）、（株）龍森製
（白色顔料（Ｃ’））
　ＤＣＦ－Ｔ－１７００７：商品名「ＤＣＦ－Ｔ－１７００７」（酸化チタン）、レジノカラー工業（株）製
（硬化剤（Ｄ））
　リカシッドＭＨ－７００：商品名「リカシッドＭＨ－７００」（４－メチルヘキサヒドロ無水フタル酸／ヘキサヒドロ無水フタル酸）、新日本理化（株）製
　合成例１：合成例１で得られた硬化剤：上記式（１’）で表される化合物
（硬化促進剤）
　ＵＣＡＴ－５００３：商品名「ＵＣＡＴ－５００３」（第四級ホスホニウムブロマイド）、サンアプロ（株）製
　ＤＢＵ・オクチル酸塩：商品名「ＤＢＵ・オクチル酸塩」、サンアプロ（株）製
　ＰＸ－４ＥＴ：商品名「ヒシコーリンＰＸ－４ＥＴ」（テトラ－ｎ－ブチルホスホニウム－ｏ，ｏ－ジエチルホスホロジチオネート）、日本化学工業（株）製
（酸化防止剤）
　ＡＯ８０：商品名「ＡＯ－８０」（フェノール系酸化防止剤）、（株）ＡＤＥＫＡ製
　ＰＥＰ３６：商品名「アデカスタブＰＥＰ３６」（リン系酸化防止剤）、（株）ＡＤＥＫＡ製
（離型剤）
　エレクトールＷＥＰ－５：商品名「エレクトールＷＥＰ－５」、日油（株）製 (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. (inorganic filler (B ′))
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. (curing agent (D))
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. (antioxidant)
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
　本発明の白色リフレクター用硬化性エポキシ樹脂組成物は、粉砕性及び／又は打錠性に優れ、さらにはべとつきが発生せず取扱いが容易であり、なおかつ硬化させることによって耐熱性に優れた硬化物を形成することができる。従って、本発明の白色リフレクター用硬化性エポキシ樹脂組成物は、生産性、及び耐熱性に優れた白色リフレクターを有する、高品質な（例えば、高耐久性の）光半導体素子搭載用基板、及び上記光半導体素子搭載用基板を光半導体装置における基板を有する、高品質な（例えば、高耐久性の）光半導体装置に好適に使用することができる。 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.
　１００：白色リフレクター
　１０１：金属配線（リードフレーム）
　１０２：光半導体素子の搭載領域
　１０３：パッケージ基板
　１０４：ボンディングワイヤ
　１０５：光半導体素子の封止材
　１０６：ダイボンディング材
　１０７：光半導体素子
　１０８：ヒートシンク
　１０９：カソードマーク 100: 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

Claims (29)

  1. 　エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とを含む加熱混合物であって、２５℃におけるずり粘度が、１０～１０００Ｐａ・ｓである加熱混合物を含む、白色リフレクター用硬化性エポキシ樹脂組成物。 A heating 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), wherein the shear viscosity at 25 ° C. is 10 to 1000 Pa · s. A curable epoxy resin composition for a white reflector, comprising a heating mixture.
  2. 　前記加熱混合物に加えて、さらに、硬化剤（Ｄ）を含む、請求項１に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The curable epoxy resin composition for a white reflector according to claim 1, further comprising a curing agent (D) in addition to the heating mixture.
  3. 　前記加熱混合物に加えて、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含む、請求項１又は２に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 3. In addition to the heating mixture, it further comprises at least one selected from the group consisting of an epoxy compound (A ′), an inorganic filler (B ′), and a white pigment (C ′). Curable epoxy resin composition for white reflectors.
  4. 　エポキシ化合物（Ａ）が、脂環式エポキシ化合物（Ａ－１）、複素環式エポキシ化合物（Ａ－２）及び芳香族エポキシ化合物（Ａ－３）からなる群より選択される少なくとも一種を含む、請求項１～３のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The epoxy compound (A) includes 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 claims 1 to 3.
  5. 　エポキシ化合物（Ａ’）が、脂環式エポキシ化合物（Ａ－１）、複素環式エポキシ化合物（Ａ－２）及び芳香族エポキシ化合物（Ａ－３）からなる群より選択される少なくとも一種を含む、請求項３又は４に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The epoxy compound (A ′) includes 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 white reflectors according to claim 3 or 4.
  6. 　無機充填剤（Ｂ）及び無機充填剤（Ｂ’）が、それぞれ独立して、シリカ、ジルコン、珪酸カルシウム、リン酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、酸化鉄、酸化アルミニウム、フォステライト、ステアタイト、スピネル、屈折率１．５未満のクレー、ドロマイト、ヒドロキシアパタイト、ネフェリンサイナイト、クリストバライト、ウォラストナイト、珪藻土、及びこれらの成型体からなる群より選択される少なくとも一種を含む、請求項１～５のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 Inorganic filler (B) and 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 at least one selected from the group consisting of these, The curable epoxy resin composition for a white reflector according to any one of 5.
  7. 　白色顔料（Ｃ）及び白色顔料（Ｃ’）が、それぞれ独立して、ガラス、屈折率１．５以上のクレー、雲母、タルク、カオリナイト、ハロイサイト、ゼオライト、酸性白土、活性白土、ベーマイト、無機酸化物、金属塩、スチレン系樹脂、ベンゾグアナミン系樹脂、尿素－ホルマリン系樹脂、メラミン－ホルマリン系樹脂、アミド系樹脂、及び中空粒子からなる群より選択される少なくとも一種を含む、請求項１～６のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 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, acid clay, activated clay, boehmite, inorganic 7. It contains at least one selected from the group consisting of oxides, metal salts, styrene resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amide resins, and hollow particles. The curable epoxy resin composition for white reflectors as described in any one of these.
  8. 　硬化剤（Ｄ）が、下記式（１）
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、Ｒaは炭素数１～６のアルキレン基を、Ｒbは水素原子又は炭素数１～６のアルキル基又はカルボキシル基をそれぞれ表す。式（１）中、複数存在するＲa、Ｒbは同一であっても異なっていても構わない。）
    で表される化合物を含む、請求項２～７のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。     The curing agent (D) is represented by the following formula (1)
    Figure JPOXMLDOC01-appb-C000001
     (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 curable epoxy resin composition for a white reflector according to any one of claims 2 to 7, comprising a compound represented by the formula:
  9. 　前記加熱混合物が、エポキシ化合物（Ａ）１００重量部に対し、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種を５～５００重量部含有する、請求項１～８のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The heated mixture contains 5 to 500 parts by weight of 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). The curable epoxy resin composition for a white reflector according to any one of 8.
  10. 　脂環式エポキシ化合物（Ａ－１）として、脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基を有する化合物（Ａ－１－１）、脂環に直接結合しているエポキシ基を有する化合物（Ａ－１－２）、及び脂環とグリシジル基とを有する化合物（Ａ－１－３）からなる群より選択される少なくとも一種を含む、請求項４～９のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 As the alicyclic epoxy compound (A-1), a compound (A-1-1) having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, which is directly bonded to the alicyclic ring. The compound (A-1-2) having an epoxy group, and at least one selected from the group consisting of a compound (A-1-3) having an alicyclic ring and a glycidyl group. The curable epoxy resin composition for white reflectors as described in any one of Claims.
  11. 　化合物（Ａ－１－１）が、シクロヘキセンオキシド基を有する化合物である、請求項１０に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The curable epoxy resin composition for a white reflector according to claim 10, wherein the compound (A-1-1) is a compound having a cyclohexene oxide group.
  12. 　化合物（Ａ－１－１）が、下記式（Ｉ－１）
    Figure JPOXMLDOC01-appb-C000002
     で表される化合物である、請求項１０に記載の白色リフレクター用硬化性エポキシ樹脂組成物。     Compound (A-1-1) is represented by the following formula (I-1)
    Figure JPOXMLDOC01-appb-C000002
     The curable epoxy resin composition for a white reflector according to claim 10, which is a compound represented by the formula:
  13. 　化合物（Ａ－１－２）が、下記式（ＩＩ）
    Figure JPOXMLDOC01-appb-C000003
     ［式（ＩＩ）中、Ｒ1はｐ価の有機基を示す。ｐは、１～２０の整数を示す。ｑは、１～５０の整数を示し、式（ＩＩ）におけるｑの和（総和）は、３～１００の整数である。Ｒ2は、下記式（ＩＩａ）～（ＩＩｃ）で表される基のいずれかを示す。但し、式（ＩＩ）におけるＲ2の少なくとも１つは式（ＩＩａ）で表される基である。
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
     ［式（ＩＩｃ）中、Ｒ3は、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアルキルカルボニル基、又は置換若しくは無置換のアリールカルボニル基を示す。］］
    で表される化合物である、請求項１０～１２のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。     Compound (A-1-2) is represented by the following formula (II)
    Figure JPOXMLDOC01-appb-C000003
     [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).
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
     [In Formula (IIc), 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 curable epoxy resin composition for a white reflector according to any one of claims 10 to 12, which is a compound represented by the formula:
  14. 　複素環式エポキシ化合物（Ａ－２）を構成する原子が、炭素原子、水素原子、酸素原子、及び窒素原子である、請求項４～１３のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The curable epoxy for a white reflector according to any one of claims 4 to 13, wherein the atoms constituting the heterocyclic epoxy compound (A-2) are a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom. Resin composition.
  15. 　複素環式エポキシ化合物（Ａ－２）が、下記式（ＩＩＩ）
    Figure JPOXMLDOC01-appb-C000007
     ［式中、Ｒ4、Ｒ5、及びＲ6は、同一又は異なって、下記式（ＩＩＩａ）
    Figure JPOXMLDOC01-appb-C000008
     ［式中、Ｒ7は、水素原子又は炭素数１～８のアルキル基を示す。］
    で表される基、又は下記式（ＩＩＩｂ）
    Figure JPOXMLDOC01-appb-C000009
     ［式中、Ｒ8は、水素原子又は炭素数１～８のアルキル基を示す。］
    で表される基を示す。但し、式（ＩＩＩ）におけるＲ4～Ｒ6の少なくとも１つは式（ＩＩＩａ）で表される基である。］
    で表される化合物である、請求項４～１４のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。     The heterocyclic epoxy compound (A-2) is represented by the following formula (III)
    Figure JPOXMLDOC01-appb-C000007
     [Wherein, R 4 , R 5 and R 6 are the same or different and are represented by the following formula (IIIa)
    Figure JPOXMLDOC01-appb-C000008
     [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)
    Figure JPOXMLDOC01-appb-C000009
     [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 curable epoxy resin composition for a white reflector according to any one of claims 4 to 14, which is a compound represented by the formula:
  16. 　芳香族エポキシ化合物（Ａ－３）が、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、及びビフェニル型エポキシ樹脂からなる群より選ばれる少なくとも１種を含む、請求項４～１５のいずれか一項に記載の硬化物。 The aromatic epoxy compound (A-3) is at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and biphenyl type epoxy resins. The cured product according to any one of claims 4 to 15, further comprising:
  17. 　エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）及び硬化剤（Ｄ）の合計１００重量部に対し、無機充填剤（Ｂ）及び無機充填剤（Ｂ’）の合計量が２００～２０００重量部である、請求項３～１６のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The total amount of the inorganic filler (B) and the inorganic filler (B ′) is 200 to 2000 parts by weight with respect to the total of 100 parts by weight 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 claims 3 to 16, wherein:
  18. 　エポキシ化合物（Ａ）、エポキシ化合物（Ａ’）と硬化剤（Ｄ）の合計１００重量部に対し、白色顔料（Ｃ）及び白色顔料（Ｃ’）の合計量が３～４００重量部である、請求項３～１７のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The total amount of the white pigment (C) and the white pigment (C ′) is 3 to 400 parts by weight with respect to 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 claims 3 to 17.
  19. 　硬化剤（Ｄ）が、２５℃で液状の硬化剤を含む、請求項２～１８のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The curable epoxy resin composition for a white reflector according to any one of claims 2 to 18, wherein the curing agent (D) contains a curing agent that is liquid at 25 ° C.
  20. 　トランスファー成型又はコンプレッション成型用樹脂組成物である、請求項１～１９のいずれか一項に記載の白色リフレクター用硬化性エポキシ樹脂組成物。 The curable epoxy resin composition for a white reflector according to any one of claims 1 to 19, which is a resin composition for transfer molding or compression molding.
  21. 　請求項１～２０のいずれか一項に記載の白色リフレクター成型用硬化性エポキシ樹脂組成物の硬化物。 A cured product of the curable epoxy resin composition for molding a white reflector according to any one of claims 1 to 20.
  22. 　請求項２１に記載の硬化物により形成された白色リフレクターを有する光半導体素子搭載用基板。 An optical semiconductor element mounting substrate having a white reflector formed of the cured product according to claim 21.
  23. 　請求項２２に記載の光半導体素子搭載用基板と、該基板に搭載された光半導体素子とを有する光半導体装置。 An optical semiconductor device comprising the optical semiconductor element mounting substrate according to claim 22 and an optical semiconductor element mounted on the substrate.
  24. 　下記工程（１）および（２）を含む、白色リフレクター用硬化性エポキシ樹脂組成物の製造方法：
    （１）エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる混合物を、加熱・混合して、加熱混合物を得る工程；及び
    （２）前記加熱混合物と、硬化剤（Ｄ）とを含む混合物を混合して、白色リフレクター用硬化性エポキシ樹脂組成物を得る工程。     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 | curing agent (D).
  25. 　前記工程（２）において、前記混合物が、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含む、請求項２４に記載の白色リフレクター用硬化性エポキシ樹脂組成物の製造方法。 25. In the step (2), 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 ′). The manufacturing method of the curable epoxy resin composition for white reflectors as described in any one of.
  26. 　下記工程（１）～（３）を含む、白色リフレクター用硬化性エポキシ樹脂組成物の硬化物の製造方法：
    （１）エポキシ化合物（Ａ）と、無機充填剤（Ｂ）及び白色顔料（Ｃ）からなる群より選択される少なくとも一種とからなる混合物を、加熱・混合して、加熱混合物を得る工程；
    （２）前記加熱混合物と、硬化剤（Ｄ）とを含む混合物を混合して、白色リフレクター用硬化性エポキシ樹脂組成物を得る工程；及び
    （３）前記白色リフレクター用硬化性エポキシ樹脂組成物を加熱して、硬化物を得る工程。     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.
  27. 　前記工程（２）において、前記混合物が、さらに、エポキシ化合物（Ａ’）、無機充填剤（Ｂ’）、及び白色顔料（Ｃ’）からなる群より選択される少なくとも一種を含む、請求項２６に記載の硬化物の製造方法。 27. In the step (2), 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 ′). The manufacturing method of hardened | cured material as described in any one of.
  28. 　硬化物が、光半導体素子搭載用基板用の白色リフレクターである、請求項２６又は２７に記載の製造方法。 The manufacturing method according to claim 26 or 27, wherein the cured product is a white reflector for a substrate for mounting an optical semiconductor element.
  29. 　請求項２８に記載の製造方法を含む、光半導体装置の製造方法。 An optical semiconductor device manufacturing method including the manufacturing method according to claim 28.
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JP2016222865A (en) * 2015-06-03 2016-12-28 株式会社ダイセル Curable epoxy resin composition for white reflector and cured article thereof, substrate for mounting optical semiconductor element and optical semiconductor device
JP2016222866A (en) * 2015-06-03 2016-12-28 株式会社ダイセル Curable epoxy resin composition for white reflector and cured article thereof, substrate for mounting optical semiconductor element and optical semiconductor device

Cited By (3)

* Cited by examiner, † Cited by third party
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CN112175350A (en) * 2019-07-05 2021-01-05 信越化学工业株式会社 Epoxy resin composition for semiconductor encapsulation and semiconductor device
CN112175350B (en) * 2019-07-05 2024-04-30 信越化学工业株式会社 Epoxy resin composition for semiconductor encapsulation and semiconductor device
WO2022148103A1 (en) * 2021-01-07 2022-07-14 天津德高化成光电科技有限责任公司 Prepolymer, encapsulating resin containing same, and use of encapsulating resin

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