WO2018135558A1 - Curable resin composition for optical reflection, cured product thereof, and optical semiconductor device - Google Patents

Curable resin composition for optical reflection, cured product thereof, and optical semiconductor device Download PDF

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Publication number
WO2018135558A1
WO2018135558A1 PCT/JP2018/001303 JP2018001303W WO2018135558A1 WO 2018135558 A1 WO2018135558 A1 WO 2018135558A1 JP 2018001303 W JP2018001303 W JP 2018001303W WO 2018135558 A1 WO2018135558 A1 WO 2018135558A1
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Prior art keywords
resin composition
curable resin
group
weight
light
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PCT/JP2018/001303
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French (fr)
Japanese (ja)
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鈴木弘世
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株式会社ダイセル
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Priority claimed from JP2017009859A external-priority patent/JP6929069B2/en
Priority claimed from JP2017009860A external-priority patent/JP2018119032A/en
Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Priority to KR1020197024268A priority Critical patent/KR20190104063A/en
Publication of WO2018135558A1 publication Critical patent/WO2018135558A1/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
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4253—Rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

Definitions

  • the present invention relates to a light-reflective curable resin composition and a cured product thereof, and an optical semiconductor device having a reflector formed of the cured product and an optical semiconductor element.
  • 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 (reflector) for reflecting light is formed in order to improve the extraction efficiency of light emitted from the optical semiconductor element.
  • the reflector is required to have high light reflectivity.
  • a resin composition in which an inorganic filler or the like is dispersed in a polyamide resin (polyphthalamide resin) having a terephthalic acid unit as an essential constituent unit is known (See Patent Documents 1 to 3).
  • thermosetting resin for light reflection containing a specific ratio of a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0, for example.
  • Resin compositions are known (see Patent Document 4).
  • it contains a thermosetting resin component and one or more filler components, the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the volume of each filler component
  • thermosetting resin composition for light reflection in which a parameter calculated from a ratio is controlled within a specific range
  • a curable resin composition for light reflection in which rubber particles and a white pigment are blended with an alicyclic epoxy compound is known (see Patent Document 6).
  • Reflectors made from the materials described in Patent Documents 1 to 6 described above are yellowed over time due to light and heat emitted from a semiconductor element in an optical semiconductor device using a high-power blue light semiconductor or white light semiconductor as a light source. Etc., and the light reflectivity decreases with time. Furthermore, with the adoption of lead-free solder, the heating temperature in the reflow process (solder reflow process) during the manufacture of the light-emitting device tends to be higher, and the reflector is also deteriorated over time due to the heat applied in such a manufacturing process. There was also a problem that the light reflectivity was deteriorated due to deterioration.
  • the present situation is that a material excellent in heat resistance and light resistance in which light reflectivity is less likely to deteriorate with time even for higher output, shorter wavelength light and high temperature is required.
  • the said reflector is generally manufactured by attaching
  • resin compositions for forming conventional reflectors are suitable for transfer molding, a reflector formed from the resin composition is excellent in heat resistance, but a reflector formed by compression molding has heat resistance. Many were relatively inferior.
  • the amount of the inorganic filler is increased in order to improve the reflectivity and heat resistance of the reflector formed with the materials described in Patent Documents 1 to 6, the viscosity of the composition increases to become a solid state. There is also a problem that it becomes difficult to form by compression molding.
  • the first object of the present invention is to provide a light-reflective material capable of forming a cured product having high light reflectivity, excellent heat resistance and light resistance, and less likely to deteriorate with time by compression molding.
  • the object is to provide a curable resin composition.
  • Another first object of the present invention is a cured product that is excellent in productivity by compression molding, has high light reflectivity, is excellent in heat resistance and light resistance, and the light reflectivity is not easily lowered over time. Is to provide.
  • another object of the present invention is to provide an optical semiconductor device that is less likely to reduce the luminance of light over time and has high reliability.
  • a characteristic that a substrate constituted by a reflector is difficult to elute into an etching solution is also required. This is because when the substrate surface elutes into the etching solution, the light reflectivity decreases (that is, the light extraction efficiency decreases), and it becomes difficult to ensure the reliability of the light emitting device.
  • the second object of the present invention is a compression molding, which has high light reflectivity, excellent heat resistance and light resistance, light reflectivity hardly deteriorates with time, and does not easily dissolve into an etching solution. It is providing the curable resin composition for light reflection which can form a thing. Another object of the present invention is to improve the productivity by compression molding, to have high light reflectivity, to have excellent heat resistance and light resistance, and to prevent light reflectivity from decreasing with time, and to etch. An object of the present invention is to provide a cured product that hardly dissolves in a liquid. Furthermore, another object of the present invention is to provide a highly reliable optical semiconductor device in which the luminance of light is less likely to decrease over time.
  • the above reflector is less susceptible to cracking when subjected to stress due to cutting or temperature change (for example, heating at a very high temperature such as a reflow process or a cooling cycle). Such a characteristic is sometimes referred to as “crack resistance”). This is because if the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it is difficult to ensure the reliability of the light emitting device.
  • the molded product is also required to have a characteristic that warpage does not easily occur. This is because if the reflector molding is warped, the dimensional stability is impaired and the quality of the optical semiconductor device is lowered.
  • the present inventor has found that a specific epoxy compound, rubber particles other than silicone rubber particles, an inorganic filler, a white pigment, a stress relaxation agent, in addition, a curable resin composition that contains a curing agent and a curing accelerator, or a curing catalyst, and is liquid at 25 ° C., can be compression molded even if the amount of inorganic filler or white pigment is increased.
  • the present inventors have found that a cured product having high light reflectivity, excellent heat resistance and light resistance, and light reflectivity hardly deteriorates over time can be formed.
  • a curable resin composition for light reflection which contains a siloxane derivative (J) and an alicyclic polyester resin (K), and is liquid at 25 ° C., or an alicyclic epoxy compound (A), rubber particles (B) , White pigment (C), inorganic filler (D), curing catalyst (G), stress relaxation agent (H), isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, two in the molecule Siloxane derivatives having the above epoxy groups J), and the curable resin composition for light reflection, which contains alicyclic polyester resin (K) and is liquid at 25 ° C., can be compression molded even if the filling amount of the inorganic filler and the white pigment is increased.
  • the present inventors have found that a cured product having high light reflectivity, excellent heat resistance and light resistance, light reflectivity hardly deteriorates with time, and hardly eluted into an etching solution can be formed.
  • the present invention has been completed based on these findings.
  • the first aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H).
  • a curable resin composition for light reflection further comprising a curing agent (E) and a curing accelerator (F) or a curing catalyst (G) and being liquid at 25 ° C. provide.
  • the second aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), a stress relaxation agent (H), Containing an isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, a siloxane derivative (J) having two or more epoxy groups in the molecule, and an alicyclic polyester resin (K);
  • a curable resin composition for light reflection which contains a curing agent (E) and a curing accelerator (F) or a curing catalyst (G) and is liquid at 25 ° C., is provided.
  • the stress relaxation agent (H) is at least one selected from the group consisting of silicone rubber particles (H1) and silicone oil (H2). It may be.
  • the silicone rubber particles (H1) may be cross-linked polydimethylsiloxane having a silicone resin on the surface.
  • the silicone oil (H2) is a polyalkylene ether-modified silicone having a structure represented by the following formula (1) having an epoxy equivalent of 3000 to 15000. It may be a compound.
  • x is an integer from 80 to 140
  • y is an integer from 1 to 5
  • z is an integer from 5 to 20.
  • R 9 is an alkylene group having 2 or 3 carbon atoms.
  • A is a polyalkylene ether group having a structure represented by the following formula (1a). (In the formula, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group.)]
  • the rubber particles (B) may be composed of a polymer containing (meth) acrylic acid ester as an essential monomer component,
  • the rubber particles (B) may have an average particle size of 10 to 500 nm and a maximum particle size of 50 to 1000 nm.
  • the alicyclic epoxy compound (A) may be a compound having a cyclohexene oxide group.
  • the alicyclic epoxy compound (A) is represented by the following formula (I-1): The compound represented by these may be included.
  • the isocyanuric acid derivative (I) is represented by the following formula (III-1): [In Formula (III-1), R 7 and R 8 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] The compound represented by these may be sufficient.
  • the alicyclic polyester resin (K) may be an alicyclic polyester resin having an alicyclic ring in the main chain.
  • the white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate. May be,
  • the inorganic filler (D) may be at least one selected from the group consisting of silica, alumina, silicon nitride, aluminum nitride, and boron nitride.
  • the light reflecting curable resin composition of the first aspect or the second aspect may be a resin composition for transfer molding or compression molding.
  • the light-reflective curable resin composition of the first aspect or the second aspect may be a reflector-forming resin composition.
  • this invention provides the hardened
  • the present invention also provides an optical semiconductor device comprising at least an optical semiconductor element and a reflector made of a cured product of the light reflecting curable resin composition of the first aspect or the second aspect.
  • the curable resin composition for light reflection according to the first aspect of the present invention has the above-described configuration, it has high light reflectivity by compression molding, and has excellent heat resistance and light resistance. A cured product that is difficult to decrease can be formed. Therefore, it is possible to provide a highly reliable optical semiconductor device in which the luminance of light hardly decreases over time.
  • the curable resin composition of the second aspect of the present invention since the curable resin composition of the second aspect of the present invention has the above-described configuration, it has high light reflectivity by compression molding, is excellent in heat resistance and light resistance, and light reflectivity decreases with time. It is possible to form a cured product that is difficult to be dissolved and hardly eluted in the etching solution. Therefore, it is possible to provide a highly reliable optical semiconductor device in which the luminance of light hardly decreases over time.
  • 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 resin composition for light reflection according to the first aspect of the present invention (sometimes simply referred to as “the curable resin composition according to the first aspect of the present invention”) is an alicyclic epoxy compound (A), rubber particles. (B), white pigment (C), inorganic filler (D), and stress relieving agent (H), and further, curing agent (E) and curing accelerator (F), or curing catalyst (G) Is a curable resin composition that is liquid at 25 ° C.
  • the curable resin composition for light reflection according to the first aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), stress relaxation.
  • a curable resin composition which is liquid at 25 ° C. containing an agent (H), a curing agent (E), and a curing accelerator (F) as essential components, or an alicyclic epoxy compound (A), rubber particles ( It is a curable resin composition that is liquid at 25 ° C. and contains B), a white pigment (C), an inorganic filler (D), a stress relaxation agent (H), and a curing catalyst (G) as essential components.
  • the curable resin composition for light reflection of the second aspect of the present invention (sometimes simply referred to as “the curable resin composition of the second aspect of the present invention”) is an alicyclic epoxy compound (A), Rubber particles (B), white pigment (C), inorganic filler (D), stress relaxation agent (H), isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, two or more in the molecule Containing a siloxane derivative (J) having an epoxy group and an alicyclic polyester resin (K), further containing a curing agent (E) and a curing accelerator (F), or a curing catalyst (G), 25 ° C. It is a curable resin composition characterized by being liquid.
  • the isocyanuric acid derivative (I) having one or more oxirane rings in the molecule may be referred to as “isocyanuric acid derivative (I)”.
  • the siloxane derivative (J) having two or more epoxy groups in the molecule may be referred to as “siloxane derivative (J)”.
  • the curable resin composition according to the second aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), and a curing agent (E).
  • a light-reflective material that is liquid at 25 ° C.
  • Curable resin composition containing essential components of a curing accelerator (F), a stress relaxation agent (H), an isocyanuric acid derivative (I), a siloxane derivative (J), and an alicyclic polyester resin (K) Curable resin composition, or alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), curing catalyst (G), stress relaxation agent (H), isocyanuric It is a curable resin composition that is liquid at 25 ° C. and contains an acid derivative (I), a siloxane derivative (J), and an alicyclic polyester resin (K) as essential components.
  • the curable resin composition of the first aspect or the second aspect of the present invention (sometimes simply referred to as “the curable resin composition of the present invention”) is not limited to the above essential components, but may be other as required. May be included.
  • the curable resin composition of the 1st aspect or 2nd aspect of this invention can be used as a thermosetting composition (thermosetting epoxy resin composition) which can be hardened
  • the “curable resin composition for light reflection” refers to a curable resin composition capable of forming a cured product having light reflectivity. Specifically, for example, a curable resin composition capable of forming a cured product having a reflectance of 50% or more (particularly 80% or more) with respect to light having a wavelength of 450 nm is preferable.
  • the curable resin composition of the first aspect or the second aspect of the present invention tends to be suitable for compression molding because it is liquid at 25 ° C., and the cured product (reflector) is excellent in light reflectivity, and There is a tendency to be excellent in heat resistance and light resistance.
  • liquid at 25 ° C.” means that the viscosity measured at 25 ° C. at normal pressure is 1000000 mPa ⁇ s or less (preferably 800000 mPa ⁇ s or less).
  • the above viscosity is measured using, for example, a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ ⁇ R24, temperature: 25 ° C., rotational speed: 0.00. It can be measured at 5 to 10 rpm.
  • the curable resin composition of the first aspect or the second aspect of the present invention that is liquid at 25 ° C. includes, for example, components (for example, an alicyclic epoxy compound (A), a liquid stress relaxation agent (H), and a curing agent. (E), a curing accelerator (F), a curing catalyst (G) and the like) are easily obtained by using a liquid component at 25 ° C.
  • components for example, an alicyclic epoxy compound (A), a liquid stress relaxation agent (H), and a curing agent. (E), a curing accelerator (F), a curing catalyst (G) and the like
  • a solid component may be used as a said component at 25 degreeC, the content is adjusted so that the curable resin composition of this invention may become a liquid state at 25 degreeC.
  • the content of components that are solid at 25 ° C. does not impair the effects of the present invention. It can be easily obtained by adjusting within the range.
  • the alicyclic epoxy compound (alicyclic epoxy resin) (A) which is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention, has an alicyclic (fatty) in the molecule (in one molecule). Group or hydrocarbon ring) and an epoxy group (oxiranyl group), and known or conventional alicyclic epoxy compounds can be used. However, in the curable resin composition of the second aspect of the present invention, those corresponding to the isocyanuric acid derivative (I) and the siloxane derivative (J) are excluded from the alicyclic epoxy compound (A).
  • alicyclic epoxy compound (A) for example, (i) an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring And (ii) a compound having an epoxy group directly bonded to the alicyclic ring with a single bond.
  • the alicyclic epoxy group is preferably a cyclohexene oxide group from the viewpoints of the curability of the curable resin composition and the heat resistance and light resistance (particularly UV resistance) of the cured product (reflector).
  • a compound having two or more cyclohexene oxide groups in the molecule is preferable, and more preferably represented by the following formula (I). It is a compound.
  • 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 (sometimes referred to as an “epoxidized alkenylene group”), a carbonyl group, Examples include an ether bond, an ester bond, a carbonate group, an amide group, and 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 the formula (I).
  • Examples of the compound in which X in the formula (I) is a single bond include (3,4,3 ′, 4′-diepoxy) bicyclohexane and the like.
  • Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And 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 examples include, for example, vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene.
  • linear or branched alkenylene groups having 2 to 8 carbon atoms such as a group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group.
  • 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 in X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxy.
  • 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 (ii) having an epoxy group bonded directly to the alicyclic ring with a single bond 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 carbon atom at the 4th or 5th position 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 methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl.
  • alkylcarbonyl group examples include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, s-butylcarbonyl group, t-butyl.
  • alkylcarbonyl group examples include methylcarbonyl group (acetyl group), ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, iso
  • arylcarbonyl group examples include arylcarbonyl groups having 6 to 20 carbon atoms such as a phenylcarbonyl group (benzoyl group), 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, and the like.
  • Examples of the substituent that the above-described alkyl group, alkylcarbonyl group, and arylcarbonyl group may have include a substituent having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms).
  • Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group and isobutyloxy group (Preferably C 1-6 alkoxy group, more preferably C 1-4 alkoxy group); alkenyloxy group such as allyloxy group (preferably C 2-6 alkenyloxy group, more preferably C 2-4 alkenyloxy group)
  • An acyloxy group such as an acetyloxy group, a propionyloxy group and a (meth) acryloyloxy group (preferably a C 1-12
  • examples of the substituent that the above-described arylcarbonyl group may have include the above-described substituted or unsubstituted alkyl group and the above-described substituted or unsubstituted alkylcarbonyl group.
  • the ratio of the group (epoxy group) represented by 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. There exists a tendency for the heat resistance of a hardened
  • the above ratio can be calculated by, for example, 1 H-NMR spectrum measurement, oxirane oxygen concentration measurement, or the like.
  • the compound represented by the formula (II) is not particularly limited.
  • an organic compound [R 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-vinylcyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) is subjected to ring-opening polymerization (cationic polymerization), and then Manufactured by epoxidation with an oxidizing agent.
  • Examples of the organic compound [R 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 alcohol such as bisphenol S; polyviny
  • the 1,2-epoxy-4-vinylcyclohexane can be produced by a known or commonly used method, and is not particularly limited.
  • 4-vinylcyclohexene obtained by dimerization reaction of butadiene is replaced with an oxidizing agent such as peracetic acid. Obtained by partial epoxidation using.
  • 1,2-epoxy-4-vinylcyclohexane a commercially available product can be used.
  • the oxidant may be a known or conventional oxidant such as hydrogen peroxide or organic peracid, and is not particularly limited.
  • the organic peracid include performic acid, peracetic acid, peroxygen. Examples include benzoic acid and trifluoroperacetic acid. Among them, peracetic acid is preferable because it is industrially available at low cost and has high stability.
  • the standard polystyrene equivalent weight average molecular weight of the compound represented by the formula (II) is not particularly limited, but is preferably 300 to 100,000, more preferably 1,000 to 10,000.
  • the weight average molecular weight is 300 or more, the mechanical strength, heat resistance, and light resistance of the cured product tend to be improved.
  • the weight average molecular weight is 100,000 or less, the viscosity does not become too high and the fluidity during molding tends to be maintained low.
  • the weight average molecular weight is measured by a gel permeation chromatography (GPC) method.
  • the equivalent (epoxy equivalent) of the epoxy group of the compound represented by the formula (II) is not particularly limited, but is preferably 50 to 1000, more preferably 100 to 500.
  • the epoxy equivalent is 50 or more, the cured product tends not to be brittle.
  • the epoxy equivalent is 1000 or less, the mechanical strength of the cured product tends to be improved.
  • the epoxy equivalent is measured according to JIS K7236: 2001.
  • the alicyclic epoxy compound (A) can be used singly or in combination of two or more.
  • the alicyclic epoxy compound (A) can also be produced by a known or commonly used method.
  • trade names “Celoxide 2021P”, “Celoxide 2081”, “EHPE3150” (above, manufactured by Daicel Corporation) ) Etc. can also be used.
  • the alicyclic epoxy compound (A) preferably exhibits a liquid state at normal temperature (25 ° C.) from the viewpoint of workability during preparation and casting. Moreover, even if it is an alicyclic epoxy compound (A) which is solid at normal temperature (25 degreeC), as long as it shows liquid state after mix
  • the curable resin composition of the first aspect or the second aspect of the present invention is (i) an alicyclic epoxy from the viewpoint of further improving the light reflectivity, heat resistance, and light resistance of the cured product (reflector). It is preferable to include at least a compound having a group, and it is more preferable to include (ii) a compound having an epoxy group bonded directly to the alicyclic ring with a single bond.
  • the content (blending amount) of the alicyclic epoxy compound (A) in the curable resin composition of the first aspect of the present invention is not particularly limited, but is 1 with respect to the curable resin composition (100% by weight). It is preferably 5 to 60% by weight, more preferably 2 to 50% by weight, still more preferably 5 to 40% by weight.
  • the content of the alicyclic epoxy compound (A) is 1.5% by weight or more, the heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) of the cured product (reflector) are further improved. There is a tendency to improve.
  • the linear expansion coefficient of the cured product (reflector) is reduced, and defects such as warping of the lead frame in the substrate for mounting an optical semiconductor element It tends to be suppressed.
  • the content (blending amount) of the alicyclic epoxy compound (A) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0 with respect to the curable resin composition (100 wt%). It is preferably 1 to 60% by weight, more preferably 0.3 to 50% by weight, and still more preferably 0.5 to 40% by weight.
  • the content of the alicyclic epoxy compound (A) is 0.1% by weight or more, the heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) of the cured product (reflector) are further improved. There is a tendency to improve.
  • the content of the alicyclic epoxy compound (A) is set to 60% by weight or less, the heat resistance and light resistance of the cured product (reflector) are further improved, the linear expansion coefficient is reduced, and the optical semiconductor element is mounted. There is a tendency that the occurrence of defects such as lead frame warpage in the circuit board is suppressed.
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition of the first aspect of the present invention is not particularly limited, but is 50% by weight or more ( For example, it is preferably 50 to 100% by weight), more preferably 60% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the ratio 50 weight% or more there exists a tendency which the heat resistance and light resistance of hardened
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition of the second aspect of the present invention is not particularly limited. % By weight is preferred, more preferably 5 to 80% by weight, and still more preferably 10 to 70% by weight. By making it in the said range, there exists a tendency for the heat resistance and light resistance of hardened
  • Examples of the compound having an epoxy group contained in the curable resin composition of the second aspect of the present invention include an alicyclic epoxy compound (A), an isocyanuric acid derivative (I), and a siloxane derivative (J),
  • Examples include a stress relaxation agent (H) having an epoxy group (such as an epoxy-modified silicone oil).
  • each component for example, alicyclic epoxy compound (A), rubber particle (B), white pigment (C) contained in the curable resin composition of the first aspect or the second aspect of the present invention.
  • the content of the formula polyester resin (K) and the like can be appropriately selected from the range described so that the total is 100% by weight or less.
  • the rubber particles (B) other than the silicone rubber particles that are essential components of the curable resin composition of the first aspect or the second aspect of the present invention (hereinafter may be simply referred to as “rubber particles (B)”), Particles other than silicone rubber particles having rubber elasticity.
  • the curable resin composition of the first aspect of the present invention comprises a rubber particle (B) containing an alicyclic epoxy compound (A), a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H). When used in combination, the cured product formed by compression molding tends to be excellent in light reflectivity, heat resistance, light resistance, and crack resistance.
  • the curable resin composition of the second aspect of the present invention comprises a rubber particle (B) containing an alicyclic epoxy compound (A), a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H). , Isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K) in combination for use in the light reflectivity, heat resistance, light resistance of the cured product formed by compression molding, and There is a tendency to be excellent in crack resistance.
  • any known or commonly used rubber particles can be used without particular limitation as long as they are other than silicone rubber particles.
  • particulate NBR acrylonitrile-butadiene rubber
  • reactive terminal carboxy examples thereof include rubber particles such as group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber).
  • CTBN group NBR
  • SBR styrene-butadiene rubber
  • the rubber particles (B) have a core part having rubber elasticity and at least one shell covering the core part from the viewpoint of good dispersibility and an effect of improving toughness (crack resistance improvement). Rubber particles having a multilayer structure (core-shell structure) composed of layers (hereinafter sometimes referred to as “core-shell type rubber particles”) are preferred.
  • the rubber particles (B) are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and an alicyclic ring on the surface. Rubber particles having a hydroxy group and / or a carboxy group (either one or both of a hydroxy group and a carboxy group) as a functional group capable of reacting with a compound having an epoxy group such as the formula epoxy compound (A) are preferred. That is, the rubber particles (B) are particularly preferably core-shell type rubber particles composed of a polymer (acrylic polymer) containing (meth) acrylic acid ester as an essential monomer component.
  • the rubber particles (B) can be used singly or in combination of two or more.
  • the polymer constituting the core portion having rubber elasticity is not particularly limited as long as it is other than a silicone compound, but methyl (meth) acrylate, (meth) acrylic It is preferable that it is a polymer which contains (meth) acrylic acid ester, such as ethyl acid and butyl (meth) acrylate, as an essential monomer component.
  • the polymer constituting the core part having rubber elasticity includes, for example, aromatic vinyl such as styrene and ⁇ -methylstyrene; nitrile such as acrylonitrile and methacrylonitrile; conjugated diene such as butadiene and isoprene; ethylene, propylene, An ⁇ -olefin such as isobutene may be included as a monomer component.
  • the polymer constituting the core portion having rubber elasticity is combined with one or more selected from the group consisting of aromatic vinyl, nitrile, and conjugated diene together with (meth) acrylic acid ester as a monomer component. It is preferable to include. That is, as the polymer constituting the core portion, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers, (meth) acrylic acid ester / aromatic And terpolymers such as group vinyl / conjugated dienes.
  • the polymer constituting the core part includes, as other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc.
  • a reactive crosslinking monomer having two or more reactive functional groups in the molecule may be contained.
  • the core part is composed of (meth) acrylic acid ester / aromatic vinyl binary copolymer (particularly butyl acrylate / styrene) or (meth) acrylic acid ester / aromatic vinyl / other monomers.
  • a core part composed of an original copolymer (particularly butyl acrylate / styrene / divinylbenzene) is preferable in that the refractive index of the core-shell type rubber particles can be easily adjusted.
  • the glass transition temperature of the polymer constituting the core portion is not particularly limited, but is preferably ⁇ 100 to 10 ° C., more preferably ⁇ 80 to ⁇ 10 ° C., and further preferably ⁇ 60 to ⁇ 20 ° C. There exists a tendency for the crack resistance of hardened
  • the glass transition temperature of the polymer which comprises the said core part means the calculated value calculated by the formula of the following Fox (refer Bull. Am. Phys. Soc., 1 (3) 123 (1956)).
  • Tg glass transition temperature (unit: K) of the polymer constituting the core portion indicates, W i is the weight fraction of the monomer i for the monomer total amount constituting the polymer constituting the core portion Indicates the rate. Further, Tg i is the glass transition temperature of the homopolymer of monomer i (unit: K) shows a.
  • the glass transition temperature of the homopolymer values described in various documents can be adopted, for example, values described in “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.) can be adopted. In addition, about the thing which is not described in literature, the value of the glass transition temperature measured by DSC method of the homopolymer obtained by superposing
  • the core part can be produced by a commonly used method.
  • the core part can be produced by a method of polymerizing the monomer by an emulsion polymerization method.
  • the whole amount of the monomer may be charged all at once and polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently for polymerization.
  • a polymerization method using seed particles may be used.
  • the rubber particle which does not have a core shell structure as a rubber particle (B)
  • the rubber particle etc. which consist only of the said core part can be used, for example.
  • the polymer constituting the shell layer of the core-shell type rubber particles is preferably a polymer different from the polymer constituting the core portion (a polymer having a different monomer composition).
  • the shell layer preferably has a hydroxy group and / or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A).
  • the polymer constituting the shell layer is preferably a polymer containing (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate as an essential monomer component.
  • (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate
  • (meth) acrylic acid esters other than butyl acrylate for example, ( (Meth) methyl acrylate, ethyl (meth) acrylate, butyl methacrylate, etc.
  • the monomer component that may be contained in addition to the (meth) acrylic acid ester examples include aromatic vinyl such as styrene and ⁇ -methylstyrene; nitrile such as acrylonitrile and methacrylonitrile.
  • the monomer component constituting the shell layer includes the (meth) acrylic acid ester alone or in combination of two or more, particularly at least aromatic vinyl. It is preferable in that the refractive index of the core-shell type rubber particles can be easily adjusted.
  • the polymer constituting the shell layer forms a hydroxy group and / or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component.
  • Hydroxy group-containing monomers eg, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate
  • carboxy group-containing monomers eg, ⁇ , ⁇ -unsaturated acids such as (meth) acrylic acid; ⁇ , ⁇ -unsaturated acid anhydrides such as maleic anhydride
  • the polymer constituting the shell layer preferably contains, as a monomer component, one or two or more selected from the above monomers in combination with (meth) acrylic acid ester. That is, the shell layer is composed of, for example, a ternary copolymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / ⁇ , ⁇ -unsaturated acid.
  • a shell layer composed of a polymer or the like is preferable.
  • the polymer constituting the shell layer includes, as the other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, trimethyl, as well as the above-described monomer.
  • a reactive crosslinking monomer having two or more reactive functional groups may be contained in the molecule such as allyl cyanurate, diallyl phthalate, butylene glycol diacrylate.
  • the glass transition temperature of the polymer constituting the shell layer is not particularly limited, but is preferably 20 to 200 ° C, more preferably 40 to 180 ° C, and still more preferably 60 to 160 ° C.
  • the glass transition temperature of the polymer is not particularly limited, but is preferably 20 to 200 ° C, more preferably 40 to 180 ° C, and still more preferably 60 to 160 ° C.
  • the glass transition temperature of the polymer is 20 ° C. or higher, the heat resistance and light resistance of the cured product tend to be further improved.
  • the glass transition temperature of the polymer is 200 ° C. or lower, the dispersibility of the rubber particles (B) and the crack resistance of the cured product tend to be improved.
  • the glass transition temperature of the polymer which comprises the said shell layer means the calculated value computed by the said Formula of Fox, For example, it can measure similarly to the glass transition temperature of the polymer which comprises the above-mentioned core.
  • Core-shell type rubber particles are obtained by covering the core part with a shell layer.
  • the method for coating the core part with the shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a polymer constituting the shell layer;
  • Examples thereof include a graft polymerization method in which the core portion having rubber elasticity is a trunk component and each component constituting the shell layer is a branch component.
  • the average particle size of the rubber particles (B) is not particularly limited, but is preferably 10 to 500 nm, more preferably 20 to 400 nm.
  • the maximum particle size of the rubber particles (B) is not particularly limited, but is preferably 50 to 1000 nm, and more preferably 100 to 800 nm.
  • the average particle size is 500 nm or less (or the maximum particle size is 1000 nm or less)
  • the dispersibility of the rubber particles (B) in the cured product is improved and the crack resistance tends to be improved.
  • the average particle size is 10 nm or more (or the maximum particle size is 50 nm or more)
  • the crack resistance of the cured product tends to be improved.
  • the refractive index of the rubber particles (B) is not particularly limited, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.58. Further, the curing obtained by curing the refractive index of the rubber particles (B) and the curable resin composition containing the rubber particles (B) (the curable resin composition of the first aspect or the second aspect of the present invention).
  • the difference from the refractive index of the object is preferably within ⁇ 0.03. By making the difference in refractive index within ⁇ 0.03, excellent light reflectivity of the cured product is ensured, and the light intensity of the optical semiconductor device tends to be kept high.
  • the refractive index of the rubber particles (B) is, for example, 1 g of rubber particles (B) is cast into a mold and compression molded at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. ⁇ A 6 mm wide test piece was cut out, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, Atago Co., Ltd.) was used in a state where the prism and the test piece were in close contact using monobromonaphthalene as an intermediate solution. And the refractive index at 20 ° C. and sodium D line can be measured.
  • the refractive index of the cured product of the curable resin composition of the first embodiment or the second embodiment of the present invention is, for example, 20 mm long by 6 mm wide from a cured product obtained by the heat curing method described in the section of the cured product below.
  • ⁇ A 1 mm thick test piece was cut out, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, Co., Ltd.) was used in a state where the prism and the test piece were in close contact using monobromonaphthalene as an intermediate solution. It can be determined by measuring the refractive index at 20 ° C. and sodium D line.
  • the rubber particle (B) content (blending amount) in the curable resin composition of the first aspect of the present invention is not particularly limited, but is 0.05 to It is preferably 20% by weight, more preferably 0.1 to 15% by weight, still more preferably 0.2 to 10% by weight.
  • the content of the rubber particles (B) is 0.05% by weight or more, the light reflectivity, heat resistance, and light resistance of the cured product tend to be more excellent.
  • cured material tend to improve.
  • the content of the rubber particles (B) is 20% by weight or less, the heat resistance and light resistance of the cured product tend to be further improved.
  • the rubber particle (B) content (blending amount) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0.01 to It is preferably 20% by weight, more preferably 0.05 to 15% by weight, still more preferably 0.1 to 10% by weight.
  • the content (blending amount) of the rubber particles (B) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is the compound having an epoxy group contained in the curable resin composition.
  • the amount is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to the total amount of 100 parts by weight.
  • the white pigment (C) which is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention, mainly imparts high light reflectivity to the cured product (reflector). Has the function of reducing the coefficient of linear expansion.
  • white pigment (C) known or commonly used white pigments can be used, and are not particularly limited.
  • Organic white pigments plastic pigments, etc.
  • resin pigments such as resin-based resins; hollow particles having a hollow structure (balloon structure), and the like.
  • 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.
  • 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.
  • those corresponding to the inorganic filler (D) are those having a refractive index of 1.5 or more as the white pigment (C) and having a refractive index of 1.5. The smaller one is the inorganic filler (D).
  • 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, there are cases where compatibility and dispersibility with other components in the curable resin composition can 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) from the viewpoint of availability, heat resistance, light resistance, and high reflectance of the cured product (reflector) and light reflectance increase rate with respect to the addition amount, inorganic oxides, inorganic Hollow particles are preferred, more preferably aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, barium sulfate, inorganic hollow particles, and more preferably titanium oxide, zirconium oxide, zinc oxide, barium sulfate.
  • the white pigment (C) is preferably titanium oxide because it has a higher refractive index.
  • 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 (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, and still more preferably 0. .1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, most preferably 0.1 to 5 ⁇ m.
  • the center particle diameter of the hollow particles 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) the trade names “R-62N”, “CR-60”, “DCF-T-17007” are particularly used from the viewpoint of improving the light reflectivity and yellowing resistance of the cured product (reflector). "DCF-T-17008”, “DCF-T-17050”, and “FTR-700” are preferable.
  • the content (blending amount) of the white pigment (C) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but with respect to the curable resin composition (100 wt%), It is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 5 to 35% by weight.
  • cured material (reflector) to improve more by making content of a white pigment (C) 0.1 weight% or more.
  • heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) tend to be further improved.
  • the content of the white pigment (C) is 50% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
  • the content (blending amount) of the white pigment (C) in the curable resin composition of the first aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100 parts by weight.
  • the amount is preferably 3 to 400 parts by weight, more preferably 10 to 350 parts by weight, still more preferably 30 to 300 parts by weight.
  • heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) tend to be further improved.
  • the content of the white pigment (C) is 400 parts by weight or less, the moldability is improved and there is a tendency to be more suitable for mass production.
  • the content (blending amount) of the white pigment (C) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of the compounds having an epoxy group contained in the curable resin composition is 100 parts by weight.
  • the amount is preferably 10 to 600 parts by weight, more preferably 30 to 500 parts by weight, still more preferably 30 to 400 parts by weight.
  • heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) tend to be further improved.
  • the content of the white pigment (C) is 600 parts by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
  • the ratio of titanium oxide to the total amount (100% by weight) of the white pigment (C) and the inorganic filler (D) is: Although not particularly limited, it is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, from the viewpoint of the balance between heat resistance (yellowing resistance) and light reflectivity of the cured product (reflector).
  • heat resistance particularly yellowing resistance
  • light resistance particularly ultraviolet resistance
  • the proportion of titanium oxide is adjusted and tends to be more suitable for mass production.
  • the curable resin composition of the first aspect or the second aspect of the present invention contains an inorganic filler (D) as an essential component separately from the white pigment (C).
  • the inorganic filler (D) mainly imparts excellent heat resistance and light resistance (particularly excellent heat resistance) to the formed cured product when the curable resin composition is formed by compression molding. Moreover, it has the function to reduce the linear expansion coefficient of hardened
  • the inorganic filler (D) a known or conventional inorganic filler can be used, and is not particularly limited.
  • Examples of the inorganic filler (D) include those obtained by subjecting the above-described inorganic filler to a known or conventional surface treatment. Among them, examples of the inorganic filler (D) include silica, alumina, silicon nitride, aluminum nitride, and boron nitride from the viewpoint of heat resistance (particularly yellowing resistance), light resistance, and fluidity of the cured product (reflector). Silica (silica filler) is more preferable.
  • 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 silica is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, scale shape, and the like. Among these, spherical silica is preferable from the viewpoint of dispersibility, and spherical silica (for example, spherical silica having an aspect ratio of 1.2 or less) is particularly preferable.
  • the center particle diameter of silica 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 (reflector).
  • 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.
  • an inorganic filler (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the inorganic filler (D) can also be produced by a known or conventional production method. For example, trade names “FB-910”, “FB-940”, “FB-950”, “FB-105” can be used.
  • the content (blending amount) of the inorganic filler (D) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is relative to the curable resin composition (100% by weight). It is preferably 10 to 90% by weight, more preferably 13 to 75% by weight, still more preferably 15 to 70% by weight, and still more preferably 20 to 70% by weight.
  • the content of the inorganic filler (D) is 10% by weight or more
  • the curable resin composition is formed by compression molding, the formed cured product has heat resistance and light resistance (particularly excellent heat resistance). Tend to be more improved.
  • the linear expansion coefficient of the cured product (reflector) tends to be low, and problems such as lead frame warpage in an optical semiconductor element mounting substrate using the reflector tend not to occur.
  • the content of the inorganic filler (D) is 90% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
  • the content (blending amount) of the inorganic filler (D) in the curable resin composition of the first aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100 wt.
  • the amount is preferably 10 to 1500 parts by weight, more preferably 50 to 1200 parts by weight, and still more preferably 70 to 1000 parts by weight.
  • the content of the inorganic filler (D) is 10 parts by weight or more
  • the curable resin composition is formed by compression molding, the formed cured product has heat resistance and light resistance (particularly excellent heat resistance). Tend to be more improved.
  • the linear expansion coefficient of the cured product (reflector) tends to be low, and problems such as lead frame warpage in an optical semiconductor element mounting substrate using the reflector tend not to occur.
  • the content of the inorganic filler (D) is set to 1500 parts by weight or less, so there is a problem such as unfilling at the time of molding (particularly transfer molding). There is a tendency to be suppressed.
  • the content (blending amount) of the inorganic filler (D) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100% by weight.
  • the amount is preferably 10 to 1500 parts by weight, more preferably 50 to 1200 parts by weight, and still more preferably 100 to 1000 parts by weight.
  • the content of the inorganic filler (D) is 10 parts by weight or more, when the curable resin composition is formed by compression molding, the formed cured product has heat resistance and light resistance (particularly excellent heat resistance). Tend to be more improved.
  • the linear expansion coefficient of the cured product (reflector) tends to be low, and problems such as lead frame warpage in an optical semiconductor element mounting substrate using the reflector tend not to occur.
  • the content of the inorganic filler (D) is 1500 parts by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
  • the maximum particle diameter of the white pigment (C) and the inorganic filler (D) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is preferably 200 ⁇ m or less, more preferably 185 ⁇ m or less. More preferably, it is 175 ⁇ m or less, and particularly preferably 150 ⁇ m or less.
  • the maximum particle size is 200 ⁇ m or less, the heat resistance of the formed cured product formed by compression molding of the curable resin composition than when using a white pigment or an inorganic filler having a maximum particle size exceeding 200 ⁇ m. , Light resistance and crack resistance (particularly excellent heat resistance) tend to be further improved.
  • the white pigment (C) and the inorganic filler (D) having a small maximum particle size, it is possible to increase the content thereof, and the light reflectivity, heat resistance, and light resistance of the cured product are further improved. There is a tendency to improve further.
  • the lower limit of the maximum particle size is, for example, 0.01 ⁇ m or more.
  • the maximum particle size is the total maximum particle size of the white pigment (C) and the inorganic filler (D) contained in the curable resin composition of the present invention.
  • the maximum particle size means the maximum particle size in the particle size distribution measured by the laser diffraction / scattering method.
  • the curing agent (E) in the curable resin composition of the first aspect or the second aspect of the present invention is an alicyclic epoxy compound (A), an epoxy-modified silicone oil described later as a stress relaxation agent (H), In the case of the 2nd aspect of this invention, it is a compound which has a function which hardens a curable resin composition by reacting with the compound which has epoxy groups, such as isocyanuric acid derivative (I) and a siloxane derivative (J).
  • the curing agent (E) a known or conventional epoxy resin curing agent can be used, and is not particularly limited.
  • acid anhydrides (acid anhydride curing agents), amines (amine curing) Agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides and the like.
  • acid anhydrides as the curing agent (E), known or conventional acid anhydride curing agents can be used, and are not particularly limited.
  • methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.
  • methylhexahydrophthalic anhydride such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride
  • dodecenyl succinic anhydride methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic acid
  • the curable resin of the first aspect or the second aspect of the present invention is obtained by dissolving in a liquid acid anhydride at 25 ° C.
  • anhydride curing agent from the viewpoint of heat resistance and light reflectivity of the cured product, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those having a substituent such as an alkyl group bonded to the ring) are preferable. .
  • amines (amine-based curing agent) as the curing agent (E) 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.
  • polyamide resin as the curing agent (E) examples include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.
  • imidazole curing agent as the curing agent (E), a known or commonly used imidazole curing agent can be used, and is not particularly limited, and examples thereof include 2-methylimidazole and 2-ethyl-4-methylimidazole.
  • Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (E) include liquid polymercaptan and polysulfide resin.
  • polycarboxylic acids examples include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and the like.
  • the curing agent (E) acid anhydrides (acid anhydride curing agents) are preferable from the viewpoints of heat resistance, light resistance, and light reflectivity of the cured product.
  • curing agent (E) can also be used individually by 1 type in the curable resin composition of the 1st aspect or 2nd aspect of this invention, and can also be used in combination of 2 or more types.
  • the curing agent can be produced by a known or conventional method.
  • trade names “Licacid MH-700”, “Licacid MH-700F”, “Licacid MH-700G”, “Licacid TH”, “Licacid CI” "HH”, “Licacid HNA-100” (manufactured by Shin Nippon Rika Co., Ltd.); trade name “HN-5500” (manufactured by Hitachi Chemical Co., Ltd.); trade names “H-TMAn-S”, "H Commercially available products such as “TMAn” (Mitsubishi Gas Chemical Co., Ltd.); trade name “YH1120” (Mitsubishi Chemical Co., Ltd.) can also be used.
  • the curable resin composition of the 1st aspect or 2nd aspect of this invention contains a hardening
  • the content is preferably 1 to 40% by weight, more preferably 3 to 35% by weight, and still more preferably 5 to 30% by weight with respect to the product (100% by weight).
  • the content of the curing agent (E) By setting the content of the curing agent (E) to 1% by weight or more, the curing becomes more sufficient, and the crack resistance of the cured product tends to be improved.
  • the content of the curing agent (E) to 40% by weight or less, there is a tendency that a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained.
  • a curable resin composition contains a hardening
  • curing agent (E) is although it does not specifically limit,
  • a curable resin composition The amount is preferably 40 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total amount of the compound having an epoxy group contained in the product. More specifically, when an acid anhydride is used as the curing agent (E), the epoxy group in the compound having all the epoxy groups contained in the curable resin composition of the first aspect or the second aspect of the present invention. It is preferable to use at a ratio of 0.5 to 1.5 equivalents per equivalent.
  • the curing agent (E) By setting the content of the curing agent (E) to 40 parts by weight or more, the curing becomes more sufficient and the crack resistance of the cured product tends to be improved. On the other hand, by setting the content of the curing agent (E) to 200 parts by weight or less, there is a tendency that a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained.
  • the curable resin composition of the first aspect or the second aspect of the present invention may contain a curing accelerator (F).
  • the curing accelerator (F) is a compound having an epoxy group (for example, an alicyclic epoxy compound (A) or an isocyanuric acid derivative (I) included in the curable resin composition of the first aspect or the second aspect of the present invention.
  • a siloxane derivative (J) and a compound having a function of accelerating the reaction rate when the epoxy-modified silicone oil described later as a stress relaxation agent (H) reacts with a curing agent such as a curing agent (E). is there.
  • the curing accelerator (F) a known or conventional curing accelerator can be used.
  • 1,8-diazabicyclo [5.4.0] undecene-7 DBU or a salt thereof (for example, phenol) Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, Octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc.
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • DBN 1,5-diazabicyclo [4.3.0] nonene-5
  • DBN 1,5-diazabicyclo [4.3.0] nonene-5
  • imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole
  • Ether 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.
  • the curing accelerator (F) can be used alone or in combination of two or more.
  • the curing accelerator (F) 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”, “12XD” developed product) (San Apro Co., Ltd.); trade names “TPP-K”, “TPP-MK” (Hokuko Chemical Co., Ltd.); Commercial products such as the name “PX-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can also be used.
  • the content (blending amount) of the curing accelerator (F) is not particularly limited, but is curable.
  • the content is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight, based on the resin composition (100% by weight).
  • the curing reaction tends to proceed more efficiently.
  • the content of the curing accelerator (F) is 5% by weight or less, the storability of the curable resin composition is further improved, or a cured product (reflector) that is more suppressed in coloring and excellent in hue. There is a tendency to obtain easily.
  • the content (blending amount) of the curing accelerator (F) is not particularly limited, but is curable.
  • the amount is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 12 parts by weight, and still more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the total amount of the compound having an epoxy group contained in the resin composition. Parts, particularly preferably 0.25 to 8 parts by weight.
  • the content of the curing accelerator is 15 parts by weight or less, the storability of the curable resin composition is further improved, or a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained.
  • the curing catalyst (G) in the curable resin composition of the first aspect or the second aspect of the present invention includes an alicyclic epoxy compound (A), an epoxy-modified silicone oil described later as a stress relaxation agent (H), and
  • a curable resin composition is obtained by initiating and / or promoting a curing reaction (polymerization reaction) of a cationically polymerizable compound such as an isocyanuric acid derivative (I) or a siloxane derivative (J). Is a compound having a function of curing.
  • the curing catalyst (G) is not particularly limited.
  • a cationic polymerization initiator photo cationic polymerization initiator, thermal cationic polymerization
  • a cationic polymerization initiator that initiates polymerization by generating cationic species by light irradiation, heat treatment, or the like.
  • Initiators, etc. Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.
  • Examples of the photocationic polymerization initiator as the curing catalyst (G) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically.
  • triarylsulfonium hexafluorophosphate eg, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate
  • sulfonium salts such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salts)
  • diaryl iodonium hexafluorophosphate Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodine Iodonium salts such as nium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridinium salts such as N-he
  • cationic photopolymerization initiator examples include, for example, trade names “UVACURE 1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States).
  • Commercial products such as Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.
  • thermal cationic polymerization initiator as the curing catalyst (G) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”.
  • thermal cationic polymerization initiator a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone
  • a compound of a chelate compound with a phenol and a phenol such as bisphenol S.
  • a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
  • a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
  • Bronsted acid salt as the curing catalyst (G), known or commonly used Bronsted acid salts can be used, and are not particularly limited.
  • imidazole as the curing catalyst (G), known or conventional imidazoles can be used, and are not particularly limited.
  • the curing catalyst (G) can be used alone or in combination of two or more.
  • a commercial item can also be used as a curing catalyst (G).
  • the content (blending amount) of the curing catalyst (G) is not particularly limited, but the curable resin composition
  • the content is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight, based on the product (100% by weight).
  • the content (blending amount) of the curing catalyst (G) in the curable resin composition of the present invention is: Although not particularly limited, the amount is preferably 0.0001 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 100 parts by weight based on the total amount of the compound having an epoxy group contained in the curable resin composition. Is 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight.
  • the stress relaxation agent (H) that is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention is a compound that can relieve internal stress in a cured product.
  • the stress relaxation agent (H) is an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler ( D)
  • white pigment (C) and inorganic are obtained by using in combination with isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K).
  • the filling amount of the filler (D) is increased, compression molding is possible, and the cured product formed by compression molding tends to be excellent in light reflectivity, heat resistance, and light resistance.
  • the stress relaxation agent (H) can relieve the internal stress of the cured product to reduce warpage of the formed product due to compression molding.
  • the stress relaxation agent (H) is not particularly limited, and examples thereof include silicone rubber particles (H1), silicone oil (H2), liquid rubber component (H3), and thermoplastic resin (H4).
  • the silicone rubber particles (H1) are not particularly limited, and examples thereof include those composed of polysiloxanes such as polymethylsiloxane and polymethylphenylsiloxane.
  • the polysiloxane constituting the silicone rubber particles (H1) is preferably crosslinked.
  • the crosslinked polysiloxane is not particularly limited. For example, it is crosslinked by a condensation reaction such as a silanol group, a radical reaction between a mercaptosilyl group and a vinylsilyl group, or an addition reaction between a vinylsilyl group and a hydrosilyl group (SiH group).
  • a condensation reaction such as a silanol group, a radical reaction between a mercaptosilyl group and a vinylsilyl group, or an addition reaction between a vinylsilyl group and a hydrosilyl group (SiH group).
  • the silicone rubber particles (H1) may be surface-treated from the viewpoint of familiarity with the resin composition, improvement in dispersibility, and adjustment of the viscosity of the resin composition after dispersion.
  • the aspect of the surface treatment is not particularly limited, and examples thereof include silicone rubber particles coated with methyl methacrylate, silicone rubber particles coated with silicone resin, and the like.
  • the average particle diameter (d 50 ) of the silicone rubber particles (H1) is not particularly limited, but is preferably 0.1 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m.
  • the maximum particle size of the silicone rubber particles (H1) is not particularly limited, but is preferably 0.1 to 250 ⁇ m, more preferably 0.1 to 150 ⁇ m. When the average particle size is 100 ⁇ m or less (or the maximum particle size is 250 ⁇ m or less), the crack resistance of the cured product tends to be further improved. On the other hand, when the average particle size is 0.1 ⁇ m or more (or the maximum particle size is 0.1 ⁇ m or more), the dispersibility of the silicone rubber particles (H1) tends to be further improved.
  • the shape of the silicone rubber particles (H1) is not particularly limited, but is preferably spherical from the viewpoint of improving workability.
  • said silicone rubber particle (H1) from a viewpoint that the cured
  • the surface of which is coated with a silicone resin is preferable, and the surface of the crosslinked polydimethylsiloxane is particularly preferable from the viewpoint of the compatibility between the resin component and the silicone rubber particles (H1).
  • the silicone rubber particles (H1) can be used alone or in combination of two or more.
  • the silicone rubber particles (H1) can be produced by a known or conventional method, and the production method thereof is, for example, a silicone rubber particle produced by the method described in JP-A-7-196815.
  • the product names “KMP-600”, “KMP-601”, “KMP-602”, “KMP-605”, “X-52-7030”, “KMP-597”, “ Commercial products such as “KMP-598”, “KMP-594”, “X-52-875”, “KMP-590”, “KMP-701” manufactured by Shin-Etsu Chemical Co., Ltd.
  • KMP-701 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the silicone oil (H2) is not particularly limited, and examples thereof include non-modified silicone oil and modified silicone oil.
  • the non-modified silicone oil is not particularly limited, and examples thereof include a polydimethylsiloxane type, a polymethylhydrogensiloxane type, and a polymethylphenylsiloxane type.
  • the modified silicone oil is not particularly limited, and for example, either a reactive silicone oil that is reactive with an epoxy resin or a non-reactive silicone oil that is not reactive with an epoxy resin may be used.
  • the reactive silicone oil include amino-modified type, epoxy-modified type, carboxyl-modified type, carbinol-modified type, methacryl-modified type, mercapto-modified type, and phenol-modified type.
  • non-reactive silicone oils include polyalkylene ether-modified types, methylstyryl-modified types, alkyl-modified types, fatty acid ester-modified types, alkoxy-modified types, and fluorine-modified types.
  • the reactive silicone oil may have a non-reactive modifying group, and examples thereof include polyalkylene ether-amino modified silicone oil, polyalkylene ether-epoxy modified silicone oil and the like, and alicyclic epoxy compound (A) Furthermore, in the case of the second aspect of the present invention, it has reactivity with compounds having an epoxy group such as isocyanuric acid derivative (I) and siloxane derivative (J), and can control fluidity and viscosity. Polyalkylene ether-epoxy modified silicone oils are preferred.
  • silicone oil (H2) a polyalkylene ether-epoxy modified silicone oil is preferable from the viewpoint that a cured product having excellent light reflectivity, heat resistance, and light resistance can be formed by compression molding.
  • a polyalkylene ether-modified silicone compound having a structure represented by the following formula (1) having an equivalent weight of 3000 to 15000 (hereinafter sometimes referred to as “polyalkylene ether-modified silicone compound (1)”) is preferred.
  • R 9 is an alkylene group having 2 or 3 carbon atoms.
  • the alkylene group having 2 or 3 carbon atoms include a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, and a trimethylene group is preferable.
  • x represents an integer of 80 to 140.
  • y represents an integer of 1 to 5.
  • z represents an integer of 5 to 20. Note that the structures in parentheses to which z is attached may be the same or different.
  • A is a polyalkylene ether group having a structure represented by the following formula (1a).
  • a and b are each independently an integer of 0 to 40.
  • a is 40 or less, the water resistance of the cured product tends to be improved.
  • b is 40 or less, the fluidity of the curable resin composition tends to be improved.
  • the total of a and b is not particularly limited, but is preferably an integer of 1 to 80. When the sum of a and b is in the range, it becomes easy to control the water resistance of the cured product and the fluidity of the curable resin composition.
  • B is a hydrogen atom or a methyl group. From the viewpoint of water resistance of the cured product, B is preferably a methyl group.
  • each structural unit in the above formula (1) may be a random type or a block type as long as two trimethylsilyl groups in the formula (1) are present at both ends.
  • the addition form of each structural unit in the formula (1a) may be a random type or a block type as long as B is present at the terminal. Further, the order of arrangement of the structural units in the above formulas (1) and (1a) is not particularly limited.
  • the epoxy equivalent of the polyalkylene ether-modified silicone compound (1) is 3000 to 15000, preferably 4000 to 15000, and more preferably 5000 to 13000.
  • the epoxy equivalent is 3000 or more, the stress relaxation inside the cured product tends to be further improved.
  • the epoxy equivalent is 15000 or less, the compatibility with the resin tends to be further improved.
  • the epoxy equivalent of the polyalkylene ether-modified silicone compound (1) can be measured according to JIS K 7236: 2001.
  • the silicone oil (H2) can be used singly or in combination of two or more.
  • the silicone oil (H2) can be produced by a known or conventional method.
  • the silicone oil (H2) produced by the method described in JP-A-2008-201904 is used.
  • a commercial product such as “SF8421” (made by Toray Dow Corning Co., Ltd.) or “Y-19268” (made by Momentive Performance Materials Japan). You can also.
  • the liquid rubber component (H3) is not particularly limited.
  • polybutadiene maleated polybutadiene, acrylated polybutadiene, methacrylated polybutadiene, epoxidized polybutadiene, acrylonitrile butadiene rubber, carboxy terminal acrylonitrile butadiene rubber, amino terminal acrylonitrile butadiene rubber.
  • the said liquid rubber component (H3) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • thermoplastic resin (H4) is not particularly limited.
  • phenoxy resin and polyimide resin are preferable from the viewpoint of heat resistance.
  • These thermoplastic resins can be used singly or in combination of two or more.
  • the glass transition temperature (Tg) of the thermoplastic resin (H4) is not particularly limited, but is preferably 200 ° C. or lower.
  • the said stress relaxation agent (H) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • said stress relaxation agent (H) from a viewpoint that the cured
  • the content (blending amount) of the stress relaxation agent (H) in the curable resin composition of the first aspect 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 alicyclic epoxy compound (A).
  • the amount is preferably 200 parts by weight, more preferably 5 to 150 parts by weight, still more preferably 8 to 120 parts by weight.
  • the content (blending amount) of the stress relaxation agent (H) in the curable resin composition of the second aspect 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 alicyclic epoxy compound (A).
  • the amount is preferably 250 parts by weight, more preferably 5 to 230 parts by weight, still more preferably 10 to 200 parts by weight.
  • the content (blending amount) of the stress relaxation agent (H) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of compounds having epoxy groups contained in the curable resin composition is 100 wt.
  • the amount is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, and still more preferably 8 to 120 parts by weight.
  • the content of the stress relaxation agent (H) in the curable resin composition (100 wt%) of the first aspect or the second aspect of the present invention is not particularly limited, but is preferably 0.1 to 20 wt%, more preferably Is 0.3 to 18% by weight, more preferably 0.5 to 15% by weight.
  • the content of the stress relaxation agent (H) 0.1% by weight or more compression molding is possible even when the white pigment (C) or inorganic filler (D) is increased, and molding is also possible.
  • the light reflectivity, heat resistance, and light resistance of the cured product thus obtained tend to be further improved. Further, the warpage of the molded product is alleviated and the dimensional stability tends to be improved.
  • the content of the stress relaxation agent (H) is 20% by weight or less, the curability of the curable resin composition tends to be further improved.
  • the curable resin composition of the first aspect of the present invention may further contain an epoxy compound other than the alicyclic epoxy compound (A) (sometimes referred to as “other epoxy compound”).
  • an epoxy compound other than the alicyclic epoxy compound (A) (sometimes referred to as “other epoxy compound”).
  • other epoxy compound the well-known thru
  • the said other epoxy compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • heterocyclic epoxy compound examples include isocyanuric acid derivatives having one or more epoxy groups in the molecule.
  • the curable resin composition of this invention contains the said isocyanuric acid derivative, there exists a tendency for the adhesiveness with respect to the electrode of cured
  • the isocyanuric acid derivative (I) having one or more oxirane rings in the molecule is a derivative of isocyanuric acid and is a compound having at least one oxirane ring in the molecule.
  • the curable resin composition of the second aspect of the present invention contains the isocyanuric acid derivative (I)
  • the light reflectivity, heat resistance, and light resistance of the cured product are improved.
  • the siloxane derivative (J) and the alicyclic polyester resin (K) are included in the curable resin composition, the light reflectivity, heat resistance, and light resistance of the cured product are further improved.
  • the number of oxirane rings in the molecule of the isocyanuric acid derivative (I) may be one or more, and is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3.
  • Examples of the isocyanuric acid derivative (I) 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 aromatic hydrocarbon group (for example, an aryl group); A cyclic group; a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • 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 a monovalent organic group 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 At least one is preferably 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 isocyanuric acid derivative (I) 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 the formulas (IIIa) and (IIIb).
  • Representative examples of the compound represented by the formula (III-1) include monoallyldiglycidyl 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 isocyanuric acid derivative (I) may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
  • the isocyanuric acid derivative (I) is preferably a compound represented by the above formulas (III-1) to (III-3) from the viewpoint of light reflectivity, heat resistance, and solubility of the cured product.
  • a compound represented by the above formula (III-1) is preferable.
  • the isocyanuric acid derivative (I) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • isocyanuric acid derivative (I) examples include trade names “TEPIC” (manufactured by Nissan Chemical Industries, Ltd.); trade names “MA-DGIC”, “DA-MGIC” (above, Shikoku Kasei Kogyo Co., Ltd.) (Commercially available) can also be used.
  • the content (blending amount) of the isocyanuric acid derivative (I) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0.05 with respect to the curable resin composition (100% by weight). Is preferably 15 to 15% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.3 to 5% by weight. By setting the content of the isocyanuric acid derivative (I) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.
  • content (blending amount) of the isocyanuric acid derivative (I) in the curable resin composition of the second aspect of the present invention is not particularly limited, the total amount of compounds having an epoxy group contained in the curable resin composition is 100% by weight.
  • the amount is preferably 1 to 60 parts by weight, more preferably 1 to 50 parts by weight, still more preferably 1 to 30 parts by weight.
  • the siloxane derivative (J) having two or more epoxy groups in the molecule which is an essential component of the curable resin composition of the second aspect of the present invention, has two or more epoxy groups in the molecule and is constituted by a siloxane bond (—Si—O—Si—).
  • the siloxane skeleton (Si—O—Si skeleton) in the siloxane derivative (J) is not particularly limited, and examples thereof include cyclic siloxane skeletons; linear silicones, cage-type and ladder-type polysilsesquioxanes, and the like. Examples include a polysiloxane skeleton.
  • the siloxane skeleton a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the light reflectivity, heat resistance, and light resistance of the cured product and suppressing the light intensity reduction of the optical semiconductor device.
  • the siloxane derivative (J) is preferably a cyclic siloxane having two or more epoxy groups in the molecule and a linear silicone having two or more epoxy groups in the molecule.
  • the siloxane derivative (J) is a cyclic siloxane having two or more epoxy groups in the molecule
  • the number of Si—O units forming the siloxane ring is Although not particularly limited, it is preferably 2 to 12, more preferably 4 to 8, from the viewpoint of improving the heat resistance and light resistance of the cured product.
  • the weight average molecular weight of the siloxane derivative (J) is not particularly limited, but is preferably 100 to 3000, more preferably 180 to 2000, from the viewpoint of improving the heat resistance and light resistance of the cured product.
  • the said weight average molecular weight of a siloxane derivative (J) is computed from the molecular weight of standard polystyrene conversion measured by GPC (gel permeation chromatography) method.
  • the number of epoxy groups in the molecule of the siloxane derivative (J) is not particularly limited as long as it is 2 or more. From the viewpoint of improving the heat resistance and light resistance of the cured product, 2 to 4 (2 3 or 4) is preferred.
  • the epoxy equivalent of the siloxane derivative (J) is not particularly limited, but is preferably 180 to 2000, more preferably 180 to 1500, and still more preferably 180 to 1000 from the viewpoint of improving the heat resistance and light resistance of the cured product. .
  • the epoxy equivalent is a value measured according to JIS K7236.
  • the epoxy group possessed by the siloxane derivative (J) is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, an epoxy composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring.
  • Group (alicyclic epoxy group) is preferable, and among them, a cyclohexene oxide group is particularly preferable.
  • siloxane derivative (J) examples include a siloxane compound represented by the following formula (IV).
  • R a is the same or different and represents an epoxy group-containing group or an alkyl group.
  • at least two R a in formula (IV) e.g., 2 to four
  • the above-mentioned group containing an epoxy group is a group containing at least one epoxy group (oxirane ring).
  • a linear or branched aliphatic group having a carbon-carbon unsaturated double bond such as an alkenyl group.
  • a group in which at least one double bond of a hydrocarbon group is epoxidized, or a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond for example, a cycloalkenyl group; a cyclohexenylethyl group, etc.
  • a group in which at least one double bond of the alkenylalkyl group or the like is epoxidized is epoxidized.
  • 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 in which at least one double bond of a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond is epoxidized is preferable.
  • alkyl group examples include straight-chain or branched chain groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group.
  • An alkyl group etc. are mentioned. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
  • n represents an integer of 2 to 12.
  • n is preferably 4 to 8, more preferably 4 or 5, from the viewpoint of thermal shock resistance of the cured product, reflow resistance and thermal shock resistance of the optical semiconductor device.
  • siloxane derivative (J) for example, 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,4,6,6 , 8,8-Hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,2,4,6,6,8- Hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl- Cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetra
  • siloxane derivative (J) examples include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169 and at least two epoxy resins in one molecule described in JP-A-2008-19422.
  • An organopolysilsesquioxane resin having a functional group can also be used.
  • the siloxane derivative (J) can be used alone or in combination of two or more.
  • siloxane derivative (J) examples are cyclic siloxanes having two or more epoxy groups in the molecule, such as trade names “X-40-2678”, “X-40-2670”, “X-40-2720” ( As described above, commercial products such as Shin-Etsu Chemical Co., Ltd.) are available.
  • the siloxane derivative (J) can be produced by a known or conventional method.
  • the content (blending amount) of the siloxane derivative (J) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0.1 to 0.1% with respect to the curable resin composition (100 wt%). It is preferably 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1.0 to 10% by weight.
  • the content (blending amount) of the siloxane derivative (J) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100 parts by weight.
  • the amount is preferably 5 to 99 parts by weight, more preferably 10 to 95 parts by weight, and still more preferably 20 to 80 parts by weight.
  • the content of the siloxane derivative (J) is set to 5 parts by weight or more, the thixotropy of the curable resin composition is increased, and the heat resistance, light resistance, and light reflectivity of the cured product tend to be further improved.
  • the content of the siloxane derivative (J) is 150 parts by weight or less, the thermal shock resistance and adhesiveness of the cured product tend to be further improved.
  • the alicyclic polyester resin (K) in the curable resin composition of the second aspect of the present invention is a polyester resin having at least an alicyclic structure (aliphatic ring structure).
  • the alicyclic polyester resin (K) improves the heat resistance, light resistance, and crack resistance of the cured product and suppresses elution into the etching solution (hereinafter referred to as “etching solution elution resistance”). It plays a role of suppressing a decrease in luminous intensity of the optical semiconductor device.
  • the alicyclic polyester resin (K) has an alicyclic (alicyclic structure) in the main chain from the viewpoint of improving heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product.
  • Polyester is preferred. That is, the alicyclic polyester resin (K) is preferably a polyester resin in which a polymer main chain is constituted by part or all of carbon atoms constituting the alicyclic ring.
  • an alicyclic polyester resin (K) can be used individually or in combination of 2 or more types.
  • the alicyclic structure in the alicyclic polyester resin (K) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a bridged ring hydrocarbon structure (for example, a bicyclic hydrocarbon). Saturated monocyclic hydrocarbon structures and saturated bridged ring hydrocarbon structures in which all of the alicyclic rings (carbon-carbon bonds constituting the alicyclic rings) are carbon-carbon single bonds are preferred. Moreover, the alicyclic structure in the alicyclic polyester resin (K) may be introduced into only one of the structural unit derived from dicarboxylic acid or the structural unit derived from diol, or both may be introduced. Well, not particularly limited.
  • the alicyclic polyester resin (K) has a structural unit derived from a monomer component having an alicyclic structure.
  • the monomer having an alicyclic structure include diols and dicarboxylic acids having a known or commonly used alicyclic structure, and are not particularly limited.
  • the alicyclic polyester resin (K) may have a structural unit derived from a monomer component having no alicyclic structure.
  • the monomer component having no alicyclic structure is not particularly limited.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides); adipic acid Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propane Diol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glyco
  • a monomer component having no alicyclic structure also includes those obtained by bonding an appropriate substituent (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) to the dicarboxylic acid or diol having no alicyclic structure.
  • an appropriate substituent for example, an alkyl group, an alkoxy group, a halogen atom, etc.
  • the ratio of the monomer unit having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin (K) is not particularly limited, but is 10 mol% or more (for example, 10 to 80). Mol%) is preferable, more preferably 25 to 70 mol%, still more preferably 40 to 60 mol%.
  • the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product may decrease.
  • the alicyclic polyester resin (K) is particularly preferably an alicyclic polyester resin containing at least one structural unit represented by the following formulas (2) to (4).
  • R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
  • R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a group selected from R 11 to R 14 may be bonded to form a ring.
  • R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
  • R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
  • R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
  • R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
  • Preferred specific examples of the structural units represented by the above formulas (2) to (4) include, for example, a structure derived from 4-methyl-1,2-cyclohexanedicarboxylic acid and ethylene glycol represented by the following formula (5) Units are listed.
  • the alicyclic polyester resin (K) having the structural unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.
  • the structural units represented by the above formulas (2) to (4) include, for example, those derived from 1,4-cyclohexanedicarboxylic acid and neopentyl glycol represented by the following formula (6):
  • a structural unit is mentioned.
  • the alicyclic polyester resin (K) having the structural unit can be obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.
  • the terminal structure of the alicyclic polyester resin (K) is not particularly limited, and may be a hydroxyl group or a carboxyl group, or a structure in which these hydroxyl group or carboxyl group is appropriately modified (for example, the terminal hydroxyl group is mono). It may be a structure esterified with a carboxylic acid or an acid anhydride, or a structure in which a terminal carboxyl group is esterified with an alcohol.
  • the total content of the structural units (total content; all monomers constituting the structural unit)
  • the unit is not particularly limited, but 20 mol% or more (for example, with respect to the total structural unit (100 mol%; all monomer units constituting the alicyclic polyester resin (K)) of the alicyclic polyester resin (K) (for example, 20 to 100 mol%), more preferably 50 to 100 mol%, still more preferably 80 to 100 mol%. If the content of the structural units represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product may decrease. is there.
  • the number average molecular weight of the alicyclic polyester resin (K) is not particularly limited, but is preferably 300 to 100,000, more preferably 300 to 30,000. If the number average molecular weight of the alicyclic polyester resin (K) is less than 300, the toughness of the cured product may not be sufficient, and crack resistance and etchant dissolution resistance may decrease. On the other hand, when the number average molecular weight of the alicyclic polyester resin (K) exceeds 100,000, the compatibility with other components (for example, the curing agent (E)) is lowered, and the mechanical properties of the cured product are adversely affected. Crack resistance and etchant elution resistance may decrease. In addition, the number average molecular weight of alicyclic polyester resin (K) can be measured as a value of standard polystyrene conversion by GPC (gel permeation chromatography) method, for example.
  • alicyclic polyester resin (K) can be used individually by 1 type or in combination of 2 or more types.
  • the alicyclic polyester resin (K) is not particularly limited and can be produced by a known or conventional method. More specifically, for example, the alicyclic polyester resin (K) may be obtained by polycondensing the above-mentioned dicarboxylic acid and diol by a conventional method, or the above-mentioned dicarboxylic acid derivative (an acid anhydride, ester). , Acid halides, and the like) and diols may be obtained by polycondensation by a conventional method.
  • the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited, but when the curing agent (E) is an essential component, the alicyclic The amount is preferably 1 to 60% by weight, more preferably 5 to 30% by weight, based on the total amount (100% by weight) of the polyester resin (K) and the curing agent (E).
  • the blending amount of the alicyclic polyester resin (K) is less than 1% by weight, the crack resistance and etching solution elution resistance of the cured product may be lowered.
  • the compounding quantity of alicyclic polyester resin (K) exceeds 60 weight%, the heat resistance of hardened
  • the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited.
  • the amount is preferably 50 to 99% by weight, more preferably 65 to 99% by weight, based on the total amount (100% by weight) of the cyclic polyester resin (K) and the curing catalyst (G).
  • the blending amount of the alicyclic polyester resin (K) is less than 50% by weight, the crack resistance and etching solution elution resistance of the cured product may be lowered.
  • the compounding quantity of alicyclic polyester resin (K) exceeds 99 weight%, the heat resistance of hardened
  • the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited, but with respect to the curable resin composition (100% by weight), The content is preferably 0.1 to 20% by weight, more preferably 0.3 to 10% by weight. If the blending amount of the alicyclic polyester resin (K) is less than 0.1% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding quantity of alicyclic polyester resin (K) exceeds 20 weight%, the heat resistance of hardened
  • the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited, but has an epoxy group contained in the curable resin composition.
  • the amount is preferably 1 to 60 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the total amount of the compound.
  • the blending amount of the alicyclic polyester resin (K) is less than 1 part by weight, the crack resistance of the cured product may be lowered.
  • the compounding quantity of alicyclic polyester resin (K) exceeds 60 weight part, the heat resistance of hardened
  • the curable resin composition of the first aspect or the second aspect 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 or compression molding is facilitated, and a cured product (reflector) can be manufactured with high productivity.
  • the release agent known or commonly used release agents can be used, and are not particularly limited.
  • fluorine release agents fluorine atom-containing compounds; such as fluorine oil and polytetrafluoroethylene
  • Silicone release agents silicone compounds; for example, silicone oil, silicone wax, silicone resin, polyorganosiloxane having a polyoxyalkylene unit
  • wax release agents wax release agents
  • 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.
  • a mold release agent in the curable resin composition of the 1st aspect or 2nd aspect of this invention, can also be used individually by 1 type, and can also be used in combination of 2 or more types. Moreover, a mold release agent can also be manufactured by a well-known thru
  • the content (mixing amount) of the release agent is not particularly limited, but is included in the curable resin composition.
  • the amount is preferably 1 to 12 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total amount of the compound having an epoxy group.
  • the curable resin composition of the first aspect or the second aspect of the present invention may contain an antioxidant.
  • an antioxidant By containing an antioxidant, it becomes possible to produce a cured product (reflector) having further excellent heat resistance (particularly yellowing resistance).
  • known or commonly used antioxidants can be used, and are not particularly limited. For example, phenol 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 alone 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”.
  • the content (blending amount) of the antioxidant is not particularly limited, but is included in the curable resin composition.
  • the amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total amount of the compound having an epoxy group.
  • the curable resin composition of the 1st aspect or 2nd aspect of this invention may contain various additives in the range which does not impair the effect of this invention other than the above-mentioned component.
  • a compound having a hydroxy group especially an aliphatic polyhydric alcohol
  • ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained as the additive, the reaction can be allowed to proceed slowly.
  • antifoaming agents, leveling agents, silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, and surfactants as long as the viscosity and light reflectivity are not impaired.
  • additives such as flame retardants, colorants, ion adsorbers, ultraviolet absorbers, light stabilizers, fluorescent brighteners, and pigments other than the white pigment (C) can be used.
  • the content of these additives is not particularly limited and can be appropriately selected.
  • fluorescent brightening agent known or commonly used fluorescent brightening agents can be used.
  • the curable resin composition of the first aspect or the second aspect of the present invention contains a fluorescent brightening agent, it is more excellent in light reflectivity, heat resistance, light resistance, and crack resistance of a cured product formed by compression molding.
  • the fluorescent brightening agent include pyrazoline derivatives, stilbene derivatives, triazine derivatives, thiazole derivatives, benzoxazole derivatives, xanthone derivatives, triazole derivatives, oxazole derivatives, thiophene derivatives, coumarin derivatives, naphthalimide derivatives, and the like.
  • the curable resin composition according to the first aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing agent (E), and curing acceleration.
  • an agent (F) and a stress relaxation agent (H) an alicyclic epoxy compound (A), rubber particles (B), a curing agent (E), a curing accelerator (F), and a stress relaxation agent
  • the viscosity at 25 ° C. of the mixture comprising H) is not particularly limited, but is preferably 5000 mPa ⁇ s or less.
  • the curable resin composition according to the first aspect of the present invention may contain the above-mentioned aliphatic polyhydric alcohol such as ethylene glycol. In this case, the above-mentioned mixture contains the alicyclic epoxy compound (A). , Rubber particles (B), curing agent (E), curing accelerator (F), stress relaxation agent (H), and aliphatic polyhydric alcohol.
  • the curable resin composition of the second aspect of the present invention is an alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), curing agent (E), curing
  • the accelerator (F), stress relaxation agent (H), isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K) are contained, the alicyclic epoxy compound (A), rubber A mixture comprising particles (B), curing agent (E), curing accelerator (F), stress relaxation agent (H), isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K).
  • the viscosity at 25 ° C. is not particularly limited, but is preferably 5000 mPa ⁇ s or less.
  • the curable resin composition of the second aspect of the present invention may contain the above-mentioned aliphatic polyhydric alcohol such as ethylene glycol, and in this case, the above-mentioned mixture contains the alicyclic epoxy compound (A).
  • the curable resin composition of the first aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing catalyst (G), And the stress relaxation agent (H), the viscosity at 25 ° C. of the mixture comprising the alicyclic epoxy compound (A), the rubber particles (B), the curing catalyst (G), and the stress relaxation agent (H) is: Although not particularly limited, it is preferably 5000 mPa ⁇ s or less.
  • the curable resin composition of the second aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing catalyst (G), stress relaxation.
  • an agent (H), an isocyanuric acid derivative (I), a siloxane derivative (J), and an alicyclic polyester resin (K) an alicyclic epoxy compound (A), rubber particles (B), a curing catalyst
  • the viscosity at 25 ° C. of the mixture comprising G), stress relaxation agent (H), isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K) is not particularly limited, but is 5000 mPa ⁇ s. The following is preferable. In the present specification, the viscosity at 25 ° C. of the above four kinds of mixtures may be collectively referred to as “resin viscosity”.
  • the resin viscosity is a viscosity measured at 25 ° C. at normal pressure.
  • the resin viscosity is preferably 5000 mPa ⁇ s or less, more preferably 4000 mPa ⁇ s or less, further preferably 3500 mPa ⁇ s or less, and particularly preferably 3000 mPa ⁇ s or less.
  • the resin viscosity is 5000 mPa ⁇ s or less, the heat resistance, light resistance, and resistance of the cured product formed by compression molding of the curable resin composition is higher than when the resin viscosity exceeds 5000 mPa ⁇ s. Cracking properties (particularly excellent heat resistance) tend to be further improved.
  • the lower limit of the resin viscosity is, for example, 100 mPa ⁇ s or more.
  • the resin viscosity is determined by using, for example, a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ ⁇ R24, temperature: 25 ° C., rotational speed: 0 It can be measured under the condition of 5 to 10 rpm.
  • the resin viscosity is, for example, a component to be used (for example, in the case of the first aspect of the present invention, an alicyclic epoxy compound (A), a curing agent (E), a curing accelerator (F), a curing catalyst (G), And in the case of the second aspect of the present invention, the alicyclic epoxy compound (A), the curing agent (E), the curing accelerator (F), the curing catalyst (G), As a stress relaxation agent (H), an isocyanuric acid derivative (I), a siloxane derivative (J), an alicyclic polyester resin (K), and the like, it becomes easy to obtain by using a liquid component at 25 ° C.
  • a solid component may be used as said component at 25 degreeC, the content is adjusted so that the said resin viscosity may be 5000 mPa * s or less. Moreover, it becomes easy to obtain by adjusting content of a rubber particle (B) and a solid stress relaxation agent (H) within the range which does not impair the effect of this invention.
  • the curable resin composition of the 1st aspect or 2nd aspect of this invention is heated, and a part of alicyclic epoxy compound (A) in this curable resin composition and a hardening
  • B-staged curable resin composition (B-stage curable resin composition) may be obtained.
  • the curable resin composition of the first or second aspect of the present invention is excellent in light reflectivity, heat resistance, and light resistance after curing, and in particular, a resin composition for transfer molding and compression molding. It can preferably be used as a resin composition.
  • the curable resin composition according to the first aspect or the second aspect of the present invention is particularly excellent in light reflectivity, heat resistance, and light resistance of a cured product (reflector) formed by compression molding.
  • the resin composition is particularly preferable.
  • the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components in a heated state as necessary.
  • the curable resin composition of the first aspect or the second aspect of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, separately. It can also be used as a multi-component (for example, two-component) composition in which two or more components that have been stored are mixed at a predetermined ratio before use.
  • the stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
  • known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
  • the rubber particles (B) are blended in a state of being preliminarily dispersed in the alicyclic epoxy compound (A) (the composition may be referred to as “rubber particle dispersed epoxy compound”). It is preferable to do. That is, the curable resin composition of the first aspect of the present invention includes the rubber particle-dispersed epoxy compound, the white pigment (C), the inorganic filler (D), the stress relaxation agent (H), and the curing agent ( It is preferable to prepare by mixing E) and a hardening accelerator (F) or a hardening catalyst (G), and another component as needed.
  • the curable resin composition according to the second aspect of the present invention includes the rubber particle-dispersed epoxy compound, a white pigment (C), an inorganic filler (D), a stress relaxation agent (H), and an isocyanuric acid derivative.
  • a siloxane derivative (J) a siloxane derivative
  • J an alicyclic polyester resin
  • K a curing agent
  • F curing accelerator
  • G a curing catalyst
  • Such a preparation method can particularly improve the dispersibility of the rubber particles (B) in the curable resin composition.
  • the blending method of the rubber particles (B) is not limited to the above method, and may be a method of blending alone.
  • the rubber particle-dispersed epoxy compound is obtained by dispersing the rubber particles (B) in the alicyclic epoxy compound (A).
  • the alicyclic epoxy compound (A) in the rubber particle-dispersed epoxy compound may be the total amount or a partial amount of the alicyclic epoxy compound (A) constituting the curable resin composition. May be.
  • the rubber particles (B) in the rubber particle-dispersed epoxy compound may be the total amount or a partial amount of the rubber particles (B) constituting the curable resin composition.
  • the viscosity of the rubber particle-dispersed epoxy compound can be adjusted, for example, by using a reactive diluent together (that is, the rubber particle-dispersed epoxy compound may further contain a reactive diluent).
  • a reactive diluent for example, an aliphatic polyglycidyl ether having a viscosity at room temperature (25 ° C.) of 200 mPa ⁇ s or less can be preferably used.
  • Examples of the aliphatic polyglycidyl ether having a viscosity (25 ° C.) of 200 mPa ⁇ s or less include cyclohexane dimethanol diglycidyl ether, cyclohexane diol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
  • the amount of the reactive diluent used can be appropriately adjusted and is not particularly limited, but is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, with respect to 100 parts by weight of the total amount of the rubber particle-dispersed epoxy compound. (For example, 5 to 25 parts by weight). If the amount used is 30 parts by weight or less, desired performance such as toughness (improvement in crack resistance) tends to be easily obtained.
  • the method for producing the rubber particle-dispersed epoxy compound is not particularly limited, and a well-known and commonly used method can be used. For example, after the rubber particles (B) are dehydrated and dried to form a powder, the rubber particles (B) are mixed and dispersed in the alicyclic epoxy compound (A), or the emulsion of the rubber particles (B) and the alicyclic epoxy compound (A And the like, followed by dehydration and the like.
  • the viscosity at 25 ° C. of the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is preferably 100 to 1,000,000 mPa ⁇ s, more preferably 200 to 800,000 mPa ⁇ s, and still more preferably 300 to 800,000 mPa ⁇ s.
  • the viscosity at 25 ° C. is set to 100 mPa ⁇ s or more, workability during casting is improved, and heat resistance and light resistance of the cured product tend to be further improved.
  • the viscosity at 25 ° C. is set to 1000000 mPa ⁇ s or less, workability during casting is improved, and defects due to casting defects tend not to occur in the cured product.
  • ⁇ Hardened product> By curing the curable resin composition of the first aspect or the second aspect of the present invention by heating, it is excellent in light reflectivity, excellent in heat resistance, light resistance, and crack resistance, and further in the second aspect of the present invention. In this case, a cured product in which elution into the etching solution is suppressed can be obtained.
  • the cured product obtained by curing the curable resin composition of the first aspect or the second aspect of the present invention that is, the cured product of the curable resin composition of the first aspect or the second aspect of the present invention is referred to as “the present invention. Sometimes referred to as “cured product”.
  • the heating temperature (curing temperature) during curing is not particularly limited, but is preferably 50 to 200 ° C, more preferably 80 to 180 ° C. Further, the heating time (curing time) at the time of curing is not particularly limited, but is preferably 60 to 1800 seconds, and more preferably 90 to 900 seconds.
  • the curing temperature and the curing time are lower than the lower limit of the above range, curing is insufficient, and when the curing temperature and the curing time are higher than the upper limit of the above range, yellowing due to thermal decomposition occurs.
  • 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.
  • the curing process may be performed in one stage (for example, compression molding only), for example, in multiple stages (for example, further heating in an oven or the like as post-curing (secondary curing) after compression molding). Also good.
  • the heating temperature at this time is preferably 50 to 200 ° C., more preferably 60 to 180 ° C., and more preferably about the same as the curing temperature.
  • the post-curing time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours.
  • the cured product of the present invention has high light reflectivity, excellent heat resistance and light resistance, and in the case of the second embodiment of the present invention, elution into the etching solution is difficult to be suppressed. For this reason, the said hardened
  • the curable resin composition of the first aspect or the second aspect of the present invention is used for LED packages (LED package components, for example, reflector materials and housing materials in optical semiconductor devices), electronic component adhesion applications, It can be preferably used as a liquid crystal display (for example, a reflector), a white substrate ink, a sealer and the like. Especially, it can use especially preferably as curable resin composition for LED packages (especially curable resin composition for reflectors in an optical semiconductor device (that is, curable resin composition for forming reflectors)).
  • the reflectance (initial reflectance) of the cured product of the present invention is not particularly limited.
  • the reflectance of light having a wavelength of 450 nm is preferably 93% or more, more preferably 94% or more, and still more preferably. 95% or more.
  • the reflectance of light at 450 to 800 nm is preferably 93% or more, more preferably 94% or more, and still more preferably 95% or more.
  • the retention ratio of the light reflectance at a wavelength of 450 nm after heating for 250 hours at 120 ° C. (sometimes referred to as “reflectance after heat aging”) to the initial reflectance ([heat aging (Reflectance after) / [Initial reflectance] ⁇ 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the retention in the case of 450 to 800 nm light is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • cured material formed by compression molding can make the said retention rate 90% or more.
  • Retention of the reflectance of the cured product of the present invention with respect to light having a wavelength of 450 nm after irradiation with ultraviolet light having an intensity of 10 mW / cm 2 for 250 hours (sometimes referred to as “reflectance after ultraviolet light aging”) with respect to the initial reflectance.
  • the rate ([reflectance after ultraviolet ray aging] / [initial reflectivity] ⁇ 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the retention in the case of 450 to 800 nm light is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the reflectance is measured using, for example, a spectrophotometer (trade name “spectrophotometer UV-2450”, manufactured by Shimadzu Corporation) using the cured product of the present invention (thickness: 3 mm) as a test piece. can do.
  • a spectrophotometer trade name “spectrophotometer UV-2450”, manufactured by Shimadzu Corporation
  • the cured product according to the second aspect of the present invention is less likely to be eluted in an etching solution (for example, an alkaline solution), and even when used as a reflector or a substrate of an optical semiconductor device, the light reflectivity is not easily lowered in the etching process.
  • the weight reduction rate after treating the cured product in the second aspect of the present invention with an 11% by weight aqueous potassium hydroxide solution at 70 ° C. for 60 minutes is not particularly limited, but is preferably 1% or less, more preferably 0.8% or less, more preferably 0.5% or less.
  • the weight reduction rate of the cured product formed by compression molding can be 0.5% or less.
  • the curable resin composition of the first aspect or the second aspect of the present invention is a curable resin composition for a reflector in an optical semiconductor device
  • the curable resin composition of the first aspect or the second aspect of the present invention is ,
  • a molding material material used for molding with a mold or the like
  • the curable resin composition of the first aspect or the second aspect of the present invention it has high light reflectivity, excellent heat resistance and light resistance, and further crack resistance.
  • a high-quality (for example, highly durable) optical semiconductor element mounting substrate having a reflector in which elution into the etching solution is suppressed can be manufactured.
  • the reflector is a member for reflecting light emitted from the optical semiconductor element in the optical semiconductor device to increase the directivity and luminance of the light and improve the light extraction efficiency.
  • a substrate used for mounting an optical semiconductor element having at least a reflector formed of the cured product of the present invention may be referred to as “optical semiconductor element mounting substrate of the present invention”.
  • the substrate for mounting an optical semiconductor element of the present invention is a cured product of the curable resin composition of the present invention (cured product obtained by curing the curable resin composition of the first aspect or the second aspect of the present invention). It is a board
  • 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.
  • An optical semiconductor element 107 is placed in the center (optical semiconductor element mounting region 102) and die-bonded.
  • the metal wiring 101 on the package substrate 103 are connected by wire bonding.
  • 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 the inner surface of the concave shape formed of at least a cured product of the curable resin composition of the first aspect or the second aspect 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, compression molding or the like
  • examples include a method in which the curable resin composition of the first aspect or the second aspect is subjected to various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by dispensing.
  • the curing conditions for forming the reflector can be appropriately selected from, for example, the conditions for forming the cured product described above. In the present invention, among other things, it is possible to prevent foaming due to a rapid curing reaction, relax stress strain due to curing, and improve toughness (crack resistance). It is preferable to cure it.
  • 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 comprising at least an optical semiconductor element as a light source and a reflector (reflecting material) made of a cured product of the curable resin composition of the first aspect or the second aspect of the present invention. is there. More specifically, 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 reflector formed of a cured product of the curable resin composition of the first aspect or the second aspect of the present invention as a reflector, the luminance of light is less likely to decrease over time, and reliability. Is expensive. FIG.
  • FIG. 2 is a schematic view (cross-sectional view) showing an example of the optical semiconductor device of the present invention.
  • 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 die bonding
  • 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.
  • FIG. 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.
  • Production Example 1 Manufacture of rubber particles
  • 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream.
  • a monomer mixture composed of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion of the rubber particles.
  • the obtained latex was frozen at ⁇ 30 ° C., dehydrated and washed with a suction filter, and then blown and dried at 60 ° C. overnight to obtain rubber particles.
  • the resulting rubber particles had an average particle size of 108 nm and a maximum particle size of 289 nm.
  • the average particle size and the maximum particle size of the rubber particles are determined based on a nanotrac TM particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0 The maximum particle size at the time of exceeding 0.000 was defined as the maximum particle size.
  • a nanotrac TM particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0
  • Production Example 2 Manufacture of rubber particle-dispersed epoxy compounds
  • the product name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4) -Epoxy) cyclohexanecarboxylate (manufactured by Daicel Corporation) and dispersed in 100 parts by weight (1000 rpm, 60 minutes) and vacuum degassed to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 1036 mPa ⁇ s). It was. The viscosity at 25 ° C.
  • Production Example 3 Manufacture of alicyclic polyester resin
  • a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser 172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 208 parts by weight of neopentyl glycol (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • 0.1 part by weight of tetrabutyl titanate manufactured by Wako Pure Chemical Industries, Ltd.
  • the pressure was reduced to 5 mmHg over 1 hour, further reduced to 0.3 mmHg or less, and then reacted at 250 ° C. for 1 hour to obtain an alicyclic polyester resin.
  • Example 1A First, in accordance with the formulation (unit: parts by weight) shown in Table 1, the rubber particle-dispersed epoxy compound obtained in Production Example 2, silicone rubber particles (trade name “KMP-600” (manufactured by Shin-Etsu Chemical Co., Ltd.), oxidation Titanium (trade name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd.) and silica (trade name “FB-970FD”, manufactured by Denka Co., Ltd.) are uniformly mixed using a dissolver, and a roll mill Was melt-kneaded under predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3 passes) to obtain a kneaded product.
  • silicone rubber particles trade name “KMP-600” (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • oxidation Titanium trade name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd.
  • silica trade name “FB-970FD”, manufactured
  • the kneaded product obtained above and the curing agent composition obtained in Production Example 4 were mixed with a self-revolving stirrer (trade name “Awa” so as to have a formulation (unit: part by weight) shown in Table 1. And uniformly mixed (2000 rpm, 5 minutes) and defoamed to obtain a curable resin composition (curable epoxy resin composition). .
  • the curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., and cured by heating and pressurizing at a pressure of 3.0 MPa for 600 seconds. The cured product was obtained by carrying out at 150 ° C. for 5 hours.
  • Examples 2A-9A, Comparative Examples 1A-8A A curable resin composition and a cured product were prepared in the same manner as in Example 1A except that the composition of the curable resin composition was changed to the compositions shown in Tables 1 and 2.
  • the epoxy compounds shown in Tables 1 and 2 were used. used.
  • Example 10A According to the formulation (unit: parts by weight) shown in Table 3, the rubber particle-dispersed epoxy compound obtained in Production Example 2, silicone rubber particles (trade name “KMP-600” (manufactured by Shin-Etsu Chemical Co., Ltd.), titanium oxide ( Product name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd., and silica (trade name “FB-970FD”, manufactured by Denka Co., Ltd.) are uniformly mixed using a dissolver, and predetermined by a roll mill. A kneaded product was obtained by melt-kneading under the conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3 passes).
  • the kneaded product obtained above and a curing catalyst (trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd.) so as to have the formulation (unit: parts by weight) shown in Table 3 Is uniformly mixed (2000 rpm, 5 minutes) using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), defoamed, and curable resin composition (Curable epoxy resin composition) was obtained.
  • the curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., and cured by heating and pressurizing at a pressure of 3.0 MPa for 600 seconds.
  • the cured product was obtained by carrying out at 150 ° C. for 5 hours.
  • Examples 11A and 12A, Comparative Examples 9A to 13A A curable resin composition and a cured product were prepared in the same manner as in Example 10A except that the composition of the curable resin composition was changed to the composition shown in Table 3.
  • the epoxy compounds shown in Table 3 were used in place of or in combination with the rubber particle-dispersed epoxy compound obtained in Production Example 2 as a constituent of the curable resin composition. .
  • curable resin compositions obtained in Examples 1A to 12A and Comparative Examples 1A to 9A were liquid at 25 ° C.
  • the curable resin compositions obtained in Comparative Examples 10A to 13A were solid at 25 ° C.
  • Example 1B According to the blending ratio (unit: parts by weight) shown in Table 4, the rubber particle-dispersed epoxy compound obtained in Production Example 2, isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, Shikoku Chemicals Co., Ltd. ), Siloxane derivatives (siloxane derivatives having two epoxy groups in the molecule; trade name “X-40-2678”, and stress relieving agents (silicone rubber particles; trade name “KMP-600”, Shin-Etsu Chemical ( Were mixed uniformly using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), and defoamed to prepare a mixture.
  • isocyanuric acid derivative monooallyl diglycidyl isocyanurate
  • MA-DGIC Shikoku Chemicals Co., Ltd.
  • Siloxane derivatives siloxane derivatives having two epoxy groups in the molecule
  • the kneaded product obtained above and the curing agent composition obtained in Production Example 4 so as to have the blending ratio (unit: parts by weight) shown in Table 4 were mixed with a self-revolving stirrer (trade name “Awatori”
  • the mixture was uniformly mixed (2000 rpm, 5 minutes) using Nertaro AR-250 "(Sinky Corp.) and defoamed to obtain a curable resin composition (curable epoxy resin composition).
  • the curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then post-cured (5 at 150 ° C. Time), a cured product was obtained.
  • Examples 2B to 17B, Comparative Examples 1B to 12B A light-reflective curable resin composition and a cured product were obtained in the same manner as in Example 1B, except that the composition of the light-reflective curable resin composition was changed as shown in Table 4 or Table 5.
  • the epoxy compound shown in Table 4 or Table 5 is used instead of or in combination with the rubber particle-dispersed epoxy compound obtained in Production Example 2. It was used.
  • Example 18B According to the blending ratio (unit: parts by weight) shown in Table 6, the rubber particle-dispersed epoxy compound obtained in Production Example 2, isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, Shikoku Kasei Kogyo Co., Ltd.
  • Siloxane derivatives siloxane derivatives having two epoxy groups in the molecule; trade name “X-40-2678”, manufactured by Shin-Etsu Chemical Co., Ltd.
  • stress relieving agents silicon dioxide rubber particles; trade name “KMP”) -600 ", manufactured by Shin-Etsu Chemical Co., Ltd.
  • the alicyclic polyester resin obtained in Production Example 3 were mixed with a self-revolving stirrer (trade name" Awatori Nerita AR-250 ", manufactured by Shinky Corporation) ) To obtain a mixture. The above mixing was carried out with stirring at 80 ° C. for 1 hour in order to dissolve MA-DGIC.
  • the kneaded product obtained above so as to have a blending ratio (unit: parts by weight) shown in Table 6 and a curing catalyst (trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd.)
  • a curing catalyst trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd.
  • a self-revolving stirrer trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.
  • uniformly mixed 2000 rpm, 5 minutes
  • defoamed and curable resin composition
  • the curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then post-cured (5 at 150 ° C. Time), a cured product was obtained.
  • Examples 19B and 20B, Comparative Examples 13B to 18B A light-reflective curable resin composition and a cured product were obtained in the same manner as in Example 18B, except that the blending composition of the light-reflective curable resin composition was changed as shown in Table 6.
  • the epoxy compounds shown in Table 6 were used as constituent components of the curable resin composition instead of or in addition to the rubber particle-dispersed epoxy compound obtained in Production Example 2. .
  • Tables 1 to 6 show the evaluation results of the number of test pieces [10 pieces] in which cracks were confirmed among 10 test pieces that were reflowed per sample. In addition, the thing in which the crack generation was recognized at the time of cutting was not evaluated about the crack generation at the time of reflow.
  • YD-128 trade name “YD-128” (bisphenol A type epoxy resin), Nippon Steel Made by Sakai Chemical Co., Ltd. (isocyanuric acid derivative)
  • TEPIC trade name “TEPIC” (triglycidyl isocyanurate)
  • MA-DGIC trade name “MA-DGIC” (monoallyl diglycidyl isocyanurate)
  • Shikoku Kasei Kogyo DA- MGIC Trade name “DA-MGIC” (diallyl monoglycidyl isocyanurate), manufactured by Shikoku Chemicals Co., Ltd.
  • X-40-2678 Trade name “X-40-2678” (siloxane derivative having two epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd.
  • X-40-2720 Trade name “X-40-2720” "(Siloxane derivative having three epoxy groups in the molecule), X-40-2670 manufactured by Shin-Etsu Chemical Co., Ltd .: trade name” X-40-2670 "(siloxane derivative having four epoxy groups in the molecule) , Shin-Etsu Chemical Co., Ltd.
  • (curing agent composition) MH-700 trade name “Licacid MH-700” (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride), manufactured by Shin Nippon Rika Co., Ltd.
  • HN-7200 trade name “HN-7200” (4-methyl A mixture of hexahydrophthalic anhydride and alicyclic polyester resin), manufactured by Hitachi Chemical Co., Ltd.
  • KMP-602 Trade name “KMP-602” (silicone resin on the surface) Cross-linked polydimethylsiloxane), manufactured by Shin-Etsu Chemical Co., Ltd.
  • SF8421 Trade name “SF8421” (polyalkylene ether-modified silicone compound represented by the formula (1)), Y- manufactured by Toray Dow Corning Co., Ltd.
  • 19268 Trade name “Y-19268” (polyalkylene ether-modified silicone compound represented by formula (1)), manufactured by Momentive Performance Materials Japan (same) (white pigment)
  • DCF-T-17050 Trade name “DCF-T-17050” (titanium oxide, average particle size 0.3 ⁇ m, maximum particle size 1 ⁇ m or less), manufactured by Resino Color Industry Co., Ltd.
  • Titanium oxide Trade name “DCF-T-17050 (Titanium oxide, average particle size 0.3 ⁇ m, maximum particle size 1 ⁇ m or less), manufactured by Resino Color Industry Co., Ltd.
  • FB-970FD (inorganic filler)
  • FB-970FD (silica, no surface treatment, average particle size 16.7 ⁇ m, maximum particle size 70 ⁇ m), manufactured by Denka Corp.
  • DAW-1025 Trade name “DAW-1025” (alumina, (Average particle size 7.9 ⁇ m, maximum particle size 32 ⁇ m), Denka Co., Ltd.
  • HF-05 trade name “HF-05” (aluminum nitride, average particle size 5 ⁇ m, maximum particle size 5 ⁇ m), Tokuyama Co., Ltd.
  • Silica Trade name “FB-970FD” (silica, no surface treatment, average particle size 16.7 ⁇ m, maximum particle size 70 ⁇ m), manufactured by Denka Co., Ltd.
  • Alumina Trade name “DAW-1025” (alumina, average particle size 7. 9 ⁇ m, maximum particle size 32 ⁇ m), aluminum nitride manufactured by Denka Co., Ltd .: Trade name “HF-05” (alumina nitride, average particle size 5 ⁇ m, maximum particle size 5 ⁇ m), Co., Ltd. Shame made
  • [1] Contains an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H), and further cured.
  • a curable resin composition for light reflection which contains an agent (E) and a curing accelerator (F) or a curing catalyst (G) and is liquid at 25 ° C.
  • the alicyclic epoxy compound (A) has (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and ( ii) For light reflection according to any one of the above [1] to [3], comprising at least one selected from the group consisting of compounds having an epoxy group directly bonded to the alicyclic ring with a single bond Curable resin composition.
  • the linking group is a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or these
  • the alicyclic epoxy compound represented by the formula (I) is a compound 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
  • the curable resin composition for light reflection according to the above [6] or [7], which is at least one selected from the group consisting of bis (3,4-epoxycyclohexylmethyl) ether.
  • R in the above formula (I-5) is an alkylene group having 1 to 8 carbon atoms (preferably a linear or branched alkylene group having 1 to 3 carbon atoms).
  • n1 to n6 each represents an integer of 1 to 30.
  • the alicyclic epoxy compound (A) is represented by the following formula (I-1)
  • R 1 represents a p-valent organic group.
  • p represents an integer of 1 to 20.
  • q represents an integer of 1 to 50. When p is an integer greater than or equal to 2, several q may be the same and may differ.
  • the sum (total) of q in the formula (II) is an integer of 3 to 100.
  • R 2 represents any one of groups represented by the following formulas (IIa) to (IIc). At least one of R 2 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.)] [11]
  • the ratio of the 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 (preferably 60 mol% or more, more
  • the content (blending amount) of the alicyclic epoxy compound (A) is 1.5 to 60% by weight (preferably 2 to 50% by weight) with respect to the curable resin composition (100% by weight),
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition is 50% by weight or more (preferably 60% by weight or more, more preferably Is 80% by weight or more, and particularly preferably 90% by weight or more).
  • the content (blending amount) of the alicyclic epoxy compound (A) is 0.1 to 60% by weight (preferably 0.3 to 50% by weight) with respect to the curable resin composition (100% by weight). %, More preferably 0.5 to 40% by weight), the curable resin composition for light reflection according to any one of the above [2] to [15].
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition is 1 to 90% by weight (preferably 5 to 80% by weight, More preferably, the curable resin composition for light reflection according to any one of [2] to [15] and [18], which is 10 to 70% by weight).
  • a rubber particle (B) other than silicone rubber particles (hereinafter sometimes simply referred to as “rubber particle (B)”) has a core portion having rubber elasticity and at least one layer covering the core portion.
  • the light-reflective curable resin composition according to any one of the above [1] to [19], which is a rubber particle having a multilayer structure (core-shell structure) composed of a shell layer.
  • the rubber particle (B) is a rubber particle having a hydroxy group and / or a carboxy group and / or a carboxy group on the surface.
  • the curable resin composition for light reflection as described in 1.
  • the refractive index of the rubber particles (B) is 1.40 to 1.60 (preferably 1.42 to 1.58), according to any one of the above [1] to [24] Curable resin composition for light reflection.
  • the difference between the refractive index of the rubber particles (B) and the refractive index of a cured product obtained by curing the curable resin composition containing the rubber particles (B) is within ⁇ 0.03.
  • the curable resin composition for light reflection according to any one of [1] to [25].
  • the content (blending amount) of the rubber particles (B) is 0.05 to 20% by weight (preferably 0.1 to 15% by weight, based on the curable resin composition (100% by weight).
  • the content (blending amount) of the rubber particles (B) is 0.01 to 20% by weight (preferably 0.05 to 15% by weight, based on the curable resin composition (100% by weight).
  • the content (blending amount) of the rubber particles (B) is 0.5 to 30 parts by weight (preferably 1) with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition.
  • the curable resin composition for light reflection according to any one of the above [1] to [28], wherein
  • the white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate, according to any one of the above [1] to [29] Curable resin composition for light reflection.
  • the center particle size of titanium oxide is 0.1 to 50 ⁇ m (preferably 0.1 to 30 ⁇ m, more preferably 0.1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, most preferably 0.1 to The curable resin composition for light reflection according to the above [31], which is 5 ⁇ m).
  • the content (blending amount) of the white pigment (C) is 0.1 to 50% by weight (preferably 1 to 40% by weight, more preferably, relative to the curable resin composition (100% by weight).
  • the content (blending amount) of the white pigment (C) is 3 to 400 parts by weight (preferably 10 to 350 parts per 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition).
  • the content (blending amount) of the white pigment (C) is 10 to 600 parts by weight (preferably 30 to 500 parts per 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition. For light reflection according to any one of the above [2] to [15], [18] to [26], and [28] to [34].
  • Curable resin composition [37] The above [31], wherein the ratio of titanium oxide to the total amount (100 wt%) of the white pigment (C) and the inorganic filler (D) is 5 to 70 wt% (preferably 10 to 60 wt%).
  • the curable resin composition for light reflection according to any one of [34] to [34].
  • the inorganic filler (D) is at least one selected from the group consisting of silica, alumina, silicon nitride, aluminum nitride, and boron nitride.
  • the silica has a center particle diameter of 0.1 to 50 ⁇ m (preferably 0.1 to 30 ⁇ m).
  • the content (blending amount) of the inorganic filler (D) is 10 to 90% by weight (preferably 13 to 75% by weight, more preferably 15% with respect to the curable resin composition (100% by weight).
  • the content (blending amount) of the inorganic filler (D) is 10 to 1500 parts by weight (preferably 50 to 100 parts by weight based on 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition).
  • the above [1], [3] to [17], [20] to [27], [29] to [35], [37] to [ 41] The curable resin composition for light reflections as described in any one of 41.
  • the content (blending amount) of the inorganic filler (D) is 10 to 1500 parts by weight (preferably 50 to Any of the above [2] to [15], [18] to [26], [28] to [34], and [36] to [41].
  • [44] The above-mentioned [1]-[ 43].
  • [45] The light-reflective curable resin according to any one of the above [1] to [44], wherein the maximum particle size of the white pigment (C) and the inorganic filler (D) is 0.01 ⁇ m or more. Composition.
  • the curable resin composition for light reflection as described in one.
  • the content (blending amount) of the curing agent (E) is 1 to 40% by weight (preferably 3 to 35% by weight, more preferably 5 to 5% by weight) with respect to the curable resin composition (100% by weight). 30% by weight)
  • the content (blending amount) of the curing agent (E) is 40 to 200 parts by weight (preferably 50 to 150 parts per 100 parts by weight of the total amount of compounds having epoxy groups contained in the curable resin composition.
  • the curable resin composition for light reflection according to any one of the above [1] to [49], wherein the curable resin composition is a part by weight.
  • the content (blending amount) of the curing accelerator (F) is 0.0001 to 5% by weight (preferably 0.001 to 1% by weight) with respect to the curable resin composition (100% by weight).
  • the content (blending amount) of the curing accelerator (F) is 0.05 to 15 parts by weight (preferably with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition).
  • the content (blending amount) of the curing catalyst (G) is 0.0001 to 5% by weight (preferably 0.001 to 1% by weight) with respect to the curable resin composition (100% by weight).
  • the curable resin composition for light reflection according to any one of the above [1] to [52].
  • the content (blending amount) of the curing catalyst (G) is 0.0001 to 15 parts by weight (preferably 0 to 100 parts by weight of the total amount of the compounds having an epoxy group contained in the curable resin composition). 0.01 to 12 parts by weight, more preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight), and the light reflection according to any one of [1] to [53] above Curable resin composition.
  • the stress relaxation agent (H) is at least one selected from the group consisting of silicone rubber particles (H1), silicone oil (H2), a liquid rubber component (H3), and a thermoplastic resin (H4).
  • the stress relaxation agent (H) is at least one selected from the group consisting of silicone rubber particles (H1) and silicone oil (H2).
  • the curable resin composition for light reflection as described.
  • the silicone rubber particles (H1) have an average particle diameter (d 50 ) of 0.1 to 100 ⁇ m (preferably 0.5 to 50 ⁇ m).
  • the curable resin composition for light reflection described in 1.
  • the silicone oil (H2) is a polyalkylene ether-modified silicone compound having a structure represented by the following formula (1) having an epoxy equivalent of 3000 to 15000 (hereinafter referred to as “polyalkylene ether-modified silicone compound (1)”).
  • the light-reflective curable resin composition according to any one of [55] to [59] above.
  • x is an integer from 80 to 140
  • y is an integer from 1 to 5
  • z is an integer from 5 to 20.
  • R 9 is an alkylene group having 2 or 3 carbon atoms (preferably trimethylene group).
  • A is a polyalkylene ether group having a structure represented by the following formula (1a). (Wherein, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group (preferably a methyl group)] [61]
  • the content (blending amount) of the stress relaxation agent (H) is 1 to 200 parts by weight (preferably 5 to 150 parts by weight, more preferably 100 parts by weight of the alicyclic epoxy compound (A). 8 to 120 parts by weight), [1], [3] to [17], [20] to [27], [29] to [35], [37] to [42], [44] to [62]
  • the content (blending amount) of the stress relaxation agent (H) is 1 to 250 parts by weight (preferably 5 to 230 parts by weight, more preferably 100 parts by weight of the alicyclic epoxy compound (A). 10 to 200 parts by weight) of [2] to [15], [18] to [26], [28] to [34], [36] to [41], and [43] to [62].
  • the curable resin composition for light reflection as described in any one.
  • the content (blending amount) of the stress relaxation agent (H) is 1 to 200 parts by weight (preferably 5 to 100 parts by weight based on 100 parts by weight of the total amount of the epoxy group-containing compounds contained in the curable resin composition).
  • the curable resin composition for light reflection according to any one of [64].
  • the content of the stress relaxation agent (H) with respect to the curable resin composition (100 wt%) is 0.1 to 20 wt% (preferably 0 with respect to the curable resin composition (100 wt%)).
  • 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.
  • R 4 to R 6 in the formula (III) are the same or different and are a group represented by the following formula (IIIa) or a group represented by the following formula (IIIb), wherein R 4 to R 6
  • [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 (preferably a hydrogen atom).
  • a compound wherein the isocyanuric acid derivative (I) is 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) [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [41], including at least one selected from the group consisting of 62],
  • the curable resin composition for light reflection according to any one of [64] to [69].
  • [R 7 and R 8 in the above formulas (III-1), (III-2) and (III-3) are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably hydrogen Atom).
  • the isocyanuric acid derivative (I) is represented by the following formula (III-1): [In Formula (III-1), R 7 and R 8 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom). ]
  • the curable resin composition for light reflection according to any one of [64] to [70].
  • the content (blending amount) of the isocyanuric acid derivative (I) is 0.05 to 15% by weight (preferably 0.1 to 10% by weight) with respect to the curable resin composition (100% by weight). More preferably 0.3 to 5% by weight) [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43]
  • the content (blending amount) of the isocyanuric acid derivative (I) is 1 to 60 parts by weight (preferably 1 to 60 parts by weight with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition).
  • the siloxane derivative (J) is at least one selected from the group consisting of a cyclic siloxane having two or more epoxy groups in the molecule and a linear silicone having two or more epoxy groups in the molecule. [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [73] The curable resin composition for light reflection as described in any one of these. [75] The above [2] to [15], [18] to [26], [28] to [34], wherein the siloxane derivative (J) is a cyclic siloxane having two or more epoxy groups in the molecule.
  • siloxane derivative (J) has 2 to 4 (2, 3, or 4) epoxy groups in the molecule [26], [28] to [34], [36] to [41], [43] to [62], [64] to [77] object.
  • the epoxy equivalent of the siloxane derivative (J) is 180 to 2000 (preferably 180 to 1500, more preferably 180 to 1000), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], and [64] to [78].
  • the epoxy group possessed by the siloxane derivative (J) is an epoxy group (alicyclic epoxy group) (preferably a cyclohexene oxide group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [79]
  • the curable resin composition for light reflection as described in any one of these.
  • R a is the same or different and represents an epoxy group-containing group or an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms). Provided that at least two R a in formula (IV) (preferably 2 to four) is a group containing an epoxy group. n represents an integer of 2 to 12 (preferably 4 to 8, more preferably 4 or 5).
  • siloxane derivative (J) contains at least one selected from the group consisting of cyclic siloxanes having two or more epoxy groups in the molecule represented by the following formula: [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [81] Curable resin composition.
  • the content (blending amount) of the siloxane derivative (J) is 0.1 to 30% by weight (preferably 0.5 to 20% by weight, based on the curable resin composition (100% by weight).
  • the above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62] The curable resin composition for light reflection according to any one of [64] to [82].
  • the content (blending amount) of the siloxane derivative (J) is 5 to 99 parts by weight (preferably 10 to 95 parts per 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). Parts by weight, more preferably 20 to 80 parts by weight), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43 ] To [62] and [64] to [83].
  • the alicyclic polyester resin (K) is an alicyclic polyester resin having an alicyclic ring in the main chain, [2] to [15], [18] to [26], [28] to [28] 34], [36] to [41], [43] to [62], and [64] to [84].
  • the ratio of monomer units having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin (K) is 10 mol% or more (for example, 10 to 80 mol%) ) (Preferably 25 to 70 mol%, more preferably 40 to 60 mol%), [2] to [15], [18] to [26], [28] to [34], [36] The curable resin composition for light reflection according to any one of [41], [43] to [62], and [64] to [85].
  • the alicyclic polyester resin (K) is an alicyclic polyester resin containing at least one selected from the group consisting of structural units represented by the following formulas (2) to (4): [2] ] To [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [86]
  • the curable resin composition for light reflection described in 1. wherein R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
  • R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a group selected from R 11 to R 14 may be bonded to form a ring.
  • R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
  • R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
  • R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms.
  • R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
  • the number average molecular weight of the alicyclic polyester resin (K) is 300 to 100,000 (preferably 300 to 30,000), [2] to [15], [18] to [26], [28] [34], [36] to [41], [43] to [62], and [64] to [90].
  • the blending amount (content) of the alicyclic polyester resin (K) is the total amount of the alicyclic polyester resin (K) and the curing agent (E) ( [2] to [15], [18] to [26], [28] to [34], which are 1 to 60% by weight (preferably 5 to 30% by weight) with respect to 100% by weight), [36] to [41], [43] to [62], and [64] to [91].
  • the blending amount (content) of the alicyclic polyester resin (K) is the total amount of the alicyclic polyester resin (K) and the curing catalyst (G) ( 100% by weight) to 50 to 99% by weight (preferably 65 to 99% by weight), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], and [64] to [91].
  • the blending amount (content) of the alicyclic polyester resin (K) is 0.1 to 20% by weight (preferably 0.3 to 10% by weight) with respect to the curable resin composition (100% by weight).
  • the blending amount (content) of the alicyclic polyester resin (K) is 1 to 60 parts by weight (preferably with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). 5 to 30 parts by weight), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [94] The curable resin composition for light reflection according to any one of [64] to [94].
  • the light-reflective curable resin composition according to any one of [1] to [95], further including a release agent.
  • the content (blending amount) of the release agent is 1 to 12 parts by weight (preferably 2 to 10 parts by weight) with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition.
  • the content (blending amount) of the antioxidant is 0.1 to 5 parts by weight (preferably 0.5 parts per 100 parts by weight of the total amount of the compounds having epoxy groups contained in the curable resin composition).
  • the cured product according to [102], wherein the reflectance (initial reflectance) of light having a wavelength of 450 nm is 93% or more (preferably 94% or more, more preferably 95% or more).
  • the retention ratio of the reflectance of light having a wavelength of 450 nm after heating at 120 ° C. for 250 hours with respect to the initial reflectance is 80% or more (preferably 85% or more, more preferably 90% or more).
  • Retention rate of light having a wavelength of 450 nm after irradiation with ultraviolet light having an intensity of 10 mW / cm 2 for 250 hours with respect to the initial reflectance is 80% or more (preferably 85% or more, more preferably 90% or more
  • An optical semiconductor device comprising at least an optical semiconductor element and a reflector made of a cured product of the light reflecting curable resin composition according to [101].
  • the curable resin composition of the present invention is a molding material (curing for light reflection) used for forming a reflector (light reflecting member) of an optical semiconductor element substrate (an optical semiconductor element mounting substrate) in an optical semiconductor device. Curable resin composition).
  • White reflector 101 Metal wiring (electrode) 102: Mounting area of optical semiconductor element 103: Package substrate 104: Bonding wire 105: Sealing material for optical semiconductor element 106: Die bonding 107: Optical semiconductor element 108: Heat sink 109: Cathode mark

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Abstract

[Problem] The purpose of the present invention is to provide a curable resin composition for optical reflection which enables the production of a reflector by compression molding, and which additionally has high light reflectivity and excellent heat resistance and light stability. [Solution] The present invention provides a curable resin composition for optical reflection which is characterized by including an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), and a stress relaxer (H), by additionally including either a curing agent (E) and a curing accelerator (F), or a curing catalyst (G), and by being in a liquid state at 25°C.

Description

光反射用硬化性樹脂組成物及びその硬化物、並びに光半導体装置Curable resin composition for light reflection, cured product thereof, and optical semiconductor device
　本発明は、光反射用硬化性樹脂組成物及びその硬化物、該硬化物により形成されたリフレクターと光半導体素子とを有する光半導体装置に関する。本願は、２０１７年１月２３日に日本に出願した、特願２０１７－００９８５９及び特願２０１７－００９８６０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 light-reflective curable resin composition and a cured product thereof, and an optical semiconductor device having a reflector formed of the cured product and an optical semiconductor element. This application claims the priority of Japanese Patent Application No. 2017-009859 and Japanese Patent Application No. 2017-009860 filed in Japan on January 23, 2017, the contents of which are incorporated herein by reference.
　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（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 (reflector) for reflecting light is formed in order to improve the extraction efficiency of light emitted from the optical semiconductor element.
　上記リフレクターには、高い光反射性を有することが求められている。従来、上記リフレクターの構成材としては、例えば、テレフタル酸単位を必須の構成単位とするポリアミド樹脂（ポリフタルアミド樹脂）中に、無機フィラー等を分散させた樹脂組成物等が知られている（特許文献１～３参照）。 The reflector is required to have high light reflectivity. Conventionally, as a constituent material of the reflector, for example, a resin composition in which an inorganic filler or the like is dispersed in a polyamide resin (polyphthalamide resin) having a terephthalic acid unit as an essential constituent unit is known ( (See Patent Documents 1 to 3).
　また、上記リフレクターの構成材としては、その他に、例えば、エポキシ樹脂を含む熱硬化性樹脂と、屈折率１．６～３．０の無機酸化物とを特定割合で含有する光反射用熱硬化性樹脂組成物が知られている（特許文献４参照）。さらに、例えば、熱硬化性樹脂成分と１以上の充填剤成分とを含有し、熱硬化性樹脂成分全体の屈折率と各充填剤成分の屈折率との差、及び、各充填剤成分の体積割合より算出されるパラメータを特定範囲に制御した光反射用熱硬化性樹脂組成物が知られている（特許文献５参照）。また、脂環式エポキシ化合物にゴム粒子と白色顔料を配合した光反射用硬化性樹脂組成物が知られている（特許文献６参照）。 In addition, as the constituent material of the reflector, for example, a thermosetting resin for light reflection containing a specific ratio of a thermosetting resin containing an epoxy resin and an inorganic oxide having a refractive index of 1.6 to 3.0, for example. Resin compositions are known (see Patent Document 4). Furthermore, for example, it contains a thermosetting resin component and one or more filler components, the difference between the refractive index of the entire thermosetting resin component and the refractive index of each filler component, and the volume of each filler component There is known a thermosetting resin composition for light reflection in which a parameter calculated from a ratio is controlled within a specific range (see Patent Document 5). Moreover, a curable resin composition for light reflection in which rubber particles and a white pigment are blended with an alicyclic epoxy compound is known (see Patent Document 6).
特開２０００－２０４２４４号公報JP 2000-204244 A 特開２００４－７５９９４号公報JP 2004-75994 A 特開２００６－２５７３１４号公報JP 2006-257314 A 特開２０１０－２３５７５３号公報JP 2010-235753 A 特開２０１０－２３５７５６号公報JP 2010-235756 A 国際公開ＷＯ２０１３／００２０５２号パンフレットInternational publication WO2013 / 002052 pamphlet
　上述の特許文献１～６に記載の材料より作製したリフレクターは、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光や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。さらに、鉛フリーはんだの採用に伴い、発光装置の製造の際のリフロー工程（はんだリフロー工程）における加熱温度がより高くなる傾向にあり、このような製造工程において加わる熱によっても上記リフレクターが経時で劣化し、光反射性が低下するという問題も発生していた。 Reflectors made from the materials described in Patent Documents 1 to 6 described above are yellowed over time due to light and heat emitted from a semiconductor element in an optical semiconductor device using a high-power blue light semiconductor or white light semiconductor as a light source. Etc., and the light reflectivity decreases with time. Furthermore, with the adoption of lead-free solder, the heating temperature in the reflow process (solder reflow process) during the manufacture of the light-emitting device tends to be higher, and the reflector is also deteriorated over time due to the heat applied in such a manufacturing process. There was also a problem that the light reflectivity was deteriorated due to deterioration.
　このため、より高出力、短波長の光や高温に対しても光反射性が経時で低下しにくい、耐熱性及び耐光性に優れる材料が求められているのが現状である。 For this reason, the present situation is that a material excellent in heat resistance and light resistance in which light reflectivity is less likely to deteriorate with time even for higher output, shorter wavelength light and high temperature is required.
　また、上記リフレクターは、一般に、該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。しかしながら、従来のリフレクターを形成するための樹脂組成物は、トランスファー成型に適したものが多いため、該樹脂組成物より形成したリフレクターは耐熱性に優れるが、コンプレッション成型により形成したリフレクターは耐熱性が比較的劣るものが多かった。
　また、特許文献１～６に記載の材料を形成したリフレクターの反射率や耐熱性を向上させるために無機充填剤の充填量を増やした場合には、組成物の粘度が上昇して固体状態となり、コンプレッション成型により形成することが困難になるという問題もあった。 Moreover, the said reflector is generally manufactured by attaching | subjecting the material (resin composition) for forming this reflector to transfer molding or compression molding. However, since many resin compositions for forming conventional reflectors are suitable for transfer molding, a reflector formed from the resin composition is excellent in heat resistance, but a reflector formed by compression molding has heat resistance. Many were relatively inferior.
In addition, when the amount of the inorganic filler is increased in order to improve the reflectivity and heat resistance of the reflector formed with the materials described in Patent Documents 1 to 6, the viscosity of the composition increases to become a solid state. There is also a problem that it becomes difficult to form by compression molding.
　従って、本発明の第１の目的は、コンプレッション成型により、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくい硬化物を形成できる光反射用硬化性樹脂組成物を提供することにある。
　また、本発明の他の第１の目的は、コンプレッション成型による生産性に優れ、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくい硬化物を提供することにある。
　さらに、本発明の他の第１の目的は、経時で光の輝度が低下しにくく、信頼性の高い光半導体装置を提供することにある。 Therefore, the first object of the present invention is to provide a light-reflective material capable of forming a cured product having high light reflectivity, excellent heat resistance and light resistance, and less likely to deteriorate with time by compression molding. The object is to provide a curable resin composition.
Another first object of the present invention is a cured product that is excellent in productivity by compression molding, has high light reflectivity, is excellent in heat resistance and light resistance, and the light reflectivity is not easily lowered over time. Is to provide.
Furthermore, another object of the present invention is to provide an optical semiconductor device that is less likely to reduce the luminance of light over time and has high reliability.
　また、光半導体装置製造におけるエッチング工程において、リフレクターで構成される基板がエッチング液（例えば、アルカリ溶液）に溶出しにくい特性も求められる。基板表面がエッチング液に溶出すると、光反射性が低下して（即ち、光の取り出し効率が低下して）、発光装置の信頼性を担保することが困難となるためである。 In addition, in an etching process in manufacturing an optical semiconductor device, a characteristic that a substrate constituted by a reflector is difficult to elute into an etching solution (for example, an alkaline solution) is also required. This is because when the substrate surface elutes into the etching solution, the light reflectivity decreases (that is, the light extraction efficiency decreases), and it becomes difficult to ensure the reliability of the light emitting device.
　従って、本発明の第２の目的は、コンプレッション成型により、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくく、エッチング液に溶出しにくい硬化物を形成できる光反射用硬化性樹脂組成物を提供することにある。
　また、本発明の他の第２の目的は、コンプレッション成型による生産性に優れ、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくく、エッチング液に溶出しにくい硬化物を提供することにある。
　さらに、本発明の他の第２の目的は、経時で光の輝度が低下しにくく、信頼性の高い光半導体装置を提供することにある。 Therefore, the second object of the present invention is a compression molding, which has high light reflectivity, excellent heat resistance and light resistance, light reflectivity hardly deteriorates with time, and does not easily dissolve into an etching solution. It is providing the curable resin composition for light reflection which can form a thing.
Another object of the present invention is to improve the productivity by compression molding, to have high light reflectivity, to have excellent heat resistance and light resistance, and to prevent light reflectivity from decreasing with time, and to etch. An object of the present invention is to provide a cured product that hardly dissolves in a liquid.
Furthermore, another object of the present invention is to provide a highly reliable optical semiconductor device in which the luminance of light is less likely to decrease over time.
　さらに、上記リフレクターには、切削加工や温度変化（例えば、リフロー工程のような非常に高温での加熱や、冷温サイクルなど）等による応力が加わった場合に、クラック（ひび割れ）を生じにくい（このような特性を「耐クラック性」と称する場合がある）等、強靭であることが求められている。リフレクターにクラックが生じてしまうと、光反射性が低下して（即ち、光の取り出し効率が低下して）、発光装置の信頼性を担保することが困難となるためである。 Furthermore, the above reflector is less susceptible to cracking when subjected to stress due to cutting or temperature change (for example, heating at a very high temperature such as a reflow process or a cooling cycle). Such a characteristic is sometimes referred to as “crack resistance”). This is because if the reflector is cracked, the light reflectivity is lowered (that is, the light extraction efficiency is lowered), and it is difficult to ensure the reliability of the light emitting device.
　さらには、上記リフレクターを成形する際に、成形物に反りが生じにくい特性も求められる。リフレクター成型物に反りが生じると、寸法安定性が損なわれて、光半導体装置の品質が低下するからである。 Furthermore, when the reflector is molded, the molded product is also required to have a characteristic that warpage does not easily occur. This is because if the reflector molding is warped, the dimensional stability is impaired and the quality of the optical semiconductor device is lowered.
　本発明者は、上記本発明の第１の課題を解決するため鋭意検討した結果、特定のエポキシ化合物と、シリコーンゴム粒子以外のゴム粒子と、無機充填剤と、白色顔料と、応力緩和剤とを含み、さらに硬化剤及び硬化促進剤、又は、硬化触媒を含み、且つ、２５℃で液状である硬化性樹脂組成物が、無機充填剤や白色顔料の充填量を増やしてもコンプレッション成型が可能であり、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくい硬化物を形成できることを見出した。
　さらに、上記本発明の第２の課題を解決するため鋭意検討した結果、脂環式エポキシ化合物（Ａ）、シリコーンゴム粒子以外のゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、応力緩和剤（Ｈ）、分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）、分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含み、２５℃において液状である光反射用硬化性樹脂組成物、又は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化触媒（Ｇ）、応力緩和剤（Ｈ）、分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）、分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含み、２５℃において液状である光反射用硬化性樹脂組成物が、無機充填剤や白色顔料の充填量を増やしてもコンプレッション成型が可能であり、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくく、エッチング液に溶出しにくい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 first problem of the present invention, the present inventor has found that a specific epoxy compound, rubber particles other than silicone rubber particles, an inorganic filler, a white pigment, a stress relaxation agent, In addition, a curable resin composition that contains a curing agent and a curing accelerator, or a curing catalyst, and is liquid at 25 ° C., can be compression molded even if the amount of inorganic filler or white pigment is increased. The present inventors have found that a cured product having high light reflectivity, excellent heat resistance and light resistance, and light reflectivity hardly deteriorates over time can be formed.
Furthermore, as a result of intensive studies to solve the second problem of the present invention, alicyclic epoxy compound (A), rubber particles other than silicone rubber particles (B), white pigment (C), inorganic filler (D ), Curing agent (E), curing accelerator (F), stress relaxation agent (H), isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, and two or more epoxy groups in the molecule. A curable resin composition for light reflection, which contains a siloxane derivative (J) and an alicyclic polyester resin (K), and is liquid at 25 ° C., or an alicyclic epoxy compound (A), rubber particles (B) , White pigment (C), inorganic filler (D), curing catalyst (G), stress relaxation agent (H), isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, two in the molecule Siloxane derivatives having the above epoxy groups J), and the curable resin composition for light reflection, which contains alicyclic polyester resin (K) and is liquid at 25 ° C., can be compression molded even if the filling amount of the inorganic filler and the white pigment is increased. The present inventors have found that a cured product having high light reflectivity, excellent heat resistance and light resistance, light reflectivity hardly deteriorates with time, and hardly eluted into an etching solution can be formed. The present invention has been completed based on these findings.
　すなわち、本発明の第１態様は、脂環式エポキシ化合物（Ａ）、シリコーンゴム粒子以外のゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、及び応力緩和剤（Ｈ）を含有し、さらに、硬化剤（Ｅ）及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）を含有し、２５℃において液状であることを特徴とする光反射用硬化性樹脂組成物を提供する。 That is, the first aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H). A curable resin composition for light reflection, further comprising a curing agent (E) and a curing accelerator (F) or a curing catalyst (G) and being liquid at 25 ° C. provide.
　また、本発明の第２態様は、脂環式エポキシ化合物（Ａ）、シリコーンゴム粒子以外のゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、応力緩和剤（Ｈ）、分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）、分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含有し、さらに、硬化剤（Ｅ）、及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）を含有し、２５℃において液状であることを特徴とする光反射用硬化性樹脂組成物を提供する。 In addition, the second aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), a stress relaxation agent (H), Containing an isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, a siloxane derivative (J) having two or more epoxy groups in the molecule, and an alicyclic polyester resin (K); A curable resin composition for light reflection, which contains a curing agent (E) and a curing accelerator (F) or a curing catalyst (G) and is liquid at 25 ° C., is provided.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物において、前記応力緩和剤（Ｈ）は、シリコーンゴム粒子（Ｈ１）及びシリコーンオイル（Ｈ２）からなる群より選択される少なくとも１種であってもよい。 In the curable resin composition for light reflection according to the first aspect or the second aspect, the stress relaxation agent (H) is at least one selected from the group consisting of silicone rubber particles (H1) and silicone oil (H2). It may be.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物において、前記シリコーンゴム粒子（Ｈ１）は、シリコーンレジンを表面に備える架橋されたポリジメチルシロキサンであってもよい。 In the curable resin composition for light reflection according to the first aspect or the second aspect, the silicone rubber particles (H1) may be cross-linked polydimethylsiloxane having a silicone resin on the surface.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物において、前記シリコーンオイル（Ｈ２）は、エポキシ当量３０００～１５０００の下記式（１）で表される構造を有するポリアルキレンエーテル変性シリコーン化合物であってもよい。
Figure JPOXMLDOC01-appb-C000005
 ［式中、ｘは８０～１４０の整数、ｙは１～５の整数、ｚは５～２０の整数である。Ｒ9は炭素数２又は３のアルキレン基である。Ａは、下記式（１ａ）で表される構造を有するポリアルキレンエーテル基である。
Figure JPOXMLDOC01-appb-C000006
 （式中、ａ及びｂはそれぞれ独立して、０～４０の整数である。Ｂは水素原子またはメチル基である。）］ In the curable resin composition for light reflection according to the first aspect or the second aspect, the silicone oil (H2) is a polyalkylene ether-modified silicone having a structure represented by the following formula (1) having an epoxy equivalent of 3000 to 15000. It may be a compound.
Figure JPOXMLDOC01-appb-C000005
 [Wherein x is an integer from 80 to 140, y is an integer from 1 to 5, and z is an integer from 5 to 20. R 9 is an alkylene group having 2 or 3 carbon atoms. A is a polyalkylene ether group having a structure represented by the following formula (1a).
Figure JPOXMLDOC01-appb-C000006
 (In the formula, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group.)]
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物において、前記ゴム粒子（Ｂ）は、（メタ）アクリル酸エステルを必須のモノマー成分とするポリマーで構成されていてもよく、表面にヒドロキシ基及び／又はカルボキシ基を有し、前記ゴム粒子（Ｂ）の平均粒子径が１０～５００ｎｍであり、最大粒子径が５０～１０００ｎｍであってもよい。 In the curable resin composition for light reflection according to the first aspect or the second aspect, the rubber particles (B) may be composed of a polymer containing (meth) acrylic acid ester as an essential monomer component, The rubber particles (B) may have an average particle size of 10 to 500 nm and a maximum particle size of 50 to 1000 nm.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物において、前記脂環式エポキシ化合物（Ａ）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 resin composition for light reflection according to the first aspect or the second aspect, the alicyclic epoxy compound (A) may be a compound having a cyclohexene oxide group.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物において、前記脂環式エポキシ化合物（Ａ）は、下記式（Ｉ－１）
Figure JPOXMLDOC01-appb-C000007
 で表される化合物を含んでいてもよい。 In the curable resin composition for light reflection according to the first aspect or the second aspect, the alicyclic epoxy compound (A) is represented by the following formula (I-1):
Figure JPOXMLDOC01-appb-C000007
 The compound represented by these may be included.
　前記第２態様の光反射用硬化性樹脂組成物において、前記イソシアヌル酸誘導体（Ｉ）が、下記式（III－１）
Figure JPOXMLDOC01-appb-C000008
 ［式（III－１）中、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。］
で表される化合物であってもよい。 In the curable resin composition for light reflection according to the second aspect, the isocyanuric acid derivative (I) is represented by the following formula (III-1):
Figure JPOXMLDOC01-appb-C000008
 [In Formula (III-1), R 7 and R 8 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
The compound represented by these may be sufficient.
　前記第２態様の光反射用硬化性樹脂組成物において、前記脂環式ポリエステル樹脂（Ｋ）が、主鎖に脂環を有する脂環式ポリエステル樹脂であってもよい。 In the curable resin composition for light reflection according to the second aspect, the alicyclic polyester resin (K) may be an alicyclic polyester resin having an alicyclic ring in the main chain.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物において、前記白色顔料（Ｃ）が、酸化チタン、酸化ジルコニウム、酸化亜鉛、及び硫酸バリウムからなる群より選択される少なくとも１種であってもよく、
　前記無機充填剤（Ｄ）が、シリカ、アルミナ、窒化ケイ素、窒化アルミニウム、及び窒化ホウ素からなる群より選択される少なくとも１種であってもよい。 In the curable resin composition for light reflection according to the first aspect or the second aspect, the white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate. May be,
The inorganic filler (D) may be at least one selected from the group consisting of silica, alumina, silicon nitride, aluminum nitride, and boron nitride.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物は、トランスファー成型用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 light reflecting curable resin composition of the first aspect or the second aspect may be a resin composition for transfer molding or compression molding.
　前記第１態様又は第２態様の光反射用硬化性樹脂組成物は、リフレクター形成用樹脂組成物であってもよい。 The light-reflective curable resin composition of the first aspect or the second aspect may be a reflector-forming resin composition.
　また、本発明は、前記第１態様又は第２態様の光反射用硬化性樹脂組成物の硬化物を提供する。 Moreover, this invention provides the hardened | cured material of the curable resin composition for light reflections of the said 1st aspect or a 2nd aspect.
　また、本発明は、光半導体素子と、前記第１態様又は第２態様の光反射用硬化性樹脂組成物の硬化物からなるリフレクターとを少なくとも備えることを特徴とする光半導体装置を提供する。 The present invention also provides an optical semiconductor device comprising at least an optical semiconductor element and a reflector made of a cured product of the light reflecting curable resin composition of the first aspect or the second aspect.
　本発明の第１態様の光反射用硬化性樹脂組成物は上記構成を有するため、コンプレッション成型により、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくい硬化物を形成することができる。このため、経時で光の輝度が低下しにくく、信頼性の高い光半導体装置を提供することができる。
　また、本発明の第２態様の硬化性樹脂組成物は上記構成を有するため、コンプレッション成型により、高い光反射性を有し、且つ、耐熱性及び耐光性に優れ、光反射性が経時で低下しにくく、エッチング液に溶出しにくい硬化物を形成することができる。このため、経時で光の輝度が低下しにくく、信頼性の高い光半導体装置を提供することができる。 Since the curable resin composition for light reflection according to the first aspect of the present invention has the above-described configuration, it has high light reflectivity by compression molding, and has excellent heat resistance and light resistance. A cured product that is difficult to decrease can be formed. Therefore, it is possible to provide a highly reliable optical semiconductor device in which the luminance of light hardly decreases over time.
In addition, since the curable resin composition of the second aspect of the present invention has the above-described configuration, it has high light reflectivity by compression molding, is excellent in heat resistance and light resistance, and light reflectivity decreases with time. It is possible to form a cured product that is difficult to be dissolved and hardly eluted in the etching solution. Therefore, it is possible to provide a highly reliable optical semiconductor device in which the luminance of light hardly decreases over time.
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).
＜光反射用硬化性樹脂組成物＞
　本発明の第１態様の光反射用硬化性樹脂組成物（単に「本発明の第１態様の硬化性樹脂組成物」と称する場合がある）は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、及び応力緩和剤（Ｈ）を含有し、さらに、硬化剤（Ｅ）及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）を含有し、２５℃において液状である硬化性樹脂組成物である。言い換えると、本発明の第１態様の光反射用硬化性樹脂組成物は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、応力緩和剤（Ｈ）、硬化剤（Ｅ）、及び硬化促進剤（Ｆ）を必須成分として含む、２５℃において液状である硬化性樹脂組成物、又は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、応力緩和剤（Ｈ）、及び硬化触媒（Ｇ）を必須成分として含む、２５℃において液状である硬化性樹脂組成物である。 <Curable resin composition for light reflection>
The curable resin composition for light reflection according to the first aspect of the present invention (sometimes simply referred to as “the curable resin composition according to the first aspect of the present invention”) is an alicyclic epoxy compound (A), rubber particles. (B), white pigment (C), inorganic filler (D), and stress relieving agent (H), and further, curing agent (E) and curing accelerator (F), or curing catalyst (G) Is a curable resin composition that is liquid at 25 ° C. In other words, the curable resin composition for light reflection according to the first aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), stress relaxation. A curable resin composition which is liquid at 25 ° C. containing an agent (H), a curing agent (E), and a curing accelerator (F) as essential components, or an alicyclic epoxy compound (A), rubber particles ( It is a curable resin composition that is liquid at 25 ° C. and contains B), a white pigment (C), an inorganic filler (D), a stress relaxation agent (H), and a curing catalyst (G) as essential components.
　また、本発明の第２態様の光反射用硬化性樹脂組成物（単に「本発明の第２態様の硬化性樹脂組成物」と称する場合がある）は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、応力緩和剤（Ｈ）、分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）、分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含有し、さらに硬化剤（Ｅ）及び硬化促進剤（Ｆ）、又は硬化触媒（Ｇ）を含有し、２５℃において液状であることを特徴とする硬化性樹脂組成物である。なお、前記分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）を「イソシアヌル酸誘導体（Ｉ）」と称する場合がある。また、分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）を「シロキサン誘導体（Ｊ）」と称する場合がある。 Moreover, the curable resin composition for light reflection of the second aspect of the present invention (sometimes simply referred to as “the curable resin composition of the second aspect of the present invention”) is an alicyclic epoxy compound (A), Rubber particles (B), white pigment (C), inorganic filler (D), stress relaxation agent (H), isocyanuric acid derivative (I) having one or more oxirane rings in the molecule, two or more in the molecule Containing a siloxane derivative (J) having an epoxy group and an alicyclic polyester resin (K), further containing a curing agent (E) and a curing accelerator (F), or a curing catalyst (G), 25 ° C. It is a curable resin composition characterized by being liquid. The isocyanuric acid derivative (I) having one or more oxirane rings in the molecule may be referred to as “isocyanuric acid derivative (I)”. Further, the siloxane derivative (J) having two or more epoxy groups in the molecule may be referred to as “siloxane derivative (J)”.
　言い換えると、本発明の第２態様の硬化性樹脂組成物は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を必須成分として含む２５℃で液状である光反射用硬化性樹脂組成物、又は脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化触媒（Ｇ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を必須成分として含む２５℃で液状である硬化性樹脂組成物である。なお、本発明の第１態様又は第２態様の硬化性樹脂組成物（単に「本発明の硬化性樹脂組成物」と称する場合がある）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、本発明の第１態様又は第２態様の硬化性樹脂組成物は、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。 In other words, the curable resin composition according to the second aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), and a curing agent (E). , A light-reflective material that is liquid at 25 ° C. containing essential components of a curing accelerator (F), a stress relaxation agent (H), an isocyanuric acid derivative (I), a siloxane derivative (J), and an alicyclic polyester resin (K) Curable resin composition, or alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), curing catalyst (G), stress relaxation agent (H), isocyanuric It is a curable resin composition that is liquid at 25 ° C. and contains an acid derivative (I), a siloxane derivative (J), and an alicyclic polyester resin (K) as essential components. In addition, the curable resin composition of the first aspect or the second aspect of the present invention (sometimes simply referred to as “the curable resin composition of the present invention”) is not limited to the above essential components, but may be other as required. May be included. In addition, the curable resin composition of the 1st aspect or 2nd aspect of this invention can be used as a thermosetting composition (thermosetting epoxy resin composition) which can be hardened | cured by heating and can be converted into a hardened | cured material.
　なお、本明細書において「光反射用硬化性樹脂組成物」とは、光反射性を有する硬化物を形成可能な硬化性樹脂組成物をいう。具体的には、例えば、波長４５０ｎｍの光に対する反射率が５０％以上（特に、８０％以上）である硬化物を形成可能な硬化性樹脂組成物が好ましい。 In the present specification, the “curable resin composition for light reflection” refers to a curable resin composition capable of forming a cured product having light reflectivity. Specifically, for example, a curable resin composition capable of forming a cured product having a reflectance of 50% or more (particularly 80% or more) with respect to light having a wavelength of 450 nm is preferable.
　本発明の第１態様又は第２態様の硬化性樹脂組成物は２５℃において液体であることにより、コンプレッション成型に適する傾向があり、その硬化物（リフレクター）は、光反射性に優れ、且つ、耐熱性及び耐光性に優れる傾向がある。なお、本明細書において「２５℃において液状」とは、常圧において２５℃で測定した粘度が１００００００ｍＰａ・ｓ以下（好ましくは、８０００００ｍＰａ・ｓ以下）であることをいう。なお、上記粘度は、例えば、デジタル粘度計（型番「ＤＶＵ－ＥＩＩ型」、（株）トキメック製）を用いて、ローター：標準１°３４’×Ｒ２４、温度：２５℃、回転数：０．５～１０ｒｐｍの条件で測定することができる。 The curable resin composition of the first aspect or the second aspect of the present invention tends to be suitable for compression molding because it is liquid at 25 ° C., and the cured product (reflector) is excellent in light reflectivity, and There is a tendency to be excellent in heat resistance and light resistance. In the present specification, “liquid at 25 ° C.” means that the viscosity measured at 25 ° C. at normal pressure is 1000000 mPa · s or less (preferably 800000 mPa · s or less). The above viscosity is measured using, for example, a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, temperature: 25 ° C., rotational speed: 0.00. It can be measured at 5 to 10 rpm.
　２５℃において液体である本発明の第１態様又は第２態様の硬化性樹脂組成物は、例えば、成分（例えば、脂環式エポキシ化合物（Ａ）、液状の応力緩和剤（Ｈ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、硬化触媒（Ｇ）等）として、２５℃で液体の成分を用いることにより得やすくなる。なお、上記成分として２５℃で固体の成分を用いてもよいが、その含有量は、本発明の硬化性樹脂組成物が２５℃において液状となるように調整される。また、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、固体の応力緩和剤（Ｈ）等の２５℃で固体である成分の含有量を、本発明の効果を損なわない範囲内で調整することによっても得やすくなる。 The curable resin composition of the first aspect or the second aspect of the present invention that is liquid at 25 ° C. includes, for example, components (for example, an alicyclic epoxy compound (A), a liquid stress relaxation agent (H), and a curing agent. (E), a curing accelerator (F), a curing catalyst (G) and the like) are easily obtained by using a liquid component at 25 ° C. In addition, although a solid component may be used as a said component at 25 degreeC, the content is adjusted so that the curable resin composition of this invention may become a liquid state at 25 degreeC. Further, the content of components that are solid at 25 ° C., such as rubber particles (B), white pigment (C), inorganic filler (D), and solid stress relieving agent (H), does not impair the effects of the present invention. It can be easily obtained by adjusting within the range.
［脂環式エポキシ化合物（Ａ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物の必須成分である脂環式エポキシ化合物（脂環式エポキシ樹脂）（Ａ）は、分子内（一分子中）に脂環（脂肪族炭化水素環）構造とエポキシ基（オキシラニル基）とを少なくとも有する化合物であり、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。ただし、本発明の第２態様の硬化性樹脂組成物においては、脂環式エポキシ化合物（Ａ）からはイソシアヌル酸誘導体（Ｉ）、及びシロキサン誘導体（Ｊ）に該当するものが除かれる。脂環式エポキシ化合物（Ａ）としては、より具体的には、例えば、（ｉ）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基（脂環式エポキシ基）を有する化合物、（ii）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が挙げられる。 [Alicyclic epoxy compound (A)]
The alicyclic epoxy compound (alicyclic epoxy resin) (A), which is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention, has an alicyclic (fatty) in the molecule (in one molecule). Group or hydrocarbon ring) and an epoxy group (oxiranyl group), and known or conventional alicyclic epoxy compounds can be used. However, in the curable resin composition of the second aspect of the present invention, those corresponding to the isocyanuric acid derivative (I) and the siloxane derivative (J) are excluded from the alicyclic epoxy compound (A). More specifically, as the alicyclic epoxy compound (A), for example, (i) an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring And (ii) a compound having an epoxy group directly bonded to the alicyclic ring with a single bond.
　上述の（ｉ）脂環式エポキシ基を有する化合物としては、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、硬化性樹脂組成物の硬化性及び硬化物（リフレクター）の耐熱性及び耐光性（特に、耐紫外線性）の観点で、シクロヘキセンオキシド基が好ましい。特に、硬化物（リフレクター）の耐熱性及び耐光性（特に、耐紫外線性）の観点で、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。
Figure JPOXMLDOC01-appb-C000009
 As the above-mentioned (i) compound having an alicyclic epoxy group, a known or conventional 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 the curability of the curable resin composition and the heat resistance and light resistance (particularly UV resistance) of the cured product (reflector). In particular, from the viewpoint of heat resistance and light resistance (particularly, ultraviolet resistance) of the cured product (reflector), a compound having two or more cyclohexene oxide groups in the molecule is preferable, and more preferably represented by the following formula (I). It is a compound.
Figure JPOXMLDOC01-appb-C000009
　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」と称する場合がある）、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、及び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 (sometimes referred to as an “epoxidized alkenylene group”), a carbonyl group, Examples include an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked. 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）ビシクロヘキサン等が挙げられる。 Examples of the compound in which X in the formula (I) is a single bond include (3,4,3 ′, 4′-diepoxy) bicyclohexane 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 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）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 (epoxidized alkenylene group) include, for example, vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene. And linear or branched alkenylene groups having 2 to 8 carbon atoms such as a group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group. 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Ｘにおける連結基としては、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 in X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxy. 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。
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
 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-C000010
Figure JPOXMLDOC01-appb-C000011
　上述の（ii）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）が挙げられる。
Figure JPOXMLDOC01-appb-C000012
 Examples of the compound (ii) having an epoxy group bonded directly to the alicyclic ring with a single bond include a compound (epoxy resin) represented by the following formula (II).
Figure JPOXMLDOC01-appb-C000012
　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。
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
 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 carbon atom at the 4th or 5th position 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-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。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 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；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 An acylamino group such as an amino group or a propionylamino group (preferably a C 1-11 acylamino group); an oxetanyl group-containing group such as an ethyl oxetanyloxy group; an acyl group such as an acetyl group or a propionyl group; an oxo group; It includes groups attached via a C 1-6 alkylene group optionally It is. 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％以上であると、硬化物の耐熱性や耐光性、機械特性等がより向上する傾向がある。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. There exists a tendency for the heat resistance of a hardened | cured material, light resistance, a mechanical characteristic, etc. to improve that the said ratio is 40 mol% or more. 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－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-vinylcyclohexane (3-vinyl-7-oxabicyclo [4.1.0] heptane) is subjected to ring-opening polymerization (cationic polymerization), and then Manufactured by epoxidation with an oxidizing agent.
　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 alcohol 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－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－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 1,2-epoxy-4-vinylcyclohexane can be produced by a known or commonly used method, and is not particularly limited. For example, 4-vinylcyclohexene obtained by dimerization reaction of butadiene is replaced with an oxidizing agent such as peracetic acid. Obtained by partial epoxidation using. Moreover, as 1,2-epoxy-4-vinylcyclohexane, 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以上であると、硬化物の機械強度や耐熱性、耐光性が向上する傾向がある。一方、重量平均分子量が１０００００以下であると、粘度が高くなり過ぎず成型時の流動性を低く維持しやすい傾向がある。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 300 or more, the mechanical strength, heat resistance, and light resistance of the cured product tend to be improved. On the other hand, when the weight average molecular weight is 100,000 or less, the viscosity does not become too high and the fluidity during molding tends to be maintained low. The weight average molecular weight is measured by a gel permeation chromatography (GPC) method.
　式（II）で表される化合物のエポキシ基の当量（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以上であると、硬化物が脆くなりにくい傾向がある。一方、エポキシ当量が１０００以下であると、硬化物の機械強度が向上する傾向がある。なお、エポキシ当量は、ＪＩＳ　Ｋ７２３６：２００１に準じて測定される。 The equivalent (epoxy equivalent) of the epoxy group of the compound represented by the formula (II) is not particularly limited, but is preferably 50 to 1000, more preferably 100 to 500. When the epoxy equivalent is 50 or more, the cured product tends not to be brittle. On the other hand, when the epoxy equivalent is 1000 or less, the mechanical strength of the cured product tends to be improved. The epoxy equivalent is measured according to JIS K7236: 2001.
　本発明の第１態様又は第２態様の硬化性樹脂組成物において脂環式エポキシ化合物（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、脂環式エポキシ化合物（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）等の市販品を使用することもできる。 In the curable resin composition of the first aspect or the second aspect of the present invention, the alicyclic epoxy compound (A) can be used singly or in combination of two or more. The alicyclic epoxy compound (A) can also be produced by a known or commonly used method. For example, trade names “Celoxide 2021P”, “Celoxide 2081”, “EHPE3150” (above, manufactured by Daicel Corporation) ) Etc. can also be used.
　脂環式エポキシ化合物（Ａ）は、調合時、及び注型時などの作業性の点から、常温（２５℃）で液状を呈するものが好ましい。また、常温（２５℃）で固体である脂環式エポキシ化合物（Ａ）であっても、配合した後に液状を呈するものであれば、含有していてもよい。 The alicyclic epoxy compound (A) preferably exhibits a liquid state at normal temperature (25 ° C.) from the viewpoint of workability during preparation and casting. Moreover, even if it is an alicyclic epoxy compound (A) which is solid at normal temperature (25 degreeC), as long as it shows liquid state after mix | blending, you may contain.
　中でも、本発明の第１態様又は第２態様の硬化性樹脂組成物は、硬化物（リフレクター）の光反射性、耐熱性、及び耐光性がより向上する観点から、（ｉ）脂環式エポキシ基を有する化合物を少なくとも含むことが好ましく、さらに（ii）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を含むことがより好ましい。 Among them, the curable resin composition of the first aspect or the second aspect of the present invention is (i) an alicyclic epoxy from the viewpoint of further improving the light reflectivity, heat resistance, and light resistance of the cured product (reflector). It is preferable to include at least a compound having a group, and it is more preferable to include (ii) a compound having an epoxy group bonded directly to the alicyclic ring with a single bond.
　本発明の第１態様の硬化性樹脂組成物における脂環式エポキシ化合物（Ａ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、１．５～６０重量％が好ましく、より好ましくは２～５０重量％、さらに好ましくは５～４０重量％である。脂環式エポキシ化合物（Ａ）の含有量を１．５重量％以上とすることにより、硬化物（リフレクター）の耐熱性（特に、耐黄変性）及び耐光性（特に、耐紫外線性）がより向上する傾向がある。一方、脂環式エポキシ化合物（Ａ）の含有量を６０重量％以下とすることにより、硬化物（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抑制される傾向がある。 The content (blending amount) of the alicyclic epoxy compound (A) in the curable resin composition of the first aspect of the present invention is not particularly limited, but is 1 with respect to the curable resin composition (100% by weight). It is preferably 5 to 60% by weight, more preferably 2 to 50% by weight, still more preferably 5 to 40% by weight. By setting the content of the alicyclic epoxy compound (A) to 1.5% by weight or more, the heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) of the cured product (reflector) are further improved. There is a tendency to improve. On the other hand, by setting the content of the alicyclic epoxy compound (A) to 60% by weight or less, the linear expansion coefficient of the cured product (reflector) is reduced, and defects such as warping of the lead frame in the substrate for mounting an optical semiconductor element It tends to be suppressed.
　本発明の第２態様の硬化性樹脂組成物における脂環式エポキシ化合物（Ａ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．１～６０重量％が好ましく、より好ましくは０．３～５０重量％、さらに好ましくは０．５～４０重量％である。脂環式エポキシ化合物（Ａ）の含有量を０．１重量％以上とすることにより、硬化物（リフレクター）の耐熱性（特に、耐黄変性）及び耐光性（特に、耐紫外線性）がより向上する傾向がある。一方、脂環式エポキシ化合物（Ａ）の含有量を６０重量％以下とすることにより、硬化物（リフレクター）の耐熱性及び耐光性がより向上し、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抑制される傾向がある。 The content (blending amount) of the alicyclic epoxy compound (A) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0 with respect to the curable resin composition (100 wt%). It is preferably 1 to 60% by weight, more preferably 0.3 to 50% by weight, and still more preferably 0.5 to 40% by weight. By setting the content of the alicyclic epoxy compound (A) to 0.1% by weight or more, the heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) of the cured product (reflector) are further improved. There is a tendency to improve. On the other hand, by setting the content of the alicyclic epoxy compound (A) to 60% by weight or less, the heat resistance and light resistance of the cured product (reflector) are further improved, the linear expansion coefficient is reduced, and the optical semiconductor element is mounted. There is a tendency that the occurrence of defects such as lead frame warpage in the circuit board is suppressed.
　本発明の第１態様の硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量（１００重量％）に対する脂環式エポキシ化合物（Ａ）の割合は、特に限定されないが、５０重量％以上（例えば、５０～１００重量％）が好ましく、より好ましくは６０重量％以上、さらに好ましくは８０重量％以上、特に好ましくは９０重量％以上である。上記割合を５０重量％以上とすることにより、硬化物（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 alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition of the first aspect of the present invention is not particularly limited, but is 50% by weight or more ( For example, it is preferably 50 to 100% by weight), more preferably 60% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight or more. By making the said ratio 50 weight% or more, there exists a tendency which the heat resistance and light resistance of hardened | cured material (reflector) improve more.
　本発明の第２態様の硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量（１００重量％）に対する脂環式エポキシ化合物（Ａ）の割合は、特に限定されないが、例えば、１～９０重量％が好ましく、より好ましくは５～８０重量％、さらに好ましくは１０～７０重量％である。上記範囲内とすることで、硬化物（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。なお、本発明の第２態様の硬化性樹脂組成物に含まれるエポキシ基を有する化合物としては、例えば、脂環式エポキシ化合物（Ａ）、イソシアヌル酸誘導体（Ｉ）、及びシロキサン誘導体（Ｊ）、エポキシ基を有する応力緩和剤（Ｈ）（エポキシ変性シリコーンオイルなど）等が挙げられる。 The ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition of the second aspect of the present invention is not particularly limited. % By weight is preferred, more preferably 5 to 80% by weight, and still more preferably 10 to 70% by weight. By making it in the said range, there exists a tendency for the heat resistance and light resistance of hardened | cured material (reflector) to improve more. Examples of the compound having an epoxy group contained in the curable resin composition of the second aspect of the present invention include an alicyclic epoxy compound (A), an isocyanuric acid derivative (I), and a siloxane derivative (J), Examples include a stress relaxation agent (H) having an epoxy group (such as an epoxy-modified silicone oil).
　なお、本明細書において、本発明の第１態様又は第２態様の硬化性樹脂組成物に含まれる各成分（例えば、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、硬化触媒（Ｇ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、脂環式ポリエステル樹脂（Ｋ）等）の含有量は、それぞれ、合計が１００重量％以下となるように、記載の範囲内から適宜選択することができる。 In addition, in this specification, each component (for example, alicyclic epoxy compound (A), rubber particle (B), white pigment (C) contained in the curable resin composition of the first aspect or the second aspect of the present invention. ), Inorganic filler (D), curing agent (E), curing accelerator (F), curing catalyst (G), stress relaxation agent (H), isocyanuric acid derivative (I), siloxane derivative (J), alicyclic ring The content of the formula polyester resin (K) and the like can be appropriately selected from the range described so that the total is 100% by weight or less.
［シリコーンゴム粒子以外のゴム粒子（Ｂ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物の必須成分であるシリコーンゴム粒子以外のゴム粒子（Ｂ）（以下、単に「ゴム粒子（Ｂ）」と称する場合がある）は、ゴム弾性を有するシリコーンゴム粒子以外の粒子である。本発明の第１態様の硬化性樹脂組成物は、ゴム粒子（Ｂ）を脂環式エポキシ化合物（Ａ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、及び応力緩和剤（Ｈ）と組み合わせて用いることにより、コンプレッション成型により形成される硬化物の光反射性、耐熱性、耐光性、及び耐クラック性に優れる傾向がある。また、本発明の第２態様の硬化性樹脂組成物は、ゴム粒子（Ｂ）を脂環式エポキシ化合物（Ａ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）と組み合わせて用いることにより、コンプレッション成型により形成される硬化物の光反射性、耐熱性、耐光性、及び耐クラック性に優れる傾向がある。 [Rubber particles other than silicone rubber particles (B)]
The rubber particles (B) other than the silicone rubber particles that are essential components of the curable resin composition of the first aspect or the second aspect of the present invention (hereinafter may be simply referred to as “rubber particles (B)”), Particles other than silicone rubber particles having rubber elasticity. The curable resin composition of the first aspect of the present invention comprises a rubber particle (B) containing an alicyclic epoxy compound (A), a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H). When used in combination, the cured product formed by compression molding tends to be excellent in light reflectivity, heat resistance, light resistance, and crack resistance. Moreover, the curable resin composition of the second aspect of the present invention comprises a rubber particle (B) containing an alicyclic epoxy compound (A), a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H). , Isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K) in combination for use in the light reflectivity, heat resistance, light resistance of the cured product formed by compression molding, and There is a tendency to be excellent in crack resistance.
　ゴム粒子（Ｂ）としては、シリコーンゴム粒子以外のものであれば、公知乃至慣用のゴム粒子を特に制限なく使用することができ、例えば、粒子状ＮＢＲ（アクリロニトリル－ブタジエンゴム）、反応性末端カルボキシ基ＮＢＲ（ＣＴＢＮ）、メタルフリーＮＢＲ、粒子状ＳＢＲ（スチレン－ブタジエンゴム）等のゴム粒子が挙げられる。ゴム粒子（Ｂ）としては、分散性が良好であり靭性向上（耐クラック性向上）の効果を得られやすい観点から、ゴム弾性を有するコア部分と、該コア部分を被覆する少なくとも１層のシェル層とからなる多層構造（コアシェル構造）を有するゴム粒子（以下、「コアシェル型ゴム粒子」と称する場合がある）が好ましい。ゴム粒子（Ｂ）は、硬化物の耐熱性及び耐光性がより向上する観点から、特に、（メタ）アクリル酸エステルを必須のモノマー成分とするポリマー（重合体）で構成され、表面に脂環式エポキシ化合物（Ａ）等のエポキシ基を有する化合物と反応し得る官能基としてヒドロキシ基及び／又はカルボキシ基（ヒドロキシ基及びカルボキシ基のいずれか一方又は両方）を有するゴム粒子が好ましい。即ち、ゴム粒子（Ｂ）は、（メタ）アクリル酸エステルを必須のモノマー成分とするポリマー（アクリル系ポリマー）で構成された、コアシェル型ゴム粒子であることが特に好ましい。なお、本発明の第１態様又は第２態様の硬化性樹脂組成物においてゴム粒子（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。 As the rubber particles (B), any known or commonly used rubber particles can be used without particular limitation as long as they are other than silicone rubber particles. For example, particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxy Examples thereof include rubber particles such as group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber). The rubber particles (B) have a core part having rubber elasticity and at least one shell covering the core part from the viewpoint of good dispersibility and an effect of improving toughness (crack resistance improvement). Rubber particles having a multilayer structure (core-shell structure) composed of layers (hereinafter sometimes referred to as “core-shell type rubber particles”) are preferred. From the viewpoint of further improving the heat resistance and light resistance of the cured product, the rubber particles (B) are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and an alicyclic ring on the surface. Rubber particles having a hydroxy group and / or a carboxy group (either one or both of a hydroxy group and a carboxy group) as a functional group capable of reacting with a compound having an epoxy group such as the formula epoxy compound (A) are preferred. That is, the rubber particles (B) are particularly preferably core-shell type rubber particles composed of a polymer (acrylic polymer) containing (meth) acrylic acid ester as an essential monomer component. In the curable resin composition of the first aspect or the second aspect of the present invention, the rubber particles (B) can be used singly or in combination of two or more.
　ゴム粒子（Ｂ）がコアシェル型ゴム粒子である場合、上記ゴム弾性を有するコア部分を構成するポリマーは、シリコーン化合物以外であれば、特に限定されないが、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等の（メタ）アクリル酸エステルを必須のモノマー成分として含むポリマーであることが好ましい。上記ゴム弾性を有するコア部分を構成するポリマーは、その他、例えば、スチレン、α－メチルスチレン等の芳香族ビニル；アクリロニトリル、メタクリロニトリル等のニトリル；ブタジエン、イソプレン等の共役ジエン；エチレン、プロピレン、イソブテン等のα－オレフィン等をモノマー成分として含んでいてもよい。 When the rubber particles (B) are core-shell type rubber particles, the polymer constituting the core portion having rubber elasticity is not particularly limited as long as it is other than a silicone compound, but methyl (meth) acrylate, (meth) acrylic It is preferable that it is a polymer which contains (meth) acrylic acid ester, such as ethyl acid and butyl (meth) acrylate, as an essential monomer component. The polymer constituting the core part having rubber elasticity includes, for example, aromatic vinyl such as styrene and α-methylstyrene; nitrile such as acrylonitrile and methacrylonitrile; conjugated diene such as butadiene and isoprene; ethylene, propylene, An α-olefin such as isobutene may be included as a monomer component.
　中でも、上記ゴム弾性を有するコア部分を構成するポリマーは、モノマー成分として、（メタ）アクリル酸エステルと共に、芳香族ビニル、ニトリル、及び共役ジエンからなる群より選択された一種又は二種以上を組み合わせて含むことが好ましい。即ち、上記コア部分を構成するポリマーとしては、例えば、（メタ）アクリル酸エステル／芳香族ビニル、（メタ）アクリル酸エステル／共役ジエン等の二元共重合体、（メタ）アクリル酸エステル／芳香族ビニル／共役ジエン等の三元共重合体等が挙げられる。 Among them, the polymer constituting the core portion having rubber elasticity is combined with one or more selected from the group consisting of aromatic vinyl, nitrile, and conjugated diene together with (meth) acrylic acid ester as a monomer component. It is preferable to include. That is, as the polymer constituting the core portion, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers, (meth) acrylic acid ester / aromatic And terpolymers such as group vinyl / conjugated dienes.
　上記コア部分を構成するポリマーは、その他のモノマー成分として、ジビニルベンゼン、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジアリルマレエート、トリアリルシアヌレート、ジアリルフタレート、ブチレングリコールジアクリレート等の分子内に２個以上の反応性官能基を有する反応性架橋モノマーを含有していてもよい。 The polymer constituting the core part includes, as other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc. A reactive crosslinking monomer having two or more reactive functional groups in the molecule may be contained.
　上記コア部分は、中でも、（メタ）アクリル酸エステル／芳香族ビニルの二元共重合体（特に、アクリル酸ブチル／スチレン）、又は（メタ）アクリル酸エステル／芳香族ビニル／その他のモノマーの三元共重合体（特に、アクリル酸ブチル／スチレン／ジビニルベンゼン）より構成されたコア部分であることが、コアシェル型ゴム粒子の屈折率を容易に調整できる点で好ましい。 The core part is composed of (meth) acrylic acid ester / aromatic vinyl binary copolymer (particularly butyl acrylate / styrene) or (meth) acrylic acid ester / aromatic vinyl / other monomers. A core part composed of an original copolymer (particularly butyl acrylate / styrene / divinylbenzene) is preferable in that the refractive index of the core-shell type rubber particles can be easily adjusted.
　上記コア部分を構成するポリマーのガラス転移温度は、特に限定されないが、－１００～１０℃が好ましく、より好ましくは－８０～－１０℃、さらに好ましくは－６０～－２０℃である。上記ポリマーのガラス転移温度を上記範囲内とすることにより硬化物の耐クラック性が向上する傾向がある。なお、上記コア部分を構成するポリマーのガラス転移温度は、下記Ｆｏｘの式により算出される計算値を意味する（Ｂｕｌｌ．Ａｍ．Ｐｈｙｓ．Ｓｏｃ．，１（３）１２３（１９５６）参照）。下記Ｆｏｘの式中、Ｔｇはコア部分を構成するポリマーのガラス転移温度（単位：Ｋ）を示し、Ｗiはコア部分を構成するポリマーを構成する単量体全量に対する単量体ｉの重量分率を示す。また、Ｔｇiは単量体ｉの単独重合体のガラス転移温度（単位：Ｋ）を示す。下記Ｆｏｘの式は、コアを構成するポリマーが単量体１、単量体２、・・・・、及び単量体ｎの共重合体である場合の式を示す。
　　　１／Ｔｇ＝Ｗ1／Ｔｇ1＋Ｗ2／Ｔｇ2＋・・・・＋Ｗn／Ｔｇn
　上記単独重合体のガラス転移温度は、各種文献に記載の値を採用することができ、例えば、「ＰＯＬＹＭＥＲ　ＨＡＮＤＢＯＯＫ　第３版」（Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ，Ｉｎｃ．発行）に記載の値を採用できる。なお、文献に記載のないものについては、単量体を常法により重合して得られる単独重合体の、ＤＳＣ法により測定されるガラス転移温度の値を採用することができる。 The glass transition temperature of the polymer constituting the core portion is not particularly limited, but is preferably −100 to 10 ° C., more preferably −80 to −10 ° C., and further preferably −60 to −20 ° C. There exists a tendency for the crack resistance of hardened | cured material to improve by making the glass transition temperature of the said polymer into the said range. In addition, the glass transition temperature of the polymer which comprises the said core part means the calculated value calculated by the formula of the following Fox (refer Bull. Am. Phys. Soc., 1 (3) 123 (1956)). Wherein the following Fox, Tg glass transition temperature (unit: K) of the polymer constituting the core portion indicates, W i is the weight fraction of the monomer i for the monomer total amount constituting the polymer constituting the core portion Indicates the rate. Further, Tg i is the glass transition temperature of the homopolymer of monomer i (unit: K) shows a. The following Fox formula shows the formula when the polymer constituting the core is a copolymer of monomer 1, monomer 2,..., And monomer n.
1 / Tg = W 1 / Tg 1 + W 2 / Tg 2 +... + W n / Tg n
As the glass transition temperature of the homopolymer, values described in various documents can be adopted, for example, values described in “POLYMER HANDBOOK 3rd edition” (published by John Wiley & Sons, Inc.) can be adopted. In addition, about the thing which is not described in literature, the value of the glass transition temperature measured by DSC method of the homopolymer obtained by superposing | polymerizing a monomer by a conventional method is employable.
　上記コア部分は、通常用いられる方法で製造することができ、例えば、上記モノマーを乳化重合法により重合する方法等により製造することができる。乳化重合法においては、上記モノマーの全量を一括して仕込んで重合してもよいし、上記モノマーの一部を重合した後、残りを連続的に又は断続的に添加して重合してもよいし、さらに、シード粒子を使用する重合方法を使用してもよい。 The core part can be produced by a commonly used method. For example, the core part can be produced by a method of polymerizing the monomer by an emulsion polymerization method. In the emulsion polymerization method, the whole amount of the monomer may be charged all at once and polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently for polymerization. Further, a polymerization method using seed particles may be used.
　なお、ゴム粒子（Ｂ）として、コアシェル構造を有しないゴム粒子を用いる場合には、例えば、上記コア部分のみからなるゴム粒子等を使用することができる。 In addition, when using the rubber particle which does not have a core shell structure as a rubber particle (B), the rubber particle etc. which consist only of the said core part can be used, for example.
　コアシェル型ゴム粒子のシェル層を構成するポリマーは、上記コア部分を構成するポリマーとは異種のポリマー（異なるモノマー組成を有するポリマー）であることが好ましい。また、上述のように、上記シェル層は、脂環式エポキシ化合物（Ａ）等のエポキシ基を有する化合物と反応し得る官能基としてヒドロキシ基及び／又はカルボキシ基を有することが好ましい。これにより、特に、脂環式エポキシ化合物（Ａ）との界面で接着性を向上させることができ、該シェル層を有するコアシェル型ゴム粒子を含む硬化性樹脂組成物を硬化させた硬化物に対して、優れた耐クラック性を発揮させることができる。また、硬化物のガラス転移温度の低下を防止することもできる。 The polymer constituting the shell layer of the core-shell type rubber particles is preferably a polymer different from the polymer constituting the core portion (a polymer having a different monomer composition). Further, as described above, the shell layer preferably has a hydroxy group and / or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A). Thereby, especially with respect to the hardened | cured material which can improve adhesiveness in an interface with an alicyclic epoxy compound (A), and hardened the curable resin composition containing the core-shell type rubber particle which has this shell layer Excellent crack resistance can be exhibited. Moreover, the fall of the glass transition temperature of hardened | cured material can also be prevented.
　上記シェル層を構成するポリマーは、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等の（メタ）アクリル酸エステルを必須のモノマー成分として含むポリマーであることが好ましい。例えば、上記コア部分における（メタ）アクリル酸エステルとしてアクリル酸ブチルを用いた場合、シェル層を構成するポリマーのモノマー成分としては、例えば、アクリル酸ブチル以外の（メタ）アクリル酸エステル（例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、メタクリル酸ブチル等）を使用することが好ましい。（メタ）アクリル酸エステル以外に含んでいてもよいモノマー成分としては、例えば、スチレン、α－メチルスチレン等の芳香族ビニル；アクリロニトリル、メタクリロニトリル等のニトリル等が挙げられる。コアシェル型ゴム粒子においては、シェル層を構成するモノマー成分として、（メタ）アクリル酸エステルと共に、上記モノマーを単独で、又は二種以上を組み合わせて含むことが好ましく、特に、少なくとも芳香族ビニルを含むことが、コアシェル型ゴム粒子の屈折率を容易に調整できる点で好ましい。 The polymer constituting the shell layer is preferably a polymer containing (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate as an essential monomer component. . For example, when butyl acrylate is used as the (meth) acrylic acid ester in the core portion, as a monomer component of the polymer constituting the shell layer, for example, (meth) acrylic acid esters other than butyl acrylate (for example, ( (Meth) methyl acrylate, ethyl (meth) acrylate, butyl methacrylate, etc.) are preferably used. Examples of the monomer component that may be contained in addition to the (meth) acrylic acid ester include aromatic vinyl such as styrene and α-methylstyrene; nitrile such as acrylonitrile and methacrylonitrile. In the core-shell type rubber particle, it is preferable that the monomer component constituting the shell layer includes the (meth) acrylic acid ester alone or in combination of two or more, particularly at least aromatic vinyl. It is preferable in that the refractive index of the core-shell type rubber particles can be easily adjusted.
　さらに、上記シェル層を構成するポリマーは、モノマー成分として、脂環式エポキシ化合物（Ａ）等のエポキシ基を有する化合物と反応し得る官能基としてのヒドロキシ基及び／又はカルボキシ基を形成するために、ヒドロキシ基含有モノマー（例えば、２－ヒドロキシエチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート等）や、カルボキシ基含有モノマー（例えば、（メタ）アクリル酸等のα，β－不飽和酸；マレイン酸無水物等のα，β－不飽和酸無水物等）を含有することが好ましい。 Further, the polymer constituting the shell layer forms a hydroxy group and / or a carboxy group as a functional group capable of reacting with a compound having an epoxy group such as an alicyclic epoxy compound (A) as a monomer component. Hydroxy group-containing monomers (eg, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate) and carboxy group-containing monomers (eg, α, β-unsaturated acids such as (meth) acrylic acid; Α, β-unsaturated acid anhydrides such as maleic anhydride) are preferably contained.
　上記シェル層を構成するポリマーは、モノマー成分として、（メタ）アクリル酸エステルと共に、上記モノマーから選択された一種又は二種以上を組み合わせて含むことが好ましい。即ち、上記シェル層は、例えば、（メタ）アクリル酸エステル／芳香族ビニル／ヒドロキシアルキル（メタ）アクリレート、（メタ）アクリル酸エステル／芳香族ビニル／α，β－不飽和酸等の三元共重合体等から構成されたシェル層であることが好ましい。 The polymer constituting the shell layer preferably contains, as a monomer component, one or two or more selected from the above monomers in combination with (meth) acrylic acid ester. That is, the shell layer is composed of, for example, a ternary copolymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / α, β-unsaturated acid. A shell layer composed of a polymer or the like is preferable.
　また、上記シェル層を構成するポリマーは、その他のモノマー成分として、コア部分と同様に、上記モノマーの他にジビニルベンゼン、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジアリルマレエート、トリアリルシアヌレート、ジアリルフタレート、ブチレングリコールジアクリレート等の分子内に２個以上の反応性官能基を有する反応性架橋モノマーを含有していてもよい。 Further, the polymer constituting the shell layer includes, as the other monomer components, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, trimethyl, as well as the above-described monomer. A reactive crosslinking monomer having two or more reactive functional groups may be contained in the molecule such as allyl cyanurate, diallyl phthalate, butylene glycol diacrylate.
　上記シェル層を構成するポリマーのガラス転移温度は、特に限定されないが、２０～２００℃が好ましく、より好ましくは４０～１８０℃、さらに好ましくは６０～１６０℃である。上記ポリマーのガラス転移温度を２０℃以上とすることにより、硬化物の耐熱性及び耐光性がより向上する傾向がある。一方、上記ポリマーのガラス転移温度を２００℃以下とすることにより、ゴム粒子（Ｂ）の分散性及び硬化物の耐クラック性が向上する傾向がある。なお、上記シェル層を構成するポリマーのガラス転移温度は、上記Ｆｏｘの式により算出される計算値を意味し、例えば、上述のコアを構成するポリマーのガラス転移温度と同様にして測定できる。 The glass transition temperature of the polymer constituting the shell layer is not particularly limited, but is preferably 20 to 200 ° C, more preferably 40 to 180 ° C, and still more preferably 60 to 160 ° C. By setting the glass transition temperature of the polymer to 20 ° C. or higher, the heat resistance and light resistance of the cured product tend to be further improved. On the other hand, when the glass transition temperature of the polymer is 200 ° C. or lower, the dispersibility of the rubber particles (B) and the crack resistance of the cured product tend to be improved. In addition, the glass transition temperature of the polymer which comprises the said shell layer means the calculated value computed by the said Formula of Fox, For example, it can measure similarly to the glass transition temperature of the polymer which comprises the above-mentioned core.
　コアシェル型ゴム粒子は、上記コア部分をシェル層により被覆することで得られる。上記コア部分をシェル層で被覆する方法としては、例えば、上記方法により得られたゴム弾性を有するコア部分の表面に、シェル層を構成するポリマーを塗布することにより被覆する方法；上記方法により得られたゴム弾性を有するコア部分を幹成分とし、シェル層を構成する各成分を枝成分としてグラフト重合する方法等が挙げられる。 Core-shell type rubber particles are obtained by covering the core part with a shell layer. Examples of the method for coating the core part with the shell layer include a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a polymer constituting the shell layer; Examples thereof include a graft polymerization method in which the core portion having rubber elasticity is a trunk component and each component constituting the shell layer is a branch component.
　ゴム粒子（Ｂ）の平均粒子径は、特に限定されないが、１０～５００ｎｍが好ましく、より好ましくは２０～４００ｎｍである。また、ゴム粒子（Ｂ）の最大粒子径は、特に限定されないが、５０～１０００ｎｍが好ましく、より好ましくは１００～８００ｎｍである。平均粒子径を５００ｎｍ以下（又は、最大粒子径を１０００ｎｍ以下）とすることにより、硬化物におけるゴム粒子（Ｂ）の分散性が向上し、耐クラック性が向上する傾向がある。一方、平均粒子径を１０ｎｍ以上（又は、最大粒子径を５０ｎｍ以上）とすることにより、硬化物の耐クラック性が向上する傾向がある。 The average particle size of the rubber particles (B) is not particularly limited, but is preferably 10 to 500 nm, more preferably 20 to 400 nm. The maximum particle size of the rubber particles (B) is not particularly limited, but is preferably 50 to 1000 nm, and more preferably 100 to 800 nm. When the average particle size is 500 nm or less (or the maximum particle size is 1000 nm or less), the dispersibility of the rubber particles (B) in the cured product is improved and the crack resistance tends to be improved. On the other hand, when the average particle size is 10 nm or more (or the maximum particle size is 50 nm or more), the crack resistance of the cured product tends to be improved.
　ゴム粒子（Ｂ）の屈折率は、特に限定されないが、１．４０～１．６０が好ましく、より好ましくは１．４２～１．５８である。また、ゴム粒子（Ｂ）の屈折率と、該ゴム粒子（Ｂ）を含む硬化性樹脂組成物（本発明の第１態様又は第２態様の硬化性樹脂組成物）を硬化させて得られる硬化物の屈折率との差は±０．０３以内であることが好ましい。屈折率の差を±０．０３以内とすることにより、硬化物の優れた光反射性が確保され、光半導体装置の光度が高く保持される傾向がある。 The refractive index of the rubber particles (B) is not particularly limited, but is preferably 1.40 to 1.60, more preferably 1.42 to 1.58. Further, the curing obtained by curing the refractive index of the rubber particles (B) and the curable resin composition containing the rubber particles (B) (the curable resin composition of the first aspect or the second aspect of the present invention). The difference from the refractive index of the object is preferably within ± 0.03. By making the difference in refractive index within ± 0.03, excellent light reflectivity of the cured product is ensured, and the light intensity of the optical semiconductor device tends to be kept high.
　ゴム粒子（Ｂ）の屈折率は、例えば、ゴム粒子（Ｂ）１ｇを型に注型して２１０℃、４ＭＰａで圧縮成型し、厚さ１ｍｍの平板を得、得られた平板から、縦２０ｍｍ×横６ｍｍの試験片を切り出し、中間液としてモノブロモナフタレンを使用してプリズムと該試験片とを密着させた状態で、多波長アッベ屈折計（商品名「ＤＲ－Ｍ２」、（株）アタゴ製）を使用し、２０℃、ナトリウムＤ線での屈折率を測定することにより求めることができる。 The refractive index of the rubber particles (B) is, for example, 1 g of rubber particles (B) is cast into a mold and compression molded at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. × A 6 mm wide test piece was cut out, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, Atago Co., Ltd.) was used in a state where the prism and the test piece were in close contact using monobromonaphthalene as an intermediate solution. And the refractive index at 20 ° C. and sodium D line can be measured.
　本発明の第１態様又は第２態様の硬化性樹脂組成物の硬化物の屈折率は、例えば、下記硬化物の項に記載の加熱硬化方法により得られた硬化物から、縦２０ｍｍ×横６ｍｍ×厚さ１ｍｍの試験片を切り出し、中間液としてモノブロモナフタレンを使用してプリズムと該試験片とを密着させた状態で、多波長アッベ屈折計（商品名「ＤＲ－Ｍ２」、（株）アタゴ製）を使用し、２０℃、ナトリウムＤ線での屈折率を測定することにより求めることができる。 The refractive index of the cured product of the curable resin composition of the first embodiment or the second embodiment of the present invention is, for example, 20 mm long by 6 mm wide from a cured product obtained by the heat curing method described in the section of the cured product below. × A 1 mm thick test piece was cut out, and a multi-wavelength Abbe refractometer (trade name “DR-M2”, Co., Ltd.) was used in a state where the prism and the test piece were in close contact using monobromonaphthalene as an intermediate solution. It can be determined by measuring the refractive index at 20 ° C. and sodium D line.
　本発明の第１態様の硬化性樹脂組成物におけるゴム粒子（Ｂ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．０５～２０重量％が好ましく、より好ましくは０．１～１５重量％、さらに好ましくは０．２～１０重量％である。ゴム粒子（Ｂ）の含有量を０．０５重量％以上とすることにより、硬化物の光反射性、耐熱性、及び耐光性がより優れる傾向がある。また、硬化物の耐クラック性が向上する傾向がある。一方、ゴム粒子（Ｂ）の含有量を２０重量％以下とすることにより、硬化物の耐熱性及び耐光性がより向上する傾向がある。 The rubber particle (B) content (blending amount) in the curable resin composition of the first aspect of the present invention is not particularly limited, but is 0.05 to It is preferably 20% by weight, more preferably 0.1 to 15% by weight, still more preferably 0.2 to 10% by weight. By setting the content of the rubber particles (B) to 0.05% by weight or more, the light reflectivity, heat resistance, and light resistance of the cured product tend to be more excellent. Moreover, there exists a tendency for the crack resistance of hardened | cured material to improve. On the other hand, when the content of the rubber particles (B) is 20% by weight or less, the heat resistance and light resistance of the cured product tend to be further improved.
　本発明の第２態様の硬化性樹脂組成物におけるゴム粒子（Ｂ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．０１～２０重量％が好ましく、より好ましくは０．０５～１５重量％、さらに好ましくは０．１～１０重量％である。ゴム粒子（Ｂ）の含有量を上記範囲内とすることにより、硬化物の耐クラック性が向上し、耐熱性及び耐光性がより優れる傾向がある。 The rubber particle (B) content (blending amount) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0.01 to It is preferably 20% by weight, more preferably 0.05 to 15% by weight, still more preferably 0.1 to 10% by weight. By making content of a rubber particle (B) into the said range, there exists a tendency which the crack resistance of hardened | cured material improves and heat resistance and light resistance are more excellent.
　本発明の第１態様又は第２態様の硬化性樹脂組成物におけるゴム粒子（Ｂ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、０．５～３０重量部が好ましく、より好ましくは１～２０重量部である。ゴム粒子（Ｂ）の含有量を上記範囲内とすることにより、硬化物の耐クラック性が向上し、耐熱性及び耐光性がより優れる傾向がある。すなわち、ゴム粒子（Ｂ）の含有量を０．５重量部以上とすることにより、硬化物の光反射性、耐熱性、及び耐光性がより優れる傾向がある。また、硬化物の耐クラック性が向上する傾向がある。一方、ゴム粒子（Ｂ）の含有量を３０重量部以下とすることにより、硬化物の耐熱性及び耐光性がより向上する傾向がある。 The content (blending amount) of the rubber particles (B) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is the compound having an epoxy group contained in the curable resin composition. The amount is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to the total amount of 100 parts by weight. By making content of a rubber particle (B) into the said range, there exists a tendency which the crack resistance of hardened | cured material improves and heat resistance and light resistance are more excellent. That is, when the content of the rubber particles (B) is 0.5 parts by weight or more, the light reflectivity, heat resistance, and light resistance of the cured product tend to be more excellent. Moreover, there exists a tendency for the crack resistance of hardened | cured material to improve. On the other hand, when the content of the rubber particles (B) is 30 parts by weight or less, the heat resistance and light resistance of the cured product tend to be further improved.
［白色顔料（Ｃ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物の必須成分である白色顔料（Ｃ）は、主に、硬化物（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、例えば、ガラス、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)]
The white pigment (C), which is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention, mainly imparts high light reflectivity to the cured product (reflector). Has the function of reducing the coefficient of linear expansion. As the white pigment (C), known or commonly used white pigments can be used, and are not particularly limited. For example, glass, clay, mica, talc, kaolinite (kaolin), halloysite, zeolite, acidic clay, active Inorganic white pigments such as clay, boehmite, pseudoboehmite, inorganic oxides, metal salts [for example, alkaline earth metal salts]; styrene resins, benzoguanamine resins, urea-formalin resins, melamine-formalin resins, amides Organic white pigments (plastic pigments, etc.) such as resin pigments such as resin-based resins; hollow particles having a hollow structure (balloon structure), and the like.
　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、屈折率が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。なお、白色顔料（Ｃ）として例示するもののうち、無機充填剤（Ｄ）にも該当するものについては、屈折率が１．５以上のものは白色顔料（Ｃ）とし、屈折率が１．５より小さいものは無機充填剤（Ｄ）とする。 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. . Of those exemplified as the white pigment (C), those corresponding to the inorganic filler (D) are those having a refractive index of 1.5 or more as the white pigment (C) and having a refractive index of 1.5. The smaller one is the inorganic filler (D).
　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、硬化性樹脂組成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, there are cases where compatibility and dispersibility with other components in the curable resin composition can be improved.
　中でも、白色顔料（Ｃ）としては、入手性、耐熱性、耐光性の観点、及び硬化物（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、無機中空粒子が好ましく、より好ましくは酸化アルミニウム、酸化マグネシウム、酸化アンチモン、酸化チタン、酸化ジルコニウム、酸化亜鉛、硫酸バリウム、無機中空粒子、さらに好ましくは酸化チタン、酸化ジルコニウム、酸化亜鉛、硫酸バリウムである。特に、白色顔料（Ｃ）としては、より高い屈折率を有する点で、酸化チタンが好ましい。 Among these, as the white pigment (C), from the viewpoint of availability, heat resistance, light resistance, and high reflectance of the cured product (reflector) and light reflectance increase rate with respect to the addition amount, inorganic oxides, inorganic Hollow particles are preferred, more preferably aluminum oxide, magnesium oxide, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, barium sulfate, inorganic hollow particles, and more preferably titanium oxide, zirconium oxide, zinc oxide, barium sulfate. In particular, the white pigment (C) is preferably titanium oxide because it has a higher refractive index.
　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（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、さらに好ましくは０．１～２０μｍ、特に好ましくは０．１～１０μｍ、最も好ましくは０．１～５μｍである。一方、白色顔料（Ｃ）として中空粒子（特に、無機中空粒子）を用いる場合、該中空粒子の中心粒径は、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 (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, and still more preferably 0. .1 to 20 μm, particularly preferably 0.1 to 10 μm, most preferably 0.1 to 5 μm. On the other hand, when hollow particles (particularly inorganic hollow particles) are used as the white pigment (C), the center particle diameter of the hollow particles 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.
　本発明の第１態様又は第２態様の硬化性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 resin composition of the first aspect or the second aspect 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 Co., Ltd.) can also be used.
　中でも、白色顔料（Ｃ）としては、特に硬化物（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 these, as the white pigment (C), the trade names “R-62N”, “CR-60”, “DCF-T-17007” are particularly used from the viewpoint of improving the light reflectivity and yellowing resistance of the cured product (reflector). "DCF-T-17008", "DCF-T-17050", and "FTR-700" are preferable.
　本発明の第１態様又は第２態様の硬化性樹脂組成物における白色顔料（Ｃ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．１～５０重量％が好ましく、より好ましくは１～４０重量％、さらに好ましくは５～３５重量％である。白色顔料（Ｃ）の含有量を０．１重量％以上とすることにより、硬化物（リフレクター）の光反射性がより向上する傾向がある。また、耐熱性（特に、耐黄変性）及び耐光性（特に、耐紫外線性）がより向上する傾向がある。一方、白色顔料（Ｃ）の含有量を５０重量％以下とすることにより、硬化物（リフレクター）の成型性が向上し、量産により適する傾向がある。 The content (blending amount) of the white pigment (C) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but with respect to the curable resin composition (100 wt%), It is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 5 to 35% by weight. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more by making content of a white pigment (C) 0.1 weight% or more. In addition, heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) tend to be further improved. On the other hand, when the content of the white pigment (C) is 50% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
　本発明の第１態様の硬化性樹脂組成物における白色顔料（Ｃ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量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１０～３５０重量部、さらに好ましくは３０～３００重量部である。白色顔料（Ｃ）の含有量が３重量部以上であることにより、硬化物（リフレクター）の光反射性がより向上する傾向がある。また、耐熱性（特に、耐黄変性）及び耐光性（特に、耐紫外線性）がより向上する傾向がある。一方、白色顔料（Ｃ）の含有量が４００重量部以下であることにより、成型性が向上し、量産により適する傾向がある。 The content (blending amount) of the white pigment (C) in the curable resin composition of the first aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100 parts by weight. The amount is preferably 3 to 400 parts by weight, more preferably 10 to 350 parts by weight, still more preferably 30 to 300 parts by weight. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more because content of a white pigment (C) is 3 weight part or more. In addition, heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) tend to be further improved. On the other hand, when the content of the white pigment (C) is 400 parts by weight or less, the moldability is improved and there is a tendency to be more suitable for mass production.
　本発明の第２態様の硬化性樹脂組成物における白色顔料（Ｃ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１０～６００重量部が好ましく、より好ましくは３０～５００重量部、さらに好ましくは３０～４００重量部である。白色顔料（Ｃ）の含有量が１０重量部以上であることにより、硬化物（リフレクター）の光反射性がより向上する傾向がある。また、耐熱性（特に、耐黄変性）及び耐光性（特に、耐紫外線性）がより向上する傾向がある。一方、白色顔料（Ｃ）の含有量が６００重量部以下であることにより、硬化物（リフレクター）の成型性が向上し、量産により適する傾向がある。 The content (blending amount) of the white pigment (C) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of the compounds having an epoxy group contained in the curable resin composition is 100 parts by weight. The amount is preferably 10 to 600 parts by weight, more preferably 30 to 500 parts by weight, still more preferably 30 to 400 parts by weight. There exists a tendency for the light reflectivity of hardened | cured material (reflector) to improve more because content of a white pigment (C) is 10 weight part or more. In addition, heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) tend to be further improved. On the other hand, when the content of the white pigment (C) is 600 parts by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
　本発明の第１態様又は第２態様の硬化性樹脂組成物に酸化チタンが含まれる場合、白色顔料（Ｃ）と無機充填剤（Ｄ）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（リフレクター）の耐熱性（耐黄変性）と光反射性のバランスの観点で、５～７０重量％が好ましく、より好ましくは１０～６０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（リフレクター）の光反射性がより向上する傾向がある。また、耐熱性（特に、耐黄変性）及び耐光性（特に、耐紫外線性）がより向上する傾向がある。一方、酸化チタンの割合を７０重量％以下とすることにより、硬化物（リフレクター）の成型性が向上し、量産により適する傾向がある。 When titanium oxide is contained in the curable resin composition of the first aspect or the second aspect of the present invention, the ratio of titanium oxide to the total amount (100% by weight) of the white pigment (C) and the inorganic filler (D) is: Although not particularly limited, it is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, from the viewpoint of the balance between heat resistance (yellowing resistance) and light reflectivity of the cured product (reflector). By making the ratio of titanium oxide 5% by weight or more, the light reflectivity of the cured product (reflector) tends to be further improved. In addition, heat resistance (particularly yellowing resistance) and light resistance (particularly ultraviolet resistance) tend to be further improved. On the other hand, by setting the proportion of titanium oxide to 70% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
［無機充填剤（Ｄ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物は、白色顔料（Ｃ）とは別に、無機充填剤（Ｄ）を必須成分として含む。無機充填剤（Ｄ）は、主に、硬化性樹脂組成物をコンプレッション成型により形成する場合において、形成された硬化物に優れた耐熱性及び耐光性（特に、優れた耐熱性）を付与する。また、硬化物（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（Ｄ）の種類によっては、硬化物（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 (D)]
The curable resin composition of the first aspect or the second aspect of the present invention contains an inorganic filler (D) as an essential component separately from the white pigment (C). The inorganic filler (D) mainly imparts excellent heat resistance and light resistance (particularly excellent heat resistance) to the formed cured product when the curable resin composition is formed by compression molding. Moreover, it has the function to reduce the linear expansion coefficient of hardened | cured material (reflector). Moreover, depending on the kind of inorganic filler (D), the light reflectivity excellent with respect to hardened | cured material (reflector) may be provided.
　無機充填剤（Ｄ）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、アルミナ、ジルコン、珪酸カルシウム、リン酸カルシウム、炭酸カルシウム、炭酸マグネシウム、炭化ケイ素、窒化ケイ素、窒化アルミニウム、窒化ホウ素、水酸化アルミニウム、酸化鉄、酸化亜鉛、酸化ジルコニウム、酸化マグネシウム、酸化チタン、酸化アルミニウム、硫酸カルシウム、硫酸バリウム、フォステライト、ステアタイト、スピネル、クレー、カオリン、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、タルク等の粉体、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（Ｄ）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（Ｄ）としては、硬化物（リフレクター）の耐熱性（特に、耐黄変性）、耐光性、及び流動性の観点で、シリカ、アルミナ、窒化ケイ素、窒化アルミニウム、窒化ホウ素が好ましく、より好ましくはシリカ（シリカフィラー）である。 As the inorganic filler (D), a known or conventional inorganic filler can be used, and is not particularly limited. For example, silica, alumina, zircon, calcium silicate, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, Silicon nitride, aluminum nitride, boron nitride, aluminum hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, calcium sulfate, barium sulfate, fosterite, steatite, spinel, clay, kaolin, dolomite , Hydroxyapatite, nepheline sinite, cristobalite, wollastonite, diatomaceous earth, talc and the like, or moldings thereof (for example, spherical beads). Examples of the inorganic filler (D) include those obtained by subjecting the above-described inorganic filler to a known or conventional surface treatment. Among them, examples of the inorganic filler (D) include silica, alumina, silicon nitride, aluminum nitride, and boron nitride from the viewpoint of heat resistance (particularly yellowing resistance), light resistance, and fluidity of the cured product (reflector). Silica (silica filler) is more preferable.
　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.
　シリカの形状は、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、球状のシリカが好ましく、特に真球状のシリカ（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 silica is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, scale shape, and the like. Among these, spherical silica is preferable from the viewpoint of dispersibility, and spherical silica (for example, spherical silica having an aspect ratio of 1.2 or less) is particularly preferable.
　シリカの中心粒径は、特に限定されないが、硬化物（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 silica 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 (reflector). 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、本発明の第１態様又は第２態様の硬化性樹脂組成物において無機充填剤（Ｄ）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（Ｄ）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」、「ＦＢ－１０５」、「ＦＢ－１０５ＦＤ」、「ＦＢ－５Ｄ」、「ＦＢ－８Ｓ」、「ＦＢ－７ＳＤＣ」、「ＦＢ－５ＳＤＣ」、「ＦＢ－３ＳＤＣ」、「ＦＢ－９ＦＤＣ」、「ＦＢ－７ＦＤＣ」、「ＦＢ－５ＦＤＣ」、「ＦＢ－９７０ＦＤ」、「ＦＢ－９７５ＦＤ」、「ＦＢ－９５０ＦＤ」、「ＦＢ－４０ＲＦＤ」等のＦＢシリーズ、商品名「ＤＡＷ－０３ＤＣ」、「ＤＡＷ－０５２５」、「ＤＡＷ－１０２５」等のＤＡＷシリーズ、商品名「ＳＧＰ」（以上、デンカ（株）製）、商品名「ＨＦ－０５」（（株）トクヤマ製）、商品名「１０μｍＳＥ－ＣＣ５」（（株）アドマテックス製）、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 addition, in the curable resin composition of the 1st aspect or 2nd aspect of this invention, an inorganic filler (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type. The inorganic filler (D) can also be produced by a known or conventional production method. For example, trade names “FB-910”, “FB-940”, “FB-950”, “FB-105” can be used. "," FB-105FD "," FB-5D "," FB-8S "," FB-7SDC "," FB-5SDC "," FB-3SDC "," FB-9FDC "," FB-7FDC ", FB series such as “FB-5FDC”, “FB-970FD”, “FB-975FD”, “FB-950FD”, “FB-40RFD”, product names “DAW-03DC”, “DAW-0525”, “DAW DAW series such as “-1025”, trade name “SGP” (manufactured by Denka), trade name “HF-05” (manufactured by Tokuyama), trade name “10 μm SE-CC5” (Admatech) Product names “MSR-2212”, “MSR-25” (above, manufactured by Tatsumori Co., Ltd.), product names “HS-105”, “HS-106”, “HS-107” (above, Micron) Commercially available products such as those manufactured by the company may also be used.
　本発明の第１態様又は第２態様の硬化性樹脂組成物における無機充填剤（Ｄ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、１０～９０重量％が好ましく、より好ましくは１３～７５重量％、さらに好ましくは１５～７０重量％、さらに好ましくは２０～７０重量％である。無機充填剤（Ｄ）の含有量を１０重量％以上とすることにより、硬化性樹脂組成物をコンプレッション成型により形成する場合において、形成された硬化物の耐熱性及び耐光性（特に、優れた耐熱性）がより向上する傾向がある。また、硬化物（リフレクター）の線膨張係数が低くなって、該リフレクターを用いた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生じにくくなる傾向がある。一方、無機充填剤（Ｄ）の含有量を９０重量％以下とすることにより、硬化物（リフレクター）の成型性が向上し、量産により適する傾向がある。 The content (blending amount) of the inorganic filler (D) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is relative to the curable resin composition (100% by weight). It is preferably 10 to 90% by weight, more preferably 13 to 75% by weight, still more preferably 15 to 70% by weight, and still more preferably 20 to 70% by weight. When the content of the inorganic filler (D) is 10% by weight or more, when the curable resin composition is formed by compression molding, the formed cured product has heat resistance and light resistance (particularly excellent heat resistance). Tend to be more improved. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and problems such as lead frame warpage in an optical semiconductor element mounting substrate using the reflector tend not to occur. On the other hand, when the content of the inorganic filler (D) is 90% by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
　本発明の第１態様の硬化性樹脂組成物における無機充填剤（Ｄ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１０～１５００重量部が好ましく、より好ましくは５０～１２００重量部、さらに好ましくは７０～１０００重量部である。無機充填剤（Ｄ）の含有量を１０重量部以上とすることにより、硬化性樹脂組成物をコンプレッション成型により形成する場合において、形成された硬化物の耐熱性及び耐光性（特に、優れた耐熱性）がより向上する傾向がある。また、硬化物（リフレクター）の線膨張係数が低くなって、該リフレクターを用いた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生じにくくなる傾向がある。一方、無機充填剤（Ｄ）の含有量を１５００重量部以下とすることにより、硬化性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。 The content (blending amount) of the inorganic filler (D) in the curable resin composition of the first aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100 wt. The amount is preferably 10 to 1500 parts by weight, more preferably 50 to 1200 parts by weight, and still more preferably 70 to 1000 parts by weight. When the content of the inorganic filler (D) is 10 parts by weight or more, when the curable resin composition is formed by compression molding, the formed cured product has heat resistance and light resistance (particularly excellent heat resistance). Tend to be more improved. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and problems such as lead frame warpage in an optical semiconductor element mounting substrate using the reflector tend not to occur. On the other hand, by setting the content of the inorganic filler (D) to 1500 parts by weight or less, the curable resin composition has good fluidity, so there is a problem such as unfilling at the time of molding (particularly transfer molding). There is a tendency to be suppressed.
　本発明の第２態様の硬化性樹脂組成物における無機充填剤（Ｄ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１０～１５００重量部が好ましく、より好ましくは５０～１２００重量部、さらに好ましくは１００～１０００重量部である。無機充填剤（Ｄ）の含有量が１０重量部以上であることにより、硬化性樹脂組成物をコンプレッション成型により形成する場合において、形成された硬化物の耐熱性及び耐光性（特に、優れた耐熱性）がより向上する傾向がある。また、硬化物（リフレクター）の線膨張係数が低くなって、該リフレクターを用いた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生じにくくなる傾向がある。一方、無機充填剤（Ｄ）の含有量が１５００重量部以下であることにより、硬化物（リフレクター）の成型性が向上し、量産により適する傾向がある。 The content (blending amount) of the inorganic filler (D) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100% by weight. The amount is preferably 10 to 1500 parts by weight, more preferably 50 to 1200 parts by weight, and still more preferably 100 to 1000 parts by weight. When the content of the inorganic filler (D) is 10 parts by weight or more, when the curable resin composition is formed by compression molding, the formed cured product has heat resistance and light resistance (particularly excellent heat resistance). Tend to be more improved. In addition, the linear expansion coefficient of the cured product (reflector) tends to be low, and problems such as lead frame warpage in an optical semiconductor element mounting substrate using the reflector tend not to occur. On the other hand, when the content of the inorganic filler (D) is 1500 parts by weight or less, the moldability of the cured product (reflector) is improved and tends to be more suitable for mass production.
　本発明の第１態様又は第２態様の硬化性樹脂組成物における白色顔料（Ｃ）及び無機充填剤（Ｄ）の最大粒子径は、特に限定されないが、２００μｍ以下が好ましく、より好ましくは１８５μｍ以下、さらに好ましくは１７５μｍ以下、特に好ましくは１５０μｍ以下である。上記最大粒子径が２００μｍ以下であると、最大粒子径が２００μｍを超える白色顔料又は無機充填剤を用いる場合よりも、硬化性樹脂組成物をコンプレッション成型により形成された形成された硬化物の耐熱性、耐光性、及び耐クラック性（特に、優れた耐熱性）がさらに優れる傾向がある。また、最大粒子径が小さい白色顔料（Ｃ）及び無機充填剤（Ｄ）を用いることにより、これらの含有量を増やすことが可能となり、硬化物の光反射性、耐熱性、及び耐光性がよりいっそう向上する傾向がある。上記最大粒子径の下限は、例えば０．０１μｍ以上である。なお、上記最大粒子径は、本発明の硬化性樹脂組成物に含まれる白色顔料（Ｃ）及び無機充填剤（Ｄ）のトータルの最大粒子径である。上記最大粒子径は、レーザー回折・散乱法で測定した粒度分布における最大の粒径を意味する。 The maximum particle diameter of the white pigment (C) and the inorganic filler (D) in the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is preferably 200 μm or less, more preferably 185 μm or less. More preferably, it is 175 μm or less, and particularly preferably 150 μm or less. When the maximum particle size is 200 μm or less, the heat resistance of the formed cured product formed by compression molding of the curable resin composition than when using a white pigment or an inorganic filler having a maximum particle size exceeding 200 μm. , Light resistance and crack resistance (particularly excellent heat resistance) tend to be further improved. Further, by using the white pigment (C) and the inorganic filler (D) having a small maximum particle size, it is possible to increase the content thereof, and the light reflectivity, heat resistance, and light resistance of the cured product are further improved. There is a tendency to improve further. The lower limit of the maximum particle size is, for example, 0.01 μm or more. The maximum particle size is the total maximum particle size of the white pigment (C) and the inorganic filler (D) contained in the curable resin composition of the present invention. The maximum particle size means the maximum particle size in the particle size distribution measured by the laser diffraction / scattering method.
［硬化剤（Ｅ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物における硬化剤（Ｅ）は、脂環式エポキシ化合物（Ａ）、応力緩和剤（Ｈ）としての後掲のエポキシ変性シリコーンオイル、さらに本発明の第２態様の場合は、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）等のエポキシ基を有する化合物と反応することにより、硬化性樹脂組成物を硬化させる働きを有する化合物である。硬化剤（Ｅ）としては、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。 [Curing agent (E)]
The curing agent (E) in the curable resin composition of the first aspect or the second aspect of the present invention is an alicyclic epoxy compound (A), an epoxy-modified silicone oil described later as a stress relaxation agent (H), In the case of the 2nd aspect of this invention, it is a compound which has a function which hardens a curable resin composition by reacting with the compound which has epoxy groups, such as isocyanuric acid derivative (I) and a siloxane derivative (J). As the curing agent (E), a known or conventional epoxy resin curing agent can be used, and is not particularly limited. For example, acid anhydrides (acid anhydride curing agents), amines (amine curing) Agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides and the like.
　硬化剤（Ｅ）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（４－メチルテトラヒドロ無水フタル酸、３－メチルテトラヒドロ無水フタル酸等）、メチルヘキサヒドロ無水フタル酸（４－メチルヘキサヒドロ無水フタル酸、３－メチルヘキサヒドロ無水フタル酸等）、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、無水フタル酸、無水マレイン酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルシクロヘキセンジカルボン酸無水物、無水ピロメリット酸、無水トリメリット酸、ベンゾフェノンテトラカルボン酸無水物、無水ナジック酸、無水メチルナジック酸、水素化メチルナジック酸無水物、４－（４－メチル－３－ペンテニル）テトラヒドロ無水フタル酸、無水コハク酸、無水アジピン酸、無水セバシン酸、無水ドデカン二酸、メチルシクロヘキセンテトラカルボン酸無水物、ビニルエーテル－無水マレイン酸共重合体、アルキルスチレン－無水マレイン酸共重合体等が挙げられる。中でも、均一な硬化性樹脂組成物を効率的に調製することができる観点、脂環式エポキシ化合物（Ａ）と混合して２５℃で液状の混合物（硬化剤組成物）としやすい観点で、２５℃で液状の酸無水物［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］が好ましい。一方、２５℃で固体状の酸無水物については、例えば、２５℃で液状の酸無水物に溶解させて液状の混合物とすることで、本発明の第１態様又は第２態様の硬化性樹脂組成物における硬化剤（Ｅ）としての取り扱い性が向上する傾向がある。酸無水物系硬化剤としては、硬化物の耐熱性、光反射性の観点で、飽和単環炭化水素ジカルボン酸の無水物（環にアルキル基等の置換基が結合したものも含む）が好ましい。 As the acid anhydrides (acid anhydride curing agents) as the curing agent (E), known or conventional acid anhydride curing agents can be used, and are not particularly limited. For example, methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride), dodecenyl succinic anhydride, methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic acid, methyl nadic acid anhydride, hydrogenated methyl Nadic acid anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride Examples include acid copolymers and alkylstyrene-maleic anhydride copolymers. Above all, from the viewpoint of efficiently preparing a uniform curable resin composition, from the viewpoint of easily mixing with the alicyclic epoxy compound (A) to form a liquid mixture (curing agent composition) at 25 ° C., 25 Preference is given to acid anhydrides [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] that are liquid at ° C. On the other hand, for the solid acid anhydride at 25 ° C., for example, the curable resin of the first aspect or the second aspect of the present invention is obtained by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture. There exists a tendency for the handleability as a hardening | curing agent (E) in a composition to improve. As the acid anhydride curing agent, from the viewpoint of heat resistance and light reflectivity of the cured product, anhydrides of saturated monocyclic hydrocarbon dicarboxylic acids (including those having a substituent such as an alkyl group bonded to the ring) are preferable. .
　硬化剤（Ｅ）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 (E), 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（Ｅ）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 (E), 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（Ｅ）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 (E) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.
　硬化剤（Ｅ）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 (E), a known or commonly used imidazole curing agent can be used, and is not particularly limited, and examples thereof include 2-methylimidazole and 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（Ｅ）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 (E) include liquid polymercaptan and polysulfide resin.
　硬化剤（Ｅ）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等が挙げられる。 Examples of the polycarboxylic acids as the curing agent (E) include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and the like.
　中でも、硬化剤（Ｅ）としては、硬化物の耐熱性、耐光性、光反射性の観点で、酸無水物類（酸無水物系硬化剤）が好ましい。なお、本発明の第１態様又は第２態様の硬化性樹脂組成物において硬化剤（Ｅ）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。なお、硬化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「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。 Among these, as the curing agent (E), acid anhydrides (acid anhydride curing agents) are preferable from the viewpoints of heat resistance, light resistance, and light reflectivity of the cured product. In addition, the hardening | curing agent (E) can also be used individually by 1 type in the curable resin composition of the 1st aspect or 2nd aspect of this invention, and can also be used in combination of 2 or more types. The curing agent can be produced by a known or conventional method. For example, trade names “Licacid MH-700”, “Licacid MH-700F”, “Licacid MH-700G”, “Licacid TH”, “Licacid CI” "HH", "Licacid HNA-100" (manufactured by Shin Nippon Rika Co., Ltd.); trade name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.); trade names "H-TMAn-S", "H Commercially available products such as “TMAn” (Mitsubishi Gas Chemical Co., Ltd.); trade name “YH1120” (Mitsubishi Chemical Co., Ltd.) can also be used.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が硬化剤（Ｅ）を含有する場合、硬化剤（Ｅ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、１～４０重量％が好ましく、より好ましくは３～３５重量％、さらに好ましくは５～３０重量％である。硬化剤（Ｅ）の含有量を１重量％以上とすることにより、硬化がより十分となり、硬化物の耐クラック性が向上する傾向がある。一方、硬化剤（Ｅ）の含有量を４０重量％以下とすることにより、着色がより抑制され色相に優れた硬化物（リフレクター）が得られやすい傾向がある。 When the curable resin composition of the 1st aspect or 2nd aspect of this invention contains a hardening | curing agent (E), content (blending amount) of a hardening | curing agent (E) is although it does not specifically limit, A curable resin composition The content is preferably 1 to 40% by weight, more preferably 3 to 35% by weight, and still more preferably 5 to 30% by weight with respect to the product (100% by weight). By setting the content of the curing agent (E) to 1% by weight or more, the curing becomes more sufficient, and the crack resistance of the cured product tends to be improved. On the other hand, by setting the content of the curing agent (E) to 40% by weight or less, there is a tendency that a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が硬化剤（Ｅ）を含有する場合、硬化剤（Ｅ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、４０～２００重量部が好ましく、より好ましくは５０～１５０重量部である。より具体的には、硬化剤（Ｅ）として酸無水物類を使用する場合、本発明の第１態様又は第２態様の硬化性樹脂組成物に含まれる全てのエポキシ基を有する化合物におけるエポキシ基１当量当たり、０．５～１．５当量となる割合で使用することが好ましい。硬化剤（Ｅ）の含有量を４０重量部以上とすることにより、硬化がより十分となり、硬化物の耐クラック性が向上する傾向がある。一方、硬化剤（Ｅ）の含有量を２００重量部以下とすることにより、着色がより抑制され色相に優れた硬化物（リフレクター）が得られやすい傾向がある。 When the curable resin composition of the 1st aspect or 2nd aspect of this invention contains a hardening | curing agent (E), content (blending amount) of a hardening | curing agent (E) is although it does not specifically limit, A curable resin composition The amount is preferably 40 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total amount of the compound having an epoxy group contained in the product. More specifically, when an acid anhydride is used as the curing agent (E), the epoxy group in the compound having all the epoxy groups contained in the curable resin composition of the first aspect or the second aspect of the present invention. It is preferable to use at a ratio of 0.5 to 1.5 equivalents per equivalent. By setting the content of the curing agent (E) to 40 parts by weight or more, the curing becomes more sufficient and the crack resistance of the cured product tends to be improved. On the other hand, by setting the content of the curing agent (E) to 200 parts by weight or less, there is a tendency that a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained.
［硬化促進剤（Ｆ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物は、硬化促進剤（Ｆ）を含んでいてもよい。硬化促進剤（Ｆ）は、本発明の第１態様又は第２態様の硬化性樹脂組成物に含まれるエポキシ基を有する化合物（例えば、脂環式エポキシ化合物（Ａ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び応力緩和剤（Ｈ）としての後掲のエポキシ変性シリコーンオイル）が硬化剤（Ｅ）等の硬化剤と反応する際、その反応速度を促進する機能を有する化合物である。硬化促進剤（Ｆ）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第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 (F)]
The curable resin composition of the first aspect or the second aspect of the present invention may contain a curing accelerator (F). The curing accelerator (F) is a compound having an epoxy group (for example, an alicyclic epoxy compound (A) or an isocyanuric acid derivative (I) included in the curable resin composition of the first aspect or the second aspect of the present invention. , A siloxane derivative (J) and a compound having a function of accelerating the reaction rate when the epoxy-modified silicone oil described later as a stress relaxation agent (H) reacts with a curing agent such as a curing agent (E). is there. As the curing accelerator (F), a known or conventional curing accelerator can be used. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, phenol) Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, Octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, etc. Secondary amines; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Ether, 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.
　本発明の第１態様又は第２態様の硬化性樹脂組成物において硬化促進剤（Ｆ）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 resin composition of the first aspect or the second aspect of the present invention, the curing accelerator (F) can be used alone or in combination of two or more.
　また、硬化促進剤（Ｆ）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。 Further, the curing accelerator (F) 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”, “12XD” (developed product) (San Apro Co., Ltd.); trade names “TPP-K”, “TPP-MK” (Hokuko Chemical Co., Ltd.); Commercial products such as the name “PX-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can also be used.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が硬化促進剤（Ｆ）を含有する場合、硬化促進剤（Ｆ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．０００１～５重量％が好ましく、より好ましくは０．００１～１重量％である。硬化促進剤（Ｆ）の含有量を０．０００１重量％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（Ｆ）の含有量を５重量％以下とすることにより、硬化性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（リフレクター）が得られやすい傾向がある。 When the curable resin composition of the first aspect or the second aspect of the present invention contains a curing accelerator (F), the content (blending amount) of the curing accelerator (F) is not particularly limited, but is curable. The content is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight, based on the resin composition (100% by weight). By setting the content of the curing accelerator (F) to 0.0001% by weight or more, the curing reaction tends to proceed more efficiently. On the other hand, by setting the content of the curing accelerator (F) to 5% by weight or less, the storability of the curable resin composition is further improved, or a cured product (reflector) that is more suppressed in coloring and excellent in hue. There is a tendency to obtain easily.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が硬化促進剤（Ｆ）を含有する場合、硬化促進剤（Ｆ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、０．０５～１５重量部が好ましく、より好ましくは０．１～１２重量部、さらに好ましくは０．２～１０重量部、特に好ましくは０．２５～８重量部である。硬化促進剤の含有量を０．０５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１５重量部以下とすることにより、硬化性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（リフレクター）が得られやすい傾向がある。 When the curable resin composition of the first aspect or the second aspect of the present invention contains a curing accelerator (F), the content (blending amount) of the curing accelerator (F) is not particularly limited, but is curable. The amount is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 12 parts by weight, and still more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the total amount of the compound having an epoxy group contained in the resin composition. Parts, particularly preferably 0.25 to 8 parts by weight. By setting the content of the curing accelerator to 0.05 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 15 parts by weight or less, the storability of the curable resin composition is further improved, or a cured product (reflector) that is more suppressed in coloring and excellent in hue is easily obtained. Tend.
［硬化触媒（Ｇ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物における硬化触媒（Ｇ）は、脂環式エポキシ化合物（Ａ）、応力緩和剤（Ｈ）としての後掲のエポキシ変性シリコーンオイル、さらに本発明の第２態様の場合は、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）等のカチオン重合性化合物の硬化反応（重合反応）を開始及び／又は促進させることにより、硬化性樹脂組成物を硬化させる働きを有する化合物である。硬化触媒（Ｇ）としては、特に限定されないが、例えば、光照射や加熱処理等を施すことによりカチオン種を発生して、重合を開始させるカチオン重合開始剤（光カチオン重合開始剤、熱カチオン重合開始剤等）や、ルイス酸・アミン錯体、ブレンステッド酸塩類、イミダゾール類等が挙げられる。 [Curing catalyst (G)]
The curing catalyst (G) in the curable resin composition of the first aspect or the second aspect of the present invention includes an alicyclic epoxy compound (A), an epoxy-modified silicone oil described later as a stress relaxation agent (H), and In the case of the second aspect of the present invention, a curable resin composition is obtained by initiating and / or promoting a curing reaction (polymerization reaction) of a cationically polymerizable compound such as an isocyanuric acid derivative (I) or a siloxane derivative (J). Is a compound having a function of curing. The curing catalyst (G) is not particularly limited. For example, a cationic polymerization initiator (photo cationic polymerization initiator, thermal cationic polymerization) that initiates polymerization by generating cationic species by light irradiation, heat treatment, or the like. Initiators, etc.), Lewis acid / amine complexes, Bronsted acid salts, imidazoles and the like.
　硬化触媒（Ｇ）としての光カチオン重合開始剤としては、例えば、ヘキサフルオロアンチモネート塩、ペンタフルオロヒドロキシアンチモネート塩、ヘキサフルオロホスフェート塩、ヘキサフルオロアルセネート塩等が挙げられ、より具体的には、例えば、トリアリールスルホニウムヘキサフルオロホスフェート（例えば、ｐ－フェニルチオフェニルジフェニルスルホニウムヘキサフルオロホスフェート等）、トリアリールスルホニウムヘキサフルオロアンチモネート等のスルホニウム塩（特に、トリアリールスルホニウム塩）；ジアリールヨードニウムヘキサフルオロホスフェート、ジアリールヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ヨードニウム［４－（４－メチルフェニル－２－メチルプロピル）フェニル］ヘキサフルオロホスフェート等のヨードニウム塩；テトラフルオロホスホニウムヘキサフルオロホスフェート等のホスホニウム塩；Ｎ－ヘキシルピリジニウムテトラフルオロボレート等のピリジニウム塩等が挙げられる。また、光カチオン重合開始剤としては、例えば、商品名「ＵＶＡＣＵＲＥ１５９０」（ダイセル・サイテック（株）製）；商品名「ＣＤ－１０１０」、「ＣＤ－１０１１」、「ＣＤ－１０１２」（以上、米国サートマー製）；商品名「イルガキュア２６４」（ＢＡＳＦ社製）；商品名「ＣＩＴ－１６８２」（日本曹達（株）製）等の市販品を好ましく使用することもできる。 Examples of the photocationic polymerization initiator as the curing catalyst (G) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically. For example, triarylsulfonium hexafluorophosphate (eg, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate), sulfonium salts such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salts); diaryl iodonium hexafluorophosphate Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodine Iodonium salts such as nium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridinium salts such as N-hexylpyridinium tetrafluoroborate It is done. Examples of the cationic photopolymerization initiator include, for example, trade names “UVACURE 1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States). Commercial products such as Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.
　硬化触媒（Ｇ）としての熱カチオン重合開始剤としては、例えば、アリールジアゾニウム塩、アリールヨードニウム塩、アリールスルホニウム塩、アレン－イオン錯体等が挙げられ、商品名「ＰＰ－３３」、「ＣＰ－６６」、「ＣＰ－７７」（以上（株）ＡＤＥＫＡ製）；商品名「ＦＣ－５０９」（スリーエム製）；商品名「ＵＶＥ１０１４」（Ｇ．Ｅ．製）；商品名「サンエイドＳＩ－６０Ｌ」、「サンエイドＳＩ－８０Ｌ」、「サンエイドＳＩ－１００Ｌ」、「サンエイドＳＩ－１１０Ｌ」、「サンエイドＳＩ－１５０Ｌ」（以上、三新化学工業（株）製）；商品名「ＣＧ－２４－６１」（ＢＡＳＦ社製）等の市販品を好ましく使用することができる。さらに、熱カチオン重合開始剤としては、アルミニウムやチタン等の金属とアセト酢酸若しくはジケトン類とのキレート化合物とトリフェニルシラノール等のシラノールとの化合物、又は、アルミニウムやチタン等の金属とアセト酢酸若しくはジケトン類とのキレート化合物とビスフェノールＳ等のフェノール類との化合物等も挙げられる。 Examples of the thermal cationic polymerization initiator as the curing catalyst (G) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”. "CP-77" (manufactured by ADEKA); trade name "FC-509" (manufactured by 3M); trade name "UVE1014" (manufactured by GE); trade name "Sun-Aid SI-60L" “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.); trade name “CG-24-61” ( Commercially available products such as BASF) can be preferably used. Further, as the thermal cationic polymerization initiator, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone Examples thereof include a compound of a chelate compound with a phenol and a phenol such as bisphenol S.
　硬化触媒（Ｇ）としてのルイス酸・アミン錯体としては、公知乃至慣用のルイス酸・アミン錯体系硬化触媒を使用することができ、特に限定されないが、例えば、ＢＦ3・ｎ－ヘキシルアミン、ＢＦ3・モノエチルアミン、ＢＦ3・ベンジルアミン、ＢＦ3・ジエチルアミン、ＢＦ3・ピペリジン、ＢＦ3・トリエチルアミン、ＢＦ3・アニリン、ＢＦ4・ｎ－ヘキシルアミン、ＢＦ4・モノエチルアミン、ＢＦ4・ベンジルアミン、ＢＦ4・ジエチルアミン、ＢＦ4・ピペリジン、ＢＦ4・トリエチルアミン、ＢＦ4・アニリン、ＰＦ5・エチルアミン、ＰＦ5・イソプロピルアミン、ＰＦ5・ブチルアミン、ＰＦ5・ラウリルアミン、ＰＦ5・ベンジルアミン、ＡｓＦ5・ラウリルアミン等が挙げられる。 As the Lewis acid / amine complex as the curing catalyst (G), a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited. For example, BF 3 .n-hexylamine, BF 3 · monoethylamine, BF 3 · benzylamine, BF 3 · diethylamine, BF 3 · piperidine, BF 3 · triethylamine, BF 3 · aniline, BF 4 - n-hexylamine, BF 4 - monoethylamine, BF 4 - benzylamine , BF 4 · diethylamine, BF 4 · piperidine, BF 4 · triethylamine, BF 4 · aniline, PF 5 · ethylamine, PF 5 · isopropylamine, PF 5 · butylamine, PF 5 · laurylamine, PF 5 · benzylamine, AsF 5. Laurylamine etc. are mentioned.
　硬化触媒（Ｇ）としてのブレンステッド酸塩類としては、公知乃至慣用のブレンステッド酸塩類を使用することができ、特に限定されないが、例えば、脂肪族スルホニウム塩、芳香族スルホニウム塩、ヨードニウム塩、ホスホニウム塩等が挙げられる。 As the Bronsted acid salt as the curing catalyst (G), known or commonly used Bronsted acid salts can be used, and are not particularly limited. For example, aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, phosphoniums. Examples include salts.
　硬化触媒（Ｇ）としてのイミダゾール類としては、公知乃至慣用のイミダゾール類を使用することができ、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 as the curing catalyst (G), known or conventional imidazoles can be used, and are not particularly limited. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl Imidazole, 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 isocyanurate, 2,4 - Amino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyl-s-triazine, etc. Is mentioned.
　本発明の第１態様又は第２態様の硬化性樹脂組成物において硬化触媒（Ｇ）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。なお、上述のように、硬化触媒（Ｇ）としては市販品を使用することもできる。 In the curable resin composition of the first aspect or the second aspect of the present invention, the curing catalyst (G) can be used alone or in combination of two or more. In addition, as above-mentioned, a commercial item can also be used as a curing catalyst (G).
　本発明の第１態様又は第２態様の硬化性樹脂組成物が硬化触媒（Ｇ）を含有する場合、硬化触媒（Ｇ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．０００１～５重量％が好ましく、より好ましくは０．００１～１重量％である。硬化触媒（Ｇ）を上記範囲内で使用することにより、耐熱性、耐光性に優れた硬化物を得ることができる。 When the curable resin composition of the first aspect or the second aspect of the present invention contains the curing catalyst (G), the content (blending amount) of the curing catalyst (G) is not particularly limited, but the curable resin composition The content is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight, based on the product (100% by weight). By using the curing catalyst (G) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が硬化触媒（Ｇ）を含有する場合、本発明の硬化性樹脂組成物における硬化触媒（Ｇ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、０．０００１～１５重量部が好ましく、より好ましくは０．０１～１２重量部、さらに好ましくは０．０５～１０重量部、特に好ましくは０．０５～８重量部である。硬化触媒（Ｇ）を上記範囲内で使用することにより、耐熱性、耐光性に優れた硬化物を得ることができる。 When the curable resin composition of the first aspect or the second aspect of the present invention contains a curing catalyst (G), the content (blending amount) of the curing catalyst (G) in the curable resin composition of the present invention is: Although not particularly limited, the amount is preferably 0.0001 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 100 parts by weight based on the total amount of the compound having an epoxy group contained in the curable resin composition. Is 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight. By using the curing catalyst (G) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.
［応力緩和剤（Ｈ）］
　本発明の第１態様又は第２態様の硬化性樹脂組成物の必須成分である応力緩和剤（Ｈ）は、硬化物中の内部応力を緩和させることができる化合物である。本発明の第１態様又は第２態様の硬化性樹脂組成物は、応力緩和剤（Ｈ）を脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、さらに本発明の第２態様の場合は、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）と組み合わせて用いることにより、白色顔料（Ｃ）や無機充填剤（Ｄ）の充填量を増加させてもコンプレッション成型が可能であり、なおかつ、コンプレッション成型により形成される硬化物の光反射性、耐熱性、及び耐光性に優れる傾向がある。また、応力緩和剤（Ｈ）により硬化物の内部の応力を緩和させて、コンプレッション成型による形成物のそりを低減することもできる。 [Stress relaxation agent (H)]
The stress relaxation agent (H) that is an essential component of the curable resin composition of the first aspect or the second aspect of the present invention is a compound that can relieve internal stress in a cured product. In the curable resin composition according to the first or second aspect of the present invention, the stress relaxation agent (H) is an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler ( D) Further, in the case of the second embodiment of the present invention, white pigment (C) and inorganic are obtained by using in combination with isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K). Even if the filling amount of the filler (D) is increased, compression molding is possible, and the cured product formed by compression molding tends to be excellent in light reflectivity, heat resistance, and light resistance. In addition, the stress relaxation agent (H) can relieve the internal stress of the cured product to reduce warpage of the formed product due to compression molding.
　上記応力緩和剤（Ｈ）としては、特に限定されず、例えば、シリコーンゴム粒子（Ｈ１）、シリコーンオイル（Ｈ２）、液状ゴム成分（Ｈ３）、熱可塑性樹脂（Ｈ４）等が挙げられる。 The stress relaxation agent (H) is not particularly limited, and examples thereof include silicone rubber particles (H1), silicone oil (H2), liquid rubber component (H3), and thermoplastic resin (H4).
　上記シリコーンゴム粒子（Ｈ１）としては、特に限定されず、例えば、ポリメチルシロキサン、ポリメチルフェニルシロキサン等のポリシロキサンから構成されるものが挙げられる。
　また、シリコーンゴム粒子（Ｈ１）を構成するポリシロキサンは、架橋されていることが好ましい。架橋されたポリシロキサンとしては、特に限定されず、例えば、シラノール基などの縮合反応、メルカプトシリル基とビニルシリル基とのラジカル反応、ビニルシリル基とヒドロシリル基（ＳｉＨ基）との付加反応などにより架橋されたポリシロキサンなどが例示されるが、反応性、反応工程上の点からは、ビニル基含有オルガノポリシロキサンとオルガノハイドロジェンポリシロキサンを白金系触媒の存在下で付加反応させて架橋されたポリシロキサンが好ましい。 The silicone rubber particles (H1) are not particularly limited, and examples thereof include those composed of polysiloxanes such as polymethylsiloxane and polymethylphenylsiloxane.
The polysiloxane constituting the silicone rubber particles (H1) is preferably crosslinked. The crosslinked polysiloxane is not particularly limited. For example, it is crosslinked by a condensation reaction such as a silanol group, a radical reaction between a mercaptosilyl group and a vinylsilyl group, or an addition reaction between a vinylsilyl group and a hydrosilyl group (SiH group). In terms of reactivity and reaction process, polysiloxane crosslinked by addition reaction of vinyl group-containing organopolysiloxane and organohydrogenpolysiloxane in the presence of a platinum-based catalyst. Is preferred.
　また、上記シリコーンゴム粒子（Ｈ１）は、樹脂組成物とのなじみ、分散性向上、及び分散後の樹脂組成物の粘度調整の観点から、表面処理されていてもよい。表面処理の態様は、特に限定されず、例えば、メチルメタクリレートで被覆されたシリコーンゴム粒子、シリコーンレジンで被覆されたシリコーンゴム粒子などが挙げられる。 The silicone rubber particles (H1) may be surface-treated from the viewpoint of familiarity with the resin composition, improvement in dispersibility, and adjustment of the viscosity of the resin composition after dispersion. The aspect of the surface treatment is not particularly limited, and examples thereof include silicone rubber particles coated with methyl methacrylate, silicone rubber particles coated with silicone resin, and the like.
　上記シリコーンゴム粒子（Ｈ１）の平均粒子径（ｄ50）は、特に限定されないが、０．１～１００μｍが好ましく、より好ましくは０．５～５０μｍである。また、上記シリコーンゴム粒子（Ｈ１）の最大粒子径は、特に限定されないが、０．１～２５０μｍが好ましく、より好ましくは０．１～１５０μｍである。平均粒子径を１００μｍ以下（又は、最大粒子径を２５０μｍ以下）とすることにより、硬化物の耐クラック性がより向上する傾向がある。一方、平均粒子径を０．１μｍ以上（又は、最大粒子径を０．１μｍ以上）とすることにより、上記シリコーンゴム粒子（Ｈ１）の分散性がより向上する傾向がある。
　また、シリコーンゴム粒子（Ｈ１）の形状も特に限定されないが、作業性を向上させる観点から、球状が好ましい。 The average particle diameter (d 50 ) of the silicone rubber particles (H1) is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm. The maximum particle size of the silicone rubber particles (H1) is not particularly limited, but is preferably 0.1 to 250 μm, more preferably 0.1 to 150 μm. When the average particle size is 100 μm or less (or the maximum particle size is 250 μm or less), the crack resistance of the cured product tends to be further improved. On the other hand, when the average particle size is 0.1 μm or more (or the maximum particle size is 0.1 μm or more), the dispersibility of the silicone rubber particles (H1) tends to be further improved.
The shape of the silicone rubber particles (H1) is not particularly limited, but is preferably spherical from the viewpoint of improving workability.
　上記シリコーンゴム粒子（Ｈ１）としては、コンプレッション成型により光反射性、耐熱性、及び耐光性に優れる硬化物を形成することができるという観点から、架橋されたポリシロキサンからなるもの、或いは、これの表面をシリコーンレジンで被覆したものが好ましく、なかでも、樹脂成分とシリコーンゴム粒子（Ｈ１）の相溶性の点から、架橋されたポリジメチルシロキサンの表面をシリコーンレジンで被覆したものが特に好ましい。 As said silicone rubber particle (H1), from a viewpoint that the cured | curing material excellent in light reflectivity, heat resistance, and light resistance can be formed by compression molding, it consists of bridge | crosslinked polysiloxane, or this The surface of which is coated with a silicone resin is preferable, and the surface of the crosslinked polydimethylsiloxane is particularly preferable from the viewpoint of the compatibility between the resin component and the silicone rubber particles (H1).
　本発明の第１態様又は第２態様の硬化性樹脂組成物においてシリコーンゴム粒子（Ｈ１）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、上記シリコーンゴム粒子（Ｈ１）としては、公知乃至慣用の方法により製造することができ、その製造方法は、例えば、特開平７－１９６８１５号公報に記載された方法により製造されたシリコーンゴム粒子を使用することができる、或いは、商品名「ＫＭＰ－６００」、「ＫＭＰ－６０１」、「ＫＭＰ－６０２」、「ＫＭＰ－６０５」、「Ｘ－５２－７０３０」、「ＫＭＰ－５９７」、「ＫＭＰ－５９８」、「ＫＭＰ－５９４」、「Ｘ－５２－８７５」、「ＫＭＰ－５９０」、「ＫＭＰ－７０１」（以上、信越化学工業（株）製）等の市販品を使用することもできる。 In the curable resin composition of the first aspect or the second aspect of the present invention, the silicone rubber particles (H1) can be used alone or in combination of two or more. The silicone rubber particles (H1) can be produced by a known or conventional method, and the production method thereof is, for example, a silicone rubber particle produced by the method described in JP-A-7-196815. Or the product names “KMP-600”, “KMP-601”, “KMP-602”, “KMP-605”, “X-52-7030”, “KMP-597”, “ Commercial products such as “KMP-598”, “KMP-594”, “X-52-875”, “KMP-590”, “KMP-701” (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used. it can.
　上記シリコーンオイル（Ｈ２）としては、特に限定されず、例えば、非変性シリコーンオイル、変性シリコーンオイル等が挙げられる。 The silicone oil (H2) is not particularly limited, and examples thereof include non-modified silicone oil and modified silicone oil.
　非変性シリコーンオイルとしては、特に限定されず、例えば、ポリジメチルシロキサンタイプ、ポリメチルハイドロジェンシロキサンタイプ、ポリメチルフェニルシロキサンタイプ等が挙げられる。 The non-modified silicone oil is not particularly limited, and examples thereof include a polydimethylsiloxane type, a polymethylhydrogensiloxane type, and a polymethylphenylsiloxane type.
　変性シリコーンオイルとしては、特に限定されず、例えば、エポキシ樹脂に対して反応性を有する反応性シリコーンオイル、エポキシ樹脂に対して反応性を有しない非反応性シリコーンオイルのいずれを用いてもよい。反応性シリコーンオイルとしては、例えば、アミノ変性タイプ、エポキシ変性タイプ、カルボキシル変性タイプ、カルビノール変性タイプ、メタクリル変性タイプ、メルカプト変性タイプ、フェノール変性タイプ等が挙げられる。非反応性シリコーンオイルとしては、例えば、ポリアルキレンエーテル変性タイプ、メチルスチリル変性タイプ、アルキル変性タイプ、脂肪酸エステル変性タイプ、アルコキシ変性タイプ、フッ素変性タイプ等が挙げられる。また、反応性シリコーンオイルは、非反応性変性基を有していてもよく、例えば、ポリアルキレンエーテル－アミノ変性シリコーンオイル、ポリアルキレンエーテル－エポキシ変性シリコーンオイル等が挙げられ、脂環式エポキシ化合物（Ａ）、さらに本発明の第２態様の場合は、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）等のエポキシ基を有する化合物との反応性を有し、流動性や粘度の制御が可能なポリアルキレンエーテル－エポキシ変性シリコーンオイルが好ましい。 The modified silicone oil is not particularly limited, and for example, either a reactive silicone oil that is reactive with an epoxy resin or a non-reactive silicone oil that is not reactive with an epoxy resin may be used. Examples of the reactive silicone oil include amino-modified type, epoxy-modified type, carboxyl-modified type, carbinol-modified type, methacryl-modified type, mercapto-modified type, and phenol-modified type. Examples of non-reactive silicone oils include polyalkylene ether-modified types, methylstyryl-modified types, alkyl-modified types, fatty acid ester-modified types, alkoxy-modified types, and fluorine-modified types. Further, the reactive silicone oil may have a non-reactive modifying group, and examples thereof include polyalkylene ether-amino modified silicone oil, polyalkylene ether-epoxy modified silicone oil and the like, and alicyclic epoxy compound (A) Furthermore, in the case of the second aspect of the present invention, it has reactivity with compounds having an epoxy group such as isocyanuric acid derivative (I) and siloxane derivative (J), and can control fluidity and viscosity. Polyalkylene ether-epoxy modified silicone oils are preferred.
　上記シリコーンオイル（Ｈ２）としては、コンプレッション成型により光反射性、耐熱性、及び耐光性に優れる硬化物を形成することができるという観点から、ポリアルキレンエーテル－エポキシ変性シリコーンオイルが好ましく、特に、エポキシ当量３０００～１５０００の下記式（１）で表される構造を有するポリアルキレンエーテル変性シリコーン化合物（以下、「ポリアルキレンエーテル変性シリコーン化合物（１）」と称する場合がある）が好ましい。
Figure JPOXMLDOC01-appb-C000016
 As the silicone oil (H2), a polyalkylene ether-epoxy modified silicone oil is preferable from the viewpoint that a cured product having excellent light reflectivity, heat resistance, and light resistance can be formed by compression molding. A polyalkylene ether-modified silicone compound having a structure represented by the following formula (1) having an equivalent weight of 3000 to 15000 (hereinafter sometimes referred to as “polyalkylene ether-modified silicone compound (1)”) is preferred.
Figure JPOXMLDOC01-appb-C000016
　上記式（１）中、Ｒ9は炭素数２又は３のアルキレン基である。炭素数が２又は３のアルキレン基としては、例えば、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、トリメチレン基が好ましい。 In the above formula (1), R 9 is an alkylene group having 2 or 3 carbon atoms. Examples of the alkylene group having 2 or 3 carbon atoms include a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group, and a trimethylene group is preferable.
　上記式（１）中、ｘは８０～１４０の整数を示す。
　上記式（１）中、ｙは１～５の整数を示す。ｙが２以上の整数の場合、ｙが付された括弧内の構造はそれぞれ同一であってもよいし、異なっていてもよい。
　上記式（１）中、ｚは５～２０の整数を示す。なお、ｚが付された括弧内の構造はそれぞれ同一であってもよいし、異なっていてもよい。 In the above formula (1), x represents an integer of 80 to 140.
In the above formula (1), y represents an integer of 1 to 5. When y is an integer of 2 or more, the structures in parentheses to which y is attached may be the same or different.
In the above formula (1), z represents an integer of 5 to 20. Note that the structures in parentheses to which z is attached may be the same or different.
　上記式（１）中、Ａは下記式（１ａ）で表される構造を有するポリアルキレンエーテル基である。
Figure JPOXMLDOC01-appb-C000017
 In the above formula (1), A is a polyalkylene ether group having a structure represented by the following formula (1a).
Figure JPOXMLDOC01-appb-C000017
　上記式（１ａ）中、ａ及びｂはそれぞれ独立して、０～４０の整数である。ａが４０以下であることにより、硬化物の耐水性が向上する傾向がある。
　一方、ｂが４０以下であることにより、硬化性樹脂組成物の流動性が向上する傾向がある。 In the above formula (1a), a and b are each independently an integer of 0 to 40. When a is 40 or less, the water resistance of the cured product tends to be improved.
On the other hand, when b is 40 or less, the fluidity of the curable resin composition tends to be improved.
　ａ及びｂの合計は、特に限定されないが、好ましくは１～８０の整数である。ａ及びｂの合計が当該範囲にあることにより、硬化物の耐水性と、硬化性樹脂組成物の流動性を制御しやすくなる。 The total of a and b is not particularly limited, but is preferably an integer of 1 to 80. When the sum of a and b is in the range, it becomes easy to control the water resistance of the cured product and the fluidity of the curable resin composition.
　上記式（１ａ）中、Ｂは水素原子、又はメチル基である。硬化物の耐水性の観点からは、Ｂはメチル基が好ましい。 In the above formula (1a), B is a hydrogen atom or a methyl group. From the viewpoint of water resistance of the cured product, B is preferably a methyl group.
　上記式（１）における各構造単位の付加形態は、式（１）中の２つのトリメチルシリル基が両末端に存在する限り、ランダム型であってもよいし、ブロック型であってもよい。また、上記式（１ａ）における各構造単位の付加形態も、Ｂが末端に存在する限り、ランダム型であってもよいし、ブロック型であってもよい。また、上記式（１）、（１ａ）における各構造単位の配列の順番も特に限定されない。 The addition form of each structural unit in the above formula (1) may be a random type or a block type as long as two trimethylsilyl groups in the formula (1) are present at both ends. Moreover, the addition form of each structural unit in the formula (1a) may be a random type or a block type as long as B is present at the terminal. Further, the order of arrangement of the structural units in the above formulas (1) and (1a) is not particularly limited.
　上記ポリアルキレンエーテル変性シリコーン化合物（１）のエポキシ当量は、上記の通り、３０００～１５０００であり、好ましくは４０００～１５０００、より好ましくは５０００～１３０００である。エポキシ当量が３０００以上であることにより、硬化物の内部の応力緩和がより向上する傾向がある。一方、エポキシ当量を１５０００以下とすることにより、樹脂との相溶性がより向上する傾向がある。
　なお、ポリアルキレンエーテル変性シリコーン化合物（１）のエポキシ当量は、ＪＩＳ　Ｋ　７２３６：２００１に準拠して測定することができる。 As described above, the epoxy equivalent of the polyalkylene ether-modified silicone compound (1) is 3000 to 15000, preferably 4000 to 15000, and more preferably 5000 to 13000. When the epoxy equivalent is 3000 or more, the stress relaxation inside the cured product tends to be further improved. On the other hand, when the epoxy equivalent is 15000 or less, the compatibility with the resin tends to be further improved.
The epoxy equivalent of the polyalkylene ether-modified silicone compound (1) can be measured according to JIS K 7236: 2001.
　本発明の第１態様又は第２態様の硬化性樹脂組成物においてシリコーンオイル（Ｈ２）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、上記シリコーンオイル（Ｈ２）としては、公知乃至慣用の方法により製造することができ、例えば、特開２００８－２０１９０４号公報に記載された方法により製造されたシリコーンオイル（Ｈ２）を使用することができ、或いは、商品名「ＳＦ８４２１」（東レ・ダウコーニング（株）製）、商品名「Ｙ－１９２６８」（モメンティブ・パフォーマンス・マテリアルズ・ジャパン（同）製）等の市販品を使用することもできる。 In the curable resin composition of the first aspect or the second aspect of the present invention, the silicone oil (H2) can be used singly or in combination of two or more. The silicone oil (H2) can be produced by a known or conventional method. For example, the silicone oil (H2) produced by the method described in JP-A-2008-201904 is used. Or use a commercial product such as “SF8421” (made by Toray Dow Corning Co., Ltd.) or “Y-19268” (made by Momentive Performance Materials Japan). You can also.
　上記液状ゴム成分（Ｈ３）としては、特に限定されず、例えば、ポリブタジエン、マレイン化ポリブタジエン、アクリル化ポリブタジエン、メタクリル化ポリブタジエン、エポキシ化ポリブタジエン、アクリロニトリルブタジエンゴム、カルボキシ末端アクリロニトリルブタジエンゴム、アミノ末端アクリロニトリルブタジエンゴム、ビニル末端アクリロニトリルブタジエンゴム、スチレンブタジエンゴム等が挙げられる。
　上記液状ゴム成分（Ｈ３）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。 The liquid rubber component (H3) is not particularly limited. For example, polybutadiene, maleated polybutadiene, acrylated polybutadiene, methacrylated polybutadiene, epoxidized polybutadiene, acrylonitrile butadiene rubber, carboxy terminal acrylonitrile butadiene rubber, amino terminal acrylonitrile butadiene rubber. Vinyl-terminated acrylonitrile butadiene rubber, styrene butadiene rubber and the like.
The said liquid rubber component (H3) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　上記熱可塑性樹脂（Ｈ４）としては、特に限定されず、例えば、ポリイミド樹脂、ポリアミド樹脂、ポリエーテルイミド樹脂、ポリエステル樹脂、ポリエステルイミド樹脂、フェノキシ樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンサルファイド樹脂、ポリエーテルケトン樹脂等が挙げられる。これらの中でも、耐熱性の観点から、フェノキシ樹脂、ポリイミド樹脂が好ましい。これらの熱可塑性樹脂は、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。 The thermoplastic resin (H4) is not particularly limited. For example, polyimide resin, polyamide resin, polyetherimide resin, polyester resin, polyesterimide resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, Examples include polyether ketone resins. Among these, phenoxy resin and polyimide resin are preferable from the viewpoint of heat resistance. These thermoplastic resins can be used singly or in combination of two or more.
　上記熱可塑性樹脂（Ｈ４）のガラス転移温度（Ｔｇ）は、特に限定されないが、２００℃以下であることが好ましい。 The glass transition temperature (Tg) of the thermoplastic resin (H4) is not particularly limited, but is preferably 200 ° C. or lower.
　上記応力緩和剤（Ｈ）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。
　上記応力緩和剤（Ｈ）としては、コンプレッション成型により光反射性、耐熱性、及び耐光性に優れる硬化物を形成することができるという観点から、シリコーンゴム粒子（Ｈ１）及びシリコーンオイル（Ｈ２）からなる群より選択される少なくとも１種が好ましく、特に、シリコーンゴム粒子（Ｈ１）としては、シリコーンレジンを表面に備える架橋されたポリジメチルシロキサンが好ましく、シリコーンオイル（Ｈ２）としては、ポリアルキレンエーテル変性シリコーン化合物（１）が好ましい。 The said stress relaxation agent (H) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
As said stress relaxation agent (H), from a viewpoint that the cured | curing material which is excellent in light reflectivity, heat resistance, and light resistance can be formed by compression molding, from silicone rubber particle (H1) and silicone oil (H2). At least one selected from the group consisting of these is preferable, and in particular, as the silicone rubber particles (H1), a crosslinked polydimethylsiloxane having a silicone resin on the surface is preferable, and as the silicone oil (H2), polyalkylene ether-modified Silicone compound (1) is preferred.
　本発明の第１態様の硬化性樹脂組成物における応力緩和剤（Ｈ）の含有量（配合量）は、特に限定されないが、脂環式エポキシ化合物（Ａ）１００重量部に対して、１～２００重量部が好ましく、より好ましくは５～１５０重量部、さらに好ましくは８～１２０重量部である。応力緩和剤（Ｈ）の含有量を１重量部以上とすることにより、白色顔料（Ｃ）や無機充填剤（Ｄ）の充填量を増やしてもコンプレッション成型が可能であり、また、成形された硬化物の光反射性、耐熱性、及び耐光性がより向上する傾向がある。また、成形品の反りが緩和されて、寸法安定性が向上する傾向がある。一方、応力緩和剤（Ｈ）の含有量を２００重量部以下とすることにより、硬化性樹脂組成物の硬化性がより向上する傾向がある。 The content (blending amount) of the stress relaxation agent (H) in the curable resin composition of the first aspect 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 alicyclic epoxy compound (A). The amount is preferably 200 parts by weight, more preferably 5 to 150 parts by weight, still more preferably 8 to 120 parts by weight. By setting the content of the stress relaxation agent (H) to 1 part by weight or more, compression molding is possible even when the white pigment (C) or inorganic filler (D) is increased, and the molded There exists a tendency for the light reflectivity, heat resistance, and light resistance of hardened | cured material to improve more. Further, the warpage of the molded product is alleviated and the dimensional stability tends to be improved. On the other hand, when the content of the stress relaxation agent (H) is 200 parts by weight or less, the curability of the curable resin composition tends to be further improved.
　本発明の第２態様の硬化性樹脂組成物における応力緩和剤（Ｈ）の含有量（配合量）は、特に限定されないが、脂環式エポキシ化合物（Ａ）１００重量部に対して、１～２５０重量部が好ましく、より好ましくは５～２３０重量部、さらに好ましくは１０～２００重量部である。応力緩和剤（Ｈ）の含有量１重量部以上とすることにより、白色顔料（Ｃ）や無機充填剤（Ｄ）の充填量を増やしてもコンプレッション成型が可能であり、また、成形された硬化物の光反射性、耐熱性、及び耐光性がより向上する傾向がある。また、成形品の反りが緩和されて、寸法安定性が向上する傾向がある。一方、応力緩和剤（Ｈ）の含有量を２５０重量部以下とすることにより、硬化性樹脂組成物の硬化性がより向上する傾向がある。 The content (blending amount) of the stress relaxation agent (H) in the curable resin composition of the second aspect 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 alicyclic epoxy compound (A). The amount is preferably 250 parts by weight, more preferably 5 to 230 parts by weight, still more preferably 10 to 200 parts by weight. By setting the content of the stress relaxation agent (H) to 1 part by weight or more, compression molding is possible even when the filling amount of the white pigment (C) or the inorganic filler (D) is increased. There exists a tendency for the light reflectivity of a thing, heat resistance, and light resistance to improve more. Further, the warpage of the molded product is alleviated and the dimensional stability tends to be improved. On the other hand, when the content of the stress relaxation agent (H) is 250 parts by weight or less, the curability of the curable resin composition tends to be further improved.
　本発明の第２態様の硬化性樹脂組成物における応力緩和剤（Ｈ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１～２００重量部が好ましく、より好ましくは５～１５０重量部、さらに好ましくは８～１２０重量部である。応力緩和剤（Ｈ）の含有量を１重量部以上とすることにより、白色顔料（Ｃ）や無機充填剤（Ｄ）の充填量を増やしてもコンプレッション成型が可能であり、また、成形された硬化物の光反射性、耐熱性、及び耐光性がより向上する傾向がある。また、成形品の反りが緩和されて、寸法安定性が向上する傾向がある。一方、応力緩和剤（Ｈ）の含有量を２００重量部以下とすることにより、硬化性樹脂組成物の硬化性がより向上する傾向がある。 The content (blending amount) of the stress relaxation agent (H) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of compounds having epoxy groups contained in the curable resin composition is 100 wt. The amount is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, and still more preferably 8 to 120 parts by weight. By setting the content of the stress relaxation agent (H) to 1 part by weight or more, compression molding is possible even when the white pigment (C) or inorganic filler (D) is increased, and the molded There exists a tendency for the light reflectivity, heat resistance, and light resistance of hardened | cured material to improve more. Further, the warpage of the molded product is alleviated and the dimensional stability tends to be improved. On the other hand, when the content of the stress relaxation agent (H) is 200 parts by weight or less, the curability of the curable resin composition tends to be further improved.
　本発明の第１態様又は第２態様の硬化性樹脂組成物（１００重量％）に対する応力緩和剤（Ｈ）の含有量は、特に限定されないが、０．１～２０重量％が好ましく、より好ましくは０．３～１８重量％、さらに好ましくは０．５～１５重量％である。応力緩和剤（Ｈ）の含有量を０．１重量％以上とすることにより、白色顔料（Ｃ）や無機充填剤（Ｄ）の充填量を増やしてもコンプレッション成型が可能であり、なおかつ、成形された硬化物の光反射性、耐熱性、及び耐光性がより向上する傾向がある。また、成形品の反りが緩和されて、寸法安定性が向上する傾向がある。一方、応力緩和剤（Ｈ）の含有量を２０重量％以下とすることにより、硬化性樹脂組成物の硬化性がより向上する傾向がある。 The content of the stress relaxation agent (H) in the curable resin composition (100 wt%) of the first aspect or the second aspect of the present invention is not particularly limited, but is preferably 0.1 to 20 wt%, more preferably Is 0.3 to 18% by weight, more preferably 0.5 to 15% by weight. By making the content of the stress relaxation agent (H) 0.1% by weight or more, compression molding is possible even when the white pigment (C) or inorganic filler (D) is increased, and molding is also possible. The light reflectivity, heat resistance, and light resistance of the cured product thus obtained tend to be further improved. Further, the warpage of the molded product is alleviated and the dimensional stability tends to be improved. On the other hand, when the content of the stress relaxation agent (H) is 20% by weight or less, the curability of the curable resin composition tends to be further improved.
　本発明の第１態様の硬化性樹脂組成物は、さらに、脂環式エポキシ化合物（Ａ）以外のエポキシ化合物（「その他のエポキシ化合物」と称する場合がある）を含んでいてもよい。上記その他のエポキシ化合物としては、分子内に１以上のエポキシ基（オキシラン環）を有する公知乃至慣用の化合物を使用することができ、特に限定されないが、例えば、芳香族エポキシ化合物（芳香族エポキシ樹脂）、脂肪族エポキシ化合物（脂肪族エポキシ樹脂）、複素環式エポキシ化合物（複素環式エポキシ樹脂）、分子内にエポキシ基を１個以上有するシロキサン誘導体等が挙げられる。上記その他のエポキシ化合物は、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。 The curable resin composition of the first aspect of the present invention may further contain an epoxy compound other than the alicyclic epoxy compound (A) (sometimes referred to as “other epoxy compound”). As said other epoxy compound, the well-known thru | or usual compound which has 1 or more epoxy groups (oxirane ring) in a molecule | numerator can be used, Although it does not specifically limit, For example, an aromatic epoxy compound (aromatic epoxy resin) ), An aliphatic epoxy compound (aliphatic epoxy resin), a heterocyclic epoxy compound (heterocyclic epoxy resin), and a siloxane derivative having one or more epoxy groups in the molecule. The said other epoxy compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.
　上記複素環式エポキシ化合物としては、例えば、分子内にエポキシ基を１個以上有するイソシアヌル酸誘導体等が挙げられる。本発明の硬化性樹脂組成物が上記イソシアヌル酸誘導体を含む場合、硬化物の電極に対する密着性、耐熱性、耐吸湿リフロー性が向上する傾向がある。 Examples of the heterocyclic epoxy compound include isocyanuric acid derivatives having one or more epoxy groups in the molecule. When the curable resin composition of this invention contains the said isocyanuric acid derivative, there exists a tendency for the adhesiveness with respect to the electrode of cured | curing material, heat resistance, and moisture absorption reflow resistance to improve.
［分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）］
　本発明の第２態様の硬化性樹脂組成物の必須成分であるイソシアヌル酸誘導体（Ｉ）は、イソシアヌル酸の誘導体であって、分子内に１個以上のオキシラン環を少なくとも有する化合物である。本発明の第２態様の硬化性樹脂組成物がイソシアヌル酸誘導体（Ｉ）を含むことにより、硬化物の光反射性、耐熱性、耐光性が向上し、上記の応力緩和剤（Ｈ）、後述のシロキサン誘導体（Ｊ）、脂環式ポリエステル樹脂（Ｋ）と同時に硬化性樹脂組成物に含まれることで、硬化物の光反射性、耐熱性、耐光性がさらに向上する。イソシアヌル酸誘導体（Ｉ）が分子内に有するオキシラン環の数は、１個以上であればよく、特に限定されないが、１～６個が好ましく、より好ましくは１～３個である。 [Isocyanuric acid derivative (I) having one or more oxirane rings in the molecule]
The isocyanuric acid derivative (I), which is an essential component of the curable resin composition of the second aspect of the present invention, is a derivative of isocyanuric acid and is a compound having at least one oxirane ring in the molecule. When the curable resin composition of the second aspect of the present invention contains the isocyanuric acid derivative (I), the light reflectivity, heat resistance, and light resistance of the cured product are improved. When the siloxane derivative (J) and the alicyclic polyester resin (K) are included in the curable resin composition, the light reflectivity, heat resistance, and light resistance of the cured product are further improved. The number of oxirane rings in the molecule of the isocyanuric acid derivative (I) may be one or more, and is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3.
　イソシアヌル酸誘導体（Ｉ）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。
Figure JPOXMLDOC01-appb-C000018
 Examples of the isocyanuric acid derivative (I) include compounds represented by the following formula (III).
Figure JPOXMLDOC01-appb-C000018
　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有機基等が挙げられる。 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 aromatic hydrocarbon group (for example, an aryl group); A cyclic group; a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. 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 a monovalent organic group 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。
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
 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 At least one is preferably a group represented by the formula (IIIa).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
　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、上記イソシアヌル酸誘導体（Ｉ）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。
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
 More specifically, the isocyanuric acid derivative (I) 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-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
　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ものを示す。 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 the formulas (IIIa) and (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 monoallyldiglycidyl 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、上記イソシアヌル酸誘導体（Ｉ）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 isocyanuric acid derivative (I) may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
　中でも、イソシアヌル酸誘導体（Ｉ）としては、硬化物の光反射性、耐熱性、及び溶解性の観点から、上記式（III－１）～（III－３）で表される化合物が好ましく、より好ましくは上記式（III－１）で表される化合物である。なお、本発明の第２態様の硬化性樹脂組成物においてイソシアヌル酸誘導体（Ｉ）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。なお、イソシアヌル酸誘導体（Ｉ）としては、例えば、商品名「ＴＥＰＩＣ」（日産化学工業（株）製）；商品名「ＭＡ－ＤＧＩＣ」、「ＤＡ－ＭＧＩＣ」（以上、四国化成工業（株）製）等の市販品を使用することもできる。 Among these, the isocyanuric acid derivative (I) is preferably a compound represented by the above formulas (III-1) to (III-3) from the viewpoint of light reflectivity, heat resistance, and solubility of the cured product. A compound represented by the above formula (III-1) is preferable. In addition, in the curable resin composition of the 2nd aspect of this invention, the isocyanuric acid derivative (I) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Examples of the isocyanuric acid derivative (I) include trade names “TEPIC” (manufactured by Nissan Chemical Industries, Ltd.); trade names “MA-DGIC”, “DA-MGIC” (above, Shikoku Kasei Kogyo Co., Ltd.) (Commercially available) can also be used.
　本発明の第２態様の硬化性樹脂組成物におけるイソシアヌル酸誘導体（Ｉ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．０５～１５重量％が好ましく、より好ましくは０．１～１０重量％、さらに好ましくは０．３～５重量％である。イソシアヌル酸誘導体（Ｉ）の含有量を上記範囲内とすることにより、耐熱性、及び耐光性に優れた硬化物を得ることができる。 The content (blending amount) of the isocyanuric acid derivative (I) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0.05 with respect to the curable resin composition (100% by weight). Is preferably 15 to 15% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.3 to 5% by weight. By setting the content of the isocyanuric acid derivative (I) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.
　本発明の第２態様の硬化性樹脂組成物におけるイソシアヌル酸誘導体（Ｉ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１～６０重量部が好ましく、より好ましくは１～５０重量部、さらに好ましくは１～３０重量部である。イソシアヌル酸誘導体（Ｉ）の含有量を上記範囲内とすることにより、耐熱性、及び耐光性に優れた硬化物を得ることができる。 Although content (blending amount) of the isocyanuric acid derivative (I) in the curable resin composition of the second aspect of the present invention is not particularly limited, the total amount of compounds having an epoxy group contained in the curable resin composition is 100% by weight. The amount is preferably 1 to 60 parts by weight, more preferably 1 to 50 parts by weight, still more preferably 1 to 30 parts by weight. By setting the content of the isocyanuric acid derivative (I) within the above range, a cured product having excellent heat resistance and light resistance can be obtained.
［分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）］
　本発明の第２態様の硬化性樹脂組成物の必須成分であるシロキサン誘導体（Ｊ）は、分子内に２個以上のエポキシ基を有し、シロキサン結合（－Ｓｉ－Ｏ－Ｓｉ－）により構成された骨格を有する化合物（シロキサン化合物）である。シロキサン誘導体（Ｊ）におけるシロキサン骨格（Ｓｉ－Ｏ－Ｓｉ骨格）としては、特に限定されないが、例えば、環状シロキサン骨格；直鎖状のシリコーンや、かご型やラダー型のポリシルセスキオキサン等のポリシロキサン骨格等が挙げられる。中でも、上記シロキサン骨格としては、硬化物の光反射性、耐熱性、耐光性を向上させて光半導体装置の光度低下を抑制する観点で、環状シロキサン骨格、直鎖状シリコーン骨格が好ましい。即ち、シロキサン誘導体（Ｊ）としては、分子内に２個以上のエポキシ基を有する環状シロキサン、分子内に２個以上のエポキシ基を有する直鎖状シリコーンが好ましい。 [Siloxane derivative (J) having two or more epoxy groups in the molecule]
The siloxane derivative (J), which is an essential component of the curable resin composition of the second aspect of the present invention, has two or more epoxy groups in the molecule and is constituted by a siloxane bond (—Si—O—Si—). A compound having a skeleton formed (siloxane compound). The siloxane skeleton (Si—O—Si skeleton) in the siloxane derivative (J) is not particularly limited, and examples thereof include cyclic siloxane skeletons; linear silicones, cage-type and ladder-type polysilsesquioxanes, and the like. Examples include a polysiloxane skeleton. Among these, as the siloxane skeleton, a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the light reflectivity, heat resistance, and light resistance of the cured product and suppressing the light intensity reduction of the optical semiconductor device. That is, the siloxane derivative (J) is preferably a cyclic siloxane having two or more epoxy groups in the molecule and a linear silicone having two or more epoxy groups in the molecule.
　シロキサン誘導体（Ｊ）が分子内に２個以上のエポキシ基を有する環状シロキサンである場合、当該シロキサン環を形成するＳｉ－Ｏ単位の数（シロキサン環を形成するケイ素原子の数に等しい）は、特に限定されないが、硬化物の耐熱性、耐光性を向上させる観点で、２～１２が好ましく、より好ましくは４～８である。 When the siloxane derivative (J) is a cyclic siloxane having two or more epoxy groups in the molecule, the number of Si—O units forming the siloxane ring (equal to the number of silicon atoms forming the siloxane ring) is Although not particularly limited, it is preferably 2 to 12, more preferably 4 to 8, from the viewpoint of improving the heat resistance and light resistance of the cured product.
　シロキサン誘導体（Ｊ）の重量平均分子量は、特に限定されないが、硬化物の耐熱性、耐光性を向上させる観点で、１００～３０００が好ましく、より好ましくは１８０～２０００である。なお、シロキサン誘導体（Ｊ）の上記重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法により測定される標準ポリスチレン換算の分子量から算出される。 The weight average molecular weight of the siloxane derivative (J) is not particularly limited, but is preferably 100 to 3000, more preferably 180 to 2000, from the viewpoint of improving the heat resistance and light resistance of the cured product. In addition, the said weight average molecular weight of a siloxane derivative (J) is computed from the molecular weight of standard polystyrene conversion measured by GPC (gel permeation chromatography) method.
　シロキサン誘導体（Ｊ）が分子内に有するエポキシ基の数は、２個以上であればよく、特に限定されないが、硬化物の耐熱性、耐光性を向上させる観点で、２～４つ（２つ、３つ、又は４つ）が好ましい。 The number of epoxy groups in the molecule of the siloxane derivative (J) is not particularly limited as long as it is 2 or more. From the viewpoint of improving the heat resistance and light resistance of the cured product, 2 to 4 (2 3 or 4) is preferred.
　シロキサン誘導体（Ｊ）のエポキシ当量は、特に限定されないが、硬化物の耐熱性、耐光性を向上させる観点で、１８０～２０００が好ましく、より好ましくは１８０～１５００、さらに好ましくは１８０～１０００である。なお、上記エポキシ当量は、ＪＩＳ　Ｋ７２３６に準じて測定される値である。 The epoxy equivalent of the siloxane derivative (J) is not particularly limited, but is preferably 180 to 2000, more preferably 180 to 1500, and still more preferably 180 to 1000 from the viewpoint of improving the heat resistance and light resistance of the cured product. . The epoxy equivalent is a value measured according to JIS K7236.
　シロキサン誘導体（Ｊ）が有するエポキシ基は、特に限定されないが、硬化物の耐熱性、耐光性を向上させる観点で、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）であることが好ましく、中でも、シクロヘキセンオキシド基であることが特に好ましい。 The epoxy group possessed by the siloxane derivative (J) is not particularly limited, but from the viewpoint of improving the heat resistance and light resistance of the cured product, an epoxy composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. Group (alicyclic epoxy group) is preferable, and among them, a cyclohexene oxide group is particularly preferable.
　シロキサン誘導体（Ｊ）としては、例えば、下記式（ＩＶ）で表されるシロキサン化合物等が挙げられる。
Figure JPOXMLDOC01-appb-C000024
 Examples of the siloxane derivative (J) include a siloxane compound represented by the following formula (IV).
Figure JPOXMLDOC01-appb-C000024
　式（ＩＶ）中、Ｒaは、同一又は異なって、エポキシ基を含有する基、又はアルキル基を示す。但し、式（ＩＶ）におけるＲaの少なくとも２つ（例えば２～４つ）はエポキシ基を含有する基である。上述のエポキシ基を含有する基は、エポキシ基（オキシラン環）を少なくとも１つ含む基であり、例えば、アルケニル基等の炭素－炭素不飽和二重結合を有する直鎖又は分岐鎖状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－炭素不飽和二重結合を有する環状の脂肪族炭化水素基（例えば、シクロアルケニル基；シクロヘキセニルエチル基等の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、炭素－炭素不飽和二重結合を有する環状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が好ましい。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、ヘキシル基、オクチル基、イソオクチル基、デシル基、ドデシル基等の炭素数１～２０の直鎖又は分岐鎖状のアルキル基等が挙げられる。中でも、炭素数１～１０の直鎖又は分岐鎖状のアルキル基が好ましい。 In formula (IV), R a is the same or different and represents an epoxy group-containing group or an alkyl group. Provided that at least two R a in formula (IV) (e.g., 2 to four) is a group containing an epoxy group. The above-mentioned group containing an epoxy group is a group containing at least one epoxy group (oxirane ring). For example, a linear or branched aliphatic group having a carbon-carbon unsaturated double bond such as an alkenyl group. A group in which at least one double bond of a hydrocarbon group is epoxidized, or a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond (for example, a cycloalkenyl group; a cyclohexenylethyl group, etc. A group in which at least one double bond of the alkenylalkyl group or the like is epoxidized. 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, a group in which at least one double bond of a cyclic aliphatic hydrocarbon group having a carbon-carbon unsaturated double bond is epoxidized is preferable. Examples of the alkyl group include straight-chain or branched chain groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group. An alkyl group etc. are mentioned. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
　式（ＩＶ）中、ｎは、２～１２の整数を示す。特に、硬化物の耐熱衝撃性、光半導体装置の耐リフロー性及び耐熱衝撃性の観点で、ｎとしては、４～８が好ましく、より好ましくは４又は５である。 In the formula (IV), n represents an integer of 2 to 12. In particular, n is preferably 4 to 8, more preferably 4 or 5, from the viewpoint of thermal shock resistance of the cured product, reflow resistance and thermal shock resistance of the optical semiconductor device.
　シロキサン誘導体（Ｊ）としては、より具体的には、例えば、２，４－ジ［２－（３－｛オキサビシクロ［４．１．０］ヘプチル｝）エチル］－２，４，６，６，８，８－ヘキサメチル－シクロテトラシロキサン、４，８－ジ［２－（３－｛オキサビシクロ［４．１．０］ヘプチル｝）エチル］－２，２，４，６，６，８－ヘキサメチル－シクロテトラシロキサン、２，４－ジ［２－（３－｛オキサビシクロ［４．１．０］ヘプチル｝）エチル］－６，８－ジプロピル－２，４，６，８－テトラメチル－シクロテトラシロキサン、４，８－ジ［２－（３－｛オキサビシクロ［４．１．０］ヘプチル｝）エチル］－２，６－ジプロピル－２，４，６，８－テトラメチル－シクロテトラシロキサン、２，４，８－トリ［２－（３－｛オキサビシクロ［４．１．０］ヘプチル｝）エチル］－２，４，６，６，８－ペンタメチル－シクロテトラシロキサン、２，４，８－トリ［２－（３－｛オキサビシクロ［４．１．０］ヘプチル｝）エチル］－６－プロピル－２，４，６，８－テトラメチル－シクロテトラシロキサン、２，４，６，８－テトラ［２－（３－｛オキサビシクロ［４．１．０］ヘプチル｝）エチル］－２，４，６，８－テトラメチル－シクロテトラシロキサン、分子内に２個以上のエポキシ基を有するシルセスキオキサン等が挙げられる。さらに具体的には、例えば、下記式で表される分子内に２個以上のエポキシ基を有する環状シロキサン等が挙げられる。
Figure JPOXMLDOC01-appb-C000025
 More specifically, as the siloxane derivative (J), for example, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6 , 8,8-Hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2,4,6,6,8- Hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl- Cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetra Siloxane, 2,4,8-tri [2- (3- {Oxavicic [4.1.0] Heptyl}) ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tri [2- (3- {oxabicyclo [4.1. 0] heptyl}) ethyl] -6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra [2- (3- {oxabicyclo [4.1. 0] heptyl}) ethyl] -2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having two or more epoxy groups in the molecule, and the like. More specifically, for example, a cyclic siloxane having two or more epoxy groups in the molecule represented by the following formula.
Figure JPOXMLDOC01-appb-C000025
　また、シロキサン誘導体（Ｊ）としては、例えば、特開２００８－２４８１６９号公報に記載の脂環式エポキシ基含有シリコーン樹脂や、特開２００８－１９４２２号公報に記載の１分子中に少なくとも２つのエポキシ官能性基を有するオルガノポリシルセスキオキサン樹脂等を用いることもできる。 Examples of the siloxane derivative (J) include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169 and at least two epoxy resins in one molecule described in JP-A-2008-19422. An organopolysilsesquioxane resin having a functional group can also be used.
　なお、本発明の第２態様の硬化性樹脂組成物においてシロキサン誘導体（Ｊ）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 resin composition of the second aspect of the present invention, the siloxane derivative (J) can be used alone or in combination of two or more.
　シロキサン誘導体（Ｊ）は、例えば、分子内に２個以上のエポキシ基を有する環状シロキサンである商品名「Ｘ－４０－２６７８」、「Ｘ－４０－２６７０」、「Ｘ－４０－２７２０」（以上、信越化学工業（株）製）等の市販品を入手可能である。また、シロキサン誘導体（Ｊ）は、公知乃至慣用の方法により製造することができる。 Examples of the siloxane derivative (J) are cyclic siloxanes having two or more epoxy groups in the molecule, such as trade names “X-40-2678”, “X-40-2670”, “X-40-2720” ( As described above, commercial products such as Shin-Etsu Chemical Co., Ltd.) are available. The siloxane derivative (J) can be produced by a known or conventional method.
　本発明の第２態様の硬化性樹脂組成物におけるシロキサン誘導体（Ｊ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．１～３０重量％が好ましく、より好ましくは０．５～２０重量％、さらに好ましくは１．０～１０重量％である。シロキサン誘導体（Ｊ）の含有量を上記範囲に制御することにより、硬化性樹脂組成物のチクソ性が高くなり、硬化物の耐熱性、耐光性、及び光反射性がより向上する傾向がある。 The content (blending amount) of the siloxane derivative (J) in the curable resin composition of the second aspect of the present invention is not particularly limited, but is 0.1 to 0.1% with respect to the curable resin composition (100 wt%). It is preferably 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1.0 to 10% by weight. By controlling the content of the siloxane derivative (J) within the above range, the thixotropy of the curable resin composition increases, and the heat resistance, light resistance, and light reflectivity of the cured product tend to be further improved.
　本発明の第２態様の硬化性樹脂組成物におけるシロキサン誘導体（Ｊ）の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、５～９９重量部が好ましく、より好ましくは１０～９５重量部、さらに好ましくは２０～８０重量部である。シロキサン誘導体（Ｊ）の含有量を５重量部以上とすることにより、硬化性樹脂組成物のチクソ性が高くなり、硬化物の耐熱性、耐光性、及び光反射性がより向上する傾向がある。一方、シロキサン誘導体（Ｊ）の含有量を１５０重量部以下とすることにより、硬化物の耐熱衝撃性、及び接着性がより向上する傾向がある。 The content (blending amount) of the siloxane derivative (J) in the curable resin composition of the second aspect of the present invention is not particularly limited, but the total amount of compounds having an epoxy group contained in the curable resin composition is 100 parts by weight. The amount is preferably 5 to 99 parts by weight, more preferably 10 to 95 parts by weight, and still more preferably 20 to 80 parts by weight. By setting the content of the siloxane derivative (J) to 5 parts by weight or more, the thixotropy of the curable resin composition is increased, and the heat resistance, light resistance, and light reflectivity of the cured product tend to be further improved. . On the other hand, when the content of the siloxane derivative (J) is 150 parts by weight or less, the thermal shock resistance and adhesiveness of the cured product tend to be further improved.
［脂環式ポリエステル樹脂（Ｋ）］
　本発明の第２態様の硬化性樹脂組成物における上記脂環式ポリエステル樹脂（Ｋ）は、脂環構造（脂肪族環構造）を少なくとも有するポリエステル樹脂である。脂環式ポリエステル樹脂（Ｋ）は、硬化物の耐熱性、耐光性、耐クラック性を向上させると共に、エッチング液への溶出を抑制し（以下、このような特性を「耐エッチング液溶出性」という）、光半導体装置の光度低下を抑制する役割を担う。特に、硬化物の耐熱性、耐光性、耐クラック性、耐エッチング液溶出性向上の観点で、脂環式ポリエステル樹脂（Ｋ）は、主鎖に脂環（脂環構造）を有する脂環式ポリエステルであることが好ましい。即ち、脂環式ポリエステル樹脂（Ｋ）は、脂環を構成する炭素原子の一部又は全部によりポリマー主鎖が構成されたポリエステル樹脂であることが好ましい。なお、脂環式ポリエステル樹脂（Ｋ）は単独で、又は２種以上を組み合わせて使用できる。 [Alicyclic polyester resin (K)]
The alicyclic polyester resin (K) in the curable resin composition of the second aspect of the present invention is a polyester resin having at least an alicyclic structure (aliphatic ring structure). The alicyclic polyester resin (K) improves the heat resistance, light resistance, and crack resistance of the cured product and suppresses elution into the etching solution (hereinafter referred to as “etching solution elution resistance”). It plays a role of suppressing a decrease in luminous intensity of the optical semiconductor device. In particular, the alicyclic polyester resin (K) has an alicyclic (alicyclic structure) in the main chain from the viewpoint of improving heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product. Polyester is preferred. That is, the alicyclic polyester resin (K) is preferably a polyester resin in which a polymer main chain is constituted by part or all of carbon atoms constituting the alicyclic ring. In addition, an alicyclic polyester resin (K) can be used individually or in combination of 2 or more types.
　脂環式ポリエステル樹脂（Ｋ）における脂環構造としては、特に限定されないが、例えば、単環炭化水素構造や橋かけ環炭化水素構造（例えば、二環系炭化水素等）などが挙げられ、特に、脂環（脂環を構成する炭素－炭素結合）が全て炭素－炭素単結合により構成された、飽和単環炭化水素構造や飽和橋かけ環炭化水素構造が好ましい。また、上記脂環式ポリエステル樹脂（Ｋ）における脂環構造は、ジカルボン酸由来の構成単位とジオール由来の構成単位のいずれか一方のみに導入されていてもよいし、両方共に導入されていてもよく、特に限定されない。 The alicyclic structure in the alicyclic polyester resin (K) is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a bridged ring hydrocarbon structure (for example, a bicyclic hydrocarbon). Saturated monocyclic hydrocarbon structures and saturated bridged ring hydrocarbon structures in which all of the alicyclic rings (carbon-carbon bonds constituting the alicyclic rings) are carbon-carbon single bonds are preferred. Moreover, the alicyclic structure in the alicyclic polyester resin (K) may be introduced into only one of the structural unit derived from dicarboxylic acid or the structural unit derived from diol, or both may be introduced. Well, not particularly limited.
　脂環式ポリエステル樹脂（Ｋ）は、脂環構造を有するモノマー成分由来の構成単位を有する。上記脂環構造を有するモノマーとしては、公知乃至慣用の脂環構造を有するジオールやジカルボン酸が挙げられ、特に限定されないが、例えば、１，２－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジカルボン酸、４－メチル－１，２－シクロヘキサンジカルボン酸、ハイミック酸、１，４－デカヒドロナフタレンジカルボン酸、１，５－デカヒドロナフタレンジカルボン酸、２，６－デカヒドロナフタレンジカルボン酸、２，７－デカヒドロナフタレンジカルボン酸などの脂環構造を有するジカルボン酸（酸無水物等の誘導体も含む）等；１，２－シクロペンタンジオール、１，３－シクロペンタンジオール、１，２－シクロペンタンジメタノール、１，３－シクロペンタンジメタノール、ビス（ヒドロキシメチル）トリシクロ［５．２．１．０］デカン等の５員環ジオール、１，２－シクロヘキサンジオール、１，３－シクロヘキサンジオール、１，４－シクロヘキサンジオール、１，２－シクロヘキサンジメタノール、１，３－シクロヘキサンジメタノール、１，４－シクロヘキサンジメタノール、２，２－ビス－（４－ヒドロキシシクロヘキシル）プロパン等の６員環ジオール、水素添加ビスフェノールＡなどの脂環構造を有するジオール（これらの誘導体も含む）等が挙げられる。 The alicyclic polyester resin (K) has a structural unit derived from a monomer component having an alicyclic structure. Examples of the monomer having an alicyclic structure include diols and dicarboxylic acids having a known or commonly used alicyclic structure, and are not particularly limited. For example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, highmic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalene Dicarboxylic acids having an alicyclic structure such as dicarboxylic acid and 2,7-decahydronaphthalenedicarboxylic acid (including derivatives such as acid anhydrides) and the like; 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1 , 2-Cyclopentanedimethanol, 1,3-cyclopentanedimethanol 5-membered ring diol such as bis (hydroxymethyl) tricyclo [5.2.1.0] decane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedi Diols having an alicyclic structure such as 6-membered ring diols such as methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis- (4-hydroxycyclohexyl) propane, and hydrogenated bisphenol A (Including these derivatives).
　脂環式ポリエステル樹脂（Ｋ）は、脂環構造を有しないモノマー成分に由来する構成単位を有していてもよい。上記脂環構造を有しないモノマー成分としては、特に限定されないが、例えば、テレフタル酸、イソフタル酸、フタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸（酸無水物等の誘導体も含む）；アジピン酸、セバシン酸、アゼライン酸、コハク酸、フマル酸、マレイン酸等の脂肪族ジカルボン酸（酸無水物等の誘導体も含む）；エチレングリコール、プロピレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ネオペンチルグリコール、１，５－ペンタンジオール、１，６－ヘキサンジオール、３－メチルペンタンジオール、ジエチレングリコール、３－メチル－１，５－ペンタンジオール、２－メチル－１，３－プロパンジオール、２，２－ジエチル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、キシリレングリコール、ビスフェノールＡのエチレンオキサイド付加物、ビスフェノールＡのプロピレンオキサイド付加物などのジオール（これらの誘導体も含む）等が挙げられる。なお、上記脂環構造を有しないジカルボン酸やジオールに適宜な置換基（例えば、アルキル基、アルコキシ基、ハロゲン原子等）が結合したものも、脂環構造を有しないモノマー成分に含まれる。 The alicyclic polyester resin (K) may have a structural unit derived from a monomer component having no alicyclic structure. The monomer component having no alicyclic structure is not particularly limited. For example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides); adipic acid Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propane Diol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5- Pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl- Diols such as 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A (including derivatives thereof) Etc. A monomer component having no alicyclic structure also includes those obtained by bonding an appropriate substituent (for example, an alkyl group, an alkoxy group, a halogen atom, etc.) to the dicarboxylic acid or diol having no alicyclic structure.
　脂環式ポリエステル樹脂（Ｋ）を構成する全モノマー単位（全モノマー成分）（１００モル％）に対する脂環を有するモノマー単位の割合は、特に限定されないが、１０モル％以上（例えば、１０～８０モル％）が好ましく、より好ましくは２５～７０モル％、さらに好ましくは４０～６０モル％である。脂環を有するモノマー単位の割合が１０モル％未満であると、硬化物の耐熱性、耐光性、耐クラック性、耐エッチング液溶出性が低下する場合がある。 The ratio of the monomer unit having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin (K) is not particularly limited, but is 10 mol% or more (for example, 10 to 80). Mol%) is preferable, more preferably 25 to 70 mol%, still more preferably 40 to 60 mol%. When the ratio of the monomer unit having an alicyclic ring is less than 10 mol%, the heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product may decrease.
　脂環式ポリエステル樹脂（Ｋ）としては、特に、下記式（２）～（４）で表される構成単位を少なくとも一種以上含む脂環式ポリエステル樹脂が好ましい。 The alicyclic polyester resin (K) is particularly preferably an alicyclic polyester resin containing at least one structural unit represented by the following formulas (2) to (4).
Figure JPOXMLDOC01-appb-C000026
 （式中、Ｒ10は直鎖、分岐鎖、又は環状の炭素数２～１５のアルキレン基を表す。また、Ｒ11～Ｒ14は、それぞれ独立に、水素原子又は直鎖状若しくは分岐鎖状の炭素数１～４のアルキル基を表し、Ｒ11～Ｒ14から選ばれる二つが結合して環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000026
 (Wherein R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms. R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a group selected from R 11 to R 14 may be bonded to form a ring.
Figure JPOXMLDOC01-appb-C000027
 （式中、Ｒ10は直鎖、分岐鎖、又は環状の炭素数２～１５のアルキレン基を表す。また、Ｒ11～Ｒ14は、それぞれ独立に、水素原子又は直鎖状若しくは分岐鎖状の炭素数１～４のアルキル基を表し、Ｒ11～Ｒ14から選ばれる二つが結合した環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000027
 (Wherein R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms. R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
Figure JPOXMLDOC01-appb-C000028
 （式中、Ｒ10は直鎖、分岐鎖、又は環状の炭素数２～１５のアルキレン基を表す。また、Ｒ11～Ｒ14は、それぞれ独立に、水素原子又は直鎖状若しくは分岐鎖状の炭素数１～４のアルキル基を表し、Ｒ11～Ｒ14から選ばれる二つが結合した環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000028
 (Wherein R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms. R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
　上記式（２）～（４）で表される構成単位の好ましい具体例としては、例えば、下記式（５）で表される４－メチル－１，２－シクロヘキサンジカルボン酸及びエチレングリコール由来の構成単位が挙げられる。当該構成単位を有する脂環式ポリエステル樹脂（Ｋ）は、例えば、メチルヘキサヒドロ無水フタル酸とエチレングリコールとを重縮合することにより得られる。
Figure JPOXMLDOC01-appb-C000029
 Preferred specific examples of the structural units represented by the above formulas (2) to (4) include, for example, a structure derived from 4-methyl-1,2-cyclohexanedicarboxylic acid and ethylene glycol represented by the following formula (5) Units are listed. The alicyclic polyester resin (K) having the structural unit can be obtained, for example, by polycondensation of methylhexahydrophthalic anhydride and ethylene glycol.
Figure JPOXMLDOC01-appb-C000029
　また、上記式（２）～（４）で表される構成単位の他の好ましい具体例としては、例えば、下記式（６）で表される１，４－シクロヘキサンジカルボン酸及びネオペンチルグリコール由来の構成単位が挙げられる。当該構成単位を有する脂環式ポリエステル樹脂（Ｋ）は、例えば、１，４－シクロヘキサンジカルボン酸とネオペンチルグリコールとを重縮合することにより得られる。
Figure JPOXMLDOC01-appb-C000030
 Other preferable specific examples of the structural units represented by the above formulas (2) to (4) include, for example, those derived from 1,4-cyclohexanedicarboxylic acid and neopentyl glycol represented by the following formula (6): A structural unit is mentioned. The alicyclic polyester resin (K) having the structural unit can be obtained, for example, by polycondensation of 1,4-cyclohexanedicarboxylic acid and neopentyl glycol.
Figure JPOXMLDOC01-appb-C000030
　なお、脂環式ポリエステル樹脂（Ｋ）の末端構造は、特に限定されず、水酸基、カルボキシル基であってもよいし、これら水酸基やカルボキシル基が適宜変性された構造（例えば、末端の水酸基がモノカルボン酸や酸無水物によりエステル化された構造や、末端のカルボキシル基がアルコールによりエステル化された構造など）であってもよい。 The terminal structure of the alicyclic polyester resin (K) is not particularly limited, and may be a hydroxyl group or a carboxyl group, or a structure in which these hydroxyl group or carboxyl group is appropriately modified (for example, the terminal hydroxyl group is mono). It may be a structure esterified with a carboxylic acid or an acid anhydride, or a structure in which a terminal carboxyl group is esterified with an alcohol.
　脂環式ポリエステル樹脂（Ｋ）が上記式（２）～（４）で表される構成単位を有する場合、該構成単位の含有量の合計量（合計含有量；該構成単位を構成する全モノマー単位）は、特に限定されないが、脂環式ポリエステル樹脂（Ｋ）の全構成単位（１００モル％；脂環式ポリエステル樹脂（Ｋ）を構成する全モノマー単位）に対し、２０モル％以上（例えば、２０～１００モル％）が好ましく、より好ましくは５０～１００モル％、さらに好ましくは８０～１００モル％である。上記式（２）～（４）で表される構成単位の含有量が２０モル％未満であると、硬化物の耐熱性、耐光性、耐クラック性、耐エッチング液溶出性が低下する場合がある。 When the alicyclic polyester resin (K) has structural units represented by the above formulas (2) to (4), the total content of the structural units (total content; all monomers constituting the structural unit) The unit is not particularly limited, but 20 mol% or more (for example, with respect to the total structural unit (100 mol%; all monomer units constituting the alicyclic polyester resin (K)) of the alicyclic polyester resin (K) (for example, 20 to 100 mol%), more preferably 50 to 100 mol%, still more preferably 80 to 100 mol%. If the content of the structural units represented by the above formulas (2) to (4) is less than 20 mol%, the heat resistance, light resistance, crack resistance, and etching solution elution resistance of the cured product may decrease. is there.
　脂環式ポリエステル樹脂（Ｋ）の数平均分子量は、特に限定されないが、３００～１０００００が好ましく、より好ましくは３００～３００００である。脂環式ポリエステル樹脂（Ｋ）の数平均分子量が３００未満であると、硬化物の強靭性が十分でなく、耐クラック性、耐エッチング液溶出性が低下する場合がある。一方、脂環式ポリエステル樹脂（Ｋ）の数平均分子量が１０００００を超えると、他の成分（例えば、硬化剤（Ｅ））との相溶性が低下し、硬化物の機械物性に悪影響が及び、耐クラック性、耐エッチング液溶出性が低下する場合がある。なお、脂環式ポリエステル樹脂（Ｋ）の数平均分子量は、例えば、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法により、標準ポリスチレン換算の値として測定することができる。 The number average molecular weight of the alicyclic polyester resin (K) is not particularly limited, but is preferably 300 to 100,000, more preferably 300 to 30,000. If the number average molecular weight of the alicyclic polyester resin (K) is less than 300, the toughness of the cured product may not be sufficient, and crack resistance and etchant dissolution resistance may decrease. On the other hand, when the number average molecular weight of the alicyclic polyester resin (K) exceeds 100,000, the compatibility with other components (for example, the curing agent (E)) is lowered, and the mechanical properties of the cured product are adversely affected. Crack resistance and etchant elution resistance may decrease. In addition, the number average molecular weight of alicyclic polyester resin (K) can be measured as a value of standard polystyrene conversion by GPC (gel permeation chromatography) method, for example.
　なお、脂環式ポリエステル樹脂（Ｋ）は１種を単独で、又は２種以上を組み合わせて使用することができる。 In addition, alicyclic polyester resin (K) can be used individually by 1 type or in combination of 2 or more types.
　脂環式ポリエステル樹脂（Ｋ）は、特に限定されず、公知乃至慣用の方法により製造することができる。より詳しくは、例えば、脂環式ポリエステル樹脂（Ｋ）を、上述のジカルボン酸とジオールとを常法により重縮合させることにより得てもよいし、上述のジカルボン酸の誘導体（酸無水物、エステル、酸ハロゲン化物等）とジオールとを常法により重縮合させることにより得てもよい。 The alicyclic polyester resin (K) is not particularly limited and can be produced by a known or conventional method. More specifically, for example, the alicyclic polyester resin (K) may be obtained by polycondensing the above-mentioned dicarboxylic acid and diol by a conventional method, or the above-mentioned dicarboxylic acid derivative (an acid anhydride, ester). , Acid halides, and the like) and diols may be obtained by polycondensation by a conventional method.
　本発明の第２態様の硬化性樹脂組成物において、脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）は、特に限定されないが、硬化剤（Ｅ）を必須成分とする場合、脂環式ポリエステル樹脂（Ｋ）と硬化剤（Ｅ）の合計量（１００重量％）に対して、１～６０重量％が好ましく、より好ましくは５～３０重量％である。脂環式ポリエステル樹脂（Ｋ）の配合量が１重量％未満であると、硬化物の耐クラック性、耐エッチング液溶出性が低下する場合がある。一方、脂環式ポリエステル樹脂（Ｋ）の配合量が６０重量％を超えると、硬化物の耐熱性が低下する場合がある。 In the curable resin composition of the second aspect of the present invention, the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited, but when the curing agent (E) is an essential component, the alicyclic The amount is preferably 1 to 60% by weight, more preferably 5 to 30% by weight, based on the total amount (100% by weight) of the polyester resin (K) and the curing agent (E). When the blending amount of the alicyclic polyester resin (K) is less than 1% by weight, the crack resistance and etching solution elution resistance of the cured product may be lowered. On the other hand, when the compounding quantity of alicyclic polyester resin (K) exceeds 60 weight%, the heat resistance of hardened | cured material may fall.
　一方、本発明の第２態様の硬化性樹脂組成物が硬化触媒（Ｇ）を必須成分とする場合、脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）は、特に限定されないが、脂環式ポリエステル樹脂（Ｋ）と硬化触媒（Ｇ）の合計量（１００重量％）に対して、５０～９９重量％が好ましく、より好ましくは６５～９９重量％である。脂環式ポリエステル樹脂（Ｋ）の配合量が５０重量％未満であると、硬化物の耐クラック性、耐エッチング液溶出性が低下する場合がある。一方、脂環式ポリエステル樹脂（Ｋ）の配合量が９９重量％を超えると、硬化物の耐熱性が低下する場合がある。 On the other hand, when the curable resin composition of the second aspect of the present invention contains the curing catalyst (G) as an essential component, the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited. The amount is preferably 50 to 99% by weight, more preferably 65 to 99% by weight, based on the total amount (100% by weight) of the cyclic polyester resin (K) and the curing catalyst (G). When the blending amount of the alicyclic polyester resin (K) is less than 50% by weight, the crack resistance and etching solution elution resistance of the cured product may be lowered. On the other hand, when the compounding quantity of alicyclic polyester resin (K) exceeds 99 weight%, the heat resistance of hardened | cured material may fall.
　本発明の第２態様の硬化性樹脂組成物において、脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）は、特に限定されないが、硬化性樹脂組成物（１００重量％）に対して、０．１～２０重量％が好ましく、より好ましくは０．３～１０重量％である。脂環式ポリエステル樹脂（Ｋ）の配合量が０．１重量％未満であると、硬化物の耐クラック性が低下する場合がある。一方、脂環式ポリエステル樹脂（Ｋ）の配合量が２０重量％を超えると、硬化物の耐熱性が低下する場合がある。 In the curable resin composition of the second aspect of the present invention, the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited, but with respect to the curable resin composition (100% by weight), The content is preferably 0.1 to 20% by weight, more preferably 0.3 to 10% by weight. If the blending amount of the alicyclic polyester resin (K) is less than 0.1% by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding quantity of alicyclic polyester resin (K) exceeds 20 weight%, the heat resistance of hardened | cured material may fall.
　一方、本発明の第２態様の硬化性樹脂組成物において、脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１～６０重量部が好ましく、より好ましくは５～３０重量部である。脂環式ポリエステル樹脂（Ｋ）の配合量が１重量部未満であると、硬化物の耐クラック性が低下する場合がある。一方、脂環式ポリエステル樹脂（Ｋ）の配合量が６０重量部を超えると、硬化物の耐熱性が低下する場合がある。 On the other hand, in the curable resin composition of the second aspect of the present invention, the blending amount (content) of the alicyclic polyester resin (K) is not particularly limited, but has an epoxy group contained in the curable resin composition. The amount is preferably 1 to 60 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the total amount of the compound. When the blending amount of the alicyclic polyester resin (K) is less than 1 part by weight, the crack resistance of the cured product may be lowered. On the other hand, when the compounding quantity of alicyclic polyester resin (K) exceeds 60 weight part, the heat resistance of hardened | cured material may fall.
［離型剤］
　本発明の第１態様又は第２態様の硬化性樹脂組成物は、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、コンプレッション成形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（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 resin composition of the first aspect or the second aspect 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 or compression molding is facilitated, and a cured product (reflector) can be manufactured with high productivity. As the release agent, known or commonly used release agents can be used, and are not particularly limited. For example, fluorine release agents (fluorine atom-containing compounds; such as fluorine oil and polytetrafluoroethylene), 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、本発明の第１態様又は第２態様の硬化性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 addition, in the curable resin composition of the 1st aspect or 2nd aspect of this invention, a mold release agent can also be used individually by 1 type, and can also be used in combination of 2 or more types. 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.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が離型剤を含有する場合、離型剤の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量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（リフレクター）の離型性がより向上し、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。 When the curable resin composition of the first aspect or the second aspect of the present invention contains a release agent, the content (mixing amount) of the release agent is not particularly limited, but is included in the curable resin composition. The amount is preferably 1 to 12 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total amount of the compound having an epoxy group. By making content of a mold release agent 1 weight part or more, there exists a tendency which the mold release property of hardened | cured material (reflector) improves more and the productivity of a 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 reflector in the substrate for mounting an optical semiconductor element can be secured.
［酸化防止剤］
　本発明の第１態様又は第２態様の硬化性樹脂組成物は、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（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 resin composition of the first aspect or the second aspect of the present invention may contain an antioxidant. By containing an antioxidant, it becomes possible to produce a cured product (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, phenol 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.
　本発明の第１態様又は第２態様の硬化性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ＰＥＰ－３６」（（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 resin composition of the first aspect or the second aspect of the present invention, the antioxidant can be used alone 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“ ADK STAB HP-10 ”,“ ADEKA STAB PEP-36 ”(Corporation) Commercial products such as ADEKA (phosphorus antioxidant) and trade name “HCA” (manufactured by Sanko Co., Ltd., phosphorus antioxidant) can also be used.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が酸化防止剤を含有する場合、酸化防止剤の含有量（配合量）は、特に限定されないが、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量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（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、色相がより良好なリフレクターが得られやすい傾向がある。 When the curable resin composition of the first aspect or the second aspect of the present invention contains an antioxidant, the content (blending amount) of the antioxidant is not particularly limited, but is included in the curable resin composition. The amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total amount of the compound having an epoxy group. By setting the content of the antioxidant to 0.1 parts by weight or more, oxidation of the cured product (reflector) is efficiently prevented, and heat resistance and yellowing resistance tend to be further improved. On the other hand, when the content of the antioxidant is 5 parts by weight or less, coloring tends to be suppressed and a reflector having a better hue tends to be obtained.
［添加剤］
　本発明の第１態様又は第２態様の硬化性樹脂組成物は、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（特に、脂肪族多価アルコール）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、粘度や光反射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、紫外線吸収剤、光安定剤、蛍光増白剤、白色顔料（Ｃ）以外の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 resin composition of the 1st aspect or 2nd aspect of this invention may contain various additives in the range which does not impair the effect of this invention other than the above-mentioned component. For example, when a compound having a hydroxy group (especially an aliphatic polyhydric alcohol) 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, and surfactants, as long as the viscosity and light reflectivity are not impaired. Conventional additives such as flame retardants, colorants, ion adsorbers, ultraviolet absorbers, light stabilizers, fluorescent brighteners, and pigments other than the white pigment (C) can be used. The content of these additives is not particularly limited and can be appropriately selected.
　上記蛍光増白剤としては、公知乃至慣用の蛍光増白剤を使用することができる。本発明の第１態様又は第２態様の硬化性樹脂組成物が蛍光増白剤を含む場合、コンプレッション成型により形成される硬化物の光反射性、耐熱性、耐光性、及び耐クラック性により優れる傾向がある。上記蛍光増白剤としては、例えば、ピラゾリン誘導体、スチルベン誘導体、トリアジン誘導体、チアゾール誘導体、ベンゾオキサゾール誘導体、キサントン誘導体、トリアゾール誘導体、オキサゾール誘導体、チオフェン誘導体、クマリン誘導体、ナフタルイミド誘導体等が挙げられる。 As the above-mentioned fluorescent brightening agent, known or commonly used fluorescent brightening agents can be used. When the curable resin composition of the first aspect or the second aspect of the present invention contains a fluorescent brightening agent, it is more excellent in light reflectivity, heat resistance, light resistance, and crack resistance of a cured product formed by compression molding. Tend. Examples of the fluorescent brightening agent include pyrazoline derivatives, stilbene derivatives, triazine derivatives, thiazole derivatives, benzoxazole derivatives, xanthone derivatives, triazole derivatives, oxazole derivatives, thiophene derivatives, coumarin derivatives, naphthalimide derivatives, and the like.
　本発明の第１態様の硬化性樹脂組成物が、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、及び応力緩和剤（Ｈ）を含有する場合、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、及び応力緩和剤（Ｈ）からなる混合物の２５℃における粘度は、特に限定されないが、５０００ｍＰａ・ｓ以下であることが好ましい。なお、本発明の第１態様の硬化性樹脂組成物は、エチレングリコール等の上述の脂肪族多価アルコールを含んでいてもよく、この場合、上述の混合物は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、応力緩和剤（Ｈ）、及び脂肪族多価アルコールからなる混合物である。 The curable resin composition according to the first aspect of the present invention includes an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing agent (E), and curing acceleration. When it contains an agent (F) and a stress relaxation agent (H), an alicyclic epoxy compound (A), rubber particles (B), a curing agent (E), a curing accelerator (F), and a stress relaxation agent ( The viscosity at 25 ° C. of the mixture comprising H) is not particularly limited, but is preferably 5000 mPa · s or less. The curable resin composition according to the first aspect of the present invention may contain the above-mentioned aliphatic polyhydric alcohol such as ethylene glycol. In this case, the above-mentioned mixture contains the alicyclic epoxy compound (A). , Rubber particles (B), curing agent (E), curing accelerator (F), stress relaxation agent (H), and aliphatic polyhydric alcohol.
　本発明のは第２態様の硬化性樹脂組成物が、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含有する場合、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）からなる混合物の２５℃における粘度は、特に限定されないが、５０００ｍＰａ・ｓ以下であることが好ましい。なお、本発明の第２態様の硬化性樹脂組成物は、エチレングリコール等の上述の脂肪族多価アルコールを含んでいてもよく、この場合、上述の混合物は、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、脂環式ポリエステル樹脂（Ｋ）、及び脂肪族多価アルコールからなる混合物である。 The curable resin composition of the second aspect of the present invention is an alicyclic epoxy compound (A), rubber particles (B), white pigment (C), inorganic filler (D), curing agent (E), curing When the accelerator (F), stress relaxation agent (H), isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K) are contained, the alicyclic epoxy compound (A), rubber A mixture comprising particles (B), curing agent (E), curing accelerator (F), stress relaxation agent (H), isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K). The viscosity at 25 ° C. is not particularly limited, but is preferably 5000 mPa · s or less. The curable resin composition of the second aspect of the present invention may contain the above-mentioned aliphatic polyhydric alcohol such as ethylene glycol, and in this case, the above-mentioned mixture contains the alicyclic epoxy compound (A). Rubber particles (B), curing agents (E), curing accelerators (F), stress relaxation agents (H), isocyanuric acid derivatives (I), siloxane derivatives (J), alicyclic polyester resins (K), and It is a mixture comprising an aliphatic polyhydric alcohol.
　一方、本発明の第１態様の硬化性樹脂組成物が、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化触媒（Ｇ）、及び応力緩和剤（Ｈ）を含有する場合、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、硬化触媒（Ｇ）、及び応力緩和剤（Ｈ）からなる混合物の２５℃における粘度は、特に限定されないが、５０００ｍＰａ・ｓ以下であることが好ましい。本発明の第２態様の硬化性樹脂組成物が、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、硬化触媒（Ｇ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含有する場合、脂環式エポキシ化合物（Ａ）、ゴム粒子（Ｂ）、硬化触媒（Ｇ）、応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）からなる混合物の２５℃における粘度は、特に限定されないが、５０００ｍＰａ・ｓ以下であることが好ましい。なお、本明細書において、上記の４種の混合物の２５℃における粘度を、総称して、「樹脂粘度」と称する場合がある。 On the other hand, the curable resin composition of the first aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing catalyst (G), And the stress relaxation agent (H), the viscosity at 25 ° C. of the mixture comprising the alicyclic epoxy compound (A), the rubber particles (B), the curing catalyst (G), and the stress relaxation agent (H) is: Although not particularly limited, it is preferably 5000 mPa · s or less. The curable resin composition of the second aspect of the present invention comprises an alicyclic epoxy compound (A), rubber particles (B), a white pigment (C), an inorganic filler (D), a curing catalyst (G), stress relaxation. In the case of containing an agent (H), an isocyanuric acid derivative (I), a siloxane derivative (J), and an alicyclic polyester resin (K), an alicyclic epoxy compound (A), rubber particles (B), a curing catalyst ( The viscosity at 25 ° C. of the mixture comprising G), stress relaxation agent (H), isocyanuric acid derivative (I), siloxane derivative (J), and alicyclic polyester resin (K) is not particularly limited, but is 5000 mPa · s. The following is preferable. In the present specification, the viscosity at 25 ° C. of the above four kinds of mixtures may be collectively referred to as “resin viscosity”.
　上記樹脂粘度は、常圧において２５℃で測定した粘度である。上記樹脂粘度は、５０００ｍＰａ・ｓ以下であることが好ましく、より好ましくは４０００ｍＰａ・ｓ以下、さらに好ましくは３５００ｍＰａ・ｓ以下、特に好ましくは３０００ｍＰａ・ｓ以下である。上記樹脂粘度が５０００ｍＰａ・ｓ以下であると、樹脂粘度が５０００ｍＰａ・ｓを超える場合よりも、硬化性樹脂組成物をコンプレッション成型により形成された形成された硬化物の耐熱性、耐光性、及び耐クラック性（特に、優れた耐熱性）がさらに優れる傾向がある。また、上記樹脂粘度が比較的低いことにより、白色顔料（Ｃ）や無機充填剤（Ｄ）等の他の成分の含有量を増やすことが可能となり、硬化物の光反射性、耐熱性、及び耐光性がよりいっそう向上する傾向がある。上記樹脂粘度の下限は、例えば１００ｍＰａ・ｓ以上である。なお、上記樹脂粘度は、例えば、デジタル粘度計（型番「ＤＶＵ－ＥＩＩ型」、（株）トキメック製）を用いて、ローター：標準１°３４’×Ｒ２４、温度：２５℃、回転数：０．５～１０ｒｐｍの条件で測定することができる。 The resin viscosity is a viscosity measured at 25 ° C. at normal pressure. The resin viscosity is preferably 5000 mPa · s or less, more preferably 4000 mPa · s or less, further preferably 3500 mPa · s or less, and particularly preferably 3000 mPa · s or less. When the resin viscosity is 5000 mPa · s or less, the heat resistance, light resistance, and resistance of the cured product formed by compression molding of the curable resin composition is higher than when the resin viscosity exceeds 5000 mPa · s. Cracking properties (particularly excellent heat resistance) tend to be further improved. Moreover, it becomes possible to increase content of other components, such as a white pigment (C) and an inorganic filler (D), because the said resin viscosity is comparatively low, and the light reflectivity of cured | curing material, heat resistance, and There is a tendency that the light resistance is further improved. The lower limit of the resin viscosity is, for example, 100 mPa · s or more. The resin viscosity is determined by using, for example, a digital viscometer (model number “DVU-EII type”, manufactured by Tokimec Co., Ltd.), rotor: standard 1 ° 34 ′ × R24, temperature: 25 ° C., rotational speed: 0 It can be measured under the condition of 5 to 10 rpm.
　上記樹脂粘度は、例えば、用いる成分（例えば、本発明の第１態様の場合は、脂環式エポキシ化合物（Ａ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、硬化触媒（Ｇ）、及び液状の応力緩和剤（Ｈ）、本発明の第２態様の場合は、脂環式エポキシ化合物（Ａ）、硬化剤（Ｅ）、硬化促進剤（Ｆ）、硬化触媒（Ｇ）、液状の応力緩和剤（Ｈ）、イソシアヌル酸誘導体（Ｉ）、シロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）等）として、２５℃で液体の成分を用いることにより得やすくなる。なお、上記成分として２５℃で固体の成分を用いてもよいが、その含有量は、上記樹脂粘度が５０００ｍＰａ・ｓ以下となるように調整される。また、ゴム粒子（Ｂ）、固体の応力緩和剤（Ｈ）の含有量を、本発明の効果を損なわない範囲内で調整することによっても得やすくなる。 The resin viscosity is, for example, a component to be used (for example, in the case of the first aspect of the present invention, an alicyclic epoxy compound (A), a curing agent (E), a curing accelerator (F), a curing catalyst (G), And in the case of the second aspect of the present invention, the alicyclic epoxy compound (A), the curing agent (E), the curing accelerator (F), the curing catalyst (G), As a stress relaxation agent (H), an isocyanuric acid derivative (I), a siloxane derivative (J), an alicyclic polyester resin (K), and the like, it becomes easy to obtain by using a liquid component at 25 ° C. In addition, although a solid component may be used as said component at 25 degreeC, the content is adjusted so that the said resin viscosity may be 5000 mPa * s or less. Moreover, it becomes easy to obtain by adjusting content of a rubber particle (B) and a solid stress relaxation agent (H) within the range which does not impair the effect of this invention.
　なお、本発明の第１態様又は第２態様の硬化性樹脂組成物は、加熱して該硬化性樹脂組成物における脂環式エポキシ化合物（Ａ）及び硬化剤（Ｅ）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樹脂組成物（Ｂステージ状態の硬化性樹脂組成物）であってもよい。 In addition, the curable resin composition of the 1st aspect or 2nd aspect of this invention is heated, and a part of alicyclic epoxy compound (A) in this curable resin composition and a hardening | curing agent (E) are made to react. B-staged curable resin composition (B-stage curable resin composition) may be obtained.
　上述のように、本発明の第１態様又は第２態様の硬化性樹脂組成物は硬化後の光反射性、耐熱性、及び耐光性に優れるため、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。中でも、本発明の第１態様又は第２態様の硬化性樹脂組成物は、コンプレッション成型によって形成された硬化物（リフレクター）の光反射性、耐熱性、及び耐光性に特に優れるため、コンプレッション成型用の樹脂組成物であることが特に好ましい。 As described above, the curable resin composition of the first or second aspect of the present invention is excellent in light reflectivity, heat resistance, and light resistance after curing, and in particular, a resin composition for transfer molding and compression molding. It can preferably be used as a resin composition. Among them, the curable resin composition according to the first aspect or the second aspect of the present invention is particularly excellent in light reflectivity, heat resistance, and light resistance of a cured product (reflector) formed by compression molding. The resin composition is particularly preferable.
　本発明の第１態様又は第２態様の硬化性樹脂組成物は、特に限定されないが、上記の各成分を、必要に応じて加熱した状態で撹拌・混合することにより調製することができる。なお、本発明の第１態様又は第２態様の硬化性樹脂組成物は、各成分があらかじめ混合されたものをそのまま使用する１液系の組成物として使用することもできるし、例えば、別々に保管しておいた２以上の成分を使用前に所定の割合で混合して使用する多液系（例えば、２液系）の組成物として使用することもできる。上記撹拌・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撹拌・混合手段を使用できる。また、撹拌・混合後、真空下にて脱泡してもよい。 The curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components in a heated state as necessary. In addition, the curable resin composition of the first aspect or the second aspect of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, separately. It can also be used as a multi-component (for example, two-component) composition in which two or more components that have been stored are mixed at a predetermined ratio before use. The stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, a self-revolving stirrer and the like can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
　特に限定されないが、ゴム粒子（Ｂ）は、あらかじめ脂環式エポキシ化合物（Ａ）中に分散させた組成物（当該組成物を「ゴム粒子分散エポキシ化合物」と称する場合がある）の状態で配合することが好ましい。即ち、本発明の第１態様の硬化性樹脂組成物は、上記ゴム粒子分散エポキシ化合物と、白色顔料（Ｃ）と、無機充填剤（Ｄ）と、応力緩和剤（Ｈ）と、硬化剤（Ｅ）及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）と、必要に応じてその他の成分とを混合することにより調製することが好ましい。また、本発明の第２態様の硬化性樹脂組成物は、上記ゴム粒子分散エポキシ化合物と、白色顔料（Ｃ）と、無機充填剤（Ｄ）と、応力緩和剤（Ｈ）と、イソシアヌル酸誘導体（Ｉ）と、シロキサン誘導体（Ｊ）と、脂環式ポリエステル樹脂（Ｋ）と、硬化剤（Ｅ）及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）と、必要に応じてその他の成分とを混合することにより調製することが好ましい。このような調製方法により、特に、硬化性樹脂組成物におけるゴム粒子（Ｂ）の分散性を向上させることができる。ただし、ゴム粒子（Ｂ）の配合方法は、上記方法に限定されず、それ単独で配合する方法であってもよい。 Although not particularly limited, the rubber particles (B) are blended in a state of being preliminarily dispersed in the alicyclic epoxy compound (A) (the composition may be referred to as “rubber particle dispersed epoxy compound”). It is preferable to do. That is, the curable resin composition of the first aspect of the present invention includes the rubber particle-dispersed epoxy compound, the white pigment (C), the inorganic filler (D), the stress relaxation agent (H), and the curing agent ( It is preferable to prepare by mixing E) and a hardening accelerator (F) or a hardening catalyst (G), and another component as needed. The curable resin composition according to the second aspect of the present invention includes the rubber particle-dispersed epoxy compound, a white pigment (C), an inorganic filler (D), a stress relaxation agent (H), and an isocyanuric acid derivative. (I), a siloxane derivative (J), an alicyclic polyester resin (K), a curing agent (E) and a curing accelerator (F), or a curing catalyst (G), and, if necessary, other It is preferred to prepare by mixing the ingredients. Such a preparation method can particularly improve the dispersibility of the rubber particles (B) in the curable resin composition. However, the blending method of the rubber particles (B) is not limited to the above method, and may be a method of blending alone.
（ゴム粒子分散エポキシ化合物）
　上記ゴム粒子分散エポキシ化合物は、ゴム粒子（Ｂ）を脂環式エポキシ化合物（Ａ）に分散させることによって得られる。なお、上記ゴム粒子分散エポキシ化合物における脂環式エポキシ化合物（Ａ）は、硬化性樹脂組成物を構成する脂環式エポキシ化合物（Ａ）の全量であってもよいし、一部の量であってもよい。同様に、上記ゴム粒子分散エポキシ化合物におけるゴム粒子（Ｂ）は、硬化性樹脂組成物を構成するゴム粒子（Ｂ）の全量であってもよいし、一部の量であってもよい。 (Rubber particle dispersed epoxy compound)
The rubber particle-dispersed epoxy compound is obtained by dispersing the rubber particles (B) in the alicyclic epoxy compound (A). The alicyclic epoxy compound (A) in the rubber particle-dispersed epoxy compound may be the total amount or a partial amount of the alicyclic epoxy compound (A) constituting the curable resin composition. May be. Similarly, the rubber particles (B) in the rubber particle-dispersed epoxy compound may be the total amount or a partial amount of the rubber particles (B) constituting the curable resin composition.
　上記ゴム粒子分散エポキシ化合物の粘度は、例えば、反応性希釈剤を併用することにより調整することができる（即ち、ゴム粒子分散エポキシ化合物は、さらに反応性希釈剤を含んでいてもよい）。上記反応性希釈剤としては、例えば、常温（２５℃）における粘度が２００ｍＰａ・ｓ以下の脂肪族ポリグリシジルエーテルを好ましく使用できる。粘度（２５℃）が２００ｍＰａ・ｓ以下の脂肪族ポリグリシジルエーテルとしては、例えば、シクロヘキサンジメタノールジグリシジルエーテル、シクロヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等が挙げられる。 The viscosity of the rubber particle-dispersed epoxy compound can be adjusted, for example, by using a reactive diluent together (that is, the rubber particle-dispersed epoxy compound may further contain a reactive diluent). As the reactive diluent, for example, an aliphatic polyglycidyl ether having a viscosity at room temperature (25 ° C.) of 200 mPa · s or less can be preferably used. Examples of the aliphatic polyglycidyl ether having a viscosity (25 ° C.) of 200 mPa · s or less include cyclohexane dimethanol diglycidyl ether, cyclohexane diol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Trimethylolpropane triglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
　上記反応性希釈剤の使用量は、適宜調整することができ、特に限定されないが、上記ゴム粒子分散エポキシ化合物全量１００重量部に対して、３０重量部以下が好ましく、より好ましくは２５重量部以下（例えば、５～２５重量部）である。使用量が３０重量部以下であると、強靭性（耐クラック性向上）等の所望の性能を得やすくなる傾向がある。 The amount of the reactive diluent used can be appropriately adjusted and is not particularly limited, but is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, with respect to 100 parts by weight of the total amount of the rubber particle-dispersed epoxy compound. (For example, 5 to 25 parts by weight). If the amount used is 30 parts by weight or less, desired performance such as toughness (improvement in crack resistance) tends to be easily obtained.
　上記ゴム粒子分散エポキシ化合物の製造方法は、特に限定されず、周知慣用の方法を使用することができる。例えば、ゴム粒子（Ｂ）を脱水乾燥して粉体とした後に、脂環式エポキシ化合物（Ａ）に混合し、分散させる方法や、ゴム粒子（Ｂ）のエマルジョンと脂環式エポキシ化合物（Ａ）とを直接混合し、続いて脱水する方法等が挙げられる。 The method for producing the rubber particle-dispersed epoxy compound is not particularly limited, and a well-known and commonly used method can be used. For example, after the rubber particles (B) are dehydrated and dried to form a powder, the rubber particles (B) are mixed and dispersed in the alicyclic epoxy compound (A), or the emulsion of the rubber particles (B) and the alicyclic epoxy compound (A And the like, followed by dehydration and the like.
　本発明の第１態様又は第２態様の硬化性樹脂組成物の２５℃における粘度は、特に限定されないが、１００～１００００００ｍＰａ・ｓが好ましく、より好ましくは２００～８０００００ｍＰａ・ｓ、さらに好ましくは３００～８０００００ｍＰａ・ｓである。２５℃における粘度を１００ｍＰａ・ｓ以上とすることにより、注型時の作業性が向上したり、硬化物の耐熱性及び耐光性がより向上する傾向がある。一方、２５℃における粘度を１００００００ｍＰａ・ｓ以下とすることにより、注型時の作業性が向上したり、硬化物に注型不良に由来する不具合が生じにくくなる傾向がある。 The viscosity at 25 ° C. of the curable resin composition of the first aspect or the second aspect of the present invention is not particularly limited, but is preferably 100 to 1,000,000 mPa · s, more preferably 200 to 800,000 mPa · s, and still more preferably 300 to 800,000 mPa · s. By setting the viscosity at 25 ° C. to 100 mPa · s or more, workability during casting is improved, and heat resistance and light resistance of the cured product tend to be further improved. On the other hand, when the viscosity at 25 ° C. is set to 1000000 mPa · s or less, workability during casting is improved, and defects due to casting defects tend not to occur in the cured product.
＜硬化物＞
　本発明の第１態様又は第２態様の硬化性樹脂組成物を加熱によって硬化させることにより、光反射性に優れ、耐熱性、耐光性、及び耐クラック性に優れ、さらに本発明の第２態様の場合は、エッチング液への溶出が抑制された硬化物を得ることができる。なお、本発明の第１態様又は第２態様の硬化性樹脂組成物を硬化させた硬化物、即ち本発明の第１態様又は第２態様の硬化性樹脂組成物の硬化物を「本発明の硬化物」と称する場合がある。硬化の際の加熱温度（硬化温度）は、特に限定されないが、５０～２００℃が好ましく、より好ましくは８０～１８０℃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、６０～１８００秒が好ましく、より好ましくは９０～９００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するので好ましくない。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、コンプレッション成型のみ）で行ってもよいし、例えば、多段階（例えば、コンプレッション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。また、ポストキュアーを行う場合、この際の加熱温度は、５０～２００℃が好ましく、より好ましくは６０～１８０℃、より好ましくは硬化温度と同程度の温度である。また、ポストキュアーを行う時間は、０．５～１０時間が好ましく、より好ましくは１～８時間である。 <Hardened product>
By curing the curable resin composition of the first aspect or the second aspect of the present invention by heating, it is excellent in light reflectivity, excellent in heat resistance, light resistance, and crack resistance, and further in the second aspect of the present invention. In this case, a cured product in which elution into the etching solution is suppressed can be obtained. The cured product obtained by curing the curable resin composition of the first aspect or the second aspect of the present invention, that is, the cured product of the curable resin composition of the first aspect or the second aspect of the present invention is referred to as “the present invention. Sometimes referred to as “cured product”. The heating temperature (curing temperature) during curing is not particularly limited, but is preferably 50 to 200 ° C, more preferably 80 to 180 ° C. Further, the heating time (curing time) at the time of curing is not particularly limited, but is preferably 60 to 1800 seconds, and more preferably 90 to 900 seconds. When the curing temperature and the curing time are lower than the lower limit of the above range, curing is insufficient, and when the curing temperature and the curing time are higher than the upper limit of the above range, yellowing due to thermal decomposition occurs. 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 stage (for example, compression molding only), for example, in multiple stages (for example, further heating in an oven or the like as post-curing (secondary curing) after compression molding). Also good. When post-curing is performed, the heating temperature at this time is preferably 50 to 200 ° C., more preferably 60 to 180 ° C., and more preferably about the same as the curing temperature. The post-curing time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours.
　本発明の硬化物は、高い光反射性を有し、耐熱性及び耐光性に優れ、さらに本発明の第２態様の場合は、エッチング液への溶出が抑制されにくい。このため、上記硬化物は劣化しにくく、経時で反射率が低下しにくく、本発明の第２態様の場合は、エッチング工程での重量減少が少ない。従って、本発明の第１態様又は第２態様の硬化性樹脂組成物は、ＬＥＤパッケージ用途（ＬＥＤパッケージの構成材、例えば、光半導体装置におけるリフレクター材、ハウジング材等）、電子部品の接着用途、液晶ディスプレイ用途（例えば、反射板など）、白色基板用インク、シーラー等として好ましく使用することができる。中でも、ＬＥＤパッケージ用の硬化性樹脂組成物（特に、光半導体装置におけるリフレクター用の硬化性樹脂組成物（即ち、リフレクター形成用の硬化性樹脂組成物））として特に好ましく使用することができる。 The cured product of the present invention has high light reflectivity, excellent heat resistance and light resistance, and in the case of the second embodiment of the present invention, elution into the etching solution is difficult to be suppressed. For this reason, the said hardened | cured material does not deteriorate easily, a reflectance does not fall easily with time, and in the case of the 2nd aspect of this invention, there is little weight loss in an etching process. Therefore, the curable resin composition of the first aspect or the second aspect of the present invention is used for LED packages (LED package components, for example, reflector materials and housing materials in optical semiconductor devices), electronic component adhesion applications, It can be preferably used as a liquid crystal display (for example, a reflector), a white substrate ink, a sealer and the like. Especially, it can use especially preferably as curable resin composition for LED packages (especially curable resin composition for reflectors in an optical semiconductor device (that is, curable resin composition for forming reflectors)).
　本発明の硬化物の反射率（初期反射率）は、特に限定されないが、例えば、波長４５０ｎｍの光の反射率が、９３％以上であることが好ましく、より好ましくは９４％以上、さらに好ましくは９５％以上である。特に、４５０～８００ｎｍの光の反射率が９３％以上であることが好ましく、より好ましくは９４％以上、さらに好ましくは９５％以上である。 The reflectance (initial reflectance) of the cured product of the present invention is not particularly limited. For example, the reflectance of light having a wavelength of 450 nm is preferably 93% or more, more preferably 94% or more, and still more preferably. 95% or more. In particular, the reflectance of light at 450 to 800 nm is preferably 93% or more, more preferably 94% or more, and still more preferably 95% or more.
　本発明の硬化物の、１２０℃で２５０時間加熱した後の波長４５０ｎｍの光の反射率（「加熱エージング後の反射率」と称する場合がある）の、初期反射率に対する保持率（［加熱エージング後の反射率］／［初期反射率］×１００）は、特に限定されないが、８０％以上であることが好ましく、より好ましくは８５％以上、さらに好ましくは９０％以上である。特に、４５０～８００ｎｍの光の場合の保持率が８０％以上であることが好ましく、より好ましくは８５％以上、さらに好ましくは９０％以上である。本発明の第１態様又は第２態様の硬化性樹脂組成物によれば、コンプレッション成型により形成された硬化物は上記保持率を９０％以上とすることが可能である。 The retention ratio of the light reflectance at a wavelength of 450 nm after heating for 250 hours at 120 ° C. (sometimes referred to as “reflectance after heat aging”) to the initial reflectance ([heat aging (Reflectance after) / [Initial reflectance] × 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. In particular, the retention in the case of 450 to 800 nm light is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. According to the curable resin composition of the 1st aspect or 2nd aspect of this invention, the hardened | cured material formed by compression molding can make the said retention rate 90% or more.
　本発明の硬化物の、強度１０ｍＷ／ｃｍ2の紫外線を２５０時間照射した後の波長４５０ｎｍの光に対する反射率（「紫外線エージング後の反射率」と称する場合がある）の、初期反射率に対する保持率（［紫外線エージング後の反射率］／［初期反射率］×１００）は、特に限定されないが、８０％以上であることが好ましく、より好ましくは８５％以上、さらに好ましくは９０％以上である。特に、４５０～８００ｎｍの光の場合の保持率が８０％以上であることが好ましく、より好ましくは８５％以上、さらに好ましくは９０％以上である。 Retention of the reflectance of the cured product of the present invention with respect to light having a wavelength of 450 nm after irradiation with ultraviolet light having an intensity of 10 mW / cm 2 for 250 hours (sometimes referred to as “reflectance after ultraviolet light aging”) with respect to the initial reflectance. The rate ([reflectance after ultraviolet ray aging] / [initial reflectivity] × 100) is not particularly limited, but is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. . In particular, the retention in the case of 450 to 800 nm light is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
　なお、上記反射率は、例えば、本発明の硬化物（厚み：３ｍｍ）を試験片とし、分光光度計（商品名「分光光度計　ＵＶ－２４５０」、（株）島津製作所製）を用いて測定することができる。 The reflectance is measured using, for example, a spectrophotometer (trade name “spectrophotometer UV-2450”, manufactured by Shimadzu Corporation) using the cured product of the present invention (thickness: 3 mm) as a test piece. can do.
　本発明の第２態様における硬化物はエッチング液（例えば、アルカリ液）に溶出しにくく、光半導体装置のリフレクターや基板として使用された場合でも、エッチング工程で光反射性が低下しにくい。本発明の第２態様における硬化物を１１重量％の水酸化カリウム水溶液に７０℃で６０分間処理した後の重量減少率は、特に限定されないが、１％以下であることが好ましく、より好ましくは０．８％以下、さらに好ましくは０．５％以下である。本発明の第２態様の硬化性樹脂組成物によれば、コンプレッション成型により形成された硬化物は上記重量減少率を０．５％以下とすることが可能である。 The cured product according to the second aspect of the present invention is less likely to be eluted in an etching solution (for example, an alkaline solution), and even when used as a reflector or a substrate of an optical semiconductor device, the light reflectivity is not easily lowered in the etching process. The weight reduction rate after treating the cured product in the second aspect of the present invention with an 11% by weight aqueous potassium hydroxide solution at 70 ° C. for 60 minutes is not particularly limited, but is preferably 1% or less, more preferably 0.8% or less, more preferably 0.5% or less. According to the curable resin composition of the second aspect of the present invention, the weight reduction rate of the cured product formed by compression molding can be 0.5% or less.
　本発明の第１態様又は第２態様の硬化性樹脂組成物が光半導体装置におけるリフレクター用の硬化性樹脂組成物である場合、本発明の第１態様又は第２態様の硬化性樹脂組成物は、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、本発明の第１態様又は第２態様の硬化性樹脂組成物を成型する（かつ硬化させる）ことによって、高い光反射性を有し、耐熱性及び耐光性に優れ、さらに耐クラック性に優れ、さらに本発明の第２態様の場合は、エッチング液への溶出が抑制された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。なお、リフレクターとは、光半導体装置において光半導体素子から発せられた光を反射させて、光の指向性及び輝度を高め、光の取り出し効率を向上させるための部材である。本発明の硬化物により形成されたリフレクターを少なくとも有する、光半導体素子搭載用に用いられる基板を、「本発明の光半導体素子搭載用基板」と称する場合がある。 When the curable resin composition of the first aspect or the second aspect of the present invention is a curable resin composition for a reflector in an optical semiconductor device, the curable resin composition of the first aspect or the second aspect of the present invention is , A molding material (material used for molding with a mold or the like) used for forming a reflector (light reflecting member) of an optical semiconductor element substrate (optical semiconductor element mounting substrate) in an optical semiconductor device . Therefore, by molding (and curing) the curable resin composition of the first aspect or the second aspect of the present invention, it has high light reflectivity, excellent heat resistance and light resistance, and further crack resistance. Further, in the case of the second aspect of the present invention, a high-quality (for example, highly durable) optical semiconductor element mounting substrate having a reflector in which elution into the etching solution is suppressed can be manufactured. The reflector is a member for reflecting light emitted from the optical semiconductor element in the optical semiconductor device to increase the directivity and luminance of the light and improve the light extraction efficiency. A substrate used for mounting an optical semiconductor element having at least a reflector formed of the cured product of the present invention may be referred to as “optical semiconductor element mounting substrate of the present invention”.
＜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、本発明の硬化性樹脂組成物の硬化物（本発明の第１態様又は第２態様の硬化性樹脂組成物を硬化させることにより得られる硬化物）により形成されたリフレクター（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第１態様又は第２態様の硬化性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 is a cured product of the curable resin composition of the present invention (cured product obtained by curing the curable resin composition of the first aspect or the second aspect of the present invention). It is a board | substrate which has at least the formed reflector (white reflector). 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. An optical semiconductor element 107 is placed in the center (optical semiconductor element mounting region 102) and die-bonded. 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 the inner surface of the concave shape formed of at least a cured product of the curable resin composition of the first aspect or the second aspect 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、コンプレッション成型等）を使用することができ、特に限定されないが、例えば、本発明の第１態様又は第２態様の硬化性樹脂組成物を、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。リフレクターを形成する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。本発明においては、中でも、急激な硬化反応による発泡を防ぎ、硬化による応力ひずみを緩和して靭性（耐クラック性）を向上させることができる点で、多段階に分けて加熱処理を施し、段階的に硬化させることが好ましい。 As a method for forming the white reflector in the substrate for mounting an optical semiconductor element of the present invention, a known or conventional molding method (for example, compression molding or the like) can be used, and is not particularly limited. Examples include a method in which the curable resin composition of the first aspect or the second aspect is subjected to various molding methods such as transfer molding, compression molding, injection molding, LIM molding (injection molding), and dam molding by dispensing. The curing conditions for forming the reflector can be appropriately selected from, for example, the conditions for forming the cured product described above. In the present invention, among other things, it is possible to prevent foaming due to a rapid curing reaction, relax stress strain due to curing, and improve toughness (crack resistance). It is preferable to cure it.
　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、光源としての光半導体素子と、本発明の第１態様又は第２態様の硬化性樹脂組成物の硬化物からなるリフレクター（反射材）とを少なくとも備える光半導体装置である。より具体的には、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、リフレクターとして本発明の第１態様又は第２態様の硬化性樹脂組成物の硬化物により形成されたリフレクターを有するため、経時で光の輝度が低下しにくく、信頼性が高い。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、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 comprising at least an optical semiconductor element as a light source and a reflector (reflecting material) made of a cured product of the curable resin composition of the first aspect or the second aspect of the present invention. is there. More specifically, 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 reflector formed of a cured product of the curable resin composition of the first aspect or the second aspect of the present invention as a reflector, the luminance of light is less likely to decrease over time, and reliability. Is expensive. 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 die bonding, 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. FIG. 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１～６における硬化性樹脂組成物の各成分の配合量の単位は重量部である。また、表１～６における「－」は、当該成分の配合を行わなかったことを意味する。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In Tables 1 to 6, the unit of the blending amount of each component of the curable resin composition is parts by weight. In Tables 1 to 6, “-” means that the component was not blended.
　製造例１
（ゴム粒子の製造）
　還流冷却器付きの１Ｌ重合容器に、イオン交換水５００ｇ、及びジオクチルスルホコハク酸ナトリウム０．６８ｇを仕込み、窒素気流下に撹拌しながら、８０℃に昇温した。ここに、ゴム粒子のコア部分を形成するために必要とする量の約５重量％分に該当するアクリル酸ブチル９．５ｇ、スチレン２．５７ｇ、及びジビニルベンゼン０．３９ｇからなる単量体混合物を一括添加し、２０分間撹拌して乳化させた後、ペルオキソ二硫酸カリウム９．５ｍｇを添加し、１時間撹拌して最初のシード重合を行った。続いて、ペルオキソ二硫酸カリウム１８０．５ｍｇを添加し、５分間撹拌した。ここに、コア部分を形成するために必要とする量の残り（約９５重量％分）のアクリル酸ブチル１８０．５ｇ、スチレン４８．８９ｇ、及びジビニルベンゼン７．３３ｇにジオクチルスルホコハク酸ナトリウム０．９５ｇを溶解させてなる単量体混合物を２時間かけて連続的に添加し、２度目のシード重合を行い、その後、１時間熟成してコア部分を得た。
　次いで、ペルオキソ二硫酸カリウム６０ｍｇを添加して５分間撹拌し、ここに、メタクリル酸メチル６０ｇ、アクリル酸１．５ｇ、及びアリルメタクリレート０．３ｇにジオクチルスルホコハク酸ナトリウム０．３ｇを溶解させてなる単量体混合物を３０分かけて連続的に添加し、シード重合を行った。その後、１時間熟成し、コア部分を被覆するシェル層を形成した。
　次いで、室温（２５℃）まで冷却し、目開き１２０μｍのプラスチック製網で濾過することにより、コアシェル構造を有するゴム粒子を含むラテックスを得た。得られたラテックスをマイナス３０℃で凍結し、吸引濾過器で脱水洗浄した後、６０℃で一昼夜送風乾燥してゴム粒子を得た。得られたゴム粒子の平均粒子径は１０８ｎｍ、最大粒子径は２８９ｎｍであった。 Production Example 1
(Manufacture of rubber particles)
In a 1 L polymerization vessel equipped with a reflux condenser, 500 g of ion-exchanged water and 0.68 g of sodium dioctylsulfosuccinate were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Here, a monomer mixture composed of 9.5 g of butyl acrylate, 2.57 g of styrene, and 0.39 g of divinylbenzene corresponding to about 5% by weight of the amount required to form the core portion of the rubber particles. Were added together and emulsified by stirring for 20 minutes, and then 9.5 mg of potassium peroxodisulfate was added and stirred for 1 hour to perform the first seed polymerization. Subsequently, 180.5 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, the remaining amount (about 95% by weight) of butyl acrylate 180.5 g, styrene 48.89 g, divinylbenzene 7.33 g and 0.95 g sodium dioctyl sulfosuccinate required to form the core portion. A monomer mixture obtained by dissolving sucrose was continuously added over 2 hours to perform seed polymerization for the second time, and then aged for 1 hour to obtain a core part.
Next, 60 mg of potassium peroxodisulfate was added and stirred for 5 minutes. Here, 0.3 g of sodium dioctylsulfosuccinate was dissolved in 60 g of methyl methacrylate, 1.5 g of acrylic acid and 0.3 g of allyl methacrylate. The monomer mixture was continuously added over 30 minutes to perform seed polymerization. Then, it aged for 1 hour and formed the shell layer which coat | covers a core part.
Next, the mixture was cooled to room temperature (25 ° C.) and filtered through a plastic mesh having an opening of 120 μm to obtain a latex containing rubber particles having a core-shell structure. The obtained latex was frozen at −30 ° C., dehydrated and washed with a suction filter, and then blown and dried at 60 ° C. overnight to obtain rubber particles. The resulting rubber particles had an average particle size of 108 nm and a maximum particle size of 289 nm.
　なお、ゴム粒子の平均粒子径、最大粒子径は、動的光散乱法を測定原理とした「ＮａｎｏｔｒａｃTM」形式のナノトラック粒度分布測定装置（商品名「ＵＰＡ－ＥＸ１５０」、日機装（株）製）を使用して試料を測定し、得られた粒度分布曲線において、累積カーブが５０％となる時点の粒子径である累積平均径を平均粒子径、粒度分布測定結果の頻度（％）が０．００％を超えた時点の最大の粒子径を最大粒子径とした。なお、上記試料としては、下記製造例２で得られたゴム粒子分散エポキシ化合物１重量部をテトラヒドロフラン２０重量部に分散させたものを用いた。 The average particle size and the maximum particle size of the rubber particles are determined based on a nanotrac ™ particle size distribution measuring device (trade name “UPA-EX150”, manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method as a measurement principle. ) Was used to measure the sample, and in the obtained particle size distribution curve, the average particle size, which is the particle size when the cumulative curve becomes 50%, is the average particle size, and the frequency (%) of the particle size distribution measurement result is 0 The maximum particle size at the time of exceeding 0.000 was defined as the maximum particle size. In addition, as said sample, what disperse | distributed 1 weight part of rubber particle dispersion | distribution epoxy compounds obtained by the following manufacture example 2 to 20 weight part of tetrahydrofuran was used.
　製造例２
（ゴム粒子分散エポキシ化合物の製造）
　製造例１で得られたゴム粒子５重量部を、窒素気流下、６０℃に加温した状態でディゾルバーを使用して、商品名「セロキサイド２０２１Ｐ」（３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート、（株）ダイセル製）１００重量部に分散させ（１０００ｒｐｍ、６０分間）、真空脱泡して、ゴム粒子分散エポキシ化合物（２５℃での粘度：１０３６ｍＰａ・ｓ）を得た。
　なお、製造例２で得られたゴム粒子分散エポキシ化合物（５重量部のゴム粒子を１００重量部のセロキサイド２０２１Ｐに分散させたもの）の２５℃での粘度は、デジタル粘度計（商品名「ＤＶＵ－ＥＩＩ型」、（株）トキメック製）を使用して測定した。 Production Example 2
(Manufacture of rubber particle-dispersed epoxy compounds)
Using a dissolver with 5 parts by weight of the rubber particles obtained in Production Example 1 heated to 60 ° C. in a nitrogen stream, the product name “Celoxide 2021P” (3,4-epoxycyclohexylmethyl (3,4) -Epoxy) cyclohexanecarboxylate (manufactured by Daicel Corporation) and dispersed in 100 parts by weight (1000 rpm, 60 minutes) and vacuum degassed to obtain a rubber particle-dispersed epoxy compound (viscosity at 25 ° C .: 1036 mPa · s). It was.
The viscosity at 25 ° C. of the rubber particle-dispersed epoxy compound obtained in Production Example 2 (5 parts by weight of rubber particles dispersed in 100 parts by weight of ceroxide 2021P) is a digital viscometer (trade name “DVU”). -EII ", manufactured by Tokimec Co., Ltd.).
　製造例３
（脂環式ポリエステル樹脂の製造）
　攪拌機、温度計及び還流冷却器を備えた反応容器に、１，４－シクロヘキサンジカルボン酸（東京化成工業（株）製）１７２重量部、ネオペンチルグリコール（東京化成工業（株）製）２０８重量部、テトラブチルチタネート（和光純薬工業（株）製）０．１重量部を仕込んで、１６０℃になるまで加熱し、さらに１６０℃から２５０℃まで４時間かけて昇温した。次いで、１時間かけて５ｍｍＨｇまで減圧し、さらに０．３ｍｍＨｇ以下まで減圧してから２５０℃で１時間反応させ、脂環式ポリエステル樹脂を得た。 Production Example 3
(Manufacture of alicyclic polyester resin)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 172 parts by weight of 1,4-cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 208 parts by weight of neopentyl glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 0.1 part by weight of tetrabutyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, heated to 160 ° C., and further heated from 160 ° C. to 250 ° C. over 4 hours. Next, the pressure was reduced to 5 mmHg over 1 hour, further reduced to 0.3 mmHg or less, and then reacted at 250 ° C. for 1 hour to obtain an alicyclic polyester resin.
　製造例４
　表１、表２、表４及び表５に示す配合割合（単位：重量部）で、商品名「リカシッドＭＨ－７００」（新日本理化（株）製）、商品名「ＨＮ－７２００」（日立化成工業（株）製）、商品名「ＨＮ－５７００」（日立化成工業（株）製）、商品名「Ｕ－ＣＡＴ　１８Ｘ」（サンアプロ（株）製）、及びエチレングリコール（和光純薬工業（株）製）を、自公転式撹拌装置（商品名「あわとり練太郎　ＡＲ－２５０」、（株）シンキー製）を使用して均一に混合し、脱泡して硬化剤組成物（「Ｋ剤」と称する場合がある）を得た。 Production Example 4
In the blending ratios (unit: parts by weight) shown in Table 1, Table 2, Table 4 and Table 5, the trade name “Licacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.), the trade name “HN-7200” (Hitachi) Kasei Kogyo Co., Ltd.), trade name “HN-5700” (manufactured by Hitachi Chemical Co., Ltd.), trade name “U-CAT 18X” (manufactured by San Apro Co., Ltd.), and ethylene glycol (Wako Pure Chemical Industries, Ltd.) Co., Ltd.) is uniformly mixed using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), defoamed, and a curing agent composition (“K May be referred to as "agent").
　実施例１Ａ
　まず、表１に示す配合処方（単位：重量部）に従って、製造例２で得たゴム粒子分散エポキシ化合物、シリコーンゴム粒子（商品名「ＫＭＰ－６００」（信越化学工業（株）製）、酸化チタン（商品名「ＤＣＦ－Ｔ－１７０５０」、レジノカラー工業（株）製）、及びシリカ（商品名「ＦＢ－９７０ＦＤ」、デンカ（株）製）を、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下（ロールピッチ：０．２ｍｍ、回転数：２５ヘルツ、３パス）で溶融混練して混練物を得た。
　次に、表１に示す配合処方（単位：重量部）となるように、上記で得た混練物と、製造例４で得た硬化剤組成物とを自公転式撹拌装置（商品名「あわとり練太郎ＡＲ－２５０」、（株）シンキー製）を使用して均一に混合し（２０００ｒｐｍ、５分間）、脱泡して、硬化性樹脂組成物（硬化性エポキシ樹脂組成物）を得た。
　上記硬化性樹脂組成物をポリエステルからなる離型フィルムで挟み込み、１５０℃のコンプレッション成型用の金型内に置き、３．０ＭＰａの圧力で６００秒間加熱及び加圧して硬化させ、その後、ポストキュアー（１５０℃で５時間）を行うことによって、硬化物を得た。 Example 1A
First, in accordance with the formulation (unit: parts by weight) shown in Table 1, the rubber particle-dispersed epoxy compound obtained in Production Example 2, silicone rubber particles (trade name “KMP-600” (manufactured by Shin-Etsu Chemical Co., Ltd.), oxidation Titanium (trade name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd.) and silica (trade name “FB-970FD”, manufactured by Denka Co., Ltd.) are uniformly mixed using a dissolver, and a roll mill Was melt-kneaded under predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3 passes) to obtain a kneaded product.
Next, the kneaded product obtained above and the curing agent composition obtained in Production Example 4 were mixed with a self-revolving stirrer (trade name “Awa” so as to have a formulation (unit: part by weight) shown in Table 1. And uniformly mixed (2000 rpm, 5 minutes) and defoamed to obtain a curable resin composition (curable epoxy resin composition). .
The curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., and cured by heating and pressurizing at a pressure of 3.0 MPa for 600 seconds. The cured product was obtained by carrying out at 150 ° C. for 5 hours.
　実施例２Ａ～９Ａ、比較例１Ａ～８Ａ
　硬化性樹脂組成物の組成を表１、２に示す組成に変更したこと以外は実施例１Ａと同様にして、硬化性樹脂組成物及び硬化物を調製した。なお、一部の実施例及び比較例においては、硬化性樹脂組成物の構成成分として、製造例２で得たゴム粒子分散エポキシ化合物に代えて又は合わせて、表１、２に示すエポキシ化合物を使用した。 Examples 2A-9A, Comparative Examples 1A-8A
A curable resin composition and a cured product were prepared in the same manner as in Example 1A except that the composition of the curable resin composition was changed to the compositions shown in Tables 1 and 2. In some examples and comparative examples, as a constituent component of the curable resin composition, instead of or in addition to the rubber particle-dispersed epoxy compound obtained in Production Example 2, the epoxy compounds shown in Tables 1 and 2 were used. used.
　実施例１０Ａ
　表３に示す配合処方（単位：重量部）に従って、製造例２で得たゴム粒子分散エポキシ化合物、シリコーンゴム粒子（商品名「ＫＭＰ－６００」（信越化学工業（株）製）、酸化チタン（商品名「ＤＣＦ－Ｔ－１７０５０」、レジノカラー工業（株）製）、及びシリカ（商品名「ＦＢ－９７０ＦＤ」、デンカ（株）製）を、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下（ロールピッチ：０．２ｍｍ、回転数：２５ヘルツ、３パス）で溶融混練して混練物を得た。
　次に、表３に示す配合処方（単位：重量部）となるように、上記で得た混練物と、硬化触媒（商品名「サンエイド　ＳＩ－１００Ｌ」、三新化学工業（株）製）とを自公転式撹拌装置（商品名「あわとり練太郎ＡＲ－２５０」、（株）シンキー製）を使用して均一に混合し（２０００ｒｐｍ、５分間）、脱泡して、硬化性樹脂組成物（硬化性エポキシ樹脂組成物）を得た。
　上記硬化性樹脂組成物をポリエステルからなる離型フィルムで挟み込み、１５０℃のコンプレッション成型用の金型内に置き、３．０ＭＰａの圧力で６００秒間加熱及び加圧して硬化させ、その後、ポストキュアー（１５０℃で５時間）を行うことによって、硬化物を得た。 Example 10A
According to the formulation (unit: parts by weight) shown in Table 3, the rubber particle-dispersed epoxy compound obtained in Production Example 2, silicone rubber particles (trade name “KMP-600” (manufactured by Shin-Etsu Chemical Co., Ltd.), titanium oxide ( Product name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd., and silica (trade name “FB-970FD”, manufactured by Denka Co., Ltd.) are uniformly mixed using a dissolver, and predetermined by a roll mill. A kneaded product was obtained by melt-kneading under the conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3 passes).
Next, the kneaded product obtained above and a curing catalyst (trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd.) so as to have the formulation (unit: parts by weight) shown in Table 3 Is uniformly mixed (2000 rpm, 5 minutes) using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), defoamed, and curable resin composition (Curable epoxy resin composition) was obtained.
The curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., and cured by heating and pressurizing at a pressure of 3.0 MPa for 600 seconds. The cured product was obtained by carrying out at 150 ° C. for 5 hours.
　実施例１１Ａ、１２Ａ、比較例９Ａ～１３Ａ
　硬化性樹脂組成物の組成を表３に示す組成に変更したこと以外は実施例１０Ａと同様にして、硬化性樹脂組成物及び硬化物を調製した。なお、一部の実施例及び比較例においては、硬化性樹脂組成物の構成成分として、製造例２で得たゴム粒子分散エポキシ化合物に代えて又は合わせて、表３に示すエポキシ化合物を使用した。 Examples 11A and 12A, Comparative Examples 9A to 13A
A curable resin composition and a cured product were prepared in the same manner as in Example 10A except that the composition of the curable resin composition was changed to the composition shown in Table 3. In some examples and comparative examples, the epoxy compounds shown in Table 3 were used in place of or in combination with the rubber particle-dispersed epoxy compound obtained in Production Example 2 as a constituent of the curable resin composition. .
　なお、実施例１Ａ～１２Ａ、比較例１Ａ～９Ａで得られた硬化性樹脂組成物は、２５℃において液状であった。一方、比較例１０Ａ～１３Ａで得られた硬化性樹脂組成物は、２５℃において固体であった。 The curable resin compositions obtained in Examples 1A to 12A and Comparative Examples 1A to 9A were liquid at 25 ° C. On the other hand, the curable resin compositions obtained in Comparative Examples 10A to 13A were solid at 25 ° C.
　実施例１Ｂ
　表４に示す配合割合（単位：重量部）に従って、製造例２で得たゴム粒子分散エポキシ化合物、イソシアヌル酸誘導体（モノアリルジグリシジルイソシアヌレート；商品名「ＭＡ－ＤＧＩＣ」、四国化成工業（株）製）、シロキサン誘導体（分子内に２つのエポキシ基を有するシロキサン誘導体；商品名「Ｘ－４０－２６７８」、及び応力緩和剤（シリコーンゴム粒子；商品名「ＫＭＰ－６００」、信越化学工業（株）製）を、自公転式撹拌装置（商品名「あわとり練太郎ＡＲ－２５０」、（株）シンキー製）を使用して均一に混合し、脱泡して、混合物を作製した。なお、上記混合は、ＭＡ－ＤＧＩＣを溶解させるために、８０℃で１時間攪拌して実施した。
　次に、表４に示す配合割合（単位：重量部）に従って、上記で得た混合物と、白色顔料（酸化チタン；商品名「ＤＣＦ－Ｔ－１７０５０」、レジノカラー工業（株）製）、無機充填剤（シリカ；商品名「ＦＢ－９７０ＦＤ」、デンカ（株）製）を、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下（ロールピッチ：０．２ｍｍ、回転数：２５ヘルツ、３パス）で溶融混練して混練物を得た。
　次に、表４に示す配合割合（単位：重量部）となるように上記で得た混練物と、製造例４で得た硬化剤組成物とを自公転式撹拌装置（商品名「あわとり練太郎ＡＲ－２５０」、（株）シンキー製）を使用して均一に混合し（２０００ｒｐｍ、５分間）、脱泡して、硬化性樹脂組成物（硬化性エポキシ樹脂組成物）を得た。
　上記硬化性樹脂組成物をポリエステルからなる離型フィルムで挟み込み、１５０℃のコンプレッション成型用金型内に置き、３．０ＭＰａの圧力で６００秒間加熱及び加圧し、その後、ポストキュアー（１５０℃で５時間）を行うことによって、硬化物を得た。 Example 1B
According to the blending ratio (unit: parts by weight) shown in Table 4, the rubber particle-dispersed epoxy compound obtained in Production Example 2, isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, Shikoku Chemicals Co., Ltd. ), Siloxane derivatives (siloxane derivatives having two epoxy groups in the molecule; trade name “X-40-2678”, and stress relieving agents (silicone rubber particles; trade name “KMP-600”, Shin-Etsu Chemical ( Were mixed uniformly using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), and defoamed to prepare a mixture. The above mixing was carried out with stirring at 80 ° C. for 1 hour in order to dissolve MA-DGIC.
Next, according to the blending ratio (unit: parts by weight) shown in Table 4, the mixture obtained above, white pigment (titanium oxide; trade name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd.), inorganic filling The agent (silica; trade name “FB-970FD”, manufactured by Denka Co., Ltd.) is uniformly mixed using a dissolver, and is subjected to predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3) by a roll mill. The kneaded product was obtained by melt kneading in a pass.
Next, the kneaded product obtained above and the curing agent composition obtained in Production Example 4 so as to have the blending ratio (unit: parts by weight) shown in Table 4 were mixed with a self-revolving stirrer (trade name “Awatori” The mixture was uniformly mixed (2000 rpm, 5 minutes) using Nertaro AR-250 "(Sinky Corp.) and defoamed to obtain a curable resin composition (curable epoxy resin composition).
The curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then post-cured (5 at 150 ° C. Time), a cured product was obtained.
　実施例２Ｂ～１７Ｂ、比較例１Ｂ～１２Ｂ
　光反射用硬化性樹脂組成物の配合組成を表４又は表５に示すように変更したこと以外は、実施例１Ｂと同様にして光反射用硬化性樹脂組成物及び硬化物を得た。なお、一部の実施例及び比較例においては、硬化性樹脂組成物の構成成分として、製造例２で得たゴム粒子分散エポキシ化合物に代えて又は合わせて、表４又は表５に示すエポキシ化合物を使用した。 Examples 2B to 17B, Comparative Examples 1B to 12B
A light-reflective curable resin composition and a cured product were obtained in the same manner as in Example 1B, except that the composition of the light-reflective curable resin composition was changed as shown in Table 4 or Table 5. In some examples and comparative examples, as a constituent component of the curable resin composition, the epoxy compound shown in Table 4 or Table 5 is used instead of or in combination with the rubber particle-dispersed epoxy compound obtained in Production Example 2. It was used.
　実施例１８Ｂ
　表６に示す配合割合（単位：重量部）に従って、製造例２で得たゴム粒子分散エポキシ化合物、イソシアヌル酸誘導体（モノアリルジグリシジルイソシアヌレート；商品名「ＭＡ－ＤＧＩＣ」、四国化成工業（株）製）、シロキサン誘導体（分子内に２つのエポキシ基を有するシロキサン誘導体；商品名「Ｘ－４０－２６７８」、信越化学工業（株）製）、応力緩和剤（シリコーンゴム粒子；商品名「ＫＭＰ－６００」、信越化学工業（株）製）、及び製造例３で得た脂環式ポリエステル樹脂を、自公転式撹拌装置（商品名「あわとり練太郎ＡＲ－２５０」、（株）シンキー製）を使用して均一に混合し、脱泡して、混合物を作製した。なお、上記混合は、ＭＡ－ＤＧＩＣを溶解させるために、８０℃で１時間攪拌して実施した。
　次に、表６に示す配合割合（単位：重量部）に従って、上記で得た混合物と、白色顔料（酸化チタン；商品名「ＤＣＦ－Ｔ－１７０５０」、レジノカラー工業（株）製）、無機充填剤（シリカ；商品名「ＦＢ－９７０ＦＤ」、デンカ（株）製）を、ディゾルバーを使用して均一に混合し、ロールミルによって所定条件下（ロールピッチ：０．２ｍｍ、回転数：２５ヘルツ、３パス）で溶融混練して混練物を得た。
　次に、表６に示す配合割合（単位：重量部）となるように上記で得た混練物と、硬化触媒（商品名「サンエイド　ＳＩ－１００Ｌ」、三新化学工業（株）製）とを自公転式撹拌装置（商品名「あわとり練太郎ＡＲ－２５０」、（株）シンキー製）を使用して均一に混合し（２０００ｒｐｍ、５分間）、脱泡して、硬化性樹脂組成物（硬化性エポキシ樹脂組成物）を得た。
　上記硬化性樹脂組成物をポリエステルからなる離型フィルムで挟み込み、１５０℃のコンプレッション成型用金型内に置き、３．０ＭＰａの圧力で６００秒間加熱及び加圧し、その後、ポストキュアー（１５０℃で５時間）を行うことによって、硬化物を得た。 Example 18B
According to the blending ratio (unit: parts by weight) shown in Table 6, the rubber particle-dispersed epoxy compound obtained in Production Example 2, isocyanuric acid derivative (monoallyl diglycidyl isocyanurate; trade name “MA-DGIC”, Shikoku Kasei Kogyo Co., Ltd. ), Siloxane derivatives (siloxane derivatives having two epoxy groups in the molecule; trade name “X-40-2678”, manufactured by Shin-Etsu Chemical Co., Ltd.), stress relieving agents (silicone rubber particles; trade name “KMP”) -600 ", manufactured by Shin-Etsu Chemical Co., Ltd.), and the alicyclic polyester resin obtained in Production Example 3 were mixed with a self-revolving stirrer (trade name" Awatori Nerita AR-250 ", manufactured by Shinky Corporation) ) To obtain a mixture. The above mixing was carried out with stirring at 80 ° C. for 1 hour in order to dissolve MA-DGIC.
Next, according to the blending ratio (unit: parts by weight) shown in Table 6, the mixture obtained above, white pigment (titanium oxide; trade name “DCF-T-17050”, manufactured by Resino Color Industry Co., Ltd.), inorganic filling The agent (silica; trade name “FB-970FD”, manufactured by Denka Co., Ltd.) is uniformly mixed using a dissolver, and is subjected to predetermined conditions (roll pitch: 0.2 mm, rotation speed: 25 Hz, 3) by a roll mill. The kneaded product was obtained by melt kneading in a pass.
Next, the kneaded product obtained above so as to have a blending ratio (unit: parts by weight) shown in Table 6 and a curing catalyst (trade name “Sun-Aid SI-100L”, manufactured by Sanshin Chemical Industry Co., Ltd.) Using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd.), uniformly mixed (2000 rpm, 5 minutes), defoamed, and curable resin composition ( A curable epoxy resin composition) was obtained.
The curable resin composition is sandwiched between release films made of polyester, placed in a mold for compression molding at 150 ° C., heated and pressurized at a pressure of 3.0 MPa for 600 seconds, and then post-cured (5 at 150 ° C. Time), a cured product was obtained.
　実施例１９Ｂ、２０Ｂ、比較例１３Ｂ～１８Ｂ
　光反射用硬化性樹脂組成物の配合組成を表６に示すように変更したこと以外は、実施例１８Ｂと同様にして光反射用硬化性樹脂組成物及び硬化物を得た。なお、一部の実施例及び比較例においては、硬化性樹脂組成物の構成成分として、製造例２で得たゴム粒子分散エポキシ化合物に代えて又は合わせて、表６に示すエポキシ化合物を使用した。 Examples 19B and 20B, Comparative Examples 13B to 18B
A light-reflective curable resin composition and a cured product were obtained in the same manner as in Example 18B, except that the blending composition of the light-reflective curable resin composition was changed as shown in Table 6. In some examples and comparative examples, the epoxy compounds shown in Table 6 were used as constituent components of the curable resin composition instead of or in addition to the rubber particle-dispersed epoxy compound obtained in Production Example 2. .
　なお、実施例１Ｂ～２０Ｂ、比較例１Ｂ～１８Ｂにおける硬化性樹脂組成物の、２５℃における性状（液状又は個体）を表４、表５及び表６の「硬化性エポキシ樹脂組成物の性状」に示す。 The properties (liquid or solid) at 25 ° C. of the curable resin compositions in Examples 1B to 20B and Comparative Examples 1B to 18B are “Properties of Curable Epoxy Resin Composition” in Tables 4, 5 and 6. Shown in
　＜評価＞
　実施例及び比較例で得られた硬化物について、下記の評価を実施した。 <Evaluation>
The following evaluation was implemented about the hardened | cured material obtained by the Example and the comparative example.
［初期反射率］
　実施例及び比較例で得られた硬化物を切削加工して、長さ３０ｍｍ×幅３０ｍｍ×厚み３ｍｍの試験片を作製した。次いで、分光光度計（商品名「分光光度計　ＵＶ－２４５０」、（株）島津製作所製）を用いて、波長４５０ｎｍの光に対する各試験片の反射率（「初期反射率」とする）を測定した。結果を表１～６に示す。
　なお、初期反射率が９５％以上であれば、光反射用材料として特に優れていると言える。 [Initial reflectance]
The cured products obtained in the examples and comparative examples were cut to prepare test pieces having a length of 30 mm × width of 30 mm × thickness of 3 mm. Next, using a spectrophotometer (trade name “Spectrophotometer UV-2450”, manufactured by Shimadzu Corporation), the reflectance (referred to as “initial reflectance”) of each test piece with respect to light having a wavelength of 450 nm is measured. did. The results are shown in Tables 1-6.
If the initial reflectance is 95% or more, it can be said that the material is particularly excellent as a light reflecting material.
［加熱エージング前後の反射率保持率］
　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１２０℃の乾燥機に入れて２５０時間放置する試験（耐熱試験）を行った後、波長４５０ｎｍの光の反射率を初期反射率と同様に測定した。そして、下記式により、反射率保持率（加熱エージング前後）を算出した。結果を表１～６に示す。
　［反射率保持率（加熱エージング前後）］＝（［加熱エージング後の反射率］／［初期反射率］）×１００
　この反射率保持率が高いほど、硬化物が耐熱性に優れることが示唆される。なお、１２０℃、２５０時間加熱後の反射率保持率が９０％以上であれば、光反射用材料として耐熱性に特に優れていると言える。 [Reflectance retention before and after heat aging]
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 120 ° C. and allowed to stand for 250 hours (heat resistance test). After the measurement, the reflectance of light having a wavelength of 450 nm was measured in the same manner as the initial reflectance. And the reflectance maintenance factor (before and after heating aging) was computed by the following formula. The results are shown in Tables 1-6.
[Reflectance retention ratio (before and after heating aging)] = ([Reflectance after heating aging] / [Initial reflectance]) × 100
It is suggested that the higher the reflectance retention, the better the cured product is in heat resistance. In addition, if the reflectance retention after heating at 120 ° C. for 250 hours is 90% or more, it can be said that the material is particularly excellent in heat resistance as a light reflecting material.
［紫外線エージング前後の反射率保持率］
　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、当該試験片に対し、強度１０ｍＷ／ｃｍ2の紫外線を２５０時間照射する試験（耐光試験）を行った後、波長４５０ｎｍの光の反射率を初期反射率と同様に測定した。そして、下記式により、反射率保持率（紫外線エージング前後）を算出した。結果を表１～６に示す。
　［反射率保持率（紫外線エージング前後）］＝（［紫外線エージング後の反射率］／［初期反射率］）×１００
　この反射率保持率が高いほど、硬化物が耐光性に優れることが示唆される。なお、強度１０ｍＷ／ｃｍ2、２５０時間照射後の反射率保持率が９０％以上であれば、光反射用材料として耐光性に特に優れていると言える。 [Reflectance retention before and after UV aging]
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 irradiated with ultraviolet light having an intensity of 10 mW / cm 2 for 250 hours (light resistance test) ), The reflectance of light having a wavelength of 450 nm was measured in the same manner as the initial reflectance. And the reflectance retention (before and after ultraviolet ray aging) was computed by the following formula. The results are shown in Tables 1-6.
[Reflectance retention (before and after ultraviolet aging)] = ([Reflectance after ultraviolet aging] / [Initial reflectance]) × 100
It is suggested that the higher the reflectance retention, the more excellent the light resistance of the cured product. In addition, it can be said that it is especially excellent in light resistance as a light-reflecting material if intensity | strength is 10 mW / cm < 2 > and the reflectance retention rate after irradiation for 250 hours is 90% or more.
［エッチング試験］
　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、当該試験片の重量（「初期重量」とする）を測定した後、７０℃の１１重量％水酸化カリウム水溶液に浸漬した。６０分後に試験片を取り出し、純水で洗浄し、６０℃で３０分間乾燥させた後の重量（「エッチング試験後重量」とする）を測定した。そして、下記式により、重量維持率（％）を算出した。結果を表４～６に示す。
　［重量維持率（％）］＝（［初期重量］－［エッチング試験後重量］）／［初期重量］×１００ [Etching test]
Using the test piece (cured product; length 30 mm × width 30 mm × 3 mm thickness) on which the initial reflectance was evaluated, the weight of the test piece (referred to as “initial weight”) was measured, and then the temperature was 11 at 70 ° C. It was immersed in a weight% potassium hydroxide aqueous solution. After 60 minutes, the test piece was taken out, washed with pure water, and dried at 60 ° C. for 30 minutes (weight after etching test) was measured. And weight maintenance factor (%) was computed by the following formula. The results are shown in Tables 4-6.
[Weight retention rate (%)] = ([Initial weight] − [Weight after etching test]) / [Initial weight] × 100
［切削加工時のクラック有無評価（強靭性評価）］
　実施例及び比較例で得られた硬化物を切削加工して、幅５ｍｍ×長さ５ｍｍ×厚さ３ｍｍの試験片を作製した。上記硬化物の切削加工には、マイクロ・カッティング・マシン（商品名「ＢＳ－３００ＣＬ」、メイワフォーシス（株）製）を使用し、切削加工の際に硬化物にクラックが生じたか否かを、デジタルマイクロスコープ（商品名「ＶＨＸ－９００」、（株）キーエンス製）を用いて観察し、確認した。表１～６には、１サンプルにつき１０個の試験片を作製し、そのうちクラックの発生が確認された試験片の個数［個／１０個］を評価結果として示す。 [Evaluation of presence or absence of cracks during cutting (toughness evaluation)]
The cured products obtained in the examples and comparative examples were cut to prepare test pieces having a width of 5 mm, a length of 5 mm, and a thickness of 3 mm. For cutting of the cured product, a micro cutting machine (trade name “BS-300CL”, manufactured by Meiwa Forsys Co., Ltd.) was used, and whether or not cracks occurred in the cured product during the cutting process. This was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation). In Tables 1 to 6, 10 test pieces were prepared for each sample, and the number of test pieces in which cracks were confirmed [pieces / 10 pieces] was shown as evaluation results.
［リフロー時のクラック有無評価（強靭性評価）］
　上記切削加工により得られた試験片（幅５ｍｍ×長さ５ｍｍ×厚さ３ｍｍ）に対し、リフロー炉（商品名「ＵＮＩ－５０１６Ｆ」、日本アントム（株）製）を用いて、２６０℃を最高温度として５秒間、全リフロー時間を９０秒としてリフロー処理を施した。その後、当該リフロー処理により試験片にクラックが生じたか否かを、デジタルマイクロスコープ（商品名「ＶＨＸ－９００」、（株）キーエンス製）を用いて観察し、確認した。表１～６には、１サンプルにつき１０個の試験片のリフロー処理を行い、そのうちクラックの発生が確認された試験片の個数［個／１０個］を評価結果として示す。
　なお、切削加工時でクラック発生が認められたものは、リフロー時のクラック発生の有無は評価しなかった。 [Evaluation of crack presence during reflow (toughness evaluation)]
Using a reflow furnace (trade name “UNI-5016F”, manufactured by Nippon Antom Co., Ltd.), the maximum temperature of 260 ° C. is applied to the test piece (width 5 mm × length 5 mm × thickness 3 mm) obtained by the above cutting process. The reflow treatment was performed at a temperature of 5 seconds and a total reflow time of 90 seconds. Thereafter, whether or not the test piece was cracked by the reflow treatment was observed and confirmed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation). Tables 1 to 6 show the evaluation results of the number of test pieces [10 pieces] in which cracks were confirmed among 10 test pieces that were reflowed per sample.
In addition, the thing in which the crack generation was recognized at the time of cutting was not evaluated about the crack generation at the time of reflow.
　［総合判定］
　表１～３において、各試験の結果、下記（１）～（５）をいずれも満たすものを○（良好）と判定した。一方、下記（１）～（５）のいずれかを満たさない場合には×（不良）と判定した。
　また、表４～６において、各試験の結果、下記（１）～（６）をいずれも満たすものを○（良好）と判定した。一方、下記（１）～（６）のいずれかを満たさない場合には×（不良）と判定した。
（１）初期反射率：光反射率が９５％以上
（２）加熱エージング前後の反射率保持率：反射率保持率が９０％以上
（３）紫外線エージング前後の反射率保持率：反射率保持率が９０％以上
（４）切削加工時のクラック有無評価：クラックが発生した個数が０個
（５）リフロー時のクラック有無評価：クラックが発生した個数が０個
（６）エッチング試験：重量維持率が０．５％以下
　結果を表１～６の「総合判定」の欄に示す。 [Comprehensive judgment]
In Tables 1 to 3, as a result of each test, those satisfying all of the following (1) to (5) were judged as ◯ (good). On the other hand, when any of the following (1) to (5) was not satisfied, it was determined as x (defective).
In Tables 4 to 6, as a result of each test, those satisfying all of the following (1) to (6) were determined to be “good”. On the other hand, when any of the following (1) to (6) was not satisfied, it was determined as x (defective).
(1) Initial reflectance: light reflectance is 95% or more (2) Reflectivity retention ratio before and after heating aging: Reflectivity retention ratio is 90% or more (3) Reflectivity retention ratio before and after ultraviolet aging: Reflectance retention ratio 90% or more (4) Evaluation of presence / absence of cracks during cutting: 0 (number of cracks generated) (5) Evaluation of presence / absence of cracks during reflow: 0 (number of cracks generated) (6) Etching test: Weight maintenance rate Is 0.5% or less. The results are shown in the column “Comprehensive Judgment” in Tables 1-6.
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　なお、表１～６に示す成分について、以下に説明する。
（ゴム粒子分散エポキシ化合物）
　製造例２で得られたゴム粒子分散エポキシ化合物
（エポキシ化合物）
　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
　ＹＤ－１２８：商品名「ＹＤ－１２８」（ビスフェノールＡ型エポキシ樹脂）、新日鐵化学（株）製
（イソシアヌル酸誘導体）
　ＴＥＰＩＣ：商品名「ＴＥＰＩＣ」（トリグリシジルイソシアヌレート）、日産化学工業（株）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
　ＤＡ－ＭＧＩＣ：商品名「ＤＡ－ＭＧＩＣ」（ジアリルモノグリシジルイソシアヌレート）、四国化成工業（株）製
（シロキサン誘導体）
　Ｘ－４０－２６７８：商品名「Ｘ－４０－２６７８」（分子内に２つのエポキシ基を有するシロキサン誘導体）、信越化学工業（株）製
　Ｘ－４０－２７２０：商品名「Ｘ－４０－２７２０」（分子内に３つのエポキシ基を有するシロキサン誘導体）、信越化学工業（株）製
　Ｘ－４０－２６７０：商品名「Ｘ－４０－２６７０」（分子内に４つのエポキシ基を有するシロキサン誘導体）、信越化学工業（株）製
（硬化剤組成物）
　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
　ＨＮ－７２００：商品名「ＨＮ－７２００」（４－メチルヘキサヒドロ無水フタル酸と脂環式ポリエステル樹脂の混合物）、日立化成工業（株）製
　ＨＮ－５７００：商品名「ＨＮ－５７００」（４－メチルヘキサヒドロ無水フタル酸／３－メチルヘキサヒドロ無水フタル酸＝７０／３０と脂環式ポリエステル樹脂の混合物）、日立化成工業（株）製
　１８Ｘ：商品名「Ｕ－ＣＡＴ　１８Ｘ」（硬化促進剤）、サンアプロ（株）製
　エチレングリコール：商品名「エチレングリコール」、和光純薬工業（株）製
（硬化触媒）
　サンエイド　ＳＩ－１００Ｌ：商品名「サンエイド　ＳＩ－１００Ｌ」、三新化学工業（株）製
（応力緩和剤）
　ＫＭＰ－６００：商品名「ＫＭＰ－６００」（シリコーンレジンを表面に備える架橋されたポリジメチルシロキサン）、信越化学工業（株）製
　ＫＭＰ－６０２：商品名「ＫＭＰ－６０２」（シリコーンレジンを表面に備える架橋されたポリジメチルシロキサン）、信越化学工業（株）製
　ＳＦ８４２１：商品名「ＳＦ８４２１」（式（１）で表されるポリアルキレンエーテル変性シリコーン化合物）、東レ・ダウコーニング（株）製
　Ｙ－１９２６８：商品名「Ｙ－１９２６８」（式（１）で表されるポリアルキレンエーテル変性シリコーン化合物）、モメンティブ・パフォーマンス・マテリアルズ・ジャパン（同）製
（白色顔料）
　ＤＣＦ－Ｔ－１７０５０：商品名「ＤＣＦ－Ｔ－１７０５０」（酸化チタン、平均粒子径０．３μｍ、最大粒子径１μｍ以下）、レジノカラー工業（株）製
　酸化チタン：商品名「ＤＣＦ－Ｔ－１７０５０」（酸化チタン、平均粒子径０．３μｍ、最大粒子径１μｍ以下）、レジノカラー工業（株）製
（無機充填剤）
　ＦＢ－９７０ＦＤ：商品名「ＦＢ－９７０ＦＤ」（シリカ、表面処理なし、平均粒子径１６．７μｍ、最大粒子径７０μｍ）、デンカ（株）製
　ＤＡＷ－１０２５：商品名「ＤＡＷ－１０２５」（アルミナ、平均粒子径７．９μｍ、最大粒子径３２μｍ）、デンカ（株）製
　ＨＦ－０５：商品名「ＨＦ－０５」（窒化アルミニウム、平均粒子径５μｍ、最大粒子径５μｍ）、（株）トクヤマ製
　シリカ：商品名「ＦＢ－９７０ＦＤ」（シリカ、表面処理なし、平均粒子径１６．７μｍ、最大粒子径７０μｍ）、デンカ（株）製
　アルミナ：商品名「ＤＡＷ－１０２５」（アルミナ、平均粒子径７．９μｍ、最大粒子径３２μｍ）、デンカ（株）製
　窒化アルミニウム：商品名「ＨＦ－０５」（窒化アルミナ、平均粒子径５μｍ、最大粒子径５μｍ）、（株）トクヤマ製 The components shown in Tables 1 to 6 will be described below.
(Rubber particle dispersed epoxy compound)
Rubber particle-dispersed epoxy compound (epoxy compound) obtained in Production Example 2
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 Co., Ltd. YD-128: trade name “YD-128” (bisphenol A type epoxy resin), Nippon Steel Made by Sakai Chemical Co., Ltd. (isocyanuric acid derivative)
TEPIC: trade name “TEPIC” (triglycidyl isocyanurate), MA-DGIC: trade name “MA-DGIC” (monoallyl diglycidyl isocyanurate), Shikoku Kasei Kogyo DA- MGIC: Trade name “DA-MGIC” (diallyl monoglycidyl isocyanurate), manufactured by Shikoku Chemicals Co., Ltd. (siloxane derivative)
X-40-2678: Trade name “X-40-2678” (siloxane derivative having two epoxy groups in the molecule), Shin-Etsu Chemical Co., Ltd. X-40-2720: Trade name “X-40-2720” "(Siloxane derivative having three epoxy groups in the molecule), X-40-2670 manufactured by Shin-Etsu Chemical Co., Ltd .: trade name" X-40-2670 "(siloxane derivative having four epoxy groups in the molecule) , Shin-Etsu Chemical Co., Ltd. (curing agent composition)
MH-700: trade name “Licacid MH-700” (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride), manufactured by Shin Nippon Rika Co., Ltd. HN-7200: trade name “HN-7200” (4-methyl A mixture of hexahydrophthalic anhydride and alicyclic polyester resin), manufactured by Hitachi Chemical Co., Ltd. HN-5700: Trade name “HN-5700” (4-methylhexahydrophthalic anhydride / 3-methylhexahydrophthalic anhydride) Acid = 70/30 and a mixture of alicyclic polyester resin), manufactured by Hitachi Chemical Co., Ltd. 18X: trade name “U-CAT 18X” (curing accelerator), manufactured by San Apro Co., Ltd. ethylene glycol: trade name “Ethylene” Glycol ", Wako Pure Chemical Industries, Ltd. (curing catalyst)
Sun-Aid SI-100L: Trade name "Sun-Aid SI-100L", manufactured by Sanshin Chemical Industry Co., Ltd. (stress relieving agent)
KMP-600: Trade name “KMP-600” (crosslinked polydimethylsiloxane with silicone resin on the surface), manufactured by Shin-Etsu Chemical Co., Ltd. KMP-602: Trade name “KMP-602” (silicone resin on the surface) Cross-linked polydimethylsiloxane), manufactured by Shin-Etsu Chemical Co., Ltd. SF8421: Trade name “SF8421” (polyalkylene ether-modified silicone compound represented by the formula (1)), Y- manufactured by Toray Dow Corning Co., Ltd. 19268: Trade name “Y-19268” (polyalkylene ether-modified silicone compound represented by formula (1)), manufactured by Momentive Performance Materials Japan (same) (white pigment)
DCF-T-17050: Trade name “DCF-T-17050” (titanium oxide, average particle size 0.3 μm, maximum particle size 1 μm or less), manufactured by Resino Color Industry Co., Ltd. Titanium oxide: Trade name “DCF-T-17050 (Titanium oxide, average particle size 0.3 μm, maximum particle size 1 μm or less), manufactured by Resino Color Industry Co., Ltd. (inorganic filler)
FB-970FD: Trade name “FB-970FD” (silica, no surface treatment, average particle size 16.7 μm, maximum particle size 70 μm), manufactured by Denka Corp. DAW-1025: Trade name “DAW-1025” (alumina, (Average particle size 7.9 μm, maximum particle size 32 μm), Denka Co., Ltd. HF-05: trade name “HF-05” (aluminum nitride, average particle size 5 μm, maximum particle size 5 μm), Tokuyama Co., Ltd. Silica : Trade name “FB-970FD” (silica, no surface treatment, average particle size 16.7 μm, maximum particle size 70 μm), manufactured by Denka Co., Ltd. Alumina: Trade name “DAW-1025” (alumina, average particle size 7. 9 μm, maximum particle size 32 μm), aluminum nitride manufactured by Denka Co., Ltd .: Trade name “HF-05” (alumina nitride, average particle size 5 μm, maximum particle size 5 μm), Co., Ltd. Shame made
　上記で説明した本発明のバリエーションを以下に付記する。
［１］脂環式エポキシ化合物（Ａ）、シリコーンゴム粒子以外のゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、及び応力緩和剤（Ｈ）を含有し、さらに、硬化剤（Ｅ）及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）を含有し、２５℃において液状であることを特徴とする光反射用硬化性樹脂組成物。
［２］脂環式エポキシ化合物（Ａ）、シリコーンゴム粒子以外のゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、応力緩和剤（Ｈ）、分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）、分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含有し、さらに、硬化剤（Ｅ）、及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）を含有し、２５℃において液状であることを特徴とする光反射用硬化性樹脂組成物。
［３］常圧において２５℃で測定した粘度が１００００００ｍＰａ・ｓ以下（好ましくは、８０００００ｍＰａ・ｓ以下）である、上記［１］又は［２］に記載の光反射用硬化性樹脂組成物。 The variations of the present invention described above are appended below.
[1] Contains an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H), and further cured. A curable resin composition for light reflection, which contains an agent (E) and a curing accelerator (F) or a curing catalyst (G) and is liquid at 25 ° C.
[2] Alicyclic epoxy compound (A), rubber particles other than silicone rubber particles (B), white pigment (C), inorganic filler (D), stress relaxation agent (H), one or more in the molecule Containing an isocyanuric acid derivative (I) having an oxirane ring, a siloxane derivative (J) having two or more epoxy groups in the molecule, and an alicyclic polyester resin (K), and further a curing agent (E), and A curable resin composition for light reflection, comprising a curing accelerator (F) or a curing catalyst (G) and being liquid at 25 ° C.
[3] The curable resin composition for light reflection according to the above [1] or [2], wherein the viscosity measured at 25 ° C. at normal pressure is 1,000,000 mPa · s or less (preferably 800,000 mPa · s or less).
［４］脂環式エポキシ化合物（Ａ）が、（ｉ）脂環を構成する隣接する２つの炭素原子と酸素原子とで構成されるエポキシ基（脂環式エポキシ基）を有する化合物、及び（ii）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からなる群より選択される少なくとも１種を含む、上記［１］～［３］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５］脂環式エポキシ化合物（Ａ）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［１］～［４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［６］脂環式エポキシ化合物（Ａ）が、下記式（Ｉ）で表される化合物を含む、上記［１］～［５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000037
 ［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。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、置換基（好ましくはアルキル基）が結合していてもよい。］
［７］連結基が、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、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、又はこれらが複数個連結した基である、上記［６］に記載の光反射用硬化性樹脂組成物。
［８］上記式（Ｉ）で表される脂環式エポキシ化合物が、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、及びビス（３，４－エポキシシクロヘキシルメチル）エーテルからなる群より選択される少なくとも１種である、上記［６］又は［７］に記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
 ［上記式（Ｉ－５）、（Ｉ－７）中のｌ、ｍは、それぞれ１～３０の整数を示す。上記式（Ｉ－５）中のＲは炭素数１～８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）である。上記式（Ｉ－９）、（Ｉ－１０）中のｎ１～ｎ６は、それぞれ１～３０の整数を示す。］
［９］脂環式エポキシ化合物（Ａ）が、下記式（Ｉ－１）
Figure JPOXMLDOC01-appb-C000040
で表される化合物を含む、上記［８］に記載の光反射用硬化性樹脂組成物。
［１０］脂環式エポキシ化合物（Ａ）が、下記式（II)で表される化合物を含む、上記［１］～［９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000041
 ［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の整数を示す。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。Ｒ2は、下記式（IIａ）～（IIｃ）で表される基のいずれかを示す。Ｒ2の少なくとも１つは、式（IIａ）で表される基である。
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
 （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。）］
［１１］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）で表される基の割合が、４０モル％以上（好ましくは６０モル％以上、より好ましくは８０モル％以上）である、上記［１０］に記載の光反射用硬化性樹脂組成物。
［１２］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［１０］又は［１１］に記載の光反射用硬化性樹脂組成物。
［１３］式（II）で表される化合物のエポキシ基の当量（エポキシ当量）が、５０～１０００（好ましくは１００～５００）である、上記［１０］～［１２］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［１４］（ｉ）脂環式エポキシ基を有する化合物を少なくとも含む、上記［１］～［１３］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［１５］さらに（ii）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を含む、上記［１４］に記載の光反射用硬化性樹脂組成物。
［１６］脂環式エポキシ化合物（Ａ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、１．５～６０重量％（好ましくは２～５０重量％、より好ましくは５～４０重量％）である、上記［１］、［３］～［１５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［１７］硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量（１００重量％）に対する脂環式エポキシ化合物（Ａ）の割合が、５０重量％以上（好ましくは６０重量％以上、より好ましくは８０重量％以上、特に好ましくは９０重量％以上）である、上記［１］、［３］～［１６］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［１８］脂環式エポキシ化合物（Ａ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．１～６０重量％（好ましくは０．３～５０重量％、より好ましくは０．５～４０重量％）である、上記［２］～［１５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［１９］硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量（１００重量％）に対する脂環式エポキシ化合物（Ａ）の割合が、１～９０重量％（好ましくは５～８０重量％、より好ましくは１０～７０重量％）である、上記［２］～［１５］、［１８］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [4] The alicyclic epoxy compound (A) has (i) a compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and ( ii) For light reflection according to any one of the above [1] to [3], comprising at least one selected from the group consisting of compounds having an epoxy group directly bonded to the alicyclic ring with a single bond Curable resin composition.
[5] The light-reflective curable resin composition according to any one of [1] to [4], wherein the alicyclic epoxy compound (A) includes a compound having a cyclohexene oxide group.
[6] The light-reflective curable resin composition according to any one of [1] to [5], wherein the alicyclic epoxy compound (A) includes a compound represented by the following formula (I): .
Figure JPOXMLDOC01-appb-C000037
 [In Formula (I), X represents a single bond or a linking group (a divalent group having one or more atoms). A substituent (preferably an alkyl group) may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group). ]
[7] The linking group is a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or these The curable resin composition for light reflection according to the above [6], wherein a plurality of are groups connected.
[8] The alicyclic epoxy compound represented by the formula (I) is a compound 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 the curable resin composition for light reflection according to the above [6] or [7], which is at least one selected from the group consisting of bis (3,4-epoxycyclohexylmethyl) ether.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
 [In the above formulas (I-5) and (I-7), l and m each represents an integer of 1 to 30. R in the above formula (I-5) is an alkylene group having 1 to 8 carbon atoms (preferably a linear or branched alkylene group having 1 to 3 carbon atoms). In the above formulas (I-9) and (I-10), n1 to n6 each represents an integer of 1 to 30. ]
[9] The alicyclic epoxy compound (A) is represented by the following formula (I-1)
Figure JPOXMLDOC01-appb-C000040
The curable resin composition for light reflection according to the above [8], comprising a compound represented by the formula:
[10] The light-reflective curable resin composition according to any one of the above [1] to [9], wherein the alicyclic epoxy compound (A) comprises a compound represented by the following formula (II): .
Figure JPOXMLDOC01-appb-C000041
 [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. When p is an integer greater than or equal to 2, several q may be the same and may differ. The sum (total) of q in the formula (II) is an integer of 3 to 100. R 2 represents any one of groups represented by the following formulas (IIa) to (IIc). At least one of R 2 is a group represented by the formula (IIa).
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
 (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.)]
[11] The ratio of the 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 (preferably 60 mol% or more, more The curable resin composition for light reflection according to the above [10], which is preferably 80 mol% or more.
[12] The light reflecting curing as described in [10] or [11] 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). Resin composition.
[13] In any one of the above [10] to [12], the epoxy group equivalent (epoxy equivalent) of the compound represented by the formula (II) is 50 to 1000 (preferably 100 to 500). The curable resin composition for light reflection as described.
[14] The light-reflective curable resin composition according to any one of the above [1] to [13], comprising (i) at least a compound having an alicyclic epoxy group.
[15] The light-reflective curable resin composition according to [14], further including (ii) a compound having an epoxy group directly bonded to the alicyclic ring with a single bond.
[16] The content (blending amount) of the alicyclic epoxy compound (A) is 1.5 to 60% by weight (preferably 2 to 50% by weight) with respect to the curable resin composition (100% by weight), The light-reflective curable resin composition according to any one of [1] and [3] to [15] above, more preferably 5 to 40% by weight.
[17] The ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition is 50% by weight or more (preferably 60% by weight or more, more preferably Is 80% by weight or more, and particularly preferably 90% by weight or more). The curable resin composition for light reflection according to any one of the above [1], [3] to [16].
[18] The content (blending amount) of the alicyclic epoxy compound (A) is 0.1 to 60% by weight (preferably 0.3 to 50% by weight) with respect to the curable resin composition (100% by weight). %, More preferably 0.5 to 40% by weight), the curable resin composition for light reflection according to any one of the above [2] to [15].
[19] The ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the compound having an epoxy group contained in the curable resin composition is 1 to 90% by weight (preferably 5 to 80% by weight, More preferably, the curable resin composition for light reflection according to any one of [2] to [15] and [18], which is 10 to 70% by weight).
［２０］シリコーンゴム粒子以外のゴム粒子（Ｂ）（以下、単に、「ゴム粒子（Ｂ）」と称する場合がある）が、ゴム弾性を有するコア部分と、該コア部分を被覆する少なくとも１層のシェル層とからなる多層構造（コアシェル構造）を有するゴム粒子である、上記［１］～［１９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２１］ゴム粒子（Ｂ）が、（メタ）アクリル酸エステルを必須モノマー成分とするポリマーで構成されるゴム粒子である、上記［１］～［２０］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２２］ゴム粒子（Ｂ）が、表面にヒドロキシ基及び／又はカルボキシ基ヒドロキシ基及びカルボキシ基のいずれか一方又は両方）を有するゴム粒子である、上記［１］～［２１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２３］ゴム粒子（Ｂ）の平均粒子径が、１０～５００ｎｍ（好ましくは２０～４００ｎｍ）である、上記［１］～［２２］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２４］ゴム粒子（Ｂ）の最大粒子径が、５０～１０００ｎｍ（好ましくは１００～８００ｎｍ）である、上記［１］～［２３］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２５］ゴム粒子（Ｂ）の屈折率が、１．４０～１．６０（好ましくは１．４２～１．５８）である、上記［１］～［２４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２６］ゴム粒子（Ｂ）の屈折率と、該ゴム粒子（Ｂ）を含む硬化性樹脂組成物を硬化させて得られる硬化物の屈折率との差が±０．０３以内である、上記［１］～［２５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２７］ゴム粒子（Ｂ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．０５～２０重量％（好ましくは０．１～１５重量％、より好ましくは０．２～１０重量％）である、上記［１］、［３］～［１７］、［２０］～［２６］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２８］ゴム粒子（Ｂ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．０１～２０重量％（好ましくは０．０５～１５重量％、より好ましくは０．１～１０重量％）である、上記［２］～［１５］、［１８］～［２６］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［２９］ゴム粒子（Ｂ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、０．５～３０重量部（好ましくは１～２０重量部）である、上記［１］～［２８］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [20] A rubber particle (B) other than silicone rubber particles (hereinafter sometimes simply referred to as “rubber particle (B)”) has a core portion having rubber elasticity and at least one layer covering the core portion. The light-reflective curable resin composition according to any one of the above [1] to [19], which is a rubber particle having a multilayer structure (core-shell structure) composed of a shell layer.
[21] The light reflection according to any one of the above [1] to [20], wherein the rubber particle (B) is a rubber particle composed of a polymer having (meth) acrylic acid ester as an essential monomer component. Curable resin composition.
[22] Any one of [1] to [21] above, wherein the rubber particle (B) is a rubber particle having a hydroxy group and / or a carboxy group and / or a carboxy group on the surface. The curable resin composition for light reflection as described in 1.
[23] The light-reflective curable resin composition according to any one of [1] to [22] above, wherein the rubber particles (B) have an average particle size of 10 to 500 nm (preferably 20 to 400 nm). object.
[24] The curable resin composition for light reflection according to any one of the above [1] to [23], wherein the rubber particles (B) have a maximum particle size of 50 to 1000 nm (preferably 100 to 800 nm). object.
[25] The refractive index of the rubber particles (B) is 1.40 to 1.60 (preferably 1.42 to 1.58), according to any one of the above [1] to [24] Curable resin composition for light reflection.
[26] The difference between the refractive index of the rubber particles (B) and the refractive index of a cured product obtained by curing the curable resin composition containing the rubber particles (B) is within ± 0.03. The curable resin composition for light reflection according to any one of [1] to [25].
[27] The content (blending amount) of the rubber particles (B) is 0.05 to 20% by weight (preferably 0.1 to 15% by weight, based on the curable resin composition (100% by weight). The light-reflective curable resin composition according to any one of [1], [3] to [17], and [20] to [26], which is preferably 0.2 to 10% by weight.
[28] The content (blending amount) of the rubber particles (B) is 0.01 to 20% by weight (preferably 0.05 to 15% by weight, based on the curable resin composition (100% by weight). The light-reflective curable resin composition according to any one of [2] to [15] and [18] to [26], which is preferably 0.1 to 10% by weight.
[29] The content (blending amount) of the rubber particles (B) is 0.5 to 30 parts by weight (preferably 1) with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition. The curable resin composition for light reflection according to any one of the above [1] to [28], wherein
［３０］白色顔料（Ｃ）が、酸化チタン、酸化ジルコニウム、酸化亜鉛、及び硫酸バリウムからなる群より選択される少なくとも１種である、上記［１］～［２９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［３１］白色顔料（Ｃ）が、酸化チタンである、上記［１］～［３０］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［３２］白色顔料（Ｃ）の中心粒径が、０．１～５０μｍである、上記［１］～［３１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［３３］酸化チタンの中心粒径が、０．１～５０μｍ（好ましくは０．１～３０μｍ、より好ましくは０．１～２０μｍ、特に好ましくは０．１～１０μｍ、最も好ましくは０．１～５μｍ）である、上記［３１］に記載の光反射用硬化性樹脂組成物。
［３４］白色顔料（Ｃ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．１～５０重量％（好ましくは１～４０重量％、より好ましくは５～３５重量％）である、上記［１］～［３３］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［３５］白色顔料（Ｃ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、３～４００重量部（好ましくは１０～３５０重量部、より好ましくは３０～３００重量部）である、上記［１］、［３］～［１７］、［２０］～［２７］、［２９］～［３４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［３６］白色顔料（Ｃ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１０～６００重量部（好ましくは３０～５００重量部、より好ましくは３０～４００重量部）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［３７］白色顔料（Ｃ）と無機充填剤（Ｄ）の総量（１００重量％）に対する酸化チタンの割合が、５～７０重量％（好ましくは１０～６０重量％）である、上記［３１］～［３４］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [30] The white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate, according to any one of the above [1] to [29] Curable resin composition for light reflection.
[31] The curable resin composition for light reflection according to any one of the above [1] to [30], wherein the white pigment (C) is titanium oxide.
[32] The light-reflective curable resin composition according to any one of [1] to [31] above, wherein the white pigment (C) has a center particle size of 0.1 to 50 μm.
[33] The center particle size of titanium oxide is 0.1 to 50 μm (preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, particularly preferably 0.1 to 10 μm, most preferably 0.1 to The curable resin composition for light reflection according to the above [31], which is 5 μm).
[34] The content (blending amount) of the white pigment (C) is 0.1 to 50% by weight (preferably 1 to 40% by weight, more preferably, relative to the curable resin composition (100% by weight). The curable resin composition for light reflection according to any one of the above [1] to [33], which is 5 to 35% by weight).
[35] The content (blending amount) of the white pigment (C) is 3 to 400 parts by weight (preferably 10 to 350 parts per 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). The above-mentioned [1], [3] to [17], [20] to [27], and [29] to [34], which are parts by weight, more preferably 30 to 300 parts by weight) Curable resin composition for light reflection.
[36] The content (blending amount) of the white pigment (C) is 10 to 600 parts by weight (preferably 30 to 500 parts per 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition. For light reflection according to any one of the above [2] to [15], [18] to [26], and [28] to [34]. Curable resin composition.
[37] The above [31], wherein the ratio of titanium oxide to the total amount (100 wt%) of the white pigment (C) and the inorganic filler (D) is 5 to 70 wt% (preferably 10 to 60 wt%). The curable resin composition for light reflection according to any one of [34] to [34].
［３８］無機充填剤（Ｄ）が、シリカ、アルミナ、窒化ケイ素、窒化アルミニウム、及び窒化ホウ素からなる群より選択される少なくとも１種である、上記［１］～［３７］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［３９］無機充填剤（Ｄ）が、シリカ（シリカフィラー）である、上記［１］～［３８］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４０］シリカの中心粒径が、０．１～５０μｍ（好ましくは０．１～３０μｍ）である、上記［３９］に記載の光反射用硬化性樹脂組成物。
［４１］無機充填剤（Ｄ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、１０～９０重量％（好ましくは１３～７５重量％、より好ましくは１５～７０重量％、さらに好ましくは２０～７０重量％）である、上記［１］～［４０］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４２］無機充填剤（Ｄ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１０～１５００重量部（好ましくは５０～１２００重量部、より好ましくは７０～１０００重量部）である、上記［１］、［３］～［１７］、［２０］～［２７］、［２９］～［３５］、［３７］～［４１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４３］無機充填剤（Ｄ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１０～１５００重量部（好ましくは５０～１２００重量部、より好ましくは１００～１０００重量部）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４４］白色顔料（Ｃ）及び無機充填剤（Ｄ）の最大粒子径が、２００μｍ以下（好ましくは１８５μｍ以下、より好ましくは１７５μｍ以下、特に好ましくは１５０μｍ以下）である、上記［１］～［４３］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４５］白色顔料（Ｃ）及び無機充填剤（Ｄ）の最大粒子径が、０．０１μｍ以上である、上記［１］～［４４］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [38] Any one of the above [1] to [37], wherein the inorganic filler (D) is at least one selected from the group consisting of silica, alumina, silicon nitride, aluminum nitride, and boron nitride. The curable resin composition for light reflection described in 1.
[39] The light-reflective curable resin composition according to any one of [1] to [38], wherein the inorganic filler (D) is silica (silica filler).
[40] The light-reflective curable resin composition according to the above [39], wherein the silica has a center particle diameter of 0.1 to 50 μm (preferably 0.1 to 30 μm).
[41] The content (blending amount) of the inorganic filler (D) is 10 to 90% by weight (preferably 13 to 75% by weight, more preferably 15% with respect to the curable resin composition (100% by weight). The curable resin composition for light reflection according to any one of the above [1] to [40], which is ˜70 wt%, more preferably 20 to 70 wt%.
[42] The content (blending amount) of the inorganic filler (D) is 10 to 1500 parts by weight (preferably 50 to 100 parts by weight based on 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). The above [1], [3] to [17], [20] to [27], [29] to [35], [37] to [ 41] The curable resin composition for light reflections as described in any one of 41.
[43] The content (blending amount) of the inorganic filler (D) is 10 to 1500 parts by weight (preferably 50 to Any of the above [2] to [15], [18] to [26], [28] to [34], and [36] to [41]. The curable resin composition for light reflection as described in any one.
[44] The above-mentioned [1]-[ 43]. The light-reflective curable resin composition according to any one of [43].
[45] The light-reflective curable resin according to any one of the above [1] to [44], wherein the maximum particle size of the white pigment (C) and the inorganic filler (D) is 0.01 μm or more. Composition.
［４６］硬化剤（Ｅ）が、酸無水物類（酸無水物系硬化剤）である、上記［１］～［４５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４７］硬化剤（Ｅ）が、２５℃で液状の酸無水物類（酸無水物系硬化剤）である、上記［１］～［４６］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４８］硬化剤（Ｅ）が、飽和単環炭化水素ジカルボン酸の無水物（環にアルキル基等の置換基が結合したものも含む）である、上記［１］～［４７］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［４９］硬化剤（Ｅ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、１～４０重量％（好ましくは３～３５重量％、より好ましくは５～３０重量％）である、上記［１］～［４８］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５０］硬化剤（Ｅ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、４０～２００重量部（好ましくは５０～１５０重量部）である、上記［１］～［４９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５１］硬化促進剤（Ｆ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．０００１～５重量％（好ましくは０．００１～１重量％）である、上記［１］～［５０］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５２］硬化促進剤（Ｆ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、０．０５～１５重量部（好ましくは０．１～１２重量部、より好ましくは０．２～１０重量部、特に好ましくは０．２５～８重量部）である、上記［１］～［５１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５３］硬化触媒（Ｇ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．０００１～５重量％（好ましくは０．００１～１重量％）である、上記［１］～［５２］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５４］硬化触媒（Ｇ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、０．０００１～１５重量部（好ましくは０．０１～１２重量部、より好ましくは０．０５～１０重量部、特に好ましくは０．０５～８重量部）である、上記［１］～［５３］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [46] The light-reflective curable resin composition according to any one of [1] to [45] above, wherein the curing agent (E) is an acid anhydride (an acid anhydride-based curing agent).
[47] The light reflecting curing as described in any one of [1] to [46] above, wherein the curing agent (E) is an acid anhydride (acid anhydride curing agent) that is liquid at 25 ° C. Resin composition.
[48] Any of the above [1] to [47], wherein the curing agent (E) is an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (including those having a substituent such as an alkyl group bonded to the ring). The curable resin composition for light reflection as described in one.
[49] The content (blending amount) of the curing agent (E) is 1 to 40% by weight (preferably 3 to 35% by weight, more preferably 5 to 5% by weight) with respect to the curable resin composition (100% by weight). 30% by weight) The curable resin composition for light reflection according to any one of [1] to [48] above.
[50] The content (blending amount) of the curing agent (E) is 40 to 200 parts by weight (preferably 50 to 150 parts per 100 parts by weight of the total amount of compounds having epoxy groups contained in the curable resin composition. The curable resin composition for light reflection according to any one of the above [1] to [49], wherein the curable resin composition is a part by weight.
[51] The content (blending amount) of the curing accelerator (F) is 0.0001 to 5% by weight (preferably 0.001 to 1% by weight) with respect to the curable resin composition (100% by weight). The curable resin composition for light reflection according to any one of the above [1] to [50].
[52] The content (blending amount) of the curing accelerator (F) is 0.05 to 15 parts by weight (preferably with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). The light according to any one of [1] to [51] above, which is 0.1 to 12 parts by weight, more preferably 0.2 to 10 parts by weight, and particularly preferably 0.25 to 8 parts by weight. A curable resin composition for reflection.
[53] The content (blending amount) of the curing catalyst (G) is 0.0001 to 5% by weight (preferably 0.001 to 1% by weight) with respect to the curable resin composition (100% by weight). The curable resin composition for light reflection according to any one of the above [1] to [52].
[54] The content (blending amount) of the curing catalyst (G) is 0.0001 to 15 parts by weight (preferably 0 to 100 parts by weight of the total amount of the compounds having an epoxy group contained in the curable resin composition). 0.01 to 12 parts by weight, more preferably 0.05 to 10 parts by weight, particularly preferably 0.05 to 8 parts by weight), and the light reflection according to any one of [1] to [53] above Curable resin composition.
［５５］応力緩和剤（Ｈ）が、シリコーンゴム粒子（Ｈ１）、シリコーンオイル（Ｈ２）、液状ゴム成分（Ｈ３）、及び熱可塑性樹脂（Ｈ４）からなる群より選択される少なくとも１種である、上記［１］～［５４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５６］応力緩和剤（Ｈ）が、シリコーンゴム粒子（Ｈ１）及びシリコーンオイル（Ｈ２）からなる群より選択される少なくとも１種である、上記［１］～［５５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５７］シリコーンゴム粒子（Ｈ１）が、シリコーンレジンを表面に備える架橋されたポリジメチルシロキサンである、上記［５５］又は［５６］に記載の光反射用硬化性樹脂組成物。
［５８］シリコーンゴム粒子（Ｈ１）の平均粒子径（ｄ50）が、０．１～１００μｍが（好ましくは０．５～５０μｍで）ある、上記［５５］～［５７］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［５９］シリコーンゴム粒子（Ｈ１）の最大粒子径が、０．１～２５０μｍ（好ましくは０．１～１５０μｍ）である、上記［５５］～［５８］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［６０］シリコーンオイル（Ｈ２）が、エポキシ当量３０００～１５０００の下記式（１）で表される構造を有するポリアルキレンエーテル変性シリコーン化合物（以下、「ポリアルキレンエーテル変性シリコーン化合物（１）」と称する場合がある）である、上記［５５］～［５９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000045
 ［式中、ｘは８０～１４０の整数、ｙは１～５の整数、ｚは５～２０の整数である。Ｒ9は炭素数２又は３のアルキレン基（好ましくはトリメチレン基）である。Ａは、下記式（１ａ）で表される構造を有するポリアルキレンエーテル基である。
Figure JPOXMLDOC01-appb-C000046
 （式中、ａ及びｂはそれぞれ独立して、０～４０の整数である。Ｂは水素原子またはメチル基（好ましくはメチル基）である。）］
［６１］ａ及びｂの合計が、１～８０の整数である、上記［６０］に記載の光反射用硬化性樹脂組成物。
［６２］ポリアルキレンエーテル変性シリコーン化合物（１）のエポキシ当量が４０００～１５０００（好ましくは５０００～１３０００）である、上記［６０］又は［６１］に記載の光反射用硬化性樹脂組成物。
［６３］応力緩和剤（Ｈ）の含有量（配合量）が、脂環式エポキシ化合物（Ａ）１００重量部に対して、１～２００重量部（好ましくは５～１５０重量部、より好ましくは８～１２０重量部）である、上記［１］、［３］～［１７］、［２０］～［２７］、［２９］～［３５］、［３７］～［４２］、［４４］～［６２］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［６４］応力緩和剤（Ｈ）の含有量（配合量）が、脂環式エポキシ化合物（Ａ）１００重量部に対して、１～２５０重量部（好ましくは５～２３０重量部、より好ましくは１０～２００重量部）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［６５］応力緩和剤（Ｈ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１～２００重量部（好ましくは５～１５０重量部、より好ましくは８～１２０重量部）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［６６］硬化性樹脂組成物（１００重量％）に対する応力緩和剤（Ｈ）の含有量が、硬化性樹脂組成物（１００重量％）に対して、０．１～２０重量％（好ましくは０．３～１８重量％、より好ましくは０．５～１５重量％）である、上記［１］～［６５］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [55] The stress relaxation agent (H) is at least one selected from the group consisting of silicone rubber particles (H1), silicone oil (H2), a liquid rubber component (H3), and a thermoplastic resin (H4). The curable resin composition for light reflection according to any one of [1] to [54] above.
[56] In any one of the above [1] to [55], the stress relaxation agent (H) is at least one selected from the group consisting of silicone rubber particles (H1) and silicone oil (H2). The curable resin composition for light reflection as described.
[57] The curable resin composition for light reflection according to the above [55] or [56], wherein the silicone rubber particles (H1) are crosslinked polydimethylsiloxane having a silicone resin on the surface.
[58] Any one of the above [55] to [57], wherein the silicone rubber particles (H1) have an average particle diameter (d 50 ) of 0.1 to 100 μm (preferably 0.5 to 50 μm). The curable resin composition for light reflection described in 1.
[59] The light reflection according to any one of [55] to [58], wherein the silicone rubber particles (H1) have a maximum particle size of 0.1 to 250 μm (preferably 0.1 to 150 μm). Curable resin composition.
[60] The silicone oil (H2) is a polyalkylene ether-modified silicone compound having a structure represented by the following formula (1) having an epoxy equivalent of 3000 to 15000 (hereinafter referred to as “polyalkylene ether-modified silicone compound (1)”). The light-reflective curable resin composition according to any one of [55] to [59] above.
Figure JPOXMLDOC01-appb-C000045
 [Wherein x is an integer from 80 to 140, y is an integer from 1 to 5, and z is an integer from 5 to 20. R 9 is an alkylene group having 2 or 3 carbon atoms (preferably trimethylene group). A is a polyalkylene ether group having a structure represented by the following formula (1a).
Figure JPOXMLDOC01-appb-C000046
 (Wherein, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group (preferably a methyl group)]
[61] The curable resin composition for light reflection according to the above [60], wherein the sum of a and b is an integer of 1 to 80.
[62] The curable resin composition for light reflection according to the above [60] or [61], wherein the polyalkylene ether-modified silicone compound (1) has an epoxy equivalent of 4000 to 15000 (preferably 5000 to 13000).
[63] The content (blending amount) of the stress relaxation agent (H) is 1 to 200 parts by weight (preferably 5 to 150 parts by weight, more preferably 100 parts by weight of the alicyclic epoxy compound (A). 8 to 120 parts by weight), [1], [3] to [17], [20] to [27], [29] to [35], [37] to [42], [44] to [62] The curable resin composition for light reflection according to any one of [62].
[64] The content (blending amount) of the stress relaxation agent (H) is 1 to 250 parts by weight (preferably 5 to 230 parts by weight, more preferably 100 parts by weight of the alicyclic epoxy compound (A). 10 to 200 parts by weight) of [2] to [15], [18] to [26], [28] to [34], [36] to [41], and [43] to [62]. The curable resin composition for light reflection as described in any one.
[65] The content (blending amount) of the stress relaxation agent (H) is 1 to 200 parts by weight (preferably 5 to 100 parts by weight based on 100 parts by weight of the total amount of the epoxy group-containing compounds contained in the curable resin composition). 150 parts by weight, more preferably 8 to 120 parts by weight), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [ 43] to [62], [64] The curable resin composition for light reflection according to any one of [64].
[66] The content of the stress relaxation agent (H) with respect to the curable resin composition (100 wt%) is 0.1 to 20 wt% (preferably 0 with respect to the curable resin composition (100 wt%)). The curable resin composition for light reflection according to any one of the above [1] to [65], which is from 3 to 18% by weight, more preferably from 0.5 to 15% by weight.
［６７］イソシアヌル酸誘導体（Ｉ）が分子内に有するオキシラン環の数が、１～６個（好ましくは１～３個）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［６６］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［６８］イソシアヌル酸誘導体（Ｉ）が、下記式（III）で表される化合物を含む、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［６７］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000047
 ［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。］
［６９］式（III）におけるＲ4～Ｒ6が、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、上記［６８］に記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
 ［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（好ましくは水素原子）を示す。］
［７０］イソシアヌル酸誘導体（Ｉ）が、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、及び下記式（III－３）で表される化合物からなる群から選ばれる少なくとも１種を含む、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［６９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
 ［上記式（III－１）、（III－２）及び式（III－３）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（好ましくは水素原子）を示す。］
［７１］前記イソシアヌル酸誘導体（Ｉ）が、下記式（III－１）
Figure JPOXMLDOC01-appb-C000053
 ［式（III－１）中、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（好ましくは水素原子）を示す。］
で表される化合物である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７０］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［７２］イソシアヌル酸誘導体（Ｉ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．０５～１５重量％（好ましくは０．１～１０重量％、より好ましくは０．３～５重量％）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［７３］イソシアヌル酸誘導体（Ｉ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１～６０重量部（好ましくは１～５０重量部、より好ましくは１～３０重量部）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７２］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [67] The above [2] to [15], [18] to [26], wherein the number of oxirane rings in the molecule of the isocyanuric acid derivative (I) is 1 to 6 (preferably 1 to 3). ], [28] to [34], [36] to [41], [43] to [62], and [64] to [66].
[68] The above [2] to [15], [18] to [26], [28] to [34], [I], wherein the isocyanuric acid derivative (I) includes a compound represented by the following formula (III): 36] to [41], [43] to [62], and [64] to [67].
Figure JPOXMLDOC01-appb-C000047
 [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. ]
[69] R 4 to R 6 in the formula (III) are the same or different and are a group represented by the following formula (IIIa) or a group represented by the following formula (IIIb), wherein R 4 to R 6 The curable resin composition for light reflection according to the above [68], wherein at least one of is a group represented by the formula (IIIa).
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
 [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 (preferably a hydrogen atom). ]
[70] A compound wherein the isocyanuric acid derivative (I) is 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) [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [41], including at least one selected from the group consisting of 62], The curable resin composition for light reflection according to any one of [64] to [69].
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
 [R 7 and R 8 in the above formulas (III-1), (III-2) and (III-3) are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably hydrogen Atom). ]
[71] The isocyanuric acid derivative (I) is represented by the following formula (III-1):
Figure JPOXMLDOC01-appb-C000053
 [In Formula (III-1), R 7 and R 8 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom). ]
The compounds represented by the above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [ 64] to [70]. The curable resin composition for light reflection according to any one of [64] to [70].
[72] The content (blending amount) of the isocyanuric acid derivative (I) is 0.05 to 15% by weight (preferably 0.1 to 10% by weight) with respect to the curable resin composition (100% by weight). More preferably 0.3 to 5% by weight) [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] The curable resin composition for light reflection according to any one of [62] and [64] to [71].
[73] The content (blending amount) of the isocyanuric acid derivative (I) is 1 to 60 parts by weight (preferably 1 to 60 parts by weight with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). The above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [50 parts by weight, more preferably 1 to 30 parts by weight] 43] to [62] and [64] to [72].
［７４］シロキサン誘導体（Ｊ）が、分子内に２個以上のエポキシ基を有する環状シロキサン、及び分子内に２個以上のエポキシ基を有する直鎖状シリコーンからなる群から選ばれる少なくとも１種を含む、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７３］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［７５］シロキサン誘導体（Ｊ）が、分子内に２個以上のエポキシ基を有する環状シロキサンである、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［７６］シロキサン環を形成するＳｉ－Ｏ単位の数が、２～１２（好ましくは４～８）である、上記［７５］に記載の光反射用硬化性樹脂組成物。
［７７］シロキサン誘導体（Ｊ）の重量平均分子量が、１００～３０００（好ましくは１８０～２０００）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７６］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［７８］シロキサン誘導体（Ｊ）が分子内に有するエポキシ基の数が、２～４つ（２つ、３つ、又は４つ）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７７］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［７９］シロキサン誘導体（Ｊ）のエポキシ当量が、１８０～２０００（好ましくは１８０～１５００、より好ましくは１８０～１０００）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７８］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［８０］シロキサン誘導体（Ｊ）が有するエポキシ基が、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）（好ましくはシクロヘキセンオキシド基）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［７９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［８１］シロキサン誘導体（Ｊ）が、下記式（ＩＶ）で表されるシロキサン化合物を含む、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［８０］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000054
 ［式（ＩＶ）中、Ｒaは、同一又は異なって、エポキシ基を含有する基、又はアルキル基（好ましくは、炭素数１～１０の直鎖又は分岐鎖状のアルキル基）を示す。但し、式（ＩＶ）におけるＲaの少なくとも２つ（好ましくは２～４つ）はエポキシ基を含有する基である。ｎは、２～１２（好ましくは４～８、より好ましくは４又は５）の整数を示す。］
［８２］シロキサン誘導体（Ｊ）が、下記式で表される分子内に２個以上のエポキシ基を有する環状シロキサンからなる群から選ばれる少なくとも１種を含む、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［８１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000055
 ［８３］シロキサン誘導体（Ｊ）の含有量（配合量）が、硬化性樹脂組成物（１００重量％）に対して、０．１～３０重量％（好ましくは０．５～２０重量％、より好ましくは１．０～１０重量％）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［８２］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［８４］シロキサン誘導体（Ｊ）の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、５～９９重量部（好ましくは１０～９５重量部、より好ましくは２０～８０重量部）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［８３］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [74] The siloxane derivative (J) is at least one selected from the group consisting of a cyclic siloxane having two or more epoxy groups in the molecule and a linear silicone having two or more epoxy groups in the molecule. [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [73] The curable resin composition for light reflection as described in any one of these.
[75] The above [2] to [15], [18] to [26], [28] to [34], wherein the siloxane derivative (J) is a cyclic siloxane having two or more epoxy groups in the molecule. , [36] to [41], [43] to [62], and [64] to [74].
[76] The curable resin composition for light reflection according to the above [75], wherein the number of Si—O units forming the siloxane ring is 2 to 12 (preferably 4 to 8).
[77] The above [2] to [15], [18] to [26], [28] to [34], wherein the siloxane derivative (J) has a weight average molecular weight of 100 to 3000 (preferably 180 to 2000). ], [36] to [41], [43] to [62], and [64] to [76].
[78] The above [2] to [15], [18] to [18], wherein the siloxane derivative (J) has 2 to 4 (2, 3, or 4) epoxy groups in the molecule [26], [28] to [34], [36] to [41], [43] to [62], [64] to [77] object.
[79] The epoxy equivalent of the siloxane derivative (J) is 180 to 2000 (preferably 180 to 1500, more preferably 180 to 1000), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], and [64] to [78].
[80] The epoxy group possessed by the siloxane derivative (J) is an epoxy group (alicyclic epoxy group) (preferably a cyclohexene oxide group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring. [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [79] The curable resin composition for light reflection as described in any one of these.
[81] The above [2] to [15], [18] to [26], [28] to [34], [81] wherein the siloxane derivative (J) contains a siloxane compound represented by the following formula (IV): 36] to [41], [43] to [62], and [64] to [80].
Figure JPOXMLDOC01-appb-C000054
 [In Formula (IV), R a is the same or different and represents an epoxy group-containing group or an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms). Provided that at least two R a in formula (IV) (preferably 2 to four) is a group containing an epoxy group. n represents an integer of 2 to 12 (preferably 4 to 8, more preferably 4 or 5). ]
[82] The above [2] to [15], wherein the siloxane derivative (J) contains at least one selected from the group consisting of cyclic siloxanes having two or more epoxy groups in the molecule represented by the following formula: [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [81] Curable resin composition.
Figure JPOXMLDOC01-appb-C000055
 [83] The content (blending amount) of the siloxane derivative (J) is 0.1 to 30% by weight (preferably 0.5 to 20% by weight, based on the curable resin composition (100% by weight). The above [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62] The curable resin composition for light reflection according to any one of [64] to [82].
[84] The content (blending amount) of the siloxane derivative (J) is 5 to 99 parts by weight (preferably 10 to 95 parts per 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). Parts by weight, more preferably 20 to 80 parts by weight), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43 ] To [62] and [64] to [83].
［８５］脂環式ポリエステル樹脂（Ｋ）が、主鎖に脂環を有する脂環式ポリエステル樹脂である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［８４］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［８６］脂環式ポリエステル樹脂（Ｋ）を構成する全モノマー単位（全モノマー成分）（１００モル％）に対する脂環を有するモノマー単位の割合が、１０モル％以上（例えば、１０～８０モル％）（好ましくは２５～７０モル％、より好ましくは４０～６０モル％）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［８５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［８７］脂環式ポリエステル樹脂（Ｋ）が、下記式（２）～（４）で表される構成単位からなる群より選ばれる少なくとも１種を含む脂環式ポリエステル樹脂である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［８６］のいずれか１つに記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000056
 （式中、Ｒ10は直鎖、分岐鎖、又は環状の炭素数２～１５のアルキレン基を表す。また、Ｒ11～Ｒ14は、それぞれ独立に、水素原子又は直鎖状若しくは分岐鎖状の炭素数１～４のアルキル基を表し、Ｒ11～Ｒ14から選ばれる二つが結合して環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000057
 （式中、Ｒ10は直鎖、分岐鎖、又は環状の炭素数２～１５のアルキレン基を表す。また、Ｒ11～Ｒ14は、それぞれ独立に、水素原子又は直鎖状若しくは分岐鎖状の炭素数１～４のアルキル基を表し、Ｒ11～Ｒ14から選ばれる二つが結合した環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000058
 （式中、Ｒ10は直鎖、分岐鎖、又は環状の炭素数２～１５のアルキレン基を表す。また、Ｒ11～Ｒ14は、それぞれ独立に、水素原子又は直鎖状若しくは分岐鎖状の炭素数１～４のアルキル基を表し、Ｒ11～Ｒ14から選ばれる二つが結合した環を形成していてもよい。）
［８８］脂環式ポリエステル樹脂（Ｋ）が、下記式（５）で表される構成単位を含む脂環式ポリエステル樹脂である、上記［８７］に記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000059
 ［８９］脂環式ポリエステル樹脂（Ｋ）が、下記式（６）で表される構成単位を含む脂環式ポリエステル樹脂である、上記［８７］又は［８８］に記載の光反射用硬化性樹脂組成物。
Figure JPOXMLDOC01-appb-C000060
 ［９０］上記式（２）～（４）で表される構成単位の含有量の合計量（合計含有量；該構成単位を構成する全モノマー単位）が、脂環式ポリエステル樹脂（Ｋ）の全構成単位（１００モル％；脂環式ポリエステル樹脂（Ｋ）を構成する全モノマー単位）に対し、２０モル％以上（例えば、２０～１００モル％）（好ましくは５０～１００モル％、より好ましくは８０～１００モル％）である、上記［８７］～［８９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［９１］脂環式ポリエステル樹脂（Ｋ）の数平均分子量が、３００～１０００００（好ましくは３００～３００００）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［９０］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［９２］硬化剤（Ｅ）を必須成分とする場合、脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）が、脂環式ポリエステル樹脂（Ｋ）と硬化剤（Ｅ）の合計量（１００重量％）に対して、１～６０重量％（好ましくは５～３０重量％）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［９１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［９３］硬化触媒（Ｇ）を必須成分とする場合、脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）が、脂環式ポリエステル樹脂（Ｋ）と硬化触媒（Ｇ）の合計量（１００重量％）に対して、５０～９９重量％（好ましくは６５～９９重量％）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［９１］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［９４］脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）が、硬化性樹脂組成物（１００重量％）に対して、０．１～２０重量％（好ましくは０．３～１０重量％）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［９３］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［９５］脂環式ポリエステル樹脂（Ｋ）の配合量（含有量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量１００重量部に対して、１～６０重量部（好ましくは５～３０重量部）である、上記［２］～［１５］、［１８］～［２６］、［２８］～［３４］、［３６］～［４１］、［４３］～［６２］、［６４］～［９４］のいずれか１つに記載の光反射用硬化性樹脂組成物。 [85] The alicyclic polyester resin (K) is an alicyclic polyester resin having an alicyclic ring in the main chain, [2] to [15], [18] to [26], [28] to [28] 34], [36] to [41], [43] to [62], and [64] to [84].
[86] The ratio of monomer units having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin (K) is 10 mol% or more (for example, 10 to 80 mol%) ) (Preferably 25 to 70 mol%, more preferably 40 to 60 mol%), [2] to [15], [18] to [26], [28] to [34], [36] The curable resin composition for light reflection according to any one of [41], [43] to [62], and [64] to [85].
[87] The alicyclic polyester resin (K) is an alicyclic polyester resin containing at least one selected from the group consisting of structural units represented by the following formulas (2) to (4): [2] ] To [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [86] The curable resin composition for light reflection described in 1.
Figure JPOXMLDOC01-appb-C000056
 (Wherein R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms. R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a group selected from R 11 to R 14 may be bonded to form a ring.
Figure JPOXMLDOC01-appb-C000057
 (Wherein R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms. R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
Figure JPOXMLDOC01-appb-C000058
 (Wherein R 10 represents a linear, branched, or cyclic alkylene group having 2 to 15 carbon atoms. R 11 to R 14 each independently represents a hydrogen atom or a linear or branched chain. And a ring in which two selected from R 11 to R 14 are bonded may be formed.
[88] The curable resin composition for light reflection according to the above [87], wherein the alicyclic polyester resin (K) is an alicyclic polyester resin containing a structural unit represented by the following formula (5).
Figure JPOXMLDOC01-appb-C000059
 [89] The light-reflective curability according to the above [87] or [88], wherein the alicyclic polyester resin (K) is an alicyclic polyester resin containing a structural unit represented by the following formula (6). Resin composition.
Figure JPOXMLDOC01-appb-C000060
 [90] The total content of the structural units represented by the above formulas (2) to (4) (total content; all monomer units constituting the structural unit) is the alicyclic polyester resin (K). 20 mol% or more (for example, 20 to 100 mol%) (preferably 50 to 100 mol%, more preferably, based on all structural units (100 mol%; all monomer units constituting alicyclic polyester resin (K)) Is 80 to 100 mol%), and the curable resin composition for light reflection according to any one of the above [87] to [89].
[91] The number average molecular weight of the alicyclic polyester resin (K) is 300 to 100,000 (preferably 300 to 30,000), [2] to [15], [18] to [26], [28] [34], [36] to [41], [43] to [62], and [64] to [90].
[92] When the curing agent (E) is an essential component, the blending amount (content) of the alicyclic polyester resin (K) is the total amount of the alicyclic polyester resin (K) and the curing agent (E) ( [2] to [15], [18] to [26], [28] to [34], which are 1 to 60% by weight (preferably 5 to 30% by weight) with respect to 100% by weight), [36] to [41], [43] to [62], and [64] to [91].
[93] When the curing catalyst (G) is an essential component, the blending amount (content) of the alicyclic polyester resin (K) is the total amount of the alicyclic polyester resin (K) and the curing catalyst (G) ( 100% by weight) to 50 to 99% by weight (preferably 65 to 99% by weight), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], and [64] to [91].
[94] The blending amount (content) of the alicyclic polyester resin (K) is 0.1 to 20% by weight (preferably 0.3 to 10% by weight) with respect to the curable resin composition (100% by weight). %) Above, [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [93] The curable resin composition for light reflection according to any one of [93].
[95] The blending amount (content) of the alicyclic polyester resin (K) is 1 to 60 parts by weight (preferably with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition). 5 to 30 parts by weight), [2] to [15], [18] to [26], [28] to [34], [36] to [41], [43] to [62], [64] to [94] The curable resin composition for light reflection according to any one of [64] to [94].
［９６］さらに、離型剤を含む、上記［１］～［９５］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［９７］離型剤の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量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［９６］に記載の光反射用硬化性樹脂組成物。
［９８］さらに、酸化防止剤を含む、上記［１］～［９７］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［９９］酸化防止剤の含有量（配合量）が、硬化性樹脂組成物に含まれるエポキシ基を有する化合物の全量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［９８］に記載の光反射用硬化性樹脂組成物。 [96] The light-reflective curable resin composition according to any one of [1] to [95], further including a release agent.
[97] The content (blending amount) of the release agent is 1 to 12 parts by weight (preferably 2 to 10 parts by weight) with respect to 100 parts by weight of the total amount of compounds having an epoxy group contained in the curable resin composition. The curable resin composition for light reflection according to the above [96].
[98] The curable resin composition for light reflection according to any one of the above [1] to [97], further comprising an antioxidant.
[99] The content (blending amount) of the antioxidant is 0.1 to 5 parts by weight (preferably 0.5 parts per 100 parts by weight of the total amount of the compounds having epoxy groups contained in the curable resin composition). The curable resin composition for light reflection according to the above [98], which is ˜3 parts by weight).
［１００］トランスファー成型用又はコンプレッション成型用樹脂組成物（好ましくは、コンプレッション成型用樹脂組成）である、上記［１］～［９９］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［１０１］リフレクター形成用樹脂組成物である、上記［１］～［１００］のいずれか１つに記載の光反射用硬化性樹脂組成物。
［１０２］上記［１］～［１０１］のいずれか１つに記載の光反射用硬化性樹脂組成物の硬化物。
［１０３］波長４５０ｎｍの光の反射率（初期反射率）が、９３％以上（好ましくは９４％以上、より好ましくは９５％以上）である、上記［１０２］に記載の硬化物。
［１０４］１２０℃で２５０時間加熱した後の波長４５０ｎｍの光の反射率の、初期反射率に対する保持率が、８０％以上（好ましくは８５％以上、より好ましくは９０％以上）である、上記［１０２］又は［１０３］に記載の硬化物。
［１０５］強度１０ｍＷ／ｃｍ2の紫外線を２５０時間照射した後の波長４５０ｎｍの光に対する反射率の、初期反射率に対する保持率が、８０％以上（好ましくは８５％以上、より好ましくは９０％以上）である、上記［１０２］～［１０４］のいずれか１つに記載の硬化物。
［１０６］１１重量％の水酸化カリウム水溶液に７０℃で６０分間処理した後の重量減少率が、１％以下（好ましくは０．８％以下、より好ましくは０．５％以下）である、上記［１０２］～［１０５］のいずれか１つに記載の硬化物。
［１０７］光半導体素子と、上記［１０１］に記載の光反射用硬化性樹脂組成物の硬化物からなるリフレクターとを少なくとも備えることを特徴とする光半導体装置。 [100] The curable resin composition for light reflection according to any one of the above [1] to [99], which is a resin composition for transfer molding or compression molding (preferably a resin composition for compression molding). .
[101] The curable resin composition for light reflection according to any one of [1] to [100], which is a resin composition for forming a reflector.
[102] A cured product of the curable resin composition for light reflection according to any one of [1] to [101].
[103] The cured product according to [102], wherein the reflectance (initial reflectance) of light having a wavelength of 450 nm is 93% or more (preferably 94% or more, more preferably 95% or more).
[104] The retention ratio of the reflectance of light having a wavelength of 450 nm after heating at 120 ° C. for 250 hours with respect to the initial reflectance is 80% or more (preferably 85% or more, more preferably 90% or more). The cured product according to [102] or [103].
[105] Retention rate of light having a wavelength of 450 nm after irradiation with ultraviolet light having an intensity of 10 mW / cm 2 for 250 hours with respect to the initial reflectance is 80% or more (preferably 85% or more, more preferably 90% or more The cured product according to any one of [102] to [104] above.
[106] The weight loss rate after treatment with an 11% by weight aqueous potassium hydroxide solution at 70 ° C. for 60 minutes is 1% or less (preferably 0.8% or less, more preferably 0.5% or less). The cured product according to any one of [102] to [105].
[107] An optical semiconductor device comprising at least an optical semiconductor element and a reflector made of a cured product of the light reflecting curable resin composition according to [101].
　本発明の硬化性樹脂組成物は、特に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（光反射用硬化性樹脂組成物）として好ましく使用することができる。 The curable resin composition of the present invention is a molding material (curing for light reflection) used for forming a reflector (light reflecting member) of an optical semiconductor element substrate (an optical semiconductor element mounting substrate) in an optical semiconductor device. Curable resin composition).
　１００：白色リフレクター
　１０１：金属配線（電極）
　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
　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 (electrode)
102: Mounting area of optical semiconductor element 103: Package substrate 104: Bonding wire 105: Sealing material for optical semiconductor element 106: Die bonding 107: Optical semiconductor element 108: Heat sink 109: Cathode mark

Claims (15)

  1. 　脂環式エポキシ化合物（Ａ）、シリコーンゴム粒子以外のゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、及び応力緩和剤（Ｈ）を含有し、さらに、硬化剤（Ｅ）及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）を含有し、２５℃において液状であることを特徴とする光反射用硬化性樹脂組成物。 Contains an alicyclic epoxy compound (A), rubber particles (B) other than silicone rubber particles, a white pigment (C), an inorganic filler (D), and a stress relaxation agent (H), and further contains a curing agent (E ) And a curing accelerator (F) or a curing catalyst (G), and is a liquid at 25 ° C., and is a curable resin composition for light reflection.
  2. 　脂環式エポキシ化合物（Ａ）、シリコーンゴム粒子以外のゴム粒子（Ｂ）、白色顔料（Ｃ）、無機充填剤（Ｄ）、応力緩和剤（Ｈ）、分子内に１個以上のオキシラン環を有するイソシアヌル酸誘導体（Ｉ）、分子内に２個以上のエポキシ基を有するシロキサン誘導体（Ｊ）、及び脂環式ポリエステル樹脂（Ｋ）を含有し、さらに、硬化剤（Ｅ）、及び硬化促進剤（Ｆ）、又は、硬化触媒（Ｇ）を含有し、２５℃において液状であることを特徴とする光反射用硬化性樹脂組成物。 Alicyclic epoxy compound (A), rubber particles other than silicone rubber particles (B), white pigment (C), inorganic filler (D), stress relaxation agent (H), one or more oxirane rings in the molecule Containing an isocyanuric acid derivative (I), a siloxane derivative (J) having two or more epoxy groups in the molecule, and an alicyclic polyester resin (K), a curing agent (E), and a curing accelerator A curable resin composition for light reflection, which contains (F) or a curing catalyst (G) and is liquid at 25 ° C.
  3. 　前記応力緩和剤（Ｈ）が、シリコーンゴム粒子（Ｈ１）及びシリコーンオイル（Ｈ２）からなる群より選択される少なくとも１種である請求項１又は２に記載の光反射用硬化性樹脂組成物。 The light-reflective curable resin composition according to claim 1 or 2, wherein the stress relaxation agent (H) is at least one selected from the group consisting of silicone rubber particles (H1) and silicone oils (H2).
  4. 　前記シリコーンゴム粒子（Ｈ１）が、シリコーンレジンを表面に備える架橋されたポリジメチルシロキサンである請求項３に記載の光反射用硬化性樹脂組成物。 The curable resin composition for light reflection according to claim 3, wherein the silicone rubber particles (H1) are cross-linked polydimethylsiloxane having a silicone resin on the surface thereof.
  5. 　前記シリコーンオイル（Ｈ２）が、エポキシ当量３０００～１５０００の下記式（１）で表される構造を有するポリアルキレンエーテル変性シリコーン化合物である請求項３又は４に記載の光反射用硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式中、ｘは８０～１４０の整数、ｙは１～５の整数、ｚは５～２０の整数である。Ｒ9は炭素数２又は３のアルキレン基である。Ａは、下記式（１ａ）で表される構造を有するポリアルキレンエーテル基である。
    Figure JPOXMLDOC01-appb-C000002
     （式中、ａ及びｂはそれぞれ独立して、０～４０の整数である。Ｂは水素原子またはメチル基である。）］     5. The light reflecting curable resin composition according to claim 3, wherein the silicone oil (H2) is a polyalkylene ether-modified silicone compound having a structure represented by the following formula (1) having an epoxy equivalent of 3000 to 15000. .
    Figure JPOXMLDOC01-appb-C000001
     [Wherein x is an integer from 80 to 140, y is an integer from 1 to 5, and z is an integer from 5 to 20. R 9 is an alkylene group having 2 or 3 carbon atoms. A is a polyalkylene ether group having a structure represented by the following formula (1a).
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, a and b are each independently an integer of 0 to 40. B is a hydrogen atom or a methyl group.)]
  6. 　前記ゴム粒子（Ｂ）が、（メタ）アクリル酸エステルを必須のモノマー成分とするポリマーで構成され、表面にヒドロキシ基及び／又はカルボキシ基を有し、前記ゴム粒子（Ｂ）の平均粒子径が１０～５００ｎｍであり、最大粒子径が５０～１０００ｎｍである請求項１～５のいずれか１項に記載の光反射用硬化性樹脂組成物。 The rubber particles (B) are composed of a polymer having (meth) acrylic acid ester as an essential monomer component, have a hydroxyl group and / or a carboxy group on the surface, and the rubber particles (B) have an average particle diameter. The curable resin composition for light reflection according to any one of claims 1 to 5, which has a particle diameter of 10 to 500 nm and a maximum particle size of 50 to 1000 nm.
  7. 　前記脂環式エポキシ化合物（Ａ）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１～６のいずれか１項に記載の光反射用硬化性樹脂組成物。 The light-reflective curable resin composition according to any one of claims 1 to 6, wherein the alicyclic epoxy compound (A) is a compound having a cyclohexene oxide group.
  8. 　前記脂環式エポキシ化合物（Ａ）が、下記式（Ｉ－１）
    Figure JPOXMLDOC01-appb-C000003
     で表される化合物を含む請求項１～７のいずれか１項に記載の光反射用硬化性樹脂組成物。     The alicyclic epoxy compound (A) is represented by the following formula (I-1)
    Figure JPOXMLDOC01-appb-C000003
     The curable resin composition for light reflection according to any one of claims 1 to 7, comprising a compound represented by the formula:
  9. 　前記イソシアヌル酸誘導体（Ｉ）が、下記式（III－１）
    Figure JPOXMLDOC01-appb-C000004
     ［式（III－１）中、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。］
    で表される化合物である請求項２～８のいずれか１項に記載の光反射用硬化性樹脂組成物。     The isocyanuric acid derivative (I) is represented by the following formula (III-1)
    Figure JPOXMLDOC01-appb-C000004
     [In Formula (III-1), R 7 and R 8 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
    The curable resin composition for light reflection according to any one of claims 2 to 8, which is a compound represented by the formula:
  10. 　前記脂環式ポリエステル樹脂（Ｋ）が、主鎖に脂環を有する脂環式ポリエステル樹脂である請求項２～９のいずれか１項に記載の光反射用硬化性樹脂組成物。 10. The light-reflective curable resin composition according to claim 2, wherein the alicyclic polyester resin (K) is an alicyclic polyester resin having an alicyclic ring in the main chain.
  11. 　前記白色顔料（Ｃ）が、酸化チタン、酸化ジルコニウム、酸化亜鉛、及び硫酸バリウムからなる群より選択される少なくとも１種であり、
    　前記無機充填剤（Ｄ）が、シリカ、アルミナ、窒化ケイ素、窒化アルミニウム、及び窒化ホウ素からなる群より選択される少なくとも１種である請求項１～１０のいずれか１項に記載の光反射用硬化性樹脂組成物。     The white pigment (C) is at least one selected from the group consisting of titanium oxide, zirconium oxide, zinc oxide, and barium sulfate;
    The light reflecting material according to any one of claims 1 to 10, wherein the inorganic filler (D) is at least one selected from the group consisting of silica, alumina, silicon nitride, aluminum nitride, and boron nitride. Curable resin composition.
  12. 　トランスファー成型用又はコンプレッション成型用樹脂組成物である請求項１～１１のいずれか１項に記載の光反射用硬化性樹脂組成物。 The curable resin composition for light reflection according to any one of claims 1 to 11, which is a resin composition for transfer molding or compression molding.
  13. 　リフレクター形成用樹脂組成物である請求項１～１２のいずれか１項に記載の光反射用硬化性樹脂組成物。 The curable resin composition for light reflection according to any one of claims 1 to 12, which is a resin composition for forming a reflector.
  14. 　請求項１～１３のいずれか１項に記載の光反射用硬化性樹脂組成物の硬化物。 A cured product of the light-reflective curable resin composition according to any one of claims 1 to 13.
  15. 　光半導体素子と、請求項１４に記載の光反射用硬化性樹脂組成物の硬化物からなるリフレクターとを少なくとも備えることを特徴とする光半導体装置。 An optical semiconductor device comprising at least an optical semiconductor element and a reflector made of a cured product of the light reflecting curable resin composition according to claim 14.
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WO2023120739A1 (en) * 2021-12-24 2023-06-29 株式会社レゾナック Epoxy resin composition and electronic component device

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