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WO2018135558A1 - Composition de résine durcissable destinée à réfléchir la lumière, produit durci obtenu à partir de ladite composition, et dispositif semi-conducteur optique - Google Patents

Composition de résine durcissable destinée à réfléchir la lumière, produit durci obtenu à partir de ladite composition, et dispositif semi-conducteur optique 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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English (en)
Japanese (ja)
Inventor
鈴木弘世
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Daicel Corp
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Daicel Corp
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Priority claimed from JP2017009860A external-priority patent/JP2018119032A/ja
Priority claimed from JP2017009859A external-priority patent/JP6929069B2/ja
Application filed by Daicel Corp filed Critical Daicel Corp
Priority to KR1020197024268A priority Critical patent/KR20190104063A/ko
Publication of WO2018135558A1 publication Critical patent/WO2018135558A1/fr
Anticipated expiration legal-status Critical
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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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/855—Optical field-shaping means, e.g. lenses
    • H10H20/856—Reflecting means

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

Le problème décrit par la présente invention est de fournir une composition de résine durcissable pour réflexion optique qui permet la production d'un réflecteur par moulage par compression, et qui présente en outre une réflectivité élevée de la lumière, une excellente résistance thermique et une excellente stabilité à la lumière. La solution selon l'invention porte sur une composition de résine durcissable pour réflexion optique qui est caractérisée en ce qu'elle comprend un composé époxy alicyclique (A), des particules de caoutchouc (B) autres que des particules de caoutchouc de silicone, un pigment blanc (C), une charge inorganique (D), et un relaxeur de contrainte (H), comprenant par ailleurs soit un agent de durcissement (E) et un accélérateur de durcissement (F), soit un catalyseur de durcissement (G), et en ce qu'elle se présente sous un état liquide à 25 °C.
PCT/JP2018/001303 2017-01-23 2018-01-18 Composition de résine durcissable destinée à réfléchir la lumière, produit durci obtenu à partir de ladite composition, et dispositif semi-conducteur optique Ceased WO2018135558A1 (fr)

Priority Applications (1)

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KR1020197024268A KR20190104063A (ko) 2017-01-23 2018-01-18 광반사용 경화성 수지 조성물 및 그의 경화물, 그리고 광반도체 장치

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JP2017-009860 2017-01-23
JP2017009860A JP2018119032A (ja) 2017-01-23 2017-01-23 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
JP2017009859A JP6929069B2 (ja) 2017-01-23 2017-01-23 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
JP2017-009859 2017-01-23

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112480847A (zh) * 2020-10-21 2021-03-12 江苏科化新材料科技有限公司 一种高耐热、低应力环氧塑封料及其制备方法
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WO2023120739A1 (fr) * 2021-12-24 2023-06-29 株式会社レゾナック Composition de résine époxyde et dispositif à composants électroniques
WO2024195569A1 (fr) * 2023-03-22 2024-09-26 信越化学工業株式会社 Composition de silicone thermoconductrice, article durci de celle-ci, et procédé de fabrication associé

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