WO2011078239A1 - 半導体発光装置用樹脂成形体用材料 - Google Patents
半導体発光装置用樹脂成形体用材料 Download PDFInfo
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- WO2011078239A1 WO2011078239A1 PCT/JP2010/073168 JP2010073168W WO2011078239A1 WO 2011078239 A1 WO2011078239 A1 WO 2011078239A1 JP 2010073168 W JP2010073168 W JP 2010073168W WO 2011078239 A1 WO2011078239 A1 WO 2011078239A1
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- WIPO (PCT)
- Prior art keywords
- resin molded
- molded body
- resin
- semiconductor light
- white pigment
- Prior art date
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- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- 238000009791 electrochemical migration reaction Methods 0.000 description 1
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- 239000008393 encapsulating agent Substances 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
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- 229910052735 hafnium Inorganic materials 0.000 description 1
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- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 239000011147 inorganic material Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- FPLYNRPOIZEADP-UHFFFAOYSA-N octylsilane Chemical compound CCCCCCCC[SiH3] FPLYNRPOIZEADP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical group CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical group CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical group CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
- H01L2224/491—Disposition
- H01L2224/49105—Connecting at different heights
- H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0091—Scattering means in or on the semiconductor body or semiconductor body package
Definitions
- the present invention relates to a material for a resin molding used for a semiconductor light emitting device including a light emitting element such as a light emitting diode, and the molding.
- a semiconductor light emitting device including a semiconductor light emitting element includes a semiconductor light emitting element 1, a resin molded body 2, a bonding wire 3, a sealing material 4, a lead frame 5, and the like.
- the structure which consists of conductive metal wirings, such as a lead frame, and an insulating resin molding is called a package.
- a material in which a white pigment is blended with a thermoplastic resin such as polyamide has been generally used (see, for example, Patent Document 1).
- Semiconductor light-emitting devices that require directivity for light emission are not only light emitted from a semiconductor light-emitting element in a desired direction, but also light emitted in a direction different from the purpose, such as resin wiring, metal wiring such as a lead frame, In addition, the light is reflected in a desired direction by a reflecting material or the like to increase luminous efficiency.
- thermoplastic resin such as polyamide is translucent, when reflecting light with a resin molding, a semiconductor light-emitting element is used by using a difference in refractive index between the resin and the white pigment by blending the resin with a white pigment.
- the luminous efficiency of the semiconductor light emitting device is increased by reflecting light from the light.
- Patent Document 1 even when a white pigment is used, the reflection efficiency is not sufficient depending on the type of the white pigment, and a light beam absorbed by the resin molded body and a light beam transmitted through the resin molded body are also emitted. Therefore, as a result, the light from the semiconductor light emitting element cannot be concentrated in the intended direction, and the light emission efficiency as the semiconductor light emitting device may be lowered.
- polyamide is a thermoplastic resin, and lead-free solder with a high melting point is actively used due to environmental problems, and the reflow temperature tends to increase. The heat softens the polyamide resin. Therefore, there is a problem with the heat resistance of the package.
- titanium oxide is used for the white pigment, which causes the following problems.
- titanium oxide has photocatalytic properties
- a semiconductor light emitting device having a wavelength of about 470 nm or less when a semiconductor light emitting device having a wavelength of about 470 nm or less is used, titanium oxide particles are generated by light emitted from the semiconductor light emitting device or light emitted from a phosphor excited by the light. A nearby resin molded body deteriorates. Therefore, when a semiconductor light emitting device that emits light in the blue region and a semiconductor light emitting device that emits light in the near ultraviolet region are used, the light resistance of the resin molded product is significantly impaired. Furthermore, since titanium oxide has an absorption wavelength in the near ultraviolet region, its color is yellowish.
- the present invention provides a material for a resin molded body that has high durability (light resistance, heat resistance) and can be used as a resin molded body for a semiconductor light-emitting device that improves LED output due to excellent reflectance. Let it be an issue. It is another object of the present invention to provide a resin molding material for a semiconductor light emitting device that can be easily molded.
- the present inventors have found that a white pigment having a specific shape characteristic in a material for a resin molded body for a semiconductor light-emitting device containing a polyorganosiloxane, a white pigment, and a curing catalyst. It has been found that the above-mentioned problems can be solved by using it. That is, the present invention is as follows. (1) A polyorganosiloxane, (B) a white pigment, and (C) a curing catalyst, wherein the (B) white pigment has the following characteristics (a) and (b): A resin molding material for a semiconductor light emitting device.
- the aspect ratio of the primary particles is 1.2 or more and 4.0 or less
- the primary particle diameter is 0.1 ⁇ m or more and 2.0 ⁇ m or less
- Secondary of the (B) white pigment The resin molded body material according to (1), wherein the center particle diameter of the particles is 0.2 ⁇ m or more and 5 ⁇ m or less.
- the resin molded material according to (1) or (2), wherein the viscosity at a shear rate of 100 s ⁇ 1 at 25 ° C. is 10 Pa ⁇ s or more and 10,000 Pa ⁇ s or less.
- a resin molded body for a semiconductor light-emitting device obtained by molding the resin molded body material according to any one of (1) to (10).
- (14) A resin molded body comprising: a step of preparing the resin molded body material according to any one of (1) to (10); and a step of molding the prepared resin molded body material by injection molding. Production method.
- the resin molded body material of the present invention it is possible to obtain a resin molded body for a semiconductor light-emitting device that has high durability (light resistance and heat resistance) and improves LED output due to excellent reflectance. Furthermore, according to the present invention, it is possible to provide a resin molding material for a semiconductor light emitting device that can be easily molded.
- the resin molded body material for a semiconductor light emitting device is a material used for molding a resin molded body for a semiconductor light emitting device. Specifically, it contains (A) a polyorganosiloxane, (B) a white pigment, and (C) a curing catalyst.
- the resin molded body for a semiconductor light emitting device is a molded body obtained by curing a material, and becomes a package for a semiconductor light emitting device by being molded together with a conductive metal wiring such as a lead frame.
- the semiconductor light emitting device is a light emitting device including a semiconductor light emitting element in the resin molded body for the semiconductor light emitting device. A schematic cross-sectional view of a semiconductor light emitting device is shown in FIG.
- the polyorganosiloxane in the present invention refers to a polymer substance in which an organic group is added to a structure having a portion in which a silicon atom is bonded to another silicon atom through oxygen.
- the polyorganosiloxane is preferably a liquid at normal temperature and pressure. This is because the material becomes easy to handle when molding the resin molded body for a semiconductor light emitting device.
- Polyorganosiloxane that is solid under normal temperature and normal pressure generally has a relatively high hardness as a cured product, but has low energy required for destruction and low toughness, light resistance and heat resistance are insufficient, This is because many products tend to discolor due to heat.
- the normal temperature refers to a temperature in the range of 20 ° C. ⁇ 15 ° C. (5-35 ° C.)
- the normal pressure refers to a pressure equal to atmospheric pressure, which is approximately one atmospheric pressure.
- the liquid means a fluid state.
- the polyorganosiloxane usually refers to an organic polymer having a siloxane bond as the main chain, and examples thereof include compounds represented by the following general composition formula (1) and mixtures thereof.
- R 1 R 2 R 3 SiO 1/2 M
- R 4 R 5 SiO 2/2 D
- R 6 SiO 3/2 T
- Q Q
- R 1 to R 6 are independently selected from an organic functional group, a hydroxyl group, and a hydrogen atom.
- the unit constituting the main polyorganosiloxane is monofunctional [R 3 SiO 0.5 ] (triorganosyl hemioxane), bifunctional [R 2 SiO] (diorganosiloxane), trifunctional [RSiO 1.5 ] (Organosilsesquioxane), tetrafunctional [SiO 2 ] (silicate), and by changing the composition ratio of these four types of units, the difference in the properties of polyorganosiloxane appears, so the desired properties Is selected as appropriate so that polyorganosiloxane is synthesized.
- methylchlorosilane can be synthesized by directly reacting methyl chloride and silicon Si at a high temperature under a Cu catalyst
- silanes having an organic group such as a vinyl group can be synthesized by a general synthetic organic chemistry method. can do.
- Silanol is produced when the isolated organochlorosilane is mixed alone or in an arbitrary ratio and hydrolyzed with water. When this silanol is dehydrated and condensed, polyorganosiloxane, which is the basic skeleton of silicone, is synthesized. .
- Polyorganosiloxane can be cured by applying heat energy, light energy, or the like in the presence of a curing catalyst.
- curing refers to changing from a state showing fluidity to a state showing no fluidity. For example, even if the object is left at an angle of 45 degrees from the horizontal for 30 minutes, it is fluid.
- the state is referred to as an uncured state, and a state having no fluidity can be determined as a cured state.
- polyorganosiloxanes such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide crosslinking type can be generally exemplified.
- Addition type polyorganosiloxane refers to a polyorganosiloxane chain crosslinked by an organic addition bond.
- a silicon-containing compound having (C1) alkenyl group such as vinylsilane and a silicon compound containing (C2) hydrosilyl group such as hydrosilane has a total hydrosilyl group amount of 0.5 times or more
- Examples include compounds having Si—C—C—Si bonds at the crosslinking point, which are obtained by mixing in an amount ratio of 2.0 times or less and reacting in the presence of an addition condensation catalyst such as (C3) Pt catalyst. it can.
- (C1) As a silicon-containing compound having an alkenyl group, the following general formula (2) R n SiO [ (4-n) / 2 ] (2) And a polyorganosiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule.
- R is the same or different substituted or unsubstituted monovalent hydrocarbon group, alkoxy group or hydroxyl group, and n is a positive number satisfying 1 ⁇ n ⁇ 2.
- the alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, or a pentenyl group.
- R is a hydrocarbon group, it is selected from alkyl groups such as methyl and ethyl groups, monovalent hydrocarbon groups having 1 to 20 carbon atoms such as vinyl and phenyl groups. Preferably, they are a methyl group, an ethyl group, and a phenyl group.
- R in the above formula is preferably a methyl group (that is, with respect to the number of Si (in mol)).
- the content of functional groups other than methyl groups is preferably 0.35 (mol) or less.)
- 80% or more of R is more preferably methyl groups.
- R may be an alkoxy group having 1 to 8 carbon atoms or a hydroxyl group, but the content of the alkoxy group or hydroxyl group is preferably 10% by weight or less of the silicon-containing compound having (C1) alkenyl group.
- n is a positive number satisfying 1 ⁇ n ⁇ 2, but if this value is 2 or more, sufficient strength cannot be obtained for adhesion between the resin molding material and a conductor such as a lead frame, If it is less than 1, synthesis of this polyorganosiloxane becomes difficult.
- vinyl group-containing polyorganosiloxane having two or more vinyl groups in the molecule include the following. Both ends vinyl polydimethylsiloxane DMS-V00, DMS-V03, DMS-V05, DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35, DMS-V41, DMS-V42, DMS-V46, DMS-V52 (both manufactured by Gelest) Both-end vinyldimethylsiloxane-diphenylsiloxane copolymer PDV-0325, PDV-0331, PDV-0341, PDV-0346, PDV-0525, PDV-0541, PDV-1625, PDV-1631, PDV-1635, PDV-1641, PDV -2331, PDV-2335 (both manufactured by Gelest) Both end vinylphenylmethylsiloxane PMV-9925 (manufactured by Gelest) Trimethyls
- examples of the (C2) silicon-containing compound having a hydrosilyl group include hydrosilane and hydrosilyl group-containing polyorganosiloxane. These may be used alone or in combination of two or more in any ratio and combination. Can do. Of these, hydrosilyl group-containing polyorganosiloxane having two or more hydrosilyl groups in the molecule is preferred.
- polyorganosiloxane containing two or more hydrosilyl groups in the molecule include the following. Both terminal hydrosilyl polydimethylsiloxane DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, DMS-H41 (all manufactured by Gelest) Both end trimethylsilyl-blocked methylhydrosiloxane-dimethylsiloxane copolymer HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-501 (all manufactured by Gelest)
- the amount of the silicon compound having (C1) alkenyl group and the silicon compound having (C2) hydrosilyl group used in the present invention is (C1) 1 mol of silicon compound having alkenyl group (number of moles of alkenyl group).
- C2) The silicon compound having a hydrosilyl group (number of moles of hydrosilyl group) is usually 0.5 mol or more, preferably 0.7 mol or more, more preferably 0.8 mol or more, and usually 2.0 mol or less, preferably Is 1.8 mol or less, more preferably 1.5 mol or less.
- the content of the reaction point (crosslinking point) that causes hydrosilylation is preferably 0.1 mmol / g or more and 20 mmol / g or less in the resin itself that does not contain a white pigment for both the alkenyl group and the hydrosilyl group. More preferably, it is 0.2 mmol / g or more and 10 mmol / g or less.
- the viscosity of the resin before adding the white pigment is usually 100,000 cp or less, preferably 20,000 cp or less, more preferably 10,000 cp or less, for ease of handling.
- the lower limit is not particularly limited, but is generally 15 cp or more in relation to volatility (boiling point).
- the weight average molecular weight of the resin is 500 or more and 100,000 or less as an average molecular weight measurement value in gel permeation chromatography measured using polystyrene of the resin as a standard substance. More preferably, it is 700 or more and 50,000 or less. Furthermore, it is more preferably 1,000 or more for the purpose of reducing volatile components (to maintain adhesion to other members) and 25,000 or less for ease of handling of the material before molding. Most preferably, it is 20,000 or less.
- Condensed polyorganosiloxane examples include compounds having Si—O—Si bonds obtained by hydrolysis and polycondensation of alkylalkoxysilanes at the crosslinking points. Specific examples thereof include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (3) and / or (4) and / or oligomers thereof.
- M represents silicon
- X represents a hydrolyzable group
- Y 1 represents a monovalent organic group
- m represents an integer of 1 or more representing the valence of M.
- N represents an integer of 1 or more representing the number of X groups.
- m ⁇ n.
- M represents silicon
- X represents a hydrolyzable group
- Y 1 represents a monovalent organic group
- Y 2 represents a u-valent organic group
- s represents 1 represents an integer of 1 or more representing the valence of M
- t represents an integer of 1 or more and s ⁇ 1 or less
- u represents an integer of 2 or more.
- condensed polyorganosiloxane known ones can be used.
- JP 2006-77234 A, JP 2006-291018 A, JP 2006-316264 A, JP 2006-336010 A, The semiconductor light-emitting device members described in JP-A-2006-348284 and International Publication No. 2006/090804 are suitable.
- condensed polyorganosiloxane Among the condensed polyorganosiloxanes, particularly preferred materials will be described below.
- polyorganosiloxane may have weak adhesion to semiconductor light emitting devices, substrates on which semiconductor light emitting devices are arranged, and resin moldings when used in semiconductor light emitting devices.
- condensed polyorganosiloxane having at least one of the following [1] and [2] is particularly preferable.
- the silicon content is 20% by weight or more.
- the measured solid Si-nuclear magnetic resonance (NMR) spectrum has at least one peak derived from Si in the following (a) and / or (b).
- B A peak whose peak top position is in a region where the chemical shift is ⁇ 80 ppm or more and less than ⁇ 40 ppm with respect to dimethylsiloxysilicon of the dimethylsilicone rubber, and the peak half-value width is 0.3 ppm or more and 5.0 ppm or less.
- White pigment> a known pigment that does not inhibit the curing of the resin can be appropriately selected as the white pigment.
- the white pigment inorganic and / or organic materials can be used.
- white means colorless and not transparent. That is, it means a color that can diffusely reflect incident light by a substance that does not have a specific absorption wavelength in the visible light region.
- inorganic particles examples include alumina (hereinafter sometimes referred to as “alumina fine powder” or “aluminum oxide”), silicon oxide, titanium oxide (titania), zinc oxide, magnesium oxide, and the like.
- Metal oxide Metal salts such as calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide; boron nitride, alumina white, colloidal silica, aluminum silicate, zirconium silicate, aluminum borate, Examples include clay, talc, kaolin, mica, and synthetic mica.
- organic fine particles that can be used as the white pigment include resin particles such as fluorine resin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, and silicone resin particles. Is not to be done.
- resin particles such as fluorine resin particles, guanamine resin particles, melamine resin particles, acrylic resin particles, and silicone resin particles.
- alumina, titanium oxide, zinc oxide, and the like are particularly preferable from the viewpoint of high whiteness and high light reflection effect and hardly deteriorate.
- alumina, boron nitride and the like are particularly preferable from the viewpoint of improving the thermal conductivity when the material is cured.
- Alumina is particularly preferable from the viewpoint of high near-ultraviolet light reflection effect and small alteration due to near-ultraviolet light. These can be used alone or in admixture of two or more.
- titanium oxide it can be contained to such an extent that problems such as photocatalytic properties, dispersibility, and whiteness do not occur.
- Specific examples of zirconia are Daiichi Rare Element Chemical Industries, Ltd. UEP-100 and the like can be mentioned, and specific examples of zinc oxide include two types of zinc oxide manufactured by Hakusui Tech Co., Ltd.
- the polyorganosiloxane preferably has a refractive index of about 1.41, and alumina particles having a refractive index of 1.76 can be suitably used as the (B) white pigment.
- the refractive index of the polyorganosiloxane is preferably 1.40 or more from the viewpoint of the hardness of the resin, and the refractive index difference with alumina tends to decrease and the reflectance tends to decrease, and the heat resistance tends to decrease. For reasons, 1.50 or less is preferable.
- the white pigment is preferably alumina in that it has a high near-ultraviolet light reflection effect and is less affected by near-ultraviolet light.
- Alumina has a low ability to absorb ultraviolet rays, and therefore can be suitably used particularly when used with a light emitting element emitting ultraviolet to near ultraviolet light.
- alumina refers to an oxide of aluminum, and its crystal form is not limited, but it is chemically stable, has a high melting point, high mechanical strength, high hardness, and high electrical insulation resistance. Alumina can be suitably used.
- the crystallite size of the alumina crystal is preferably 500 to 2,000, more preferably 700 to 1,500, and more preferably 900 to 1,300. It is particularly preferred that A crystallite is the largest group that can be regarded as a single crystal.
- the fact that the primary particle diameter of alumina is in the above range and the crystallite size of the alumina crystal is in the above range means that the size of the primary particles is different from the size of the crystallites. It means that it is composed of crystallites.
- the pipe, screw, mold and the like are less worn during molding and impurities due to wear are less likely to be mixed.
- the crystallite size can be confirmed by X-ray diffraction measurement.
- X-ray diffraction measurement when alumina has crystallinity, a peak appears at a position determined according to the crystal type.
- the crystallite diameter (crystallite size) can be calculated from the half-value width of this peak according to Scherrer's equation.
- alumina contains an element other than aluminum or oxygen as an impurity, it is colored because it has absorption in the visible light region, which is not preferable. For example, if it contains even a small amount of chromium, it is generally called a ruby and exhibits a red color. If iron or titanium is contained as an impurity, it is generally called a sapphire and exhibits a blue color. As the alumina in the present invention, it is preferable to use a chromium, iron and titanium content of 0.02% by weight or less, preferably 0.01% by weight or less.
- the heat conductivity at the time of curing of the resin molded body material of the present invention is preferably higher as described above.
- alumina having a purity of 98% or more it is more preferable to use 99% or more alumina, and it is particularly preferable to use low soda alumina.
- boron nitride it is also preferable to use boron nitride, and it is particularly preferable to use boron nitride having a purity of 99% or more.
- titanium oxide in a semiconductor light emitting device using a light emitting element having an emission peak wavelength of 420 nm or more, titanium oxide can also be suitably used as a white pigment.
- Titanium oxide titanium oxide
- the white pigment of the present invention is preferably a rutile type that is stable at high temperatures, has a high refractive index, and has a relatively high light resistance, rather than an anatase type that has a large ultraviolet absorption ability and photocatalytic ability and is unstable at high temperatures.
- the reflectance of light having a wavelength of 420 nm or more will be higher than when alumina is used alone, and the ratio of white pigment in the material is small or Even when the thickness of the material is thin, the reflectance tends not to decrease. Since the ratio of the white pigment in the material can be reduced by the combined use of titania, the degree of freedom of the material composition is increased, and the filling amount of components other than the white pigment can be increased. Moreover, the high reflectance of a thin material is very advantageous in that the degree of freedom of the shape of the resin molded body is increased. Further, even a thin resin molded body that cannot be increased in thickness or a resin molded body having a fine structure can be expected to have an effect of increasing the brightness of the semiconductor light-emitting device due to the high reflectance of the material.
- a white pigment surface-treated with a silane coupling agent is used, the hardness of the entire resin molded material can be improved.
- the molding cycle can be shortened and burrs can be suppressed. Or a material excellent in moldability.
- the aspect ratio is larger than 4.0, it is difficult to be highly reflective, and wear of pipes, screws, molds, etc. is likely to occur during molding. There is a tendency for the reflectivity to decrease and dielectric breakdown to occur easily.
- the aspect ratio is generally used as a simple method for quantitatively expressing the shape of particles and the like.
- the major axis length (maximum major axis) of a particle measured by observation with an electron microscope such as SEM is the minor axis length. It is obtained by dividing by the length (the length of the longest part perpendicular to the major axis).
- a plurality of points for example, 10 points
- the same calculation result can be obtained by measuring 30 points and 100 points.
- the aspect ratio is an indicator of whether the shape of the particle is fibrous, rod-like, or spherical.
- the aspect ratio is large when the particle is fibrous, and is 1.0 when the particle is spherical.
- the preferable shape of the white pigment (B) excludes those formed in a spherical shape and a true spherical shape.
- an extremely long and narrow shape also reduces the reflectance, and is therefore excluded from the white pigment (B) according to the present invention.
- the white pigment tends to clog the mold gap and hardly generates burrs, but in the case of a spherical shape, it tends to pass through the mold gap and easily generate burrs.
- the particles whose aspect ratio falls within the above range preferably occupies 60% by volume or more, more preferably 70% by volume or more, and particularly preferably 80% by volume or more of the entire white pigment (B). (B) It is a matter of course for those skilled in the art that the white pigment does not have to satisfy the above aspect ratio range.
- a general method such as surface treatment or polishing of a white pigment may be employed. It can also be achieved by crushing (pulverizing) the white pigment to make it fine, or by producing the white pigment by firing.
- the white pigment (B) in the present invention has the chemical composition described in 1-2. Inorganic fine particles / organic fine particles exemplified in the above.
- the shape is preferably (c) a crushed shape.
- the crushed shape means a shape obtained by finely pulverizing a white pigment mainly by crushing (pulverizing), a rounded shape with few crystal corners by processing after crushing, by firing, etc.
- the shape of the produced non-spherical pigment is also included. That is, it is the meaning except the thing formed in spherical shape and a perfect spherical shape on the character of a manufacturing process.
- materials using crushed white pigments are more likely to exhibit high reflectivity due to scattering, and are particularly short-wavelength light in the near ultraviolet region (especially light having a wavelength of 360 nm to 460 nm). ) Reflection is large. Further, it may be advantageous in terms of economy compared to spherical pigments. Thereby, in the semiconductor light-emitting device using this resin molding, LED output can be improved.
- the primary particle diameter of (B) white pigment in this invention is 0.1 micrometer or more and 2 micrometers or less.
- the lower limit is preferably 0.15 ⁇ m or more, more preferably 0.2 ⁇ m or more, particularly preferably 0.25 ⁇ m or more, and the upper limit is preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, particularly preferably 0. .5 ⁇ m or less.
- the primary particle size is in the above range, the material is easy to express high reflectivity by combining the backscattering tendency and the scattered light intensity, and the reflection with respect to light having a short wavelength particularly in the near ultraviolet region is increased, which is preferable. .
- the white pigment tends to have low reflectance because the scattered light intensity is low. If the primary particle diameter is too large, the scattered light intensity tends to increase, but the reflectance tends to be forward scattering. It tends to be smaller. In addition, when the primary particle diameter is in the above range, it is preferable from the viewpoint of moldability, such as easy adjustment to a viscosity suitable for molding and low wear of the mold.
- the primary particle diameter is larger than the above range, the impact on the mold due to contact with the pigment particles tends to be large and the wear of the mold tends to be severe, and when using a white pigment whose primary particle diameter is smaller than the above range
- the material tends to be highly viscous and the filling amount of the white pigment cannot be increased, it tends to be difficult to achieve compatibility between material properties such as high reflection and moldability.
- the material in order to obtain a material that can be suitably used for liquid injection molding, it is necessary that the material has a thixotropic property of a certain level or more.
- Adding a white pigment with a primary particle size of 0.1 ⁇ m or more and 2.0 ⁇ m or less to the composition has a large thixotropy-imparting effect and makes it easy to mold with few burrs and shorts, so viscosity and thixotropy are easy. Can be adjusted.
- a white pigment having a primary particle diameter larger than 2 ⁇ m can be used in combination for the purpose of increasing the filling rate of the white pigment in the resin composition.
- the primary particle in the present invention refers to an individual of the smallest unit that can be clearly separated from other particles constituting the powder, and the primary particle size is the particle size of the primary particle measured by observation with an electron microscope such as SEM. Say.
- agglomerated particles formed by agglomeration of primary particles are called secondary particles.
- the center particle size of secondary particles is determined by dispersing the powder in a suitable dispersion medium (for example, water in the case of alumina) and using a particle size analyzer. Says the measured particle size.
- a suitable dispersion medium for example, water in the case of alumina
- the longest length that is, the length of the major axis is taken as the particle diameter.
- the aspect ratio and primary particle diameter of the white pigment can be measured even after molding (after curing). What is necessary is just to observe the cross section of a molded article with electron microscopes, such as SEM, and to measure the primary particle diameter and aspect ratio of the white pigment exposed to the cross section.
- the major axis length (maximum major axis) of the particles measured by observation with an electron microscope such as SEM is divided by the minor axis length (the length of the longest part perpendicular to the major axis).
- a plurality of points for example, 10 points
- the same calculation result can be obtained by measuring 30 points and 100 points.
- the white pigment preferably has a secondary particle central particle size (hereinafter sometimes referred to as “secondary particle size”) of 0.2 ⁇ m or more, and 0.3 ⁇ m or more. More preferred.
- the upper limit is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 2 ⁇ m or less.
- the secondary particle size When the secondary particle size is larger than the above range, the material tends to become non-uniform due to the precipitation of the white pigment, the moldability is impaired due to the wear of the mold or the clogging of the gate, and the reflection of the material is uniform. Sexuality may be impaired.
- a white pigment having a secondary particle size larger than 10 ⁇ m can be used in combination.
- the central particle size means the particle size at the point where the volume-based particle size distribution curve of cumulative% intersects the horizontal axis of 50%, and generally refers to what is called 50% particle size (D 50 ) and median size. .
- the ratio y / x between the primary particle size x of the (B) white pigment and the center particle size y of the secondary particles is usually 1 or more, preferably more than 1 and particularly preferably 1.2 or more. Also, it is usually 10 or less, preferably 5 or less.
- (B) from a preferable shape of the white pigment, a spherical shape or a true spherical shape That is, the primary particles are hardly agglomerated, and the primary particle diameter and the center particle diameter of the secondary particles are substantially equal.
- the content of the white pigment (B) in the resin molded body material for a semiconductor light-emitting device is appropriately selected depending on the particle size and type of the pigment used and the difference in refractive index between the polyorganosiloxane and the pigment.
- A 20 parts by weight or more, preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and usually 900 parts by weight or less, preferably 600 parts by weight or less, more preferably 100 parts by weight or more based on polyorganosiloxane. 400 parts by weight or less. When it is within the above range, reflectivity, moldability and the like are good.
- the material has a thixotropic property of a certain level or more.
- a white pigment having a primary particle size of 0.1 ⁇ m or more and 2.0 ⁇ m or less is blended in the composition, the thickening occurs and the effect of imparting thixotropy is great.
- (B) alumina is used as the white pigment with respect to the total amount of the resin molded body material. It is preferable to add at least 90 parts by weight.
- (B) boron nitride as a white pigment is preferably added in an amount of 30 parts by weight or more and 90 parts by weight or less based on the total amount of the resin molded material. Alumina and boron nitride may be used in combination.
- the (C) curing catalyst in the present invention is a catalyst for curing the polyorganosiloxane of (A).
- the polyorganosiloxane is cured by the catalyst and the polymerization reaction is accelerated.
- This catalyst includes an addition polymerization catalyst and a condensation polymerization catalyst depending on the curing mechanism of the polyorganosiloxane.
- the addition polymerization catalyst is a catalyst for promoting the hydrosilylation addition reaction between the alkenyl group in the component (C1) and the hydrosilyl group in the component (C2).
- the addition polymerization catalyst include platinum black , Platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum catalyst such as platinum bisacetoacetate, palladium catalyst, rhodium catalyst, etc. And platinum group metal catalysts.
- the blending amount of the (C3) addition polymerization catalyst can be a catalytic amount.
- acids such as hydrochloric acid, nitric acid, sulfuric acid, organic acids, alkalis such as ammonia and amines, metal chelate compounds, and the like can be used, and Ti, Ta, Zr, Al, Hf are preferable.
- a metal chelate compound containing any one or more of Zn, Sn, and Pt can be used.
- the metal chelate compound preferably contains one or more of Ti, Al, Zn, and Zr, and more preferably contains Zr.
- the resin molding material for a semiconductor light emitting device of the present invention preferably further contains (D) a curing rate control agent.
- the curing rate control agent is for controlling the curing rate in order to improve the molding efficiency when molding the resin molding material, and includes a curing retarder or a curing accelerator.
- the curing retarder examples include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide, and these may be used in combination.
- the compound containing an aliphatic unsaturated bond examples include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol.
- maleic esters such as ene-yne compounds and dimethyl malate.
- compounds having a triple bond are preferred.
- organophosphorus compound examples include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.
- organic sulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like.
- nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like.
- tin compounds examples include stannous halide dihydrate and stannous carboxylate.
- organic peroxide examples include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.
- curing retarders from the viewpoint of good retarding activity and good availability of raw materials, benzothiazole, thiazole, dimethylmalate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.
- the addition amount of the curing retarder can be variously set, the lower limit of the preferable addition amount with respect to 1 mol of the (C) curing catalyst to be used is 10 ⁇ 1 mol or more, more preferably 1 mol or more, and the upper limit of the preferable addition amount is 10 3 mol. Below, more preferably 50 mol or less. Moreover, these hardening retarders may be used independently and may be used together 2 or more types.
- the curing accelerator is not particularly limited as long as it can cure a thermosetting resin.
- imidazoles dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 -Methylimidazole tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate, and the like.
- imidazoles are preferably used from the viewpoint of high reaction acceleration.
- imidazoles examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, etc. 2E4MZ, 2PZ-CN, 2PZ-CNS (Shikoku Chemicals Co., Ltd.) and the like.
- the addition amount of the curing accelerator may be added in the range of 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the total of (A) the polyorganosiloxane thermosetting resin and (C) the curing catalyst. preferable.
- the molding of the resin molding material becomes easy. For example, there is an advantage that the filling rate into the mold becomes high or there is no leakage from the mold when molding by injection molding, and burrs are hardly generated.
- a white pigment that does not satisfy one or both of the following characteristics (a) and (b), such as fibrous alumina, can be contained separately from the above-described white pigment.
- the aspect ratio of primary particles is 1.2 or more and 4.0 or less
- the primary particle diameter is 0.1 ⁇ m or more and 2.0 ⁇ m or less. It is easy to control the viscosity and thixotropy of the product and can be suitably used. Quartz beads, glass beads, glass fibers, etc. are preferred because they can be expected not only as an effect of fluidity control, but also as an effect of increasing the strength and toughness of the material after thermosetting and an effect of reducing the linear expansion coefficient of the material.
- the silica fine particles used in the present invention are not particularly limited, but the specific surface area by the BET method is usually 50 m 2 / g or more, preferably 80 m 2 / g or more, more preferably 100 m 2 / g or more. . Moreover, it is 300 m ⁇ 2 > / g or less normally, Preferably it is 200 m ⁇ 2 > / g or less. If the specific surface area is too small, the addition effect of silica fine particles is not recognized, and if it is too large, dispersion treatment in the resin becomes difficult.
- the silica fine particles for example, those obtained by hydrophobizing the surface by reacting a silanol group present on the surface of the hydrophilic silica fine particles with a surface modifier may be used.
- Examples of the surface modifier include alkylsilane compounds, and specific examples include dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.
- Examples of the silica fine particles include fumed silica. Fumed silica is produced by oxidizing and hydrolyzing SiCl 4 gas with a flame of 1100 to 1400 ° C. in which a mixed gas of H 2 and O 2 is burned. The primary particles of fumed silica are spherical ultrafine particles whose main component is amorphous silicon dioxide (SiO 2 ) having an average particle size of about 5 to 50 nm. Secondary particles that are several hundred nm are formed.
- fumed silica is an ultrafine particle and is produced by rapid cooling, the surface structure is in a chemically active state.
- Specific examples include “Aerosil” (registered trademark) manufactured by Nippon Aerosil Co., Ltd., and examples of hydrophilic Aerosil (registered trademark) include “90”, “130”, “150”, “200”, Examples of “300” and hydrophobic Aerosil® include “R8200”, “R972”, “R972V”, “R972CF”, “R974”, “R202”, “R805”, “R812”, “R812S”. ”,“ RY200 ”,“ RY200S ”, and“ RX200 ”.
- a polyorganosiloxane having an effect as a liquid thickener can be partly blended with the (A) polyorganosiloxane.
- the viscosity at 25 ° C. is usually 0.001 Pa ⁇ s to 3 Pa ⁇ s, preferably 0.001 Pa ⁇ s to 1 Pa ⁇ s, more preferably 0.001 Pa ⁇ s to 0. 7 Pa ⁇ s or less, and the hydroxyl value is usually 1.0 ⁇ 10 ⁇ 2 to 7.7 ⁇ 10 ⁇ 5 mol / g, preferably 1.0 ⁇ 10 ⁇ 2 to 9.5 ⁇ 10 ⁇ 5 mol.
- each molecule contains a hydroxyl group bonded to at least one silicon atom (ie, a silanol group).
- a straight-chain organopolysiloxane can be blended.
- the hydroxyl group-containing linear organopolysiloxane as a liquid thickener does not contain a functional group involved in hydrosilylation addition reaction such as alkenyl group and / or SiH group in the molecule.
- the hydroxyl group may be bonded to the silicon atom at the end of the molecular chain, bonded to the silicon atom at the non-end of the molecular chain (in the middle of the molecular chain), or bonded to both of them.
- a linear organopolysiloxane containing hydroxyl groups bonded to silicon atoms at both ends of the molecular chain that is, ⁇ , ⁇ -dihydroxydiorganopolysiloxane is desirable.
- Examples of the organic group bonded to the silicon atom include monovalent hydrocarbon groups such as alkyl groups such as methyl, ethyl and propyl, and allyl groups such as phenyl groups, and the diorganosiloxane constituting the main chain of the organopolysiloxane.
- the repeating unit is preferably one or a combination of two or more of dimethylsiloxane units, diphenylsiloxane units, methylphenylsiloxane units and the like.
- the blending amount of the polyorganosiloxane as the liquid thickener is usually 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0, when the total amount of the polyorganosiloxane (A) is 100 parts by weight. It can be about 5 to 3 parts by weight.
- inorganic fibers such as glass fibers may be included, and in order to increase the thermal conductivity, boron nitride, aluminum nitride having high thermal conductivity, Fibrous alumina or the like can be contained separately from the above-mentioned white pigment.
- quartz beads, glass beads and the like can be contained. If the content of these additives is too small, the desired effect cannot be obtained, and if the content is too large, the viscosity of the resin molded body material for semiconductor devices increases and affects the workability, so that a sufficient effect is exhibited.
- the material can be appropriately selected within a range that does not impair the workability of the material. Usually, it is 500 parts by weight or less, preferably 200 parts by weight or less with respect to 100 parts by weight of the polyorganosiloxane.
- the above resin molding materials include ion migration (electrochemical migration) inhibitors, anti-aging agents, radical inhibitors, ultraviolet absorbers, adhesion improvers, flame retardants, surfactants, storage stability. Improving agent, antiozonant, light stabilizer, thickener, plasticizer, coupling agent, antioxidant, thermal stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus-based excess An oxide decomposing agent, a lubricant, a pigment, a metal deactivator, a physical property adjusting agent and the like can be contained within a range not impairing the object and effect of the present invention.
- a coupling agent a silane coupling agent is mentioned, for example.
- the silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule.
- the group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable.
- silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- (Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryl
- the preferred contents of the components (A) to (E) in the resin molded body material for a semiconductor light emitting device of the present invention are as follows.
- the content of the (A) polyorganosiloxane in the resin molded material of the present invention is not limited as long as it can be used as a normal resin molded material, but it is usually 15% by weight or more of the total material, 50 % By weight or less, preferably 20% by weight or more and 40% by weight or less, more preferably 25% by weight or more and 35% by weight or less.
- the liquid thickener which is (D) hardening rate control agent and other components contained in a material is polyorganosiloxane, it shall be contained in content of said (A).
- the content of the white pigment (B) in the resin molded material of the present invention is not limited as long as it can be used as a normal resin molded material, but is usually 30% by weight or more and 85% by weight of the entire material. %, Preferably 40% to 80% by weight, more preferably 45% to 70% by weight.
- the content of the (E) fluidity modifier in the resin molded material of the present invention is not limited as long as it does not impair the effects of the present invention, but is usually 55% by weight or less of the entire material, preferably It is 2 to 50% by weight, more preferably 5 to 45% by weight.
- the ratio of the total amount of (B) white pigment and (E) fluidity modifier to the whole resin molded material is preferably 50% by weight or more, more preferably 60% by weight or more. 65 wt% or more is particularly preferable, 85 wt% or less is preferable, and 80 wt% or less is more preferable.
- the resin molded body material for a semiconductor light emitting device of the present invention preferably has a viscosity of 10 Pa ⁇ s or more and 10,000 Pa ⁇ s or less at a shear rate of 100 s ⁇ 1 at 25 ° C.
- the viscosity is more preferably from 50 Pa ⁇ s to 5,000 Pa ⁇ s, more preferably from 100 Pa ⁇ s to 2,000 Pa ⁇ s, from the viewpoint of molding efficiency when molding a resin molded body for a semiconductor device. More preferably, it is 150 Pa ⁇ s or more and 1,000 Pa ⁇ s or less.
- the resin molding material for a semiconductor light-emitting device of the present invention has a shear rate of 1 s ⁇ 1 at 25 ° C. relative to a viscosity at a shear rate of 100 s ⁇ 1 at 25 ° C.
- the viscosity ratio (1 s ⁇ 1 / 100 s ⁇ 1 ) is preferably 15 or more, more preferably 20 or more, and particularly preferably 30 or more.
- the upper limit is preferably 500 or less, and more preferably 300 or less.
- the viscosity of the resin molded material for a semiconductor light emitting device of the present invention is, in particular, a viscosity at a shear rate of 100 s ⁇ 1 at 25 ° C. of 1,000 Pa ⁇ s or less, and a shear rate at 25 ° C. it preferably has a specific viscosity at a shear rate 1s -1 at 25 ° C. for viscosity at 100s -1 (1s -1 / 100s -1 ) is 15 or more.
- the ratio of the viscosity at the shear rate of 1 s ⁇ 1 to the viscosity at the shear rate of 100 s ⁇ 1 is 15 or more, the occurrence of burrs and short molds (unfilled) is small, and the measurement time of the material at the time of molding, The molding cycle can be shortened, the molding is easy to stabilize, and the material has high molding efficiency.
- burrs due to the material seeping out from minute gaps in the mold are likely to occur, and a post-processing step for removing the burrs is necessary.
- the viscosity at a shear rate of 100 s ⁇ 1 and the viscosity at a shear rate of 1 s ⁇ 1 at 25 ° C. are measured using, for example, an ARES-G2-strain-controlled rheometer (manufactured by TA Instruments Japan Co., Ltd.). Can be measured.
- (B) white pigment having a primary particle size of 0.1 ⁇ m or more and 2.0 ⁇ m or less, more preferably (B) white pigment, fumed silica or quartz beads.
- the viscosity of the material can be controlled within the above range.
- a white pigment with a secondary particle size larger than 2 ⁇ m especially when using a pigment with a central particle size of 5 ⁇ m or more, use a fluidity modifier in a fine region with a large thixotropic effect.
- the primary particle size of the white pigment itself is sufficiently small, it can be used only with the white pigment without being used in combination with the fluidity adjusting agent, and the flow having a relatively large central particle size of about several ⁇ m or more. You may combine with a sex modifier.
- a semiconductor light emitting device heat is generated by light emitted from a semiconductor light emitting element, and the amount of generated heat is larger particularly when the output of the element is large. In this case, the phosphor layer adjacent to the resin molded body is deteriorated due to heat generation, and the durability of the apparatus is lowered.
- the present inventors have a resin molded body and a semiconductor light emitting device configured using the resin molded body because the thermal conductivity at the time of curing, that is, when the resin molded body is formed by molding, is in the above range. The present inventors have found that the durability of the device is improved because heat dissipation against heat generated by light emitted from the semiconductor light emitting element is improved.
- the thermal conductivity is less than 0.4, the phosphor layer included in the device tends to be thermally deteriorated due to heat generated by light emitted from the semiconductor light emitting element in the device.
- the thermal conductivity can be controlled within the above range by using alumina or boron nitride as the white pigment (B) contained in the resin molding material for a semiconductor light emitting device.
- the resin molding using the resin molding material of the present invention can maintain a high reflectance with respect to visible light.
- the reflectance of light at 460 nm is preferably 80% or more, and more preferably 90% or more.
- the reflectance of light having a wavelength of 400 nm is preferably 60% or more, more preferably 80% or more, and further preferably 90% or more.
- the reflectance of the resin molded body refers to the reflectance when the molded body obtained by thermosetting the resin molded body material of the present invention and molded into a thickness of 0.4 mm is measured.
- the thermosetting can be performed, for example, by curing at 180 ° C.
- the reflectance of the resin molding can be controlled by the type of resin (for example, the reflectance can be controlled by changing the refractive index of the resin), the type of filler, the particle size and content of the filler, and the like. it can.
- the injection molding method can be performed using an injection molding machine.
- the cylinder set temperature may be appropriately selected according to the material, but is usually 100 ° C. or lower, preferably 80 ° C. or lower, and more preferably 60 ° C. or lower.
- the mold temperature is 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower.
- the injection time varies depending on the material, but is usually several seconds or less than 1 second.
- the molding time may be appropriately selected according to the gelation speed and curing speed of the material, but usually 3 seconds or more and 600 seconds or less, preferably 5 seconds or more and 200 seconds or less, more preferably 10 seconds or more and 60 seconds or less. It is.
- mold gap accuracy of 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less is required.
- Preheating the lead frame before entering the mold is also effective in suppressing the generation of burrs along the lead. Further, when the resin is molded, by placing the mold in a vacuum atmosphere, the penetration of the material into the narrow space is promoted, and the generation of air voids in the molded product can be prevented.
- the shape of the graph rises to an S shape when the degree of curing is represented by a graph. If the initial curing rises too early, unfilling of the mold may occur.
- the molding cycle can be shortened, and the mold release property is improved by curing shrinkage.
- the time to completion of curing is usually within 60 seconds, preferably within 30 seconds, and more preferably within 10 seconds. You may post-cure as needed.
- the curing rate can be adjusted not only by selection of the platinum catalyst species, the amount of catalyst, the use of a curing rate control agent, the degree of crosslinking of the polyorganosiloxane, but also by molding conditions such as mold temperature, filling rate, injection pressure, and the like.
- the compression molding method can be performed using a compression molding machine.
- the molding temperature may be appropriately selected depending on the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower.
- the molding time may be appropriately selected according to the curing rate of the material, but is usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less.
- the transfer molding method can be performed using a transfer molding machine.
- the molding temperature may be appropriately selected depending on the material, but is usually 80 ° C. or higher and 300 ° C. or lower, preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower.
- the molding time may be appropriately selected according to the gelation speed and curing speed of the material, but usually 3 seconds or more and 1200 seconds or less, preferably 5 seconds or more and 900 seconds or less, more preferably 10 seconds or more and 600 seconds or less. It is.
- post-curing can be performed as necessary, and the post-curing temperature is 100 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C. or higher and 200 ° C. or lower. It is.
- the post-curing time is usually 3 minutes or more and 24 hours or less, preferably 5 minutes or more and 10 hours or less, more preferably 10 minutes or more and 5 hours or less.
- the resin molded body for a semiconductor light emitting device of the present invention is usually used as a semiconductor light emitting device with a semiconductor light emitting element mounted thereon.
- the semiconductor light emitting device includes a semiconductor light emitting element 1, a resin molded body 2, a bonding wire 3, a sealing material 4, a lead frame 5, and the like.
- a package what consists of electroconductive materials, such as lead frame 5, and an insulating resin molding is called a package.
- the semiconductor light emitting device 1 uses a near ultraviolet semiconductor light emitting device that emits light having a wavelength in the near ultraviolet region, a purple semiconductor light emitting device that emits light in a purple region, a blue semiconductor light emitting device that emits light in a blue region, and the like. It emits light having a wavelength of 350 nm or more and 520 nm or less. Although only one semiconductor light emitting element is mounted in FIG. 1, it is possible to arrange a plurality of semiconductor light emitting elements in a linear or planar manner as shown in FIG. By arranging the semiconductor light emitting element 1 in a planar shape, surface illumination can be obtained, and such an embodiment is suitable when it is desired to further increase the output.
- the resin molded body 2 constituting the package is molded together with the lead frame 5.
- the shape of the package is not particularly limited, and may be a planar type or a cup type.
- the resin molded body 2 may be entirely made of the resin molded body material of the present invention, or a part thereof may be made of the resin molded body material of the present invention.
- the resin molded body of the reflector portion 102 is replaced with the resin molded body material of the present invention as shown in FIG. The mode which shape
- the lead frame 5 is made of a conductive metal, and plays a role of supplying power from outside the semiconductor light emitting device and energizing the semiconductor light emitting element 1.
- the bonding wire 3 has a role of fixing the semiconductor light emitting element 1 to the package. Further, when the semiconductor light emitting element 1 is not in contact with the lead frame as an electrode, the conductive bonding wire 3 plays a role of supplying power to the semiconductor light emitting element 1.
- the bonding wire 3 is bonded to the lead frame 5 by applying pressure and applying heat and ultrasonic vibration.
- the resin molded body 2 made of the resin molded body material of the present invention can make the exposed area of the lead frame 5 extremely small.
- the resin molded body obtained by molding the resin molded body material of the present invention tends to have the same or higher reflectivity as the lead frame material (for example, silver), the package can be obtained even if the exposed area of the resin molded body is increased. High reflectance can be maintained. Therefore, by using a package made of the resin molded body material of the present invention, a semiconductor light emitting device having a configuration different from that of the conventional package can be obtained.
- FIG. 3 shows a semiconductor light emitting device 200 with a conventional package. In the semiconductor light emitting device of FIG. 3, the exposed area of the lead frame 204 is large.
- the reflectance of the resin molded body 201 is lower than that of the lead frame 204, so that the surface area of the lead frame 204 using a material with high reflectance is increased in order for the semiconductor light emitting device to achieve high brightness. There was a need to do.
- the lead frame 204 may be discolored due to discoloration, but as shown in FIG. By reducing the exposed area of the lead frame 5, it is possible to prevent a decrease in light emission efficiency due to such discoloration of the lead frame.
- the resin molded body 2 constituting the package is mounted with the semiconductor light emitting element 1 and sealed with a sealing material 4 in which a phosphor is mixed.
- the sealing material 4 is a mixture in which a phosphor is mixed with a binder resin, and the phosphor converts excitation light from the semiconductor light emitting element 1 and emits fluorescence having a wavelength different from that of the excitation light.
- the sealing material also serves as the phosphor layer.
- the phosphor contained in the sealing material 4 is appropriately selected according to the wavelength of the excitation light of the semiconductor light emitting device 1.
- a semiconductor light emitting device that emits white light
- white light when a semiconductor light emitting element that emits blue light is used as an excitation light source, white light is generated by including green and red phosphors in the phosphor layer. Can do.
- white light In the case of a semiconductor light emitting device that emits violet light, white light is generated by including blue and yellow phosphors in the phosphor layer, or by including blue, green, and red phosphors in the phosphor layer. be able to.
- the binder resin contained in the sealing material 4 may be appropriately selected from light-transmitting resins that are generally used for sealing materials. Specific examples include an epoxy resin, a silicone resin, an acrylic resin, and a polycarbonate resin, and it is preferable to use a silicone resin.
- the semiconductor light emitting device 1 ⁇ / b> C includes a casing 101 having a window portion, a reflector portion 102, a light source portion 103, and a heat sink 104.
- the light source unit 103 includes a light emitting unit 105 on a wiring board.
- a COB (Chip on Board) format in which a semiconductor light emitting element is directly mounted on the wiring substrate 106, or a type in which a semiconductor light emitting device as shown in FIG. Either of these is acceptable.
- the semiconductor light emitting element When the light source unit 103 is in the COB format, the semiconductor light emitting element may be sealed without using a frame material by a sealing resin formed in a dome shape or a flat plate shape.
- One or more semiconductor light emitting elements may be mounted on the wiring board 106.
- the reflector unit 102 and the heat sink 104 may be integrated with the housing 101 or may be separate, and can be used as necessary. From the viewpoint of heat dissipation, it is preferable that the light source unit 103, the casing 101, and the heat sink 104 are in contact with each other with a single structure or a high thermal conductive sheet or grease.
- the window 107 can be made of a known transparent resin, optical glass, or the like, and may be flat or curved.
- the phosphor portion may be provided in the light source portion 103 or the window portion 107.
- the phosphor portion is disposed at a position away from the light emitting element.
- the phosphor layer When the phosphor layer is provided on the window 107, the phosphor layer can be manufactured on a transparent window material (not shown) by a method such as screen printing, die coating, or spray coating. In such a case, since the semiconductor light emitting element and the phosphor layer are arranged at a distance, it is possible to prevent the phosphor layer from being deteriorated by the energy of light from the semiconductor light emitting element, and to emit light. The output of the device can also be improved.
- the distance between the semiconductor light emitting element and the phosphor layer of the window 107 is preferably 5 to 50 mm.
- each phosphor color to be used has a multi-layer structure in which each phosphor color to be used is applied in order to reduce self-resorption of fluorescence and reabsorption between RGB phosphors, or a pattern such as stripes or dots. Or may be formed.
- the shape of each part of the semiconductor light emitting device 1C is not limited to that shown in the figure, and may include a curved surface part or an attached device such as a light control device or a circuit protection device if necessary.
- the part to which the resin molded body according to the present invention (hereinafter simply referred to as “optical member”) is applied is not particularly limited as described above.
- the semiconductor light emitting device 1 ⁇ / b> C illustrated in FIG. 2 it can be used for each member of the housing 101, the reflector unit 102, the light source unit 103, the light emitting unit 105, and the wiring substrate 106. Since the resin molded body according to the present invention has a high reflectance of ultraviolet to visible light and is excellent in heat resistance and light resistance, the number of necessary semiconductor light-emitting elements can be reduced to provide an inexpensive, high-brightness, and highly durable lighting device. .
- the semiconductor light emitting device package of the present invention is characterized in that it can maintain a high reflectance not only for visible light but also for near ultraviolet light and ultraviolet light having a wavelength shorter than purple.
- the reflectance of light having wavelengths of 360, 400, and 460 nm is usually 60% or more, preferably 80% or more, and more preferably 90% or more.
- the semiconductor light emitting device package provided with the resin molding of the present invention having a high reflectance from the ultraviolet light region to the visible light region has extremely excellent characteristics that cannot be recognized by the conventional semiconductor light emitting device package.
- the semiconductor light emitting device package made of a resin such as polysiloxane has characteristics that have not been easily conceived by those skilled in the art, and has extremely high technical significance.
- the semiconductor light emitting device package of the present invention normally has a chip mounting surface and a bottom surface on the opposite side of the chip mounting surface.
- the distance between the chip mounting surface and the bottom surface that is, the thickness of the semiconductor light emitting device package is usually 100 ⁇ m or more, preferably 200 ⁇ m or more.
- it is 3000 micrometers or less normally, Preferably it is 2000 micrometers or less. If the thickness is too thin, there is a risk that light will be transmitted to the bottom surface and the reflectance will decrease, and the package will have insufficient strength and will be deformed due to handling, etc. If it is too thick, the package itself will be thick and bulky. Application application of the semiconductor light emitting device is limited.
- a liquid thermosetting polyorganosiloxane (1) having 1500 mPa ⁇ s and a platinum concentration of 3.4 ppm was obtained.
- the silica fine particles correspond to (E) fluidity adjuster, and the polyorganosiloxane: silica fine particles (weight ratio) is changed from 80:20 to 89.5: 10.5 so as to have the above viscosity.
- E fluidity adjuster
- silica fine particles (weight ratio) is changed from 80:20 to 89.5: 10.5 so as to have the above viscosity.
- the primary particle diameter of white pigment and aspect ratio of primary particles was measured by SEM observation of the white pigment (alumina powder) used in the examples. When there was variation in the particle diameter, several points (for example, 10 points) were observed with an SEM, and the average value was obtained as the particle diameter. In particular, when the difference between the small particle size and the large particle size is about 5 times or more except for fine particles and coarse particles contained in a very small amount, the maximum and minimum values are recorded.
- the major axis length (maximum major axis) and minor axis length (the length of the longest part perpendicular to the major axis) are also measured, and the major axis length is adopted as the primary particle diameter.
- the value obtained by dividing (maximum major axis) by the minor axis length was taken as the aspect ratio. The results are shown in Table 1.
- Examples 2 to 9 and Comparative Examples 1 to 7 As the white pigment, those listed in Table 2 were used.
- (E) Silica fine particles “AEROSIL RX200 as a fluidity modifier” The test pieces having the thicknesses shown in Table 2 were obtained under the same conditions as in Example 1 except that the formulation of “” was added at the weight ratio shown in Table 2.
- the white pigments A to J are those described in Table 1.
- the white pigment I titania has a surface coated with a thin film of silica and alumina.
- “-” indicates that measurement has not been performed.
- the reflectance of 460 nm light when the thickness of the test piece was 120 ⁇ m was higher in Examples 2 and 9 than Comparative Example 5, and a relatively high reflectance was maintained even with a thin material.
- Example 9 in which titania was blended with alumina it was found that the decrease in reflectance was small when the thickness of the test piece was reduced.
- Example 10 Using the material of Example 3, a package for a semiconductor light-emitting device was formed by liquid injection molding together with a copper lead frame plated with silver on the entire surface.
- the package was a cup-shaped surface-mount package in which the resin part had a recess having a length of 3.2 mm, a width of 2.7 mm, a height of 1.4 mm, and an opening having a diameter of 2.4 mm. Molding was performed under conditions of a mold temperature of 170 ° C. and a curing time of 20 seconds. When the molded package was observed, no burrs were generated and the package did not have a short mold.
- Example 11 Using the material of Example 3, a package for a semiconductor light-emitting device was formed by liquid injection molding together with a copper lead frame plated with silver on the entire surface.
- the package was a cup-shaped surface-mount package having a recess having a length of 5 mm, a width of 5 mm, a height of 1.5 mm, and an opening having a diameter of 3.6 mm. Molding was performed under the conditions of a mold at 150 ° C. and a curing time of 180 seconds. The molded package was cut with a microtome while frozen in liquid nitrogen, and SEM observation of the package cross section was performed. The primary particle diameter of alumina exposed in the cross section was 0.3 ⁇ m, and the aspect ratio of the primary particles was 1.42.
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Abstract
Description
また、ポリアミドを用いたパッケージは、ポリアミドが熱可塑性樹脂であり、環境問題より融点の高い鉛フリー半田が積極的に使用されリフロー温度が高くなる傾向にある現状では、その熱によりポリアミド樹脂が軟化してしまうため、パッケージの耐熱性に問題がある。また、ポリアミドは紫外線、熱により、光劣化、熱劣化が起こるため、近年実用化が進んでいる青色~近紫外線半導体発光素子のようなエネルギーの高い波長領域まで発光域を持つ発光素子を用いた場合、光による劣化が特に問題となる。また、より明るい発光素子が求められている現状においては、半導体発光素子から発せられる光束の大きな光、発熱により、熱劣化、光劣化の問題がより顕在化する。
まず、樹脂組成物を調製する工程において、樹脂であるポリオルガノシロキサンに酸化チタンを添加し混合する場合には、酸化チタンは樹脂に対する分散性が低いという問題がある。このため、樹脂組成物を硬化した後の樹脂成形体において、酸化チタンが均一に分散しておらず樹脂成形体内での反射率が一定ではなく、その結果半導体発光装置から発せられる光線の均一性の点で問題がある。
また、酸化チタンは光触媒性があるために、波長470nm程度以下の半導体発光素子を用いる場合には、半導体発光素子が発する光や、その光によって励起される蛍光体が発する光により、酸化チタン粒子近傍の樹脂成形体が劣化する。そのため、青色領域の光を発する半導体発光素子、および近紫外領域の光を発する半導体発光素子を用いた場合に、樹脂成形体の耐光性が著しく損なわれる。
さらに、酸化チタンは近紫外領域に吸収波長を持つために色が黄色味を帯びている。そのため半導体発光素子からの発光スペクトルを変化させ、半導体発光装置が発する光の白色性、演色性に問題を生じさせる。特に現在積極的に研究されている白色半導体発光装置では白色性、演色性が大きな要求事項となっており、この点に於いても不利である。
すなわち、本発明は以下の通りである。
(1)(A)ポリオルガノシロキサン、(B)白色顔料、および(C)硬化触媒を含有し、前記(B)白色顔料が、以下の特性(a)および(b)を有することを特徴とする、半導体発光装置用樹脂成形体用材料。
(a)一次粒子のアスペクト比が1.2以上4.0以下であること
(b)一次粒子径が0.1μm以上2.0μm以下であること
(2)前記(B)白色顔料の二次粒子の中心粒径が0.2μm以上5μm以下であることを特徴とする、(1)に記載の樹脂成形体用材料。
(3)25℃における剪断速度100s-1での粘度が10Pa・s以上10,000Pa・s以下であることを特徴とする、(1)または(2)に記載の樹脂成形体用材料。
(4)剪断速度100s-1での粘度に対する剪断速度1s-1での粘度の比が15以上であることを特徴とする、(3)に記載の樹脂成形体用材料。
(5)前記(B)白色顔料がアルミナであることを特徴とする、(1)~(4)の何れかに記載の樹脂成形体用材料。
(6)前記(B)白色顔料の一次粒子径xと二次粒子の中心粒径yの比y/xが1以上10以下であることを特徴とする、(1)~(5)の何れかに記載の樹脂成形体用材料。
(7)(A)ポリオルガノシロキサンが、常温、常圧下で液体の熱硬化性ポリオルガノシロキサンであることを特徴とする、(1)~(6)の何れかに記載の樹脂成形体用材料。
(8)さらに(D)硬化速度制御剤を含有する、(1)~(7)の何れかに記載の樹脂成形体用材料。
(9)さらに(E)流動性調整剤を含有することを特徴とする、(1)~(8)のいずれかに記載の樹脂成形体用材料。
(10)樹脂成形体用材料全体に対する、(B)白色顔料及び(E)流動性調整剤の含有量の合計が、50重量%以上であることを特徴とする、(9)に記載の樹脂成形体用材料。
(11)(1)~(10)の何れかに記載の樹脂成形体用材料を成形してなる半導体発光装置用樹脂成形体。
(12)厚さ0.4mmにおいて、波長400nmにおける光反射率が60%以上であることを特徴とする、(11)に記載の樹脂成形体。
(13)前記樹脂成形体が液状射出成形により成形されたことを特徴とする、(11)または(12)に記載の樹脂成形体。
(14)(1)~(10)のいずれかに記載の樹脂成形体用材料を調製する工程、及び前記調製された樹脂成形体用材料を射出成形により成形する工程、を含む樹脂成形体の製造方法。
(15)(11)~(13)のいずれかに記載の樹脂成形体を有する半導体発光装置。
(16)(A)ポリオルガノシロキサン、(B)白色顔料、および(C)硬化触媒を含有し、
25℃における剪断速度100s-1での粘度が10Pa・s以上10,000Pa・s以下であり、かつ、
剪断速度100s-1での粘度に対する剪断速度1s-1での粘度の比が15以上であることを特徴とする、半導体発光装置用樹脂成形体用材料。
<1.半導体発光装置用樹脂成形体用材料>
本発明において半導体発光装置用樹脂成形体用材料とは、半導体発光装置用樹脂成形体の成形に用いる材料である。具体的には、(A)ポリオルガノシロキサン、(B)白色顔料、および(C)硬化触媒を含有する。
ここで、半導体発光装置用樹脂成形体とは、材料を硬化させた成形体であり、リードフレームなどの導電性金属配線と共に成形することにより半導体発光装置用パッケージとなる。また、半導体発光装置とは、上記半導体発光装置用樹脂成形体に半導体発光素子を含む発光装置である。半導体発光装置の断面の略図を図1に示す。
本発明におけるポリオルガノシロキサンとは、ケイ素原子が酸素を介して他のケイ素原子と結合した部分を持つ構造に有機基が付加している高分子物質を指す。ここでポリオルガノシロキサンは、常温常圧下において液体であることが好ましい。これは、半導体発光装置用樹脂成形体を成形する際に、材料の扱いが容易となるからである。また、常温常圧下において固体のポリオルガノシロキサンは、一般的に硬化物としての硬度は比較的高いが、破壊に要するエネルギーが小さく靭性が低いものや、耐光性、耐熱性が不十分で光や熱により変色しやすいものが多い傾向にあるからである。
なお、上記常温とは20℃±15℃(5~35℃)の範囲の温度をいい、常圧とは大気圧に等しい圧力をいい、ほぼ一気圧である。また、液体とは流動性の有る状態をいう。
(R1R2R3SiO1/2)M(R4R5SiO2/2)D(R6SiO3/2)T(SiO4/2)Q ・・・(1)
ここで、上記式(1)中、R1からR6は独立して、有機官能基、水酸基、水素原子から選択される。またM、D、TおよびQは0以上1未満であり、M+D+T+Q=1を満足する数である。
主なポリオルガノシロキサンを構成する単位は、1官能型[R3SiO0.5](トリオルガノシルヘミオキサン)、2官能型[R2SiO](ジオルガノシロキサン)、3官能型[RSiO1.5](オルガノシルセスキオキサン)、4官能型[SiO2](シリケート)であり、これら4種の単位の構成比率を変えることにより、ポリオルガノシロキサンの性状の違いが出てくるので、所望の特性が得られるように適宜選択し、ポリオルガノシロキサンの合成を行う。
上記構成単位が1~3官能型のポリオルガノシロキサンは、オルガノクロロシラン(一般式RnSiCl4-n(n=1~3))と呼ばれる一連の有機ケイ素化合物をもとにして合成することができる。例えば、メチルクロロシランは塩化メチルとケイ素SiとをCu触媒下高温で直接反応させて合成することができ、また、ビニル基などの有機基を持つシラン類は、一般の有機合成化学の手法によって合成することができる。
単離されたオルガノクロロシランを、単独で、あるいは任意の割合で混合し、水により加水分解を行うとシラノールが生成し、このシラノールが脱水縮合するとシリコーンの基本骨格であるポリオルガノシロキサンが合成される。
ポリオルガノシロキサンは、硬化のメカニズムにより分類すると、通常、付加重合硬化タイプ、縮重合硬化タイプ、紫外線硬化タイプ、パーオキサイド架硫タイプなどのポリオルガノシロキサンを挙げることができる。これらの中では、付加重合硬化タイプ(付加型ポリオルガノシロキサン)、および縮合硬化タイプ(縮合型ポリオルガノシロキサン)が好適である。中でも、副生成物の発生が無く、また、反応が可逆性でないヒドロシリル化(付加重合)によって硬化するポリオルガノシロキサンのタイプがより好適である。これは、成形加工時に副生成物が発生すると、成形容器内の圧を上昇させたり、硬化材料中に泡として残存したりする傾向にあるからである。
以下、付加型ポリオルガノシロキサン、および縮合型ポリオルガノシロキサンについて説明する。
付加型ポリオルガノシロキサンとは、ポリオルガノシロキサン鎖が、有機付加結合により架橋されたものをいう。代表的なものとしては、例えばビニルシラン等の(C1)アルケニル基を有する珪素含有化合物と、例えばヒドロシラン等の(C2)ヒドロシリル基を含有する珪素化合物とを総ヒドロシリル基量が0.5倍以上、2.0倍以下となる量比で混合し、(C3)Pt触媒などの付加縮合触媒の存在下反応させて得られるSi-C-C-Si結合を架橋点に有する化合物等を挙げることができる。
RnSiO〔(4-n)/2〕・・・(2)
で表わされる、1分子中にケイ素原子に結合したアルケニル基を少なくとも2個有するポリオルガノシロキサンが挙げられる。
ただし、式(2)中、Rは同一または異種の置換または非置換の1価炭化水素基、アルコキシ基、または水酸基で、nは1≦n<2を満たす正の数である。
上記(C1)アルケニル基を有する珪素含有化合物においてアルケニル基とは、ビニル基、アリル基、ブテニル基、ペンテニル基などの炭素数2~8のアルケニル基であることが好ましい。Rが炭化水素基である場合は、メチル基、エチル基などのアルキル基、ビニル基、フェニル基等の炭素数1~20の1価炭化水素基から選択される。好ましくは、メチル基、エチル基、フェニル基である。
両末端ビニルポリジメチルシロキサン
DMS-V00、DMS-V03、DMS-V05、DMS-V21、DMS-V22、DMS-V25、DMS-V31、DMS-V33、DMS-V35、DMS-V41、DMS-V42、DMS-V46、DMS-V52(いずれもGelest社製)
両末端ビニルジメチルシロキサン-ジフェニルシロキサンコポリマー
PDV-0325、PDV-0331、PDV-0341、PDV-0346、PDV-0525、PDV-0541、PDV-1625、PDV-1631、PDV-1635、PDV-1641、PDV-2331、PDV-2335(いずれもGelest社製)
両末端ビニルフェニルメチルシロキサン
PMV-9925(Gelest社製)
トリメチルシリル基封鎖ビニルメチルシロキサン-ジメチルシロキサンコポリマー
VDT-123、VDT-127、VDT-131、VDT-153、VDT-431、VDT-731、VDT-954(いずれもGelest社製)
ビニルT-構造ポリマー
VTT-106、MTV-124(いずれもGelest社製)
両末端ヒドロシリルポリジメチルシロキサン
DMS-H03、DMS-H11、DMS-H21、DMS-H25、DMS-H31、DMS-H41(いずれもGelest社製)
両末端トリメチルシリル封鎖メチルヒドロシロキサン-ジメチルシロキサンコポリマー
HMS-013、HMS-031、HMS-064、HMS-071、HMS-082、HMS-151、HMS-301、HMS-501(いずれもGelest社製)
また、ヒドロシリル化を起こす反応点(架橋点)の含有量は、アルケニル基およびヒドロシリル基ともに白色顔料を含まない樹脂自体中において0.1mmol/g以上、20mmol/g以下であることが好ましい。さらに好ましくは0.2mmol/g以上、10mmol/g以下である。
縮合型ポリオルガノシロキサンとしては、例えば、アルキルアルコキシシランの加水分解・重縮合で得られるSi-O-Si結合を架橋点に有する化合物を挙げることができる。具体的には、下記一般式(3)および/若しくは(4)で表わされる化合物、並びに/またはそのオリゴマーを加水分解・重縮合して得られる重縮合物が挙げられる。
式(3)中、Mは、ケイ素を表わし、Xは、加水分解性基を表わし、Y1は、1価の有機基を表わし、mは、Mの価数を表わす1以上の整数を表わし、nは、X基の数を表わす1以上の整数を表わす。但し、m≧nである。
縮合型ポリオルガノシロキサンの中で、特に好ましい材料について、以下に説明する。
ポリオルガノシロキサンは、一般に半導体発光装置に用いた場合、半導体発光素子や半導体発光素子を配置する基板や、樹脂成形体等との接着性が弱いことがあるが、これらと密着性が高いポリオルガノシロキサンとするため、特に、以下の[1]および[2]のうち1つ以上の特徴を有する縮合型ポリオルガノシロキサンが好ましい。
[1]ケイ素含有率が20重量%以上である。
[2]測定した固体Si-核磁気共鳴(NMR)スペクトルにおいて、下記(a)および/または(b)のSiに由来するピークを少なくとも1つ有する。
(b)ピークトップの位置がジメチルシリコーンゴムのジメチルシロキシケイ素を基準としてケミカルシフト-80ppm以上、-40ppm未満の領域にあり、ピークの半値幅が0.3ppm以上5.0ppm以下であるピーク。
なお、縮合型ポリオルガノシロキサンにおいては、縮合反応の進行に伴い脱離成分が発生するが、成形加工方法により、該成分の成形加工性への影響が大きくない場合に用いることができる。その場合には、特に縮合型ポリオルガノシロキサン中のシラノール含有率が0.01重量%以上、10重量%以下であることが好ましい。
本発明において白色顔料は、樹脂の硬化を阻害しない公知の顔料を適宜選択する事ができる。白色顔料としては無機および/または有機の材料を用いる事ができる。ここで白色とは、無色であり透明ではない事をいう。すなわち可視光領域に特異な吸収波長を持たない物質により入射光を乱反射させる事ができる色をいう。
また、白色顔料として用いることができる有機微粒子としては、弗素樹脂粒子、グアナミン樹脂粒子、メラミン樹脂粒子、アクリル樹脂粒子、シリコーン樹脂粒子等の樹脂粒子などを挙げることができるが、いずれもこれらに限定されるものではない。中でも白色度が高く少量でも光反射効果が高く変質しにくい点からは、アルミナ、酸化チタン、酸化亜鉛などが特に好ましい。また、材料硬化時の熱伝導率向上の点からは、アルミナ、窒化硼素などが特に好ましい。また、近紫外線の光反射効果が高く、近紫外線による変質が小さい観点からも、アルミナは特に好ましい。
これらは、単独もしくは2種以上混合して用いる事ができる。
酸化チタンを用いる場合は、光触媒性、分散性、白色性等の問題が出ない程度に含有する事ができる。
アルミナの一次粒子径が上記の範囲であり、かつ、アルミナ結晶の結晶子サイズが上記の範囲であるということは、一次粒子のサイズと結晶子のサイズが異なること、即ち、一次粒子が複数の結晶子によって構成されることを意味する。
アルミナ結晶の結晶子サイズが上記範囲である場合には、成形時に配管、スクリュー、金型などの磨耗が少なく、磨耗による不純物が混入しにくい点で、好ましい。
上記結晶子サイズは、X線回折測定により確認することができる。X線回折測定では、アルミナが結晶性を有している場合、結晶型に応じて決まった位置にピークが出る。そして、このピークの半値幅からScherrerの式にしたがって結晶子径(結晶子サイズ)を計算することができる。
本発明の樹脂成形体用材料の硬化時の熱伝導率は、前述のとおり高い方が好ましいが、熱伝導率を高くするためには、純度が98%以上のアルミナを用いることが好ましく、純度99%以上のアルミナを用いることがより好ましく、特に低ソーダアルミナを用いることが好ましい。また、熱伝導率を高くするためには、窒化硼素を用いることも好ましく、純度が99%以上の窒化硼素を用いることが特に好ましい。
酸化チタンは屈折率が高く、ポリオルガノシロキサンとの屈折率差が大きいため少ない添加量でも高反射となりやすいことから、アルミナと酸化チタンを併用してもよい。例えば、アルミナに対する酸化チタンの重量比(アルミナ:酸化チタン)が、50:50~95:5となる割合で混合することができる。アルミナに酸化チタンを少量添加することで、アルミナを単独で使用した場合よりも420nm以上の波長の光の反射率が高くなる可能性があり、さらに、材料中の白色顔料の割合が小さい場合や、材料の厚みが薄い場合にも反射率が下がりにくい傾向がある。チタニアの併用により材料中の白色顔料の割合を小さくできるため、材料組成の自由度が上がり、白色顔料以外の成分の充填量を上げることができる。また、薄い材料の反射率が高いことは、樹脂成形体の形状の自由度が上がる点で非常に有利である。また、厚みを大きくできない薄い樹脂成形体や細かい構造の樹脂成形体でも材料の反射率が高いことで、半導体発光装置の明るさを増す効果が期待できる。
本発明における(B)白色顔料の一次粒子のアスペクト比は1.2以上4.0以下であることを特徴としている。
上記(B)白色顔料のアスペクト比は、1.25以上であることが好ましく、1.3以上であることがより好ましく、1.4以上であることが更に好ましい。一方、上限は、3.0以下であることが好ましく、2.5以下であることがより好ましく、2.2以下であることが更に好ましく、2.0以下であることが特に好ましく、1.8以下であることが最も好ましい。
アスペクト比が上記範囲である場合には、散乱により高反射率を発現しやすく、特に近紫外領域の短波長の光の反射が大きい。これにより、かかる樹脂成形体を用いた半導体発光装置において、LED出力を向上させることができる。
また、アスペクト比が上記範囲である白色顔料を使用することは、金型の磨耗が少ないなど、成形性の観点からも好ましい。アスペクト比が上記範囲よりも大きい場合、顔料粒子の角部との接触により金型の磨耗が激しくなることがあり、逆に、アスペクト比が小さい白色顔料を使用する場合にも材料中の顔料の充填密度を上げられるため金型と顔料との接触頻度が上がり、金型が磨耗しやすい傾向になる。さらに、アスペクト比が上記範囲である白色顔料を使用すると、材料粘度の調整が容易となり、成形に適した粘度に調整することで、成形サイクルを短縮することができたり、バリを抑えることができたり、成形性に優れた材料となる。
特にアスペクト比が4.0よりも大きい場合には、高反射になりにくく、また、成形時に配管、スクリュー、金型等の磨耗が発生しやすく、磨耗による不純物の混入により成形した樹脂成形体の反射率低下や、絶縁破壊が起こりやすい傾向にある。
本発明では、アスペクト比が上記範囲であることにより、(B)白色顔料の好ましい形状からは、球状、真球状に形成されたものが除かれる。また、極端に細長い形状のものも、かえって反射率を低下させてしまうため、本発明に係る(B)白色顔料からは除かれる。アスペクト比が上記範囲である場合、白色顔料が金型の隙間に詰まりやすく、バリが発生しにくいが、球状では金型の隙間を素通りしバリが発生しやすい傾向がある。
本発明では、アスペクト比が上記範囲に含まれる粒子が(B)白色顔料全体の60体積%以上、より好ましくは70体積%以上、特に好ましくは80体積%以上を占めることが好ましく、必ずしも全ての(B)白色顔料が上記アスペクト比の範囲を満たさなければいけないわけではないことは当業者が当然に理解できる事項である。
ここで(c)破砕形状とは、主に白色顔料を破砕(粉砕)によって微細化した形状をいい、破砕後の処理により結晶の角が少ない丸みを帯びた形状となったもの、焼成などによって生成した球状でない顔料の形状も含まれる。すなわち、製造工程の性格上、球状、真球状に形成されたものを除く趣旨である。破砕形状の白色顔料を使用した材料では、球状の白色顔料を使用した材料に比べ、散乱により高反射率を発現しやすく、特に近紫外領域の短波長の光(特に、波長360nm~460nmの光)の反射が大きい。また、球状の顔料に比べて、経済面でも有利な場合がある。これにより、かかる樹脂成形体を用いた半導体発光装置において、LED出力を向上させることができる。
一次粒子径が上記範囲である場合には、後方散乱傾向と散乱光強度を兼ね備えることで材料が高反射率を発現しやすく、特に近紫外領域等の短波長の光に対する反射が大きくなり、好ましい。
白色顔料は、一次粒子径が小さすぎると散乱光強度が小さいため反射率は低くなる傾向にあり、一次粒子径が大きすぎると散乱光強度は大きくなるが、前方散乱傾向になるため反射率は小さくなる傾向にある。
また、一次粒子径が上記範囲である場合には、成形に適した粘度への調整が容易である、金型の磨耗が少ないなど、成形性の観点からも好ましい。一次粒子径が上記範囲よりも大きい場合、顔料粒子との接触による金型への衝撃が大きく金型の磨耗が激しくなる傾向があり、一次粒子径が上記範囲よりも小さい白色顔料を使用する場合には、材料が高粘度になりやすく、白色顔料の充填量を上げられないため、高反射等の材料特性と成形性との両立が難しくなる傾向にある。
特に、液状射出成形に好適に使用できる材料とするためには材料にある程度以上のチキソトロピー性を持たせることが必要である。一次粒子径が0.1μm以上2.0μm以下の白色顔料を組成物中に添加するとチキソトロピー性付与効果が大きく、バリやショートが少なく成形しやすい組成物とするために、粘度とチキソトロピー性を容易に調整することができる。
なお、樹脂組成物中の白色顔料の充填率を上げる等の目的で、一次粒子径が2μmよりも大きい白色顔料を併用することもできる。
白色顔料のアスペクト比と一次粒子径は、成形後(硬化後)であっても測定することができる。SEMなどの電子顕微鏡によって成形品の断面を観察し、断面に露出した白色顔料の一次粒子径とアスペクト比を計測すればよい。
本発明ではSEMなどの電子顕微鏡観察により計測した粒子の長軸長さ(最大長径)を短軸長さ(長径に垂直方向で最も長い部分の長さ)で除して求めるものとする。軸長さにばらつきがある場合は、複数点(例えば10点)をSEMで計測し、その平均値から算出することができる。あるいは、30点、100点を計測しても同様の算出結果を得ることができる。
二次粒径が上記範囲である場合には、成形性の観点で好ましい材料が得られ易い。また、成形に適した粘度への調整が容易で、金型の磨耗が少ない。加えて、白色顔料が金型の隙間を通過しにくいためバリが発生しにくく、かつ、金型のゲートに詰まりにくいため成形時のトラブルが起こりにくい。二次粒径が上記範囲よりも大きい場合には、白色顔料の沈降により材料が不均一となる傾向にあり、金型の磨耗やゲートの詰まりにより成形性が損なわれたり、材料の反射の均一性が損なわれたりすることがある。
なお、樹脂組成物中の白色顔料の充填率を上げる等の目的で、二次粒径が10μmよりも大きい白色顔料を併用することもできる。なお、中心粒径とは積算%の体積基準粒度分布曲線が50%の横軸と交差するポイントの粒子径を言い、一般的に50%粒子径(D50)、メディアン径と呼ばれるものを指す。
ここで、一次粒子径xと二次粒子の中心粒径yの比y/xが上記範囲であることにより、(B)白色顔料の好ましい形状からは、球状、真球状に形成されたもの(即ち、一次粒子がほとんど凝集しておらず、一次粒子径と二次粒子の中心粒径がほぼ等しいもの)が除かれる。
一次粒子径xと二次粒子の中心粒径yの比y/xが上記範囲である場合には、散乱により高反射率を発現しやすく、特に近紫外領域の短波長の光の反射が大きい。これにより、かかる樹脂成形体を用いた半導体発光装置において、LED出力を向上させることができる。また、成形に適した材料粘度への調整も容易である。
本発明において半導体発光装置用樹脂成形体材料中の(B)白色顔料の含有量は、使用する顔料の粒径や種類、ポリオルガノシロキサンと顔料の屈折率差により適宜選択される。(A)ポリオルガノシロキサン100重量部に対し通常20重量部以上、好ましくは50重量部以上、更に好ましくは100重量部以上であり、通常900重量部以下、好ましくは600重量部以下、更に好ましくは400重量部以下である。
上記範囲内であると反射率、成形性等が良好である。上記下限未満である場合には光線が透過してしまい半導体発光装置の反射効率が低下する傾向にあり、上限よりも大きい場合には材料の流動性が悪化することにより成形性が低下する傾向にある。
特に、液状射出成形に好適に使用できる材料とするためには材料にある程度以上のチキソトロピー性を持たせることが必要である。一次粒子径が0.1μm以上2.0μm以下の白色顔料を組成物中に配合すると著しい増粘が起こり、チキソトロピー性付与効果が大きいが、そのような形状の白色顔料を組成物全体の30重量%以上含有させることで、バリやショートが少なく成形しやすい材料にすることができ、さらに、粘度とチキソトロピー性を調整することが容易となる。
また、後述する樹脂成形体用材料の熱伝導率を0.4以上3.0以下の範囲に制御するためには、(B)白色顔料としてアルミナを樹脂成形体用材料全体量に対して40重量部以上90重量部以下添加することが好ましい。あるいは、(B)白色顔料として窒化硼素を樹脂成形体用材料全体量に対して30重量部以上90重量部以下添加することが好ましい。なお、アルミナと窒化硼素を併用してもよい。
本発明における(C)硬化触媒とは、(A)のポリオルガノシロキサンを硬化させる触媒である。ポリオルガノシロキサンは触媒により重合反応が早まり硬化する。この触媒はポリオルガノシロキサンの硬化機構により付加重合用触媒、縮合重合用触媒がある。
これらの触媒は半導体発光装置用樹脂成形体材料として配合した際の安定性、被膜の硬度、無黄変性、硬化性などを考慮して選択される。
添加量が上記範囲であると半導体発光装置用樹脂成形体材料の硬化性、保存安定性が良好であり、加えて成形した樹脂成形体の品質が良好である。添加量が上限値を超えると樹脂成形体材料の保存安定性に問題が生じる場合があり、下限値未満では硬化時間が長くなり樹脂成形体の生産性が低下し、未硬化成分により樹脂成形体の品質が低下する傾向にある。
本発明の半導体発光装置用樹脂成形体用材料は、さらに(D)硬化速度制御剤を含有することが好ましい。ここで硬化速度制御剤とは、樹脂成形体用材料を成形する際に、その成形効率を向上させるために硬化速度を制御するためのものであり、硬化遅延剤または硬化促進剤が挙げられる。
脂肪族不飽和結合を含有する化合物としては、3-ヒドロキシ-3-メチル-1-ブチン、3-ヒドロキシ-3-フェニル-1-ブチン、1-エチニル-1-シクロヘキサノール等のプロパギルアルコール類、エン-イン化合物類、ジメチルマレート等のマレイン酸エステル類等が例示される。脂肪族不飽和結合を含有する化合物の中でも、三重結合を有する化合物が好ましい。有機リン化合物としては、トリオルガノフォスフィン類、ジオルガノフォスフィン類、オルガノフォスフォン類、トリオルガノフォスファイト類等が例示される。有機イオウ化合物としては、オルガノメルカプタン類、ジオルガノスルフィド類、硫化水素、ベンゾチアゾール、チアゾール、ベンゾチアゾールジサルファイド等が例示される。窒素含有化合物としては、アンモニア、1~3級アルキルアミン類、アリールアミン類、尿素、ヒドラジン等が例示される。スズ系化合物としては、ハロゲン化第一スズ2水和物、カルボン酸第一スズ等が例示される。有機過酸化物としては、ジ-t-ブチルペルオキシド、ジクミルペルオキシド、ベンゾイルペルオキシド、過安息香酸t-ブチル等が例示される。
これらの硬化遅延剤のうち、遅延活性が良好で原料入手性がよいという観点からは、ベンゾチアゾール、チアゾール、ジメチルマレート、3-ヒドロキシ-3-メチル-1-ブチン、1-エチニル-1-シクロヘキサノールが好ましい。
硬化遅延剤の添加量は種々設定できるが、使用する(C)硬化触媒1molに対する好ましい添加量の下限は10-1mol以上、より好ましくは1mol以上であり、好ましい添加量の上限は103mol以下、より好ましくは50mol以下である。また、これらの硬化遅延剤は単独で使用してもよく、2種以上併用してもよい。
上記イミダゾール類としては、例えば、2-メチルイミダゾール、2-エチル-4-メチルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾリウムトリメリテート等が挙げられ、商品名としては、2E4MZ、2PZ-CN、2PZ-CNS(四国化成工業株式会社)等がある。硬化促進剤の添加量は、(A)ポリオルガノシロキサン熱硬化性樹脂と(C)硬化触媒の合計100重量部に対して、0.1重量部以上10重量部以下の範囲で添加することが好ましい。
半導体装置用樹脂成形体用材料中には、上記(A)ポリオルガノシロキサン、(B)白色顔料、(C)硬化触媒、(D)硬化速度制御剤以外に、本発明の要旨を損なわない限り、必要に応じて他の成分を1種、または2種以上を任意の比率および組み合わせで含有させることができる。
例えば、半導体発光装置用樹脂成形体用材料の流動性コントロールや白色顔料の沈降抑制の目的で、固体粒子を流動性調整剤(E)として含有させることができる。流動性調整剤(E)としては、含有させることで樹脂成形体用材料の粘度が高くなる常温から成形温度付近で固体の粒子であれば特に限定されないが、発光素子からの光や蛍光体により波長変換された光を吸収する性質が無いか非常に小さく、材料の反射率を極端に低下させないもので、光や熱による変色、変質が小さく耐久性が高いものが好ましい。具体的には、シリカ微粒子、石英ビーズ、ガラスビーズ、ガラス繊維などの無機物繊維、窒化ホウ素、窒化アルミ等が挙げられる。また、例えば、繊維状アルミナのように、以下の特性(a)および(b)のいずれか、もしくは両方を満たさない白色顔料を前述の白色顔料とは別に含有させることができる。
(a)一次粒子のアスペクト比が1.2以上4.0以下であること
(b)一次粒子径が0.1μm以上2.0μm以下であること
中でもチキソトロピー性付与効果が大きいシリカ微粒子は、組成物の粘度やチキソトロピー性をコントロールしやすく、好適に使用できる。石英ビーズ、ガラスビーズ、ガラス繊維などは、流動性調整剤としての効果のみならず、材料の熱硬化後の強度、靭性を高める効果や材料の線膨張係数を下げる効果も期待できるため好ましく、シリカ微粒子と併用するか単独で使用してもよい。
本発明に使用するシリカ微粒子は、特に限定されるものではないが、BET法による比表面積が、通常50m2/g以上、好ましくは80m2/g以上、さらに好ましくは100m2/g以上である。また、通常300m2/g以下、好ましくは200m2/g以下である。比表面積が小さすぎるとシリカ微粒子の添加効果が認められず、大きすぎると樹脂中への分散処理が困難になる。シリカ微粒子は、例えば親水性のシリカ微粒子の表面に存在するシラノール基と表面改質剤を反応させることにより表面を疎水化したものを使用してもよい。
シリカ微粒子としては、例えばフュームドシリカを挙げることができる。フュームドシリカは、H2とO2との混合ガスを燃焼させた1100~1400℃の炎でSiCl4ガスを酸化、加水分解させることにより作製される。フュームドシリカの一次粒子は、平均粒径が5~50nm程度の非晶質の二酸化ケイ素(SiO2)を主成分とする球状の超微粒子であり、この一次粒子がそれぞれ凝集し、粒径が数百nmである二次粒子を形成する。フュームドシリカは、超微粒子であるとともに、急冷によって作製されるため、表面の構造が化学的に活性な状態となっている。
具体的には、例えば日本アエロジル株式会社製「アエロジル」(登録商標)が挙げられ、親水性アエロジル(登録商標)の例としては、「90」、「130」、「150」、「200」、「300」、疎水性アエロジル(登録商標)の例としては、「R8200」、「R972」、「R972V」、「R972CF」、「R974」、「R202」、「R805」、「R812」、「R812S」、「RY200」、「RY200S」「RX200」が挙げられる。
この液状増粘剤としてのヒドロキシル基含有直鎖状オルガノポリシロキサンは、分子中にアルケニル基および/またはSiH基等のヒドロシリル化付加反応に関与する官能性基を含有しないものであり、分子中のヒドロキシル基は分子鎖末端のケイ素原子に結合したものであっても、分子鎖非末端(分子鎖途中)のケイ素原子に結合したものであっても、これらの両方に結合したものであってもよいが、好ましくは分子鎖両末端のケイ素原子に結合したヒドロキシル基を含有する直鎖状オルガノポリシロキサン(すなわち、α、ω‐ジヒドロキシジオルガノポリシロキサン)であることが望ましい。
このケイ素原子に結合した有機基としてはメチル、エチル、プロピル等のアルキル基やフェニル基等のアリル基などの一価炭化水素基が挙げられ、該オルガノポリシロキサンの主鎖を構成するジオルガノシロキサン繰返し単位としてはジメチルシロキサン単位、ジフェニルシロキサン単位、メチルフェニルシロキサン単位等の一種または二種以上の組み合わせであることが好ましい。具体的には、α、ω‐ジヒドロキシジメチルポリシロキサン、α、ω‐ジヒドロキシジフェニルポリシロキサン、α、ω‐ジヒドロキシメチルフェニルポリシロキサン、α、ω‐ジヒドロキシ(ジメチルシロキサン・ジフェニルシロキサン)共重合体、α、ω‐ジヒドロキシ(ジメチルシロキサン・メチルフェニルシロキサン)共重合体等が挙げられる。
液状増粘剤としてのポリオルガノシロキサンの配合量は(A)ポリオルガノシロキサン全体を100重量部とした時、通常、0~10重量部、好ましくは0.1~5重量部、より好ましくは0.5~3重量部程度とすることができる。
これらの添加する場合の含有量は、少なすぎると目的の効果か得られず、多すぎると半導体装置用樹脂成形体用材料の粘度が上がり、加工性に影響するので、十分な効果が発現し、材料の加工性を損なわない範囲で適宜選択できる。通常、ポリオルガノシロキサン100重量部に対し500重量部以下、好ましくは200重量部以下である。
なお、カップリング剤としては例えばシランカップリング剤が挙げられる。シランカップリング剤としては、分子中に有機基と反応性のある官能基と加水分解性のケイ素基を各々少なくとも1個有する化合物であれば特に限定されない。有機基と反応性のある基としては、取扱い性の点からエポキシ基、メタクリル基、アクリル基、イソシアネート基、イソシアヌレート基、ビニル基、カルバメート基から選ばれる少なくとも1個の官能基が好ましく、硬化性および接着性の点から、エポキシ基、メタクリル基、アクリル基が特に好ましい。加水分解性のケイ素基としては取扱い性の点からアルコキシシリル基が好ましく、反応性の点からメトキシシリル基、エトキシシリル基が特に好ましい。
好ましいシランカップリング剤としては、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン等のエポキシ官能基を有するアルコキシシラン類;3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルトリエトキシシラン、メタクリロキシメチルトリメトキシシラン、メタクリロキシメチルトリエトキシシラン、アクリロキシメチルトリメトキシシラン、アクリロキシメチルトリエトキシシラン等のメタクリル基あるいはアクリル基を有するアルコキシシラン類が例示できる。
本発明の樹脂成形体用材料中における(A)ポリオルガノシロキサンの含有量は、通常樹脂成形体用材料として用いることができる範囲であれば限定されないが、通常材料全体の15重量%以上、50重量%以下であり、好ましくは20重量%以上、40重量%以下であり、より好ましくは25重量%以上、35重量%以下である。なお、材料中に含まれる(D)硬化速度制御剤やその他成分である液状増粘剤がポリオルガノシロキサンである場合は上記(A)の含有量に含まれるものとする。
本発明の樹脂成形体用材料中における(B)白色顔料の含有量は、通常樹脂成形体用材料として用いることができる範囲であれば限定されないが、通常材料全体の30重量%以上、85重量%以下であり、好ましくは40重量%以上80重量%以下であり、より好ましくは45重量%以上、70重量%以下である。
本発明の樹脂成形体用材料中における(E)流動性調整剤の含有量は、本発明の効果を阻害しない範囲であれば限定されないが、通常材料全体の55重量%以下であり、好ましくは2重量%以上50重量%以下であり、より好ましくは5重量%以上、45重量%以下である。
また、樹脂成形体用材料全体に対する、(B)白色顔料及び(E)流動性調整剤の合計量の比が、50重量%以上であることが好ましく、60重量%以上であることがより好ましく、65重量%以上であることが特に好ましく、また、85重量%以下であることが好ましく、80重量%以下であることがより好ましい。
本発明の半導体発光装置用樹脂成形体用材料は、25℃における剪断速度100s-1での粘度が10Pa・s以上10,000Pa・s以下であることが好ましい。上記粘度は、半導体装置用樹脂成形体を成形する際の成形効率の観点から、50Pa・s以上5,000Pa・s以下であることがより好ましく、100Pa・s以上2,000Pa・s以下であることがさらに好ましく、150Pa・s以上1,000Pa・s以下であることが特に好ましい。
加えて、後述するようにチキソトロピー性の観点から、本発明の半導体発光装置用樹脂成形体用材料は25℃での剪断速度100s-1での粘度に対する25℃での剪断速度1s-1での粘度の比(1s-1/100s-1)が15以上であることが好ましく、20以上であることがより好ましく、30以上であることが特に好ましい。一方、上限は、500以下であることが好ましく、300以下であることがより好ましい。
また、本発明の半導体発光装置用樹脂成形体用材料の粘度としては、特に、25℃における剪断速度100s-1での粘度が1,000Pa・s以下であり、かつ、25℃での剪断速度100s-1での粘度に対する25℃での剪断速度1s-1での粘度の比(1s-1/100s-1)が15以上であることが好ましい。
成形性のよい材料とするためには、材料に一定以上のチキソトロピー性を持たせることが必要であるが、25℃における剪断速度100s-1での粘度が10Pa・s以上10,000Pa・s以下であり、剪断速度100s-1での粘度に対する剪断速度1s-1での粘度の比が15以上である場合、バリやショートモールド(未充填)の発生が少なく、成形時の材料の計量時間や成形サイクルを短縮でき、成形も安定しやすく、成形効率の高い材料となる。
特に液状樹脂材料を用いたLIM成形では、金型の微小隙間から材料が染み出すことに起因するバリが発生しやすく、バリを除去する後処理工程が必要であった。一方、バリの発生を抑えるために金型の隙間を小さくするとショートモールド(未充填)が発生しやすくなる等の問題があった。樹脂成形体用材料の粘度が上記範囲にある場合、このような問題を解決することができ、樹脂成形体のLIM成形を容易に、成形性良く行うことができる。剪断速度100s-1での粘度が10,000Pa・sより大きいと、樹脂の流れが悪いため金型への充填が不十分となったり、射出成形を行う際に材料供給に時間がかかるため成形サイクルが長くなったりするなどして、成形効率が低下する傾向にある。また、上記粘度が10Pa・sより小さいと、金型の隙間から材料が漏れてバリが発生したり、金型の隙間に射出圧力が逃げやすくなるため成形が安定しにくくなったり、やはり成形効率が低下する傾向にある。特に成形体が小さい場合にはバリを除去するための後処理も困難になるため、バリの発生を抑えることは成形性には重要である。
25℃における剪断速度100s-1での粘度に対する25℃における剪断速度1s-1での粘度の比が15未満の場合、つまり剪断速度1s-1での粘度が比較的小さい場合は、成形機や金型の隙間にも材料が入り込みやすくなったり、バリが非常に発生しやすくなったり、ノズル部で液ダレしやすくなったり、射出圧力が材料に伝わりにくく成形が安定しにくくなったりするなど、成形のコントロールが難しくなることがある。LIM成形ではスプルー部のパーティングラインの樹脂漏れが問題になりやすいが、本発明の粘度範囲に調整することは樹脂漏れ抑制にも効果がある。
これらの25℃における剪断速度100s-1での粘度と剪断速度1s-1での粘度は、例えばARES-G2-歪制御型レオメータ(ティー・エイ・インスツルメント・ジャパン株式会社製)を用いて測定することができる。
二次粒子の中心粒径が2μmよりも大きい白色顔料を用いる場合、特に中心粒径が5μm以上のものを用いる場合には、チキソトロピー性付与効果が大きい微細領域の流動性調整剤を併用することが好ましいが、(B)白色顔料自体の一次粒径が十分小さい場合には、流動性調整剤と併用せず白色顔料のみでも使用でき、更に中心粒径が比較的大きい数μm程度以上の流動性調整剤と組み合わせても良い。
本発明の半導体発光装置用樹脂成形体用材料は、硬化時の熱伝導率が0.4以上3.0以下であることが好ましく、0.6以上2.0以下であることがより好ましい。硬化時の熱伝導率は、例えばアイフェイズ・モバイル(アイフェイズ社製)を用いて測定することができる。
ここで硬化時とは、180℃で4分間熱硬化させた時をいう。
かかる問題に対し、本発明者らは、硬化時の、すなわち成形により樹脂成形体とした時の熱伝導率が上記範囲であることにより、樹脂成形体およびそれを用いて構成した半導体発光装置において半導体発光素子から発せられる光による発熱に対する放熱性が向上するため、該装置の耐久性が向上することを見出した。
上記熱伝導率が0.4より小さいと、該装置において半導体発光素子から発せられる光による発熱により該装置に含まれる蛍光体層が熱劣化する傾向にある。
上記熱伝導率は、半導体発光装置用樹脂成形体用材料に含有させる(B)白色顔料としてアルミナや窒化硼素を用いることにより上記範囲に制御することができる。
また、本発明の樹脂成形体用材料を用いた樹脂成形体は、可視光について高反射率を維持することができることが好ましい。具体的には、460nmの光の反射率が80%以上であることが好ましく、90%以上であることがより好ましい。また、波長400nmの光の反射率が60%以上であることが好ましく、80%以上であることがより好ましく、90%以上であることが更に好ましい。
ここで、樹脂成形体の反射率は、本発明の樹脂成形体用材料を熱硬化させて、厚さ0.4mmに成形した成形体を測定した場合の反射率をいう。前記熱硬化は、例えば、10kg/cm2の圧力下、180℃で4分間、硬化させることにより行うことができる。
樹脂成形体の反射率は、樹脂の種類(例えば、樹脂の屈折率を変えることにより反射率を制御することができる。)やフィラーの種類、フィラーの粒径や含有量などにより制御することができる。
本発明の半導体発光装置用樹脂成形体の成形方法として圧縮成形法、トランスファー成形法、および射出成形法を例示する事ができる。これらのうち、好ましい成形方法としては、無駄な硬化物が発生せず二次加工が不要である(すなわちバリが発生しにくい)点から、樹脂成形体の成形工程の自動化、成形サイクルの短縮化、成形品のコスト削減が可能になる等大きなメリットがある、射出成形法、特に液状射出成形法(LIM成形)が挙げられる。LIM成形とトランスファー成形とを比較すると、LIM成形は、成形形状の自由度が高く、成形機および金型が比較的安価であるというメリットがある。
また、樹脂の成形の際、金型を真空雰囲気下に置くことで、狭い空間への材料の浸透が促進され、成形品内にエアボイドの発生を防ぐことができる。
液状射出成形(LIM成形)における硬化時間については、硬化度をグラフで表した際に、グラフの形がS字に立ち上がると良い。初期の硬化の立ち上がりが早すぎると金型への未充填が発生する場合がある。バリの発生を抑え、かつ金型への未充填を防止するには、材料の硬化速度のコントロールと粘度調整が非常に重要である。金型に樹脂材料が充填された後は、成形サイクルを短縮でき、硬化収縮により離型性が上がるので、硬化は早いほど良い。
硬化終了までの時間は通常60秒以内、好ましくは30秒以内、さらに好ましくは10秒以内である。必要に応じてポストキュアを行ってもよい。硬化速度は白金触媒種の選択、触媒量、硬化速度制御剤の使用、ポリオルガノシロキサンの架橋度のほか、金型温度、充填速度、射出圧力等の成形条件によっても調節できる。
本発明の半導体発光装置用樹脂成形体は、通常半導体発光素子を搭載して半導体発光装置として用いられる。半導体発光装置は、例えば図1に示す様に、半導体発光素子1、樹脂成形体2、ボンディングワイヤ3、封止材4、リードフレーム5等から構成される。この場合、リードフレーム5等の導電性材料と絶縁性の樹脂成形体からなるものを、パッケージと称する。
ボンディングワイヤ3は、半導体発光素子1をパッケージに固定する役割を有する。また、半導体発光素子1が電極となるリードフレームと接触していない場合には、導電性のボンディングワイヤ3が半導体発光素子1への電源供給の役割を担う。ボンディングワイヤ3は、リードフレーム5に圧着し、熱及び超音波の振動を与えることで接着させる。
本発明の樹脂成形体用材料からなる樹脂成形体2は、リードフレーム5の露出面積を極めて小さくすることが可能である。本発明の樹脂成形体材料を成形した樹脂成形体は、リードフレームの材料(例えば銀など)と反射率が同等乃至は高い傾向にあるため、樹脂成形体の露出面積を大きくしても、パッケージの高い反射率を維持することができる。そのため、本発明の樹脂成形体用材料からなるパッケージを用いることで、従来型のパッケージとは異なる構成の半導体発光装置を得ることもできる。例えば、図3には従来型のパッケージを備えた半導体発光装置200を示す。図3の半導体発光装置は、リードフレーム204の露出面積が大きい。これは、樹脂成形体201の反射率がリードフレーム204と比較して低いため、半導体発光装置が高輝度を実現するためには、反射率の高い材料を用いているリードフレーム204の表面積を大きくする必要があった。このようなリードフレーム204の露出面積が大きい場合には、パッケージを発光装置に備えて使用した場合にリードフレームの変色が生じることで発光効率が低下する場合があるが、図1のように、リードフレーム5の露出面積を小さくすることで、このようなリードフレームの変色に起因する発光効率の低下を防ぐことができる。
封止材4に含まれるバインダー樹脂は、通常封止材に用いられることが知られている透光性の樹脂を適宜選択すればよい。具体的にはエポキシ樹脂、シリコーン樹脂、アクリル樹脂、ポリカーボネート樹脂などが挙げられ、シリコーン樹脂を用いることが好ましい。
本実施形態の半導体発光装置1Cは、窓部を有する筐体101、リフレクター部102、光源部103、ヒートシンク104から構成されている。光源部103は配線基板上に発光部105を備えており、配線基板106に直接半導体発光素子が実装されたCOB(Chip on Board)形式、図1のような半導体発光装置が表面実装された形式のいずれでも良い。光源部103がCOB形式である場合は、半導体発光素子はドーム状又は平板状に成形された封止樹脂により枠材を使用せず封止されていても良い。また、配線基板106上に実装される半導体発光素子は1個でも複数個でもよい。リフレクター部102及びヒートシンク104は筐体101と一体型であっても別々であってもよく、必要に応じて用いることが出来る。放熱の観点から光源部103、筐体101、ヒートシンク104は一体構造もしくは高熱伝導性シートやグリースなどを介し隙間なく接していることが好ましい。窓部107は公知の透明樹脂や光学ガラスなどを用いることが出来、平板状であっても曲面を有していてもよい。
上記半導体発光装置1Cの各部の形状は図に示す限りではなく、曲面部を有していたり必要に応じ調光装置や回路保護装置など付属の装置がついていても良い。
本発明の半導体発光装置パッケージは、可視光のみならず、紫色よりも短い波長の近紫外光、紫外光についても高反射率を維持することができることが特徴である。波長360、400および460nmの光の反射率が、それぞれ通常60%以上、好ましくは80%以上、更に好ましくは90%以上である。紫外光領域から可視光領域まで高反射率を有する本発明の樹脂成形体を備えた半導体発光装置パッケージは、従来の半導体発光装置パッケージに認められないきわめて優れた特性を有する。特にポリシロキサン等の樹脂製の半導体発光装置パッケージにおいては、これまで当業者が容易に想到できなかった特性であり、技術的意義が極めて高い。
本発明の半導体発光装置パッケージは、通常、チップ装着面と前記チップ装着面と反対側に底面を有する。この場合、前記チップ装着面と底面の間の距離、すなわち半導体発光装置パッケージの厚みは、通常100μm以上、好ましくは200μm以上である。また、通常3000μm以下であり好ましくは2000μm以下である。厚みが薄すぎると底面に光が透過して反射率が低下する、パッケージの強度が不十分で取り扱い上変形する、などの問題が生じるおそれがあり、厚すぎるとパッケージ自体も厚く嵩高くなるため、半導体発光装置の適用用途が限られる。
[ポリオルガノシロキサン(1)の合成]
ビニル基含有ポリジメチルシロキサン(ビニル基:1.2mmol/g含有、シリカ微粒子を添加して粘度を1000mPa・sに調整したもの。また、白金錯体触媒6.8ppmを含有。)とヒドロシリル基含有ポリジメチルシロキサン(ビニル基:0.3mmol/g含有、ヒドロシリル基:1.8mmol/g含有、シリカ微粒子を添加して粘度を2100mPa・sに調整したもの。)とを1:1で混合し、粘度1500mPa・s、白金濃度3.4ppmの液状熱硬化性ポリオルガノシロキサン(1)を得た。
なお、シリカ微粒子は、(E)流動性調整剤に相当し、上記の粘度となるようにポリオルガノシロキサン:シリカ微粒子(重量比)が、80:20から、89.5:10.5となるように添加した。
ビニル基含有ポリジメチルシロキサン(ビニル基:0.3mmol/g含有、粘度3500mPa・s。白金錯体触媒8ppm含有。)と、ヒドロシリル基含有ポリジメチルシロキサン(ビニル基:0.1mmol/g含有、ヒドロシリル基:4.6mmol/g含有、粘度600mPa・s)と、硬化遅延成分((D)硬化速度制御剤)含有ポリジメチルシロキサン(ビニル基:0.2mmol/g含有、ヒドロシリル基:0.1mmol/g含有、アルキニル基:0.2mmol/g含有、500mPa・s)とを、100:10:5で混合し、白金濃度7ppmの液状熱硬化性ポリオルガノシロキサン(2)を得た。
なお、この液状熱硬化性ポリオルガノシロキサン(2)の屈折率は、1.41であった。
(A)上記で得られた液状熱硬化性ポリオルガノシロキサン(1)、(B)白色顔料(後掲の表1参照)、(E)流動性調整剤としてシリカ微粒子「AEROSIL RX200」(比表面積140m2/g)を表2に示す重量比で配合し、攪拌により白色顔料とシリカ微粒子を前記(1)に分散させ、白色の樹脂成形体用材料を得た。これらの材料を、熱プレス機にて180℃、10kg/cm2、硬化時間240秒の条件で硬化させ、直径13mmの円形の試験片(テストピース)を得た。なお、各試験片の厚みは、表2に記載の通りである。
実施例で用いた白色顔料(アルミナ粉体)のSEM観察により一次粒子径を計測した。粒子径にばらつきがある場合は、数点(例えば10点)をSEM観察し、その平均値を粒子径としてもとめた。特にばらつきが大きく、例えば、極微量含まれる微小粒子や粗大粒子を除き、小粒径と大粒径の差が5倍程度以上あるような場合には、その最大値および最小値を記録した。また、長軸長さ(最大長径)と短軸長さ(長径に垂直方向で最も長い部分の長さ)も計測し、一次粒子径については長軸の長さを採用し、長軸長さ(最大長径)を短軸長さ(長径に垂直方向で最も長い部分の長さ)で除した値をアスペクト比とした。結果を表1に示す。
10~20mgの白色顔料(アルミナ粉体)に0.2%のポリリン酸ナトリウム水溶液10gを加え、超音波振動でアルミナを分散させた。この分散液を用いて白色顔料の二次粒子の体積基準の中心粒径D50を日機装株式会社製 マイクロトラックMT3000IIにて測定した。なお、中心粒径D50は、積算%の体積基準粒度分布曲線が50%の横軸と交差するポイントの粒子径を言う。結果を表1に示す。
PANalytical社製 X´Pert Pro MPDにてアルミナ粉体のX線回折測定を行ない、結晶系を求めた。さらに、α-アルミナについては(113)結晶子サイズをScherrerの式より算出した。
白色顔料として、表2に記載のものを用い、(A)液状熱硬化性ポリオルガノシロキサン(1)又は(2)、(B)白色顔料、(E)流動性調整剤としてシリカ微粒子「AEROSIL RX200」の配合を表2に示す重量比で配合したこと以外は、実施例1と同様の条件で、表2に記載の厚さの試験片を得た。
なお、表2において、白色顔料A~Jは、表1に記載のものである。
上記実施例1~9および比較例1~7の各試験片について、コニカミノルタ社製SPECTROPHOTOMETER CM-2600dを用いて測定径6mmにて360nmから740nmの波長における反射率を測定した。結果を表3、および図4に示す。なお、実施例2、実施例9及び比較例5の各試験片については、試験片が極端に薄い場合の反射率も併せて測定した。
また、試験片の厚み120μmでの460nm光の反射率は、実施例2、9では比較例5に比べて高く、薄い材料でも比較的高い反射率を維持した。特にアルミナにチタニアを配合した実施例9では、試験片の厚みを薄くしたときの反射率の低下が小さいことが判明した。
実施例1~7、比較例2、比較例4、比較例5、及び比較例6の各樹脂成形体用材料について、レオメトリクス社製RMS-800にてパラレルプレートを用い、測定温度25℃で粘度測定を行った。
その結果を表4、および図5に示す。実施例1~7の何れの材料も、25℃における剪断速度1s-1および100s-1での粘度、並びにその傾きが樹脂成形体の成形に適していることがわかる。一方比較例では、粘度の値が実施例と大きくことなることがわかる。なお、比較例6では粘度が高すぎて、パラレルプレートとサンプル間ですべりが生じ、正確な測定ができなかった。
実施例3の材料を用いて、全面銀メッキした銅リードフレームと共に液状射出成形により半導体発光装置用パッケージを成形した。該パッケージは、樹脂部が縦3.2mm×横2.7mm×高さ1.4mm、開口部の直径2.4mmの凹部を有するカップ状の表面実装型パッケージであった。成形は金型温度170℃、硬化時間20秒の条件で行った。成形したパッケージを観察したところ、バリの発生はなく、ショートモールドの無いパッケージであった。
実施例3の材料を用いて、全面銀メッキした銅リードフレームと共に液状射出成形により半導体発光装置用パッケージを成形した。該パッケージは、縦5mm×横5mm×高さ1.5mm、開口部の直径3.6mmの凹部を有するカップ状の表面実装型パッケージであった。成形は金型150℃、硬化時間180秒の条件で行った。成形したパッケージを液体窒素で凍結した状態でミクロトームにより切削し、パッケージ断面のSEM観察を行った。断面に露出したアルミナの一次粒子径は0.3μm、一次粒子のアスペクト比は1.42であった。
2 樹脂成形体
3 ボンディングワイヤ
4 封止材
5 リードフレーム
1C 半導体発光装置
101 筐体
102 リフレクター部
103 光源部
104 ヒートシンク
105 発光部
106 配線基板
107 窓部
200 従来型半導体発光装置
201 樹脂成形体
202 半導体発光素子
203 封止材
204 リードフレーム
Claims (16)
- (A)ポリオルガノシロキサン、(B)白色顔料、および(C)硬化触媒を含有し、前記(B)白色顔料が、以下の特性(a)および(b)を有することを特徴とする、半導体発光装置用樹脂成形体用材料。
(a)一次粒子のアスペクト比が1.2以上4.0以下であること
(b)一次粒子径が0.1μm以上2.0μm以下であること - 前記(B)白色顔料の二次粒子の中心粒径が0.2μm以上5μm以下であることを特徴とする、請求項1に記載の樹脂成形体用材料。
- 25℃における剪断速度100s-1での粘度が10Pa・s以上10,000Pa・s以下であることを特徴とする、請求項1または請求項2に記載の樹脂成形体用材料。
- 剪断速度100s-1での粘度に対する剪断速度1s-1での粘度の比が15以上であることを特徴とする、請求項3に記載の樹脂成形体用材料。
- 前記(B)白色顔料がアルミナであることを特徴とする、請求項1~4のいずれか一項に記載の樹脂成形体用材料。
- 前記(B)白色顔料の一次粒子径xと二次粒子の中心粒径yの比y/xが1以上10以下であることを特徴とする、請求項1~5の何れか一項に記載の樹脂成形体用材料。
- (A)ポリオルガノシロキサンが、常温、常圧下で液体の熱硬化性ポリオルガノシロキサンであることを特徴とする、請求項1~6の何れか一項に記載の樹脂成形体用材料。
- さらに(D)硬化速度制御剤を含有する、請求項1~7の何れか一項に記載の樹脂成形体用材料。
- さらに(E)流動性調整剤を含有することを特徴とする、請求項1~8のいずれか1項に記載の樹脂成形体用材料。
- 樹脂成形体用材料全体に対する、(B)白色顔料及び(E)流動性調整剤の含有量の合計が、50重量%以上であることを特徴とする、請求項9に記載の樹脂成形体用材料。
- 請求項1~10の何れか一項に記載の樹脂成形体用材料を成形してなる半導体発光装置用樹脂成形体。
- 厚さ0.4mmにおいて、波長400nmにおける光反射率が60%以上であることを特徴とする、請求項11に記載の樹脂成形体。
- 前記樹脂成形体が液状射出成形により成形されたことを特徴とする、請求項11または12に記載の樹脂成形体。
- 請求項1~10のいずれか一項に記載の樹脂成形体用材料を調製する工程、及び前記調製された樹脂成形体用材料を射出成形により成形する工程、を含む樹脂成形体の製造方法。
- 請求項11~13のいずれか一項に記載の樹脂成形体を有する半導体発光装置。
- (A)ポリオルガノシロキサン、(B)白色顔料、および(C)硬化触媒を含有し、
25℃における剪断速度100s-1での粘度が10Pa・s以上10,000Pa・s以下であり、かつ、
剪断速度100s-1での粘度に対する剪断速度1s-1での粘度の比が15以上であることを特徴とする、半導体発光装置用樹脂成形体用材料。
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Also Published As
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US20120286220A1 (en) | 2012-11-15 |
KR101720822B1 (ko) | 2017-03-28 |
TWI488891B (zh) | 2015-06-21 |
JP2016130321A (ja) | 2016-07-21 |
JP2016076724A (ja) | 2016-05-12 |
JP6217831B2 (ja) | 2017-10-25 |
TW201130891A (en) | 2011-09-16 |
US9105822B2 (en) | 2015-08-11 |
KR20120114290A (ko) | 2012-10-16 |
JP6066002B2 (ja) | 2017-01-25 |
JP2017043780A (ja) | 2017-03-02 |
US20140091266A1 (en) | 2014-04-03 |
JP5857746B2 (ja) | 2016-02-10 |
JPWO2011078239A1 (ja) | 2013-05-09 |
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