WO2013025832A1 - Réflecteur pour diode électroluminescente et logement associé - Google Patents
Réflecteur pour diode électroluminescente et logement associé Download PDFInfo
- Publication number
- WO2013025832A1 WO2013025832A1 PCT/US2012/050989 US2012050989W WO2013025832A1 WO 2013025832 A1 WO2013025832 A1 WO 2013025832A1 US 2012050989 W US2012050989 W US 2012050989W WO 2013025832 A1 WO2013025832 A1 WO 2013025832A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reflector
- light
- filler
- emitting diode
- fluororesin
- Prior art date
Links
- 239000000945 filler Substances 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000000465 moulding Methods 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 100
- 239000004408 titanium dioxide Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 40
- 229920001577 copolymer Polymers 0.000 claims description 26
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 15
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 15
- 239000002318 adhesion promoter Substances 0.000 claims description 11
- -1 hexafluoropropylene, chlorotrifluoroethylene Chemical group 0.000 claims description 11
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000565 sealant Substances 0.000 abstract description 16
- 229920001296 polysiloxane Polymers 0.000 abstract description 10
- 230000001747 exhibiting effect Effects 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 238000000748 compression moulding Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- 239000000155 melt Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004954 Polyphthalamide Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920006375 polyphtalamide Polymers 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 150000002484 inorganic compounds Chemical group 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000004956 Amodel Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000002845 discoloration Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000004590 silicone sealant Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
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- 229920001721 polyimide Polymers 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0808—Mirrors having a single reflecting layer
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a reflector for a light-emitting diode that has excellent heat resistance, UV stability, weather resistance, adhesivity to sealant, and has high reflectance of 85% or higher in the 400 nm to 700 nm wavelength range.
- the present invention further relates to an LED housing containing this reflector.
- Light-emitting diodes are compact and can be used for lighting for longer periods of time than filament bulbs, and are highly efficient in transforming electrical energy.
- LEDs are widely utilized for home electric appliances, LED indicators, and illuminated operation switches.
- LEDs are divided into general (visible wavelength) LEDs and ultraviolet LEDs according to the wavelengths used.
- LEDs includes automobile dashboards, backlighting of display units of display devices (LCD displays, personal computer monitors, compact game devices, and portable telephone units), indoor illumination sources, indoor/outdoor display devices, and traffic display devices, for example.
- display devices LCD displays, personal computer monitors, compact game devices, and portable telephone units
- indoor illumination sources indoor/outdoor display devices
- traffic display devices for example.
- white LEDs combined with a fluorescent material for achieving a high level of color rendering property include: banknote identifying devices (light sources for banknote
- identifying sensors air cleaners utilizing photocatalysts (for households, vehicles, refrigerators); contaminant treatments; fluorescent light sources for biological, medical, and analytical applications in the medical field; sterilization and retention of freshness of vegetables and food items in the foodstuff field; UV-setting light sources for electronic parts/inks; medical apparatuses; fluorescent-acryl-based illumination; UV light source motors; light sources for ultraviolet actinometers, spectroanalyses, and excitation of fluorescent agents; and sterilization light sources for medical
- a conventional light-emitting device in which an LED chip is mounted is generally provided with a reflector (3) having a concave aperture part, a LED chip (2) mounted in the concave aperture part, and a curing resin mold (1 ) for sealing the aforementioned concave aperture part.
- the reflector is mounted on a substrate to form a housing (5).
- the reflector is a molded product that is obtained by, for example, molding ceramic or white reflecting resin.
- Japanese patent no. 4576276 describes an LED housing formed of a porous alumina ceramic.
- the porous alumina ceramic has excellent heat resistance, UV light stability, and weather resistance and can obtain high reflectance by controlling the pore diameter and the porosity.
- the manufacture cost was high, and the productivity was poor.
- thermoplastic resins have been used to lower the manufacture cost of the LED housing.
- certain polyamide group resins do not melt even at 300°C.
- Comparative example 1 because rutile-type titanium dioxide used as a filler has a refractive index of 2.7, it exhibits a high reflectance in the visible wavelength range, but its reflectance drops when the wavelength is 430 nm or less. Rutile-type titanium dioxide has a 3.0-eV band gap, and according to J. Phys. Chem. B, Vol. 107, pp. 5709-5716 (2003), this is believed to result in low reflectance at wavelengths of 430 nm or less. In addition, transformation of absorbed energy into heat and a photocatalytic action of the titanium dioxide are considered responsible for the progressive deterioration of the resin.
- Fluororesins for example, such as polytetrafluoroethylene
- PTFE tetrafluoroethylene-perfluoro(alkoxy vinyl ether) copolymer
- PFA tetrafluoroethylene-perfluoro(alkoxy vinyl ether) copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- tetrafluoroethylene-hexafluoropropylene-perfluoro(alkoxy vinyl ether) copolymer are widely utilized for piping for transporting acidic and alkaline chemical solutions, solvents, and paints; such chemical industrial products as containers and tanks for storing chemical solutions; and such electrical industrial products as tubes, rollers, and electric wires due to their excellent characteristics such as heat resistance, light resistance, weather resistance, chemical resistance, high-frequency electric characteristics, and flame resistance. As such, they are considered for use as LED reflector resins.
- an LED reflector and a housing containing said reflector that achieve a high reflectance with little drop in reflectance in the 400 nm to 700 nm wavelength range while exhibiting excellent heat resistance, light resistance, weather resistance, and adhesivity to a sealant is in demand.
- the purpose of the present invention is to provide a reflector and a housing for an LED that achieves a high reflectance with little drop in reflectance in the 400 nm to 700 nm wavelength range while exhibiting excellent heat resistance, UV light stability, weather resistance, and adhesivity to sealants.
- the present invention provides a reflector for a light-emitting diode that is obtained by molding a fluororesin containing a filler having an average particle size less than 1 .0 ⁇ and a band gap greater than 3.0 Ev.
- the difference between the maximum value and the minimum value of the reflectance of the reflector in the 380 nm to 400 nm wavelength range is in excess of 25%.
- the reflectance of the reflector over the wavelength range of 400 nm to 700 nm is 85% or greater.
- the fluororesin is a homopolymer of tetrafluoroethylene or a copolymer comprising tetrafluoroethylene and at least one monomer selected from the group consisting of hexafluoropropylene, chlorotrifluoroethylene, perfluoro(a!koxy vinyl ether), vinyiidene fluoride, vinyl fluoride, ethylene, and propylene.
- the filler has a refractive index of 1 .5 or greater. In one embodiment of the reflector for a light-emitting diode, the filler has an average particles size greater than 0.01 ⁇ but less than 1 .0 ⁇ .
- the filler is at least one selected from the group consisting of metal oxide and metal sulfide.
- the filler is selected from the group consisting of anatase-type titanium dioxide, tin dioxide, niobium pentoxide, and zinc sulfide.
- the amount of filler is 0.1 to 50 weight percent based on the combined weights of said filler and said fluororesin.
- the fluororesin composition further comprises an adhesion promoter.
- the present invention provides a housing containing the above described reflector for a light-emitting diode.
- the present invention provides a molded article containing a fluororesin and a filler having an average particle size less than 1 .0 ⁇ and a band gap greater than 3.0 eV.
- the present invention provides a molded article that is obtained by molding a fluororesin containing a filler having an average particle size less than 1 .0 ⁇ and a band gap greater than 3.0 eV.
- an LED reflector and a housing containing said reflector that achieve a high reflectance with little drop in reflectance in the 400 nm to 700 nm wavelength range while exhibiting excellent heat resistance, UV light stability, weather resistance, and adhesivity to a sealant are provided.
- the present reflector provides a high reflectance of 85% or higher in the 400 nm to 700 nm wavelength range.
- a filler having an average particle size less than 1 .0 ⁇ is dispersed evenly inside the reflector of the present invention, the reflectance is higher than ever can be achieved using a smaller amount of filler.
- Figure 1 is a schematic diagram showing the housing having the reflector for LED.
- 1 is the sealant
- 2 is the LED chip
- 3 is the reflector
- 4 is the substrate
- 5 is the housing.
- Figure 2 is a schematic diagram showing the reflector for LED in a tape configuration.
- 1 is the sealant
- 2 is the LED chip
- 3 is the reflector
- 4 is the substrate
- 6 is the gap.
- Figure 3 is a graph showing the wavelength dependency of the reflectance of molded products over the wavelength range of 350 nm to 450 nm.
- Figure 4 is a graph showing the wavelength dependency of the reflectance of molded products over the wavelength range of 350 nm to 700 nm.
- Figure 5 is a photo obtained using an electron microscope of a fracture cross-section of the fluororesin composition of Application
- Figure 6 is a photo obtained using an electron microscope of a fracture cross-section of the fluororesin composition of Comparative Example 2.
- the fluororesin used in the present invention is a homopolymer of tetrafluoroethylene (TFE), in another embodiment the fluororesin is a copolymer (TFE copolymer) that comprises TFE and at least one kind of monomer (comonomer) copolymerizable with TFE.
- TFE copolymer a copolymer that comprises TFE and at least one kind of monomer (comonomer) copolymerizable with TFE.
- Fluororesin may be used alone or as a mixture comprising two or more fluororesins.
- the comonomer is contained in the polymer at least in such a sufficient amount that the melting point of the fluororesin becomes substantially lower than the melting point of the TFE homopolymer (poly tetrafluoroethylene (PTFE)).
- Fluororesin used in the present invention is preferably a melt-moldable fluororesin.
- Melt molding refers to a molding method that utilizes a known conventional melt molding device; whereby, a molded product, for example, a film, fibers, or a tube, having sufficient levels of strength and durability to suit an intended purpose can be created from a molten substance by letting the polymer flow in its molten state.
- the melt-moldable fluororesin used in the present invention is a copolymer comprising 40-98% of repeat unit arising from TFE and 2 to 60 mol% of comonomer that is copolymerizable with TFE.
- comonomers include hexafluoropropylene (HFP), chlorotrifluoroethylene, perfluoroalkoxytrifluoroethylene, vinylidene fluoride, vinyl fluoride, ethylene, and propylene.
- perfluoro(alkyl vinyl ether) having 1 to 6 carbon atoms are of utility as perfluoroalkoxytrifluoroethylenes.
- perfluoro(alkyl vinyl ether) (PAVE) alkyl group has 1 to 5 carbon atoms, preferably, linear or branched alkyl group having 1 to 4 carbon atoms.
- the TFE copolymer may be a copolymer comprising multiple kinds of PAVE monomers and TFE. The amount of repeating units arising from PAVE in the TFE/PAVE copolymer is from 1 to 20 wt%.
- Example fluororesins include FEP (TFE-HFP copolymer), PFA (TFE-PAVE copolymer), TFE-HFP-PAVE copolymer wherein the PAVE comprises perfluoro(ethy! vinyl ether) (PEVE) and/or peril uoro(propyi vinyl ether), MFA (TFE-perfluoro(methyl vinyl ether)), (PMVE)-PAVE copolymer wherein the alkyl group of the PAVE has 2 or more carbon atoms, and THV (TFE-HFP-vinylidene fluoride (VF2) copolymer.
- PFA (TFE-PAVE copolymer) is preferred.
- Fluororesin can include one of the
- TFE copolymers alone or a mixture comprising two or more such TFE copolymers.
- a single TFE copolymer or two or more kinds of TFE copolymer can be mixed with a TFE homopolymer.
- the TFE copolymer used in the present invention has a melt flow rate (MFR) of approximately 0.5 to 100 g/10 min., preferably, 0.5 to 50 g/10 min., when measured at the standard temperature of the specific TFE copolymer in accordance with ASTM D-1238.
- MFR melt flow rate
- the melt viscosity of the TFE copolymer used in the present invention is at least 10 2 Pa s, preferably 10 2 Pa s to 10 6 Pa s, and more preferably from 10 3 Pa s to 10 5 Pa s.
- the content of the TFE copolymer in the fluororesin composition is 50-99.9 wt%, preferably, 60-99 wt%, or more preferably, 70-95 wt%.
- melt- moldable fluororesin There is no special restriction imposed on the form of the melt- moldable fluororesin as long as it is suitable for melt molding; and a wide variety of forms, such as powder, a granular product of powder, flakes, pellets, and beads, are of utility.
- the filler used in the present invention having an average particle size less than 1 .0 ⁇ is a light-reflecting compound that has a high refractive index and a high reflectance in the 400 nm to 700 nm
- This light-reflecting compound has an average particle size less than 1 .0 ⁇ , preferably, greater than 0.01 ⁇ but less than 1 .0 ⁇ , more preferably, greater than 0.1 ⁇ but less than 1 .0 ⁇ , or even more preferably, greater than 0.2 ⁇ but less than 1 .0 ⁇ . It is not desirable for the average particle size of the light-reflecting compound to be 1 .0 ⁇ or greater because the light scattering effect is diminished and the reflectance drops.
- the average particle diameter for example, can be measured by particle size analyzer (for example, made by CILAS Co., CILAS 990, CILAS 1090, and CILAS 1 190) according to the procedure of ISO 13320.
- the filler used in the present invention has a band gap in excess of
- the band gap can be measured, for example, using a UV-3101 PC recording spectrophotometer manufactured by Shimadzu Corporation, in accordance with the method described in Band Gap of Anatase T1O2 3.27 eV in Journal of Molecular Catalysis A Chemical 338, 18 (201 1 ).
- the filler used in the present invention has a refractive index of 1 .5 or greater, preferably 2.0 or greater. It is not desirable for the refractive index to be lower than 1 .5 because a high reflectance can not be achieved.
- Examples of fillers used in the present invention include metal oxides and metal sulfides. Metal oxides are preferred.
- Example fillers include: anatase-type titanium dioxide ( ⁇ 2, reflectance: 2.5; band gap: 3.27 eV), tin dioxide (SnO2, reflectance: 2.0; band gap: 3.8eV), niobium pentoxide (Nb 2 O 5 , reflectance: 2.3; band gap: 3.4eV), zinc oxide (ZnO, reflectance: 2.0; band gap: 3.3eV) and zinc sulfide (ZnS, reflectance: 2.37; band gap: 3.6eV).
- Anatase-type titanium dioxide is preferred and available commercially, for example, TA-300 manufactured by Fuji Titanium Industry Co., Ltd.
- the dispersed condition of the filler in the molded product can be observed using a field-emission-type scanning electron microscope, for example, and S-4500 SEM manufactured by Hitachi, Ltd.
- the amount of filler in the fluororesin composition is from 0.1 to 50 weight percent, preferably from 1 to 40 weight percent, and more preferably from 5 to 30 weight percent, based on the combined weight of filler and fluororesin. It is not desirable for the filler to be less than 0.1 wt% because the reflectance of the obtained reflector is poor. Also, it is not desirable for the amount of filler to exceed 50 wt% because injection molding of the fluororesin composition becomes difficult due to its high melt viscosity, and the strength and the durability of the obtained molded product will deteriorate.
- the fluororesin of the present invention optionally further contains an adhesion promoter for the purpose of improving the adhesivity of the fluororesin composition to an LED sealant such as silicone, epoxy resin, or a mixture of these materials.
- an adhesion promoter for the purpose of improving the adhesivity of the fluororesin composition to an LED sealant such as silicone, epoxy resin, or a mixture of these materials.
- the adhesion promoter is an inorganic compound or an organic polymer.
- the inorganic compound is hydrophilic in order to enhance the wettability of the fluororesin
- the surface of the inorganic compound adhesion promoters can also include functional groups such as hydroxyl groups, vinyl groups, or silane groups (e.g., from silane coupling agents) that promote bonding with silicone or epoxy during curing.
- Alumina is an example of an inorganic compound type adhesion promoter.
- the organic polymer can be any polymer that shows high thermal resistance and adhesion to sealant such as silicone or epoxy.
- Example such polymers include thermal resistant silicone powder, or polar polymers such as polyimide, Nafion®, PEI (polyetherimide), PES (polyethersulfone), and the like.
- the amount of adhesion promoter in the fluororesin composition is from 0.1 to 20 weight percent, preferably from 0.5 to 10 weight percent, and more preferably from 1 to 5 weight percent, based on the combined weights of fluororesin, filler and adhesion promoter.
- alumina is used as the adhesion promoter, if the alumina is less than 0.1 weight percent, a sufficient level of adhesivity of the fluororesin to the sealant can not be achieved. It is not desirable for the alumina to exceed 20 weight percent because the reflectance of the obtained reflector will decrease.
- the fluororesin and the filler may be mixed either before the melt molding or simultaneously with the melt molding.
- a commonly utilized mixing method can be used as a method for mixing them; and a known conventional disperser/blender, for example, a co-coagulation method as disclosed in Japanese Kokai Patent Application No. 2007- 1 19769, a planetary mixer, a high-speed impeller disperser, a rotary drum- type mixer, a screw-type mixer, a belt conveyor mixing method, a ball mill, a pebble mill, a sand mill, a roll mill, an attritor, and a bead mill, may be utilized for this purpose.
- a device that is capable of evenly dispersing the fluororesin and the filler is preferred.
- the fluororesin composition obtained by mixing the fluororesin and the filler before the melt molding may take a variety of forms, for example, a powdery material, a granular product of a powdery material, flakes, pellets, and beads.
- a wet mixing of the kind described below is also of utility.
- a fluororesin coated with a filler can be obtained by dissolving a filler into an aqueous solution or an organic solvent functioning as a carrier and then spraying the filler solution onto a fluororesin.
- light drying is desirable in order to let the aforementioned aqueous solution or the organic solvent to evaporate.
- methanol, ethanol, chloroform, and toluene for example, are of utility.
- an organic solvent that allows the filler to be dissolved easily is desirable.
- Any known conventional molding method may be used as a method for melt-molding the fluororesin composition.
- Compression molding, extrusion molding, transfer molding, flow molding, injection molding, rotational molding, lining molding, foam extrusion molding, and film molding, are of utility. Extrusion molding and injection molding are preferred.
- the molded product obtained through the aforementioned melt molding method has a high reflectance with little drop in reflectance in the 400 nm to 700 nm wavelength range, and exhibits excellent heat resistance, UV light stability, and weather resistance.
- the molded product exhibits a reflectance of 85% or higher in the 400 nm to 700 nm
- the reflector and therefor a light-emitting diode housing utilizing the reflector achieves a high reflectance of 85% or higher in the 400 nm to 700 nm wavelength range while exhibiting excellent heat resistance, US light stability, and weather resistance.
- Reflectances of the molded products shown in Figure 3 in the 350 nm to 700 nm wavelength range can be obtained by measuring
- a single layer of said reflector can be utilized also as a cover layer equipped with insulating, adhering, and reflecting functions in addition to the concave-shaped reflector shown in Figure 1 .
- the housing of the present invention refers to a housing wherein a reflector mounted with an LED chip is attached to a substrate.
- the LED chip is sealed off using a sealant.
- a differential scanning calorimeter (Pyris 1 Type DSC manufactured by PerkinElmer, Inc.) was used. After approximately 10 mg of sample was weighed, put in a special aluminum pan, and crimped using a special crimper, the sample was placed in a DSC body and heated to 360 ° C from 150 ° C at the rate of 10 ° C/min. Its peak melting point (Tm) was obtained based on a melting curve obtained then.
- a melt indexer equipped with a corrosion-resistant cylinder, a die, and a piston in compliance with D-1238-95 (manufactured by Toyo Seiki Co., Ltd.) was used. After 5 g of sample powders were filled in the cylinder that was maintained at 372 ⁇ 1 ° C and held for 5 minutes, they were extruded through a die orifice under the load of 5 kg (the piston and a weight); and the extrusion rate then (g/10 min.) was obtained as an MFR.
- Reflectance of an approximately 1 .5-mm thick sample produced by means of melt compression molding was measured under the following condition.
- a method in which light having a wavelength of 350 nm-700 nm was emitted to the reflective layer formed on the front surface of a sample at an incident angle of 10 ° , and the transmitted light was let go without providing any reflector on the back surface of the sample was used.
- a spectral reflectance relative reflectance in contrast to a standard white board
- a spectrophotometer having an integrating sphere mounted on a detector (U-4500 manufactured by Hitachi, Ltd.).
- a fluororesin and a filler were melt-blended according to the composition shown in Table 1 at 350 ° C, which was approximately 40 ° C higher than the melting point (approximately 308 ° C) of the fluororesin, at 100 rpm for 5 minutes using a melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a melt blender
- Shear/bonding strength was measured (25 ° C, tension speed of
- Niobium pentoxide Nb 2 O 5 powder from Kojundo Chemical Lab. Co., Ltd. (Average particle size 0.4 ⁇ )
- Rutile-type titanium dioxide Rutile-type titanium dioxide.
- Ti-Pure registered trademark
- R-900 manufactured by E. I. DuPont de Nemours and Company (Average particle size 0.41 ⁇ )
- Adhesion promoter a-alumina. A31 manufactured by Nippon Light Metal Co., Ltd.; average particle size 5.2 ⁇
- LED sealant Silicone. ASP-1010 (A B) manufactured by
- anatase-type titanium dioxide (TA-300 manufactured by Fuji Titanium Industry Co., Ltd) and 150 ml of pure water were put into a beaker (2L) and stirred at 150 rpm for 10 minutes using the downflow propeller-type 4-blade mixer. Then, 372.9 g of PFA aqueous dispersion obtained by means of emulsion polymerization was added so that the titanium dioxide content became 15 wt% with respect to
- anatase-type titanium dioxide (TA-300 manufactured by Fuji Titanium Industry Co., Ltd) and 200 ml of pure water were put into a beaker (2L) and stirred at 150 rpm for 10 minutes using the downflow propeller-type 4-blade mixer. Then, 372.9 g of PFA aqueous dispersion obtained by means of emulsion polymerization was added such that the titanium dioxide content became 20 wt% with respect to
- Niobium pentoxide particles (Nb 2 O 5 powder from Kojundo Chemical Lab. Co., Ltd.) and fluororesin PFA (PFA440HPJ manufactured by DuPont-Mitsui Fluorochemical Co., Ltd.) were melt-blended according to the composition shown in Table 1 at 350 ° C and 100 rpm for 5 minutes using the melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a fluororesin composition.
- the melt blender KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.
- the niobium pentoxide particles were found to be dispersed evenly.
- reflectances of an approximately 1 .5-mm thick sample which was produced from the fluororesin at 350 ° C by means of melt compression molding, were measured. The results obtained are summarized in Table 1 .
- Zinc dioxide particles (FINEX-30 powder manufactured by Sakai Chemical Industry Co., Ltd.) and fluororesin PFA (PFA440HPJ manufactured by DuPont-Mitsui Fluorochemical Co., Ltd.) were melt- blended according to the composition shown in Table 1 at 350 ° C and 100 rpm for 5 minutes using the melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a fluororesin composition. When the dispersion state of the zinc dioxide particles was checked in a fracture cross-section of the obtained fluororesin composition using an electron microscope, the zinc dioxide particles were found to be dispersed evenly. Also, reflectances of an approximately 1 .5-mm thick sample, which was produced from the fluororesin at 350 ° C by means of melt compression molding, were measured. The results obtained are summarized in Table 1 .
- a-alumina (A31 manufactured by Nippon Light Metal Co., Ltd.) was added to the complex composition obtained in Application example 3 until the alumina content became 1 wt% with respect to fluororesin PFA and melt-blended at 350 ° C and 100 rpm for 5 minutes using the melt blender (KF-70V compact segment mixer manufactured by Toyo Seiki Co., Ltd.) in order to obtain a fluororesin composition.
- Rutile-type titanium dioxide Ti-Pure® R-900 manufactured by E. I. DuPont de Nemours and Company
- fluororesin PFA fluororesin
- Comparative Example 2 After anatase-type titanium dioxide (TA-300 manufactured by Fuji Titanium Industry Co., Ltd.) and fluororesin PFA (PFA440HPJ manufactured by DuPont-Mitsui Fluorochemical Co., Ltd.) were put in a polyester bag and shaken for 5 minutes, and a sheet was created from the mixture by means of melt compression molding at 350 ° C, this sheet was cut into small pieces, and the same melt compression molding was carried out again in order to create an approximately 1 .5-mm thick sample.
- TA-300 manufactured by Fuji Titanium Industry Co., Ltd.
- fluororesin PFA PFA440HPJ manufactured by DuPont-Mitsui Fluorochemical Co., Ltd.
- the present invention involves dispersing the anatase-type titanium dioxide evenly in its primary particle state such as by applying a shearing force during the melt blending, thereby resulting in high levels of reflection in the 400 nm-700 nm wavelength range.
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Abstract
L'invention concerne un réflecteur pour une diode électroluminescente, ainsi qu'un logement contenant ce réflecteur. Le réflecteur selon l'invention permet d'obtenir une réflectance élevée présentant une faible baisse sur la gamme de longueurs d'onde comprise entre 400 nm et 700 nm et il présente d'excellentes résistance thermique, stabilité aux rayons UV, résistance aux intempéries et adhésivité à des produits de scellement à base de silicone et d'époxy. Ledit réflecteur est obtenu par moulage d'une fluororésine contenant une charge présentant une taille moyenne de particules inférieure à 1 µm et une largeur de bande interdite supérieure à 3 eV. Le réflecteur selon l'invention présente une réflectance de 85% ou supérieure sur la gamme de longueurs d'onde comprise entre 400 nm et 700 nm.
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WO2017148905A1 (fr) * | 2016-03-04 | 2017-09-08 | Solvay Specialty Polymers Italy S.P.A. | Composition de fluoropolymère pour composants d'appareils électroluminescents |
US9899579B2 (en) | 2013-11-07 | 2018-02-20 | Koninklijke Philips N.V. | Substrate for LED with total-internal reflection layer surrounding LED |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US9899579B2 (en) | 2013-11-07 | 2018-02-20 | Koninklijke Philips N.V. | Substrate for LED with total-internal reflection layer surrounding LED |
WO2017148905A1 (fr) * | 2016-03-04 | 2017-09-08 | Solvay Specialty Polymers Italy S.P.A. | Composition de fluoropolymère pour composants d'appareils électroluminescents |
KR20180120723A (ko) * | 2016-03-04 | 2018-11-06 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 발광 장치의 구성요소용 플루오로중합체 조성물 |
CN108779288A (zh) * | 2016-03-04 | 2018-11-09 | 索尔维特殊聚合物意大利有限公司 | 用于发光装置的部件的氟聚合物组合物 |
CN108779288B (zh) * | 2016-03-04 | 2021-11-16 | 索尔维特殊聚合物意大利有限公司 | 用于发光装置的部件的氟聚合物组合物 |
US11427662B2 (en) | 2016-03-04 | 2022-08-30 | Solvay Specialty Polymers Italy S.P.A. | Fluoropolymer composition for components of light emitting apparatuses |
KR102665124B1 (ko) | 2016-03-04 | 2024-05-14 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 발광 장치의 구성요소용 플루오로중합체 조성물 |
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