WO2017209172A1 - Composition de polyester pour plaques réfléchissantes à del, plaques réfléchissantes à del et dispositif émetteur de lumière comportant ladite plaque réfléchissante - Google Patents

Composition de polyester pour plaques réfléchissantes à del, plaques réfléchissantes à del et dispositif émetteur de lumière comportant ladite plaque réfléchissante Download PDF

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Publication number
WO2017209172A1
WO2017209172A1 PCT/JP2017/020208 JP2017020208W WO2017209172A1 WO 2017209172 A1 WO2017209172 A1 WO 2017209172A1 JP 2017020208 W JP2017020208 W JP 2017020208W WO 2017209172 A1 WO2017209172 A1 WO 2017209172A1
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polyester
mass
polyester composition
led
acid
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PCT/JP2017/020208
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English (en)
Japanese (ja)
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詩門 金井
宇治 重松
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株式会社クラレ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

Definitions

  • the present invention relates to a polyester composition for an LED reflector, an LED reflector made of the composition, and a light emitting device including the reflector.
  • LEDs Light emitting diodes
  • LEDs have many advantages such as low power consumption and long life compared to conventional white and fluorescent lamps, and thus are applied to various fields, such as mobile phone displays, It has been used for relatively small electrical and electronic products such as backlights for liquid crystal panels such as personal computers and liquid crystal televisions.
  • an LED package mainly includes an LED, a lead frame, a reflector that also serves as a housing, and a sealing member that seals a semiconductor light emitting element.
  • a material used for the reflector heat-resistant plastic is known.
  • Patent Document 1 discloses an LED reflector using a polyamide composition having a dicarboxylic acid unit containing a 1,4-cyclohexanedicarboxylic acid unit and a diamine unit containing an aliphatic diamine unit having 4 to 18 carbon atoms, It is described that high reflectance and whiteness are maintained even after LED light irradiation for a long period of time.
  • Patent Document 2 discloses a light-emitting diode assembly housing including a poly (1,4-cyclohexanedimethanol terephthalate) composition containing titanium dioxide, which exhibits good light reflectance, good UV resistance, It has been described that it has color stability due to.
  • the heat-resistant plastic reflector is required to have heat resistance because it is exposed to a temperature of 100 to 200 ° C. for several hours when the conductive adhesive or sealant is thermally cured during LED package manufacture. Further, it is required to maintain a high light reflectance without causing discoloration or the like due to high heat during LED package manufacture or use.
  • Patent Documents 1 and 2 there is room for improvement in the techniques of Patent Documents 1 and 2 with respect to maintaining the high light reflectance of the LED reflector in the environment during manufacture and use, particularly in a high temperature environment.
  • the present invention has a high light reflectivity, and even when exposed to heat assumed in the manufacturing process and use environment of the LED package, the light reflectivity is small and high light reflectivity. It aims at providing the polyester composition for LED reflecting plates which can maintain LED, the reflecting plate obtained by shape
  • the present inventors have found that the above-described problems can be solved by the polyester composition containing a specific inorganic phosphorus compound. That is, the present invention relates to the following [1] to [12].
  • a polyester composition for LED reflector wherein the polyester composition contains polyester (A) and titanium oxide (B), and the polyester (A) contains 50 mol% or more of terephthalic acid. And a structural unit derived from a diol containing 50 mol% or more of 1,4-cyclohexanedimethanol, and phosphoric acid, phosphate, condensed phosphoric acid, condensed phosphate, Containing one or more inorganic phosphorus compounds (C) selected from the group consisting of phosphorous acid, phosphite, hypophosphorous acid, and hypophosphite, A) The polyester composition for an LED reflector, wherein the content of the inorganic phosphorus compound (C) is 0.10 to 3.50 parts by mass with respect to 100 parts by mass.
  • the mass ratio [(D) component / (E) component] of the phenolic antioxidant (D) to the organophosphorus antioxidant (E) is 0.20 to 3.00.
  • R 11 to R 13 are each independently an alkyl group having 1 or 2 carbon atoms
  • R 14 to R 17 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Yes, * represents a bond with a phosphorus atom.
  • R 21 to R 23 are each independently an alkyl group having 1 or 2 carbon atoms
  • R 24 to R 26 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Yes, ** represents a bond.
  • Polyester composition for board. [9]
  • the polyester (A) has a structural unit derived from dicarboxylic acid containing 75 to 100 mol% of terephthalic acid and a structural unit derived from diol containing 75 to 100 mol% of 1,4-cyclohexanedimethanol.
  • An LED reflector comprising the polyester composition for LED reflectors according to any one of [1] to [10].
  • a light emitting device comprising the LED reflecting plate according to [11].
  • the present invention has a high light reflectance, and even when it is exposed to heat assumed in the manufacturing process or use environment of the LED package, the light reflectance is hardly lowered and a high light reflectance can be maintained.
  • a polyester composition for an LED reflector, a reflector obtained by molding the composition, and a light emitting device including the reflector can be provided.
  • polyester composition for LED reflector The polyester composition for LED reflector of the present invention (hereinafter also referred to as “polyester composition”) is a polyester composition for LED reflector, and the polyester composition comprises polyester (A) and titanium oxide (B). And the polyester (A) is a polyester having a structural unit derived from a dicarboxylic acid containing 50 mol% or more of terephthalic acid and a structural unit derived from a diol containing 50 mol% or more of 1,4-cyclohexanedimethanol.
  • inorganic phosphorus compounds (C) are contained, and the content of the inorganic phosphorus compound (C) with respect to 100 parts by mass of the polyester (A) is 0.10 to 3. 0 parts by mass and LED reflector for polyester compositions.
  • the polyester composition of the present invention has high light reflectivity, and even when exposed to heat assumed in the manufacturing process and use environment of the LED package, there is little decrease in light reflectivity and high light reflectivity. Can be maintained.
  • the inorganic phosphorus compound (C) stabilizes the terminal carboxy group of the polyester (A), thereby suppressing the thermal discoloration of the polyester, and as a result, reflecting light. It is thought that the decrease in rate is suppressed.
  • the said effect is hardly expressed as content of an inorganic phosphorus compound (C) is less than 0.10 mass part with respect to 100 mass parts of polyester (A).
  • the polyester composition of the present invention contains a polyester (A), and the polyester (A) contains 50 mol% of a structural unit derived from dicarboxylic acid containing 50 mol% or more of terephthalic acid and 1,4-cyclohexanedimethanol. And a structural unit derived from the diol contained above.
  • the polyester (A) By containing the polyester (A), a reflector having high heat resistance and light reflectivity, having little decrease in light reflectivity even after being exposed to heat, and maintaining a high light reflectivity is obtained. Can do.
  • the total content of the structural unit derived from the dicarboxylic acid and the structural unit derived from the diol in the polyester (A) is preferably 85 mol% or more, more preferably 90 mol%, from the viewpoint of improving heat resistance. That's it.
  • the polyester (A) will be described in more detail.
  • the polyester (A) includes a structural unit derived from dicarboxylic acid, and the content of terephthalic acid in the dicarboxylic acid is 50 mol% or more. Thereby, the heat resistance of the obtained reflecting plate improves.
  • the content of terephthalic acid units in the dicarboxylic acid is preferably 60 mol% or more, more preferably 75 mol% or more, and still more preferably 90 mol% or more.
  • the dicarboxylic acid constituting the polyester (A) may contain a dicarboxylic acid other than terephthalic acid within a range of less than 50 mol%.
  • dicarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; 1,3-cyclopentanedicarboxylic acid, 1 Cycloaliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid 1,3-phenylenedioxydiacetic acid, diphenic acid, diphenylmethane-4,4′-dicarboxylic acid
  • the polyester (A) may contain a constitutional unit derived from a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid or the like within a range where melt molding is possible.
  • the total amount of dicarboxylic acid and diol in the total amount of monomers constituting the polyester (A) is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass. % Or more, particularly preferably 100% by mass.
  • the polyester (A) contains a structural unit derived from a diol, and the content of 1,4-cyclohexanedimethanol in the diol is 50 mol% or more. This improves the moldability and heat resistance of the resulting reflector, has high light reflectivity, has little decrease in light reflectivity even after being exposed to heat, and can maintain high light reflectivity. it can.
  • the content of 1,4-cyclohexanedimethanol in the diol is preferably 60 mol% or more, more preferably 75 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less.
  • the trans isomer ratio of 1,4-cyclohexanedimethanol is preferably high.
  • the ratio of trans isomer is preferably 50 to 100% by mass, more preferably 60 to 100% by mass.
  • the diol constituting the polyester (A) may contain other diols other than 1,4-cyclohexanedimethanol within a range of less than 50 mol%.
  • examples of such other diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -Butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, Aliphatic diols such as 1,12-dodecanediol; 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohe
  • the polyester (A) may contain a structural unit derived from a trihydric or higher polyhydric alcohol such as trimethylolpropane, glycerol, pentaerythritol, or the like within a range where melt molding is possible.
  • the polyester (A) is a polycyclohexanediene having a structural unit derived from a dicarboxylic acid containing 75 to 100 mol% of terephthalic acid and a structural unit derived from a diol containing 75 to 100 mol% of 1,4-cyclohexanedimethanol. Methylene terephthalate is preferred. As a result, it is possible to obtain a reflector that has high heat resistance and light reflectivity, and has a small decrease in light reflectivity even after being exposed to heat, and maintains high light reflectivity.
  • the melting point of the polyester (A) used in the present invention is preferably 250 to 350 ° C, more preferably 260 to 320 ° C, still more preferably 270 to 300 ° C, and still more preferably 280 to 290 ° C.
  • the melting point is 250 ° C. or higher, the toughness effect by the polyester (A) is sufficiently exhibited, and when it is 350 ° C. or lower, good moldability can be obtained without lowering the fluidity.
  • fusing point can be measured by the method described in the Example.
  • the polyester (A) used in the present invention can be produced using any method known as a method for producing polyester.
  • a method for producing polyester for example, it can be produced by adding a catalyst such as a titanium compound or a phosphorus compound, a molecular weight adjusting agent or the like as necessary, and subjecting a dicarboxylic acid component and a diol component to a condensation polymerization reaction.
  • a catalyst such as a titanium compound or a phosphorus compound, a molecular weight adjusting agent or the like as necessary
  • a dicarboxylic acid component and a diol component to a condensation polymerization reaction.
  • the phosphorus compound may remain in the produced polyester (A).
  • the residual amount of the phosphorus compound is usually 0.05 in the polyester (A). For example, it is less than 0.01% by mass.
  • the molar ratio of the dicarboxylic acid component to the diol component (dicarboxylic acid component / diol component) subjected to the polycondensation reaction is preferably 0.80 to 0 from the viewpoint of improving the moldability and the light reflectance. .99, more preferably 0.83 to 0.99, and still more preferably 0.85 to 0.99.
  • the polyester composition of the present invention contains titanium oxide (B).
  • the titanium oxide (B) imparts light reflectivity to the resulting reflector, and by including the titanium oxide, the thermal conductivity and heat resistance of the reflector are improved, Even after being exposed to light, the light reflectance is hardly lowered and a high light reflectance can be maintained.
  • the titanium oxide (B) include titanium monoxide (TiO), titanium trioxide (Ti 2 O 3 ), titanium dioxide (TiO 2 ), and any of these may be used. Is preferred. Titanium dioxide preferably has a rutile or anatase crystal structure, and more preferably has a rutile crystal structure.
  • the average particle diameter of the titanium oxide (B) is preferably 0.10 to 0.50 ⁇ m, more preferably 0.15 to 0.40 ⁇ m, and still more preferably 0.20 to 0, from the viewpoint of improving light reflectance. .30 ⁇ m.
  • the average particle diameter of titanium oxide (B) can be determined by image analysis using electron microscopy. Specifically, the major axis and minor axis are measured for 1,000 or more titanium oxide particles photographed using a transmission electron microscope, and the average value is taken as the average particle diameter.
  • the shape of the titanium oxide (B) is not particularly limited, but the aggregate shape is preferably indefinite.
  • the titanium oxide (B) may be subjected to surface treatment from the viewpoint of enhancing dispersibility in the polyester composition.
  • the surface treatment agent include metal oxides such as silica, alumina, zirconia, tin oxide, antimony oxide, and zinc oxide; organosilicon compounds such as silane coupling agents and silicones; organic titanium compounds such as titanium coupling agents; Examples include organic substances such as organic acids and polyols.
  • the polyester composition of the present invention is selected from the group consisting of phosphoric acid, phosphate, condensed phosphoric acid, condensed phosphate, phosphorous acid, phosphite, hypophosphorous acid, and hypophosphite. Containing one or more inorganic phosphorus compounds (C).
  • the LED reflector obtained by molding the composition can suppress discoloration such as yellowing and a decrease in whiteness, and is particularly exposed to heat assumed in the manufacturing process and use environment of the LED package. In this case, the light reflectance is hardly lowered and a high light reflectance can be maintained. Although this reason is not certain, it is considered that the inorganic phosphorus compound (C) contributes to stabilization of the terminal carboxy group of the polyester (A).
  • phosphoric acid and condensed phosphoric acid phosphorous acid, and hypophosphorous acid
  • phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid etc. can be mentioned.
  • Phosphate and condensed phosphate, phosphite, and hypophosphite are not particularly limited, and examples thereof include metal salts of phosphoric acid, metal salts of pyrophosphoric acid, metal salts of metaphosphoric acid, and phosphorous acid. Examples thereof include metal salts of acids and metal salts of hypophosphorous acid.
  • the inorganic phosphorus compound (C) is preferably an anhydride.
  • the inorganic phosphorus compound (C) is preferably a hypophosphite, more preferably an alkaline earth metal salt of hypophosphorous acid.
  • the inorganic phosphorus compound (C) includes monosodium phosphate, disodium phosphate, trisodium phosphate, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, sodium pyrophosphate, sodium metaphosphate, meta Examples thereof include calcium phosphate, sodium hypophosphite, calcium hypophosphite and the like. Among these, sodium hypophosphite and calcium hypophosphite are more preferable, and calcium hypophosphite is more preferable.
  • the polyester composition of the present embodiment can further contain an organic phosphorus antioxidant (E) described later from the viewpoint of heat discoloration.
  • the polyester composition of the present invention preferably contains at least one selected from the group consisting of a phenolic antioxidant (D) and an organophosphorus antioxidant (E).
  • a phenolic antioxidant (D) By containing the phenol-based antioxidant (D), it is possible to capture radicals generated by heat and suppress a decrease in light reflectance of the resulting reflector.
  • the organophosphorus antioxidant (E) By containing the organophosphorus antioxidant (E), the peroxide generated by heat can be decomposed.
  • phenolic antioxidant (D) the phenol which contains at least 1 group shown by following formula (2) in the molecule
  • numerator from a viewpoint which suppresses the improvement of light reflectivity, and the fall of light reflectivity.
  • System antioxidants are preferred.
  • As shown by the following formula (2) by having an alkyl group at the ortho position of the hydroxy group, it is likely to become a more stable phenoxy radical, and has a higher scavenging ability for radicals generated by heat.
  • R 21 to R 23 are each independently an alkyl group having 1 or 2 carbon atoms
  • R 24 to R 26 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Yes, ** represents a bond.
  • R 21 to R 23 are preferably a methyl group from the viewpoint of suppressing a decrease in light reflectance, that is, represented by —C (R 21 ) (R 22 ) (R 23 ).
  • the group to be selected is preferably a t-butyl group.
  • R 24 and R 25 are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms from the viewpoint of the stability of the phenoxy radical generated after trapping the radical generated by heat, Preferably it is a hydrogen atom.
  • R 26 is preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, from the viewpoint of suppressing a decrease in light reflectance.
  • a methyl group or a t-butyl group is preferred.
  • R 21 to R 23 are methyl groups from the viewpoint of improving the light reflectance and suppressing the light reflectance.
  • R 26 is a methyl group or a t-butyl group.
  • the phenolic hydroxyl group represented by the following formula (3) More preferred is a phenolic antioxidant having a t-butyl group at the ortho position.
  • R 31 and R 32 each independently represents a hydrogen atom or a methyl group
  • R 33 represents a methyl group or a t-butyl group
  • X 1 is a divalent divalent having 1 to 20 carbon atoms.
  • Z represents a monovalent to tetravalent organic group
  • n is an integer of 1 to 4.
  • R 31 and R 32 are preferably a hydrogen atom from the viewpoint of the stability of the phenoxy radical generated after capturing the radical generated by heat, and X 1 is an improvement in light reflectance. And from a viewpoint of suppressing the fall of a light reflectance, the bivalent organic group shown by following formula (4) is preferable.
  • R 4 represents a single bond or an alkylene group having 1 to 17 carbon atoms
  • Y represents an oxygen atom or a group represented by —NH—.
  • *** represents the formula (3).
  • phenolic antioxidant represented by the formula (3) when n is 1, Z is a monovalent organic group, and monofunctional phenolic oxidation having a t-butyl group at the ortho position of the phenolic hydroxyl group. It is an inhibitor (hereinafter also referred to as “monofunctional phenolic antioxidant”).
  • Y in the formula (4) is preferably an oxygen atom and R 4 is preferably from the viewpoint of suppressing an improvement in light reflectance and a decrease in light reflectance. Is a single bond.
  • Z in the formula (3) is preferably an alkyl group having 5 to 25 carbon atoms, more preferably an alkyl group having 10 to 22 carbon atoms, still more preferably an alkyl group having 15 to 20 carbon atoms, and more More preferred is an alkyl group having 18 carbon atoms, and even more preferred is an n-octadecyl group.
  • the monofunctional phenolic antioxidant include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.
  • Examples of commercially available products include “Adekastab AO-50” (trade name, manufactured by ADEKA Corporation), “IRGANOX1076” (trade name, manufactured by BASF Japan Co., Ltd.), and the like.
  • phenolic antioxidant represented by the formula (3) when n is 2, Z is a divalent organic group and has a t-butyl group at the ortho position of the phenolic hydroxyl group. It is an inhibitor (hereinafter also referred to as “bifunctional phenolic antioxidant”).
  • R 4 in the formula (4) is preferably a single bond.
  • Z in the formula (3) is preferably from the viewpoint of improving the light reflectivity and suppressing the decrease in the light reflectivity.
  • a linear or branched alkylene group having 1 to 10 carbon atoms more preferably a linear or branched alkylene group having 4 to 8 carbon atoms, still more preferably an alkylene group having 6 carbon atoms, and still more preferably.
  • Z in the formula (3) is an alkylene group having 1 to 10 carbon atoms from the viewpoint of improving the light reflectivity and suppressing the decrease in the light reflectivity.
  • One or more selected are more preferable, and a divalent organic group having a spiro skeleton derived from pentaerythritol represented by the following formula (5) is more preferable.
  • X 2 in the ether group, the thioether group, and the divalent organic group represented by the following formula (5) represents a linear or branched alkylene group having 1 to 10 carbon atoms.
  • X 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms.
  • X 2 in the formula (5) is preferably a linear or branched alkylene group having 1 to 7 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms, Preferred is a branched butylene group having 4 carbon atoms, that is, X 2 in the formula (5) is preferably represented by the following formula (5 ′).
  • bifunctional phenolic antioxidant examples include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], hexamethylene bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.
  • IRGANOX 1035 “IRGANOX 1098”, “IRGANOX 245”, “IRGANOX 259” (trade names, all manufactured by BASF Japan Ltd.), “Adekatab AO-80” (trade names, ADEKA Corporation) And “Sumilizer GA-80” (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
  • phenolic antioxidant represented by the formula (3) when n is 3, Z is a trivalent organic group, and a trifunctional phenolic oxidation having a t-butyl group at the ortho position of the phenolic hydroxyl group It is an inhibitor (hereinafter also referred to as “trifunctional phenol-based antioxidant”).
  • trifunctional phenolic antioxidant include tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene and the like.
  • commercially available products include “Adekatab AO-20” (trade name, manufactured by ADEKA Corporation), “Adekastab AO-330” (trade name, manufactured by ADEKA Corporation), and the like.
  • phenolic antioxidant represented by the formula (3) when n is 4, Z is a tetravalent organic group, and a tetrafunctional phenolic oxidation having a t-butyl group at the ortho position of the phenolic hydroxyl group. It is an inhibitor (hereinafter also referred to as “tetrafunctional phenolic antioxidant”).
  • tetrafunctional phenolic antioxidant In the tetrafunctional phenol-based antioxidant used in the present invention, Y in the formula (4) is preferably an oxygen atom and R 4 is preferably from the viewpoint of suppressing an improvement in light reflectance and a decrease in light reflectance.
  • Z in the formula (3) is preferably a carbon atom from the viewpoint of improving the light reflectance and suppressing the decrease in the light reflectance.
  • the tetrafunctional phenolic antioxidant include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].
  • Examples of commercially available products include “Adekastab AO-60” (trade name, manufactured by ADEKA Corporation), “IRGANOX1010” (trade name, manufactured by BASF Japan Corporation), and the like.
  • the phenol-based antioxidant (D) used in the present invention is n-octadecyl-3- (3,5-di-t-butyl-4) from the viewpoint of improving the light reflectance and suppressing the light reflectance.
  • -Hydroxyphenyl) propionate IRGANOX1076)
  • N, N′-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide] IRGANOX1098)
  • 2,2-thio-diethylene Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] IRGANOX1035)
  • 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane Sumili zer GA-80
  • the polyester composition of the present invention preferably contains an organophosphorus antioxidant (E) (hereinafter also referred to as “component (E)”). Moreover, it is preferable that this organophosphorus antioxidant (E) contains 3 or more groups shown by following formula (1) in the molecule
  • organophosphorus antioxidant (E) the peroxide generated by heat is decomposed, and in combination with the phenolic antioxidant (D), it has high light reflectivity, A reflector with little decrease in light reflectance even after being exposed to heat can be obtained.
  • As shown by the following formula (1) by having an alkyl group in the ortho position adjacent to the bonding portion with the phosphorus atom, it has a higher decomposition ability for the peroxide generated by heat.
  • R 11 to R 13 are each independently an alkyl group having 1 or 2 carbon atoms
  • R 14 to R 17 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Yes, * represents a bond with a phosphorus atom.
  • R 11 to R 13 are preferably a methyl group from the viewpoint of suppressing a decrease in light reflectance, that is, represented by —C (R 11 ) (R 12 ) (R 13 ).
  • the group to be selected is preferably a t-butyl group.
  • R 15 is preferably a secondary or tertiary alkyl group having 3 to 7 carbon atoms, more preferably a tertiary alkyl group having 4 or 5 carbon atoms, still more preferably t- It is a butyl group.
  • R 14 and R 16 are each independently preferably a hydrogen atom or a carbon number of 1 to 2 from the viewpoint of reducing steric hindrance and improving the reactivity with a peroxide generated by heat. And more preferably a hydrogen atom.
  • R 17 is preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms from the viewpoint of reducing steric hindrance and improving the reactivity with a peroxide generated by heat. More preferably, it is a hydrogen atom.
  • organophosphorus antioxidant (E) from the viewpoint of suppressing a decrease in light reflectance, phosphites and phosphones containing three or more groups represented by the formula (1) in the molecule
  • One or more selected from acid esters are preferable, and one or more selected from organic phosphorus antioxidants represented by the following general formulas (6) to (7) are more preferable.
  • R 61 , R 63 and R 64 each independently represents a hydrogen atom or a methyl group, and R 62 represents an alkyl group having 1 to 10 carbon atoms.
  • R 62 is preferably a secondary or tertiary alkyl group having 3 to 7 carbon atoms, more preferably a tertiary alkyl group having 4 or 5 carbon atoms, still more preferably t- It is a butyl group.
  • R 61 , R 63 and R 64 are preferably hydrogen atoms from the viewpoint of reducing steric hindrance and improving the reactivity with peroxide generated by heat.
  • the organophosphorus antioxidant represented by the formula (6) is preferably tris (2,4-di-t-butylphenyl) phosphite. Examples of commercially available products include “IRGAFOS168” (trade name, manufactured by BASF Japan Ltd.).
  • R 71 , R 73 , R 74 , R 75 , R 77 , and R 78 each independently represent a hydrogen atom or a methyl group, and R 72 and R 76 are each independently a carbon number.
  • R 72 and R 76 are each independently a carbon number.
  • X 3 represents a single bond, —O—, —S—, —SO 2 — or a divalent organic group having 1 to 10 carbon atoms.
  • R 72 and R 76 are preferably a secondary or tertiary alkyl group of an alkyl group having 3 to 7 carbon atoms, more preferably a tertiary alkyl group having 4 or 5 carbon atoms. More preferably, it is a t-butyl group.
  • R 71 , R 73 , R 74 , R 75 , R 77 , and R 78 are preferably hydrogen atoms.
  • X 3 which is a divalent organic group is preferably a single bond.
  • Examples of the organic phosphorus antioxidant represented by the formula (7) include tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite, tetrakis (2,4-di-t-). Butyl-5-methylphenyl) -4,4′-biphenylenephosphonite and the like, and tetrakis (2,4-di-t-butyl) is used from the viewpoint of improving the light reflectivity and suppressing the decrease of the light reflectivity. Phenyl) -4,4′-biphenylenephosphonite is preferred.
  • Examples of commercially available products include “Hostanox P-EPQ” (trade name, manufactured by Clariant Japan Co., Ltd.), “GSY-P101” (trade name, manufactured by Sakai Chemical Industry Co., Ltd.), and the like. These organic phosphorus antioxidants can be used alone or in combination of two or more.
  • organic phosphorus antioxidant (E) examples include tris (2,4-di-t-butylphenyl) phosphite (“IRGAFOS168”) and tetrakis (2,2) from the viewpoint of suppressing a decrease in light reflectance.
  • IRGAFOS168 tris (2,4-di-t-butylphenyl) phosphite
  • tetrakis (2,2) from the viewpoint of suppressing a decrease in light reflectance.
  • One or more selected from 4-di-t-butylphenyl) -4,4′-biphenylenephosphonite (“Hostanox P-EPQ”) is preferred, and tetrakis (2,4-di-t-butylphenyl) -4 4,4′-biphenylenephosphonite (“Hostanox P-EPQ”) is more preferred.
  • a suitable combination of the phenolic antioxidant (D) and the organophosphorus antioxidant (E) is n-octadecyl-3 from the viewpoint of improving light reflectance and suppressing light reflectance.
  • -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate IRGANOX1076), N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propion Amido] (IRGANOX 1098), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX1035), 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-teto One or more selected from oxaspiro [5.5] undecane (Sumilizer GA
  • the polyester composition of the present invention preferably further contains a reinforcing material (F).
  • a reinforcing material (F) By including the reinforcing material (F), the moldability and mechanical strength of the resulting reflector can be improved.
  • said reinforcing material (F) what has various shapes, such as fibrous form, flat form, needle shape, powder form, cloth shape, can be used.
  • fibrous reinforcing materials such as glass fiber, carbon fiber, aramid fiber, liquid crystal polymer (LCP) fiber, metal fiber; flat reinforcing material such as mica and talc; potassium titanate whisker, aluminum borate whisker, Acicular reinforcing materials such as calcium carbonate whisker, magnesium sulfate whisker, wollastonite, sepiolite, zonotlite, zinc oxide whisker; silica, alumina, barium carbonate, magnesium carbonate, aluminum nitride, boron nitride, potassium titanate, aluminum silicate ( Kaolin, clay, pyrophyllite, bentonite), calcium silicate, magnesium silicate (attapulgite), aluminum borate, calcium sulfate, barium sulfate, magnesium sulfate, asbestos, glass beads, carbon black, silver Powdery reinforcing materials such as phyto, carbon nanotubes, silicon carbide, sericite, hydrotalcite, molybdenum disulfide,
  • These reinforcing materials can be used alone or in combination of two or more.
  • those subjected to surface treatment may be used from the viewpoint of enhancing dispersibility in the polyester composition and from the viewpoint of enhancing adhesiveness with the polyester (A).
  • the surface treatment agent include coupling agents such as silane coupling agents and titanium coupling agents; polymer compounds such as acrylic resins, urethane resins and epoxy resins; and other low molecular compounds.
  • the reinforcing material (F) used in the present invention is preferably at least one selected from a fibrous reinforcing material and a needle-shaped reinforcing material from the viewpoint of cost reduction and mechanical strength improvement.
  • a fibrous reinforcing material is more preferable, and glass fiber is more preferable.
  • a needle-like reinforcing material is more preferable.
  • at least one selected from glass fiber, wollastonite, potassium titanate whisker, calcium carbonate whisker, and aluminum borate whisker is preferable, and glass fiber and wollastonite.
  • the average fiber length of the glass fiber is preferably 1 to 10 mm, more preferably 1 to 7 mm, and still more preferably 2 to 4 mm.
  • the cross-sectional shape of glass fiber is not specifically limited, From a viewpoint of productivity and mechanical strength, a non-circular cross section or a circular cross section is preferable, and a circular cross section is more preferable from a viewpoint of cost control.
  • the glass fiber having an irregular cross section means that the length of the outer circumference of the cross section is the length of the outer circumference of the glass fiber cross section having a true circular cross section having the same cross sectional area in the cross section perpendicular to the length direction of the fiber.
  • the glass fiber having a cross-sectional shape of 1.05 times to 1.7 times.
  • the cross-sectional shape an eyebrow shape in which the central portion in the longitudinal direction of the cross-section is constricted, and an oval shape or an oval shape having a portion substantially parallel to a symmetric position with respect to the center of gravity of the cross-section are preferable.
  • the average fiber diameter of the glass fiber is preferably 6 to 20 ⁇ m, more preferably 6 to 15 ⁇ m, from the viewpoint of improving mechanical strength.
  • the average fiber length and average fiber diameter of the glass fiber can be determined by image analysis using electron microscopy in the same manner as the measurement of the average particle diameter of titanium oxide (B) described above.
  • the polyester composition of the present invention preferably further contains a light stabilizer (G) from the viewpoint of preventing discoloration of the resulting reflector and suppressing a decrease in light reflectance.
  • a light stabilizer (G) examples include compounds having an ultraviolet absorption effect such as benzophenone compounds, salicylate compounds, benzotriazole compounds, acrylonitrile compounds, other conjugated compounds, and radical scavenging ability such as hindered amine compounds. A certain compound etc. are mentioned.
  • a compound having high affinity with the polyester (A) and having an amide bond in the molecule is preferable from the viewpoint of improving heat resistance.
  • a compound having an ultraviolet absorption effect and a compound having a radical scavenging ability in combination.
  • These light stabilizers can be used alone or in combination of two or more.
  • the polyester composition of the present invention comprises nigrosine and other organic or inorganic colorants; antistatic agents; crystal nucleating agents such as talc; plasticizers; waxes such as polyolefin waxes and higher fatty acid esters; Other ingredients such as molds and lubricants can be further blended.
  • blending another component with the polyester composition of this invention it is preferable that each content of another component is 5 mass parts or less with respect to 100 mass parts of polyester (A).
  • the content of the polyester (A) used in the present invention is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably from the viewpoint of improving the moldability to the LED reflector and the heat resistance. Is 50% by mass or more, and from the viewpoint of obtaining a high light reflectance of the obtained reflector, it is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
  • the content of titanium oxide (B) used in the present invention is 20 parts by mass or more, preferably 25 parts by mass or more, more preferably 100 parts by mass of polyester (A) from the viewpoint of obtaining high light reflectance. Is 30 parts by mass or more, and is 90 parts by mass or less, preferably 85 parts by mass or less, more preferably 80 parts by mass or less, from the viewpoint of improving moldability to the LED reflector and heat resistance.
  • the content of the inorganic phosphorus compound (C) used in the present invention is 0.10 to 3.50 parts by mass with respect to 100 parts by mass of the polyester (A). If it is less than 0.10 parts by mass, the effect of improving heat resistance is hardly exhibited. Moreover, when it exceeds 3.50 mass part, fluidity
  • the content of the inorganic phosphorus compound (C) is preferably 0.20 parts by mass or more, more preferably 0.30 parts by mass or more, and still more preferably 0.000 parts by mass with respect to 100 parts by mass of the polyester (A).
  • it is 2.50 mass parts or less, More preferably, it is 2.20 mass parts or less, Especially preferably, it is 2.00 mass parts or less, More preferably, it is 1.50 mass parts or less.
  • the content of the inorganic phosphorus compound (C) is preferably 0.20 to 3.00 parts by mass, more preferably 0.50 to 2.80 parts by mass with respect to 100 parts by mass of the polyester (A).
  • the content is more preferably 0.70 to 2.50 parts by mass, still more preferably 0.70 to 2.00 parts by mass, and particularly preferably 0.70 to 1.50 parts by mass.
  • the content of the phenol-based antioxidant (D) used in the present invention is 0.000 parts by mass with respect to 100 parts by mass of the polyester (A) from the viewpoint of obtaining a high light reflectance and suppressing the decrease in the light reflectance. It is 10 parts by mass or more, preferably 0.13 parts by mass or more, more preferably 0.15 parts by mass or more, and suppresses a decrease in light reflectance caused by defects such as gas burning due to gas generated during molding. From this viewpoint, it is 0.80 part by mass or less, preferably 0.75 part by mass or less, more preferably 0.60 part by mass or less.
  • the mass ratio of the inorganic phosphorus compound (C) to the organophosphorus antioxidant (E) [(C) component / (E) component] is a viewpoint of obtaining a high light reflectance, and the light reflectance. From the viewpoint of suppressing the decrease in the flow rate and the viewpoint of improving the fluidity, it is preferably 0.50 or more, more preferably 1.00 or more, still more preferably 1.50 or more, still more preferably 2.00 or more, Particularly preferably, it is 3.00 or more, preferably 30.00 or less, more preferably 18.00 or less, still more preferably 16.00 or less, still more preferably 15.00 or less, particularly preferably 10 0.000 or less, more preferably 8.00 or less, and most preferably 6.00 or less.
  • the total content of the phenolic antioxidant (D) and the organic phosphorus antioxidant (E) in the polyester composition of the present invention is preferably 1.5 parts by mass with respect to 100 parts by mass of the polyester (A).
  • it is 1.0 mass part or less more preferably. If the total content is 1.5 parts by mass or less, the amount of gas generated at the time of molding the polyester composition is small, so that a gas residue is left on the surface of the molded product, leaving a gas burn mark, or discoloration upon heating. It is possible to avoid problems such as.
  • the mass ratio of the phenolic antioxidant (D) to the organophosphorus antioxidant (E) [(D) component / (E) component] is a viewpoint that obtains a high light reflectance, and light. From the viewpoint of suppressing the decrease in reflectivity, it is preferably 0.20 or more, more preferably 0.50 or more, still more preferably 0.70 or more, and defects such as gas burning due to gas generated during molding. From the viewpoint of suppressing the decrease in light reflectivity associated with, it is preferably 3.00 or less, more preferably 2.00 or less, still more preferably 1.50 or less, and even more preferably 1.00 or less.
  • the content of the reinforcing material (F) used in the present invention is preferably at least 5 parts by mass, more preferably at least 10 parts by mass with respect to 100 parts by mass of the polyester (A), from the viewpoint of improving heat resistance and mechanical strength. Further, it is preferably 15 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less, from the viewpoint of obtaining a high light reflectance and suppressing a decrease in light reflectance.
  • the content of the light stabilizer (G) used in the present invention is preferably 0 with respect to 100 parts by mass of the polyester (A) from the viewpoint of preventing discoloration of the resulting reflector and suppressing a decrease in light reflectance.
  • the polyester composition of the present invention can be prepared by mixing the above-described components according to a known method. For example, a method of adding each component during the condensation polymerization reaction of the polyester (A), a method of dry blending the polyester (A) and other components, a method of melt-kneading each component using an extruder, and the like can be mentioned. . Among these, the method of melt kneading each component using an extruder is preferable because it is easy to operate and a uniform composition can be obtained.
  • the extruder used at this time is preferably a twin screw type, and the melt kneading temperature is preferably in the range of 5 ° C. to 350 ° C. higher than the melting point of the polyester (A).
  • the LED reflector of the present invention can be obtained by molding the polyester composition of the present invention.
  • the reflecting plate can be obtained by a molding method generally used for a thermoplastic resin composition, such as injection molding, extrusion molding, press molding, blow molding, calendar molding, and casting molding.
  • a reflector can also be obtained by a molding method that combines the above molding methods.
  • injection molding is preferable from the viewpoint of ease of molding, mass productivity, and cost reduction.
  • the LED reflector of the present invention can be composite-molded with the polyester composition and another polymer, and further, the polyester composition can be composited with a molded body or fabric made of metal.
  • the LED reflector of the present invention is characterized in that the reflectance of light having a wavelength of 460 nm as measured by a spectrophotometer can be maintained at a high level with little reduction even after being exposed to heat.
  • the content of titanium oxide (B) is 54.5 parts by mass with respect to 100 parts by mass of polyester (A)
  • the amount of decrease in light reflectance from the initial reflectance after short-term heating at 170 ° C. for 5 hours is Preferably it is 3.5% or less, More preferably, it is 3.0% or less, More preferably, it is 2.5% or less. Thereby, the fall of the light reflectivity after being exposed to heat in the manufacturing process of an LED package can be suppressed.
  • the amount of decrease in light reflectance from the initial reflectance after heating for reflow for 20 seconds at a peak temperature of 260 ° C. is preferably 6.0% or less, more preferably 5.5% or less. More preferably, it is 5.0% or less, and still more preferably 4.5% or less. Thereby, the fall of a light reflectivity can be suppressed also in a long-term use environment.
  • the initial reflectance of light having a wavelength of 460 nm by the spectrophotometer of the LED reflector of the present invention is preferably, for example, when the content of titanium oxide (B) is 54.5 parts by mass with respect to 100 parts by mass of polyester (A). It is 93% or more, more preferably 94% or more, and still more preferably 95% or more. Each of the reflectances is measured by the method described in the examples.
  • the LED reflecting plate of the present invention maintains a high light reflectance (reflectance with respect to light in the vicinity of a wavelength of 460 nm) with little decrease in light reflectance even after being exposed to heat, particularly in the manufacturing process and use environment of the LED package. To do. Therefore, the LED reflector of the present invention can be suitably used as, for example, a reflector for LEDs used in backlight light sources, lighting fixtures, various lamps of automobiles, etc., and a light emitting device including the LED reflector of the present invention has a long life. It becomes.
  • the light-emitting device of the present invention includes the LED reflector of the present invention.
  • Examples of the light emitting device of the present invention include a backlight light source, an illumination light source, and light sources for various lamps of automobiles.
  • FIG. 1 shows an example of a typical configuration of a light emitting device of the present invention.
  • FIG. 1 schematically shows a light-emitting device (LED device) 1 of an SMD (surface mounted device) type.
  • the semiconductor light emitting element 10 is disposed in a package-like portion 50 formed by the substrate 20 and the reflector (housing) 30, and the package-like portion 50 is filled with a sealing member 40 (light transmissive resin). ing.
  • the light emitting device of the present invention is not limited to the following elements.
  • the semiconductor light emitting device 10 can suitably use one having an emission peak wavelength in a wavelength region of 500 nm or less.
  • the semiconductor light emitting device is not limited to a semiconductor light emitting device having a single light emission peak, and a semiconductor light emitting device having a plurality of light emission peaks can also be used.
  • when it has a some light emission peak you may have a 1 or 2 or more light emission peak in the area
  • a semiconductor light emitting element having an emission peak in a long wavelength region (501 nm to 780 nm) of visible light can also be used.
  • the configuration of the semiconductor light emitting element 10 is not particularly limited as long as it has the above wavelength characteristics.
  • a semiconductor in which a semiconductor such as GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlN, InN, AlInGaP, InGaN, GaN, or AlInGaN is formed as a light emitting layer can be used.
  • the light emitting layer may contain an arbitrary dopant.
  • a plurality of semiconductor light emitting elements 10 can be used as appropriate.
  • two light emitting elements capable of emitting green light and one light emitting element capable of emitting blue and red light can be provided.
  • the method for connecting the semiconductor light emitting element 10 to the substrate 20 is not particularly limited, but a conductive epoxy or silicone adhesive can be used. Furthermore, a metal having a low melting point can be used to efficiently transfer heat generated from the semiconductor light emitting element to the substrate. For example, Sn / Ag / Cu (melting point 220 degrees), Sn / Au (melting point 282 degrees), etc. can be illustrated.
  • the package is a member on which the semiconductor light emitting element 10 is mounted, and a part or the whole is formed of the above-described LED reflector of the present invention.
  • the package may be composed of a single member or may be configured by combining a plurality of members.
  • the package preferably has a recess (cup-shaped portion).
  • One example of the package is a combination of a reflector (housing) and a substrate. For example, in FIG. 1, a desired shape is formed on the substrate 20 so as to form a recess (cup-shaped portion).
  • a reflector (housing) 30 is bonded to form a package.
  • substrate 20 and the reflector 30 are formed from the LED reflecting plate of this invention which shape
  • the concave portion (cup-shaped portion) formed in the package has a bottom portion and a side portion, and the area of the cross section perpendicular to the optical axis is continuous from the bottom portion toward the light extraction direction of the light emitting device or A portion composed of a space having a shape that gradually increases.
  • the shape of the bottom part and the side part is not particularly limited as long as this condition is satisfied.
  • the sealing member 40 is a member formed so as to cover the semiconductor light emitting element 10 and is provided mainly for the purpose of protecting the semiconductor light emitting element 10 from the external environment.
  • a transparent thermosetting resin can be used for the sealing member 40 for the purpose of protecting the semiconductor light emitting element 10 and the wiring.
  • the transparent thermosetting resin include thermosetting resins including epoxy or silicone.
  • the silicone a resin type, a rubber type, or a gel type can be used according to the required characteristics of the package.
  • the reflector 30 can be treated with a rare gas plasma such as argon.
  • the sealing member 40 can also be provided such that a plurality of layers made of different materials are stacked on the semiconductor light emitting element 10.
  • the sealing member 40 may contain a phosphor.
  • a phosphor By using the phosphor, part of the light from the semiconductor light emitting element 10 can be converted into light having a different wavelength, and the emission color of the light emitting device can be changed or corrected. Any phosphor can be used as long as it can be excited by light from the semiconductor light emitting element 10.
  • lanthanoid elements such as Ce
  • One or more selected from the rare earth aluminates, rare earth silicates to be activated, organic compounds and organic complexes mainly activated by lanthanoid elements such as Eu are preferably used.
  • a plurality of types of phosphors can be combined and contained in the sealing member 40.
  • a phosphor that emits light when excited by light from the semiconductor light emitting element 10 and a phosphor that emits light when excited by light from the phosphor can also be used in combination.
  • a light diffuser such as titanium dioxide or zinc oxide in the sealing member 40
  • light diffusion in the sealing member 40 can be promoted to reduce light emission unevenness.
  • the reflector 30 which is the LED reflector of the present invention is disposed on the substrate 20 which is the LED reflector of the present invention.
  • the semiconductor light emitting element 10 is mounted, and the electrodes of the semiconductor light emitting element 10 and the wiring pattern on the substrate 20 are connected by leads.
  • a liquid silicone sealant comprising a main agent and a curing agent is prepared and potted on a cup-shaped part. In this state, the silicone sealant is cured by heating to about 150 ° C. Then, heat is dissipated in the air.
  • FIG. 2 shows a schematic diagram of the light emitting device 2 of the present invention having another configuration.
  • the same elements as those of the light emitting device 1 are denoted by the same reference numerals.
  • a lead frame 80 is used instead of the substrate, and the semiconductor light emitting element 10 is mounted on the lead frame 80.
  • Other configurations are the same as those of the light emitting device 1.
  • FIG. 3 shows a schematic diagram of the light emitting device 3 of the present invention having another configuration.
  • the same elements as those of the light emitting device 1 are denoted by the same reference numerals.
  • substrate 70 which is an LED reflecting plate of this invention is used. Desired wiring 71 is provided on the substrate 70.
  • the casing (reflector) is not used, and the sealing member 60 can be formed by molding using a desired mold after mounting the semiconductor light emitting element 10 as shown in the figure. Alternatively, a sealing member 60 molded in a desired shape in advance may be prepared and bonded to the substrate 70 so as to cover the semiconductor light emitting element 10.
  • the SMD type light emitting device has been described as a configuration example of the present invention.
  • a semiconductor light emitting element is mounted on a lead frame having a cup-shaped portion, and the semiconductor light emitting element and a part of the lead frame are sealed.
  • the present invention can also be applied to a so-called bullet-type light emitting diode that is covered with a member.
  • the present invention can also be applied to a flip chip type light emitting device in which a semiconductor light emitting element is mounted on a substrate or a lead frame in a so-called flip chip form.
  • the melting point of polyester is the melting that appears when the temperature is increased from 30 ° C. to 350 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter “DSC822” manufactured by METTLER TOLEDO.
  • the peak temperature was the melting point (° C.). When there are a plurality of melting peaks, the melting point is the peak temperature of the melting peak on the highest temperature side.
  • each component used by the Example and the comparative example is as follows.
  • Polycyclohexane having a structural unit derived from dicarboxylic acid containing 100 mol% of terephthalic acid and a structural unit derived from diol containing 100 mol% of 1,4-cyclohexanedimethanol having a trans isomer ratio of 69% Dimethylene terephthalate (melting point: 290 ° C., molar ratio (dicarboxylic acid component / diol component): 0.98)
  • Titanium oxide (B) B-1: Titanium dioxide (average particle size 0.25 ⁇ m, refractive index 2.71)
  • E-1 Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite (the following formula (9), manufactured by Clariant Japan Co., Ltd., trade name: “Hostanox P-EPQ”) )
  • F-1 Glass fiber (manufactured by Nitto Boseki Co., Ltd., trade name: “CS3J256S”, average fiber diameter 11 ⁇ m, average fiber length 3 mm, circular cross section)
  • G-1 N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide (manufactured by Clariant Japan Co., Ltd., trade name: “Nylostab S- EED ”)
  • Examples 1 to 4 and Comparative Examples 1 to 2 Polyester (A-1), titanium dioxide (B-1), inorganic phosphorus compound (C-1), phenolic antioxidant (D-1), organic phosphorus antioxidant (E-1), light stabilizer (G-1), the release agent, and the nucleating agent were dry blended according to the formulation shown in Table 1.
  • a test piece having a predetermined shape was prepared and used for evaluation. The results are shown in Table 2.
  • the polyester compositions of Examples 1 to 4 have an initial reflectance, a reflectance after short-term heating, and a reflectance after a reflow test as compared with Comparative Examples 1 and 2. Both are expensive.
  • the polyester compositions of Examples 1 to 4 all have a bar flow flow length of 50 mm or more, indicating that the moldability is excellent. Therefore, the polyester composition of the present invention has a high light reflectivity, and even when exposed to heat assumed in the manufacturing process and use environment of the LED package, the light reflectivity does not decrease so much and the light reflectivity is high. The rate can be maintained.
  • the reflector obtained by molding the polyester composition for LED reflector of the present invention has a high light reflectance, and even when exposed to heat assumed in the manufacturing process and use environment of the LED package. A decrease in reflectance is small, and a high light reflectance can be maintained. For this reason, the light-emitting device provided with the said reflecting plate becomes long life. Moreover, the polyester composition for LED reflectors of the present invention is also excellent in moldability.

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Abstract

L'invention porte sur une composition de polyester pour des plaques réfléchissantes à DEL, la composition contenant un polyester (A) et de l'oxyde de titane (B), le polyester (A) ayant un motif constitutif dérivé d'un acide dicarboxylique contenant 50 % en mole ou plus d'acide téréphtalique et un motif constitutif dérivé d'un diol contenant 50 % en mole ou plus de 1,4-cyclohexanediméthanol. Ladite composition de polyester pour des plaques réfléchissantes à DEL contient en outre un composé de phosphore inorganique (C) comprenant un ou plusieurs composés choisis dans le group comprenant l'acide phosphorique, les sels de phosphate, l'acide phosphorique condensé, les sels de phosphate condensés, l'acide phosphoreux, les sels de phosphite, l'acide hydrophosphoreux et les sels d'hydrophosphite ; la teneur en composé de phosphore inorganique (C) par rapport à 100 parties en masse du polyester (A) est de 0,10 parties en masse à 3,50 parties en masse.
PCT/JP2017/020208 2016-05-31 2017-05-31 Composition de polyester pour plaques réfléchissantes à del, plaques réfléchissantes à del et dispositif émetteur de lumière comportant ladite plaque réfléchissante WO2017209172A1 (fr)

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