WO2013125454A1 - Résine polyester pour plaque réfléchissante pour led montée en surface - Google Patents

Résine polyester pour plaque réfléchissante pour led montée en surface Download PDF

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Publication number
WO2013125454A1
WO2013125454A1 PCT/JP2013/053639 JP2013053639W WO2013125454A1 WO 2013125454 A1 WO2013125454 A1 WO 2013125454A1 JP 2013053639 W JP2013053639 W JP 2013053639W WO 2013125454 A1 WO2013125454 A1 WO 2013125454A1
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Prior art keywords
acid
polyester resin
mol
temperature
glycol
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PCT/JP2013/053639
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English (en)
Japanese (ja)
Inventor
戸川　惠一朗
浩尚 佐々木
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020147021563A priority Critical patent/KR101848970B1/ko
Priority to CN201380010667.3A priority patent/CN104136487B/zh
Priority to JP2013509766A priority patent/JP6048832B2/ja
Publication of WO2013125454A1 publication Critical patent/WO2013125454A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • 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

Definitions

  • the present invention relates to a polyester resin that can be used as a material suitable for a reflector for a surface-mounted LED having excellent moldability, fluidity, dimensional stability, low water absorption, solder heat resistance, surface reflectance, and the like. Furthermore, this invention relates to the polyester resin which can be used for the material suitable for the reflector for surface mount type LED which is excellent in gold
  • LEDs light-emitting diodes
  • LEDs are used for lighting fixtures, optical elements, mobile phones, backlights for liquid crystal displays, automobile console panels, traffic lights, etc. by utilizing features such as low power consumption, long life, high brightness, and miniaturization. It is applied to display boards.
  • surface mounting technology is used to achieve lightness, thinness, and miniaturization.
  • a surface-mounted LED is generally composed of a light-emitting LED chip, a lead wire, a reflector that also serves as a case, and a sealing resin.
  • each component In order to join the entire component mounted on an electronic board with lead-free solder
  • each component must be formed of a material that can withstand the soldering reflow temperature of 260 ° C.
  • the melting point (melting peak temperature) of the material is required to be 280 ° C. or higher.
  • the reflector in addition to these heat resistances, surface reflectivity for efficiently extracting light and durability against heat and ultraviolet rays are required. From this point of view, various heat-resistant plastic materials such as ceramics, semi-aromatic polyamides, liquid crystal polymers, and thermosetting silicones have been studied.
  • high refractive fillers such as titanium oxide are dispersed in semi-aromatic polyamides and polyesters.
  • the resin made has a good balance of mass productivity, heat resistance, surface reflectance, etc., and is most commonly used.
  • Patent Documents 1 and 2 have been proposed as polyester resin compositions for LED reflectors.
  • a dicarboxylic acid component comprising from 0 to 10 mol% of an aromatic dicarboxylic acid residue; and (b) i) a 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue from 1 to 99 mol%; and ii)
  • Disclosed is a glycol component containing 1-99 mol% 1,4-cyclohexanedimethanol residues (wherein the total mol% of dicarboxylic acid component is 100 mol% and the total mol% of glycol component is 100 mol%)
  • the mechanical properties tend to be good, there are problems in moldability and light
  • Patent Document 3 (A) 100 parts by mass of a polyester resin, (B) 2 to 50 parts by mass of a phosphinate whose anion portion is a calcium salt or aluminum salt of phosphinic acid, and (C) titanium dioxide 0.5
  • a flame retardant polyester resin composition for a reflector of an illuminating device using a semiconductor light emitting element as a light source characterized in that it contains 0.01 to 3 parts by mass of (D) a polyolefin resin having a polar group (D).
  • D a polyolefin resin having a polar group
  • Patent Document 4 100 parts by mass of wholly aromatic thermotropic liquid crystal polyester, 97 to 85% by mass of titanium oxide obtained by a production method including a roasting step, 3 to 15% by mass of aluminum oxide (including hydrate) (Total of 100% by mass of both) comprising 8 to 42 parts by mass of titanium oxide particles surface-treated, 25 to 50 parts by mass of glass fibers, and 0 to 8 parts by mass of other inorganic fillers.
  • Resin composition obtained through a melt-kneading step including a step of supplying at least a part of the glass fiber from a position 30% or more downstream with respect to the total length of the cylinder of the biaxial kneader using a shaft kneader.
  • Patent Document 5 discloses a dry unsaturated polyester resin composition containing at least an unsaturated polyester resin, a polymerization initiator, an inorganic filler, a white pigment, a release agent, and a reinforcing material, wherein the unsaturated polyester resin is The total amount of the inorganic filler and the white pigment is in the range of 44 to 74% by mass with respect to the total amount of the composition. The proportion of the white pigment in the total amount of the inorganic filler and the white pigment is 30% by mass or more, and the unsaturated polyester resin is mixed with the unsaturated alkyd resin and the crosslinking agent.
  • polyesters and polyamides are used while having problems in heat-resistant coloring, light resistance and moldability.
  • the required melting point of the polyester resin that can be used for the surface mount LED reflector is 280 ° C. or higher, preferably 290 ° C. or higher, and the aromatic ring concentration is high.
  • the required melting point of the polyester resin that can be used for the surface mount LED reflector is 280 ° C. or higher, preferably 290 ° C. or higher, and the aromatic ring concentration is high.
  • no polyester resin that can be used for a surface mount LED reflector satisfying these requirements has been reported so far.
  • An object of the present invention is to provide a polyester resin that can be used as a material suitable for a reflector for a surface-mounted LED having excellent light resistance. Furthermore, an object of the present invention is to provide a high melting point that can be applied to a gold / tin eutectic soldering process and to ensure a long-term reliability, and a low water absorption for reducing swelling of a molded product due to moisture in the soldering process. Another object of the present invention is to provide a polyester resin that can be used as a material suitable for a reflector for a surface mount LED that has achieved light resistance during outdoor use or long-term use.
  • the present inventor can advantageously perform injection molding and reflow soldering processes while satisfying the characteristics as an LED reflector, and further, gold / tin eutectic solder heat resistance, low water absorption As a result of intensive studies on the composition of polyester having excellent properties and light resistance, the present invention has been completed.
  • the present invention has the following configuration.
  • a polyester resin for a surface-mounted LED reflector comprising an acid component composed of 4,4′-biphenyldicarboxylic acid and another dicarboxylic acid and a glycol component as constituent components and a melting point of 280 ° C. or higher.
  • the other dicarboxylic acid constituting the polyester resin is terephthalic acid and / or 2,6-naphthalenedicarboxylic acid.
  • Polyester resin comprising an acid component composed of 4,4′-biphenyldicarboxylic acid and another dicarboxylic acid and a glycol component as constituent components and a melting point of 280 ° C. or higher.
  • the polyester resin for surface-mounted LED reflectors according to any one of (3), wherein the difference between the melting point (Tm) and the temperature-falling crystallization temperature (Tc2) of the polyester resin is 40 ° C.
  • the polyester resin of the present invention is excellent in workability such as moldability at the time of injection molding and solder heat resistance in addition to high heat resistance and low water absorption when used in a material used for a reflector for a surface mount LED. Therefore, it is possible to industrially advantageously manufacture a reflector for a surface mount LED that highly satisfies all necessary characteristics.
  • the polyester resin of the present invention has a high melting point and excellent heat resistance, it can be applied to a gold / tin eutectic solder process, and furthermore, since the aromatic ring concentration is high, it has heat resistance, toughness, and weather resistance. It is possible to exhibit characteristics such as excellent properties and excellent adhesion to the sealing material.
  • the polyester resin of the present invention is intended to be used for a material used for a reflector for a surface mount LED.
  • the surface mount type LED includes a chip LED type using a printed wiring board, a gull wing type using a lead frame, a PLCC type, and the like.
  • the polyester resin of the present invention is formed by injection molding all these reflectors. Can be manufactured.
  • the polyester resin of the present invention is a polyester resin for a surface-mounted LED reflector having an acid component composed of 4,4′-biphenyldicarboxylic acid and other dicarboxylic acid and a glycol component as constituent components and a melting point of 280 ° C. or higher. .
  • the polyester resin of the present invention realizes excellent light resistance in addition to high melting point and low water absorption in order to impart high reliability.
  • 4,4′-biphenyldicarboxylic acid and other dicarboxylic acids An acid component and a glycol component consisting of the above are used as constituent components, and the melting point is 280 ° C. or higher.
  • the polyester resin can have a melting point of 280 ° C. or higher by having the following configuration.
  • the melting point of the polyester resin is preferably 290 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 310 ° C. or higher.
  • the upper limit of the melting point of the polyester resin is not particularly set, but is 340 ° C. or lower due to the limitation of the raw material components that can be used.
  • the polyester resin preferably contains 4,4′-biphenyldicarboxylic acid in an amount of 30 mol% or more, more preferably 4,4′-biphenyldicarboxylic acid in an amount of 50 mol% or more, still more preferably 60 mol% or more. Particularly preferred is 63 mol% or more, and most preferred is 70 mol% or more. If 4,4′-biphenyldicarboxylic acid is less than 30 mol% of the total acid component, moldability, solder heat resistance, and light resistance tend to be lowered. The amount of 4,4′-biphenyldicarboxylic acid is preferably 90 mol% or less of the total acid component.
  • dicarboxylic acids are aromatic dicarboxylic acids such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenoxyethane dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, etc.
  • Aliphatic dicarboxylic acids such as acid, adipic acid, sebacic acid, succinic acid, glutaric acid and dimer acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid and the like, and among them, terephthalic acid, 2,6-naphthalenedicarboxylic acid, or a mixture thereof is preferable from the viewpoint of polymerizability, cost, and heat resistance. .
  • polyoxycarboxylic acids such as p-oxybenzoic acid and oxycaproic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenylsulfonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof You may use together.
  • the acid component constituting the polyester resin the total of 4,4′-biphenyldicarboxylic acid and other dicarboxylic acids is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, 97 mol% or more is particularly preferable, and may be 100 mol%.
  • glycol component of the polyester resin examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2-methyl-1 , 3-propanediol, 2 Ethyl-1,3-propanediol, neopentyl
  • one or two selected from ethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propanediol, neopentyl glycol, and 1,4-butanediol are considered due to heat resistance, polymerizability, molding, cost, and the like.
  • a mixture of species or more is preferred. More preferably, it is at least one selected from ethylene glycol and 1,4-butanediol.
  • diethylene glycol may be produced as a by-product during the production of the polyester resin to become a copolymer component.
  • diethylene glycol as a by-product is about 1 to 5 mol% with respect to ethylene glycol incorporated in the polyester resin, although it depends on production conditions.
  • polyhydric polyols such as a trimethylol ethane, a trimethylol propane, glycerol, and a pentaerythritol.
  • the polyester resin of the present invention is preferably 160 mol% or more, more preferably 180 mol% or more, even more preferably the total of the above-mentioned dicarboxylic acid component and glycol component when the total components are 200 mol%. Is 190 mol% or more and may be 200 mol% (in this case, 100 mol% of dicarboxylic acid component and 100 mol% of glycol component).
  • 4,4′-biphenyldicarboxylic acid is preferably 63 mol% or more, more preferably 70 mol% or more as the acid component. Further, in this case, in order to achieve a more desirable high melting point, it is more preferable that 4,4′-biphenyldicarboxylic acid is 75 mol% or more as an acid component, and 80 mol% or more is particularly preferable.
  • metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- [4-sulfophenoxy] isophthalic acid, or 2-sulfo-1,4-butanediol, 2,5 -A dicarboxylic acid or diol containing a sulfonic acid metal base such as a metal salt such as dimethyl-3-sulfo-2,5-hexanediol may be used in the total acid component or in a range of 20 mol% or less of the total diol component. Good.
  • At least 1 type of compound chosen from the compound of Ge, Sb, Ti, Al, Mn, or Mg is used. These compounds are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, ethylene glycol slurries and the like.
  • Examples of the Ge compound include amorphous germanium dioxide, crystalline germanium dioxide powder or ethylene glycol slurry, a solution obtained by heating and dissolving crystalline germanium dioxide in water, or a solution obtained by adding ethylene glycol to this and heat treatment.
  • a solution in which germanium dioxide is dissolved by heating in water or a solution in which ethylene glycol is added and heated.
  • compounds such as germanium tetroxide, germanium hydroxide, germanium oxalate, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, and germanium phosphite can also be used.
  • the amount used is preferably 10 to 150 ppm, more preferably 13 to 100 ppm, still more preferably 15 to 70 ppm, most preferably 15 as the residual amount of Ge in the polyester based on the mass of the polyester resin. It is in the range of ⁇ 50 ppm.
  • Ti compounds include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate, and partial hydrolysates thereof, titanium acetate, titanyl oxalate, titanyl ammonium oxalate, titanyl oxalate Sodium, titanyl oxalate, titanyl calcium oxalate, titanyl succinate, titanyl succinate, titanium trimellitic acid, titanium sulfate, titanium chloride, titanium halide hydrolyzate, titanium oxalate, titanium fluoride, titanium hexafluoride Potassium acid, ammonium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, titanium acetylacetonate, hydroxy polycarboxylic acid or nitrogen-
  • Sb compound examples include antimony trioxide, antimony acetate, antimony tartrate, antimony potassium tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony.
  • the amount of Sb remaining in the produced polymer is preferably 50 to 300 ppm, more preferably 50 to 250 ppm, still more preferably 50 to 200 ppm, and most preferably 50 to 180 ppm, based on the mass of the polyester resin. Add as follows.
  • Al compounds include aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, and other inorganic acid salts, aluminum n-propoxide, aluminum iso-propoxide
  • Aluminum alkoxides such as aluminum n-butoxide and aluminum t-butoxide
  • aluminum chelate compounds such as aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, trimethylaluminum, triethylaluminum, etc.
  • the Al compound is preferably in the range of 5 to 200 ppm, more preferably 10 to 100 ppm, still more preferably 10 to 50 ppm, and most preferably 12 to 30 ppm, based on the mass of the polyester resin, as the residual amount of Al in the produced polymer. Add as follows.
  • an alkali metal compound or an alkaline earth metal compound may be used in combination as necessary.
  • the alkali metal or alkaline earth metal is preferably at least one selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and the use of an alkali metal or a compound thereof is preferable. More preferred. When using an alkali metal or a compound thereof, use of Li, Na, K is particularly preferable.
  • alkali metal and alkaline earth metal compounds examples include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid.
  • Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert- Alkoxides such as butoxy, chelate compounds and the like acetylacetonate, hydr
  • the alkali metal compound or alkaline earth metal compound is added to the reaction system as a powder, an aqueous solution, an ethylene glycol solution, or the like.
  • the alkali metal compound or alkaline earth metal compound is added so that the residual amount of these elements in the produced polymer is preferably in the range of 1 to 50 ppm with respect to the mass of the polyester resin.
  • the polyester resin according to the present invention is at least one selected from the group consisting of silicon, manganese, iron, cobalt, zinc, gallium, strontium, zirconium, niobium, molybdenum, indium, tin, hafnium, thallium, tungsten.
  • These metal compounds include saturated aliphatic carboxylates such as acetates of these elements, unsaturated aliphatic carboxylates such as acrylates, aromatic carboxylates such as benzoic acid, and halogens such as trichloroacetic acid.
  • Hydroxycarboxylates such as carboxylates and lactates
  • inorganic acid salts such as carbonates
  • organic sulfonates such as 1-propanesulfonate
  • organic sulfates such as lauryl sulfate
  • oxides oxides
  • hydroxides chlorides Products, alkoxides, acetylacetonates, and the like
  • metal compounds are added so that the residual amount of these metal compound elements per ton of the produced polymer is preferably in the range of 0.05 to 3.0 mol.
  • These metal compounds can be added at any stage of the polyester formation reaction step.
  • phosphoric acid phosphoric acid esters such as polyphosphoric acid and trimethyl phosphate, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, phosphine compounds
  • at least one phosphorus compound selected from the group consisting of: Specific examples include phosphoric acid, phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, Phosphoric acid, phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester
  • the P compound is preferably in the range of 5 to 100 ppm, more preferably 10 to 90 ppm, still more preferably 10 to 80 ppm, and most preferably 20 to 70 ppm, based on the mass of the polyester resin, as the residual amount of P in the produced polymer. Add as follows.
  • an Al compound When used as the polycondensation catalyst, it is preferably used in combination with a phosphorus compound, and is preferably used as a solution or slurry in which an aluminum compound and a phosphorus compound are previously mixed in a solvent.
  • a more preferable phosphorus compound is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is a phosphorus compound.
  • a phosphonic acid compound is preferable because of its great effect of improving physical properties and improving catalytic activity.
  • the use of a compound having an aromatic ring structure is preferable because the physical property improving effect and the catalytic activity improving effect are great.
  • the solution, slurry, etc. of the catalyst and stabilizer described above are bubbled with an inert gas having an oxygen concentration of 5 ppm or less, preferably 3 ppm or less, more preferably 2 ppm or less, most preferably 1 ppm or less at the time of preparation or after preparation.
  • an inert gas having an oxygen concentration of 5 ppm or less, preferably 3 ppm or less, more preferably 2 ppm or less, most preferably 1 ppm or less at the time of preparation or after preparation.
  • the acid value of the polyester resin of the present invention is preferably 1 to 40 eq / ton.
  • the acid value exceeds 40 eq / ton, light resistance tends to decrease.
  • the acid value is less than 1 eq / ton, the polycondensation reactivity tends to decrease and the productivity tends to deteriorate.
  • the polyester resin of the present invention has a melting point (Tm) in DSC measurement of 280 ° C. or higher, preferably 290 ° C. or higher, more preferably 300 ° C. or higher, particularly preferably 310 ° C. or higher, and most preferably 320 ° C. or higher. .
  • the upper limit of Tm of the polyester resin of the present invention is preferably 340 ° C. or lower for the following reason. When Tm exceeds the above upper limit, the processing temperature required for injection molding the composition using the polyester resin of the present invention becomes extremely high, so that the polyester resin decomposes during processing, and the desired physical properties and appearance are obtained. It may not be possible.
  • Tm when Tm is less than the above lower limit, the crystallization rate is slow, and in some cases, molding may be difficult, and further, solder heat resistance may be reduced.
  • a Tm of 310 ° C. or higher is preferable because it satisfies the reflow solder heat resistance of 280 ° C. and can be applied to a gold / tin eutectic solder process.
  • the polyester resin of the present invention preferably has a difference between the melting point (Tm) and the cooling crystallization temperature (Tc2) in DSC measurement of 40 ° C. or less, more preferably 35 ° C. or less, and most preferably 30 ° C. or less. is there.
  • the temperature-falling crystallization temperature (Tc2) is a temperature at which crystallization starts when the temperature is lowered from a temperature higher by 10 ° C. or more than the melting point in DSC measurement.
  • the melting point (Tm) and the cooling crystallization temperature (Tc2) are measured by the methods described in the Examples section below. When the difference between the melting point (Tm) and the temperature-falling crystallization temperature (Tc2) is 40 ° C.
  • the intrinsic viscosity (IV) of the polyester resin of the present invention is preferably 0.10 to 0.70 dl / g, more preferably 0.20 to 0.65 dl / g, still more preferably 0.25 to 0.00. 60 dl / g.
  • the polyester resin of the present invention has an excellent balance of low water absorption and fluidity in addition to a high melting point and moldability, and also has excellent weather resistance. For this reason, the polyester resin composition obtained from such a polyester resin has a high melting point of 280 ° C. or higher in the molding of a reflector for a surface-mounted LED, so that it has heat resistance, crystallinity (moldability), heat yellowing, It is a polyester resin composition suitable for a reflector for a surface-mounted LED having excellent weather resistance and low water absorption.
  • the polyester resin of the present invention can be produced by a conventionally known production method.
  • a direct esterification method in which an acid component composed of 4,4′-biphenyldicarboxylic acid and another dicarboxylic acid is directly reacted with a glycol component to distill water to esterify, followed by polycondensation under reduced pressure, or 4 It is produced by a transesterification method in which an acid component consisting of dimethyl 4,4'-biphenyldicarboxylate and other dimethyl dicarboxylate and a glycol component are reacted to distill methyl ester by diesterification, followed by polycondensation under reduced pressure.
  • the polyester resin of the present invention By blending the polyester resin of the present invention with titanium oxide, a reinforcing material, a non-fibrous or non-needle filler, and making a polyester resin composition, the material is suitable for a reflector for a surface mount LED. I can do it. When blended, mechanical strength and weather resistance tend to be improved.
  • Titanium oxide is blended to increase the surface reflectance of the reflector.
  • Dititanium trioxide (Ti 2 O 3 ), and the like, and particularly rutile titanium dioxide (TiO 2 ) is preferably used.
  • the average particle size of titanium oxide is generally in the range of 0.05 to 2.0 ⁇ m, preferably 0.15 to 0.5 ⁇ m, and may be used alone or in combination with titanium oxides having different particle sizes. May be used.
  • the titanium oxide component concentration is 90% or more, preferably 95% or more, and more preferably 97% or more.
  • titanium oxide that has been surface-treated with a metal oxide such as silica, alumina, zinc oxide, zirconia, a coupling agent, an organic acid, an organic polyhydric alcohol, or siloxane can be used.
  • the proportion of titanium oxide is preferably 0.5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the polyester resin.
  • the ratio of titanium oxide is less than the above lower limit, the surface reflectance is lowered, and when it exceeds the upper limit, molding processability may be lowered, such as a significant decrease in physical properties and fluidity.
  • the reinforcing material is blended in order to improve the moldability of the polyester resin composition and the strength of the molded product, and at least one selected from a fibrous reinforcing material and a needle-shaped reinforcing material is used.
  • a fibrous reinforcing material include glass fiber, carbon fiber, boron fiber, ceramic fiber, and metal fiber.
  • the acicular reinforcing material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, and carbonic acid. Calcium whiskers, magnesium sulfate whiskers, wollastonite and the like can be mentioned.
  • glass fibers chopped strands or continuous filament fibers having a length of 0.1 mm to 100 mm can be used.
  • a glass fiber having a circular cross section and a non-circular cross section can be used as the cross-sectional shape of the glass fiber.
  • the diameter of the circular cross-section glass fiber is 20 ⁇ m or less, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • a glass fiber having a non-circular cross section is preferred from the viewpoint of physical properties and fluidity.
  • Non-circular cross-section glass fibers include those that are substantially oval, substantially oval, or substantially bowl-shaped in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8. It is preferable.
  • the flatness is assumed to be a rectangle with the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of the rectangle is the major axis, and the length of the short side is the minor axis. It is the ratio of major axis / minor axis.
  • the thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 ⁇ m and the major axis is about 2 to 100 ⁇ m. Further, glass fibers are preferably used in the form of chopped strands which are formed into fiber bundles and cut to a fiber length of about 1 to 20 mm.
  • the difference in refractive index from the copolyester resin is large, so use a material whose refractive index is increased by changing the glass composition or surface treatment. It is preferable to do.
  • the proportion of the reinforcing material is preferably 0 to 100 parts by mass, more preferably 5 to 100 parts by mass, and further preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polyester resin.
  • the reinforcing material is not an essential component, but if the proportion is 5 parts by mass or more, the mechanical strength of the molded product is preferably improved. When the ratio of the reinforcing material exceeds the above upper limit, the surface reflectance and the moldability tend to be lowered.
  • non-fibrous or non-needle fillers include reinforcing fillers, conductive fillers, magnetic fillers, flame retardant fillers, thermal conductive fillers, thermal yellowing suppression fillers, etc., specifically glass. Beads, glass flakes, glass balloons, silica, talc, kaolin, mica, alumina, hydrotalcite, montmorillonite, graphite, carbon nanotubes, fullerene, indium oxide, tin oxide, iron oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide , Calcium hydroxide, red phosphorus, calcium carbonate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, barium sulfate, and non-acicular wollastonite, potassium titanate, aluminum borate , Magnesium sulfate, acetate Neshiumu, zinc oxide, calcium carbonate, and the like.
  • fillers may be used not only alone but also in combination of several kinds. Among these, talc is preferable because Tc1 is lowered and moldability is improved.
  • the addition amount of the filler may be selected as an optimum amount, but it is possible to add a maximum of 50 parts by mass with respect to 100 parts by mass of the polyester resin, but from the viewpoint of the mechanical strength of the resin composition, it is 0.
  • the amount is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass.
  • the fibrous reinforcing material and the filler are preferably used after being treated with an organic treatment or a coupling agent, or used in combination with a coupling agent at the time of melt compounding.
  • the ring agent any of a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent may be used, and among them, an aminosilane coupling agent and an epoxy silane coupling agent are particularly preferable.
  • additives of the conventional polyester resin composition for LED reflectors can be used for the said polyester resin composition.
  • Additives include stabilizers, impact modifiers, flame retardants, mold release agents, slidability improvers, colorants, fluorescent brighteners, plasticizers, crystal nucleating agents, thermoplastic resins other than polyester, and the like.
  • the above-mentioned polyester resin composition can be produced by blending the above-described constituent components by a conventionally known method. Examples include a method in which each component is added during the polycondensation reaction of the polyester resin, a polyester resin and other components are dry blended, or each component is melt-kneaded using a twin screw type extruder. be able to.
  • the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
  • the measured value described in the Example is measured by the following method.
  • the temperature was raised at a rate of temperature rise of 20 ° C./minute, held at 330 ° C. for 3 minutes, and then cooled from 330 ° C. to 130 ° C. at a rate of 10 ° C./minute.
  • the peak temperature of the melting peak observed when the temperature was raised was defined as the melting point (Tm), and the peak temperature of the crystallization peak observed when the temperature was decreased was the lowered crystallization temperature (Tc2).
  • Preheating was performed. Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C./min, held at the predetermined temperature for 10 seconds, and then cooled. The set temperature was increased from 240 ° C. every 5 ° C., and the highest set temperature at which the surface did not swell or deformed was defined as the reflow heat resistant temperature, which was used as an index of solder heat resistance.
  • ⁇ Reflow heat resistant temperature is 260 ° C or higher and lower than 280 ° C.
  • X Reflow heat resistant temperature is lower than 260 ° C.
  • test piece for evaluation was prepared. This test piece was irradiated with UV light at an illuminance of 50 mW / cm 2 in an environment of 63 ° C. and 50% RH using a super accelerated weathering tester “I Super UV Tester SUV-F11”. The light reflectance at a wavelength of 460 nm of the test piece was measured before irradiation and 60 hours after irradiation.
  • the retention rate of the light reflectivity of the post-irradiation test piece relative to the light reflectivity of the pre-irradiation test piece was evaluated according to the following criteria. ⁇ : Retention rate 90% or more ⁇ : Retention rate less than 90% to 85% or more ⁇ : Retention rate less than 85%
  • the resin under slight pressure was discharged into water as a strand, cooled, and then cut with a cutter to obtain a cylindrical pellet having a length of about 3 mm and a diameter of about 2 mm.
  • the intrinsic viscosity of the obtained polyester was 0.60 dl / g, and the resin composition was 65 mol% of 4,4′-biphenyldicarboxylic acid, 35 mol% of terephthalic acid, and 98 of ethylene glycol according to 1 H-NMR measurement. 0.2 mol% and diethylene glycol were 1.8 mol%.
  • the characteristic values of the obtained polyester resin are shown in Table 1.
  • polyester resin was obtained in the same manner as in the polymerization of the polyester resin of Synthesis Example 1 except that the amount and type of raw materials used were changed. Table 1 shows the characteristic values of the obtained polyester resins.
  • Diethylene glycol is a by-product of condensation of ethylene glycol.
  • Synthesis Example 8 In a 20 liter stainless steel autoclave with a stirrer, 3542 g of dimethyl 4,4'-biphenyldicarboxylate, 1400 g of high purity dimethyl terephthalic acid, ethylene glycol, manganese acetate 2 g, and 0.86 g of germanium dioxide in an amount three times the acid component.
  • the intrinsic viscosity of the obtained polyester was 0.60 dl / g, and the resin composition was 65 mol% of 4,4′-biphenyldicarboxylic acid, 35 mol% of terephthalic acid, and 98 of ethylene glycol according to 1 H-NMR measurement. 0.2 mol% and diethylene glycol were 1.8 mol%.
  • the characteristic values of the obtained polyester resin are shown in Table 1.
  • the pressure in the reaction system was gradually decreased to 13.3 Pa (0.1 Torr) while the temperature was raised to 280 ° C. over 60 minutes, and a polycondensation reaction was further performed at 280 ° C. and 13.3 Pa. Subsequent to releasing the pressure, the resin under slight pressure was discharged into water as a strand, cooled, and then cut with a cutter to obtain a cylindrical pellet having a length of about 3 mm and a diameter of about 2 mm.
  • the obtained PET had an IV of 0.61 dl / g, and the resin composition was 100 mol% terephthalic acid, 98.0 mol% ethylene glycol, and 2.0 mol% diethylene glycol, as determined by 1 H-NMR. It was.
  • the characteristic values of the obtained polyester resin are shown in Table 2.
  • the autoclave was pressurized to 22 kg / cm 2 .
  • the reaction was continued for 1 hour, and then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours.
  • the reaction was carried out while gradually removing water vapor and maintaining the pressure at 22 kg / cm 2 .
  • the pressure was reduced to 10 kg / cm 2 over 30 minutes and the reaction was further continued for 1 hour to obtain a prepolymer having an intrinsic viscosity [ ⁇ ] of 0.25 dl / g. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less.
  • a white polyamide having a melting point of 310 ° C., an intrinsic viscosity [ ⁇ ] of 1.33 dl / g, and a terminal sealing rate of 90% was obtained by solid-phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours. Obtained.
  • Examples 1 to 8, Comparative Examples 1 to 5 Using the polyester resin and polyamide resin obtained in the above synthesis examples and comparative synthesis examples, using the twin-screw extruder STS-35 manufactured by Coperion Co., Ltd. with the components and mass ratios shown in Tables 3 and 4, the melting point of the resin Melting and kneading was performed at + 15 ° C. to obtain a resin composition for evaluation.
  • the materials used other than the resin are as follows.
  • Titanium oxide manufactured by Ishihara Sangyo Co., Ltd., Taipei CR-60, rutile TiO 2 , average particle size 0.2 ⁇ m
  • Reinforcing material Glass fiber (manufactured by Nitto Boseki Co., Ltd., CS-3J-324)
  • Mold release agent Magnesium stearate Stabilizer: Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Specialty Chemicals)
  • polyester resin compositions and polyamide resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were subjected to evaluation of various properties. The results are shown in Tables 3 and 4.
  • the melting point of the polyester resin by DSC is 280 ° C or higher, it can be applied to the reflow soldering process, and if the melting point exceeds 310 ° C, the reflow heat resistance temperature is 280 ° C or higher.
  • the reflow heat resistance temperature is 280 ° C or higher.
  • it has excellent adhesion with sealing materials, which are important characteristics for LED applications, and surface reflectance.
  • moldability, fluidity It was confirmed that the dimensional stability, low water absorption, and excellent light resistance were excellent.
  • the polyamide resin of Comparative Example 5 has a high melting point, the reflow heat resistant temperature could not satisfy 280 ° C. or higher due to water absorption due to the amide structure.
  • the polyester resin of the present invention is excellent in workability such as moldability at the time of injection molding and solder heat resistance in addition to high heat resistance and low water absorption when used in a material used for a reflector for a surface mount LED. Therefore, the surface-mounted LED reflector can be industrially advantageously produced while highly satisfying the required characteristics.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Led Device Packages (AREA)

Abstract

Cette invention permet d'obtenir une résine polyester pouvant être utilisée dans un matériau de plaque réfléchissante convenable pour LED montée en surface, ladite résine ayant une excellente résistance thermique, une excellente aptitude au moulage lors du moulage par injection, une excellente basse absorbabilité d'eau, et une excellente réflexivité superficielle. La résine polyester pour plaque réfléchissante pour LED montée en surface selon l'invention contient : à titre de composants constitutifs, un acide 4,4'-biphényldicarboxylique, un composant acide comprenant d'autres acides dicarboxyliques, et un composant de glycol. Elle a un point de fusion d'au moins 280°C et, dans l'idéal, au moins 30 % en mol du composant acide total est représenté par l'acide 4,4'-biphényldicarboxylique, les autres acides dicarboxyliques étant l'acide téréphtalique et/ou l'acide 2,6-naphtalène- dicarboxylique.
PCT/JP2013/053639 2012-02-24 2013-02-15 Résine polyester pour plaque réfléchissante pour led montée en surface WO2013125454A1 (fr)

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KR1020147021563A KR101848970B1 (ko) 2012-02-24 2013-02-15 표면 실장형 ｌｅｄ 반사판용 폴리에스테르 수지
CN201380010667.3A CN104136487B (zh) 2012-02-24 2013-02-15 表面安装型led反射板用聚酯树脂
JP2013509766A JP6048832B2 (ja) 2012-02-24 2013-02-15 表面実装型ｌｅｄ反射板用ポリエステル樹脂

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* Cited by examiner, † Cited by third party
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JP2015093943A (ja) * 2013-11-13 2015-05-18 東洋紡株式会社 Ｌｅｄ反射板用ポリエステル樹脂組成物
JP2015138194A (ja) * 2014-01-23 2015-07-30 パナソニックＩｐマネジメント株式会社 光反射体用成形材料、光反射体及び照明器具
JP2016536405A (ja) * 2013-11-12 2016-11-24 エスケー ケミカルズ カンパニー リミテッド ポリシクロへキシレンジメチレンテレフタレート樹脂組成物
US20220049049A1 (en) * 2018-10-16 2022-02-17 Toyobo Co., Ltd. Polyester resin for heat-shrinkable film, heat-shrinkable film, heat-shrinkable label, and packaged product

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JP2001527144A (ja) * 1997-12-30 2001-12-25 ディーエスエム エヌ．ブイ． コポリエステル物品
JP2004285510A (ja) * 2003-03-20 2004-10-14 Toyobo Co Ltd 共重合ポリエステル繊維
JP2004300622A (ja) * 2003-03-31 2004-10-28 Toyobo Co Ltd 共重合ポリエステル繊維
JP2005179566A (ja) * 2003-12-22 2005-07-07 Toyobo Co Ltd 二軸延伸ポリエステルフィルム

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JPH0762071A (ja) * 1993-06-15 1995-03-07 Nippon Petrochem Co Ltd 全芳香族ポリエステルおよびその組成物
JP2001527144A (ja) * 1997-12-30 2001-12-25 ディーエスエム エヌ．ブイ． コポリエステル物品
JP2004285510A (ja) * 2003-03-20 2004-10-14 Toyobo Co Ltd 共重合ポリエステル繊維
JP2004300622A (ja) * 2003-03-31 2004-10-28 Toyobo Co Ltd 共重合ポリエステル繊維
JP2005179566A (ja) * 2003-12-22 2005-07-07 Toyobo Co Ltd 二軸延伸ポリエステルフィルム

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016536405A (ja) * 2013-11-12 2016-11-24 エスケー ケミカルズ カンパニー リミテッド ポリシクロへキシレンジメチレンテレフタレート樹脂組成物
JP2015093943A (ja) * 2013-11-13 2015-05-18 東洋紡株式会社 Ｌｅｄ反射板用ポリエステル樹脂組成物
JP2015138194A (ja) * 2014-01-23 2015-07-30 パナソニックＩｐマネジメント株式会社 光反射体用成形材料、光反射体及び照明器具
US20220049049A1 (en) * 2018-10-16 2022-02-17 Toyobo Co., Ltd. Polyester resin for heat-shrinkable film, heat-shrinkable film, heat-shrinkable label, and packaged product

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CN104136487A (zh) 2014-11-05
TWI554543B (zh) 2016-10-21
KR20140138120A (ko) 2014-12-03
TW201343711A (zh) 2013-11-01
JP6048832B2 (ja) 2016-12-21
KR101848970B1 (ko) 2018-04-13
JPWO2013125454A1 (ja) 2015-07-30

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