KR20160016858A - Polyester resin, and polyester resin composition for surface-mount-type LED reflective plate which comprises same - Google Patents

Abstract

A polyester resin comprising a dicarboxylic acid component containing an aromatic dicarboxylic acid in an amount of 50 mol% or more and a glycol component containing 4,4'-biphenyldimethanol in an amount of 15 mol% or more, Resin is disclosed. (C) selected from the group consisting of the polyester resin (A), the titanium oxide (B), the fibrous reinforcement and the needle reinforcement, and the nonfibrous or non-needle filler (D) , 0.5 to 100 parts by mass, 0 to 100 parts by mass and 0 to 50 parts by mass of the titanium oxide (B), the reinforcing material (C) and the nonfibrous or non-needle filler (D) are added to 100 parts by mass of the resin (A) The present invention also provides a polyester resin composition which is characterized in that it is present as a polyester resin. Such a polyester resin composition is suitable for use in a surface-mounted LED reflector.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin and a polyester resin composition for a surface mount type LED reflector using the polyester resin,

The present invention relates to a polyester resin which is excellent in moldability, fluidity, dimensional stability, low water absorbency, solder heat resistance, surface reflectance and the like and further has excellent resistance to gold / tin soldering heat resistance, light resistance, And a polyester resin composition suitable for use in a reflector for LED.

BACKGROUND ART Recently, LED (light emitting diode) has been applied to a lighting apparatus, an optical element, a cellular phone, a backlight for a liquid crystal display, an automobile console panel, a signaling apparatus, a display board and the like by taking advantage of features such as low power consumption, long life, high brightness and miniaturization. In addition, surface mounting technology is used to realize light weight shortening in applications that emphasize designability and portability.

Surface mount LEDs are generally composed of LED chips, lead wires, reflectors, and encapsulant resin that emit light. Since all the components mounted on the electronic board are bonded by lead-free solder, each component has a solder reflow temperature of 260 Lt; RTI ID = 0.0 > C. ≪ / RTI > A melting point (melting peak temperature) of 280 DEG C or more is required as the material. In particular, reflectors are required to have surface reflectance and durability against heat or ultraviolet rays in order to efficiently extract light, in addition to these heat resistance. From these viewpoints, various heat-resistant plastic materials such as ceramics, semi-aromatic polyamides, liquid crystal polymers, and thermosetting silicon have been studied. Among them, resins obtained by dispersing a high refractive index filler such as titanium oxide or the like in a semiaromatic polyamide or polyester, Heat resistance, surface reflectance, and the like, and thus it is most widely used. In recent years, along with the commercialization of LEDs, it has been required to further improve workability and reliability of the reflector, and it is required to improve the heat-resistant coloring property and light resistance of the long-term.

As a polyester resin composition for an LED reflector, for example, Patent Documents 1 to 5 have been proposed.

In Patent Documents 1 and 2, (a) i) 70 to 100 mol% of terephthalic acid residue, ii) 0 to 30 mol% of aromatic dicarboxylic acid residue having 20 or less carbon atoms, and iii) aliphatic dicarboxylic acid residue (I) 1 to 99 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and ii) 1,4- - a glycol component comprising 1 to 99 mol% of cyclohexane dimethanol residues, wherein the total molar percentage of the dicarboxylic acid component is 100 mol% and the total molar percentage of the glycol component is 100 mol% Has been disclosed, which tends to be good in mechanical properties but has a problem in moldability and light resistance.

In Patent Document 3, (A) 2 to 50 parts by mass of a phosphinic acid salt (B) in which the anion moiety is a calcium salt or aluminum salt of phosphinic acid with respect to 100 parts by mass of a polyester resin, (C) 0.5 to 30 parts by mass And (D) 0.01 to 3 parts by mass of a polyolefin resin having a polar group. The flame retardant polyester resin composition for a reflector of a lighting device according to claim 1, wherein the flame retardant polyester resin composition comprises a gold / tin solder heat resistance, There is a problem in light resistance.

In Patent Document 4, 100 parts by mass of a wholly aromatic thermotropic liquid crystal polyester, 97 to 85% by mass of titanium oxide obtained by a process including a roasting process, and 3 to 15% by mass of aluminum oxide (including a hydrate) 8 to 42 parts by mass of titanium oxide particles obtained by surface-treating the above glass fibers with 10 to 50% by mass of the glass fibers, 25 to 50 parts by mass of glass fibers and 0 to 8 parts by mass of other inorganic fillers, And a step of supplying a part of the component at a position on the downstream side of not less than 30% with respect to the entire length of the cylinder of the biaxial kneader through a melt-kneading step. However, the resin composition has a problem in heat resistance and weather resistance.

Patent Document 5 discloses a dry unsaturated polyester resin composition comprising at least an unsaturated polyester resin, a polymerization initiator, an inorganic filler, a white pigment, a releasing agent and a reinforcing material, wherein the unsaturated polyester resin is contained in an amount of 14 to 40 mass % Of 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, and the ratio of the white pigment to the total amount of the inorganic filler and the white pigment Is not less than 30% by mass, and the unsaturated polyester resin is a mixture of an unsaturated alkyd resin and a crosslinking agent. The unsaturated polyester resin composition for LED reflector has problems in moldability and light resistance.

In addition, various polyamides have been used as reflectors for surface mount type LEDs up to now, but there has been a problem in heat resistance coloring property, light resistance and water absorbability.

As described above, conventionally proposed polyesters and polyamides have problems in terms of heat resistance, heat resistance, and moldability.

In recent years, development for lighting purposes has also been actively carried out. In consideration of the development for lighting purposes, further reduction in production cost, improvement in performance, improvement in lifetime, and improvement in long-term reliability are further demanded. For this reason, gold / tin process soldering which is less deteriorated and has high thermal conductivity is used instead of the conventional epoxy resin / silver paste for bonding the lead frame and the LED chip as an improvement of reliability. However, in the case of the gold / tin process soldering, a temperature of 280 ° C or more and less than 290 ° C is applied, and thus the resin used requires a melting point of 290 ° C or more in order to withstand the process. Furthermore, in order to prevent the occurrence of swelling (blister) on the surface of the molded article due to moisture in the resin even in the processing of the gold / tin process soldering, the resin is required to have low water absorption.

As described above, a polyester resin composition sufficiently satisfying the characteristics usable for the surface-mounted LED reflector has not been reported so far.

Japanese Patent Publication No. 2008-544030 Japanese Patent Publication No. 2008-544031 Japanese Patent Application Laid-Open No. 2010-270177 Japanese Patent Application Laid-Open No. 2008-231368 Japanese Patent No. 4844699

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art described above, and its object is to provide a resin composition which is excellent in moldability, fluidity, dimensional stability, low water absorbency, solder heat resistance, surface reflectance and light resistance at the time of injection molding, A polyester resin which achieves a high melting point to which a gold / tin process soldering process is applicable, a low water absorbency for reducing the swelling of a molded article due to moisture in a brazing process, and a light resistance during outdoor use or long- And a polyester resin composition for a surface mount LED reflector using the same.

In order to achieve the above object, the inventors of the present invention have found that it is possible to advantageously perform an injection molding or a reflow soldering process while satisfying the characteristics as a reflector for an LED, and furthermore to provide a poly As a result of intensive studies on the composition of the ester, the present invention has been completed.

That is, the present invention has the following constitutions (1) to (11).

(1) A polyester resin comprising a dicarboxylic acid component containing at least 50 mol% of an aromatic dicarboxylic acid and a glycol component containing at least 15 mol% of 4,4'-biphenyl dimethanol, Lt; / RTI > or more.

(2) the aromatic dicarboxylic acid comprises at least one dicarboxylic acid selected from the group consisting of 4,4'-biphenyldicarboxylic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acid (1).

(3) the glycol component other than 4,4'-biphenyl dimethanol constituting the polyester resin is at least one selected from the group consisting of ethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propanediol, neopentyl glycol, The polyester resin according to (1) or (2), wherein the polyester resin comprises at least one glycol selected from the group consisting of butanediol.

(4) The polyester resin according to any one of (1) to (3), wherein the difference between the melting point (Tm) of the polyester resin and the crystallization temperature (Tc2)

(5) The polyester resin according to any one of (1) to (4), wherein the acid value of the polyester resin is 1 to 40 eq / t.

(6) One or more reinforcements (C) selected from the group consisting of the polyester resin (A), the titanium oxide (B), the fibrous reinforcement material and the needle-like reinforcement material according to any one of (1) (B), the reinforcing material (C), and the nonfibrous or non-needle-like filler (D) are contained in an amount of 0.5% by weight based on 100 parts by weight of the polyester resin (A) To 100 parts by mass, 0 to 100 parts by mass, and 0 to 50 parts by mass, based on 100 parts by mass of the resin composition.

(7) The polyester resin composition according to (6), wherein the non-fibrous or non-needle-like filler (D) is talc and contains 0.1-5 parts by mass of talc with respect to 100 parts by mass of the polyester resin (A) .

(8) The polyester resin composition according to (6) or (7), wherein the reflow soldering heat resistance temperature is 260 占 폚 or higher.

(9) The polyester resin composition according to any one of (6) to (8), wherein the solder reflow endothermic temperature is 280 占 폚 or higher.

(10) The polyester resin composition according to any one of (6) to (9), wherein the melting peak temperature (Tm) of the polyester resin composition is 280 占 폚 or more and the difference between the melting peak temperature (Tm) A polyester resin composition according to any one of the preceding claims.

(11) A reflector for surface-mount type LED, which is obtained by molding using the polyester resin composition according to any one of (6) to (10).

The polyester resin of the present invention is excellent in workability such as moldability at the time of injection molding and heat resistance of soldering, in addition to high heat resistance and low water absorption. Therefore, since the polyester resin composition of the present invention uses such a polyester resin, it is industrially advantageous to produce a reflector for surface-mounted type LED which satisfies all the necessary characteristics.

The polyester resin composition of the present invention can be applied to a soldering process of a gold / tin process because the polyester resin as a main component has a high melting point of 280 DEG C or more and excellent heat resistance, and furthermore, the aromatic ring concentration is high, , And can exhibit characteristics such as excellent light resistance and excellent adhesion to an encapsulating material.

The polyester resin of the present invention has properties suitable as a material used for a molded article such as a film, a sheet, an injection molded article, a deformed molded article and the like, particularly, a surface mounted LED reflector. The polyester resin composition of the present invention is also intended to be used for a surface-mounted LED reflector. 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 composition of the present invention can be produced by injection molding all of these reflectors.

The polyester resin composition of the present invention comprises at least one reinforcing material (C) selected from the group consisting of a polyester resin (A), a titanium oxide (B), a fibrous reinforcing material and a needle reinforcing material, and a fibrous or non- .

The polyester resin (A) is blended for realizing excellent anti-UV property in addition to a high melting point and a low water absorbency in order to give high reliability. The polyester resin (A) is a dicarboxylic acid containing an aromatic dicarboxylic acid in an amount of 50 mol% Component and 4,4'-biphenyl dimethanol in an amount of 15 mol% or more, and has a melting point of 280 ° C or higher. The melting point of the polyester resin (A) is preferably 290 DEG C or higher, more preferably 300 DEG C or higher, and still more preferably 310 DEG C or higher. The upper limit of the melting point of the polyester resin (A) is not particularly limited, but is 340 占 폚 or lower from the limit of the usable raw material components. The melting point is measured by the method described in the section of the embodiment.

Examples of the aromatic dicarboxylic acid used as the dicarboxylic acid component of the polyester resin (A) include 4,4'-biphenyldicarboxylic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, and the like. Of the above aromatic dicarboxylic acids, 4,4'-biphenyldicarboxylic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, or a mixture thereof are preferable from the viewpoints of polymerizability, cost and heat resistance. The aromatic dicarboxylic acid is at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, still more preferably at least 80 mol%, particularly preferably at least 50 mol% of the dicarboxylic acid component from the viewpoint of heat resistance Is 90 mol% or more, and may be 100 mol%. Examples of dicarboxylic acids other than aromatic dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, glutaric acid and dimeric acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 1,2-cyclo And alicyclic dicarboxylic acids such as hexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid. Further, polyvalent carboxylic acids such as oxyacids such as p-oxybenzoic acid and oxycaproic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenylsulfonetetracarboxylic acid and biphenyltetracarboxylic acid, The anhydride thereof may be used in combination.

The 4,4'-biphenyl dimethanol used as the glycol component of the polyester resin (A) should contain at least 15 mol% of the total glycol component, and preferably 4,4'-biphenyl dimethanol More preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, and most preferably 70 mol% or more. 4,4'-biphenyldimethanol is added to improve moldability, solder heat resistance, and light resistance. If the ratio is less than the above-mentioned value, these properties tend to deteriorate. Examples of glycol components other than 4,4'-biphenyldimethanol 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-cyclohexanediol ethanol, 3-methyl- Methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, Propane diol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-n-butyl- Di-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl-1,3-propanediol, 2,2- Propanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, triethylene glycol Recycled, aliphatic glycols such as polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol and polypropylene glycol, hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis (? -Hydroxyethoxy) Bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2- Bis (p-hydroxyphenyl) ethane, bisphenol A, an alkylene oxide adduct of bisphenol A, and the like. Among the above-mentioned glycols, one or two selected from ethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propanediol, neopentyl glycol 1,4-butanediol and the like are preferably selected from heat resistance, Mixtures of species or more are preferred. More preferably, it is one or a mixture of two or more selected from ethylene glycol and 1,4-butanediol. When ethylene glycol is used as the glycol component, diethylene glycol may be produced as a by-product in the production of the polyester resin (A) to form a copolymerized component. In this case, diethylene glycol as a by-product is about 1 to 5 mol% based on the ethylene glycol charged into the polyester resin although it depends on the production conditions. Further, multivalent polyols such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol may be used in combination.

The polyester resin is preferably at least 160 mol%, more preferably at least 180 mol%, further preferably at least 190 mol%, based on the total amount of the dicarboxylic acid component and the glycol component, %, And may be 200 mol%. However, in any case, the dicarboxylic acid component is 100 mol% and the glycol component is not more than 100 mol%.

Also, metal salts such as 5-sulfoisophthalic acid, 4-sulfonated naphthalene-2,7-dicarboxylic acid and 5- [4-sulfophenoxy] isophthalic acid, 5-dimethyl-3-sulfo-2,5-hexanediol, and other dicarboxylic acids or diols containing a sulfonic acid metal base in the range of 20 mol% or less of the total acid component or the entire diol component do.

The catalyst used in producing the polyester resin (A) is not particularly limited, but it is preferable to use at least one compound selected from compounds of Ge, Ti, Sb, Al, Mn or Mg. These compounds are added to the reaction system as a powder, an aqueous solution, an ethylene glycol solution, a slurry of ethylene glycol or the like.

Further, as a stabilizer for the resin, there may be mentioned a group consisting of phosphoric acid esters such as phosphoric acid, polyphosphoric acid and trimethylphosphate, phosphonic acid-based compounds, phosphinic acid-based compounds, phosphine oxide-based compounds, aposphonic acid-based compounds, Is preferably used as the phosphorus compound.

The acid value of the polyester resin (A) is preferably 1 to 40 eq / ton. When the acid value exceeds 40 eq / ton, the light resistance tends to decrease. When the acid value is less than 1 eq / ton, the polycondensation reactivity is lowered and the productivity tends to deteriorate.

The polyester resin (A) of the present invention has a melting point (Tm) in the DSC measurement of 280 占 폚 or higher, preferably 290 占 폚 or higher, more preferably 300 占 폚 or higher, particularly preferably 310 占 폚 or higher, Gt; 320 < / RTI > On the other hand, the upper limit of the polyester resin melting point (Tm) of the present invention is preferably 340 ° C or lower. When the Tm exceeds 340 캜, the processing temperature required for injection molding of the composition using the polyester resin (A) of the present invention becomes extremely high, so that the polyester resin is decomposed at the time of processing, May not be obtained. On the contrary, when the Tm is less than the lower limit, the crystallization speed is slowed, and molding may become difficult in some cases, and furthermore, the soldering heat resistance may be lowered. When Tm is 310 占 폚 or more, it is preferable because it satisfies reflow soldering heat resistance at 280 占 폚 and is applicable to a gold / tin process brazing process.

In the polyester resin (A) of the present invention, the difference between the melting point (Tm) and the crystallization temperature (Tc2) of the temperature during the DSC measurement is preferably 42 ° C or lower, more preferably 40 ° C or lower, still more preferably 35 ° C or lower , And most preferably 30 DEG C or less. (Tc2) is a temperature at which crystallization starts when the temperature is lowered by at least 10 deg. C higher than the melting point in the DSC measurement. The melting point (Tm) and the temperature for crystallization at a low temperature (Tc2) are measured by the method described in the embodiment. When the difference between the melting point (Tm) and the temperature-lowering crystallization temperature (Tc2) is lower than the above-mentioned temperature, the crystallization proceeds easily, and the dimensional stability and physical properties can be sufficiently exhibited. On the other hand, when the difference between the melting point (Tm) and the cold crystallization temperature (Tc2) exceeds the above-mentioned temperature, since the reflection plate for LED is formed by a short cycle of injection molding, crystallization may not proceed sufficiently, There is a problem that deformation or crystal shrinkage occurs during heating in a post-process, causing peeling from the encapsulant or the lead frame, resulting in lack of reliability.

The intrinsic viscosity (IV) of the polyester resin (A) is preferably from 0.10 to 0.70 dl / g, more preferably from 0.20 to 0.65 dl / g, and still more preferably from 0.25 to 0.60 dl / g.

The polyester resin (A) is present in the polyester resin composition of the present invention preferably in a proportion of 25 to 90 mass%, more preferably 40 to 75 mass%. If the proportion of the polyester resin (A) is less than the above lower limit, the mechanical strength is lowered, and if it exceeds the upper limit, the blending amount of the titanium oxide (B) and the reinforcement (C) is insufficient.

The titanium oxide (B) is blended to increase the surface reflectance of the reflector. For example, titanium dioxide (TiO ₂ ), rutile type and anatase type titanium dioxide (TiO ₂ ) produced by a sulfuric acid method or a chlorine method, Ti ₂ O ₃ ), and particularly, rutile type titanium dioxide (TiO ₂ ) is preferably used. The average particle diameter of the titanium oxide (B) is generally in the range of 0.05 to 2.0 占 퐉, preferably 0.15 to 0.5 占 퐉. The titanium oxide (B) may be used singly or in combination with titanium oxide having different particle diameters. The titanium oxide component concentration is at least 90 mass%, preferably at least 95 mass%, and more preferably at least 97 mass%. The titanium oxide (B) may be a product obtained by surface-treating with a metal oxide such as silica, alumina, zinc oxide or zirconia, a coupling agent, an organic acid, an organic polyhydric alcohol or a siloxane.

The proportion of the titanium oxide (B) is 0.5 to 100 parts by mass, preferably 10 to 80 parts by mass, based on 100 parts by mass of the polyester resin (A). If the ratio of the titanium oxide (B) is less than the lower limit, the surface reflectance is lowered. If the ratio is higher than the upper limit, the physical properties are drastically reduced but the flowability is lowered.

The reinforcing material (C) is blended to improve the moldability of the polyester resin composition and the strength of the molded article, and at least one selected from a fibrous reinforcement material and an acicular reinforcement material is used. Examples of the fibrous reinforcement material include glass fiber, carbon fiber, boron fiber, ceramic fiber and metal fiber. Examples of the reinforcement material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, calcium carbonate whisker, Magnesium sulfate whiskers, wollastonite, and the like. As the glass fiber, it is possible to use a cord strand or continuous filament fiber having a length of 0.1 mm to 100 mm. As the cross-sectional shape of the glass fiber, glass fibers having a circular cross section and a non-circular cross section can be used. The diameter of the circular cross-section glass fiber is preferably 20 占 퐉 or less, more preferably 15 占 퐉 or less, and further preferably 10 占 퐉 or less. Further, glass fibers having a non-circular cross section are preferable from the viewpoints of physical properties and fluidity. As the non-circular cross section glass fiber, it is preferable that the cross section perpendicular to the longitudinal direction of the fiber includes a substantially oval shape, a substantially circular shape, and a cocoon shape, and the flatness is 1.5 to 8. Here, the flatness is a rectangle having a minimum area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber. The length of the long side of the rectangle is referred to as a long diameter, and the ratio of the long diameter to the short diameter to be. The thickness of the glass fiber is not particularly limited, but it has a short diameter of 1 to 20 mu m and a long diameter of about 2 to 100 mu m. Further, the glass fiber may be preferably a fiber strand having a fiber bundle cut into a fiber length of about 1 to 20 mm. Further, in order to increase the surface reflectance of the polyester resin composition, it is preferable that the difference in refractive index from the polyester resin is large. Therefore, it is preferable to use a resin having an increased refractive index by changing the glass composition or surface treatment.

The ratio of the reinforcing material (C) is 0 to 100 parts by mass, preferably 5 to 100 parts by mass, and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polyester resin (A). Although the reinforcing material (C) is not an essential component, if the ratio is 5 parts by mass or more, the mechanical strength of the molded product is improved, which is preferable. When the ratio of the reinforcing material (C) exceeds the upper limit, surface reflectivity and molding processability tend to be lowered.

Examples of the non-fibrous or non-needle-like filler (D) include reinforcing fillers, conductive fillers, magnetic fillers, flame retardant fillers, heat conductive fillers and heat yellowing inhibiting fillers. Specific examples thereof include glass beads, glass flakes, , Silica, talc, kaolin, mica, alumina, hydrotalcite, montmorillonite, graphite, carbon nanotube, fullerene, indium oxide, tin oxide, iron oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, Magnesium hydroxide, zinc oxide, magnesium carbonate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, barium sulfate and wollastonite other than needle beds, potassium titanate, aluminum borate, zinc sulfate and calcium carbonate. These fillers may be used alone or in combination of several species. Of these, talc is preferable because it has an effect of accelerating the crystallization and improves the moldability. The amount of the filler to be added may be selected in an optimum amount. It is possible to add up to 50 parts by mass to 100 parts by mass of the polyester resin (A), but it is preferably 0.1 to 20 parts by mass from the viewpoint of the mechanical strength of the resin composition, And preferably 1 to 10 parts by mass. When talc is used, it is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the polyester resin (A). The fibrous reinforcement and the filler are preferably treated with an organic treatment or a coupling agent to improve the affinity with the polyester resin, or used in combination with a coupling agent during the melt synthesis. Examples of the coupling agent include silane coupling agents, A titanate-based coupling agent, and an aluminum-based coupling agent may be used. Of these, an aminosilane coupling agent and an epoxy silane coupling agent are particularly preferable.

Various additives of the conventional polyester resin composition for LED reflector can be used in the polyester resin composition of the present invention. Examples of additives include stabilizers, impact modifiers, flame retardants, release agents, sliding improvers, colorants, fluorescent whitening agents, plasticizers, nucleating agents, and thermoplastic resins other than polyester.

Examples of the stabilizer for the resin composition include organic antioxidants such as hindered phenol antioxidants, sulfur-based antioxidants and phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones and imidazoles, ultraviolet absorbers, A copper compound, and the like. Examples of the copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cupric iodide, cupric bromide, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, copper sulfide, And copper salts of organic carboxylic acids such as copper acetate and the like. As the constituent components other than the copper compound, those containing a halogenated alkali metal compound are preferable. Examples of the halogenated alkali metal compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, Potassium, potassium iodide, and the like. These additives may be used alone or in combination of several species. The amount of the stabilizer to be added may be selected in an optimum amount, and it is possible to add up to 5 parts by mass to 100 parts by mass of the polyester resin (A).

A thermoplastic resin different from the polyester resin (A) may be added to the polyester resin composition of the present invention. For example, polyamide (PA), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), fluororesin, aramid resin, polyetheretherketone (PEEK) (PEK), polyetherimide (PEI), thermoplastic polyimide, polyamideimide (PAI), polyetherketone ketone (PEKK), polyphenylene ether (PPE), polyether sulfone (PES) (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polycarbonate Styrene copolymer (ABS), polymethylpentene (TPX), polystyrene (PS), polymethyl methacrylate, acrylonitrile-styrene copolymer (AS) and acrylonitrile-butadiene-styrene copolymer (ABS). These thermoplastic resins may be blended in a molten state by melt kneading, but the thermoplastic resin may be dispersed in the polyester resin composition of the present invention as a fibrous or granular phase. The amount of the thermoplastic resin to be added may be selected in an optimum amount, and it is possible to add up to 50 parts by mass to 100 parts by mass of the polyester resin (A).

Examples of the impact modifier include an ethylene-propylene rubber (EPM), an ethylene-propylene-diene rubber (EPDM), an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, an ethylene-methacrylic acid copolymer, , Styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS) Acrylic ester copolymer, a polyester block copolymer having polybutylene terephthalate or polybutylene naphthalate as a hard segment and polytetramethylene glycol or polycaprolactone or polycarbonate diol as a soft segment, Nylon elastomer, urethane elastomer, acrylic elastomer, silicone rubber, fluorine-based elastomer There may be mentioned polymer particles having a core shell structure consisting of polymers of different kinds. The amount of the impact modifier may be selected in an optimum amount, and it is possible to add up to 30 parts by mass to 100 parts by mass of the polyester resin (A).

When a thermoplastic resin other than the polyester resin (A) and an impact resistance improver are added to the polyester resin composition of the present invention, a reactive group capable of reacting with the polyester is preferably copolymerized. As the reactive group, A group capable of reacting with a hydroxyl group and / or a carboxyl group. Specific examples thereof include an acid anhydride group, an epoxy group, an oxazoline group, an amino group, and an isocyanate group. Among them, an epoxy group and an isocyanate group are most excellent in reactivity. It has been reported that the thermoplastic resin having a reactive group reacting with the polyester resin is finely dispersed in the polyester, thereby shortening the distance between the particles and greatly improving the impact resistance.

As the flame retardant, a combination of a halogen-based flame retardant and a flame retardant auxiliary is preferable. Examples of the halogen-based flame retardant include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, Brominated diphenylmethane, bromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, and brominated crosslinked aromatic polymer. As the flame retardant auxiliary, antimony trioxide, antimony pentoxide, sodium antimonate, zinc tartrate, zinc borate, montmorillonite Layer silicate, fluorine-based polymer, silicon, and the like. Among them, a combination of dibromo styrene as the halogen-based flame retardant and antimony trioxide, sodium antimonate, and zinc stannate is preferable as the flame retardant aid in terms of heat stability. Examples of the non-halogen flame retardant include melamine cyanurate, lignin, metal salts of phosphinic acid, and compounds of nitrogen-phosphorous acid-based compounds. In particular, a combination of a phosphinic acid metal salt and a nitrogen-phosphorus-based compound is preferable, and the nitrogen-phosphorus-based compound includes a reaction product of a melamine or a condensate of melamine such as melam, melem or melon with polyphosphoric acid or a mixture thereof. As other flame retardant and flame retardant, it is preferable to add a hydrotalcite compound or an alkaline compound as a metal corrosion preventive such as a mold when these flame retardants are used. The amount of the flame retardant to be added may be selected in an optimal amount, and it is possible to add up to 50 parts by mass to 100 parts by mass of the polyester resin (A).

Examples of the release agent include long-chain fatty acids or esters or metal salts thereof, amide compounds, polyethylene waxes, silicones, and polyethylene oxides. As long-chain fatty acids, the number of carbon atoms is preferably at least 12, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid and the like. Partial or total carboxylic acid is esterified with monoglycol or polyglycol Or a metal salt may be formed. Examples of the amide compound include ethylene bisterephthalamide and methylene bis stearyl amide. These release agents may be used alone or as a mixture. The amount of the releasing agent to be added may be selected in an optimum amount, and it is possible to add up to 5 parts by mass to 100 parts by mass of the polyester resin (A).

Since the polyester resin composition of the present invention contains the polyester resin (A) as described above, the melting peak temperature (Tm) in the DSC measurement is preferably 280 ° C or higher, more preferably 290 ° C or higher, More preferably 300 DEG C or more, particularly preferably 310 DEG C or more, and most preferably 320 DEG C or more. On the other hand, the upper limit of the Tm of the polyester resin composition of the present invention is preferably not higher than 340 캜.

Further, since the polyester resin composition of the present invention contains the polyester resin (A) as described above, it is preferable that the difference between the melting peak temperature (Tm) and the temperature-lowering crystallization temperature (Tc2) More preferably 40 占 폚 or lower, more preferably 35 占 폚 or lower, still more preferably 30 占 폚 or lower.

The polyester resin (A) is excellent in balance of low water absorbency and fluidity in addition to high melting point and moldability, and furthermore, excellent in light resistance. For this reason, the polyester resin composition of the present invention obtained from such a polyester resin (A) is capable of forming a thin film and a high cycle in addition to having a high melting point and a low water absorption of 280 ° C or more in reflector molding of the surface mount type LED.

The polyester resin composition of the present invention can be produced by compounding each of the above-described components in a conventionally known method. For example, each component may be added at the time of the polycondensation reaction of the polyester resin (A), or the polyester resin (A) and other components may be dry-blended, or each component may be melt-kneaded using a twin screw extruder .

Example

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The measured values described in the examples were measured by the following methods.

(1) Intrinsic viscosity of polyester resin (IV)

Was determined from the solution viscosity at 30 DEG C in a mixed solvent of 1,1,2,2-tetrachloroethane / phenol (2: 3 weight ratio).

(2) Acid value

0.1 g of the polyester resin was dissolved in 10 ml of benzyl alcohol, and the solution was titrated using a solution of 0.1 N of NaOH in methanol / benzyl alcohol (1/9 by volume).

(3) the melting point (Tm) of the polyester resin, the melting peak temperature (Tm) of the resin composition, the crystallization temperature (Tc2)

(DSC) manufactured by Seiko Electronics Industry Co., Ltd., RDC-220. The temperature was raised at a rate of temperature rise of 20 占 폚 / min, maintained at 330 占 폚 for 3 minutes, and then decreased from 330 占 폚 to 130 占 폚 at 10 占 폚 / min. In the case where it was not melted at 330 ° C, the temperature was maintained at 340 ° C for 3 minutes and then decreased from 340 ° C to 130 ° C at 10 ° C / minute. The melting point (Tm) of the melting peak observed at the time of temperature rise and the peak temperature of the crystallization peak observed at the time of temperature lowering were determined as the temperature-lowering crystallization temperature (Tc2).

(4) Moldability and dimensional stability

Using Toshiba Mechanical Injection Molding Machine EC-100, the cylinder temperature was set at the melting point of the resin + 20 캜, the mold temperature was set at 125 캜, and a mold for flat plate having a length of 100 mm, a width of 100 mm and a thickness of 1 mm Injection molding was carried out. Molding at an injection speed of 50 mm / sec, a holding pressure of 30 MPa, an injection time of 10 seconds, and a cooling time of 10 seconds. Moldability evaluation was carried out on the basis of the following criteria.

&Amp; cir &: A molded article is obtained without any problem.

△: Sometimes the spool remains in the mold.

X: The releasability is insufficient and the molded article is stuck or deformed to the mold.

Further, in order to evaluate the dimensional stability of the obtained molded article, the molded article was heated at 180 캜 for 1 hour. Dimensions in the direction perpendicular to the flow direction before and after heating were measured, and the amount of dimensional change was obtained as follows.

The dimensional stability evaluation was carried out according to the following criteria.

○: The dimensional change is less than 0.2%

X: The dimensional change amount is 0.2% or more

(5) Soldering heat resistance

Using a Toshiba machine injection molding machine EC-100, a test piece for UL combustion test having a length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mm was set at a cylinder temperature set at a melting point of the resin + 20 ° C and a mold temperature of 140 ° C, A test piece was prepared. The test piece was allowed to stand in an atmosphere at 85 캜 and 85% RH (relative humidity) for 72 hours. The test piece was preheated by raising the temperature from room temperature to 150 ° C over 60 seconds in an air reflow furnace (manufactured by Aitec Corporation, AIS-20-82C), and then preheating was carried out at a heating rate of 0.5 ° C / min up to 190 ° C . Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C / minute, maintained at a predetermined temperature for 10 seconds, and then cooled. The set temperature was increased from 240 deg. C to 5 deg. C intervals, and the soldering heat resistance was evaluated based on the following criteria, with the highest set temperature at which no surface swelling or deformation occurred, as the reflow heat resisting temperature.

◎: Reflow heat resistance temperature is 280 ° C or higher

O: Reflow heat resistance temperature is 260 占 폚 or more and less than 280 占 폚

X: Reflow heat resistance temperature is less than 260 占

(6) Diffuse reflectance

Using Toshiba Mechanical Injection Molding Machine EC-100, the cylinder temperature was set to the melting point of the resin + 20 캜, the mold temperature was set at 140 캜, a flat plate having a length of 100 mm, a width of 100 mm and a thickness of 2 mm was injection- Respectively. Using this test piece, an integrating sphere manufactured by the company was installed in a magnetic spectrophotometer " U3500 " manufactured by Hitachi, Ltd., and the reflectance at a wavelength of 350 nm to 800 nm was measured. For the comparison of reflectance, the diffuse reflectance at a wavelength of 460 nm was determined. Barium sulphate was used as a reference.

(7) Saturated water absorption rate

Using Toshiba Mechanical Injection Molding Machine EC-100, the cylinder temperature was set to the melting point of the resin + 20 占 폚, the mold temperature was set at 140 占 폚, a flat plate having a length of 100 mm, a width of 100 mm and a thickness of 1 mm was injection- Respectively. The test piece was immersed in hot water at 80 캜 for 50 hours, and the saturated water uptake rate was determined from the following equation in terms of the weight at the time of absorption of saturated water and at the time of drying.

(8) Fluidity

Toshiba Machine Manufacturing Injection Molding Machine EC-100 was used to set the cylinder temperature to 330 캜 and the mold temperature to 120 캜 and set injection pressure set value 40%, injection rate set value 40%, weighing 35 ㎜, injection time 6 sec, A test piece for evaluation was prepared by injection molding with a measuring mold of a flow length of 1 mm in width and 0.5 mm in thickness under the condition of a time of 10 seconds. The flow rate (mm) of this specimen was measured as a flowability evaluation.

(9) Silicone adhesion

Using Toshiba Mechanical Injection Molding Machine EC-100, the cylinder temperature was set to the melting point of the resin + 20 캜, the mold temperature was set at 140 캜, a flat plate having a length of 100 mm, a width of 100 mm and a thickness of 2 mm was injection- Respectively. A silicone sealing material (ASP-1110, manufactured by Shinetsu Silicone Co., Ltd., sealant hardness D60) was coated on one side of the test piece so as to have a coating thickness of about 100 占 퐉, preheated at 100 占 폚 for 1 hour, Curing treatment was performed for one hour to form a sealant film on one side of the test piece.

Next, a checkerboard test (1 mm wide cross cut 100 checkerboards) based on JIS K5400 was performed on the encapsulating material coat on the test piece, and the adhesion was evaluated based on the following criteria.

○: Number of peeled checkerboards 10 or less

X: peeling at the formation of checkerboard before peeling test

(10) Light fastness

Using Toshiba Mechanical Injection Molding Machine EC-100, the cylinder temperature was set to the melting point of the resin + 20 캜, the mold temperature was set at 140 캜, a flat plate having a length of 100 mm, a width of 100 mm and a thickness of 2 mm was injection- Respectively. This specimen was subjected to ultraviolet irradiation at an illuminance of 50 mW / cm 2 under an environment of 63 ° C and 50% RH by using a super-accelerated weathering tester "Eye Super UV Tester SUV-F11". The light reflectance of the test piece at a wavelength of 460 nm was measured before irradiation and after 60 hours of irradiation. The light reflectance of the test piece before irradiation was evaluated by the following standard.

◎: 95% or higher retention rate

○: Maintenance rate less than 95% ~ 90%

△: Maintenance rate less than 90% ~ 85%

X: Less than 85% maintenance rate

(11) Heat Sulfur Degeneration

Using Toshiba Mechanical Injection Molding Machine EC-100, the cylinder temperature was set to the melting point of the resin + 20 캜, the mold temperature was set at 140 캜, a flat plate having a length of 100 mm, a width of 100 mm and a thickness of 2 mm was injection- Respectively. This specimen was treated in a hot-air dryer at 150 ° C for 2 hours to confirm the yellowing of the sample by the naked eye and evaluated according to the following criteria.

○: No change

Δ: Slightly yellowed

×: yellowed

(Example 1)

3,880 g of high purity dimethyl terephthalic acid, 2,782 g of 4,4'-biphenyl dimethanol, 1,922 g of ethylene glycol, 2 g of manganese dioxide and 0.86 g of germanium dioxide were placed in a 20-liter stainless steel autoclave equipped with a stirrer, The pressure of the reaction system was gradually lowered to 13.3 Pa (0.1 Torr) while raising the temperature to 300 DEG C, and a polycondensation reaction was further performed at 310 DEG C and 13.3 Pa. After the pressure was released, unpressed resin was discharged in the form of strands in water, cooled and 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 is 0.60 ㎗ / g, the resin composition of the resulting polyester is ¹ to 100 mole% of terephthalic acid by the H-NMR measurement, 4,4'-it is 65.0 mol% phenyl-dimethanol, ethylene glycol and 34.5 mol%, D And ethylene glycol was 0.5 mol%. The composition and characteristic values of the obtained polyester resin are shown in Table 1.

(Examples 2 to 4)

Each polyester resin was obtained in the same manner as in the polymerization of the polyester resin of Example 1, except that the amount and type of raw materials used were changed. Table 1 shows the composition and the characteristic values of each of the obtained polyester resins. Also, diethylene glycol is a byproduct of ethylene glycol condensation.

(Example 5)

3,880 g of high purity dimethyl terephthalic acid, 2,782 g of 4,4'-biphenyl dimethanol, 1,922 g of ethylene glycol, 2 g of manganese dioxide and 0.86 g of germanium dioxide were placed in a 20-liter stainless steel autoclave equipped with a stirrer, 8 g was added and the temperature of the reaction system was gradually lowered to 13.3 Pa (0.1 Torr) while raising the temperature to 300 deg. C over 60 minutes, and further polycondensation reaction was carried out at 310 deg. C and 13.3 Pa. Subsequent to the pneumatic pressure, the unpressed resin was discharged in the form of strands in water, cooled and 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 is 0.60 ㎗ / g, the resin composition of the resulting polyester is ¹ to 100 mole% of terephthalic acid by the H-NMR measurement, 4,4'-it is 65.0 mol% phenyl-dimethanol, ethylene glycol and 34.5 mol%, D And ethylene glycol was 0.5 mol%. The composition and characteristic values of the obtained polyester resin are shown in Table 1.

(Comparative Example 1)

To a 20-liter stainless steel autoclave equipped with a stirrer, high-purity terephthalic acid and two-fold molar amount of ethylene glycol were charged, and triethylamine was added in an amount of 0.3 mol% based on the acid component. Water was distilled off at 250 DEG C under a pressure of 0.25 MPa To obtain a mixture (hereinafter referred to as a BHET mixture) of bis (2-hydroxyethyl) terephthalate and an oligomer having an esterification ratio of about 95%. To this BHET mixture was added germanium dioxide (100 ppm as Ge) as a polymerization catalyst, followed by stirring at 250 캜 for 10 minutes under atmospheric pressure in a nitrogen atmosphere. Thereafter, the temperature of the reaction system was gradually lowered to 13.3 Pa (0.1 Torr) while the temperature was raised to 280 deg. C over 60 minutes, and a polycondensation reaction was further carried out at 280 deg. C and 13.3 Pa. Subsequent to the pneumatic pressure, the unpressed resin was discharged in the form of strands in water, cooled and 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 polyester had an intrinsic viscosity of 0.61 dl / g. The resin composition had 100 mol% of terephthalic acid, 98.0 mol% of ethylene glycol and 2.0 mol% of diethylene glycol by ¹ H-NMR measurement. Table 2 shows the composition and the characteristic values of the obtained polyester resin.

(Comparative Examples 2 to 4)

Each polyester resin was obtained in the same manner as in the polymerization of the polyester resin of Comparative Example 1, except that the kind of raw materials used was changed. Table 2 shows the composition and the characteristic values of each of the obtained polyester resins.

(Comparative Example 5: polyamide resin)

(18.0 mol) of 1,9-nonanediamine, 316.58 g (2.0 mol) of 2-methyl-1,8-octanediamine, 73.27 g (0.60 mol) of benzoic acid, 6.5 g of hydrate (0.1 wt% with respect to the raw material) and 6 liters of distilled water were placed in an autoclave having an internal volume of 20 liters and purged with nitrogen. The mixture was stirred at 100 占 폚 for 30 minutes and the internal temperature was raised to 210 占 폚 over 2 hours. At this time, the autoclave was stepped up to 22 kg / cm 2. The reaction was continued for 1 hour as it was, then the temperature was raised to 230 ° C, and then the temperature was maintained at 230 ° C for 2 hours. The steam was gradually removed and the reaction was carried out while maintaining the pressure at 22 kg / cm 2. Next, the pressure was lowered to 10 kg / cm < 2 > over 30 minutes and further reacted for 1 hour to obtain a prepolymer having an intrinsic viscosity [?] Of 0.25 dl / g. This was dried at 100 DEG C under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid phase polymerization at 230 DEG C under 0.1 mmHg for 10 hours to obtain a white polyamide resin having a melting point of 310 DEG C, an intrinsic viscosity [?] Of 1.33 dl / g and an end sealing ratio of 90%. The composition and the characteristic values of the obtained polyamide resin are shown in Table 2.

(Examples 6 to 13 and Comparative Examples 6 to 10)

The polyester resin (A) or the polyamide resin was melted and kneaded at a melting point + 15 占 폚 using a twin-screw extruder STS-35 manufactured by Copper Co., Ltd. in mass ratios with the components shown in Tables 3 and 4, , And the resin compositions of Comparative Examples 6 to 10 were obtained. Details of the materials other than the polyester resin (A) in Tables 3 and 4 are as follows.

Titanium oxide (B): Taipei CR-60 manufactured by Ishihara Sangyo Co., Ltd., rutile type TiO ₂ , average particle diameter 0.2 μm

Reinforced material (C): glass fiber (CS-3J-324 manufactured by Nitto Co., Ltd.), needle-shaped Walasato (NYGLOS8 manufactured by NYCO,

Filler (D): Talc (Micron White 5000A manufactured by Hayashi Kasei Co., Ltd.)

Release agent: Magnesium stearate

Stabilizer: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, Irganox 1010)

The resin compositions obtained in Examples 6 to 13 and Comparative Examples 6 to 10 were provided for various characteristic evaluations. The evaluation results are also shown in Tables 3 and 4.

From the Tables 1 and 3, it was confirmed that in the resin compositions (Examples 6 to 13) using the polyester resins (Examples 1 to 5) satisfying the requirements of the present invention, the melting peak temperature by DSC of the polyester resin composition was 280 ° C Or more, and when the melting peak temperature exceeds 310 DEG C, the reflow endothermic temperature is 280 DEG C or higher. Therefore, the solder heat resistance applicable to the gold / tin soldering process is exhibited, while the LED It is possible to confirm the remarkable effect that the adhesiveness to the sealing material and the surface reflectance which are important characteristics in use are excellent, and furthermore, the moldability, fluidity, dimensional stability, low water absorbability, light resistance and heat resistance yellowing are excellent. On the other hand, in Table 2 and Table 4, it was impossible to satisfy all of these characteristics in the resin compositions (Comparative Examples 6 to 9) using the polyester resins (Comparative Examples 1 to 4) which did not satisfy the requirements of the present invention. Since the polyamide resin of Comparative Example 5 has a high melting point but is water-absorbing due to the amide structure, the resin composition (Comparative Example 10) using the polyamide resin of Comparative Example 5 does not satisfy the reflow heat resistance temperature of 280 deg. Light resistance and heat resistance yellowing were also inferior.

The polyester resin composition of the present invention is not only excellent in heat resistance, moldability, fluidity and water absorbency, but also is excellent in adhesion to an encapsulating material for LED applications and further has a specific light resistance So that it can be suitably used for a reflector for a surface mount type LED while highly satisfying necessary characteristics.

Claims (11)

A polyester resin comprising a dicarboxylic acid component containing at least 50 mol% of aromatic dicarboxylic acid and a glycol component containing at least 15 mol% of 4,4'-biphenyldimethanol and having a melting point of 280 ° C or higher By weight. The method according to claim 1,
Characterized in that the aromatic dicarboxylic acid comprises at least one dicarboxylic acid selected from the group consisting of 4,4'-biphenyldicarboxylic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid. Suzy. 3. The method according to claim 1 or 2,
The glycol component other than 4,4'-biphenyl dimethanol constituting the polyester resin is composed of ethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propanediol, neopentyl glycol and 1,4-butanediol Lt; RTI ID = 0.0 > 1, < / RTI > 4. The method according to any one of claims 1 to 3,
Wherein a difference between a melting point (Tm) of the polyester resin and a crystallization temperature (Tc2) at a temperature lower than 42 占 폚. 5. The method according to any one of claims 1 to 4,
Wherein the polyester resin has an acid value of 1 to 40 eq / t. At least one reinforcing material (C) selected from the group consisting of the polyester resin (A), the titanium oxide (B), the fibrous reinforcement material and the needle reinforcing material according to any one of claims 1 to 5, (B), the reinforcing material (C), and the non-fibrous or non-needle-like filler (D) are contained in an amount of 0.5 to 100 parts by mass, and 0 to 100 parts by mass, respectively, based on 100 parts by mass of the polyester resin (A) To 100 parts by mass and 0 to 50 parts by mass of the polyester resin composition. The method according to claim 6,
Wherein the non-fibrous or non-needle-like filler (D) is talc and contains 0.1 to 5 parts by mass of talc with respect to 100 parts by mass of the polyester resin (A). 8. The method according to claim 6 or 7,
Wherein the solder reflow endothermic temperature is 260 占 폚 or higher. 9. The method according to any one of claims 6 to 8,
And the solder reflow endothermic temperature is 280 占 폚 or higher. 10. The method according to any one of claims 6 to 9,
Wherein the polyester resin composition has a melting peak temperature (Tm) of 280 占 폚 or more and a difference between a melting peak temperature (Tm) and a temperature-falling crystallization temperature (Tc2) of 42 占 폚 or less. A reflector for a surface-mount type LED, which is obtained by molding using the polyester resin composition according to any one of claims 6 to 10.