Polyester resin composition and molded product manufactured therefrom

Abstract

A polyester resin composition of the present invention comprises: about 100 parts by weight of a polyester resin including repeating units represented by chemical formula 1; about 5-30 parts by weight of glass fiber containing sodium (Na) and magnesium (Mg) in a ratio of about 0.5:1-2:1; and about 0.1-5 parts by weight of sodium pyrophosphate. The polyester resin composition has excellent transparency, heat resistance, molding processability, balance therebetween, and the like.

Description

Polyester resin composition and molded article manufactured therefrom

[0001] The present invention relates to a polyester resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a polyester resin composition for a light-emitting diode reflector housing, which has excellent transparency, heat resistance, molding processability, and a balance of these physical properties, and a molded article manufactured therefrom.

[0002]

[0003] Light-emitting diodes (LEDs) and organic light-emitting diodes (OLEDs) are rapidly replacing conventional light sources due to their superior energy efficiency and long lifespan, and are gaining popularity. Typically, LEDs are combined with component materials such as reflectors, reflector cups, scramblers, and reflector housings to form a LED package, maximizing luminous efficiency through high reflectivity. Previously, high-heat, high-whiteness polyester resin compositions were developed for application to these component materials.

[0004] However, recently, due to changes in the structure of light-emitting diodes (e.g., flip chip type), processability, productivity, etc., there is a demand for characteristics that simultaneously satisfy high heat resistance and high transmittance, and there is a problem that it is difficult to satisfy these conditions with existing polyester resin compositions.

[0005] Therefore, there is a need to develop a polyester resin composition for a light-emitting diode reflector housing that has excellent transparency, heat resistance, moldability (fluidity), and a balance of these properties.

[0006] The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2013-0076733, etc.

[0007]

[0008] The purpose of the present invention is to provide a polyester resin composition having excellent transparency, heat resistance, molding processability, and a balance of these physical properties.

[0009] Another object of the present invention is to provide a molded article formed from the polyester resin composition.

[0010] Another object of the present invention is to provide a semiconductor device including a light-emitting diode reflector housing formed from the polyester resin composition.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below.

[0012]

[0013] 1. One aspect of the present invention relates to a polyester resin composition. The polyester resin composition comprises: about 100 parts by weight of a polyester resin comprising a repeating unit represented by the following chemical formula 1; about 5 to about 30 parts by weight of glass fiber having a sodium (Na) and magnesium (Mg) content ratio (Na:Mg) of about 0.5:1 to about 2:1; and about 0.1 to about 5 parts by weight of sodium pyrophosphate.

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1, Ar is an arylene group having 6 to 18 carbon atoms, R1 and R3 are each independently a linear alkylene group having 1 to 10 carbon atoms, and R2 is a cyclic alkylene group having 5 to 12 carbon atoms.

[0017] 2. In the above 1 specific example, the polyester resin may include a repeating unit represented by the following chemical formula 1a.

[0018] [Chemical Formula 1a]

[0019]

[0020] 3. In the above 1 or 2 specific examples, the content ratio of sodium (Na) and magnesium (Mg) (Na:Mg) of the glass fiber may be about 0.6:1 to about 1.5:1.

[0021] 4. In the above 1 to 3 specific examples, the weight ratio of the glass fiber and the sodium pyrophosphate may be about 1:0.01 to about 1:0.3.

[0022] 5. In the above 1 to 4 specific examples, the polyester resin composition may have a light transmittance of about 70 to about 85% of a 1 mm thick specimen measured according to ASTM D1003.

[0023] 6. In the above 1 to 5 specific examples, the polyester resin composition has a load of 18.56 kgf / cm according to ASTM D648. 2 , the heat distortion temperature (HDT) of a 6.4 mm thick specimen measured under conditions of a heating rate of 120°C / hr may be about 245 to about 270°C.

[0024] 7. In the above 1 to 6 specific examples, the polyester resin composition has an injection temperature of 300°C, a mold temperature of 60°C, and an injection pressure of 1,500 kgf / cm. 2 After injection molding in a spiral-shaped mold with a thickness of 0.5 mm under conditions of an injection speed of 120 mm / s, the measured spiral flow length of the specimen may be about 120 to about 170 mm.

[0025] 8. Another aspect of the present invention relates to a molded article. The molded article is formed from a polyester resin composition according to any one of 1 to 7 above.

[0026] 9. In the above 8 specific examples, the molded product may be a light-emitting diode reflector housing.

[0027] 10. Another aspect of the present invention relates to a semiconductor device. The semiconductor device comprises a light-emitting diode reflector housing formed from a polyester resin composition according to any one of 1 to 7.

[0028]

[0029] The present invention has the effect of providing a polyester resin composition having excellent transparency, heat resistance, molding processability, and balance of physical properties thereof, and a molded article manufactured therefrom.

[0030]

[0031] FIG. 1 is a cross-sectional view of a semiconductor device including a light-emitting diode reflector housing formed from a polyester resin composition according to one embodiment of the present invention.

[0032]

[0033] Hereinafter, the present invention will be described in detail as follows.

[0034] A polyester resin composition according to the present invention comprises (A) a polyester resin; (B) glass fiber; and (C) sodium pyrophosphate.

[0035] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0036]

[0037] (A) Polyester resin

[0038] A polyester resin according to one specific example of the present invention is applied together with glass fiber and sodium pyrophosphate having a sodium and magnesium content ratio within a specific range, thereby improving transparency, heat resistance, molding processability, and physical property balance of the polyester resin composition, and may include a repeating unit represented by the following chemical formula 1.

[0039] [Chemical Formula 1]

[0040]

[0041] In the above chemical formula 1, Ar is an arylene group having 6 to 18 carbon atoms, R1 and R3 are each independently a linear alkylene group having 1 to 10 carbon atoms, and R2 is a cyclic alkylene group having 5 to 12 carbon atoms. Here, -R1-R2-R3- is derived from an alicyclic diol, and the total number of carbon atoms may be 7 to 22. The polyester resin has a ring-shaped structure in the main chain and has a high melting temperature, for example, about 200°C or higher, but is not limited thereto.

[0042] In a specific example, the polyester resin may be prepared by a known polycondensation method using a dicarboxylic acid component including an aromatic dicarboxylic acid and its derivatives and a diol component including an alicyclic diol.

[0043] In specific examples, the dicarboxylic acid component may include, but is not limited to, terephthalic acid, isophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and the like. These may be used singly or in combination of two or more.

[0044] In a specific example, the alicyclic diol may be an alicyclic diol having 7 to 22 carbon atoms, such as 1,4-cyclohexanedimethanol (CHDM), but is not limited thereto.

[0045] In a specific example, the polyester resin may be a polycyclohexanedimethylene terephthalate (PCT) resin including a repeating unit represented by the following chemical formula 1a.

[0046] [Chemical Formula 1a]

[0047]

[0048] In a specific example, the polyester resin may contain the repeating unit represented by the above chemical formula 1a in an amount of about 50 to about 100 mol% based on 100 mol% of the total repeating units. Within this range, the polyester resin composition may have excellent injection processability, impact resistance, rigidity, and the like.

[0049] In a specific example, the polyester resin may have a weight average molecular weight of about 3,000 to about 200,000 g / mol, for example, about 5,000 to about 150,000 g / mol, as measured by gel permeation chromatography (GPC) in a hexafluoroisopropanol (HFIP) solvent. Within this range, the polyester resin composition may have excellent injection processability, impact resistance, rigidity, and the like.

[0050]

[0051] (B) Glass fiber

[0052] According to one specific example of the present invention, glass fiber can be applied to the polyester resin together with sodium pyrophosphate or the like to improve the transparency, heat resistance, molding processability, and physical property balance of the polyester resin composition, and glass fiber having a sodium (Na) and magnesium (Mg) content ratio (Na:Mg) of about 0.5:1 to about 2:1 can be used.

[0053] In a specific example, the sodium and magnesium content ratio (Na:Mg) of the glass fiber may be about 0.5:1 to about 2:1, for example, about 0.6:1 to about 1.5:1. When the sodium and magnesium content ratio of the glass fiber is less than about 0.5:1, there is a concern that the transparency of the polyester resin composition may be reduced, and when it exceeds about 2:1, there is a concern that the transparency of the polyester resin composition may be reduced. Here, the sodium and magnesium content of the glass fiber can be measured (inorganic quantitative analysis) using ICP-OES (Inductively Coupled Plasma Optical Emission spectroscopy) after removing the surface treatment agent (sizing agent) of the glass fiber.

[0054] In specific embodiments, the glass fibers may include circular cross-sectional glass fibers, flat-shaped glass fibers, combinations thereof, and the like.

[0055] In a specific example, the circular cross-section glass fiber may be a glass fiber having an average diameter of a circular cross-section measured using an optical microscope of about 5 to about 15 μm, for example, about 6 to about 14 μm. Within this range, the rigidity, impact resistance, etc. of the polyester resin composition may be excellent.

[0056] In a specific example, the flat glass fiber may have an aspect ratio of a cross-section measured by an optical microscope of about 1.5 to about 4, for example, about 2 to about 4, and a short diameter of about 6 to about 10 μm, for example, about 6 to about 9 μm. In this range, the rigidity, impact resistance, etc. of the polyester resin composition may be excellent.

[0057] In a specific example, the glass fibers may have an average length of about 1 to about 5 mm before extrusion, and an average length of about 100 to about 700 μm, for example, about 110 to about 690 μm, after extrusion (processing). Within this range, the impact resistance, rigidity, appearance characteristics, etc. of the polyester resin composition may be excellent.

[0058] In a specific example, the glass fiber may be coated with a surface treatment agent to increase bonding strength with components such as polyester resin. The surface treatment agent may include, but is not limited to, a silane compound, a urethane compound, an epoxy compound, or the like.

[0059] In a specific example, the glass fiber may be included in an amount of, for example, about 5 to about 30 parts by weight, for example, about 10 to about 25 parts by weight, relative to about 100 parts by weight of the polyester resin. If the content of the glass fiber is less than about 5 parts by weight relative to about 100 parts by weight of the polyester resin, there is a concern that the heat resistance, etc. of the polyester resin composition may be reduced, and if it exceeds about 30 parts by weight, there is a concern that the transparency, molding processability, etc. of the polyester resin composition may be reduced.

[0060]

[0061] (C) Sodium pyrophosphate

[0062] Sodium pyrophosphate according to one specific example of the present invention can be applied to the polyester resin together with the glass fiber, etc., to improve the transparency, heat resistance, molding processability, and physical property balance of the polyester resin composition, and sodium pyrophosphate used in a typical thermoplastic resin composition can be used.

[0063] In a specific example, the sodium pyrophosphate may be included in an amount of about 0.1 to about 5 parts by weight, for example, about 0.5 to about 3 parts by weight, specifically about 0.6 to about 2.4 parts by weight, relative to about 100 parts by weight of the polyester resin. If the content of the sodium phosphate salt is less than about 0.1 parts by weight relative to about 100 parts by weight of the polyester resin, there is a concern that the molding processability (fluidity) of the polyester resin composition may be reduced, and if it exceeds about 5 parts by weight, there is a concern that the heat resistance of the polyester resin composition may be reduced.

[0064] In a specific example, the weight ratio of the glass fiber and the sodium pyrophosphate may be about 1:0.01 to about 1:0.3, for example, about 1:0.02 to about 1:0.2, specifically about 1:0.03 to about 1:0.15. In this range, the molding processability, heat resistance, transparency, etc. of the polyester resin composition may be more excellent.

[0065]

[0066] A polyester resin composition according to one embodiment of the present invention may further include conventional additives depending on the intended use, as long as the desired effect is not impaired. Examples of such additives include, but are not limited to, antioxidants, flame retardants, anti-drip agents, nucleating agents, release agents, lubricants, antistatic agents, stabilizers, pigments, dyes, and combinations thereof.

[0067] In a specific example, when the additive is used, the content may be about 20 parts by weight or less, for example, about 0.1 to about 15 parts by weight, based on about 100 parts by weight of the polyester resin, but is not limited thereto.

[0068]

[0069] A polyester resin composition according to one specific embodiment of the present invention can be manufactured by a known method. For example, each component and, if necessary, additives can be mixed using a Henschel mixer, V blender, tumbler blender, ribbon blender, etc., and then melt-extruded at a temperature of about 250 to about 350°C using a single-screw extruder or twin-screw extruder to manufacture pellets.

[0070] In a specific example, the polyester resin composition may have a light transmittance of about 70 to about 85%, for example, about 72 to about 83%, of a 1 mm thick specimen measured according to ASTM D1003.

[0071] In a specific example, the polyester resin composition has a load of 18.56 kgf / cm according to ASTM D648. 2 , the heat distortion temperature (HDT) of a 6.4 mm thick specimen measured under conditions of a heating rate of 120°C / hr may be about 245 to about 270°C, for example, about 250 to about 265°C.

[0072] In a specific example, the polyester resin composition has an injection temperature of 300°C, a mold temperature of 60°C, and an injection pressure of 1,500 kgf / cm. 2 After injection molding in a spiral-shaped mold with a thickness of 0.5 mm under conditions of an injection speed of 120 mm / s, the measured spiral flow length of the specimen may be about 120 to about 170 mm, for example, about 130 to about 160 mm.

[0073]

[0074] A molded article according to one specific embodiment of the present invention is formed from the polyester resin composition. For example, a molded article can be manufactured using the polyester resin composition using a known molding method such as injection molding, double injection molding, or thermoforming.

[0075] In a specific example, the molded article has excellent transparency, heat resistance, molding processability, and a balance of these properties, and can be applied without limitation as long as it satisfies both high heat resistance and high transmittance and is used for purposes that transmit light. For example, it can be used as a housing for light-emitting devices such as components for various electrical and electronic products, indoor and outdoor lighting, automobile lighting, and display devices, and is particularly useful as a light-emitting diode (LED) reflector housing.

[0076] FIG. 1 is a cross-sectional view of a semiconductor device including a light-emitting diode reflector housing formed from a polyester resin composition according to one specific example of the present invention. As illustrated in FIG. 1, the polyester resin composition of the present invention can be formed into a cup-shaped light-emitting diode reflector housing (20), and can be formed into various other shapes. The semiconductor device includes the light-emitting diode reflector housing (20), and for example, a cup-shaped light-emitting diode reflector housing (20) can be formed in which an electrode (not shown) is formed on an upper portion of a substrate (10), and which has a concave portion so that a light-emitting diode (LED) 30 can be mounted on the upper portion of the electrode (not shown). The light-emitting diode (LED) 30 can be mounted in the concave portion, and the light-emitting diode (LED) 30 can be sealed by a sealing resin (40) so as to be protected from the outside. Additionally, a light emitting diode (LED) 30 may be connected to the electrode via a wire (not shown). For example, the light emitting diode (LED) 30 may be of a horizontal chip type (wire bond type), and the semiconductor device may be of a flip chip type. Various modifications and variations of the above configuration can be made by those skilled in the art to which the present invention pertains based on this description.

[0077]

[0078] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0079]

[0080] Example

[0081] The specifications of each component used in the following examples and comparative examples are as follows.

[0082] (A) Polyester resin

[0083] Polycyclohexanedimethylene terephthalate resin (Manufacturer: SK Chemicals, Product name: Puratan 0502) was used.

[0084] (B) Glass fiber

[0085] (B1) Glass fiber (manufacturer: Nittobo, product name: CSG 3PA-820, content ratio (Na:Mg): 0.7:1) was used.

[0086] (B2) Glass fiber (Manufacturer: KCC, Product name: CS321-EC10-3, Content ratio (Na:Mg): 1.22:1) was used.

[0087] (B3) Glass fiber (manufacturer: Owenscorning, product name: 183F, content ratio (Na:Mg): 0.06:1) was used.

[0088] (B4) Glass fiber (manufacturer: Vetrotex, product name: CS952-10P, content ratio (Na:Mg): 2.87:1) was used.

[0089] (C) Sodium phosphate salt

[0090] (C1) Sodium pyrophosphate (Manufacturer: Innophos, Product name: SAPP) was used.

[0091] (C2) Sodium hexametaphosphate (manufacturer: INNOPHOS) was used.

[0092]

[0093] Examples 1 to 6 and Comparative Examples 1 to 7

[0094] Each of the above components was added in the amounts shown in Tables 1 and 2 below, and then extruded at about 300°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 36 and a diameter of 45 mm. The manufactured pellets were dried at about 100°C for about 4 hours or more, and then injected using a 6 oz injection molding machine (injection (molding) temperature: about 300°C, mold temperature: about 120°C) to produce polyester resin composition specimens. The physical properties of the manufactured specimens were measured by the following methods, and the results are shown in Tables 1 and 2.

[0095]

[0096] Method of measuring physical properties

[0097] (1) Light transmittance (unit: %): The light transmittance of a 1 mm thick specimen was measured using an NDH-5000 haze meter according to ASTM D1003.

[0098] (2) Heat deflection temperature (HDT, unit: ℃): Based on ASTM D648, load 18.56 kgf / cm 2 , the heat deformation temperature of a 6.4 mm thick specimen was measured under conditions of a heating rate of 120℃ / hr.

[0099] (3) Spiral flow length (unit: mm): A polyester resin composition specimen in the form of a pellet was injected at an injection temperature of 300°C, a mold temperature of 60°C, and an injection pressure of 1,500 kgf / cm. 2 After injection molding in a spiral-shaped mold with a thickness of 0.5 mm under conditions of an injection speed of 120 mm / s, the spiral flow length of the specimen was measured.

[0100]

[0101] Example 123456(A) (parts by weight) 100100100100100100(B1) (parts by weight) 1017.62517.617.6-(B2) (parts by weight)-----17.6(B3) (parts by weight)------(B4) (parts by weight)------(C1) (parts by weight) 1.51.51.50.62.41.5(C2) (parts by weight)------Light transmittance (%) 837672757277Heat distortion temperature (℃) 251252259255251253Spiral flow length (mm) 151145135142147139

[0102]

[0103] Comparative Example 1234567(A) (parts by weight)100100100100100100100100(B1) (parts by weight)135--17.617.617.6(B2) (parts by weight)-------(B3) (parts by weight)--17.6----(B4) (parts by weight)---17.6---(C1) (parts by weight)1.51.51.51.5010-(C2) (parts by weight)------1.5Light Transmittance (%)85636158717373Heat Distortion Temperature (℃)221261255252250235229Spiral Flow Length (mm)15599137145109150105

[0104]

[0105] From the above results, it can be seen that the polyester resin composition according to the present invention has excellent transparency (light transmittance), heat resistance (heat distortion temperature), molding processability (spiral flow length), and a balance of these physical properties.

[0106] On the other hand, when the glass fiber is applied in an amount less than the content range of the present invention (Comparative Example 1), it can be seen that heat resistance, etc. are reduced, and when the glass fiber is applied in an amount exceeding the content range of the present invention (Comparative Example 2), it can be seen that transparency, moldability (fluidity), etc. are reduced, and when the glass fiber (B3) having a sodium and magnesium content ratio less than the range of the present invention is applied instead of the glass fiber of the present invention (Comparative Example 3), it can be seen that transparency, etc. are reduced, and when the glass fiber (B4) having a sodium and magnesium content ratio exceeding the range of the present invention is applied (Comparative Example 4), it can be seen that transparency, etc. are reduced. In addition, when sodium pyrophosphate is not applied (Comparative Example 5), it can be seen that molding processability (fluidity) etc. is reduced, and when sodium pyrophosphate is applied in excess of the content range of the present invention (Comparative Example 6), it can be seen that heat resistance etc. is reduced, and when sodium hexametaphosphate (C2) is applied instead of the sodium pyrophosphate of the present invention (Comparative Example 7), it can be seen that heat resistance, molding processability (fluidity) etc. are reduced.

[0107]

[0108] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. About 100 parts by weight of a polyester resin containing a repeating unit represented by the following chemical formula 1; About 5 to about 30 parts by weight of glass fiber having a sodium (Na) and magnesium (Mg) content ratio (Na:Mg) of about 0.5:1 to about 2:1; and A polyester resin composition characterized by comprising about 0.1 to about 5 parts by weight of sodium pyrophosphate; [Chemical Formula 1] In the above chemical formula 1, Ar is an arylene group having 6 to 18 carbon atoms, R1 and R3 are each independently a linear alkylene group having 1 to 10 carbon atoms, and R2 is a cyclic alkylene group having 5 to 12 carbon atoms.

2. A polyester resin composition according to claim 1, characterized in that the polyester resin comprises a repeating unit represented by the following chemical formula 1a. [Chemical Formula 1a] 3. A polyester resin composition according to claim 1 or 2, characterized in that the content ratio (Na:Mg) of sodium (Na) and magnesium (Mg) of the glass fiber is about 0.6:1 to about 1.5:

1.

4. A polyester resin composition according to any one of claims 1 to 3, characterized in that the weight ratio of the glass fiber and the sodium pyrophosphate is about 1:0.01 to about 1:0.

3.

5. A polyester resin composition according to any one of claims 1 to 4, characterized in that the polyester resin composition has a light transmittance of about 70 to about 85% of a 1 mm thick specimen measured according to ASTM D1003.

6. In any one of the first to fifth clauses, the polyester resin composition has a load of 18.56 kgf / cm according to ASTM D648. 2 A polyester resin composition characterized in that the heat distortion temperature (HDT) of a 6.4 mm thick specimen measured under conditions of a heating rate of 120°C / hr is about 245 to about 270°C.

7. In any one of the first to sixth paragraphs, the polyester resin composition has an injection temperature of 300°C, a mold temperature of 60°C, and an injection pressure of 1,500 kgf / cm. 2 A polyester resin composition characterized in that the spiral flow length of the measured specimen is about 120 to about 170 mm after injection molding in a spiral-shaped mold having a thickness of 0.5 mm under conditions of an injection speed of 120 mm / s.

8. A molded product characterized by being formed from a polyester resin composition according to any one of claims 1 to 7.

9. A molded product according to claim 8, characterized in that the molded product is a light-emitting diode reflector housing.

10. A semiconductor device characterized by comprising a light-emitting diode reflector housing formed from a polyester resin composition according to any one of claims 1 to 7.

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