Thermoplastic resin composition and molded article produced therefrom

Abstract

A thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a polyester resin comprising a repeating unit represented by chemical formula 1; about 5-50 parts by weight of a polyarylethersulfone resin; and about 0.005-1.5 parts by weight of a metal phosphorus-based compound. The thermoplastic resin composition has excellent metal adhesion, heat resistance, rigidity, fluidity, the balance of these physical properties, and the like.

Description

Thermoplastic resin composition and molded article manufactured therefrom

[0001] The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent metal bonding properties, heat resistance, rigidity, fluidity, and a balance of these physical properties, and a molded article manufactured therefrom.

[0002]

[0003] Nano molding technology (NMT) is a technology that improves the interfacial bonding strength between resin and metal by filling micro-holes formed by surface treatment with resin during the injection molding process.

[0004] In such nanomolding technology, the types of resins capable of filling micro-holes are limited. In particular, for NMT resins used in mobile devices, polybutylene terephthalate (PBT) is generally used because it must possess chemical resistance and mechanical properties capable of withstanding additional processes such as CNC processing and anodizing.

[0005] Furthermore, for IT and mobile materials, high-temperature processes are designed to enhance design and stability, necessitating the development of polymer materials with excellent heat resistance during such processes. While commonly used PBT materials possess excellent intermetallic bonding strength, their insufficient heat resistance during high-temperature processes like deposition and PVD limits their direct application.

[0006] Therefore, there is a need to develop thermoplastic resin compositions with excellent metal bonding properties, heat resistance, rigidity, fluidity, and a balance of these physical properties.

[0007] The background technology of the present invention is disclosed in Korean registered patent No. 10-0709878, etc.

[0008]

[0009] The objective of the present invention is to provide a thermoplastic resin composition having excellent metal bonding properties, heat resistance, rigidity, fluidity, and a balance of these physical properties.

[0010] Another objective of the present invention is to provide a molded article formed from the thermoplastic resin composition.

[0011] The above and other objectives 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 thermoplastic resin composition. The thermoplastic resin composition comprises about 100 parts by weight of a polyester resin comprising repeating units represented by the following chemical formula 1; about 5 to about 50 parts by weight of a polyarylethersulfone resin; and about 0.005 to about 1.5 parts by weight of a metal phosphorus-based compound:

[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 embodiment, 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 embodiments, the polyester resin may have a weight-average molecular weight of about 3,000 to about 200,000 g / mol as measured by gel permeation chromatography.

[0021] 4. In the above 1 to 3 embodiments, the polyarylethersulfone resin may include repeating units represented by the following chemical formula 2.

[0022] [Chemical Formula 2]

[0023]

[0024] 5. In the above embodiments 1 to 4, the polyarylethersulfone resin is, in accordance with ASTM D3835, at a temperature of 400°C and 1,000 sec -1 Under shear rate conditions, the melt viscosity measured by a capillary viscometer flow meter can be about 150 to about 400 Pa·s.

[0025] 6. In the above 1 to 5 embodiments, the metal phosphorus-based compound may include one or more of zinc phosphate, sodium phosphate, magnesium phosphate, and aluminum phosphate.

[0026] 7. In the above 1 to 6 embodiments, the weight ratio of the polyarylethersulfone resin and the metal phosphorus-based compound may be about 1:0.0001 to about 1:0.1.

[0027] 8. In the above 1 to 7 embodiments, the thermoplastic resin composition may be formed by insert injection molding in accordance with ISO 19095, so that the 1.2 cm × 0.3 cm cross-sections of each specimen are joined together, and the metal bonding strength measured under 50 mm / min may be about 28 to about 50 MPa.

[0028] 9. In the above embodiments 1 to 8, the thermoplastic resin composition is subjected to a load of 18.56 kgf / cm² in accordance with ASTM D648. 2 The heat distortion temperature (HDT) of a 6.4 mm thick specimen measured under a heating rate of 120℃ / hr may be approximately 269 to approximately 290℃.

[0029] 10. In the above embodiments 1 to 9, the thermoplastic resin composition has a tensile strength of about 1,300 to about 1,700 kgf / cm² of a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638. 2 It could be.

[0030] 11. In the above 1 to 10 embodiments, the thermoplastic resin composition may have a melt-flow index (MI) of about 20 to about 45 g / 10 min measured at 300°C and a 5 kg load condition according to ASTM D1238.

[0031] 12. Another aspect of the present invention relates to a molded article. The molded article is characterized by being formed from a thermoplastic resin composition according to any one of 1 to 11.

[0032] 13. Another aspect of the present invention relates to a composite material. The composite material is characterized by comprising: a plastic member formed from a thermoplastic resin composition according to any one of 1 to 11; and a metal member in contact with the plastic member.

[0033] 14. In the above 13 embodiments, the metal member may include one or more metals among aluminum, titanium, iron, and zinc.

[0034]

[0035] The present invention has the effect of providing a thermoplastic resin composition having excellent metal bonding properties, heat resistance, rigidity, fluidity, and a balance of these physical properties, and a molded article formed therefrom (plastic member of a composite material, etc.).

[0036]

[0037] The present invention will be described in detail below.

[0038] The thermoplastic resin composition according to the present invention comprises (A) a polyester resin; (B) a polyarylethersulfone resin; and (C) a metal phosphorus-based compound.

[0039] In this specification, "a to b" indicating a numerical range is defined as "≥a and ≤b".

[0040]

[0041] (A) Polyester resin

[0042] A polyester resin according to one embodiment of the present invention can be applied together with a polyarylethersulfone resin, a metal phosphorus-based compound, etc., to improve the metal bonding properties, heat resistance, stiffness, fluidity, and balance of the physical properties of a thermoplastic resin composition, and may include a repeating unit represented by the following chemical formula 1.

[0043] [Chemical Formula 1]

[0044]

[0045] In the above chemical formula 1, Ar is an arylene group having 6 to 18 carbon atoms, R1 and R3 are each independently linear alkylene groups 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 a diolicyclic diol and may have a total carbon number of 7 to 22. The polyester resin has a high melting temperature containing a ring-shaped structure in the main chain, which may be, for example, 200°C or higher, but is not limited thereto.

[0046] In a specific example, the polyester resin may be prepared according to a known polycondensation method using a dicarboxylic acid component including an aromatic dicarboxylic acid and its derivatives, and a diol component including a diol alicyclic.

[0047] In a specific example, 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, etc. These may be used individually or in a mixture of two or more types.

[0048] In a specific example, the above-mentioned cycloaliphatic diol may be used as a cycloaliphatic diol having 7 to 22 carbon atoms, such as 1,4-cyclohexanedimethanol (CHDM), but is not limited thereto.

[0049] In a specific example, the polyester resin may be a polycyclohexanedimethylene terephthalate (PCT) resin comprising repeating units represented by the following chemical formula 1a.

[0050] [Chemical Formula 1a]

[0051]

[0052] 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 in a hexafluoroisopropanol (HFIP) solvent by gel permeation chromatography (GPC). Within this range, the heat resistance, injection moldability, impact resistance, rigidity, etc. of the thermoplastic resin composition may be excellent.

[0053]

[0054] (B) Polyarylethersulfone resin

[0055] A polyarylethersulfone resin according to one embodiment of the present invention can be applied together with a polyester resin, a metal phosphorus-based compound, etc., to improve the metal bonding properties, heat resistance, stiffness, fluidity, and balance of the physical properties of a thermoplastic resin composition, and a polyarylethersulfone resin used in a conventional thermoplastic resin composition can be used.

[0056] In a specific example, the polyarylethersulfone resin may be a polyarylethersulfone resin (polyphenylsulfone resin) containing repeating units represented by the following chemical formula 2.

[0057] [Chemical Formula 2]

[0058]

[0059] In a specific example, the polyarylethersulfone resin is prepared according to ASTM D3835 at a temperature of 400°C and 1000 sec -1 The melt viscosity measured by a capillary viscometer under shear rate conditions may be about 150 to about 400 Pa·s, for example, about 200 to about 350 Pa·s. Within the above range, the heat resistance, stiffness, etc. of the thermoplastic resin composition may be excellent.

[0060] In a specific example, the polyarylethersulfone resin may have a weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 20,000 to about 100,000 g / mol, for example, about 35,000 to about 50,000 g / mol. Within this range, the metal bonding properties, chemical resistance, heat resistance, etc. of the thermoplastic resin composition may be excellent.

[0061] In a specific example, the polyarylethersulfone resin may be included in an amount of about 5 to about 50 parts by weight, for example, about 10 to about 45 parts by weight, with respect to about 100 parts by weight of the polyester resin. If the content of the polyarylethersulfone resin is less than about 5 parts by weight with respect to about 100 parts by weight of the polyester resin, there is a risk that the metal bonding properties of the thermoplastic resin composition will be reduced, and if it exceeds about 50 parts by weight, there is a risk that the heat resistance, rigidity, fluidity, etc. of the thermoplastic resin composition will be reduced.

[0062]

[0063] (C) Metallic phosphorus compounds

[0064] A metal phosphorus-based compound according to one embodiment of the present invention can be applied together with a polyester resin, a polyarylethersulfone resin, etc., to improve the metal bonding properties, heat resistance, stiffness, fluidity, and balance of the physical properties of a thermoplastic resin composition.

[0065] In a specific example, the metal phosphorus-based compound may include one or more of zinc phosphate, sodium phosphate, magnesium phosphate, and aluminum phosphate. For example, zinc phosphate prepared by reacting zinc oxide with phosphoric acid, commercially available zinc phosphate, etc. may be used.

[0066] In a specific example, the metal phosphorus-based compound may have an average particle size of about 0.5 to about 3 μm, for example, about 1 to about 3 μm, measured by a particle size analyzer, and may have a purity of about 99% or more. Within the above range, the metal bonding properties, heat resistance, rigidity, fluidity (moldability), etc. of the thermoplastic resin composition may be excellent.

[0067] In a specific example, the metal phosphorus-based compound may be included in an amount of about 0.005 to about 1.5 parts by weight, for example, about 0.01 to about 1 part by weight, per about 100 parts by weight of the polyester resin. If the content of the metal phosphorus-based compound is less than about 0.005 parts by weight per about 100 parts by weight of the polyester resin, there is a risk that the fluidity (moldability) of the thermoplastic resin composition may be reduced, and if it exceeds about 1.5 parts by weight, there is a risk that the metal bondability, heat resistance, rigidity, etc. of the thermoplastic resin composition may be reduced.

[0068] In a specific example, the weight ratio of the polyarylethersulfone resin and the metal phosphorus-based compound may be about 1:0.0001 to about 1:0.1, for example, about 1:0.0003 to about 1:0.05, for example, about 1:0.0004 to about 1:0.04. Within the above range, the metal bonding properties, heat resistance, mechanical properties, etc. of the thermoplastic resin composition may be superior.

[0069]

[0070] A thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of such additives include, but are not limited to, flame retardants, antioxidants, anti-dripping agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, and mixtures thereof. When using such additives, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, with respect to about 100 parts by weight of the polyester resin.

[0071]

[0072] A thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets produced by mixing the above components and melt-extruding them using a conventional twin-screw extruder at about 240 to about 300°C, for example, about 260 to about 290°C.

[0073] In a specific example, the thermoplastic resin composition may be formed by joining an aluminum-based metal specimen of size 1.2 cm × 4 cm × 0.3 cm and a thermoplastic resin composition specimen of size 1.2 cm × 4 cm × 0.3 cm through insert injection molding in accordance with ISO 19095 so that the 1.2 cm × 0.3 cm cross-sections of each specimen are joined together, and the metal bonding strength measured under a condition of 50 mm / min may be about 28 to about 50 MPa, for example, about 30 to about 45 MPa.

[0074] In a specific example, the thermoplastic resin composition has a load of 18.56 kgf / cm² in accordance with ASTM D648. 2 The heat distortion temperature (HDT) of a 6.4 mm thick specimen measured under a heating rate of 120℃ / hr may be about 269 to about 290℃, for example, about 270 to about 280℃.

[0075] In a specific example, the thermoplastic resin composition has a tensile strength of about 1,300 to about 1,700 kgf / cm² of a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638. 2 , for example, about 1,310 to about 1,650 kgf / cm² 2 It could be.

[0076] In a specific example, the thermoplastic resin composition may have a melt-flow index (MI) of about 20 to about 45 g / 10 min, for example, about 21 to about 40 g / 10 min, measured according to ASTM D1238 at 300°C and a 5 kg load.

[0077]

[0078] The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be produced into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention belongs. Since the molded article exhibits excellent metal bonding properties, heat resistance, rigidity, fluidity, and a balance of these physical properties, it is useful as an interior and exterior material for electronic devices, an interior and exterior material for automobiles, and an interior and exterior material for portable electronic communication devices.

[0079]

[0080] The composite material according to the present invention may include a plastic member formed from the thermoplastic resin composition; and a metal member in contact with the plastic member.

[0081] In a specific embodiment, the plastic member and the metal member may be in direct contact without an adhesive intermediary. For example, the plastic member and the metal member may be manufactured in a form that is integrated by insert injection molding.

[0082] In a specific example, the metal member may include one or more metals among aluminum, titanium, iron, and zinc.

[0083]

[0084] The present invention is to be explained more specifically through the following examples, but these examples are for illustrative purposes only and should not be interpreted as limiting the invention.

[0085]

[0086] Examples

[0087] The specifications of each component used in the examples and comparative examples below are as follows.

[0088] (A) Polyester resin

[0089] Polycyclohexanedimethylene terephthalate resin (Manufacturer: SK Chemicals, Product name: SKYPURA 0502, Weight average molecular weight: approx. 65,000 g / mol) was used.

[0090] (B) Polyarylethersulfone resin

[0091] Polyphenylsulfone resin (Manufacturer: BASF, Product name: Ultrason P2010, Melt viscosity: approximately 230 Pa·s) was used.

[0092] (C) Metallic phosphorus compounds

[0093] Zinc phosphate (manufacturer: Budenheim, product name: BUDIT T21) was used.

[0094]

[0095] Examples 1 to 5 and Comparative Examples 1 to 4

[0096] After adding each of the above components in the amounts listed in Tables 1 and 2 below, pellets were prepared by extrusion at approximately 280°C. A twin-screw extruder with L / D=44 and a diameter of 45 mm was used for extrusion. The prepared pellets were dried at approximately 100°C for at least 4 hours, and then injection molded in a 6 oz injection molding machine (molding temperature: approximately 270°C, mold temperature: approximately 150°C) to produce specimens. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

[0097]

[0098] Methods for measuring physical properties

[0099] (1) Metal bonding strength (unit: MPa): In accordance with ISO 19095, an aluminum-based metal specimen and a thermoplastic resin composition specimen were bonded by insert injection molding (injection temperature: 270°C, mold temperature: 150°C), and the bonding strength was measured at 50 mm / min. Here, the metal specimen used was an aluminum-based metal specimen with a TRI surface treatment from Geo Nation to facilitate bonding with the resin composition specimen. In addition, the metal and thermoplastic resin composition specimens used were 1.2 cm × 4 cm × 0.3 cm in size, and the bonding strength was measured by joining the 1.2 cm × 0.3 cm cross-sections together.

[0100] (2) Heat distortion temperature (HDT, unit: ℃): According to ASTM D648, load 18.56 kgf / cm² 2 The heat deformation temperature of a 6.4 mm thick specimen was measured under conditions of a heating rate of 120℃ / hr.

[0101] (3) Tensile strength (unit: kgf / cm²) 2 In accordance with ASTM D638, the tensile strength of a 3.2 mm thick specimen was measured at 5 mm / min.

[0102] (4) Melt-flow Index (Unit: g / 10 min): According to ASTM D1238, the Melt-flow Index (MI) was measured at 300°C with a load of 5 kg.

[0103]

[0104] Example 1 2345(A) (parts by weight) 100 100 100 100 100 (B) (parts by weight) 11.1 25 42.9 25 25(C) (parts by weight) 0.1 25 0.1 25 0.1 25 0.0 11 Metal bonding strength (MPa) 30.5 31.4 32.3 31.7 30.4 Heat distortion temperature (°C) 27 327 1270 27 1270 Tensile strength (kgf / cm² 2 )1,590 1,480 1,360 1,510 1,320 Molten Flow Index (g / 10min) 33.1 27.8 24.7 21.3 35.2

[0105]

[0106] Comparative Example 1234(A) (parts by weight) 100 100 100 100(B) (parts by weight) 155 2525(C) (parts by weight) 0.1 25 0.1 25 0.00 12 Metal bonding strength (MPa) 24.0 32.7 32.1 27.4 Heat distortion temperature (°C) 27 42 66 27 12 68 Tensile strength (kgf / cm²) 2 )1,510 1,280 1,520 1,240 Molten Flow Index (g / 10min) 34.3 17.1 16.7 40.6

[0107]

[0108] From the above results, it can be seen that the thermoplastic resin composition according to the present invention exhibits excellent metal bonding properties (metal bonding strength), heat resistance (heat distortion temperature), stiffness (tensile strength), fluidity (melt flow index), and the balance of these physical properties.

[0109] On the other hand, it can be seen that when polyarylethersulfone resin is applied in an amount less than the content range of the present invention (Comparative Example 1), the metal bonding properties of the thermoplastic resin composition are reduced, and when polyarylethersulfone resin is applied in an amount exceeding the content range of the present invention (Comparative Example 2), the heat resistance, stiffness, and fluidity of the thermoplastic resin composition are reduced. In addition, it can be seen that when a metal phosphorus-based compound is applied in an amount less than the content range of the present invention (Comparative Example 3), the fluidity of the thermoplastic resin composition is reduced, and when a metal phosphorus-based compound is applied in an amount exceeding the content range of the present invention (Comparative Example 4), the metal bonding properties, heat resistance, and stiffness of the thermoplastic resin composition are reduced.

[0110]

[0111] The present invention has been described above with reference to embodiments. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the invention.

Claims

1. About 100 parts by weight of a polyester resin comprising a repeating unit represented by the following chemical formula 1; About 5 to about 50 parts by weight of polyarylethersulfone resin; and A thermoplastic resin composition characterized by comprising about 0.005 to about 1.5 parts by weight of a metal phosphorus-based compound: [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 thermoplastic 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 thermoplastic resin composition according to claim 1 or 2, characterized in that the polyester resin has a weight-average molecular weight of about 3,000 to about 200,000 g / mol as measured by gel permeation chromatography.

4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyarylethersulfone resin comprises a repeating unit represented by the following chemical formula 2. [Chemical Formula 2] 5. In any one of claims 1 to 4, the polyarylethersulfone resin is, in accordance with ASTM D3835, at a temperature of 400°C and 1,000 sec -1 A thermoplastic resin composition characterized by a melt viscosity of about 150 to about 400 Pa·s measured by a capillary viscometer under shear rate conditions.

6. A thermoplastic resin composition according to any one of claims 1 to 5, wherein the metal phosphorus-based compound comprises one or more of zinc phosphate, sodium phosphate, magnesium phosphate, and aluminum phosphate.

7. A thermoplastic resin composition characterized in that, in any one of claims 1 to 6, the weight ratio of the polyarylethersulfone resin and the metal phosphorus-based compound is about 1:0.0001 to about 1:0.

1.

8. A thermoplastic resin composition according to any one of claims 1 to 7, wherein the thermoplastic resin composition is characterized in that, in accordance with ISO 19095, an aluminum-based metal specimen of size 1.2 cm × 4 cm × 0.3 cm and a thermoplastic resin composition specimen of size 1.2 cm × 4 cm × 0.3 cm are joined so that the 1.2 cm × 0.3 cm cross-sections of each specimen are joined to each other, and the metal bonding strength measured under a condition of 50 mm / min is about 28 to about 50 MPa.

9. In any one of claims 1 to 8, the thermoplastic resin composition is, in accordance with ASTM D648, a load of 18.56 kgf / cm² 2 A thermoplastic resin composition characterized by a heat distortion temperature (HDT) of a 6.4 mm thick specimen measured under a heating rate of 120℃ / hr being approximately 269 to approximately 290℃.

10. In any one of claims 1 to 9, the thermoplastic resin composition has a tensile strength of about 1,300 to about 1,700 kgf / cm² of a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638. 2 A thermoplastic resin composition characterized by being 11. A thermoplastic resin composition according to any one of claims 1 to 10, wherein the thermoplastic resin composition has a melt-flow index (MI) of about 20 to about 45 g / 10 min measured at 300°C and a 5 kg load condition in accordance with ASTM D1238.

12. A molded article characterized by being formed from a thermoplastic resin composition according to any one of claims 1 to 11.

13. A plastic member formed from a thermoplastic resin composition according to any one of claims 1 to 11; and A composite material characterized by including a metal member in contact with the plastic member.

14. A composite material according to claim 13, characterized in that the metal member comprises one or more metals selected from aluminum, titanium, iron, and zinc.

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