KR20240046991A - Thermoplastic resin composition, method for preparing the same and molded article therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a manufacturing method thereof, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition, boron nitride, graphite, and a flame retardant in a predetermined composition ratio to achieve thermal conductivity, electrical insulation, heat resistance, and flame retardancy. Provided is a thermoplastic resin composition, a method for manufacturing the same, and a molded article containing the same, which are all secured at a certain level or higher.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article containing the same {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE SAME AND MOLDED ARTICLE THEREFROM}

The present invention relates to a thermoplastic resin composition, a manufacturing method thereof, and a molded article containing the same. More specifically, the present invention relates to a thermoplastic resin composition, a method for manufacturing the same, and a molded article containing the same. More specifically, the present invention relates to a polycarbonate resin containing a predetermined heat dissipating filler and a flame retardant to ensure all electrical insulation, thermal conductivity, and flame retardancy. It relates to a thermoplastic resin composition, a manufacturing method thereof, and a molded article containing the same.

Polycarbonate resin (hereinafter referred to as 'PC resin') has excellent mechanical properties, heat resistance, dimensional stability, and optical properties, and is actively applied in various fields such as electrical and electronic products and automobile interior materials.

In particular, in the automotive field, as the demand for miniaturization and weight reduction of components has recently increased, the circuit integration of electrical components and electrical/electronic components is increasing. As a result, heat dissipation problems due to increased heat generation of internal circuits are becoming a major issue.

Accordingly, in order to implement thermal conductivity in PC resin, carbon-based fillers such as graphite have been applied in the past, but in this case, since electrical conductivity increases at the same time, it is difficult to apply to parts that require insulation such as connectors.

Meanwhile, with the popularization of electric vehicles due to environmental regulations, high flame retardancy is required for automobile interior materials. However, when the content of flame retardants is increased, there is a problem that mechanical properties are deteriorated.

Therefore, there is an urgent need to develop PC resins that have all of electrical insulation, thermal conductivity, and flame retardancy that can be applied to electrical and electronic products or automobile interior materials.

Korean Patent No. 10-1596546

In order to solve the problems of the prior art as described above, the purpose of the present invention is to provide a thermoplastic resin composition that is excellent in electrical insulation, thermal conductivity, and flame retardancy.

Additionally, the present invention aims to provide a method for producing the thermoplastic resin composition and a molded article manufactured including the same.

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

In order to achieve the above object, the present invention includes (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, and (C) 5 to 20% by weight of graphite with an average particle diameter of 50 to 200㎛. and (D) 3.3 to 10% by weight of a bisphenol-based phosphate flame retardant.

In addition, the present invention includes (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite, and (D) 3.3 to 10% by weight of bisphenol-based phosphate flame retardant. It provides a thermoplastic resin composition, wherein the weight ratio (A:B) of (A) polycarbonate resin and (B) boron nitride is 1 to 2:1.

In addition, the present invention includes (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite, and (D) 3.3 to 10% by weight of bisphenol-based phosphate flame retardant. It includes, the sum of the weight of (B) boron nitride and (C) graphite is 45 to 55% by weight, and the weight ratio (B:C) of (B) boron nitride and (C) graphite is 3 to 5:1. It provides a thermoplastic resin composition characterized in that:

The weight ratio (A:B) of the (A) polycarbonate resin and (B) boron nitride may preferably be 1 to 2:1.

The sum of the weight of (B) boron nitride and (C) graphite may preferably be 45 to 55% by weight.

The weight ratio (B:C) of (B) boron nitride and (C) graphite may preferably be 3 to 5:1.

The polycarbonate resin (A) preferably has a weight average molecular weight of 5,000 to 25,000 g/mol.

The (A) polycarbonate resin may preferably have a linear thermal expansion coefficient of 30 to 90 × 10 ^-6 mm/mm/°C, as measured according to ASTM D696.

The (B) boron nitride may preferably have an average particle diameter of 28 to 65㎛.

The (B) boron nitride may preferably have a BET specific surface area of 0.5 to 10 m ² /g.

The (C) graphite may preferably be flake type graphite.

The (C) graphite may preferably have an apparent density of 0.1 to 1.0 g/cm ³ at 25°C.

The (D) bisphenol-based phosphate flame retardant may preferably have a viscosity of 10,000 to 17,000 mPa·s at 25°C.

The (D) bisphenol-based phosphate flame retardant may preferably have a viscosity of 100 to 500 mPa·s at 70°C.

The thermoplastic resin composition may preferably include (E) one or more additives selected from the group consisting of anti-dripping agents, antioxidants, lubricants, and magnesium oxide, in which case (A) polycarbonate resin, (B) nitriding The additive (E) may be included in an amount of 0.5 to 5% by weight based on a total of 100% by weight of boron, (C) graphite, (D) bisphenol-based phosphate flame retardant, and (E) additive.

The thermoplastic resin composition preferably has T.I. calculated by Equation 1 below: The index value may be 0.001 to 1.22.

[Equation 1]

T.I. index = [(thermal conductivity - 7) × (surface resistance - 12) × {(heat distortion temperature - 100) × 0.1}]

(In Equation 1 above, thermal conductivity is a value in units of W/m·K measured in accordance with ASTM E1461, surface resistance is an exponent of 10 of the value in units of Ω/sq measured in accordance with IEC 60093, and thermal strain Temperature indicates the value in ℃ measured under the conditions of load 0.45 MPa and thickness 4 mm according to ISO 75)

In addition, the present invention includes (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite with an average particle diameter of 50 to 200㎛, and (D) bisphenol-based A method for producing a thermoplastic resin composition comprising 3.3 to 10% by weight of a phosphate flame retardant and kneading and extruding at 200 to 300° C. is provided.

Additionally, the present invention provides a molded article comprising the thermoplastic resin composition.

According to the present invention, there is an effect of providing a thermoplastic resin composition that is excellent in electrical insulation, thermal conductivity, and flame retardancy and is suitable as a heat dissipation material for electrical and electronic products or automobile interior materials, a manufacturing method thereof, and a molded article manufactured therefrom.

Hereinafter, the thermoplastic resin composition of this base, its manufacturing method, and molded article will be described in detail.

The present inventors confirmed that high flame retardancy was achieved while simultaneously improving the conflicting characteristics of electrical insulation and thermal conductivity by adjusting the composition ratio while adding a predetermined heat dissipation filler and flame retardant to PC resin, and based on this, they devoted themselves to further research and invented the present invention. was completed.

The thermoplastic resin composition of the present invention includes (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite with an average particle diameter of 50 to 200㎛, and (D) It is characterized in that it contains 3.3 to 10% by weight of a bisphenol-based phosphate flame retardant, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

In addition, the thermoplastic resin composition of the present invention contains (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite, and (D) 3.3% by weight of bisphenol-based phosphate flame retardant. to 10% by weight, and the weight ratio (A:B) of (A) polycarbonate resin and (B) boron nitride is 1 to 2:1, and in this case, electrical insulation, thermal conductivity and flame retardancy are All have excellent benefits.

In addition, the thermoplastic resin composition of the present invention contains (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite, and (D) 3.3% by weight of bisphenol-based phosphate flame retardant. to 10% by weight, the sum of the weight of (B) boron nitride and (C) graphite is 45 to 55% by weight, and the weight ratio (B:C) of (B) boron nitride and (C) graphite is 3. It is characterized in that it is 5:1, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

In the present description, the component ratio of the copolymer or resin may refer to the content of the units constituting the copolymer, or may refer to the content of the monomers added during polymerization of the copolymer.

In this description, content means weight percent unless otherwise defined.

Hereinafter, each component constituting the thermoplastic resin composition of the present material will be examined in detail as follows.

(A) Polycarbonate resin

The polycarbonate resin (A) is contained in an amount of 30 to 60% by weight in a total of 100% by weight of the thermoplastic resin composition, preferably 35 to 55% by weight, more preferably 35 to 52% by weight, even more preferably. It may be included at 38 to 50% by weight, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

In the present disclosure, a total of 100% by weight of the thermoplastic resin composition means that the total weight of (A) polycarbonate resin to (D) bisphenol-based phosphate flame retardant is 100% by weight, and also includes (E) additives. In this case, it may mean that the total weight of (A) polycarbonate resin to (E) additives is 100% by weight.

For example, the (A) polycarbonate resin may have a weight average molecular weight of 5,000 to 25,000 g/mol, preferably 7,000 to 20,000 g/mol, more preferably 8,000 to 15,000 g/mol, and within this range, the electric It has superior insulation and thermal conductivity.

In this description, unless otherwise defined, the weight average molecular weight is chromatographed using tetrahydrofuran (THF) as an eluent and gel chromatography (GPC) filled with porous silica as a column packing material at a temperature of 40°C. It can be obtained as a relative value to a standard PS (Standard polystyrene) sample by using tetrahydrofuran (THF) as a solvent. At this time, as a specific measurement example, solvent: THF, column temperature: 40℃, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection volume: 5㎕, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), Equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI Temperature: 35℃, Data processing: Agilent ChemStation S/W, test method (Mn, Mw, and PDI): Can be measured under OECD TG 118 conditions.

For example, the (A) polycarbonate resin may have a linear thermal expansion coefficient of 30 to 90 × 10 ^-6 mm/mm/℃, preferably 40 to 85 × 10 ^-6 mm/mm, as measured according to ASTM D696. /°C, more preferably 50 to 80 × 10 ^-6 mm/mm/°C, even more preferably 60 to 75 × 10 ^-6 mm/mm/°C, within this range without deterioration of electrical insulation It has the advantage of superior thermal conductivity.

In this description, the Coefficient of Linear Thermal Expansion refers to the change in length per unit temperature due to temperature increase within a certain temperature range according to ASTM D696. For example, it can be measured using TMA (ThermoMechanic Analysis). , as a specific measurement example, the MD (machine direction) direction measured while increasing the temperature at a temperature increase rate of 5℃/min in the temperature range of -40℃ to 82℃ for a specimen with width, length, and thickness of 5 mm × 5 mm × 0.5 mm, respectively. It can be expressed by measuring the change in length.

For example, the (A) polycarbonate resin has a flow index of 25 to 35 g/10min, preferably 27 to 35 g/10min, more preferably 27 to 35 g/10min, as measured under the conditions of a temperature of 300°C and a load of 1.2kg according to ASTM D1238. May be 28 to 34 g/10min, and within this range, excellent molding processability and physical property balance are achieved.

The type of polycarbonate resin (A) is not particularly limited, but for example, it may be a polymerized resin containing a bisphenol-based monomer and a carbonate precursor.

The bispinol-based monomers include, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)sulfoxide. (4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3 ,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2 ,2-bis(4-hydroxy-3chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) ) propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane and α,ω-bis[3-(ο-hydroxyphenyl)propyl] It may be one or more types selected from the group consisting of polydimethylsiloxane.

The carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis ( It may be one or more selected from the group consisting of diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate.

The (A) polycarbonate resin may be, for example, at least one selected from the group consisting of linear polycarbonate resin, branched polycarbonate resin, and polyestercarbonate copolymer resin, and is preferably linear polycarbonate. It may be a resin, in which case fluidity is improved, resulting in better molding processability and appearance characteristics.

A preferred example of the linear polycarbonate resin may be a bisphenol-A polycarbonate resin.

The manufacturing method of the polycarbonate resin (A) is not particularly limited as long as it is a manufacturing method commonly applied in this technical field, and commercially available products may be used as long as they follow the definition of the present invention.

(B) Boron nitride

The (B) boron nitride (BN) is contained in an amount of 30 to 50% by weight, preferably 32 to 44% by weight, more preferably 33 to 44% by weight, and even more preferably 33 to 44% by weight, based on a total of 100% by weight of the thermoplastic resin composition. It may be included in an amount of 33 to 43% by weight, and in this case, there is an advantage in that it has superior thermal conductivity without deteriorating electrical insulation.

For example, the boron nitride (B) may have an average particle diameter of 28 to 65 ㎛, preferably 30 to 62 ㎛, more preferably 32 to 55 ㎛, and even more preferably 33 to 40 ㎛, In this case, there is an advantage of superior thermal conductivity without deterioration of electrical insulation.

In the present disclosure, the average particle diameter of inorganic particles such as boron nitride can be measured by a measurement method commonly used in the technical field to which the present invention pertains, for example, by measuring 20 to 50 particles using an optical microscope or an electron microscope. It can be calculated as the average value of measured long-axis particle diameters.

For example, the boron nitride (B) may have a BET specific surface area of 0.5 to 10 m ² /g, preferably 0.7 to 5 m ² /g, more preferably 1 to 4 m ² /g, In this case, there is an advantage of superior thermal conductivity without deterioration of electrical insulation.

In this material, the BET specific surface area of the inorganic particles can be measured by a measurement method commonly used in the technical field to which the present invention pertains, for example, using a BET analysis equipment (Surface Area and Porosity Analyzer ASAP 2020, Micromeritics Co., Ltd.) through a nitrogen gas adsorption method. ) can be used to measure.

For example, the boron nitride (B) may be a hexagonal type crystal.

(C) Graphite

The (C) graphite is included in an amount of 5 to 20% by weight, preferably 5 to 17% by weight, more preferably 7 to 15% by weight, even more preferably 8 to 100% by weight of the total 100% by weight of the thermoplastic resin composition. It may be included at 13% by weight, in which case it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

The (C) graphite may be, for example, flake type graphite, in which case it has the advantage of superior thermal conductivity without deterioration of electrical insulation and superior manufacturing efficiency.

For example, the (C) graphite may have an apparent density of 0.1 to 1.0 g/cm ³ at 25°C, preferably 0.1 to 0.7 g/cm ³ , more preferably 0.2 to 0.5 g/cm ³ , and even more. Preferably, it may be 0.3 to 0.4 g/cm ³ , and in this case, there is an advantage of superior thermal conductivity without deterioration of electrical insulation.

In this description, apparent density refers to the weight relative to the volume measured without a separate tapping process to remove voids between particles contained in the powder sample, until no further change in volume is confirmed. It is distinguished from tapping density, which indicates the weight of the volume measured after tapping, and can be measured by a method commonly used in the field to which the present invention pertains. As a specific example, it can be measured based on ASTM B329-06.

For example, the (C) graphite may have an average particle diameter of 50 to 200 ㎛, preferably 55 to 180 ㎛, more preferably 60 to 160 ㎛, even more preferably 62 to 150 ㎛, even more preferably It may be 65 to 130㎛, and in this case, there is an advantage of superior thermal conductivity without deterioration of electrical insulation.

The (C) graphite may have an average particle diameter of 50 to 200 ㎛, for example, 50 to 100 ㎛, preferably 55 to 95 ㎛, more preferably 60 to 90 ㎛, even more preferably 62 ㎛. It may be from 85㎛ to 85㎛, and in this case, there is an advantage of superior thermal conductivity without deterioration of electrical insulation.

The (C) graphite may be, for example, expanded graphite-free, including flake graphite but not expanded graphite. In this case, thermal conductivity, surface resistance, and heat distortion temperature are maintained without deterioration of other physical properties. There is an advantage that can be secured at a desired level, and as a specific example, T.I. calculated using Equation 1 above. It is easy to adjust the index value within a predetermined range, so it has the advantage of being suitable for application in fields that require high levels of thermal conductivity, electrical insulation, and heat resistance.

In the present disclosure, expanded graphite free means that expanded graphite is not artificially included in the thermoplastic resin composition, and specifically means included in less than 0.1% by weight or 0% by weight.

(D) Bisphenol-based phosphate flame retardant

The (D) bisphenol-based phosphate flame retardant is contained in an amount of 3.3 to 10% by weight, preferably 3.3 to 9% by weight, more preferably 3.4 to 8% by weight, and even more preferably 3.4 to 8% by weight, based on a total of 100% by weight of the thermoplastic resin composition. It may be included in an amount of 3.5 to 7% by weight, preferably 3.5 to 5.5% by weight, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity and flame retardancy.

For example, the (D) bisphenol-based phosphate flame retardant may have a viscosity of 10,000 to 17,000 mPa·s at 25°C, preferably 11,000 to 15,000 mPa·s, more preferably 12,000 to 14,000 mPa·s, In this case, there is an advantage in stably realizing flame retardancy while containing relatively less flame retardant than before.

For example, the (D) bisphenol-based phosphate flame retardant may have a viscosity of 100 to 500 mPa·s at 70°C, preferably 100 to 400 mPa·s, more preferably 110 to 300 mPa·s, In this case, there is an advantage of superior flame retardancy without deterioration of heat resistance and mechanical properties.

The (D) bisphenol-based phosphate flame retardant may be, for example, a non-halogen-based flame retardant, and in this case, it does not contain a halogen-based compound and can provide an environmentally friendly advantage.

For example, the (D) bisphenol-based phosphate flame retardant may have a molecular weight of 500 to 950 g/mol, preferably 600 to 800 g/mol, more preferably 600 to 750 g/mol, and in this case, heat resistance And there is an advantage of superior flame retardancy without deterioration of mechanical properties.

(E) Additives

The thermoplastic resin composition may optionally include one or more additives (hereinafter referred to as '(E) additives') selected from the group consisting of anti-dripping agents, antioxidants, lubricants, and magnesium oxide, in which case (A) 0.5 to 5% by weight, preferably 0.7 to 4% by weight, based on a total of 100% by weight of polycarbonate resin, (B) boron nitride, (C) graphite, (D) bisphenol-based phosphate flame retardant, and (E) additives, More preferably, it can be included at 0.8 to 3% by weight, and even more preferably at 0.8 to 2% by weight, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

The (E) additive may include, for example, one or more, preferably two or more, selected from the group consisting of anti-dripping agents, antioxidants, lubricants and magnesium oxide, and more preferably anti-dripping agents, antioxidants and lubricants. It may include two or more types selected from the group consisting of, more preferably, an anti-dripping agent, an antioxidant, and a lubricant.

The anti-drip agent includes, for example, polytetrafluoroethylene (PTFE), a mixture of PTFE and styrene-acrylonitrile (SAN) resin (PTFE/SAN), a mixture of PTFE and poly methyl methacrylate (PMMA) (PTFE/PMMA), polyamide, polysilicon, and TFE-HFP (tetrafluoroethylene-hexafluoropropylene) copolymers may be used, preferably at least one selected from the group consisting of PTFE/SAN and PTFE/PMMA, more preferably PTFE/SAN. It can be. The PTFE/SAN and PTFE/PMMA may preferably be a mixture of PTFE and SAN or PMMA at a weight ratio of 1:0.5 to 1.5, respectively, and in one embodiment, may be a mixture of PTFE and SAN or PMMA at a weight ratio of 1:1.

The antioxidant may include, for example, a phenolic antioxidant, a phosphorus antioxidant, or a mixture thereof, and is preferably a phenolic antioxidant. In this case, it prevents oxidation by heat during the extrusion process and improves mechanical properties and heat resistance. This has excellent effects.

The phenolic antioxidant is, for example, N,N'-hexane-1,6-diyl-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)], pentaerythritol tetrakis [3-(3',5'-di-t-butyl-4-hydroxyphenyl) propionate](pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], CAS No. 6683-19-8), N,N′-hexamethylene-bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), triethylene glycol-bis[3-(3- t-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl- 2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethyl It may be one or more types selected from the group consisting of benzyl)isocyanurate and hindered phenol-based heat stabilizers. In this case, heat resistance can be greatly improved while maintaining a high balance of physical properties.

The hindered phenol-based heat stabilizer is, for example, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Octadecyl 3-(3,5-di-tert-butyl-4) -hydroxyphenyl)propionate, CAS number 2082-79-3), 2,2'-methylenebis(4-methyl-6-t-butylphenol), hexamethylene glycol-bis(3,5-di-t-butyl- 4-hydroxyhydrocinnamate), triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxy-benzyl)benzene, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenol) pro Cypionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-3-methyl-phenol), distearyl -3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenylacryl rate, and 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10 -It may be one or more types selected from the group consisting of tetraoxaspiro[5,5]undecane. The heat stabilizer is preferably pentaerythritol tetrakis [3-(3',5'-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl 3-(3,5-di-tert) -Butyl-4-hydroxyphenyl)propionate or a mixture thereof.

The phosphorus-based antioxidant is, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and tris (2,6-di-tert-butylphenyl) phosphite. Phyte, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl di. Phenyl phosphite, monooctyldiphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) ) Octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, stearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate , and it may be one or more types selected from the group consisting of trimethyl phosphate.

For example, the lubricant may be one or more selected from the group consisting of fatty acid amide compounds, montan wax, silicone oil, olefin wax, and pentaerythritol stearate, and preferably olefin wax and pentaerythritol stearate. It may be one or more types selected from the group consisting of, in which case not only is the molding processability and mold release property excellent, but the noise resistance and friction characteristics can be further improved.

The fatty acid amide compounds include, for example, stearamide, behenamide, ethylene bis(stearamide), ethylene bis 12-hydroxy stearamide [N,N'-ethylene bis(12), -hydroxystearamide)], erucamide, oleamide, and ethylene bis oleamide.

For example, the montan wax may be montan wax, montan ester wax, or a mixture thereof.

For example, the silicone oil may be one or more selected from the group consisting of dimethyl silicone oil, methyl hydrogen silicone oil, ester-modified silicone oil, hydroxy silicone oil, carbinol-modified silicone oil, vinyl silicone oil, and silicone acrylate.

The olefin-based wax may be, for example, polyethylene wax, polypropylene wax, or a mixture thereof.

For example, the pentaerythritol stearate may be one or more selected from the group consisting of pentaerythritol monostearate, pentaerythritol dirastearate, and pentaerythritol tetrastearate. there is.

For example, the magnesium oxide may undergo a crushing and/or classification process to have an average particle diameter of 100 ㎛ or less, specifically 10 to 100 ㎛, preferably 30 to 80 ㎛, more preferably 40 to 70 ㎛, In this case, there is an advantage in that the compatibility with the resin is improved and the desired physical properties are sufficiently expressed.

In this description, crushing and classification are not particularly limited as long as they are crushing and classification methods commonly used in the technical field to which the present invention pertains.

Thermoplastic resin composition

The thermoplastic resin composition of the present invention includes (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite, and (D) 3.3 to 3.3 to 10% by weight of bisphenol-based phosphate flame retardant. It is characterized in that it contains 10% by weight, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

The weight ratio (A:B) of the (A) polycarbonate resin and (B) boron nitride may be, for example, 1 to 2:1, preferably 1 to 1.7:1, more preferably 1 to 1.5:1. , more preferably 1 to 1.4:1, and in this case, there is an advantage in that electrical insulation, thermal conductivity, and flame retardancy are all excellent.

The weight ratio (B:C) of (B) boron nitride and (C) graphite may be, for example, 3 to 5:1, preferably 3.5 to 5:1, more preferably 3.8 to 4.8:1, and more preferably 3.8 to 4.8:1. Preferably it may be 3.9 to 4.7:1, more preferably 4.0 to 4.6:1, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

The sum of the weight of (B) boron nitride and (C) graphite contained in the thermoplastic resin composition may be, for example, 45 to 55% by weight, preferably 46 to 54% by weight, more preferably 47 to 54% by weight. %, more preferably 48 to 53 wt%, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

For example, when the thermoplastic resin composition includes magnesium oxide, the sum of the weight of (B) boron nitride, (C) graphite, and magnesium oxide may be 45 to 55% by weight, preferably 47 to 55% by weight. , more preferably within the range of 48 to 53% by weight, and even more preferably within the range of 49 to 53% by weight.

The thermoplastic resin composition includes, for example, (B) boron nitride, (C) graphite, and (E) a heat dissipating filler such as magnesium oxide, which may be included as an additive, within the above range, thereby realizing high thermal conductivity and electrical power. It has the advantage of excellent insulation.

In this description, heat dissipation filler refers to a component added to a thermoplastic resin material (plastic) to improve heat dissipation performance.

For example, the thermoplastic resin composition has a thermal conductivity measured according to ASTM E1461 of 7 W/m·K or more, preferably 7.01 to 20 W/m·K, more preferably 7.1 to 15 W/m·K, More preferably, it may be 7.1 to 10 W/m·K, and within this range, there is an advantage in that the heat dissipation characteristics are superior without deterioration of other physical properties.

In this description, thermal conductivity is not particularly limited when measured by a measurement method commonly used in the technical field to which the present invention pertains, and can specifically be obtained by calculating using Equation 2 below.

[Equation 2]

Thermal conductivity (W/m·K) = C × ρ × α

(In Equation 2 above, C means specific heat (J/g·K), ρ means specific gravity, and α means thermal diffusivity (mm ² /sec).)

In this description, specific heat can be measured using a Differential Scanning Calorimeter (DSC) according to ISO 11357-4 and distilled water as a standard sample, and specific gravity can be measured under conditions of 25°C according to ISO 1183. Thermal diffusivity can be measured under the conditions of 25°C and 50 RH% relative humidity using a specimen with a width of 1 inch and a thickness of 0.5 mm based on the laser flash method (ASTM E1461).

For example, the thermoplastic resin composition may have an exponent of 10 of surface resistance (Ω/sq) measured in accordance with IEC 60093 of 12.1 or more, preferably 12.1 to 15, more preferably 12.5 to 15, even more preferably May be 12.8 to 14.5, more preferably 13 to 14, and within this range, there is an advantage of superior electrical insulation without deterioration of other physical properties.

In this paper, the surface resistance is measured by 4-point probe measurement using a surface resistance meter (SRM-110) on a square specimen of size 100mm × 100mm × 30mm under the conditions of 25℃ and 50 RH% relative humidity in accordance with IEC 60093. It can be expressed as the average value measured for more than one sample.

The thermoplastic resin composition is, for example, according to ISO 75 The heat distortion temperature (HDT) measured under the conditions of a load of 0.45 MPa and a thickness of 4 mm may be 102°C or higher, preferably 102 to 130°C, more preferably 103 to 125°C, and even more preferably 105 to 123°C. It has the advantage of excellent balance of heat resistance and mechanical properties within this range.

For example, the thermoplastic resin composition has T.I. calculated by Equation 1 below. The index (Thermal conductive & Electrically Insulating index) value may be 0.001 to 1.22, preferably 0.005 to 1.20, more preferably 0.01 to 1.18, more preferably 0.02 to 1.16, even more preferably 0.03 to 1.15. It has the advantage of excellent balance of heat resistance and mechanical properties within this range. In particular, it can be applied to fields that require both high levels of thermal conductivity and electrical insulation by adjusting the thermal conductivity, electrical insulation, and heat resistance properties within a predetermined range. There are the following suitable advantages.

[Equation 1]

T.I. index = [(thermal conductivity - 7) × (surface resistance - 12) × {(heat distortion temperature - 100) × 0.1}]

(In Equation 1 above, thermal conductivity is a value in units of W/m·K measured in accordance with ASTM E1461, surface resistance is an exponent of 10 of the value in units of Ω/sq measured in accordance with IEC 60093, and thermal strain Temperature indicates the value in ℃ measured under the conditions of load of 0.45 MPa and thickness of 4 mm according to ISO 75.)

For example, the thermoplastic resin composition can satisfy the V-0 grade in flame retardancy measured under a specimen thickness of 1.5 mm according to the UL 94 standard (Vertical Burning Test). In this case, it has excellent flame retardancy and is suitable for use in fields that require a high level of flame retardancy. There are advantages that make it suitable for application.

For example, the thermoplastic resin composition has a flow index of 10 g/10 min or more, preferably 10 to 30 g/10 min, more preferably 15 to 30 g/, as measured under ASTM D1238 at a temperature of 300°C and a load of 1.2 kg. It may be 10 min, more preferably 20 to 30 g/10 min, and within this range, superior molding processability is achieved without deterioration of other physical properties.

Method for producing thermoplastic resin composition

The method for producing the thermoplastic resin composition of the present invention includes (A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite, and (D) bisphenol-based phosphate. It is characterized by including 3.3 to 10% by weight of a flame retardant and kneading and extruding at 200 to 300 ° C. In this case, there are advantages in that electrical insulation, thermal conductivity, and flame retardancy are all excellent.

For example, the kneading and extruding steps may be carried out at a temperature and a screw rotation speed of the extruder of 200 to 300°C and 200 to 350 rpm, preferably 220 to 280°C and 240 to 300 rpm, respectively. In this case, the desired electrical insulation properties are achieved. , it has the advantage of both excellent thermal conductivity and flame retardancy.

The kneading and extruding steps may be performed using, for example, one or more types selected from the group consisting of a single-screw extruder, a twin-screw extruder, and a Banbury mixer. Using this, the composition is uniformly mixed and then extruded to form, for example, a pellet. A thermoplastic resin composition can be obtained, and in this case, it has the effect of preventing deterioration of mechanical properties and heat resistance from occurring and providing excellent appearance quality.

For example, the method for producing the thermoplastic resin composition includes, in addition to the additives (E), optionally using UV stabilizers (light stabilizers), pigments, colorants, antistatic agents, antibacterial agents, processing aids, compatibilizers, suppressants, matting agents, It may further include one or more additional additives selected from the group consisting of anti-friction agents and anti-wear agents. The additional additive is 0.01 to 10 parts by weight based on 100 parts by weight of the total weight of the (A) polycarbonate resin, (B) boron nitride, (C) graphite, (D) bisphenol-based phosphate flame retardant, and (E) additive, It may further be included in an amount of 0.05 to 7 parts by weight, 0.1 to 5 parts by weight, or 0.5 to 4.5 parts by weight, and within this range, the desired physical properties of the thermoplastic resin composition of the present base are well realized without deteriorating the desired physical properties. There is.

The UV stabilizers include, for example, triazine-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, indole-based UV absorbers, quinolinone-based UV absorbers, benzoate-based UV absorbers, cyanoacrylate-based UV absorbers, and benzooxa. It may be one or more types selected from the group consisting of sol-based ultraviolet absorbers, and is preferably a benzotriazole-based ultraviolet absorber. In this case, it has an excellent balance of physical properties and further improves light resistance.

The triazine-based UV absorber is, for example, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2 -Hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2 ,4-Diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)- 1,3,5-triazine, 2,6-diphenyl-4-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-( 2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5- Triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-prop Oxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-tris( 2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-dodecyloxyphenyl)- 1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy -4-ethoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-methoxycarbonyl) Propyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-ethoxycarbonylethyloxyphenyl)-1,3,5-triazine, 2,4 ,6-tris(2-hydroxy-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5-triazine, 2,4 ,6-tris(2-hydroxy-3-methyl-4-ethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-prop Oxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine, 2,4, 6-tris(2-hydroxy-3-methyl-4-butoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-hexyloxy Phenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6 -Tris(2-hydroxy-3-methyl-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-benzyloxy Phenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-ethoxyethoxyphenyl)-1,3,5-triazine, 2,4 ,6-tris(2-hydroxy-3-methyl-4-butoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4 -Propoxyethoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-3-methyl-4-methoxycarbonylpropyloxyphenyl)-1,3,5 -Triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-ethoxycarbonylethyloxyphenyl) -1,3,5-triazine, 2,4,6-tris (2 -Hydroxy-3-methyl-4-(1-(2-ethoxyhexyloxy)-1-oxopropan-2-yloxy)phenyl)-1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3, It may be one or more selected from the group consisting of 5-triazin-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol.

The benzophenone-based ultraviolet absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4- Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2-hydroxy-4- Dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydride Roxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis( 5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and 4 , 4'-bis(diethylamino)benzophenone may be one or more selected from the group consisting of.

The benzotriazole-based UV absorber is, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-2'-hydroxy-3',2-(2'-hydroxy-3'- tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5'-bis(α,α-dimethylbenzyl)phenyl-benzotriazole, 2 -(2'-Hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5 -Chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5 '-di-tert-amyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2-(2'-hyde Roxy-3'-(3”,4”,5”,6”-tetrahydrophthalimidemethyl)-5’-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di- tert-pentylphenyl), 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl) -6-(2H-benzotriazol-2-yl)phenol] may be one or more selected from the group consisting of.

For example, the indole-based UV absorber may be 2-[(1-methyl-2-phenyl-1H-indol-3-yl)methylene]propandinitrile.

For example, the quinolinone-based ultraviolet absorber may be 4-hydroxy-3-[(phenylimino)methyl]-2(1H)-quinolinone.

The benzoate-based ultraviolet absorber is, for example, 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, 2,6-di-t-butyl Phenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and n-octadecyl- It may be one or more types selected from the group consisting of 3,5-di-t-butyl-4-hydroxybenzoate.

The cyanoacrylate-based ultraviolet absorber is, for example, 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3-(3',4'-methylenedioxy) It may be phenyl)-acrylate, or a mixture thereof.

The pigment may be an inorganic pigment or an organic pigment.

For example, the inorganic pigment may be one or more selected from the group consisting of ultramarine-based pigments, titanium dioxide, and zinc sulfide.

The organic pigments include, for example, perrinone-based pigments, anthraquinone-based pigments, perylene-based pigments, phthalocyanine-based pigments, azo-based pigments, indigo-based pigments, dioxazine-based pigments, quinacridone-based pigments, methane-based pigments, quinoline-based pigments, and isoindrin. It may be one or more types selected from the group consisting of paddy-based pigments and phthalone-based pigments.

The antistatic agent may include, for example, one or more types of anionic surfactants and non-ionic surfactants, but is not limited thereto.

The colorants, antibacterial agents, processing aids, compatibilizers, suppressants, matting agents, anti-friction agents, anti-wear agents, etc. are not particularly limited as long as they are commonly used in the technical field to which the present invention pertains.

molded product

The molded article of the present invention is characterized by comprising a thermoplastic resin composition of the present base, and in this case, it has the advantage of excellent electrical insulation, thermal conductivity, and flame retardancy.

The molded article may preferably be manufactured by including the step of injecting a melt kneaded product or pellet of the thermoplastic resin composition according to the present invention using an injection machine, and the molded article manufactured in this way has all of electrical insulation, thermal conductivity, and flame retardancy. It is excellent and has the advantage of being suitable for fields that require both electrical insulation and heat dissipation characteristics, and has the advantage of being suitable for electrical and electronic components, especially automotive electrical components such as connectors, and electric vehicle parts.

The injection step may be performed by, for example, injection molding, injection compression molding, extrusion molding, blow molding, press molding, pressure molding, heat bend molding, compression molding, calendar molding, or rotation molding. At this time, the size and thickness of the molded product can be appropriately adjusted depending on the purpose of use, and it can be manufactured in the form of a flat plate or curved surface depending on the purpose of use.

In describing the thermoplastic resin composition, its manufacturing method, and molded article of the present disclosure, it is stated that other conditions and equipment not explicitly described can be appropriately selected within the range commonly practiced in the industry and are not particularly limited. do.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that such changes and modifications fall within the scope of the attached patent claims.

[Example]

The materials used in the following examples and comparative examples are as follows.

(A-1) Polycarbonate resin: measured at a temperature of 300°C and a load of 1.2 kg according to ASTM D1238. Bisphenol A type PC resin (weight average molecular weight 9,000) with a flow index of 30 g/10min and a linear thermal expansion coefficient of 65 to 70 × 10 ^-6 mm/mm/℃ measured at a temperature of -40 to 82°C according to ASTM D696 g/mol)

(B-1) Boron nitride: hexagonal BN with an average particle diameter of 35㎛ and a BET specific surface area of 2 m ² /g.

(B-2) Boron nitride: Hexagonal BN with an average particle diameter of 20㎛ and a BET specific surface area of 3 m ² /g.

(B-3) Boron nitride: average particle diameter is 100㎛, BET specific surface area is Hexagonal BN with 3 m ² /g

(C-1) Graphite: flake graphite with an average particle diameter of 75 to 81㎛ (apparent density of 0.35 to 0.37 g/cm ³ )

(C-2) Graphite: Expanded graphite with an average particle diameter of 350㎛ (apparent density 0.2 g/cm ³ )

(D-1) Bisphenol-based phosphate flame retardant: Bisphenol A diphosphate flame retardant with a viscosity of 12,800 to 13,100 mPa·s at 25°C and a viscosity of 120 to 220 mPa·s at 70°C.

(D-2) Phenyl phosphate flame retardant: 1,3-phenylene bis phosphate flame retardant of powder type at 25°C

(E1) Anti-drip agent: PTFE/SAN mixed anti-drip agent (weight ratio 1:1, Porcera Xflon-G)

(E2) Antioxidant: Irganox 1076 (BASF)

(E3) Lubricant: PETS-AHS (FACI)

Examples 1 to 6 and Comparative Examples 1 to 11

Components (A) to (E) were mixed using a super mixer in the amounts shown in Tables 1 and 3 below, and then extruded using a twin-screw extruder (screw diameter 40 mm, L/D=42). It was extruded under extrusion conditions of 260°C and a screw rotation speed of 250 rpm to form a pellet.

The prepared thermoplastic resin composition in the form of pellets was dried at 100°C for more than 2 hours, and then injection molded in an injection machine under the conditions of an injection temperature of 260°C, a mold temperature of 60°C, and an injection speed of 30 mm/sec to prepare a specimen, which was incubated at room temperature (20 to 26°C) for more than 48 hours, and then the physical properties were measured.

[Test example]

The physical properties of the specimens prepared in the above Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 1 and 3 below.

* Specific heat (J/g·K): Based on ISO 11357-4, a specimen measuring 5 mm wide, 5 mm long, and 2 mm thick was used as a standard sample using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). was measured using distilled water.

* Specific gravity: Measured under conditions of 25°C using a specimen with a width of 10 mm, a height of 10 mm, and a thickness of 2 mm, according to ISO 1183.

* Thermal diffusivity (mm ² /sec); According to ASTM E1461, measurements were made under the conditions of 25°C and 50 RH% relative humidity using a specimen with a width of 1 inch and a thickness of 0.5 mm.

* Thermal conductivity (W/m·K): Using the specific heat, specific gravity, and thermal diffusivity values measured above, it was calculated using Equation 2 below.

[Equation 2]

Thermal conductivity (W/m·K) = C × ρ × α

(In Equation 2 above, C means the specific heat (J/g·K) value, ρ means the specific gravity value, and α means the thermal diffusivity (mm ² /sec) value.)

* Surface resistance index (10^E Ω/sq): In accordance with IEC 60093, using a surface resistance meter (SRM-110) using a square specimen of 100mm × 100mm × 30mm at 25℃ and 50 RH% relative humidity. It is an exponent value of 10 of the value obtained by measuring with a 4-point probe measurement method, and the average value measured for 5 or more samples is calculated and expressed.

* Heat distortion temperature (℃): Measured under a load condition of 0.45 MPa using a specimen with a thickness of 4 mm according to ISO-75.

*T.I. Index: T.I. is a value calculated using Equation 1 below using the measured thermal conductivity, surface resistance index, and heat distortion temperature values. The index was obtained.

[Equation 1]

T.I. index = [(thermal conductivity - 7) × (surface resistance - 12) × {(heat distortion temperature - 100) × 0.1}]

(In Equation 1 above, thermal conductivity is a value in units of W/m·K measured in accordance with ASTM E1461, surface resistance is an exponent of 10 of the value in units of Ω/sq measured in accordance with IEC 60093, and thermal strain Temperature indicates the value in ℃ measured under the conditions of load 0.45 MPa and thickness 4 mm according to ISO 75)

* Flame retardancy (grade): Measured with an injection specimen with a thickness of 1.5 mm according to the UL 94 standard (Vertical Burning Test). If it meets the V-0 grade according to the UL 94 standard, it is O, if it does not meet the V-0 grade. Case was written as X.

division Example One 2 3 4 5 6 A-1 PC 45.2 43.7 43.2 41.7 44.0 48.2 B-1 BN (35㎛) 40.0 40.0 42.0 40.0 40.0 34.5 B-2 BN (20㎛) - - - - - - B-3 BN (100㎛) - - - - - - C-1 flake graphite (80㎛) 10.0 10.0 10.0 10.0 8.7 11.5 C-2 Expanded graphite (350㎛) - - - - - - D-1 flame retardant 3.5 5.0 3.5 7.0 6.0 4.5 D-2 flame retardant - - - - - - E-1 anti-dripping agent 0.5 0.5 0.5 0.5 0.5 0.5 E-2 stabilizator 0.4 0.4 0.4 0.4 0.4 0.4 E-3 active 0.4 0.4 0.4 0.4 0.4 0.4 Thermal conductivity (W/mK) 7.1 7.32 7.8 7.4 7.2 7.1 Surface resistance (10^E Ω/sq) 13 13 13 13 14 12.5 Heat distortion temperature (℃) 114 108.5 114 105 107 110 Flame retardant V-0 grade (@1.5T) O O O O O O TI index 0.140 0.272 1.120 0.200 0.280 0.050

division Comparative example One 2 3 4 5 6 A-1 PC 48.7 58.7 48.7 43.7 56.7 33.7 B-1 BN (35㎛) 50.0 - 35.0 35.0 23.0 52.0 B-2 BN (20㎛) - - - - - - B-3 BN (100㎛) - - - - - - C-1 flake graphite (80㎛) - 40.0 15.0 15.0 14.0 8.0 C-2 Expanded graphite (350㎛) - - - - - - D-1 flame retardant - - - - 5.0 5.0 D-2 flame retardant - - - 5.0 - - E-1 anti-dripping agent 0.5 0.5 0.5 0.5 0.5 0.5 E-2 stabilizator 0.4 0.4 0.4 0.4 0.4 0.4 E-3 active 0.4 0.4 0.4 0.4 0.4 0.4 Thermal conductivity (W/mK) 6.12 9.8 8.32 8.19 7.2 6.9 Surface resistance (10^E Ω / sq) 16 5 10 10 10 14 Heat distortion temperature (℃) 135.1 130.5 134.9 101.2 108.5 108.5 Flame retardant V-0 grade (@1.5T) X X X X O O TI index -12.355 -59.780 -9.214 -0.286 -0.340 -0.170

division Comparative example 7 8 9 10 11 A-1 PC 45.7 38.2 43.7 43.7 43.7 B-1 BN (35㎛) 40.0 40.0 - - 40.0 B-2 BN (20㎛) - - 40.0 - - B-3 BN (100㎛) - - - 40.0 - C-1 flake graphite (80㎛) 10.0 10.0 10 10 - C-2 Expanded graphite (350㎛) - - - - 10 D-1 flame retardant 3.0 10.5 5.0 5.0 5.0 D-2 flame retardant - - - - - E-1 anti-dripping agent 0.5 0.5 0.5 0.5 0.5 E-2 stabilizator 0.4 0.4 0.4 0.4 0.4 E-3 active 0.4 0.4 0.4 0.4 0.4 Thermal conductivity (W/mK) 7 7.2 6.2 6.7 6.0 Surface resistance (10^E Ω/sq) 13 13 13 13 13 Heat distortion temperature (℃) 115 98 108 109 108.5 Flame retardant V-0 grade (@1.5T) X O O O O TI index 0 -0.040 -0.640 -0.270 -0.850

Referring to Tables 1 to 3, Examples 1 to 6 prepared according to the present invention were found to be superior in thermal conductivity, electrical insulation, heat resistance, and flame retardancy compared to Comparative Examples 1 to 11D.

On the other hand, Comparative Examples 1 to 11 were T.I. It was found that the index significantly deviated from the scope of the present invention and that the thermal conductivity, electrical insulation, heat resistance and/or flame retardancy were poor.

As a result, it was confirmed that the thermoplastic resin composition of the example prepared according to the present invention is suitable for application as a heat dissipation material requiring a high level of flame retardancy and heat resistance, such as automobile electrical components, integrated circuits such as electrical and electronic components, and lighting housings. .

Claims (15)

(A) 30 to 60% by weight of polycarbonate resin;
(B) 30 to 50% by weight of boron nitride;
(C) 5 to 20% by weight of graphite with an average particle diameter of 50 to 200㎛; and
(D) 3.3 to 10% by weight of a bisphenol-based phosphate flame retardant;
Thermoplastic resin composition.
According to clause 1,
Characterized in that the weight ratio (A:B) of the (A) polycarbonate resin and (B) boron nitride is 1 to 2:1.
Thermoplastic resin composition.
According to clause 1,
Characterized in that the sum of the weight of (B) boron nitride and (C) graphite is 45 to 55% by weight.
Thermoplastic resin composition.
According to clause 1,
Characterized in that the weight ratio (B:C) of (B) boron nitride and (C) graphite is 3 to 5: 1.
Thermoplastic resin composition.
According to clause 1,
The (A) polycarbonate resin is characterized in that the weight average molecular weight is 5,000 to 25,000 g/mol.
Thermoplastic resin composition.
According to clause 1,
The (A) polycarbonate resin is characterized in that the linear thermal expansion coefficient measured according to ASTM D696 is 30 to 90 × 10 ^-6 mm/mm/℃.
Thermoplastic resin composition.
According to clause 1,
The boron nitride (B) has an average particle diameter of 28 to 65㎛ and a BET specific surface area of 0.5 to 10 m ² /g.
Thermoplastic resin composition.
According to clause 1,
The (C) graphite is characterized in that it is flake type graphite.
Thermoplastic resin composition.
According to clause 1,
The (C) graphite is characterized in that the apparent density is 0.1 to 1.0 g/cm ³ at 25°C.
Thermoplastic resin composition.
According to clause 1,
The (D) bisphenol-based phosphate flame retardant is characterized in that the viscosity is 10,000 to 17,000 mPa·s at 25°C.
Thermoplastic resin composition.
According to clause 1,
The (D) bisphenol-based phosphate flame retardant is characterized in that the viscosity is 100 to 500 mPa·s at 70°C.
Thermoplastic resin composition.
According to clause 1,
Based on the total weight of the thermoplastic resin composition, (E) one or more additives selected from the group consisting of anti-dripping agents, antioxidants, lubricants, and magnesium oxide,
0.5 to 5% by weight of the (E) additive based on a total of 100% by weight of the (A) polycarbonate resin, (B) boron nitride, (C) graphite, (D) bisphenol-based phosphate flame retardant, and (E) additive. Characterized by including
Thermoplastic resin composition.
According to clause 1,
The thermoplastic resin composition is characterized in that the TI index value calculated by Equation 1 below is 0.001 to 1.22.
Thermoplastic resin composition.
[Equation 1]
TI index = [(thermal conductivity - 7) × (surface resistance - 12) × {(heat distortion temperature - 100) × 0.1}]
(In Equation 1 above, thermal conductivity is a value in units of W/m·K measured in accordance with ASTM E1461, surface resistance is an exponent of 10 of the value in units of Ω/sq measured in accordance with IEC 60093, and thermal strain Temperature indicates the value in ℃ measured under the conditions of load 0.45 MPa and thickness 4 mm according to ISO 75)
(A) 30 to 60% by weight of polycarbonate resin, (B) 30 to 50% by weight of boron nitride, (C) 5 to 20% by weight of graphite with an average particle diameter of 50 to 200㎛, and (D) 3.3 to 3.3 to 3.3% by weight of bisphenol-based phosphate flame retardant. Kneading and extruding at 200 to 300°C, including 10% by weight.
Method for producing a thermoplastic resin composition.
Characterized by comprising the thermoplastic resin composition of any one of claims 1 to 13.
Molded product.